Basic Water Quality Laboratory Procedures Manual.pdf

49331-88

DREL/2010Basic Water Quality

LaboratoryProcedures Manual

© Hach Company, 1996. All rights reserved. Printed in U.S.A. lr 09-06-96-1ED

ii

TABLE OF CONTENTS

PROCEDURES ..................................................................................................................... 1

ALKALINITY, Phenolphthalein and Total ...............................................................................3Using Sulfuric Acid with a Digital Titrator ............................................................................3

BROMINE, DPD Method ........................................................................................................11

CARBON DIOXIDE, Using Sodium Hydroxide with a Digital Titrator ................................19

CHLORIDE, Using Silver Nitrate with a Digital Titrator .......................................................23

CHLORINE, FREE, DPD Method ..........................................................................................27

CHLORINE, TOTAL, DPD Method .......................................................................................35

CHROMIUM, HEXAVALENT, 1,5-Diphenylcarbohydrazide Method .................................43

CONDUCTIVITY, Using Pocket Pal™ Conductivity Tester .................................................51

COPPER, Bicinchoninate Method ...........................................................................................57

FLUORIDE, SPADNS Method ...............................................................................................65

HARDNESS, TOTAL, Using EDTA with a Digital Titrator ..................................................73

IODINE, DPD Method.............................................................................................................81

IRON, TOTAL, FerroVer Method...........................................................................................89

NITRATE, HR, Cadmium Reduction Method.........................................................................97

NITROGEN, AMMONIA, Salicylate Method ......................................................................105

OXYGEN, DISSOLVED, Azide Modification of Winkler Method Using Digital Titrator..........................................................................111Using a 300-mL BOD Bottle ..............................................................................................111Using a 60-mL BOD Bottle ................................................................................................113

pH, Hach One® Combination pH Electode Method with a EC 10 Portable Meter ................117Sample pH Measurement ....................................................................................................117Two-Standard Calibration in Automatic Mode with Temperature Probe ..........................117

PHOSPHORUS, ACID HYDROLYZABLE, Hydrolysis to Orthophosphate Method...............................................................................123

PHOSPHORUS, REACTIVE, (Also called Orthophosphate) PhosVer® 3 (Ascorbic Acid) Method .................................127

SULFATE, SulfaVer® 4 Method............................................................................................135

TURBIDITY, Using the 2100P Turbidimeter........................................................................143

GENERAL INFORMATION ........................................................................................ 147

HOW TO ORDER.............................................................................................................. 149

iii

iv

PROCEDURES

1

2

Method 8203

ALKALINITY (10 - 4000 mg/L as CaCO3)

Phenolphthalein and Total For water, wastewater and seawater

Using Sulfuric Acid with a Digital Titrator

1. Select the sample volume and Sulfuric Acid (H2SO4) Titration Cartridge corresponding to the expected alkalinity concentration as mg/L calcium carbonate (CaCO3) from Table 1.

Note: See Sampling and Storage following these steps.

2. Insert a clean delivery tube into the titration cartridge. Attach the cartridge to the titrator body. See General Description, Step-by-Step, of the Digital Titrator Manual for assembly instructions, if necessary.

3. Turn the delivery knob to eject a few drops of titrant. Reset the counter to zero and wipe the tip.

Note: For added convenience use the TitraStir® stirring apparatus, see General Description, Step 3 in Step-by-Step, of the Digital Titrator Manual.

4. Use a graduated cylinder or pipet to measure the sample volume from Table 1. Transfer the sample into a clean 250-mL erlenmeyer flask. Dilute to about the 100-mL mark with demineralized water, if necessary.

Table 1

Range (mg/L as CaCO3)

Sample Volume (mL)

Titration Cartridge (H2SO4)

Catalog Number

Digit Multiplier

10-4040-160

100-400200-800500-2000

1000-4000

10025

100502010

0.16000.16001.6001.6001.6001.600

14388-0114388-0114389-0114389-0114389-0114389-01

0.10.41.02.05.0

10.0

3

ALKALINITY, continued

5. Add the contents of one Phenolphthalein Indicator Powder Pillow and swirl to mix.

Note: A solution of one pH 8.3 Buffer Powder Pillow and one Phenolphthalein Powder Pillow in 50 mL of demineralized water is recommended as a comparison for determining the proper end-point color.

Note: Four drops of Phenolphthalein Indicator Solution may be substituted for the Phenolphthalein Indicator Powder Pillow.

6. If the solution turns pink, titrate to a colorless end point. Place the delivery tube tip into the solution and swirl the flask while titrating with sulfuric acid. Record the number of digits required.

Note: If the solution is colorless before titrating with Sulfuric acid, the Phenolphthalein (P) alkalinity is zero; proceed with Step 8.

7. Calculate:

Digits Required x Digit Multiplier = mg/L CaCO3 P Alkalinity

8. Add the contents of one Bromcresol Green-Methyl Red Indicator Powder Pillow to the flask and swirl to mix.

Note: Four drops of Methyl Purple Indicator Solution may be substituted for the Bromcresol Green-Methyl Red Indicator Powder Pillow. Titrate from green to a gray end point (pH 5.1).

Note: Four drops of Bromcresol Green-Methyl Red Indicator Solution may be substituted for the Bromcresol Green-Methyl Red Indicator Powder Pillow.

4


9. Continue the titration with sulfuric acid to a light greenish blue-gray (pH 5.1), a light violet-gray (pH 4.8), or a light pink (pH 4.5) color, as required by the sample composition; see Table 2. Record the number of digits required.

Note: A solution of one Bromcresol Green-Methyl Red Powder Pillow and one pillow of the appropriate pH buffer in 50 mL of demineralized water is recommended as a comparison for judging the proper end-point color. If the pH 3.7 end point is used, use a Bromphenol Blue Powder Pillow instead of a Bromcresol Green-Methyl Red and titrate to a green end point.

10. Calculate:

Total Digits Required x Digit Multiplier = mg/L as CaCO3 Total (T or M) Alkalinity

Note: Carbonate, bicarbonate and hydroxide concentrations may be expressed individually using the relationships shown in Table 3 on page 7.

Note: meq/L Alkalinity = mg/L as CaCO3 ÷ 50.

Table 2

Sample CompositionEnd

Point

Alkalinity about 30 mg/LAlkalinity about 150 mg/LAlkalinity about 500 mg/LSilicates or Phosphates presentIndustrial waste or complex system

pH 5.1pH 4.8pH 4.5pH 4.5pH 3.7

5


Sampling and StorageCollect samples in clean plastic or glass bottles. Fill completely and captightly. Avoid excessive agitation or prolonged exposure to air. Samplesshould be analyzed as soon as possible after collection but can be stored atleast 24 hours by cooling to 4 oC (39 oF) or below. Warm to roomtemperature before analyzing.

Alkalinity RelationshipTotal alkalinity primarily includes hydroxide, carbonate and bicarbonatealkalinities. The concentration of these alkalinities in a sample may bedetermined when the phenolphthalein and total alkalinities are known(see Table 3).

To use the table follow these steps:

a) Does the phenolphthalein alkalinity equal zero? If yes, use Row 1.

b) Does the phenolphthalein alkalinity equal total alkalinity? If yes, use Row 2.

c) Multiply the phenolphthalein alkalinity by 2.

Table 3

Row Result of TitrationHydroxide Alkalinity

is equal to:

Carbonate Alkalinityis equal to:

Bicarbonate Alkalinity

is equal to:

1Phenolphthalein

Alkalinity = 00 0 Equal to Total

Alkalinity

2Phenolphthalein

Alkalinity equal to Total Alkalinity

Total Alkalinity 0 0

3

Phenolphthalein Alkalinity less than one

half of Total Alkalinity

0 2 times the Phenolphthalein

Alkalinity

Total Alkalinity minus two times

Phenolphthalein Alkalinity

4Phenolphthalein

Alkalinity equal to one half of Total Alkalinity

0 2 times the Phenolphthalein

Alkalinity

0

5

Phenolphthalein Alkalinity greater than

one half of Total Alkalinity

2 times the Phenolphthalein

minus Total Alkalinity

2 times the difference between

Total and Phenolphthalein

Alkalinity

0

6


7

d) Select Row 3, 4, or 5 based on comparing the result of Step c with the total alkalinity.

e) Perform the required calculations in the appropriate row, if any.

f) Check your results. The sum of the three alkalinity types will equal the total alkalinity.

For example:A sample has 170 mg/L as CaCO3 phenolphthalein alkalinity and 250 mg/Las CaCO3 total alkalinity. What is the concentration of hydroxide, carbonateand bicarbonate alkalinities?

The phenolphthalein alkalinity does not equal 0 (it is 170 mg/L), see Step a.

The phenolphthalein alkalinity does not equal total alkalinity (170 mg/L vs 250 mg/L), see Step b.

The phenolphthalein alkalinity multiplied by 2 = 340 mg/L, see Step c.

Because 340 mg/L is greater than 250 mg/L, select Row 5. see Step d.

The hydroxide alkalinity is equal to: (See Step e)

The carbonate alkalinity is equal to:

The bicarbonate alkalinity equals 0 mg/L.

Check: (See Step f)

The above answer is correct; the sum of each type equals the total alkalinity.

Accuracy Check Standard Additions Method

This accuracy check should be performed when interferences are suspected orto verify analytical technique.

1. Snap the neck off an Alkalinity Voluette® Ampule Standard, 0.500 N.

2. Use a TenSette® Pipet to add 0.1 mL of standard to the sample titrated in Steps 6 or 9. Resume titration back to the same end point. Record the number of digits needed.

340 250 – 90 mg/L hydroxide alkalinity=

250 170– 80=

80 2× 160 mg/L carbonate alkalinity=

90 mg/L hydroxide alkalinity 160 mg/L carbonate alkalinity +0 mg/L bicarbonate alkalinity 250 mg/L =

+


8

3. Repeat, using two more additions of 0.1 mL. Titrate to the end point after each addition.

4. Each 0.1 mL addition of standard should require 25 additional digits of 1.600 N titrant or 250 digits of 0.1600 N titrant. If these uniform increases do not occur, refer to Appendix A, Accuracy Check and Standard Additions in the Digital Titrator Manual to determine the cause.

Interferences• Highly colored or turbid samples may mask the color change at the

end point. Use a pH meter for these samples.

• Chlorine may interfere with the indicators. Add one drop of 0.1 N Sodium Thiosulfate to eliminate this interference.

Summary of MethodThe sample is titrated with sulfuric acid to a colorimetric end pointcorresponding to a specific pH. Phenolphthalein alkalinity is determined bytitration to a pH of 8.3, as evidenced by the color change of phenolphthaleinindicator, and indicates the total hydroxide and one half the carbonate present.M (methyl orange) or T (total) alkalinity is determined by titration to a pHbetween 3.7 and 5.1, and includes all carbonate, bicarbonate and hydroxide.

REQUIRED REAGENTS(varies with sample characteristics)Alkalinity Reagent Set (about 100 tests)

Includes: (1) 943-99, (1) 942-99, (1) 14389-01, (1) 14388-01, .............................. 22719-00Description Unit Cat. NoBromcresol Green-Methyl Red Powder Pillows...................................... 100/pkg........... 943-99Phenolphthalein Powder Pillows ............................................................. 100/pkg........... 942-99Sulfuric Acid Titration Cartridge, 1.600 N.................................................... each....... 14389-01Sulfuric Acid Titration Cartridge, 0.1600 N.................................................. each....... 14388-01Water, demineralized .......................................................................................4 L ........... 272-56

REQUIRED APPARATUSClippers, for opening pillows......................................................................... each........... 968-00Digital Titrator ............................................................................................... each....... 16900-01Flask, erlenmeyer, 250 mL ............................................................................ each........... 505-46

Select one or more based on sample concentrationCylinder, graduated, 10 mL ........................................................................... each........... 508-38Cylinder, graduated, 25 mL ........................................................................... each........... 508-40Cylinder, graduated, 50 mL ........................................................................... each........... 508-41Cylinder, graduated, 100 mL ......................................................................... each........... 508-42


OPTIONAL REAGENTSDescription Unit Cat. NoAlkalinity Standard Solution,

Voluette Ampule 0.500 N Na2CO3, 10 mL .............................................16/pkg .......14278-10Bromcresol Green-Methyl Red Indicator Solution ........................ 100 mL MDB .......23292-32Bromphenol Blue Indicator Solution ............................................. 100 mL MDB .......14552-32Bromphenol Blue Powder Pillows ...........................................................100/pkg .......14550-99Buffer Powder Pillows, pH 3.7...................................................................25/pkg .......14551-68Buffer Powder Pillows, pH 4.5...................................................................25/pkg ...........895-68Buffer Powder Pillows, pH 4.8...................................................................25/pkg ...........896-68Buffer Powder Pillows, pH 5.1...................................................................25/pkg ...........897-68Buffer Powder Pillows, pH 8.3...................................................................25/pkg ...........898-68Methyl Purple Indicator Solution................................................... 100 mL MDB .......21934-32Phenolphthalein Indicator Solution, 5 g/L ....................................100 mL MDB* ...........162-32Sodium Thiosulfate Standard Solution, 0.1 N................................ 100 mL MDB ...........323-32

OPTIONAL APPARATUSBottle, wash, poly, 500 mL ............................................................................each ...........620-11Clamp, 2-prong extension, 38 mm .................................................................each .......21145-00Clamp Holder .................................................................................................each ...........326-00Demineralizer Assembly, 473 mL..................................................................each .......21846-00Delivery Tubes, with 180° hook...................................................................5/pkg .......17205-00Delivery Tubes, 90° with hook for TitraStir.................................................5/pkg .......41578-00Hach One Combination pH Electrode with Temp .........................................each .......48600-22pH Meter, EC 10, portable .............................................................................each .......50050-00Pipet, TenSette, 0.1 to 1.0 mL ........................................................................each .......19700-01Pipet tips for 19700-01 TenSette pipet .......................................................50/pkg .......21856-96Pipet, volumetric, Class A, 10 mL .................................................................each .......14515-38Pipet, volumetric, Class A, 20 mL .................................................................each .......14515-20Pipet, volumetric, Class A, 25 mL .................................................................each .......14515-40Pipet, volumetric, Class A, 50 mL .................................................................each .......14515-41Pipet, volumetric, Class A, 100 mL ...............................................................each .......14515-42Pipet Filler, safety bulb...................................................................................each .......14651-00Stand, Stirrer/Electrode holder, 115 Vac ........................................................each .......45300-01Stand, Stirrer/Electrode holder, 230Vac .........................................................each .......45300-02Support ring stand ..........................................................................................each ...........563-00TitraStir Mixer/Stand Assembly, 115 Vac......................................................each .......19400-00TitraStir Mixer/Stand, Assembly, 230 Vac.....................................................each .......19400-10

For technical support and ordering information, see General Information section.In the U.S.A. call 800-227-4224 to place an order.Outside the U.S.A.—Contact the Hach office or distributor serving you.

* Contact Hach for larger sizes.

9

10

Method 8016

BROMINE (0 to 4.50 mg/L) For water, wastewater, and seawater

DPD Method* (Powder Pillows or AccuVac Ampuls)

Using Powder Pillows

* Adapted from Standard Methods for the Examination of Water and Wastewater

1. Enter the stored program number for bromine (Br2) powder pillows.

Press: 5 0 ENTER

The display will show:

Dial nm to 530

Note: The Pour-Thru Cell can be used with 25-mL reagents only.

2. Rotate the wavelength dial until the small display shows:

530 nm

When the correct wavelength is dialed in the display will quickly show: Zero Sample

then: mg/L Br2

3. Insert the 10-mL Cell Riser into the cell compartment.

4. Fill a sample cell with 10 mL of sample.

Note: Samples must be analyzed immediately.

5. Add the contents of one DPD Total Chlorine Powder Pillow to the sample cell (the prepared sample).

Swirl to mix.

Note: A pink color will develop if bromine is present.

6. Press:SHIFT TIMER

A three-minute reaction period will begin.

7. When the timer beeps, the display will show: mg/L Br2

Fill a second sample cell (the blank) with 10 mL of sample.

8. Place the blank into the cell holder. Close the light shield.

530 nm

11

BROMINE, continued

9. Press: ZERO


Zeroing. . .

then: 0.00 mg/L Br2

10. Within three minutes after the timer beeps, place the prepared sample into the cell holder. Close the light shield.

11. Press: READ


Reading. . .

then the result in mg/L Br2 will be displayed.

Note: If the sample temporarily turns yellow after reagent addition, or shows OVER-RANGE, dilute a fresh sample and repeat the test. A slight loss of bromine may occur during dilution. Multiply the result by the appropriate dilution factor; see Sample Dilution Techniques in Section I of the DR/2010 Spectrophotometer Procedures Manual.

12

BROMINE, continued

Using AccuVac Ampuls

1. Enter the stored program number for bromine (Br2) AccuVac Ampuls.

Press: 5 5 ENTER


Dial nm to 530


530 nm


then: mg/L Br2

Note: Samples must be analyzed immediately.

3. Fill a zeroing vial (the blank) with at least 10 mL of sample. Collect at least 40 mL of sample in a 50-mL beaker.

4. Fill DPD Total Chlorine Reagent AccuVac Ampul with sample.

Note: Keep the tip immersed while the ampul fills completely.

5. Quickly invert the ampul several times to mix. Wipe off any liquid or fingerprints.

Note: A pink color will form if bromine is present.

6. Press:

SHIFT TIMER


7. Place the AccuVac Vial Adapter into the cell holder.

Note: Place the grip tab at the rear of the cell holder.

8. When the timer beeps, the display will show: mg/L Br2 AV

Place the blank into the cell holder. Close the light shield.

530 nm

13

BROMINE, continued

14

Sampling and StorageAnalyze samples for bromine immediately after collection. Bromine is astrong oxidizing agent, and it is unstable in natural waters. It reacts rapidlywith various inorganic compounds and more slowly oxidizes organiccompounds. Many factors, including reactant concentrations, sunlight, pH,temperature, and salinity influence decomposition of bromine in water.

Avoid plastic containers since these may have a large bromine demand.Pretreat glass sample containers to remove any bromine demand by soakingin a dilute bleach solution (1 mL commercial bleach to l liter of demineralizedwater) for at least 1 hour. Rinse thoroughly with demineralized or distilledwater. If sample containers are rinsed thoroughly with demineralized ordistilled water after use, only occasional pre-treatment is necessary.

A common error in testing for bromine is introduced when a representativesample is not obtained. If sampling from a tap, let the water flow for at least5 minutes to ensure a representative sample. Let the container overflow with

9. Press: ZERO


Zeroing. . . .

then: 0.00 mg/L Br2 AV

10. Within three minutes after the timer beeps, place the AccuVac Ampul into the cell holder. Close the light shield.

11. Press: READ


Reading. . . .

then the result in mg/L Br2 will be displayed.

Note: If the sample temporarily turns yellow after sample addition, or shows OVER-RANGE, dilute a fresh sample and repeat the test. A slight loss of bromine may occur during dilution. Multiply the result by the appropriate dilution factor; see Sample Dilution Techniques in Section I of the DR/2010 Spectrophotometer Procedures Manual.

BROMINE, continued

the sample several times, then cap the sample container so there is noheadspace (air) above the sample. If sampling with a sample cell, rinse thecell several times with the sample, then carefully fill to the 10-mL mark.Perform the bromine analysis immediately.

Accuracy CheckStandard Additions Method (using powder pillows)

a) Perform a sample analysis and record the result.

b) Snap the top off a LR Chlorine PourRite™ Ampule Standard Solution, 25-30 mg/L Cl2.

c) Use a TenSette Pipet to add 0.1 mL of the standard to the reacted sample (this is the spiked sample). Swirl to mix.

d) Place the spiked sample into the DR/2010 Spectrophotometer and read the spiked sample result.

e) Calculate the equivalent concentration of mg/L bromine added to the sample:

f) The spiked sample result (step d) should reflect the analyzed sample result (step a) + the added, calculated mg/L Br2 (step e).

g) If these increases do not occur, see Standard Additions in Section I of the DR/2010 Spectrophotometer Procedures Manual for more information.

Standard Additions Method (using AccuVac Ampuls)a) Snap the top off a LR Chlorine PourRite Ampule Standard

Solution, 25-30 mg/L Cl2.

b) Use a graduated cylinder to measure 25 mL of sample into each of two beakers.

c) Use a TenSette Pipet to add 0.2 mL of the standard to one of the beakers (this is the spiked sample). Swirl to mix.

d) Fill a DPD Total Chlorine AccuVac Ampul completely from each beaker.

e) Analyze the spiked and unspiked sample as described in the procedure.

mg/L Bromine

0.1 (vol. standard added) Certificate value (mg/L Chlorine)× 2.25×10.1 (sample + standard volume)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

=

15

BROMINE, continued

16

f) Calculate the equivalent concentration of mg/L bromine added to the sample:

g) The spiked sample result should reflect the analyzed sample result + the added, calculated mg/L Br2 (step f).

h) If these increases do not occur, see Standard Additions in Section I of the DR/2010 Spectrophotometer Procedures Manual for more information.

PrecisionIn a single laboratory using standard solutions of 1.00 mg/L chlorine(equivalent to 2.25 mg/L bromine) and two representative lots ofreagent with the DR/2010 Spectrophotometer, a single operatorobtained a standard deviation of ±0.012 mg/L chlorine. This isequivalent to ±0.027 mg/L bromine.

In a single laboratory using a standard solution of 1.10 mg/L chlorine(equivalent to 2.48 mg/L bromine) and two representative lots ofAccuVac Ampuls with the DR/2010 Spectrophotometer, a singleoperator obtained a standard deviation of ±0.009 mg/L chlorine. This isequivalent to ±0.019 mg/L bromine.

InterferencesSamples containing more than 300 mg/L alkalinity or 150 mg/Lacidity as CaCO3 may not develop the full amount of color, or it mayinstantly fade. Neutralize these samples to a pH of 6 to 7 with 1 Nsulfuric acid or 1 N sodium hydroxide. Determine the amount requiredon a separate 10 mL sample. Add the same amount to the sample to betested. Correct the test result for volume additions; see Correction forVolume Additions in Section I of the DR/2010 SpectrophotometerProcedures Manual for more information.

Chlorine, iodine, ozone, bromamines, and oxidized forms of manganeseand chromium also may react and show as bromine. Compensate for theeffects of oxidized manganese or chromium by adjusting the pH to 6 to 7 asdescribed above. Add 3 drops of 30 g/L potassium iodide to 25 mL ofsample, mix, and wait one minute. Add 3 drops of 5 g/L Sodium Arseniteand mix. Analyze 10 mL of this sample as described above. (If chromium ispresent, allow exactly the same reaction period with DPD for bothanalyses.) Subtract the result of this test from the original analysis to obtainthe correct bromine result.

mg/L Bromine

0.2 (vol. standard added) Certificate value (mg/L Chlorine)× 2.25×25.2 (sample + standard volume)

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

=

BROMINE, continued

17

DPD Total Chlorine Reagent Powder Pillows and AccuVac Ampuls containa buffer formulation which will withstand high (>1000 mg/L) levels ofhardness without interference.

Summary of MethodBromine reacts with DPD (N,N-diethyl-p-phenylenediamine) to form amagenta color which is proportional to the total bromine concentration.

REQUIRED REAGENTS (Using Powder Pillows)Quantity Required

Description Per Test Unit Cat. No.DPD Total Chlorine Reagent Powder Pillows................1 pillow ..... 100/pkg..............21056-69

REQUIRED REAGENTS (Using AccuVac Ampuls)DPD Total Chlorine Reagent AccuVac Ampuls.............1 ampul ....... 25/pkg..............25030-25

REQUIRED APPARATUS (Using Powder Pillows)Cell Riser, 10-mL sample cell ................................................................. each..............45282-00Sample Cells, 10-mL, matched pair ......................................................... pair..............24954-02

REQUIRED APPARATUS (Using AccuVac Ampuls)Adapter, AccuVac Vial ........................................................ 1................. each..............43784-00Beaker, 50 mL ..................................................................... 1................. each..................500-41Vial, zeroing ........................................................................ 1................. each..............21228-00

OPTIONAL REAGENTSChlorine Standard Solution, PourRite ampule, 25-30 mg/L, 10 mL... 20/pkg..............26300-20Potassium Iodide Solution, 30 g/L .........................................100 mL* MDB..................343-32Sodium Arsenite, 5 g/L ..........................................................100 mL* MDB................1047-32Sodium Hydroxide Standard Solution, 1 N............................100 mL* MDB................1045-32Sulfuric Acid Standard Solution, 1 N.....................................100 mL* MDB................1270-32Water, demineralized................................................................................. 4 L..................272-56

OPTIONAL APPARATUSAccuVac Snapper Kit .............................................................................. each..............24052-00Ampule Breaker Kit ................................................................................ each..............21968-00Cylinder, graduated, 25 mL..................................................................... each..................508-40pH Meter, EC10, portable ....................................................................... each..............50050-00pH Indicator Paper, 1 to 11 pH units............................................. 5 rolls/pkg..................391-33Pipet, TenSette, 0.1 to 1.0 mL ................................................................. each..............19700-01Pipet Tips, for 19700-01 TenSette Pipet ............................................. 50/pkg..............21856-96

* Contact Hach for larger sizes

BROMINE, continued

OPTIONAL 25 ML ANALYSIS ITEMSDescription Unit Cat. No.DDPD Total Chlorine Reagent Powder Pillows ................................100/pkg ............. 14064-99Pour-Thru Cell Assembly ........................................................................each ............. 45215-00Sample Cell, 25 mL, matched pair ...........................................................pair ............. 20950-00


18

Method 8205

CARBON DIOXIDE (10 - 1000 mg/L as CO2) For water, wastewater and seawater

Using Sodium Hydroxide with a Digital Titrator

1. Select a sample size and a Sodium Hydroxide (NaOH) Titration Cartridge corresponding to the expected carbon dioxide (CO2) concentration; see Table 1.


2. Insert a clean delivery tube into the titration cartridge. Attach the cartridge to the titrator body. See General Description, Step-by-Step, of the Digital Titrator Manual for assembly instructions if necessary.


Note: For added convenience use the TitraStir® Stirring Apparatus, see General Description, Step 3 in Step-by-Step, of the Digital Titrator Manual.

4. Collect a water sample directly into the titration flask by filling to the appropriate mark.

Note: Minimize agitation because carbon dioxide may be lost.

Note: For most accurate results, check the calibration of the erlenmeyer flask by measuring the proper volume in a graduated cylinder. Mark the proper volume on the flask with a permanent marker.

Table 1

Range (mg/L as CO2)

Sample Volume (mL)

Titration Cartridge (N NaOH)

Catalog Number

Digit Multiplier

10-5020-100

100-400200-1000

200100200100

0.36360.36363.6363.636

14378-0114378-0114380-0114380-01

0.10.21.02.0

19

CARBON DIOXIDE, continued

Sampling and StorageCollect samples in clean plastic or glass bottles. Fill completely and captightly. Avoid excessive agitation or prolonged exposure to air. Analyzesamples as soon as possible after collection. If immediate analysis is notpossible, the samples may be stored for at least 24 hours by cooling to 4 °C(39 °F) or below. Before analysis, warm the samples to room temperature.


This accuracy check should be performed when interferences are suspectedor to verify analytical technique.

1. Snap the neck off a Carbon Dioxide Voluette Ampule Standard forCarbon Dioxide, 10,000 mg/L CO2.

2. Use a TenSette Pipet to add 0.1 mL of standard to the sample titrated in Step 6. Resume titration back to the same end point. Record the number of digits required.

5. Add the contents of one Phenolphthalein Indicator Powder Pillow and mix.

Note: Four drops of Phenolphthalein Indicator Solution may be substituted for the Phenolphthalein Indicator Powder Pillow.

Note: If a pink color forms, no carbon dioxide is present.

6. Place the delivery tube tip into the solution and swirl the flask gently while titrating with sodium hydroxide from colorless to a light pink color that persists for 30 seconds. Record the number of digits required.

7. Calculate:

Total Digits Required x Digit Multiplier = mg/L as CO2

20


3. Repeat, using additions of 0.2 mL and 0.3 mL. Titrate to the same end point after each addition.

4. Each 0.1 addition of standard should require 50 additional digits of 0.3636 N titrant or five digits of 3.636 N titrant. If these uniform increases do not occur, refer to Appendix A, Accuracy Check and Standard Additions in the Digital Titrator Manual to determine the cause.

Interferences• Other acid components in the sample will be titrated and interfere

directly in this determination.

• Sodium hydroxide standard solutions tend to lose strength slowly with age and should be checked periodically by titrating a known standard. Check the solution frequently (monthly) by titrating 100 mL of Potassium Acid Phthalate Standard Solution, 100 mg/L CO2, or 100 mL of Potassium Acid Phthalate Standard Solution, 400 mg/L CO2, using Phenolphthalein Indicator Solution. The titration should require 500 digits of the 0.3636 N Sodium Hydroxide Titration Cartridge or 200 digits of the 3.636 N Sodium Hydroxide Titration Cartridge. If more than 525 or 210 of digits of the sodium hydroxide is required, replace it with a fresh supply.

Summary of MethodAcidity due to carbon dioxide in a sample is titrated with sodiumhydroxide to a phenolphthalein end point. Strong acids are assumed to beabsent or of insignificant concentration. Request Hach Water AnalysisHandbook, Publication 8353, to obtain additional information on carbondioxide determinations.

REQUIRED REAGENTS(varies with sample characteristics)Carbon Dioxide Reagent Set (about 100 tests)

Includes: (1) 942-99, (1) 14378-01, (1) 14380-01 .....................................................22727-00Description Unit Cat. No.Phenolphthalein Powder Pillows..............................................................100/pkg ...........942-99Sodium Hydroxide Titration Cartridge, 0.3636 N .........................................each .......14378-01Sodium Hydroxide Titration Cartridge, 3.636 N ...........................................each .......14380-01Water, demineralized........................................................................................4 L ...........272-56

21


REQUIRED APPARATUSDescription Unit Cat. No.Digital Titrator ............................................................................................... each....... 16900-01

Select one or more based on sample concentrationFlask, erlenmeyer, 250 mL ............................................................................ each........... 505-46Flask, erlenmeyer, 125 mL ............................................................................ each........... 505-43

OPTIONAL REAGENTSCarbon Dioxide Standard Solution, Voluette Ampule,

10,000 mg/L as CO2, 10 mL................................................................... 16/pkg....... 14275-10Phenolphthalein Indicator Solution, 5 g/L....................................100 mL MDB*........... 162-32Potassium Acid Phthalate Standard Solution, 100 mg/L as CO2..............100 mL.......... 2261-42Potassium Acid Phthalate Standard Solution, 400 mg/L as CO2..............500 mL......... 1885-49

OPTIONAL APPARATUSClamp, 2-prong extension, 38 mm ................................................................ each....... 21145-00Clamp Holder................................................................................................. each........... 326-00Cylinder, Graduated, 100 mL ........................................................................ each........... 508-42Cylinder, Graduated, 250 mL ........................................................................ each........... 508-46Delivery Tubes, with 180° hook .................................................................. 5/pkg....... 17205-00Delivery Tubes, 90° with hook for TitraStir Assembly ............................... 5/pkg....... 41578-00pH Meter, EC 10, portable ............................................................................. each....... 50050-00Pipet, TenSette, 0.1 to 1.0 mL........................................................................ each....... 19700-01Pipet tips for 19700-01 TenSette pipet ...................................................... 50/pkg....... 21856-96Pipet Filler, safety bulb .................................................................................. each ....... 14651-00Pipet, Volumetric, Class A, 100 mL .............................................................. each....... 14515-42Stand, Stirrer/Electrode holder, 115 Vac........................................................ each....... 45300-01Stand, Stirrer/Electrode holder, 230Vac......................................................... each....... 45300-02Support ring stand.......................................................................................... each........... 563-00TitraStir Mixer/Stand Assembly, 115 Vac ..................................................... each....... 19400-00TitraStir Mixer/Stand, Assembly, 230 Vac .................................................... each....... 19400-10



22

Method 8207

CHLORIDE (10 - 10,000 mg/L as Cl-)

Using Silver Nitrate with a Digital Titrator For water, wastewater, and seawater

1. Select the sample volume and Silver Nitrate Titration Cartridge corresponding to the expected chloride concentration from Table 1.

2. Insert a clean delivery tube into the titration cartridge. Attach the cartridge to the titrator body. See General Description Section, Step-by-Step, of the Digital Titrator Manual for assembly instructions, if necessary.



4. Use a graduated cylinder or pipet to measure the sample volume from Table 1. Transfer the sample into a clean 250-mL erlenmeyer flask. Dilute to about the 100-mL mark with demineralized water, if necessary.


Table 1

Range (mg/L as Cl-)

Sample Volume

(mL)

Titration Cartridge (N AgNO3)

Catalog Number

Digit Multiplier

10-4025-100

100-400250-1000

1000-40002500-10000

10040502052

0.22560.22561.1281.1281.1281.128

14396-0114396-0114397-0114397-0114397-0114397-01

0.10.25

1.02.5

10.025.0

23

CHLORIDE, continued

24

Sampling and StorageCollect at least 100 to 200 mL of sample in a clean glass or polyethylenecontainer. Samples may be stored up to 7 days before analysis.


This accuracy check should be performed when interferences are suspectedor to verify analytical technique.

1. Snap the neck off a Chloride Voluette Ampule Standard, 12,500 mg/L Cl-.

2. Use a TenSette Pipet to add 0.1 mL of standard to the sample after titration in Step 6. Resume titration back to the same end point. Record the number of digits required.

3. Repeat, using additions of 0.2 and 0.3 mL. Titrate to the end point after each addition.

4. Each 0.1 mL addition of standard should require 12.5 additional digits of 2.256 N titrant, 25 digits of 1.128 N titrant and 125 digits of 0.2256 N titrant. If these uniform increases do not occur, refer to Appendix A, Accuracy Check and Standard Additions in the Digital Titrator Manual to determine the cause.

Interferences • Iron in excess of 10 mg/L masks the end point.

• Orthophosphate in excess of 25 mg/L will precipitate the silver.

5. Add the contents of one Chloride 2 Indicator Powder Pillow and swirl to mix.

Note: Results will still be accurate if a small amount of the powder does not dissolve.

6. Place the delivery tube tip into the solution and swirl the flask while titrating with silver nitrate from a yellow to red-brown color. Record the number of digits required.

7. Calculate:Digits Required x Digit Multiplier = mg/L Chloride

Note: Results may be expressed as mg/L sodium chloride by multiplying the mg/L chloride by 1.65.

Note: meq/L Chloride = mg/L Cl- ÷ 35.45.

CHLORIDE, continued

• Sulfite in excess of 10 mg/L interferes. Eliminate sulfite interference by adding three drops of 30% hydrogen peroxide in Step 4.

• Remove sulfide interference by adding the contents of one Sulfide Inhibitor Reagent Powder Pillow to about 125 mL of sample, mixing for one minute, and filtering through a folded filter paper.

• Cyanide, iodide and bromide interfere directly and titrate as chloride.

• Neutralize strongly alkaline or acid samples to a pH of 2 to 7 with 5.25 N Sulfuric Acid Standard Solution or 5.0 N Sodium Hydroxide Standard Solution. Determine the amount of acid or base necessary in a separate sample because pH electrodes will introduce chloride into the sample.

Summary of Method The sample is titrated with Silver Nitrate Standard Solution in thepresence of potassium chromate (from the Chloride 2 Indicator Powder).The silver nitrate reacts with the chloride present to produce insolublewhite silver chloride. After all the chloride has been precipitated, thesilver ions react with the excess chromate present to form a red-brownsilver chromate precipitate, marking the end point of the titration.

Request Hach Water Analysis Handbook, Publication 8353, to obtainadditional information on chloride determinations.

REQUIRED REAGENTS Silver Nitrate Chloride Reagent Set (about 50 tests) Includes: (2) 1057-66, (1) 14396-01, (1) 14397-01, (about 50 tests)............................22880-00Description Unit Cat. No.Chloride 2 Indicator Powder Pillows .........................................................50/pkg .........1057-66Silver Nitrate Titration Cartridge, 0.2256 N ..................................................each .......14396-01Silver Nitrate Titration Cartridge, 1.128 N ....................................................each .......14397-01Water, demineralized........................................................................................4 L ...........272-56

REQUIRED APPARATUSClippers, for opening pillows .........................................................................each ...........968-00Digital Titrator................................................................................................each .......16900-01Flask, erlenmeyer, 250 mL.............................................................................each ...........505-46

Select one or more based on sample concentrationCylinder, graduated, 10 mL............................................................................each ...........508-38Cylinder, graduated, 25 mL............................................................................each ...........508-40Cylinder, graduated, 50 mL............................................................................each ...........508-41Cylinder, graduated, 100 mL..........................................................................each ...........508-42

25

CHLORIDE, continued

OPTIONAL REAGENTSDescription Unit Cat. No.Chloride Standard Solution, 1000 mg/L Cl- .............................................500 mL........... 183-49Chloride Standard Solution,

Voluette Ampule, 12,500 mg/L Cl-, 10 mL............................................ 16/pkg....... 14250-10Hydrogen Peroxide, 30%, ACS ................................................................200 mL........... 144-45Sodium Hydroxide Standard Solution, 5.0 N .................................100 mL MDB......... 2450-32Sulfide Inhibitor Powder Pillows............................................................. 100/pkg......... 2418-99Sulfuric Acid Standard Solution, 5.25 N ........................................100 mL MDB......... 2449-32

OPTIONAL APPARATUSBottle, wash, poly, 500 mL ............................................................................ each........... 620-11Clamp, 2-prong extension, 38 mm ................................................................ each....... 21145-00Clamp Holder................................................................................................. each........... 326-00Demineralizer Assembly, 473 mL ................................................................. each....... 21846-00Delivery Tubes, with 180° hook .................................................................. 5/pkg....... 17205-00Delivery Tubes, 90° with hook for TitraStir ................................................ 5/pkg....... 41578-00Filter Paper, folded, 12.5 cm.................................................................... 100/pkg......... 1894-57Funnel, poly, 65 mm ...................................................................................... each......... 1083-67Hach One Combination pH Electrode with Temp ......................................... each....... 48600-22pH Meter, EC 10, portable ............................................................................. each....... 50050-00Pipet, TenSette, 0.1 to 1.0 mL........................................................................ each....... 19700-01Pipet tips for 19700-01 TenSette pipet ...................................................... 50/pkg....... 21856-96Pipet, volumetric, Class A, 2 mL................................................................... each....... 14515-36Pipet, volumetric, Class A, 5 mL................................................................... each....... 14515-37Pipet, volumetric, Class A, 10 mL................................................................. each....... 14515-38Pipet, volumetric, Class A, 20 mL................................................................. each....... 14515-20Pipet, volumetric, Class A, 25 mL................................................................. each....... 14515-40Pipet, volumetric, Class A, 50 mL................................................................. each....... 14515-41

OPTIONAL APPARATUSPipet, volumetric, Class A, 100 mL............................................................... each....... 14515-42Pipet Filler, safety bulb .................................................................................. each....... 14651-00Stand, Stirrer/Electrode holder, 115 Vac........................................................ each....... 45300-01Stand, Stirrer/Electrode holder, 230Vac......................................................... each....... 45300-02Support ring stand.......................................................................................... each........... 563-00TitraStir Mixer/Stand Assembly, 115 Vac ..................................................... each....... 19400-00TitraStir Mixer/Stand Assembly, 230 Vac ..................................................... each....... 19400-10


26

Method 8021

CHLORINE, FREE (0 to 2.00 mg/L) For water, wastewater, and seawater

DPD Method* (Powder Pillows or AccuVac® Ampuls) USEPA accepted for reporting wastewater and drinking water analyses**


* Adapted from Standard Methods for the Examination of Water and Wastewater.** Procedure is equivalent to USEPA method 330.5 for wastewater and Standard Method 4500-Cl G for drinking water.

1. Enter the stored program number for free and total chlorine (Cl2) powder pillows.

Press: 8 0 ENTER


Dial nm to 530



530 nm


then: mg/L Cl2

3. Insert the 10-mL Cell Riser into the sample compartment.

4. Fill a sample cell with 10 mL of sample (the blank). Place it into the cell holder. Close the light shield.

Note: Samples must be analyzed immediately and cannot be preserved for later analysis.

530 nm

27

CHLORINE, FREE, continued

5. Press: ZERO


Zeroing. . .

then: 0.00 mg/L Cl2

6. Fill another cell with 10 mL of sample.

7. Add the contents of one DPD Free Chlorine Powder Pillow to the sample cell (the prepared sample). Stopper the cell and shake for 20 seconds.

Note: A pink colorwill develop if free chlorine is present.

Note: Shaking dissipates bubbles which may form in samples containing dissolved gases.

8. Immediately (within one minute of reagent addition) remove stopper and place the prepared sample into the cell holder. Close the light shield.

Note: Proceed immediately to Step 9.

9. Press: READ


Reading. . .

then the result in mg/L chlorine (Cl2) will be displayed.

Note: If the sample temporarily turns yellow after reagent addition, or shows OVER-RANGE, dilute a fresh sample and repeat the test. A slight loss of chlorine may occur during dilution. Multiply the result by the appropriate dilution factor; see Sample Dilution Techniques (Section I of the DR/2010 Spectrophotometer Procedures Manual).

28

CHLORINE, FREE continued


1. Enter the stored program number for free and total chlorine (Cl2) AccuVac Ampuls.

Press: 8 5 ENTER


Dial nm to 530


530 nm


then: mg/L Cl2



4. Fill a DPD Free Chlorine Reagent AccuVac Ampul with sample.



Note: A pink color will form if chlorine is present.

6. Place the AccuVac Vial Adapter into the cell holder of the instrument.



8. Press: ZERO


Zeroing. . .

then: 0.00 mg/L Cl2 AV

530 nm

29


Sampling and StorageAnalyze samples for chlorine immediately after collection. Free chlorineis a strong oxidizing agent, and it is unstable in natural waters. It reactsrapidly with various inorganic compounds and more slowly oxidizesorganic compounds. Many factors, including reactant concentrations,sunlight, pH, temperature, and salinity influence decomposition of freechlorine in water.

Avoid plastic containers since these may have a large chlorine demand.Pretreat glass sample containers to remove any chlorine demand bysoaking in a dilute bleach solution (1 mL commercial bleach to l liter ofdemineralized water) for at least 1 hour. Rinse thoroughly withdemineralized or distilled water. If sample containers are rinsedthoroughly with demineralized or distilled water after use, onlyoccasional pre-treatment is necessary.

9. Immediately (within one minute of sample addition) place the AccuVac Ampul into the cell holder. Close the light shield.

Note: Proceed immediately to Step 10.

10. Press: READ


Reading. . .

then the result in mg/L Cl2 will be displayed.

Note: If the sample temporarily turns yellow after sample addition, or shows OVER-RANGE, dilute a fresh sample and repeat the test. A slight loss of chlorine may occur during dilution. Multiply the result by the appropriate dilution factor; see Sample Dilution Techniques (Section I of the DR/2010 Spectrophotometer Procedures Manual).

30


31

Do not use the same sample containers for free and total chlorine. If traceiodide from the total chlorine reagent is carried over into the free chlorinedetermination, monochloramine will interfere. It is best to use separate,dedicated sample containers for free and total chlorine determinations.

A common error in testing for chlorine is introduced when arepresentative sample is not obtained. If sampling from a tap, let the waterflow for at least 5 minutes to ensure a representative sample. Let thecontainer overflow with the sample several times, then cap the samplecontainer so there is no headspace (air) above the sample. If samplingwith a sample cell, rinse the cell several times with the sample, thencarefully fill to the 10-mL mark. Perform the chlorine analysisimmediately.



b) Snap the top off a LR Chlorine PourRite™ Ampule Standard Solution, 25-30 mg/L Cl2.



e) Calculate the equivalent concentration of mg/L chlorine added to the sample:

f) The spiked sample result (step d) should reflect the analyzed sample result (step a) + the added, calculated mg/L Cl2 (step e).





mg/L Chlorine

0.1 vol. standard added( ) Certificate value mg L Cl2⁄( )×10.1 sample( standard volume )+

---------------------------------------------------------------------------------------------------------------------------------------------------

=




e) Analyze the spiked and unspiked sample as described in the procedure.

f) Calculate the equivalent concentration of mg/L chlorine added to the sample:

g) The spiked sample result should reflect the analyzed sample result + the added, calculated mg/L Cl2 (step f).


PrecisionIn a single laboratory using a standard solution of 1.00 mg/L chlorine andtwo representative lots of reagents with the DR/2010 Spectrophotometer,a single operator obtained standard deviations of ±0.012 mg/L chlorine.

In a single laboratory using a standard solution of 1.10 mg/L chlorine and tworepresentative lots of AccuVac Ampuls with the DR/2010 Spectrophotometer,a single operator obtained a standard deviation of ±0.009 mg/L chlorine.

Estimated Detection Limit (EDL)The EDL for program 80 and program 85 is 0.01 mg/L CL2. The EDL is thecalculated lowest average concentration in a demineralized water matrixthat is different from zero with a 99% level of confidence. For moreinformation on derivation and use of Hach’s estimated detection limit, seeSection I of the DR/2010 Spectrophotometer Procedures Manual.

Interferences• Samples containing more than 250 mg/L alkalinity or 150 mg/L acidity

as CaCO3 may not develop the full amount of color, or the color may instantly fade. Neutralize these samples to a pH of 6 to 7 with 1 N sulfuric acid, or 1 N sodium hydroxide. Determine the amount required on a separate 25-mL sample; then add the same amount to the sample to be tested.

mg/L Chlorine

0.2 vol. standard added( ) Certificate value mg L Cl2⁄( )×25.2 sample( standard volume )+

---------------------------------------------------------------------------------------------------------------------------------------------------

=

32


• Samples containing monochloramine will cause a gradual drift to higher chlorine readings. When read within one minute of reagent addition, 3.0 mg/L monochloramine will cause an increase of less than 0.1 mg/L in the free chlorine reading.

• Bromine, iodine, ozone, oxidized manganese, and chromium also may react and show as chlorine. To compensate for the effects of oxidized manganese or chromium adjust pH to 6 to 7 as described above, then add 3 drops of potassium iodide, 30 g/L, to 25 mL of sample, mix and wait 1 minute. Add 3 drops of sodium arsenite, 5 g/L, and mix. Analyze 10 mL of this sample as described above. (If chromium is present, allow exactly the same reaction period with the DPD for both analyses.) Subtract the result of this test from the original analysis to obtain the correct chlorine result.

• DPD Free Chlorine Reagent Powder Pillows and AccuVac Ampuls contain a buffer formulation which will withstand high (at least 1000 mg/L) levels of hardness without interference.

Summary of MethodChlorine in the sample as hypochlorous acid or hypochlorite ion (freechlorine or free available chlorine) immediately reacts with DPD(N,N-diethyl-p-phenylenediamine) indicator to form a magenta colorwhich is proportional to the chlorine concentration.


Description Per Test Unit Cat. No.DPD Free Chlorine Reagent Powder Pillows, 10 mL ....1 pillow .... 100/pkg..............21055-69

REQUIRED REAGENTS (Using AccuVac Ampuls)DPD Free Chlorine Reagent AccuVac Ampuls..............1 ampul ...... 25/pkg..............25020-25

REQUIRED APPARATUS (Using Powder Pillows)Cell Riser, 10-mL sample cell ................................................................. each..............45282-00Sample Cell, 10-mL, matched pair........................................................... pair..............24954-02Stopper, hollow, No 2, LDPE, fits 10 & 25-mL cells ......... 1............... 6/pkg............. 14480-00

REQUIRED APPARATUS (Using AccuVac Ampuls)Adapter, AccuVac Vial ........................................................ 1................. each..............43784-00Beaker, 50 mL ..................................................................... 1................. each..................500-41Vial, Zeroing........................................................................ 1................. each..............21228-00

33


OPTIONAL REAGENTSDescription Unit Cat. No.Chlorine Standard Solution, PourRite ampule,

25-30 mg/L, 10 m .............................................................................20/pkg ............ 26300-20DPD Free Chlorine Reagent w/dispensing cap.................................250 tests ............. 21055-29Potassium Iodide Solution, 30 g/L ........................................ 100 mL* MDB ................ 343-32Sodium Arsenite, 5 g/L.......................................................... 100 mL* MDB ............... 1047-32Sodium Hydroxide Standard Solution, 1.000 N .................... 100 mL* MDB .............. 1045-32Sulfuric Acid Standard Solution, 1.000 N ............................. 100 mL* MDB .............. 1270-32Water, demineralized ................................................................................ 4 L ................. 272-56

OPTIONAL APPARATUSAccuVac Snapper Kit...............................................................................each ............ 24052-00Ampule Breaker Kit.................................................................................each ............ 21968-00Cylinder, graduated, 25 mL .....................................................................each ................. 508-40pH Meter, EC10, portable .......................................................................each ............. 50050-00pH Paper, 1 to 11 pH units .............................................................5 rolls/pkg ................. 391-33Pipet, TenSette, 0.1 to 1.0 mL..................................................................each ............. 19700-01Pipet Tips, for 19700-01 TenSette Pipet ..............................................50/pkg ............. 21856-96

OPTIONAL 25 ML ANALYSIS ITEMSDPD Free Chlorine Reagent Powder Pillows, 25 mL........................100/pkg ............. 14070-99Pour-Thru Cell Assembly Kit ..................................................................each ............. 45215-00Sample Cell, 25-mL, matched pair ...........................................................pair ............. 20950-00


* Marked Dropper Bottle - contact Hach for larger sizes.

34

35

Method 8167

CHLORINE, TOTAL (0 to 2.00 mg/L) For water, wastewater and seawater

DPD Method* (Powder Pillows or AccuVac Ampuls) USEPA accepted for reporting water and wastewater**


* Adapted from Standard Methods for the Examination of Water and Wastewater.** Procedure is equivalent to USEPA method 330.5 for wastewater and Standard Method 4500-Cl Gfor drinking water.

1. Enter the stored program number for free and total chlorine (Cl2) powder pillows.

Press: 8 0 ENTER


Dial nm to 530



530 nm


then: mg/L Cl2

3. Insert the 10-mL Cell Riser into the sample compartment.

4. Fill a 10-mL sample cell with 10 mL of sample.


5. Add the contents of one DPD Total Chlorine Powder Pillow to the sample cell (the prepared sample). Stopper the sample cell and shake for 20 seconds. Remove the stopper.

Note: Shaking dissipates bubbles which may form.

6. Press:

SHIFT TIMER


Note: A pink color will develop if chlorine is present.

7. When the timer beeps, the display will show: mg/L Cl2

Fill another sample cell (the blank) with 10 mL of sample. Place it into the cell holder. Close the light shield.

8. Press: ZERO


Zeroing. . .

then: 0.00 mg/L Cl2

530 nm

CHLORINE, TOTAL, continued


10. Press: READ


Reading. . .

then the result in mg/L chlorine (Cl2) willbe displayed.

Note: It the sample temporarily turns yellow after reagent addition, or shows OVER-RANGE, dilute a fresh sample and repeat the test. A slight loss of chlorine may occur during dilution. Multiply the result by the appropriate dilution factor; see Sample Dilution Techniques (Section I of the DR/2010 Spectrophotometer Procedures Manual).

36



1. Enter the stored program number for free and total chlorine (Cl2) AccuVac Ampuls.

Press: 8 5 ENTER


DIAL nm TO 530


530 nm


then: mg/L Cl2



4. Fill a DPD Total Chlorine Reagent AccuVac Ampul with sample.



Note: A pink color will form if chlorine is present.

6. Press:

SHIFT TIMER


7. Place the AccuVac Vial Adapter in the cell holder of the instrument.


8. When the timer beeps, the display will show: mg/L Cl2 AV


530 nm

37


Sampling and StorageAnalyze samples for chlorine immediately after collection. Chlorine is astrong oxidizing agent, and it is unstable in natural waters. It reactsrapidly with various inorganic compounds and more slowly oxidizesorganic compounds. Many factors, including reactant concentrations,sunlight, pH, temperature and salinity influence decomposition ofchlorine in water.

Avoid plastic containers since these may have a large chlorine demand.Pretreat glass sample containers to remove any chlorine demand by soakingin a dilute bleach solution (1 mL commercial bleach to l liter of demineralizedwater) for at least 1 hour. Rinse thoroughly with demineralized or distilledwater. If sample containers are rinsed thoroughly with demineralized ordistilled water after use, only occasional pre-treatment is necessary.

9. Press: ZERO


Zeroing. . .

then: 0.00 mg/L Cl2 AV

10. Within three minutes after the timer beeps, place the AccuVac Ampul into the cell holder. Close the light shield.

11. Press: READ


Reading. . .

then the result in mg/L chlorine (Cl2) will be displayed.

Note: If the sample temporarily turns yellow after sample addition, or shows OVER-RANGE, dilute a fresh sample and repeat the test. A slight loss of chlorine may occur during dilution. Multiply the result by the appropriate dilution factor; see Sample Dilution Techniques (Section I of the DR/2010 Spectrophotometer Procedures Manual).

38


Do not use the same sample containers for free and total chlorine. If traceiodide from the total chlorine reagent is carried over into the free chlorinedetermination, monochloramine will interfere. It is best to use separate,dedicated sample containers for free and total chlorine determinations.

A common error in testing for chlorine is introduced when a representativesample is not obtained. If sampling from a tap, let the water flow for at least5 minutes to ensure a representative sample. Let the container overflow withthe sample several times, then cap the sample containers so there is noheadspace (air) above the sample. If sampling with a sample cell, rinse thecell several times with the sample, then carefully fill to the 10-mL mark.Perform the chlorine analysis immediately.



b) Snap the top off a LR Chlorine PourRite Ampule Standard Solution, 25-30 mg/L Cl2.



e) Calculate the equivalent concentration of mg/L chlorine added to the sample:

f) The spiked sample result (step d) should reflect the analyzed sample result (step a) + the added, calculated mg/L Cl2 (step e).

g) If these increases do not occur, see Standard Additions in Section I DR/2010 Spectrophotometer Procedures Manual for more information.





mg L Chlorine⁄

0.1 vol. standard added( ) Certificate value mg L Cl2⁄( )×10.1 sample standard volume+( )

----------------------------------------------------------------------------------------------------------------------------------------------------

=

39



e) Analyzed the spiked and unspiked sample as described in the procedure.

f) Calculate the equivalent concentration of mg/L chlorine added to the sample:

g) The spiked sample result should reflect the analyzed sample result + the added, calculated mg/L Cl2 (step f).


PrecisionIn a single laboratory, using a standard solution of 1.00 mg/L chlorine andtwo lots of reagents with the DR/2010 Spectrophotometer, a singleoperator obtained standard deviations of ±0.012 mg/L chlorine.

In a single laboratory, using a standard solution of 1.10 mg/L chlorine andtwo representative lots of AccuVac Ampuls with the DR/2010Spectrophotometer, a single operator obtained a standard deviation of±0.009 mg/L chlorine.

Estimated Detection Limit (EDL)The EDL for programs 80 and 85 is 0.01 mg/L CL2. The EDL is thecalculated lowest average concentration in a demineralized water matrixthat is different from zero with a 99% level of confidence. For moreinformation on derivation and use of Hach’s estimated detection limit, seeSection I of the DR/2010 Spectrophotometer Procedures Manual.

Interferences• Samples containing more than 300 mg/L alkalinity or 150 mg/L

acidity as CaCO3 may not develop the full amount of color, or it may instantly fade. Neutralize these samples to a pH of 6 to 7 with 1 N sulfuric acid, or 1 N sodium hydroxide. Determine the amount required on a separate 10 mL sample. Add the same amount to the sample to be tested. Correct for volume additions; see Corrections for Volume Additions in Section I of the DR/2010 Spectrophotometer Procedures Manual.

mg L Chlorine⁄

0.2 vol. standard added( ) Certificate value mg L Cl2⁄( )×25.2 sample standard volume+( )

----------------------------------------------------------------------------------------------------------------------------------------------------

=

40


• Bromine, iodine, ozone, oxidized manganese, and chromium also may react and read as chlorine. To compensate for the effects of oxidized manganese or chromium, adjust the pH to between 6 and 7 as described above; then add 3 drops of potassium iodide, 30 g/L, to 25 mL of sample, mix, and wait one minute. Add 3 drops of sodium arsenite, 5 g/L, and mix. Analyze 10 mL of this sample as described above. (If chromium is present, allow exactly the same reaction period with the DPD for both analyses.) Subtract the result of this test from the original analysis to obtain the correct chlorine result.

• DPD Total Chlorine Reagent Powder Pillows and AccuVac Ampuls contain a buffer formulation which will withstand high levels of hardness (at least 1000 mg/L) without interference.

Summary of MethodChlorine can be present in water as free available chlorine and ascombined available chlorine. Both forms can exist in the same water andbe determined together as the total available chlorine. Free chlorine ispresent as hypochlorous acid and/or hypochlorite ion. Combined chlorineexists as monochloramine, dichloramine, nitrogen trichloride and otherchloro derivatives.

The combined chlorine oxidizes iodide in the reagent to iodine. Theiodine reacts with DPD (N, N-diethyl-p-phenylenediamine) along withfree chlorine present in the sample to form a red color which isproportional to the total chlorine concentration. To determine theconcentration of combined chlorine, run water free chlorine and totalchlorine tests. Subtract the results of the free chlorine test from the resultsof the total chlorine test to obtain combined chlorine.


Description Per Test Unit Cat. No.DPD Total Chlorine Reagent Powder Pillows................1 pillow ..... 100/pkg..............21056-69

REQUIRED REAGENTS (Using AccuVac Ampuls)DPD Total Chlorine Reagent AccuVac Ampuls.............1 ampul ....... 25/pkg..............25030-25

REQUIRED APPARATUS (Using Powder Pillows)Quantity Required

Description Per Test Unit Cat. No.Cell Riser, 10-mL sample cell ................................................................. each..............45282-00Sample Cell, 10-mL, matched pair........................................................... pair..............24954-02Stopper, hollow, No. 2, LDPE, fits 10 & 25-mL cells......... 1............... 6/pkg..............14480-01

41


REQUIRED APPARATUS (Using AccuVac Ampuls)Adapter, AccuVac vial .........................................................1 .................each ............. 43784-00Beaker, 50 mL......................................................................1 .................each ................. 500-41Vial, zeroing.........................................................................1 .................each ............. 21228-00

OPTIONAL REAGENTSChlorine Standard Solution,

PourRite ampule, 25-30 mg/L, 10 mL..............................................20/pkg ............. 26300-20DPD Total Chlorine Reagent w/dispensing cap ...............................250 tests ............. 21056-29Potassium Iodide Solution, 30 g/L......................................... 100 mL* MDB ................. 343-32Sodium Arsenite, 5 g/L.......................................................... 100 mL* MDB ............... 1047-32Sodium Hydroxide Standard Solution, 1 N ........................... 100 mL* MDB ............... 1045-32Sulfuric Acid Standard Solution, 1 N .................................... 100 mL* MDB ............... 1270-32Water, demineralized ................................................................................ 4 L ................. 272-56

OPTIONAL APPARATUSAccuVac Snapper Kit...............................................................................each ............. 24052-00Ampule Breaker Kit.................................................................................each ............. 21968-00Cylinder, graduated, 25 mL .....................................................................each ................. 508-40pH Indicator Paper, 1 to 11 pH units .............................................5 rolls/pkg ................. 391-33pH Meter, EC10, portable ........................................................................each ............. 50050-00Pipet, TenSette, 0.1 to 1.0 mL..................................................................each ............. 19700-01Pipet Tips, for 19700-01 TenSette Pipet ..............................................50/pkg ............. 21856-96

OPTIONAL 26 ML ANALYSIS ITEMSDPD Total Chlorine Reagent Powder Pillows ...................................100/pkg ............. 14064-99Pour-Thru Cell Assembly Kit ..................................................................each ............. 45215-00Sample Cell, 25-mL, matched pair ...........................................................pair ............. 20950-00


* Marked Dropper Bottle - contact Hach for larger sizes.

42

Method 8023

CHROMIUM, HEXAVALENT (0 to 0.60 mg/L Cr6+) For water and wastewater

1,5-Diphenylcarbohydrazide Method* (Powder Pillows or AccuVac Ampuls) USEPA accepted for wastewater analyses**


* Adapted from Standard Methods for the Examination of Water and Wastewater.** Procedure is equivalent to USGS method I-1230-85 for wastewater.

1. Enter the stored program number for hexavalent chromium (Cr6+).

Press: 90 ENTER


Dial nm to 540



540 nm

When the correct wavelength is dialed, the display will quickly show:

Zero Sample

then: mg/L Cr6+



540 nm

43

CHROMIUM, HEXAVALENT, continued

5. Add the contents of one ChromaVer® 3 Reagent Powder Pillow to the cell (the prepared sample). Swirl to mix.

Note: A purple color will form if Cr6+ is present.

Note: At high chromium levels a precipitate will form. Dilute sample according to Sample Dilution Techniques (Section I of the DR/2010 Spectrophotometer Procedures Manual).

6. Press: SHIFT TIMER

A five-minute reaction period will begin.

7. Fill another sample cell with 10 mL of sample (the blank).

Note: For turbid samples, add the contents of one Acid Reagent Powder Pillow. This ensures turbidity dissolved by the acid in the ChromaVer 3 Chromium Reagent is also dissolved in the blank.

8. When the timer beeps, the display will show: mg/L Cr6+


9. Press: ZERO


Zeroing. . .

then: 0.00 mg/L Cr6+

10. Place the prepared sample into the cell holder. Close the light shield.

11. Press: READ


Reading. . .

then the results in mg/L hexavalent chromium will be displayed.

Forms Na CrOCrOCr

2 4

42-

6+

44



1. Enter the stored program number for hexavalent chromium.

Press: 9 5 ENTER


Dial nm to 540


540 nm


then: mg/L Cr6+ AV

3. Fill the zeroing vial with at least 10 mL of sample (the blank). Collect at least 40 mL of sample in a 50-mL beaker.

Note: For turbid samples, add the contents of one Acid Reagent Powder Pillow to 10 mL of the blank. This ensures turbidity dissolved by the acid in the ChromaVer 3 Chromium Reagent is also dissolved in the blank.



5. Fill a ChromaVer 3 Reagent AccuVac Ampul (the prepared sample) with sample.


Note: ChromaVer 3 should be white to tan in color. Replace if it is brown or green.


Note: A purple color will form if hexavalent chromium is present.



8. When the timer beeps the display will show:

mg/L Cr6+ AV


540 nm

45


Sampling and StorageCollect samples in a cleaned glass or plastic container. Store at 4 °C (39 °F)up to 24 hours. Samples must be analyzed within 24 hours.

Accuracy CheckStandard Additions Method

a) Snap the neck off a Chromium Voluette Ampule Standard, 12.5 mg/L Cr6+.

b) Use the TenSette Pipet to add 0.1 mL, 0.2 mL and 0.3 mL of standard, respectively, to three 25-mL samples contained in 25-mL mixing cylinders. Mix each thoroughly.

c) Transfer 10 mL of each solution into a 10-mL sample cell.

d) Analyze each sample as described above. The chromium concentration should increase 0.05 mg/L for each 0.1 mL of standard added.

e) If these increases do not occur, see Standard Additions in Section I of the DR/2010 Spectrophotometer Procedures Manual for more information.

9. Press: ZERO


Zeroing. . .

then:

0.00 mg/L Cr6+ AV


11. Press: READ


Reading. . .

then the result in mg/L hexavalent chromium will be displayed.

Forms Na CrOCrOCr

2 4

42-

6+

46


47

Standard Solution MethodPrepare a 0.25-mg/L Cr6+ solution by pipetting 5.00 mL of hexavalentchromium standard solution, 50.0 mg/L Cr6+, into a 1000-mL volumetricflask and diluting to the mark with demineralized water. Prepare thissolution daily. Perform the chromium procedure as described above. Themg/L Cr6+ reading should be 0.25 mg/L Cr6+.

Method PerformancePrecision

In a single laboratory using a standard solution of 0.4 mg/L Cr6+ and tworepresentative lots of reagent with the DR/2010 Spectrophotometer, asingle operator obtained a standard deviation of ±0.003 mg/L Cr6+.

In a single laboratory using a standard solution of 0.4 mg/L Cr6+ and tworepresentative lots of AccuVac Ampuls with the DR/2010 Spectrophotometer,a single operator obtained a standard deviation of ±0.001 mg/L Cr6+.

Estimated Detection Limit (EDL)The EDL for program 90 (powder pillows) and program 95 (AccuVacAmpuls) is 0.01 mg/L Cr6+.

The EDL is the calculated lowest average concentration in a demineralizedwater matrix that is different from zero with a 99% level of confidence. Formore information on derivation and use of Hach’s estimated detection limit,see Section I of the DR/2010 Spectrophotometer Procedures Manual.

Interferences• The following substances do not interfere in the test, up to the

following concentration:

• Vanadium interference can be overcome by waiting ten minutes before reading.

• Highly buffered samples or extreme sample pH may exceed the buffering capacity of the reagents and require sample pretreatment; see Interference, pH, in Section I of the DR/2010 Spectrophotometer Procedures Manual.

Substance Concentration

Mercurous & Mercuric Ions Interferes Slightly

Iron 1 mg/L

Vanadium 1 mg/L


Summary of MethodHexavalent chromium is determined by the 1,5-diphenylcarbohydrazidemethod using a single dry powder formulation called ChromaVer 3Chromium Reagent. This reagent contains an acidic buffer combined with1,5-diphenylcarbohydrazide, which reacts to give a purple color which isproportional to the amount of hexavalent chromium present.

REQUIRED REAGENTS AND APPARATUS (Using Powder Pillows)Quantity Required

Description Per Test Unit Cat. No.Cell Riser, 10 mL sample cell........................................................................ each....... 45282-00ChromaVer 3 Chromium Reagent.................................. 1 pillow.............. 50/pkg........... 126-46Sample cell, with 10-mL mark, matched pair................................................. pair....... 24954-02

REQUIRED REAGENTS AND APPARATUS (Using AccuVac Ampuls)ChromaVer 3 AccuVac Ampuls..................................... 1 ampul.............. 25/pkg....... 25050-25Adapter, AccuVac Vial.........................................................1 ....................... each....... 43784-00Beaker, 50 mL......................................................................1 ....................... each........... 500-41Sample Cell, 25 x 54 mm, 10 mL, with cap ........................1 ....................... each....... 21228-00

OPTIONAL REAGENTSAcid Reagent Powder Pillows ................................................................... 50/pkg......... 2126-66Chromium, Hexavalent, Standard Solution, 50 mg/L Cr6+ .......................100 mL........... 810-42Chromium, Hexavalent, Standard Solution, Voluette ampule, 12.5 mg/L Cr6+, 10 mL................................................ 16/pkg....... 14256-10Nitric Acid, ACS.......................................................................................500 mL........... 152-49Nitric Acid Solution, 1:1...........................................................................500 mL......... 2540-49Sodium Hydroxide Solution, 5.0 N .............................................. 59 mL* SCDB......... 2450-26Water, demineralized .......................................................................................4 L........... 272-56


48


OPTIONAL APPARATUSDescription Unit Cat. No.AccuVac Snapper Kit .....................................................................................each .......24052-00Ampule Breaker Kit .......................................................................................each .......21968-00Cylinder, graduated, mixing, 25 mL ..............................................................each .......20886-40Flask, volumetric, Class A, 1000 mL.............................................................each .......14574-53pH Indicator Paper, 1 to 11 pH ............................................................5 rolls/pkg ...........391-33pH Meter, EC10, portable ..............................................................................each .......50050-00Pipet, serological, 2 mL...............................................................................each 5 ...........532-36Pipet, TenSette, 0.1 to 1.0 mL ........................................................................each .......19700-01Pipet Tips, for 19700-01 TenSette Pipet ....................................................50/pkg .......21856-96Pipet, volumetric, 5.00 mL, Class A ..............................................................each .......14515-37Pipet Filler, safety bulb...................................................................................each .......14651-00

OPTIONAL 25 ML ANALYSIS ITEMSChromaVer 3 Chromium Reagent (for 25 mL samples) ............................50/pkg .......12066-66Clippers, for opening pillows .........................................................................each ...........968-00Pour-Thru Cell Assembly Kit

(for 25-mL samples/reagents only) .............................................................each .......45215-00Sample cell, with 25-mL mark, matched pair .................................................pair .......20950-00


49

50

Method 8160

CONDUCTIVITY (0.2 to 4.0 mS/cm; 10 to 1999 mg/L TDS)

Using Pocket Pal™ Conductivity Tester For water and wasetwater

1. Add approximately 30 mL of the sample to a 50-mL plastic beaker.

Note: Calibration is necessary; see Calibration following these steps.

Note: For best results, calibration standard and samples should be at the same temperature (25 °C). When measured at different temperatures, the Pocket Pal compensates by adjusting the reading 2% per °C. The accuracy of these temperature-compensated readings is ±10% for 0-50 °C.

2. Immerse the tip of the calibrated Pocket Pal Conductivity Tester one inch (2.5 cm) below the surface of the sample and stir gently.

3. When the digital display stabilizes, read and record the display. The correct value in TDS as mg/L NaCl is determined by multiplying the reading by the number in the upper left hand corner display.

Note: Readings may not stabilize for up to 2 minutes. This is a function of the temperature sensor.

Note: If the display reads 22 and the number in the upper left display is 10, the correct value is 220 TDS as mg/L NaCl.

4. Rinse the electrode with demineralized water, and remove the excess by wiping the tip with a tissue before continuing to the next sample.

Note: To maintain or improve performance, periodically clean the stainless steel electrode by rinsing it in alcohol.

5. When testing is complete, rinse the electrode with demineralized water. Slide the on/off switch to off. Cover the electrode with the protective cap before storing.

51

CONDUCTIVITY, continued

Calibration of Pocket Pal Conductivity Testera) Choose a Sodium Chloride Standard Solution that is about the

same TDS level as the sample(s). See Optional Reagent list at the end of this procedure.

b) Pour about 30 mL of the appropriate standard into a 50-mL beaker.

c) Slide the on/off switch on top of the Pocket Pal Conductivity Tester to on. See Figure 1.

d) Remove the protective cap from the bottom of the instrument. Immerse the electrode tip one inch (2.5 cm) below the surface of the standard solution. If necessary, calibrate the instrument by adjusting the calibration trimmer near the pocket clip on the back of the instrument. See Figure 2. Use the trim tool (screwdriver) provided to turn the screw. Adjust the value listed for the TDS on the standard label. Be sure to multiply the displayed number by the number in the upper left corner of the display to obtain the correct TDS in mg/L.

Figure 1Pocket Pal Components

Figure 2Calibration Trimmer

52


Sampling and StorageCollect samples in clean plastic or glass bottles. Analyze samples as soon aspossible after collection. However, samples may be stored at least 24 hours bycooling to 4 °C (39 °F) or below. The conductivity tester will compensate forany variation of temperature from 25 °C.

Water sample containing oils, grease, or fats will coat the electrode and affectthe accuracy of the readings. If this occurs, clean the probe with a strongdetergent solution, then thoroughly rinse with demineralized water, Mineralbuildup on the probe can be removed with 1:1 Hydrochloric Acid Solution.

ConversionsThe following table provides equations for converting the conductivityreadings to other units of measure.

InterferencesWhen measuring conductivity, the following items should be consideredto ensure accurate results:

• If measuring very low levels of conductivity, protect the sample from atmospheric gases (carbon dioxide, ammonia). These gases dissolve readily in water and may cause a rapid change in conductivity. To minimize these effects, boil the sample, then place in a covered container for cooling.

From To Use this Equation

mS/cm µS/cm mS/cm x 1000

µS/cm mS/cm µS/cm x 0.001

µS/cm µmhos/cm µS/cm x 1

mS/cm mmhos/cm mS/cm x 1

µS/cm mg/L TDS µS/cm x 0.5

g/L TDS mg/L TDS g/L TDS x 1000

mS/cm g/L TDS mS/cm x 0.5

mg/L TDS g/L TDS mg/L TDS x 0.001

mg/L TDS gpg TDS mg/L TDS x 0.05842

g/L TDS gpg TDS g/L TDS x 58.42

µS/cm ohms cm 1,000,000 ÷ µS/cm

mS/cm ohms cm 1,000 ÷ mS/cm

53


• If the sample contains high levels of hydroxide (boiler water for example), neutralize to avoid inaccurate high results. Neutralize by adding 4 drops of Phenolphthalein Indicator Solution to 50 mL of sample, then adding Gallic Acid Solution, drop-wise, until the pink color completely disappears.

Accuracy CheckPour a Sodium Chloride Standard Solution with a conductivity value inthe same range as the sample into a beaker. Perform the conductivitymeasurements as described above. The conductivity reading should bethe same as listed on the Standard Solution label if the meter iscalibrated correctly.

Summary of MethodElectrolytic conductivity is the capacity of ions in a solution to carryelectrical current and is the reciprocal of the solution resistivity. Current iscarried by inorganic dissolved solids (e.g., chloride, nitrate, sulfate, andphosphate anions) and cations (e.g., sodium, calcium, magnesium, iron,and aluminum). Organic material like oils, phenols, alcohols, and sugarsdo not carry electrical current well and thus do not have enoughconductivity for a useful estimate of concentration.

Measuring conductivity is done by measuring the resistance occurring in anarea of the test solution defined by the probe’s physical design. Voltage isapplied between the two electrodes immersed in the solution, and thevoltage drop caused by the resistance of the solution is used to calculateconductivity per centimeter. The basic unit of measure for conductivity isthe Siemen (or mho), the reciprocal of the ohm in the resistancemeasurement. Because ranges normally found in aqueous solutions aresmall, milliSiemens/cm (10-3 S or mS/cm) and microSiemens/cm (10-6 S orµS/cm) are used most commonly.

REQUIRED REAGENTS AND APPARATUSDescription Unit Cat. No.Pocket Pal Conductivity Tester ..................................................................................... 44375-00Beaker, poly, 50 mL....................................................................................... each......... 1080-41

OPTIONAL REAGENTS AND APPARATUSDescription Unit Cat. No.Battery, optional, 1.4V Zinc-Air .................................................................. 4/pkg....... 23678-00Gallic Acid Solution SCDB........................................................................59 mL....... 14423-26

54


OPTIONAL REAGENTS AND APPARATUS, continuedDescription Unit Cat. NoHydrochloric Acid Solution, 6.0 N .......................................................... 500 mL ...........884-49Sodium Chloride Standard Solution,

1000 ±10 µS/cm, 500 ±5 mg/L TDS..................................................... 100 mL .......14400-42Sodium Chloride Standard Solution,

1990 ±20 µS/cm, 995 ±10 mg/L TDS................................................... 100 mL .........2105-42Sodium Chloride Standard Solution,

18000 ± 50µS/cm, 9000 ±25 mg/L TDS............................................... 100 mL .......23074-42Wash Bottle, 125-mL .....................................................................................each ...........620-14Water, demineralized.........................................................................................4L ...........272-56


55

56

Method 8506

COPPER (0 to 5.00 mg/L) For water, wastewater and seawater*

Bicinchoninate Method** (Powder Pillows or AccuVac Ampuls); USEPA approved for reporting wastewater analysis (digestion needed; See Section II of the DR/2010 Spectrophotometer Procedures Manual)***


* Pretreatment required; see Interferences (Using Powder Pillows)** Adapted from Nakano, S., Yakugaku Zasshi, 82 486-491 (1962) [Chemical Abstracts, 58 3390e (1963)]*** Powder Pillows only: Federal Register, 45 (105) 36166 (May 29, 1980)

1. Enter the stored program number for copper (Cu), bicinc-honinate powder pillows.

Press: 1 3 5 ENTER


Dial nm to 560

Note: The Pour-Thru Cell can be used for 25 mL reagents only.


560 nm

When the correct wavelength is dialed, the display will quickly show: Zero Sample

then: mg/L Cu Bicn

Note: Determination of total copper needs a prior digestion (see Digestion, Section II of the DR/2010 Spectrophotometer Procedures Manual).



Note: Determine a reagent blank for each new lot of reagent. Use demineralized water in place of the sample in the procedure. Subtract this value from each result obtained.

Note: Adjust pH of stored samples before analysis.

560 nm

57

COPPER, continued

5. Add the contents of one CuVer 1 Copper Reagent Powder Pillow to the sample cell (the prepared sample). Swirl to mix.

Note: A purple color will develop if copper is present.


A two-minute reaction period will begin.

Note: Accuracy is not affected by undissolved powder.

7. When the timer beeps, the display will show: mg/L Cu Bicn

Fill a second 10-mL sample cell (the blank) with 10 mL of sample.


9. Press: ZERO


Zeroing. . .

then: 0.00 mg/L Cu Bicn

10. Within thirty minutes after the timer beeps, place the prepared sample into the cell holder. Close the light shield.

11. Press: READ


Reading. . .

then the result in mg/L copper will be displayed.

58

COPPER, continued

Using AccuVac Ampuls Method 8026

1. Enter the stored program number for copper (Cu), bicinchoninate AccuVac Ampuls.

Press: 1 4 0 ENTER


Dial nm to 560



560 nm


then: mg/L Cu Bicn AV


Note: Determine a reagent blank for each new lot of reagent. Repeat procedure using demineralized water in place of the sample. Subtract this value from each result obtained with this lot of reagent.

4. Fill a CuVer 2 AccuVac Ampul with sample.



Note: A purple color will form if copper is present.

Note: Accuracy is not affected by undissolved powder





8. When the timer beeps, the display will show:

mg/L Cu Bicn AV


560 nm

59

COPPER, continued

Sampling and StorageCollect samples in acid-cleaned glass or plastic containers. Adjust the pH to 2 orless with nitric acid (about 2 mL per liter). Store preserved samples up to sixmonths at room temperature. Before analysis, adjust the pH to 4 to 6 with 8 Npotassium hydroxide. Do not exceed pH 6, as copper may precipitate. Correctthe test result for volume additions; see Correction for Volume Additions inSection I of the DR/2010 Spectrophotometer Procedures Manual for moreinformation. If only dissolved copper is to be determined, filter the samplebefore acid addition using the labware listed under Optional Apparatus.


a) Fill three 25-mL graduated mixing cylinders with 25 mL of sample.

a) Snap the neck off a Copper PourRite Standard Ampule, 75 mg/L as Cu.

b) Use the TenSette Pipet to add 0.1, 0.2, and 0.3 mL of standard, respectively, to the mixing cylinders. Stopper and mix thoroughly.

c) For analysis with AccuVac Ampuls, transfer the solutions to dry, clean 50-mL beakers to fill the vials. For analysis with powder pillows, transfer only 10 mL of the solution to 10-mL sample cells.

d) Analyze each sample as described in the procedure. The copper concentration should increase about 0.3 mg/L for each 0.1 mL of standard added.

9. Press: ZERO


Zeroing. . .

then:

0.00 mg/L Cu Bicn AV

10. Within thirty minutes after the timer beeps, place the AccuVac Ampul in the cell holder. Close the light shield.

11. Press: READ


Reading. . .

then the result in mg/L copper will be displayed.

60

COPPER, continued


Standard Solution MethodPrepare a 3.00 mg/L copper standard by pipetting 3.00 mL of CopperStandard Solution, 100 mg/L as Cu, into 100-mL volumetric flask. Dilute tovolume with demineralized water and mix well. Prepare this solution daily.

PrecisionIn a single laboratory, using a standard solution of 2.00 mg/L Cu and tworepresentative lots of reagent with the DR/2010 Spectrophotometer, asingle operator obtained a standard deviation of ±0.007 mg/L Cu.

In a single laboratory, using a standard solution of 2.00 mg/L Cu and tworepresentative lots of AccuVac Ampuls with the DR/2010 Spectrophotometer,a single operator obtained a standard deviation of ±0.007 mg/L Cu.

Estimated Detection Limit (EDL)The EDL for program 135 (Powder Pillows) and program 492 (AccuVacAmpuls) is 0.02 mg/L Cu. The EDL is the calculated lowest averageconcentration in a demineralized water matrix that is different from zerowith a 99% level of confidence. For more information on derivation anduse of Hach’s estimated detection limit, see Section I of the DR/2010Spectrophotometer Procedures Manual.

Interferences Using Powder Pillows

• If the sample is extremely acidic (pH 2 or less) a precipitate may form. Add 8 N Potassium Hydroxide Standard Solution drop-wise while swirling to dissolve the turbidity. Read the mg/L Cu. If the turbidity remains and turns black, silver interference is likely. Eliminate silver interference by adding 10 drops of saturated Potassium Chloride Solution to 75 mL of sample, followed by filtering through a fine or highly retentive filter. Use the filtered sample in the procedure.

• Cyanide interferences prevent sufficient color development but can be overcome by adding 0.2 mL of formaldehyde to the 10 mL sample. Wait four minutes before taking the reading. Multiply the test results by 1.02 to correct for sample dilution by the formaldehyde.

61

COPPER, continued

• To test samples such as seawater containing high levels of hardness, iron, or aluminum, analyze a 25 mL sample volume with a CuVer® 2 Copper Reagent Powder Pillow instead of a CuVer 1 Pillow and the 10 mL sample volume (the taller 25 mL sample cells are required). Results obtained will include total dissolved copper (free and complexed).

• To differentiate free copper from that complexed to EDTA or other complexing agents, analyze a 25 mL sample volume with a Free Copper Reagent Powder Pillow instead of the CuVer 1 pillow and the 10 mL sample volume (the taller 25 mL sample cells are required). Final results will be free copper only. Add a Hydrosulfite Reagent Powder Pillow to the developed sample and re-read the result. This result will include the total dissolved copper (free and complexed).

Using AccuVac Ampuls• The CuVer 2 Reagent contained in the AccuVac Ampuls is formulated to

withstand high levels of calcium, iron and aluminum without interference.

• Unlike CuVer 1 Reagent, CuVer 2 reacts directly with copper which is complexed by chelants such as EDTA. If free copper is to be determined separately from complexed copper, see the Powder Pillow Interference section above.

• If the sample is very acidic it should be adjusted to a pH greater than 4 before analysis. If a turbidity forms and turns black, silver interference is likely. This can be eliminated by adding 10 drops of saturated Potassium Chloride Solution to 75 mL of sample, followed by filtration through a fine filter using the labware listed under Optional Apparatus. Use the filtered sample in the procedure.

• Cyanide interferences prevent sufficient color development but can be overcome by adding 0.5 mL of formaldehyde to 25 mL of sample. Wait four minutes before taking the reading. Multiply final results by 1.02 to correct for sample dilution.

Summary of MethodCopper in the sample reacts with a salt of bicinchoninic acid contained inCuVer 1 or 2 Copper Reagent to form a purple colored complex inproportion to the copper concentration. This method includes proceduresfor both powder pillow and AccuVac Ampul reagents.

62

COPPER, continued


Description Per Test Unit Cat. No.CuVer 1 Copper Reagent

Powder Pillows, 10 mL sample 1 pillow ......... ...100/pkg .......21058-69

REQUIRED REAGENTS (Using AccuVac Ampuls)CuVer 2 Copper Reagent AccuVac Ampuls...................1 ampul ..............25/pkg .......25040-25

REQUIRED APPARATUSCell Riser, 10 mL ................................................................ 1........................each .......45282-00Sample Cell, 10 mL, matched pair ...................................... 2.........................pair .......24954-02

REQUIRED APPARATUS (Using AccuVac Ampuls)Adapter, AccuVac vial......................................................... 1........................each .......43784-00Beaker, 50 mL ..................................................................... 1........................each ...........500-41Vial, zeroing ........................................................................ 1........................each .......21228-00

OPTIONAL REAGENTSCopper Standard Solution, 100 mg/L....................................................... 100 mL ...........128-42Copper PourRite Standard Ampule, 75 mg/L Cu, 2 mL............................20/pkg .......14247-20CuVer 2 Reagent Powder Pillows, 25 mL..................................................25/pkg .......21882-68Formaldehyde, 37% ..................................................................... 100 mL* MDB .........2059-32Free Copper Reagent Powder Pillows......................................................100/pkg .......21186-69Hydrochloric Acid Solution, 6 N ............................................................. 500 mL ...........884-49Hydrosulfite Reagent Powder Pillows......................................................100/pkg .......21188-69Nitric Acid, ACS ...................................................................................... 500 mL ...........152-49Nitric Acid Solution, 1:1 .......................................................................... 500 mL .........2540-49Potassium Chloride Solution, saturated .......................................... 50 mL SCDB ...........765-26Potassium Hydroxide Standard Solution, 8.0 N........................... 100 mL* MDB ...........282-32Sodium Hydroxide Solution, 5.0 N.............................................. 100 mL* MDB .........2450-32Water, demineralized........................................................................................4 L ...........272-56


63

COPPER, continued

OPTIONAL APPARATUSDescription Unit Cat. No.AccuVac Snapper Kit..................................................................................... each....... 24052-00Ampule Breaker Kit....................................................................................... each....... 21968-00Cylinder, graduated, mixing, 25 mL.............................................................. each....... 20886-40Cylinder, graduated, polypropylene, 25 mL .................................................. each......... 1081-40Cylinder, graduated, 100 mL ......................................................................... each........... 508-42Filter Paper, folded, 12.5 cm ................................................................... 100/pkg......... 1894-57Filter Pump .................................................................................................... each......... 2131-00Flask, volumetric, 100 mL............................................................................. each........... 547-42Funnel, polypropylene, 65 mm ...................................................................... each......... 1083-67Hot Plate, 3 1/2" diameter, 120 Vac............................................................... each....... 12067-01Hot Plate, 3 1/2" diameter, 240 Vac............................................................... each....... 12067-02pH Indicator Paper, 1 to 11 pH ............................................................ 5 rolls/pkg........... 391-33pH Meter, EC10, portable .............................................................................. each....... 50050-00Pipet, TenSette, 0.1 to 1.0 mL........................................................................ each....... 19700-01Pipet Tips, for 19700-01 TenSette Pipet .................................................... 50/pkg....... 21856-96Pipet, volumetric, Class A, 3.00 mL.............................................................. each....... 14515-03Pipet Filler, safety bulb .................................................................................. each....... 14651-00

OPTIONAL 25 ML ANALYSIS ITEMSCuVer 1 Copper Reagent Powder Pillows ................................................. 50/pkg....... 14188-99Clippers, for opening pillows......................................................................... each........... 968-00Pour-Thru Cell Assembly Kit (for 25 mL reagents only).............................. each....... 45215-00Sample Cell, 25 mL, matched pair ................................................................. pair....... 20950-00


64

Method 8029

FLUORIDE (0 to 2.00 mg/L F-) For water, wastewater and seawater

SPADNS Method* (Reagent Solution or AccuVac Ampuls); USEPA accepted for reporting wastewater and drinking water analysis (distillation required; see Section I of the DR/2010 Spectrophotometer Procedures Manual.)**

Using SPADNS Reagent Solution

* Adapted from Standard Methods for the Examination of Water and Wastewater** Procedure is equivalent to Standard Methods 4500F-B,D for drinking water and wastewater.

1. Enter the stored program number for fluoride (F-).

Press: 1 9 0 ENTER


Dial nm to 580

Note: The Pour-Thru Cell cannot be used with this procedure.


580 nm

When the correct wavelength is dialed in, the display will quickly show: Zero Sample

then: mg/L F-

Note: Approach the wavelength setting from higher to lower values.


4. Measure 10.0 mL of sample into a dry 10-mL sample cell (the prepared sample).

Note: Use a graduated cylinder or pipet.

580 nm

65

FLUORIDE, continued

5. Measure 10.0 mL of demineralized water into a second dry sample cell (the blank).

Note: Use a graduated cylinder or pipet.

Note: The sample and blank should be at the same temperature (±1 °C). Temperature adjustments may be made before or after reagent addition.

6. Pipet 2.00 mL of SPADNS Reagent into each cell. Swirl to mix.

Note: SPADNS Reagent is toxic and corrosive; use care while measuring.

Note: The SPADNS Reagent must be measured accurately.


A one minute reaction period will begin.

8. When the timer beeps, the display will show: mg/L F-


9. Press: ZERO


Zeroing. . .

then: 0.00 mg/L F-


11. Press: READ


Reading. . .

then the result in mg/L F- will be displayed.

66

FLUORIDE, continued


1. Enter the stored program number for fluoride (F-) AccuVac Ampuls.

Press: 1 9 5 ENTER


Dial nm to 580


580 nm


then: mg/L F- AV

Note: Approach the wavelength setting from higher to lower values.

3. Collect at least 40 mL of sample in a 50-mL beaker. Pour at least 40 mL of demineralized water into a second beaker.

4. Fill a SPADNS Fluoride Reagent AccuVac Ampul with sample by breaking the tip on the bottom of the beaker. Fill a second AccuVac Ampul with demineralized water (the blank) in the same manner.


5. Quickly invert the ampuls several times to mix. Wipe off any liquid or fingerprints.


A one-minute reaction period will begin.

7. Place the AccuVac Vial Adapter into the cell holder of the instrument.


8. When the timer beeps, the display will show: mg/L F- AV


580 nm

67

FLUORIDE, continued

Sampling and StorageCollect samples in plastic bottles. Samples may be stored up to 28 days.

Accuracy CheckStandard Solution Method

A variety of standard solutions covering the entire range of the test is availablefrom Hach. Use these in place of sample to verify technique. Minor variationsbetween lots of reagent become measurable above 1.5 mg/L.While results inthis region are usable for most purposes, better accuracy may be obtained bydiluting a fresh sample 1:1 with demineralized water and retesting. Multiply theresult by 2.

PrecisionIn a single laboratory, using standard solutions of 1.00 mg/L fluoride andtwo lots of SPADNS Reagent with the DR/2010 Spectrophotometer, asingle operator obtained standard deviations of ±0.02 mg/L fluoride.

Estimated Detection Limit (EDL)The EDL for program 190 is 0.02 mg/L F-. The EDL is the calculatedlowest average concentration in a demineralized water matrix that isdifferent from zero with a 99% level of confidence. For more informationon derivation and use of Hach’s estimated detection limit, see Section I ofthe DR/2010 Spectrophotometer Procedures Manual.

9. Press: ZERO


Zeroing. . .

then:0.00 mg/L F- AV

10. Place the AccuVac Ampul containing the sample into the instrument. Close the light shield.

11. Press: READ


Reading. . .

then the result in mg/L F- will be displayed.

68

FLUORIDE, continued

The EDL for program 195 is 0.02 mg/L F-. The EDL is the calculatedlowest average concentration in a demineralized water matrix that isdifferent from zero with a 99% level of confidence. For more informationon derivation and use of Hach’s estimated detection limit, see Section I ofthe DR/2010 Spectrophotometer Procedures Manual.

Interferences• This test is sensitive to small amounts of interference. Glassware must

be very clean. Repeating the test with the same glassware is recommended to ensure that results are accurate.

• The following substances interfere to the extent shown:

• SPADNS Reagent contains enough arsenite to eliminate interference up to 5 mg/L chlorine. For higher chlorine levels, add one drop of Sodium Arsenite Solution to 25 mL of sample for each 2 mg/L of chlorine.

• To check for interferences from aluminum, read the concentration one minute after reagent addition, then again after 15 minutes. An appreciable increase in concentration suggests aluminum interference. Waiting two hours before making the final reading will eliminate the effect of up to 3.0 mg/L aluminum.

• Most interferences can be eliminated by distilling the sample from an acid solution as described below:

a) Set up the distillation apparatus for the general purpose distillation. See the Hach Distillation Apparatus Manual. Turn on the water and make certain it is flowing through the condenser.

b) Measure 100 mL of sample into the distillation flask. Add a magnetic stirring bar and turn on the heater power switch. Turn the stir control to 5.

Substance Concentration Error

Alkalinity (as CaCO3) 5000 mg/L -0.1 mg/L F-

Aluminum 0.1 mg/L -0.1 mg/L F-

Chloride 7000 mg/L +0.1 mg/L F-

Iron, ferric 10 mg/L -0.1 mg/L F-

Phosphate, ortho 16 mg/L +0.1 mg/L F-

Sodium Hexametaphosphate 1.0 mg/L +0.1 mg/L F-

Sulfate 200 mg/L +0.1 mg/L F-

69

FLUORIDE, continued

70

c) Cautiously measure 150 mL of StillVer® Distillation Solution (2:1 Sulfuric Acid) into the flask. If high levels of chloride are present, add 5 mg silver sulfate for each mg/L chloride present.

d) Turn the heat control to setting 10, with the thermometer in place. The yellow pilot lamp shows when the heater is on.

e) When the temperature reaches 180 °C (about one hour), turn the still off.

f) Dilute the collected distillate to 100 mL, if necessary. Analyze the distillate by the above method.

Summary of MethodThe SPADNS Method for fluoride determination involves the reaction offluoride with a red zirconium-dye solution. The fluoride combines with part ofthe zirconium to form a colorless complex, thus bleaching the red color in anamount proportional to the fluoride concentration. This method is approved bythe USEPA for NPDES and NPDWR reporting purposes when the sampleshave been distilled. Seawater and wastewater samples require distillation. SeeOptional Apparatus for distillation Apparatus listing.

REQUIRED REAGENTS (Using Solution)Quantity Required

Description Per Test Unit Cat. No.SPADNS Reagent for Fluoride ........................................ 4 mL .............. 500 mL.......... 444-49Water, demineralized ...................................................... 10 mL ..................... 4 L........... 272-56

REQUIRED APPARATUS (Using Solution)Cell Riser, 10 mL.................................................................1 ....................... each....... 45282-00Cylinder, graduated, 10 mL .................................................1 ....................... each........... 508-38Pipet Filler safety bulb .........................................................1 ....................... each....... 14651-00Pipet, volumetric, Class A, 10.00 mL..................................1 ....................... each....... 14515-38Pipet, volumetric, Class A, 5 mL.........................................1 ....................... each....... 14515-37Sample Cell, 10 mL, matched pair .....................................2 ........................ pair....... 24954-02Thermometer, -20 to 105°C .................................................1 ....................... each......... 1877-01

REQUIRED REAGENTS (Using AccuVac Ampuls)SPADNS Fluoride Reagent AccuVac Ampuls.............. 2 ampuls ............. 25/pkg....... 25060-25Water, demineralized .......................................................varies...................... 4 L........... 272-56

FLUORIDE, continued

REQUIRED APPARATUS (Using AccuVac Ampuls) Quantity Required

Description Per Test Unit Cat. No.Adapter, AccuVac Vial ........................................................ 1........................each .......43784-00Beaker, 50 mL ..................................................................... 2........................each ...........500-41

OPTIONAL REAGENTSFluoride Standard Solution, 0.2 mg/L F- .................................................. 473 mL ...........405-02Fluoride Standard Solution, 0.4 mg/L F- .................................................. 473 mL ...........405-04Fluoride Standard Solution, 0.5 mg/L F- .................................................. 473 mL ...........405-05Fluoride Standard Solution, 0.6 mg/L F- .................................................. 473 mL ...........405-06Fluoride Standard Solution, 0.8 mg/L F- .................................................. 473 mL ...........405-08Fluoride Standard Solution, 1.0 mg/L F- .................................................. 946 mL ...........291-16Fluoride Standard Solution, 1.0 mg/L F- .................................................. 473 mL ...........291-11Fluoride Standard Solution, 1.2 mg/L F- .................................................. 473 mL ...........405-12Fluoride Standard Solution, 1.4 mg/L F- .................................................. 473 mL ...........405-14Fluoride Standard Solution, 1.5 mg/L F- .................................................. 473 mL ...........405-15Fluoride Standard Solution, 1.6 mg/L F- .................................................. 473 mL ...........405-16Fluoride Standard Solution, 1.8 mg/L F- .................................................. 473 mL ...........405-18Fluoride Standard Solution, 2.0 mg/L F- .................................................. 473 mL ...........405-20Silver Sulfate, ACS ......................................................................................113 g ...........334-14Sodium Arsenite Solution .............................................................. 100 mL MDB .........1047-32StillVer Distillation Solution .................................................................... 500 mL ...........446-49

OPTIONAL APPARATUSAccuVac Snapper Kit .....................................................................................each .......24052-00Cylinder, graduated, 100 mL..........................................................................each ...........508-42Cylinder, graduated, 250 mL..........................................................................each ...........508-46Distillation Heater and Support Apparatus Set, 115 V, 50/60 Hz ..................each .......22744-00Distillation Heater and Support Apparatus Set, 230 V, 50/60 Hz ..................each .......22744-02Distillation Apparatus General Purpose Accessories.....................................each .......22653-00pH/ISE Meter, EC20, portable .......................................................................each .......50075-00Pipet, TenSette, 1.0 to 10.0 mL ......................................................................each .......19700-10Pipet Tips, for 19700-10 TenSette Pipet ....................................................50/pkg .......21997-96


71

72

Method 8213

HARDNESS, TOTAL (10 - 4000 mg/L as CaCO3)

Using EDTA with a Digital Titrator For water, wastewater and seawater

1. Select a sample size and an EDTA Titration Cartridge corresponding to the expected total hardness as calcium carbonate (CaCO3) concentration. Use Table 1 on page 74 for concentrations in mg/L or Table 2 on page 74 for concentrations in German degrees of hardness (G.d.h.).

Note: One German degree hardness equals 17.9 mg/L hardness as CaCO3.

Note: Collect at least 100 mL of sample in a glass or polyethylene container. Samples may be held up to seven days before analysis if stored at 4 oC and acidified to pH 2 with concentrated nitric acid. Neutralize acidified sample to pH 7 with ammonium hydroxide before testing.




4. Use a graduated cylinder or pipet to measure the sample volume from Table 1 or Table 2. Transfer the sample into a clean 250-mL erlenmeyer flask. Dilute to about the 100-mL mark with demineralized water, if necessary.

73

5. Add 2 mL of Buffer Solution, Hardness, 1, and swirl to mix.

6. Add the contents of one ManVer® 2 Hardness Indicator Powder Pillow and swirl to mix.

Note: Four drops of ManVer Hardness Indicator Solution or a 0.1 g scoop of ManVer 2 Hardness Indicator Powder may be substituted for the powder pillow.

7. Place the delivery tube tip into the solution and swirl the flask while titrating with EDTA from red to pure blue. Record the number of digits required.

Note: Titrate slowly near the end point because the reaction is slow, especially in cold samples.

8. Use one of the following formulas to calculate the final concentration:Digits Required x Digit Multiplier (Table 1) = mg/L Total Hardness as CaCO3

Digits Required x Digit Multiplier (Table 2) = G.d.h.

Note: The magnesium concentration may be determined by subtracting the results of the calcium determination from the above total hardness determination.

Table 1

Table 2

Range (mg/L as CaCO3)

Sample Volume

(mL)

Titration Cartridge (M EDTA)

Catalog Number

Digit Multiplier

10-4040-160

100-400200-800

500-20001000-4000

10025

100502010

0.08000.08000.8000.8000.8000.800

14364-0114364-0114399-0114399-0114399-0114399-01

0.10.41.02.05.0

10.0

Range (G.d.h.)Sample Volume

(mL)

Titration Cartridge (M EDTA)

Catalog Number

Digit Multiplier

1-44-16

10-4025-100>100

10025502010

0.14280.14280.7140.7140.714

14960-0114960-0114959-0114959-0114959-01

0.010.040.10.250.5

HARDNESS, TOTAL, continued

74


Hardness Relationships


To verify analytical technique use 20 mL of the Calcium Standard Solution,1000 mg/L as CaCO3. Perform the procedure as described above. Thissolution will read 1000 mg/L or 55.9 G.d.h.

Perform this accuracy check when interferences are suspected.

1. Snap the neck off a Hardness Voluette Ampule Standard, 10,000 mg/Las CaCO3.

2. Use a TenSette Pipet to add 0.1 mL of standard to the sample titrated in Step 7. Resume titration back to the same end point. Record the number of digits required.

3. Repeat, using two more additions of 0.1 mL. Titrate to the end point after each addition.

4. Each 0.1 mL addition of standard should require 10 additional digits of 0.800 M titrant, 100 digits of 0.0800 M titrant, 11 digits of 0.714 M, or 56 digits of 0.1428 M titrant. If these uniform increases do not occur, refer to Appendix A, Accuracy Check and Standard Additions in the Digital Titrator Manual to determine the cause.

Interferences• Although less common than calcium and magnesium, other

polyvalent metal ions cause the same hardness effects and will be included in the results.

• Some transition and heavy metals complex the indicator and prevent the color change at the end point.

• Iron does not interfere up to 15 mg/L. Above this level it causes a red-orange to green end point which is sharp and usable up to 30 mg/L iron. Substitute a 0.0800 M CDTA or 0.800 M CDTA titration cartridge for the 0.0800 M EDTA or 0.800 M EDTA titration cartridges, respectively, if iron interference is probable.

mg/L Total Hardness as Ca mg/L Total Hardness as (CaCO3) 0.400×=

mg/L Total Hardness (as CaCO3) =

mg/L Ca (as CaCO3) + mg/L Mg (as CaCO3 )

75


• Manganese titrates directly up to 20 mg/L but masks the end point above this level. Adding a 0.1-gram scoop of hydroxylamine hydrochloride monohydrate raises this level to 200 mg/L manganese.

DANGERPotassium cya-nide is toxic. Always add it after the potassium hydroxide. Excess potassium cya-nide does not affect results. All cyanide wastes should be disposed of by adding an excess of strongly alkaline sodium hypochlorite solution (bleach) with stirring. Use good ventilation. Allow to stand for 24 hours before disposal.

• Copper interferes at levels of 0.10 and 0.20 mg/L. Cobalt and nickel interfere at all levels and must be absent or masked. A 0.5-gram scoop of potassium cyanide removes interference from up to 100 mg/L copper, 100 mg/L zinc, 100 mg/L cobalt and 100 mg/L nickel. It raises the permissible aluminum level to 1 mg/L. Metals masked with cyanide will not be included in the hardness result.

• Orthophosphate causes a slow end point and polyphosphate must be absent for accurate results.

• Acidity and alkalinity at 10,000 mg/L (as CaCO3) do not interfere.

• Saturated sodium chloride solutions do not give a distinct end point, but the titration can be run directly on sea water.

• Adding the contents of one CDTA Magnesium Salt Powder Pillow removes metal interferences at or below the levels shown in Table 3.

• If more than one metal is present at or above the concentrations shown above, an additional CDTA Magnesium Salt Powder Pillow may be required.

• Results obtained by this procedure include the hardness contributed by the metals. If the concentration of each metal is known, a correction can be applied to obtain the calcium and magnesium hardness concentration. The hardness (in mg/L as CaCO3) contributed by each mg/L of metal is listed below, and can be subtracted from the total hardness value obtained above to determine the calcium and magnesium hardness. See Table 4.

Table 3

Metal CDTA Removes Interference Below This Level

Aluminum 50 mg/L

Cobalt 200 mg/L

Copper 100 mg/L

Iron 100 mg/L

Manganese 200 mg/L

Nickel 400 mg/L

Zinc 300 mg/L

76


.

• Barium, strontium and zinc titrate directly.

• Highly buffered samples or extreme sample pH may exceed the buffering capacity of the reagents and require sample pretreatment: see Interferences, pH, Section I of the DR/2010 Spectrophotometer Procedures Manual.

Summary of MethodAfter the sample is buffered to pH 10.1, ManVer 2 Hardness Indicator isadded, and forms a red complex with a portion of the calcium andmagnesium in the sample. EDTA titrant reacts first with the free calciumand magnesium ions, then with those bound to the indicator, causing it tochange to a blue color at the end point.

Table 4

Metal Hardness Contributed by Each mg/L of Metal

Aluminum 3.710

Barium 0.729

Cobalt 1.698

Copper 1.575

Iron 1.792

Manganese 1.822

Nickel 1.705

Strontium 1.142

Zinc 1.531

77


78

REQUIRED REAGENTSTotal Hardness Reagent Set (about 100 tests)

Includes: (1) 424-32, (1) 851-49, (1) 14364-01, (1) 14399-01 ................................. 22720-00Description Unit Cat. No.Buffer Solution, Hardness 1............................................................100 mL MDB........... 424-32ManVer 2 Hardness Indicator Powder Pillow.......................................... 100/pkg........... 851-99Water, demineralized .......................................................................................4 L........... 272-56

Select one or more based on sample concentrationEDTA Titration Cartridge, 0.0800 M............................................................. each....... 14364-01EDTA Titration Cartridge, 0.1428 M............................................................. each....... 14960-01EDTA Titration Cartridge, 0.714 M............................................................... each....... 14959-01EDTA Titration Cartridge, 0.800 M............................................................... each....... 14399-01

REQUIRED APPARATUSClippers, for opening pillows......................................................................... each........... 968-00Digital Titrator ............................................................................................... each....... 16900-01Flask, erlenmeyer, 250 mL ............................................................................ each........... 505-46Select one or more based on sample concentrationCylinder, graduated, 10 mL ........................................................................... each........... 508-38Cylinder, graduated, 25 mL ........................................................................... each........... 508-40Cylinder, graduated, 50 mL ........................................................................... each........... 508-41Cylinder, graduated, 100 mL ......................................................................... each........... 508-42

OPTIONAL REAGENTSAmmonium Hydroxide, 10%........................................................100 mL MDB*....... 14736-32Calcium Chloride Standard Solution, 1000 mg/L as CaCO3 ..................1000 mL........... 121-53CDTA Magnesium Salt Powder Pillows.................................................. 100/pkg....... 14080-99CDTA Titration Cartridge, 0.0800 M ............................................................ each....... 14402-01CDTA Titration Cartridge, 0.800 M .............................................................. each....... 14403-01Calcium Standard Solution, Voluette Ampule,

10,000 mg/L as CaCO3, 10 mL .............................................................. 16/pkg......... 2187-10Hydroxylamine Hydrochloride, Monohydrate, ACS................................... 113 g........... 246-14ManVer 2 Hardness Indicator Powder ......................................................... 113 g........... 280-14ManVer Hardness Indicator Solution............................................100 mL MDB*........... 425-32Nitric Acid Solution, 1:1...........................................................................500 mL......... 2540-49Nitric Acid, ACS.......................................................................................500 mL........... 152-49Potassium Cyanide, ACS ............................................................................. 125 g........... 767-14



OPTIONAL APPARATUSDescription Unit Cat. No.Bottle, wash, poly, 500 mL ............................................................................each ...........620-11Clamp 2-prong, extension, 38 mm .................................................................each .......21145-00Clamp Holder .................................................................................................each ...........326-00Demineralizer Assembly, 473 mL..................................................................each .......21846-00Delivery Tubes, with 180° hook...................................................................5/pkg .......17205-00Delivery Tubes, 90o with hook.....................................................................5/pkg .......41578-00pH meter, EC 10, portable..............................................................................each .......50050-00Hach One Combination pH Electrode with Temp .........................................each .......48600-22pH Indicator Paper, 1.0 to 11 pH..........................................................5 rolls/pkg ...........391-33Pipet, TenSette, 0.1 to 1.0 mL ........................................................................each .......19700-01Pipet Tips, for 19700-01 TenSette Pipet ....................................................50/pkg .......21856-96Pipet, volumetric, Class A, 10 mL .................................................................each .......14515-38Pipet, volumetric, Class A, 20 mL .................................................................each .......14515-20Pipet, volumetric, Class A, 25 mL .................................................................each .......14515-40Pipet, volumetric, Class A, 50 mL .................................................................each .......14515-41Pipet, volumetric, Class A, 100 mL ...............................................................each .......14515-42Pipet Filler safety bulb ...................................................................................each .......14651-00Spoon, measuring, 1.0 gram...........................................................................each ...........510-00Spoon, measuring, 0.5 gram...........................................................................each ...........907-00Support ring stand ..........................................................................................each ...........563-00TitraStir Mixer/Stand Assembly, 115 Vac......................................................each .......19400-00TitraStir Mixer/Stand Assembly, 230 Vac......................................................each ...... 19400-10


79

80

Method 8031

IODINE (0 TO 7.00 mg/L) For water, wastewater and seawater

DPD Method* (Powder Pillows or AccuVac Ampuls)


* Adapted from Palin, A.T., Inst. Water Eng., 21 (6) 537-547 (1967)

1. Enter the stored program number for iodine (I2) powder pillows.

Press: 2 4 0 ENTER


Dial nm to 530



530 nm


then: mg/L I2


4. Fill a cell with 10 mL of sample.


5. Add the contents of one DPD Total Chlorine Powder Pillow to the sample cell (the prepared sample). Swirl to mix.

Note: A pink color will develop if iodine is present.



7. When the timer beeps the display will show: mg/L I2

Fill a second sample cell with 10 mL of sample (the blank). Place it into the cell holder.

8. Press: ZERO


Zeroing. . . .

then: 0.00 mg/L I2

530 nm

81

IODINE, continued


10. Press: READ


Reading. . . .

then the result in mg/L I2 will be displayed.

Note: If the sample temporarily turns yellow after reagent addition, or reads OVER-RANGE, dilute a fresh sample. Repeat the test. A slight loss of iodine may occur during dilution. Apply the appropriate dilution factor; see Sample Dilution Techniques (Section I of the DR/2010 Spectrophotometer Procedures Manual).

82

IODINE, continued


1. Enter the stored program number for iodine (I2) AccuVac Ampuls.

Press: 2 4 2 ENTER


Dial nm to 530


530 nm


then: mg/L I2 AV



4. Fill a DPD Total Chlorine Reagent AccuVac Ampul with sample.



Note: A pink color will form if iodine is present.

6. Press:

SHIFT TIMER




8. When the timer beeps the display will show:

mg/L I2 AV


530 nm

83

IODINE, continued

84

Sampling and StorageAnalyze samples for iodine immediately after collection. Free iodine is astrong oxidizing agent, and it is unstable in natural waters. It reacts rapidlywith various inorganic compounds and more slowly oxidizes organiccompounds. Many factors, including reactant concentrations, sunlight, pH,temperature and salinity influence decomposition of iodine in water.

Avoid plastic containers since these may have a large iodine demand.Pretreat glass sample containers to remove any iodine demand by soaking ina dilute bleach solution (1 mL commercial bleach to l liter of demineralizedwater) for at least 1 hour. Rinse thoroughly with demineralized or distilledwater. If sample containers are rinsed thoroughly with demineralized ordistilled water after use, only occasional pre-treatment is necessary.

A common error in testing for iodine is introduced when a representativesample is not obtained. If sampling from a tap, let the water flow for atleast 5 minutes to ensure a representative sample. Let the containeroverflow with the sample several times, then cap the sample containers so

9. Press: ZERO


Zeroing. . . .

then: 0.00 mg/L I2 AV

10. Within three minutes after the timer beeps, place the AccuVac Ampul into cell holder. Close the light shield.

11. Press: READ


Reading. . . .

then the result in mg/L I2 will be displayed.

Note: If the sample temporarily turns yellow after sample addition, or shows OVER-RANGE, dilute a fresh sample. Repeat the test. A slight loss of iodine may occur during dilution. Apply the appropriate dilution factor; see Sample Dilution Techniques (Section I of the DR/2010 Spectrophotometer Procedures Manual).

IODINE, continued

there is no headspace (air) above the sample. If sampling with a samplecell, rinse the cell several times with the sample, then carefully fill to the10-mL mark. Perform the analysis immediately.

Standard Additions Method (using powder pillows)a) Perform a sample analysis and record the result.

b) Snap the top off a LR Chlorine PourRite Ampule Standard Solution, 25-30 mg/L Cl2.



e) Calculate the equivalent concentration of mg/L iodine added to the sample:

f) The spiked sample result (step d) should reflect the analyzed sample result (step a) + the added, calculated mg/L I2 (step e).







e) Analyzed the spiked and unspiked sample as described in the procedure.

f) Calculate the equivalent concentration of mg/L iodine added to the sample:

mg/L Iodine =0.1 (vol. standard added) Certificate value (mg/L Chlorine) 3.6××10.1 (sample + standard volume)

-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

mg/L Iodine 0.2 (vol. standard added) Certificate value (mg/L Chlorine) 3.6××25.2 (sample + standard volume)

-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------=

85

IODINE, continued

g) The spiked sample result should reflect the analyzed sample result + the added, calculated mg/L I2 (step f).


PrecisionIn a single laboratory using a standard solution of 1.00 mg/L chlorine andtwo representative lots of reagent with the DR/2010 Spectrophotometer, asingle operator obtained a standard deviation of ±0.012 chlorine. This isequivalent to ±0.04 mg/L iodine.

In a single laboratory using a standard solution of 1.10 mg/L chlorine and tworepresentative lots of AccuVac Ampuls with the DR/2010 Spectrophotometer,a single operator obtained a standard deviation of ±0.009 mg/L chlorine. Thisis equivalent to ±0.03 mg/L iodine.

InterferencesSamples containing more than 300 mg/L alkalinity or 150 mg/L acidity asCaCO3 may not develop the full amount of color, or it may instantly fade.Neutralize these samples to a pH of 6 to 7 with 1 N sulfuric acid or 1 Nsodium hydroxide. Determine the amount required on a separate 25-mLsample. Add the same amount to the sample to be tested. Correct forvolume additions.

Bromine, chlorine, ozone and oxidized forms of manganese andchromium also may react and read as iodine. To compensate for theeffects of oxidized manganese or chromium adjust pH to 6 to 7 asdescribed above. Add three drops of potassium iodide, 30 g/L, to 10 mLof sample, mix and wait one minute. Add three drops of sodium arsenite,5 g/L, and mix. Analyze 10 mL of this sample as described above. (Ifchromium is present, allow the same reaction period with the DPD forboth analyses). Subtract the result of this test from the original analysis toobtain the correct iodine result.

DPD Reagent Powder Pillows and AccuVac Ampuls are formulatedwith a buffer which will withstand high levels (1000 mg/L) of hardnesswithout interference.

Summary of MethodIodine reacts with DPD (N, N-diethyl-p-phenylenediamine) to form amagenta color which is proportional to the total iodine concentration.

86

IODINE, continued


Description Per Test Unit Cat. No.DPD Total Chlorine Reagent Powder Pillow, 10 mL .................................................1 pillow ............100/pkg .......21056-69

REQUIRED APPARATUS (Using Powder Pillows)Cell Riser, 10-mL ................................................................ 1........................each .......45282-00Sample Cell, 10 mL, matched pair ...................................... 2.........................pair .......24954-02

REQUIRED REAGENTS (Using AccuVac Ampuls)DPD Total Chlorine Reagent AccuVac Ampuls.............1 ampul ..............25/pkg .......25030-25

REQUIRED APPARATUS (Using AccuVac Ampuls)Adapter, AccuVac Vial ........................................................ 1........................each .......43784-00Beaker, 50 mL ..................................................................... 1........................each ...........500-41 Vial, zeroing ........................................................................ 1........................each .......21228-00

OPTIONAL REAGENTSChlorine Standard Solution PourRite Ampule,

25 to 30 mg/L Cl2 ................................................................................20/pkg .......26300-20Potassium Iodide Solution, 30 g/L ............................................... 100 mL* MDB ...........343-32Sodium Arsenite Solution, 5 g/L.................................................. 100 mL* MDB .........1047-32Sodium Hydroxide Standard Solution, 1 N.................................. 100 mL* MDB .........1045-32Sulfuric Acid Standard Solution, 1 N........................................... 100 mL* MDB .........1270-32Water, demineralized........................................................................................4 L ...........272-56

OPTIONAL APPARATUSAccuVac Snapper Kit .....................................................................................each .......24052-00Ampule Breaker Kit .......................................................................................each .......21968-00Cylinder, graduated, 25 mL............................................................................each ...........508-40pH Meter, EC10, portable ..............................................................................each .......50050-00pH Indicator Paper, 1 to 11 pH units....................................................5 rolls/pkg ...........391-33Pipet, TenSette, 0.1 to 1.0 mL ........................................................................each .......19700-01Pipet Tips, for 19700-01 TenSette Pipet ....................................................50/pkg .......21856-96

OPTIONAL 25-ML ANALYSIS ITEMSDescription Unit Cat. No.DPD Total Chlorine Reagent Powder Pillows..........................................100/pkg .......14064-99Pour-Thru Cell Assembly Kit ........................................................................each .......45215-00Sample Cell, 25-mL, matched pair..................................................................pair .......20950-00For technical support and ordering information, see General Information section.In the U.S.A. call 800-227-4224 to place an order.


87

88

Method 8008

IRON, TOTAL (0 to 3.00 mg/L) For Water, Wastewater, and Seawater

FerroVer Method* (Powder Pillows or AccuVac Ampuls) USEPA approved for reporting wastewater analysis (digestion is required; see Section II of the DR/2010 Spectrophotometer Procedures Manual)**


* Adapted from Standard Methods for the Examination of Water and Wastewater.** Federal Register, 45 (126) 43459 (June 27, 1980).

1. Enter the stored program number foriron (Fe) FerroVer, powder pillows.

Press: 2 6 5 ENTER


Dial nm to 510


Note: The Pour-Thru cell may be used with 25-mL reagents only.


510 nm


then: mg/L Fe FV

3. Insert the cell riser for 10-mL sample cells.

4. Fill a clean sample cell with 10 mL of sample.

Note: Determination of total iron needs a prior digestion; use the mild, vigorous or Digesdahl digestion (Section II of the DR/2010 Spectrophotometer Procedures Manual).

510 nm

89

IRON, TOTAL, continued

5. Add the contents of one FerroVer Iron Reagent Powder Pillow to the sample cell (the prepared sample). Swirl to mix.

Note: An orange color will form if iron is present.



A three minute reaction period will begin.

Note: Samples containing visible rust should be allowed to react at least five minutes.

7. When the timer beeps, the display will show: mg/L Fe FV

Fill another sample cell with 10 mL of sample (the blank).


Note: For turbid samples, treat the blank with one 0.1-gram scoop of RoVer Rust Remover (use 0.2-g for 25-mL samples). Swirl to mix.

9. Press: ZERO


Zeroing . . .

then:

0.00 mg/L Fe FV

10. Within thirty minutes after the timer beeps, place the prepared sample into the cell holder. Close the light shield.

11. Press: READ


Reading . . .

then the result in mg/L iron will be displayed.

90



1. Enter the stored program number for iron (Fe), AccuVac ampuls.

Press: 2 6 7 ENTER


Dial nm to 510


Note: Determination of total iron needs a prior digestion; use the mild, vigorous or Digesdahl digestion (Section II of the DR\2010 Spectrophotometer Procedures Manual).


510 nm


then:mg/L Fe FV AV


Note: For turbid samples, treat the blank with one 0.1 g scoop of RoVer Rust Remover. Swirl to mix.

4. Fill a FerroVer AccuVac Ampul with sample.



Note: An orange color will form if iron is present.

Note: Accuracy isnot affected by undissolved powder.



Note: Samples containing visible rust should be allowed to react at least five minutes.

7. When the timer beeps, the display will show: mg/L Fe FV AV

Place the AccuVac Vial Adapter into the cell compartment.



510 nm

91


Sampling and StorageCollect samples in acid-cleaned glass or plastic containers. No acid addition isnecessary if analyzing the sample immediately. To preserve samples, adjustthe pH to 2 or less with nitric acid (about 2 mL per liter). Preserved samplesmay be stored up to six months at room temperature. Adjust the pH tobetween 3 and 5 with 5.0 N sodium hydroxide Standard Solution beforeanalysis. Correct the test result for volume additions; see Correcting forVolume Additions in Section I of the DR/2010 Spectrophotometer ProceduresManual for more information.

If only dissolved iron is to be determined, filter the sample before acidaddition using the labware listed under Optional Apparatus.



b) Snap the neck off a 50 mg/L Iron Voluette Ampule Standard Solution.

c) Use the TenSette Pipet to add 0.1, 0.2, and 0.3 mL of standard, respectively, to the three mixing cylinders and mix thoroughly.

d) For analysis using AccuVac Ampuls, transfer solutions to dry, clean 50-mL beakers to facilitate filling of the ampuls. For analysis with powder pillows, transfer only 10 mL of solution to the 10-mL sample cells.

9. Press: ZERO


Zeroing . . .

then:

0.00 mg/L Fe FV AV

10. Within 30 minutes after the timer beeps, place the AccuVac ampul into the cell holder. Close the light shield.

11. Press: READ


Reading . . .

then the result in mg/L iron will be displayed.

92


e) Analyze each standard addition sample as described above. The iron concentration should increase 0.2 mg/L for each 0.1 mL of standard added.

f) If these increases do not occur, see Standard Additions in Section I of the DR/2010 Spectrophotometer Procedures Manual for troubleshooting information.

Standard Solution MethodPrepare a 1.00 mg/L iron standard by diluting 1.00 mL of Iron StandardSolution, 100 mg/L Fe, to 100 mL with demineralized water. Or dilute 1.00mL of an Iron Voluette Ampule Standard Solution (50 mg/L) to 50 mL in avolumetric flask. Prepare this solution daily. Run the test, following theprocedure for powder pillows or AccuVacs, using the 1.00 mg/L IronStandard Solution. Results should be between 0.90 mg/L and 1.10 mg/L Fe.

PrecisionIn a single laboratory, using a standard solution of 1.000 mg/L Fe and tworepresentative lots of powder pillow reagents with the DR/2010, a singleoperator obtained a standard deviation of ±0.006 mg/L.

In a single laboratory, using a standard solution of 1.000 mg/L Fe and tworepresentative lots of AccuVac ampuls with the DR/2010, a singleoperator obtained a standard deviation of ±0.009 mg/L Fe.

Estimated Detection Limit (EDL)The EDL for program 265 (Powder Pillows) and program 267 (AccuVacAmpuls) is 0.02 mg/L Fe. The EDL is the calculated lowest averageconcentration in a demineralized water matrix that is different from zerowith a 99% level of confidence. For more information on derivation anduse of Hach’s estimated detection limit, see Section I of the DR/2010Spectrophotometer Procedures Manual.

Interferences

• The following will not interfere below the levels shown:

Chloride 185,000 mg/L

Calcium 10,000 mg/L as CaCO3

Magnesium 100,000 mg/L as CaCO3

Molybdate Molybdenum 50 mg/L as Mo

93


• A large excess of iron will inhibit color development. A diluted sample should be tested if there is any doubt about the validity of a result.

• FerroVer Iron Reagent Powder Pillows and AccuVac Ampuls contain a masking agent which eliminates potential interferences from copper.

• Samples containing some forms of iron oxide require the mild, vigorous or Digesdahl digestion, see Section II of the DR/2010 Spectrophotometer Procedures Manual. After digestion, adjust the pH to between 2.5 and 5 with ammonium hydroxide.

• Samples containing large amounts of sulfide should be treated as follows in a fume hood or well ventilated area: Add 5 mL of hydrochloric acid to 100 mL of sample and boil for 20 minutes. Adjust the pH to between 2.5 and 5 with 5 N sodium hydroxide and readjust the volume to 100 mL with demineralized water. Analyze as described above.

• Highly buffered samples or extreme sample pH may exceed the buffering capacity of the reagents and require sample pretreatment; see Section I, Interferences, pH Interferences of the DR/2010 Spectrophotometer Procedures Manual.

Summary of Method FerroVer Iron Reagent reacts with all soluble iron and most insolubleforms of iron in the sample, to produce soluble ferrous iron. This reactswith the 1,10-phenanthroline indicator in the reagent to form an orangecolor in proportion to the iron concentration.


Description Per Test Unit Cat No.FerroVer Iron Reagent Powder Pillows, 10 mL samples ............................................................... 1 pillow............ 100/pkg....... 21057-69

REQUIRED REAGENTS (Using AccuVac Ampuls)FerroVer Iron Reagent AccuVac Ampuls ...................... 1 ampul.............. 25/pkg....... 25070-25

REQUIRED APPARATUS (Using Powder Pillows)Cell Riser, 10 mL sample cell..............................................1 ....................... each....... 45282-00Sample Cell, 10 mL, matched pair ................................................................ each....... 24954-02

94


REQUIRED APPARATUS (Using AccuVac Ampuls)Quantity Required

Description Per Test Unit Cat. No.Adapter, AccuVac vial......................................................... 1........................each ...... 43784-00Beaker, 50 mL ..................................................................... 1........................each ...........500-41Vial, Zeroing...................................................................................................each .......21228-00

OPTIONAL REAGENTSAmmonium Hydroxide, ACS................................................................... 500 mL ...........106-49Hydrochloric Acid Standard Solution, 6 N .............................................. 500 mL ...........884-49Hydrochloric Acid, ACS .......................................................................... 500 mL ...........134-49Iron Standard Solution, 100 mg/L............................................................ 100 mL .......14175-14Iron Voluette Ampule Standard, 50 mg/L ..................................................16/pkg .......14254-10Nitric Acid, ACS ...................................................................................... 500 mL ...........152-49Nitric Acid Solution, 1:1 .......................................................................... 500 mL .........2540-49RoVer Rust Remover.................................................................................... 454 g ...........300-11Rust Suspension .............................................................................. 15 mL SCDB .........1279-36Sodium Hydroxide Standard Solution, 5.0 N................................. 100 mL MDB .........2450-32Water, demineralized........................................................................................4 L ...........272-56

OPTIONAL APPARATUSDescription Unit Cat. No.AccuVac Snapper Kit .....................................................................................each .......24052-00Ampule Breaker Kit .......................................................................................each .......21968-00Clippers, Shears 7 1/4 " ..................................................................................each .......23694-00Cylinder, graduated, glass, 25 mL..................................................................each ...........508-40Cylinder, graduated, poly, 25 mL...................................................................each .........1081-40Cylinder, graduated, poly, 100 mL.................................................................each .........1081-42Cylinder, Mixing, 25 mL................................................................................each .......20886-40Digesdahl Digestion Apparatus......................................................................each .......23130-20Filter Discs, glass, 47 mm ..............................................................................each .........2530-00Filter Holder, membrane ................................................................................each .........2340-00Filter Pump.....................................................................................................each .........2131-00Flask, erlenmeyer, 250 mL.............................................................................each ...........505-46Flask, filtering, 500 mL..................................................................................each ...........546-49Flask, volumetric, Class A, 50 mL.................................................................each .......14574-41Flask, volumetric, Class A, 100 mL...............................................................each .......14574-42Hot Plate, 3 1/2" diameter, 120 Vac ...............................................................each .......12067-01Hot Plate, 3 1/2" diameter, 240 Vac ...............................................................each .......12067-02pH Meter, EC10, portable ..............................................................................each .......50050-00pH Indicator Paper, 1 to 11 pH.......................................................................each ...........391-33Pipet Filler, safety bulb...................................................................................each .......14651-00Pipet, serological, 2 mL..................................................................................each ...........532-36

95


OPTIONAL APPARATUS, continuedDescription Unit Cat. No.Pipet, serological, 5 mL ................................................................................. each........... 532-37Pipet, TenSette, 0.1 to 1.0 mL........................................................................ each....... 19700-01Pipet Tips, for 19700-01 TenSette Pipet ................................................... 50/pkg....... 21856-96Pipet, volumetric, Class A, 1.00 mL.............................................................. each....... 14515-35Spoon, measuring, 0.1 g................................................................................. each........... 511-00

OPTIONAL 25 ML ANALYSIS ITEMSFerroVer Reagent Powder Pillows, 25 mL .............................................. 100/pkg........... 854-99Pour-Thru Cell Assembly Kit (for 25-mL reagents only) ............................. each....... 45215-00Sample Cell, 25 mL, matched pair ................................................................. pair....... 20950-00Spoon, measuring, 0.2 g................................................................................. each........... 638-00


96

Method 8039

NITRATE, HR (0 to 30.0 mg/L NO3--N) For water, wastewater, and seawater*

Cadmium Reduction Method (Powder Pillows or AccuVac Ampuls)


* For seawater, a manual calibration is required; see Interferences following the procedure.

1. Enter the stored program number for high range nitrate nitrogen (NO3

--N).

Press: 3 5 5 ENTER


Dial nm to 500

Note: The Pour-Thru Cell can be used if rinsed well with demineralized water after use. Avoid pouring any cadmium particles into the cell.


500 nm

When the correct wavelength is dialed in, the display will quickly show: Zeroing. . .

then: mg/L NO3--N HR


Note: A reagent blank must be determined on each new lot of NitraVer® 5 Nitrate Reagent. Perform Steps 3 to 12 using demineralized water as the sample. Subtract this value from each result obtained with this lot of reagent.

4. Add the contents of one NitraVer 5 Nitrate Reagent Powder Pillow to the cell (the prepared sample). Stopper.

500 nm

97

NITRATE, HR, continued


Shake the cell vigorously until the timer beeps in one minute.

Note: Shaking time and technique influence color development. For most accurate results, make successive tests on a standard solution. Adjust the shaking time to obtain the correct result.

6. When the timer beeps, press:

SHIFT TIMER


Note: An amber color will develop if nitrate nitrogen is present.

7. Fill another sample cell with 25 mL of sample (the blank).


mg/L NO3--N HR


9. Press: ZERO


Zeroing. . .

then:

0.0 mg/L NO3--N HR

10. Remove the stopper. Place the prepared sample into the cell holder. Close the light shield.

Note: A cadmium deposit will remain after the NitraVer 5 Nitrate Reagent Powder dissolves and will not affect results.

11. Press: READ


Reading. . .

then the result in mg/L nitrate nitrogen (NO3

--N) will be displayed

Note: Rinse the sample cell immediately after use to remove all cadmium particles.

98



1. Enter the stored program number for high range nitrate nitrogen (NO3

--N)-AccuVac Ampuls.

Press: 3 6 1 ENTER


Dial nm to 500


500 nm


then:

mg/L NO3--N HR AV

3. Collect at least 40 mL of sample in a 50-mL beaker. Fill a NitraVer 5 Nitrate Reagent AccuVac Ampul with sample.


Note: A reagent blank must be determined on each new lot of NitraVer 5 Reagent. Repeat Steps 3 to 11 using demineralized water as the sample. Subtract this value from each result obtained with this lot of reagent.


A one-minute mixing period will begin. Invert the ampul repeatedly until the timer beeps. Wipe off any liquid or fingerprints.

Note: Shaking time and technique influence color development. For most accurate results, make successive tests on a 10 mg/L Nitrate Nitrogen Standard Solution. Adjust the shaking time to obtain the correct result.

500 nm

99


5. When the timer beeps, press:

SHIFT TIMER


Note: A cadmium deposit will remain after the NitraVer 5 Nitrate Reagent Powder dissolves and will not affect results.

Note: An amber color will develop if nitrate nitrogen is present.

6. Fill a zeroing vial with at least 10 mL of sample (the blank).




mg/L NO3--N HR AV


9. Press: ZERO


Zeroing. . .

then:

0.0 mg/L NO3--N HR AV

10. Place the AccuVac ampul into the cell holder. Close the light shield.

11. Press: READ


Reading. . .

then the nitrate result in mg/L nitrogen (NO3

--N) will be displayed.

100


101

Sampling and StorageCollect samples in clean plastic or glass bottles. Store at 4 °C (39 °F) or lowerif the sample is to be analyzed within 24 to 48 hours. Warm to roomtemperature before running the test. For storage periods up to 14 days, adjustsample pH to 2 or less with sulfuric acid, ACS, (about 2 mL per liter).Sample refrigeration is still required.

Before testing the stored sample, warm to room temperature. Neutralizethe sample with 5.0 N Sodium Hydroxide Standard Solution.

Do not use mercury compounds as preservatives.

Correct test results for volume additions; see Correction for VolumeAdditions in Section I of the DR/2010 Spectrophotometer ProceduresManual for more information.


a) Snap the neck off a fresh High Range Nitrate Nitrogen Voluette Ampule Standard, 500 mg/L NO3

--N.

b) Use the TenSette Pipet to add 0.1, 0.2, and 0.3 mL of standard to three 25-mL samples. Mix each thoroughly. (For AccuVac Ampuls, use 50-mL beakers.)

c) Analyze each sample as described above. The nitrogen concentration should increase 2.0 mg/L for each 0.1 mL of standard added.

d) If these increases do not occur, see Standard Additions in Section I of the DR/2010 Spectrophotometer Procedures Manual for more information.

Standard Solution MethodUse a 10.0 mg/L Nitrate Nitrogen Standard Solution listed under OptionalReagents to check test accuracy. Or, this can be prepared by diluting 1.00 mL ofsolution from a High Range Nitrate Nitrogen Voluette Ampule StandardSolution, 500 mg/L NO3

--N, to 50.0 mL with demineralized water. Use thisstandard in place of sample in Step 3 of the procedures.

PrecisionIn a single laboratory using standard solutions of 20.0 mg/L nitrate nitrogen(NO3

--N) and two representative lots of reagent with the DR/2010Spectrophotometer, a single operator obtained a standard deviation of +0.8mg/L nitrate nitrogen.


Using standard solutions of 30.0 mg/L (NO3--N) and one representative

lot of AccuVac Ampuls with the DR/2010 Spectrophotometer, a singleoperator obtained a standard deviation of +2.3 mg/L nitrate nitrogen.

Interferences• Compensate for nitrite interference as follows:

a) Add Bromine Water, 30 g/L, drop-wise to the sample in Step 3 until a yellow color remains.

b) Add one drop of Phenol Solution, 30 g/L, to destroy the color.

c) Proceed with Step 3. Report results as total nitrate and nitrite.

• Strong oxidizing and reducing substances will interfere.

• Ferric iron causes high results and must be absent.

• Chloride concentrations above 100 mg/L will cause low results. The test may be used at high chloride levels (i.e., seawater), but a calibration must be performed using standards spiked to the same chloride concentration. See User Stored Programs in the DR/2010 Sprectrophotometer Instrument Manual for more information.

• Highly buffered samples or extreme sample pH may exceed the buffering capacity of the reagents and require sample pretreatment; see pH Interferences, Section I of the DR/2010 Spectrophotometer Procedures Manual.

Summary of MethodCadmium metal reduces nitrates present in the sample to nitrite. Thenitrite ion reacts in an acidic medium with sulfanilic acid to form anintermediate diazonium salt. This salt couples to gentisic acid to form anamber-colored product.


Description Per Test Unit Cat. No.NitraVer 5 Nitrate Reagent Powder Pillows, 25 mL...... 1 pillow............ 100/pkg....... 14034-99

REQUIRED REAGENTS (Using AccuVac Ampuls)NitraVer 5 Nitrate Reagent AccuVac Ampul................. 1 ampul.............. 25/pkg....... 25110-25

102


REQUIRED APPARATUS (Using Powder Pillows)Quantity Required

Description Per Test Unit Cat. No.Stopper, rubber, size 2 ......................................................... 1....................12/pkg .........2118-02Sample Cell, 25 mL, matched pair ..................................................................pair .......20950-00

REQUIRED APPARATUS (Using AccuVac Ampuls)Adapter, AccuVac Vial ........................................................ 1........................each .......43784-00Beaker, 50 mL ..................................................................... 1........................each ...........500-41Zeroing Vial......................................................................... 1........................each .......21228-00

OPTIONAL REAGENTSDescription Unit Cat. No.Bromine Water, 30 g/L ............................................................................. 29 mL* .........2211-20Nitrate Nitrogen standard Solution, 10 mg/L NO3

--N ............................. 500 mL ...........307-49Nitrate Nitrogen Standard Solution, Voluette Ampule, 500 mg/L (NO3

--N), 10 mL....................................................................................16/pkg .......14260-10Phenol Solution, 30 g/L.............................................................................. 29 mL .........2112-20Sodium Hydroxide Standard Solution, 5.0 N........................................... 59 mL* .........2450-26Sulfuric Acid, ACS................................................................................. 500 mL* ...........979-49Water, demineralized........................................................................................4 L ...........272-56

OPTIONAL APPARATUSAccuVac Snapper Kit .....................................................................................each .......24052-00Ampule Breaker Kit .......................................................................................each .......21968-00Cylinder, graduated, 25 mL............................................................................each .........1081-40Dropper, for 1-oz bottle..................................................................................each .........2258-00pH Indicator Paper, 1 to 11 pH.............................................................5 rolls/pkg ...........391-33pH Meter, EC10, portable ..............................................................................each .......50050-00Pipet, serological, 2 mL..................................................................................each ...........532-36Pipet, TenSette, 0.1 to 1.0 mL ........................................................................each .......19700-01Pipet Tips, for 19700-01 TenSette Pipet ....................................................50/pkg .......21856-96Pipet, volumetric, Class A, 1.00 mL ..............................................................each .......14515-35Pipet Filler, safety bulb...................................................................................each .......14651-00Pour-Thru Cell Assembly Kit ........................................................................each .......45215-00Sample Cells, 1-inch, polystyrene, disposable...........................................12/pkg .......24102-12Thermometer, -20 to 105 °C...........................................................................each .........1877-01



103

104

Method 8155

NITROGEN, AMMONIA (0 to 0.50 mg/L NH3-N) For water, wastewater, seawater

Salicylate Method*

1. Enter the stored program number for ammonia nitrogen (NH3-N), salicylate method.

Press: 3 8 5 ENTER


Dial nm to 655


2. Rotate the wavelength dial until display shows:

655 nm


then: mg/L NH3-N Salic


4. Pour 10 mL of sample into a 10-mL sample cell (the prepared sample).

5. Pour 10 mL of demineralized water into a second 10-mL sample cell (the blank).

6. Add the contents of one Ammonia Salicylate Reagent Powder Pillow to each sample cell. Stopper. Shake to dissolve.



8. When the timer beeps add the contents of one Ammonia Cyanurate Reagent Powder Pillow to each sample cell. Stopper. Shake to dissolve.

Note: A green color will develop if ammonia nitrogen is present.

* Adapted from Clin. Chim. Acta., 14 403 (1966)

655 nm

FILL LINEFILL LINE

105

NITROGEN, AMMONIA, continued


A 15-minute reaction period will begin.

10. When the timer beeps, place the blank into the cell holder. Close the light shield.

11. Press: ZERO


Zeroing. . .

then:

0.00 mg/L NH3-N Salic


13. Press: READ


Reading. . .

then the result in mg/L ammonia as nitrogen (NH3-N) will be displayed.

106


Sampling and StorageCollect samples in clean plastic or glass bottles. Most reliable results areobtained when samples are analyzed as soon as possible after collection.

If chlorine is known to be present, the sample must be treated immediatelywith sodium thiosulfate. Add one drop of Sodium Thiosulfate StandardSolution, 0.1 N, for each 0.3 mg of chlorine present in a one liter sample.

To preserve the sample, adjust the pH to 2 or less with concentrated sulfuric acid(about 2 mL per liter). Store samples at 4 °C or less. Samples preserved in thismanner can be stored up to 28 days. Just before testing the stored sample, warmto room temperature and neutralize with 5.0 N Sodium Hydroxide StandardSolution. Correct the test result for volume additions; see Correction for VolumeAdditions, in Section I of the DR/2010 Spectrophotometer Procedures Manualfor more detailed information.


a) Measure 25 mL of sample into three 25-mL mixing cylinders.

b) Use the TenSette Pipet to add 0.2, 0.4, and 0.6 mL of Nitrogen Ammonia Standard Solution, 10 mg/L as NH3-N to the three samples. Mix well.

c) Analyze a 10-mL portion of sample as described above. The ammonia nitrogen concentration should increase 0.08 mg/L for each 0.2 mL of standard added.

d) If these increases do not occur, see Standard Additions in Section I of the DR/2010 Spectrophotometer Procedures Manual for more information.

Standard Solution MethodPrepare a 0.20 mg/L nitrogen ammonia standard by diluting 2.00 mL ofthe Ammonia Nitrogen Standard Solution, 10 mg/L, to 100 mL withdemineralized water. Or, using the TenSette Pipet, prepare a 0.20 mg/Lnitrogen ammonia standard by diluting 0.4 mL of a Nitrogen AmmoniaVoluette Standard Solution, 50 mg/L as NH3-N, to 100 mL withdemineralized water.

PrecisionIn a single laboratory using a standard solution of 0.20 mg/Lnitrogen ammonia (NH3-N) and two representative lots of reagentwith the DR/2010 Spectrophotometer, a single operator obtained astandard deviation of +0.015 mg/L nitrogen ammonia.

107


Interferences

• The following ions may interfere when present in concentrations exceeding those listed below:

• Sulfide will intensify the color. Eliminate sulfide interference as follows:

a) Measure about 350 mL of sample in a 500-mL erlenmeyer flask.

b) Add the contents of one Sulfide Inhibitor Reagent Powder Pillow. Swirl to mix.

c) Filter the sample through a folded filter paper.

d) Use the filtered solution in Step 4.

• Iron interferes with the test. Eliminate iron interference as follows:

a) Determine the amount of iron present in the sample following one of the Iron, Total procedures.

b) Add the same iron concentration to the demineralized water sample in Step 5.

• The interference from iron in the sample will then be successfully blanked out in Step 11.

• Extremely acidic or alkaline samples should be adjusted to approximately pH 7. Use 1 N Sodium Hydroxide Standard Solution for acidic samples or 1 N Sulfuric Acid Standard Solution for basic samples.

• Less common interferences such as hydrazine and glycine will cause intensified colors in the prepared sample.

Calcium 1000 mg/L as CaCO3

Magnesium 6000 mg/L as CaCO3

Nitrite 12 mg/L as NO2--N

Nitrate 100 mg/L as NO3--N

Orthophosphate 100 mg/L as PO43--P

Sulfate 300 mg/L as SO42-

108


• Turbidity and sample color will give erroneous high values. Samples with severe interferences require distillation. Albuminoid nitrogen samples also require distillation. Hach recommends the distillation procedure using the Hach General Purpose Distillation Set. See Optional Apparatus listing. The distillation procedure is detailed in the Nitrogen, Ammonia--Nessler Method in the DR/2010 Spectrophotometer Procedures Manual.

Summary of MethodAmmonia compounds combine with chlorine to form monochloramine.Monochloramine reacts with salicylate to form 5-aminosalicylate. The5-aminosalicylate is oxidized in the presence of a sodium nitroprussidecatalyst to form a blue-colored compound. The blue color is masked bythe yellow color from the excess reagent present to give a final green-colored solution.

REQUIRED REAGENTS AND APPARATUSCat. No.

Nitrogen Ammonia Reagent Set For 10-mL Samples (100 Tests)................................26680-00 Includes: (2) 26531-49, (2) 26532-99

Quantity RequiredDescription Per Test Unit Cat. No.Ammonia Cyanurate Reagent Powder Pillows .............2 pillows ...........100/pkg .......26531-99Ammonia Salicylate Reagent Powder Pillows ..............2 pillows ...........100/pkg .......26532-99Stopper, hollow, polyethylene, #1 ....................................... 2......................6/pkg .......14480-01

OPTIONAL REAGENTSNitrogen Ammonia Standard Solution,

10 mg/L as (NH3-N) ............................................................................. 500 mL ...........153-49Nitrogen Ammonia, Voluette Ampule,

50 mg/L as (NH3-N), 10 mL...................................................................16/pkg .......14791-10Sodium Hydroxide Standard Solution, 1.0 N................................. 100 mL MDB .........1045-32Sodium Hydroxide Standard Solution, 5.0 N............................................. 59 mL .........2450-26Sodium Thiosulfate Standard Solution, 0.1 N................................ 100 mL MDB ...........323-32Sulfide Inhibitor Reagent Powder Pillows ...............................................100/pkg .........2418-99Sulfuric Acid, concentrated, ACS ............................................................ 500 mL ...........979-49Sulfuric Acid Standard Solution, 1.0 N.......................................... 100 mL MDB .........1270-32Water, demineralized........................................................................................4 L ...........272-56

109


OPTIONAL APPARATUSDescription Unit Cat. No.Cylinder, graduated, polypropylene, 500 mL ................................................ each......... 1081-49Distillation Heater and Support Apparatus, 115 V ........................................ each....... 22744-00Distillation Heater and Support Apparatus, 230 V ........................................ each....... 22744-02Distillation Set, General Purpose................................................................... each....... 22653-00Filter Paper, folded, 12.5 cm........................................................................... 100......... 1894-57Flask, erlenmeyer, polypropylene, 500 mL ................................................... each......... 1082-49Flask, volumetric, Class A, 100 mL .............................................................. each....... 14574-42Funnel, poly, 65 mm ...................................................................................... each......... 1083-67pH Meter, EC10, portable .............................................................................. each....... 50050-00Pipet Filler, safety bulb .................................................................................. each....... 14651-00Pipet, TenSette, 0.1 to 1.0 mL........................................................................ each....... 19700-01Pipet Tips, for 19700-01 TenSette Pipet .................................................... 50/pkg....... 21856-96Pipet, volumetric, Class A, 2.0 mL................................................................ each....... 14515-36Thermometer, -20 to 105 °C .......................................................................... each......... 1877-01

OPTIONAL 25-ML ANALYSIS ITEMSNitrogen Ammonia Reagent Set, 25-mL test (100 Tests)............................................. 22437-00 Includes: (8) 23955-68, (8) 23953-68Ammonia Cyanurate Reagent Powder Pillows.......................................... 25/pkg....... 23955-68Ammonia Salicylate Reagent Powder Pillows........................................... 25/pkg....... 23953-68Clippers, large ................................................................................................ each........... 968-00Pour-Thru Cell Assembly Kit ........................................................................ each....... 45215-00Sample Cell, 25-mL, matched pair ................................................................. pair....... 20950-00


110

111

Methods 8215 and 8332

OXYGEN, DISSOLVED (1 to greater than 10 mg/L DO)

Azide Modification of Winkler Method Using Digital Titrator For water, wastewater and seawater

Using a 300-mL BOD Bottle Method 8215

1. Collect a water sample in a clean 300-mL BOD bottle.

Note: Allow the sample to overflow the bottle for 2-3 minutes to ensure air bubbles are not trapped.

Note: If samples cannot be analyzed immediately, see Sampling and Storage following these steps.

2. Add the contents of one Manganous Sulfate Powder Pillow and one Alkaline Iodide-Azide Reagent Powder Pillow.

3. Immediately insert the stopper so air is not trapped in the bottle. Invert several times to mix.

Note: A flocculent precipitate will form. It will be orange-brown if oxygen is present or white if oxygen is absent. The floc settles slowly in salt water and normally requires 5 additional minutes before proceeding to Step 5.

4. Wait until the floc in the solution has settled. Again invert the bottle several times and wait until the floc has settled.

Note: Waiting until floc has settled twice assures complete reaction of the sample and reagents.

5. Remove the stopper and add the contents of one Sulfamic Acid Powder Pillow. Replace the stopper without trapping air in the bottle and invert the prepared sample several times to mix.

Note: The floc will dissolve and leave a yellow color if oxygen is present.

6. Select a sample volume and Sodium Thiosulfate Titration Cartridge corresponding to the expected dissolved oxygen (D.O.) concentration from Table 1 on page 113.




OXYGEN, DISSOLVED, continued

9. Use a graduated cylinder to measure the sample volume from Table 1. Transfer the sample into a 250-mL erlenmeyer flask.

10. Place the delivery tube tip into the solution and swirl the flask while titrating with sodium thiosulfate to a pale yellow color.

11. Add two 2-mL droppers of Starch Indicator Solution and swirl to mix.

Note: A dark blue color will develop.

12. Continue the titration to a colorless end point. Record the number of digits required.

Table 1

13. Calculate:Digits Required x Digit Multiplier = mg/L Dissolved Oxygen

Range (mg/L D.O.)

Sample Volume (mL)

Titration Cartridge

(N Na2S2O3)

Catalog Number

Digit Multiplier

1-52-10>10

200100200

0.2000.2002.000

22675-0122675-0114401-01

0.010.020.1

112


113

Using a 60-mL BOD Bottle Method 8332

1. Collect a water sample in a clean 60-mL glass-stoppered BOD bottle.

Note: Allow the sample to overflow the bottle for 2-3 minutes to ensure air bubbles are not trapped.

Note: If samples cannot be analyzed immediately, see Sampling and Storage following these steps.

Note: Follow this procedure when using the 60-mL glass-stoppered BOD Bottle supplied with DREL Portable Laboratories.

2. Add the contents of one Dissolved Oxygen 1 Reagent Powder Pillow and one Dissolved Oxygen 2 Reagent Powder Pillow

3. Immediately insert the stopper so air is not trapped in the bottle. Invert several times to mix.

Note: A flocculent precipitate will form. It will be orange-brown if oxygen is present or white if oxygen is absent. The floc settles slowly in salt water and normally requires 5 additional minutes before proceeding to Step 5.

4. Wait until the floc in the solution has settled and the top half of the solution is clear. Again invert the bottle several times and wait until the floc has settled.

Note: Results are not affected if the floc does not settle or if some of the reagent powder does not dissolve.

5. Remove the stopper and add the contents of one Dissolved Oxygen 3 Powder Pillow. Replace the stopper without trapping air in the bottle and invert several times to mix.

Note: The floc will dissolve and leave a yellow color if oxygen is present.

6. Accurately measure 20 mL of the prepared sample and transfer it to a 250-mL erlenmeyer flask.

7. Attach a clean straight-stem delivery tube to a 0.2000 N Sodium Thiosulfate Titration Cartridge. Twist the cartridge onto the titrator body. See General Description, Step-by-Step, of the Digital Titrator Manual for assembly instructions if necessary

8. Flush the delivery tube by turning the delivery knob to eject a few drops of titrant. Reset the counter to zero and wipe the tip.



Sampling and StorageSampling and sample handling are important in obtaining meaningfulresults. The dissolved oxygen content of the sample changes with depth,turbulence, temperature, sludge deposits, light, microbial action,mixing, travel time, and other factors. A single dissolved oxygen testrarely reflects the over-all condition of a body of water. Several samplestaken at different times, locations and depths are recommended for mostreliable results.

Collect samples in clean BOD Bottles (see Step 1). If storage is necessary, runSteps 1-5 of the procedure and store in the dark at 10-20 °C. Seal the bottlewith water by pouring a small volume of water into the flared lip area of astopper bottle. Snap a BOD Bottle Cap over the flared lip. Samples preservedlike this can be held 4-8 hours. Begin with Step 6 when analyzing.

Accuracy CheckCheck the strength of the Sodium Thiosulfate Solution by using anIodate-Iodide Standard Solution which is equivalent to 10 mg/Ldissolved oxygen. For the 300-mL procedure, begin at Step 5, addingthe Sulfamic Acid Powder Pillow. For the 60-mg/L procedure, begin theanalysis at Step 5 adding the Dissolved Oxygen 3 Powder Pillow. Thetitration should take 10 mL. If more than 10.5 is required to reach theend point, replace the Sodium Thiosulfate Solution.

9. Titrate the prepared solution with 0.2000 N Sodium Thiosulfate until the sample changes from yellow to colorless. Record the number of digits.

10. Calculate:

Digits required x 0.1 = mg/L Dissolved Oxygen

114


115

InterferencesNitrite interference is eliminated by the azide in the reagents. Otherreducing or oxidizing substances may interfere. If these are present, usean alternate method, such as the High Range Dissolved Oxygen Method(colorimetric) in the DR/2010 Spectrophotometer Manual, or adissolved oxygen electrode and meter.

Summary of MethodSamples are treated with manganous sulfate and alkaline iodide-azidereagent to form an orange-brown precipitate. Upon acidification of thesample, this floc reacts with iodide to produce free iodine as triiodide inproportion to the oxygen concentration. The iodine is titrated withsodium thiosulfate to a colorless end point.

REQUIRED REAGENTS for 300-mL BOD Bottle(Varies with sample characteristics)Dissolved Oxygen Reagent Set (about 50 tests)

Includes: (2) 1072-68, (2) 1071-68, (1) 22675-01, (1) 349-32, (2) 20762-68 ...........22722-00Description Unit Cat. No.Alkaline Iodide-Azide Powder Pillows ......................................................25/pkg .........1072-68Manganous Sulfate Powder Pillows...........................................................25/pkg .........1071-68Sodium Thiosulfate Titration Cartridge, 0.2000 N ........................................each .......22675-01Sodium Thiosulfate Titration Cartridge. 2.00 N ............................................each .......14401-01Starch Indicator Solution.............................................................. 100 mL MDB* ...........349-32Sulfamic Acid Powder Pillows...................................................................25/pkg .......20762-68

REQUIRED APPARATUS for 300-mL BOD BottleBottle, with stopper, BOD, 300-mL ...............................................................each ...........621-00Clippers, for opening pillows .........................................................................each ...........968-00Cylinder, graduated, 250-mL .........................................................................each ...........508-46Digital Titrator................................................................................................each .......16900-01Flask, erlenmeyer, 250-mL.............................................................................each ...........505-46

REQUIRED REAGENTS for 60-mL BOD BottleDissolved Oxygen 1 Reagent Powder Pillows .........................................100/pkg ...........981-99Dissolved Oxygen 2 Reagent Powder Pillows .........................................100/pkg ...........982-99Dissolved Oxygen 3 Reagent Powder Pillows ...........................................25/pkg ...........987-68Sodium Thiosulfate Titration Cartridge, 0.2000 N ........................................each .......22675-01


REQUIRED APPARATUS for 60-mL BOD BottleDescription Unit Cat. NoBottle, with stopper, BOD, 60-mL................................................................. each......... 1909-02Clippers, for opening pillows......................................................................... each........... 968-00Beaker, 50-mL ............................................................................................... each........... 508-41Digital Titrator ............................................................................................... each....... 16900-01Flask, erlenmeyer, 250 mL ............................................................................ each........... 505-46

OPTIONAL REAGENTSIodate-Iodide Standard Solution, 10 mg/L as DO ..................................500 mL*........... 401-49

OPTIONAL APPARATUSCap, BOD Bottle, plastic ............................................................................. 6/pkg......... 2419-06Clamp Holder................................................................................................. each........... 326-00Clamp, 2-prong, extension, 38 mm................................................................ each....... 21145-00Delivery Tubes, with 180° hook .................................................................. 5/pkg....... 17205-00Delivery Tubes, 90° with hook .................................................................... 5/pkg....... 41578-00Dissolved Oxygen Meter, DO175 Portable with probe ................................. each....... 50175-00Sewage Sampler, Lab-Line ............................................................................ each........... 427-00Support ring stand.......................................................................................... each........... 563-00TitraStir Mixer/Stand Assembly, 115 Vac ..................................................... each....... 19400-00TitraStir Mixer/Stand Assembly, 230 Vac ..................................................... each....... 19400-10

Procedures and kits for portable dissolved oxygen measurements using this method are available from Hach.



116

Method 8156

pH For water and wastewater

Hach One® Combination pH Electode Method with a EC 10 Portable MeterUSEPA approved for reporting*

Sample pH Measurement (Calibration is required)

* Procedure is equivalent to USEPA method 150.1 and Standard 4500-H+ for water and wastewater.

1. Press the Dispenser Button once (it will click). Rinse and blot dry.

2. Swirl the sample and place the electrode in the container. Be sure the entire sensing end is submerged.

3. Record the pH value when the display is stable.

4. Rinse the electrode thoroughly with demineralized water and blot dry.

Two-Standard Calibration in Automatic Mode with Temperature Probe

1. Press the POWER key. The display will light.

2. Ensure the meter is in pH mode.

Note: Be sure no air bubbles are trapped inside the tip of the electrode or dispenser tubing.

3. Press the CAL key. The slope data of the previous calibration or a default slope will appear. Then the meter will go into measure mode with “P1” (Point 1) in the display.

Note: Hach buffers are available as powders or solutions. They are color-coded for added convenience.

4. Place the electrode into a pH 4 buffer solution and press the dispenser button. The temperature will show the actual solution temperature and “ATC” (Automatic Temperature Compensation) will appear in the display if the temperature probe is connected.

Note: Buffer solutions (pH 4, 7 and 10) may be used in any order.

FILL LINE

FILL LINE

117

pH, continued

5. When the display stabilizes, the meter will beep and show the temperature corrected value for the pH 4 buffer and a ready indicator. Press YES to accept this value for the first buffer.

6. Rinse the electrode with demineralized water and blot dry with a paper towel.

7. Place the electrode in the pH 7 buffer and press the dispenser button.

8. When the display stabilizes it will beep and show the temperature corrected value for the pH 7 buffer and “ready”. Press the YES key to accept this value for the second buffer.

Note: Pressing any key other than the YES key at this point will cancel the calibration values entered and the meter will default to the previous slope and adjust the offset only.

9. The slope will appear in the display. It should be 59.0 ±3 (mV/decade). Press the YES key to accept this slope. Rinse the electrode with demineralized water or a portion of the sample to be measured. Blot dry with a paper towel.

10. Place the electrode into the sample. Press the Dispenser Button. The meter will measure the sample pH.

Note: Repeat step 10 for each sample. Check the calibration against 7.0 pH Buffer after every 10 samples. A value outside the range of 6.95-7.05 indicates the analyst should recalibrate.

11. To review, press the CAL key to show the electrode slope in the display. The slope should be 59.0 ±3 mV/decade. The meter will then attempt to re-calibrate. Press MODE again to return to measurement mode.

Note: For other calibrations or more complete operation instructions, refer to the instrument manual.

FILL LINE

FILL LINE

118

pH, continued

Sampling and StorageCollect samples in clean plastic or glass bottles. Fill completely and cap tightly.Cool to 4 °C (39 °F) and determine pH within six hours. If samples cannot beanalyzed within six hours, report the actual holding time with the results.

Interferences• Acid error is negligible.

• Sodium error, usually present in alkaline solutions, is low, but increases at pH values higher than pH 11.

Hach One pH ElectodeShort-term Storage

Between measurements, store the electrode in a pH Electrode StorageSolution. If electrode storage solution is not available, use one of thefollowing solutions:

1. 200 mL of pH 7 buffer with one gram of potassium chloride added(this is the preferred solution).

2. pH 7 buffer solution.

For measurements of low-ionic strength sample, condition the electrodeby soaking in demineralized water for 1 to 2 hours.

Long-term Laboratory StorageFor storage greater than 2 weeks, continue to store the electrode in pHElectrode Storage Solution. Maintain the AgCl concentration around thewire by periodically (every few days) pumping electrolyte through theelectrode. Add demineralized water as needed to maintain the liquid levelaround the electrode.

Long-term Field or Shelf StorageReplace the black cap (Cat. No. 42389-00) that was on the electrodewhen it was shipped. Periodically check the cotton ball in the tip of thecap for moisture, adding a few drops of the pH electrode storagesolution when necessary.

If it becomes necessary to replace the cotton ball, add a few drops of pHElectrode Storage Solution or pH 7 buffer to the replacement cotton andplace it into the end of the cap. Maintain the moisture as above. Saltcrystals may grow on the electrode tip. These are not harmful and may beremoved by rinsing the tip with demineralized water.

119

pH, continued

Normal CleaningIf the electrode response time slows, the cause may be a fouled referenceelement or a contaminated glass bulb. Normal cleaning or reconditioningof the electrode can be performed in the following manner:

Immerse the electrode tip in 0.1N Hydrochloric Acid followed byimmersion in 0.1N Sodium Hydroxide and again in 0.1N HydrochloricAcid, each for a 2-minute period. Rinse with demineralized water andsoak in demineralized water for at least 15 minutes.

Remove oils and fats by immersing the electrode tip in a detergentsolution such as Alconox™. Use a brush or ultrasonic bath if necessary.Avoid scratching the glass bulb.

Remove organic films from the glass bulb by using an appropriatesolvent, such as methanol or acetone.

If these steps fail to improve electrode response, replace the electrode.

EC10 Portable pH Meter Battery ReplacementReplace the 9V alkaline battery in the EC 10 pH meter with a battery ofsimilar specifications (Hach Cat. No. 50110-00) when the display dims.Refer to the meter manual for installation. Estimated battery life isapproximately 40 hours of use. An optional eliminator is also available.

Summary of MethodThe Hach One Combination pH Electrode responds to the hydrogen ionconcentration (activity) by developing an electrical potential at the glass/liquid interface. At a constant temperature, this potential varies linearlywith the pH of the solution being measured. The electrode has a free-diffusion junction which eliminates clogging problems.

REQUIRED REAGENTS AND APPARATUSDescription Unit Cat. No.Buffer Powder Pillows, pH 4 and 7 ........................................................... 20/pkg....... 22992-64KCl Reference Electrode Gel Cartridge ...................................................... 2/pkg....... 25469-02Beaker, Griffin, 100 mL................................................................................. each....... 22994-42Clippers, for opening powder pillows............................................................ each........... 968-00EC10 pH Meter and Hach One pH Electrode, case, accessories................... each....... 50050-10Hach One Combination pH Electrode w/Temp (replacement) ...................... each....... 48600-22

120

pH, continued

121

OPTIONAL REAGENTSDescription Unit Cat. No.Buffer Powder Pillows, pH 4 (red).............................................................50/pkg .......22269-66Buffer Powder Pillows, pH 7 (yellow) .......................................................50/pkg .......22270-66Buffer Powder Pillows, pH 9......................................................................50/pkg .......14107-66Buffer Powder Pillows, pH 10 (blue) .........................................................15/pkg .......22271-95Buffer Solution, pH 4 (red) ...................................................................... 500 mL .......22834-49Buffer Solution, pH 7 (yellow)................................................................. 500 mL .......22835-49Buffer Solution, pH 10 (blue) .................................................................. 500 mL .......22836-49pH Electrode Storage Solution................................................................. 450 mL .......50301-49pH Electrode Storage Solution Powder Pillows...........................................pk/20 .......26573-64Water, demineralized........................................................................................4 L ...........272-56

OPTIONAL APPARATUSBeaker, poly, 50 mL .......................................................................................each .........1080-41Clippers, for opening powder pillows ............................................................each ...........968-00Cylinder, mixing, graduated, 50 mL ..............................................................each .........1896-41Electromagnetic stirrer and electrode holder, (115 V North American) ........each .......45300-01Electromagnetic stirrer and electrode holder, (230 V) ...................................each .......45300-02Battery Eliminator, for EC10 pH Meter, 115 V, UL/CSA approved

with North American style plug..................................................................each .......50070-00Battery Eliminator, for EC10 pH Meter, 230 V, VDE approved

with Continental European style plug.........................................................each .......50070-01Battery, replacement, 9V ...............................................................................each .......50110-00EC20 Portable pH/ISE Meter, Case Accessories (no electrode)....................each .......50075-10EC30 Benchtop pH Meter with Hach One Electrode,

(115 V with North American style plug) ....................................................each .......50100-10EC30 Benchtop pH Meter with Hach One Electrode,

(230 V with Continental European style plug) ...........................................each .......50100-11EC40 Benchtop pH/ISE Meter with Hach One Electrode,

(115 V with North American style plug) ....................................................each .......50125-10EC40 Benchtop pH Meter with Hach One Electrode,

(230 V with Continental European style plug) ...........................................each .......50125-11CO150 Portable Conductivity Meter, Probe, Case Accessories.....................each .......50150-00Comb. pH Electrode with Temperature (Gel Filled) ......................................each .......50200-00Comb. pH Electrode (Refillable)....................................................................each .......50215-00Temperature Probe .........................................................................................each .......50270-00Stir Bar, 22.2 x 4.76 mm (7/8 x 3/16”)...........................................................each .......45315-00Thermometer, armored, -20 to 105 °C ...........................................................each .........1877-01


122

Method 8180

PHOSPHORUS, ACID HYDROLYZABLE

Hydrolysis to Orthophosphate Method* For water, wastewater, and seawater

* Adapted from Standard Methods for the Examination of Water and Wastewater.

1. Measure 25 mL of sample into a 50-mL erlenmeyer flask using a graduated cylinder.

Note: Wash all glassware with 6 N hydrochloric acid. Rinse with demineralized water.

2. Add 2.0 mL of 5.25 N Sulfuric Acid Solution.

Note: Use the 1-mL calibrated dropper provided.

3. Place the flask (the prepared sample) on a Heatab Cookit stove or hot plate. Boil gently for 30 minutes.

Note: Maintain the volume near 20 mL by adding small amounts of demineralized water. Do not exceed 20 mL. This is more easily accomplished with a "doubleboiler" technique. Place the flask in a pan or beaker of boiling water which is just deeper than the solution level in the flask. Continue boiling for 30 minutes.

4. Cool the prepared sample to room temperature.

30:00

123

PHOSPHORUS, ACID HYDROLYZABLE, continued

5. Add 2.0 mL of 5.0 N Sodium Hydroxide Solution to the prepared sample. Swirl to mix.

Note: Use the 1-mL calibrated dropper provided.

6. Pour the prepared sample into a graduated cylinder. Add demineralized water rinsings from the flask to return the volume to 25 mL. Proceed with the appropriate reactive phosphorus test.

Note: Results of the reactive phosphorus test at this point will include the orthophosphate plus the acid-hydrolyzable (condensed) phosphate. The condensed phosphate concentration is determined by subtracting the results of a reactive phosphorus test on an untreated sample from this result. Make sure both results are in the same units.

124


Sampling and StorageThe most reliable results are obtained when samples are analyzed immediately.If prompt analysis is not possible, samples may be preserved up to 24 hours bycooling to 4 °C (39 °F). Warm to room temperature before testing.

InterferencesIf the sample is turbid, use 50 mL of sample and double the reagentvolumes. Use 25 mL of the hydrolyzed sample to zero the instrument inthe reactive phosphorus procedure. This compensates for any turbiditydissolved by this procedure.

Summary of MethodThis procedure lists the necessary steps to convert condensed phosphateforms (meta-, pyro- or other polyphosphates) to reactive orthophosphatebefore analysis. The procedure uses acid and heat to hydrolyze thesample. Organic phosphates are not converted to orthophosphate by thisprocess, but a very small fraction may be unavoidably included in theresult. Thus, the “acid hydrolyzable” phosphate results are primarily ameasure of inorganic phosphorus. This procedure must be followed byone of the reactive phosphorus (orthophosphate) analysis methods fordetermination of the phosphorous content of the sample.

The following reagents and apparatus are required in addition to thoserequired for the reactive phosphorus test.

125


REQUIRED REAGENTSQuantity Required

Description Per Test Unit Cat. No.Sodium Hydroxide Solution, 5.0 N ................................. 2 mL ......100 mL* MDB ..... 2450-32Sulfuric Acid Solution, 5.25 N ........................................ 2 mL .......100 mL* MDB..... 2449-32

REQUIRED APPARATUSCylinder, graduated, 25 mL .................................................2 ....................... each........... 508-40Flask, erlenmeyer, 50 mL ....................................................1 ....................... each........... 505-71Heatab Cookit stove, with 1 box of Heatabs.................................................. each......... 2206-00Heatab replacements .................................................................................. 21/pkg......... 2207-00

OPTIONAL REAGENTSDescription Unit Cat. No.Hydrochloric Acid, 6 N ............................................................................500 mL........... 884-49Water, demineralized .......................................................................................4 L........... 272-56

OPTIONAL APPARATUSDescription Unit Cat. No.Cylinder, graduated, 50 mL ........................................................................... each........... 508-41Flask, erlenmeyer, 125 mL ............................................................................ each........... 505-43Hot Plate, 3 1/2" diameter, 120 Vac............................................................... each....... 12067-01Pad, cooling, 4" x 4" ...................................................................................... each....... 18376-00pH indicator Paper, 1 to 11 pH ............................................................ 5 rolls/pkg........... 391-33pH Meter, EC10, portable .............................................................................. each....... 50050-00



126

Method 8048

PHOSPHORUS, REACTIVE (0 to 2.50 mg/L PO43-) For water, wastewater, seawater

(Also called Orthophosphate) PhosVer® 3 (Ascorbic Acid) Method* (Powder Pillows or AccuVac Ampuls) USEPA Accepted for wastewater analysis reporting**


* Adapted from Standard Methods for the Examination of Water and Wastewater.** Procedure is equivalent to USEPA method 365.2 and Standard Method 4500-P-E for wastewater.

1. Enter the stored program number for reactive phosphorus, ascorbic acid method, powder pillows.Press: 4 9 0 ENTER

The display will show:Dial nm to 890



890 nm


then: mg/L PO43- PV

3. Insert a 10-mL Cell Riser into the cell compartment.


890 nm

127

PHOSPHORUS, REACTIVE, continued

5. Add the contents of one PhosVer 3 Phosphate Powder Pillow for 10-mL sample to the cell (the prepared sample). Swirl immediately to mix.

Note: A blue color will form if phosphate is present.



Note: Use a 10 minute reaction period if determining total phosphorus following the acid-persulfate digestion.

7. Fill a second 10-mL sample cell with 10 mL of sample (this is the blank).

8. When the timer beeps, the display will show: mg/L PO4

3- PV


9. Press: ZERO


Zeroing. . .

then:

0.00 mg/L PO43- PV


Note: Run a reagent blank for this test. Use demineralized water in place of the sample in Steps 4 and 7. Subtract this result from all test results run with this lot of PhosVer 3.

11. Press: READ


Reading. . .

then the results in mg/L PO4

3- will be displayed.

128



1. Enter the stored program number for reactive phosphorus, ascorbic acid method, AccuVac Ampuls.

Press: 4 9 2 ENTER


Dial nm to 890


890 nm


then: mg/L PO43- PV AV




5. Fill a PhosVer 3 Phosphate Reagent AccuVac Ampul with sample.


6. Place an ampul cap securely over the tip of the ampul. Shake the ampul for approximately 30 seconds. Wipe off any liquid and fingerprints.

Note: A blue color will form if phosphate is present.





mg/L PO43- PV AV

Place the zeroing vial into the cell holder.

890 nm

:30

129


130

Sampling and StorageCollect sample in plastic or glass bottles that have been cleaned with 1:1Hydrochloric Acid Solution and rinsed with demineralized water. Do notuse commercial detergents containing phosphate for cleaning glasswareused in phosphate analysis.

Analyze samples immediately after collection for best results. If promptanalysis is impossible, preserve samples for up to 48 hours by filteringimmediately and storing samples at 4 °C.



b) Snap the neck off a Phosphate Voluette Ampule Standard Solution, 50 mg/L PO4

3-.

c) Use the TenSette Pipet to add 0.1 mL, 0.2 mL, and 0.3 mL of standard, respectively, to the three mixing cylinders. Stopper each and mix thoroughly.

d) For analysis with AccuVac Ampuls, transfer solutions to dry, clean 50-mL beakers to fill the vials. For analysis with powder pillows, transfer only 10 mL of solution to the 10 mL sample cells.

9. Press: ZERO


Zeroing. . .

then:

0.00 mg/L PO43- PV AV

10. Place the AccuVac Ampul into the cell holder.

Note: Run a reagent blank for the test. Use demineralized water in place of the sample in Step 3. Subtract this result from all results with this lot of ampuls.

11. Press: READ


Reading. . .

then the result in mg/L PO4



e) Analyze each standard addition sample as described in the procedure. The phosphate concentration should increase 0.2 mg/L for each 0.1 mL of standard added.

f) If these increases do not occur, see Standard Additions in Section I of the DR/2010 Spectrophotometer Procedures Manual for more information.

Standard Solution MethodPrepare a 2.0 mg/L PO4

3- standard solution by pipetting 4.0 mL of PhosphateStandard Solution, 50 mg/L as PO4

3-, into a 100-mL volumetric flask. Diluteto volume with demineralized water. Stopper and invert to mix. Use thissolution in place of the sample in the procedure to insure the accuracy of thetest. The mg/L PO4

3- reading should be 2 mg/L.

Interferences• Large amounts of turbidity may cause inconsistent results in the phosphate

tests because the acid present in the powder pillow may dissolve some of the suspended particles and because of variable desorption of orthophosphate from the particles. For highly turbid or colored samples, add the contents of one Phosphate Pretreatment Powder Pillow to 10 mL of sample. Mix well. Use this solution to zero the instrument.

• The PhosVer 3 Phosphate Reagent Powder Pillows should be stored in a cool, dry environment.

• The following may interfere when present in concentrations exceeding these listed below:

• Arsenate and hydrogen sulfide do interfere.

• Highly buffered samples or extreme sample pH may exceed the buffering capacity of the reagents and require sample pretreatment; see Interferences, pH, in Section I of the DR/2010 Spectrophotometer Procedures Manual.

Aluminum 200 mg/L

Chromium 100 mg/L

Copper 10 mg/L

Iron 100 mg/L

Nickel 300 mg/L

Silica 50 mg/L

Silicate 10 mg/L

Zinc 80 mg/L

131


PrecisionIn a single laboratory using a standard solution of 1.00 mg/L PO4

3- andtwo lots of reagents with the DR/2010 Spectrophotometer, a singleoperator obtained a standard deviation of ±0.01 mg/L PO4

3-.

In a single laboratory using a standard solution of 1.00 mg/L PO43- and two

representative lots of AccuVac Ampuls with the DR/2010 Spectrophotometer,a single operator obtained a standard deviation of ±0.02 mg/L PO4

3-.

Estimated Detection Limit (EDL)The EDL for program 490 is 0.01 mg/L PO4

3-. The EDL is the calculatedlowest average concentration in a demineralized water matrix that isdifferent from zero with a 99% level of confidence. For more informationon derivation and use of Hach’s estimated detection limit, see Section I ofthe DR/2010 Spectrophotometer Procedures Manual.

The EDL for program 492 is 0.01 mg/L PO43-. The EDL is the calculated

lowest average concentration in a demineralized water matrix that isdifferent from zero with a 99% level of confidence. For more informationon derivation and use of Hach’s estimated detection limit, see Section I ofthe DR/2010 Spectrophotometer Procedures Manual.

Summary of MethodOrthophosphate reacts with molybdate in an acid medium to produce aPhosphomolybdate complex. Ascorbic acid then reduces the complex,giving an intense molybdenum blue color.


Description Per Test Unit Cat. No.PhosVer 3 Phosphate Reagent Powder Pillows10 mL sample size ......................................................... 1 Pillow............ 100/pkg....... 21060-69

REQUIRED APPARATUS (Using Powder Pillows)Cell Riser, 10-mL.................................................................1 ....................... each....... 45282-00Sample Cell, 10 mL, matched pair ......................................2 ........................ pair....... 24954-02

REQUIRED REAGENTS (Using AccuVac Ampuls)PhosVer 3 Phosphate Reagent AccuVac Ampuls .......... 1 ampul.............. 25/pkg....... 25080-25

REQUIRED APPARATUS (Using AccuVac Ampuls)Adapter, AccuVac Vial.........................................................1 ....................... each....... 43784-00Beaker, 50 mL......................................................................1 ....................... each........... 500-41Cap, ampul, blue ..................................................................1 ................... 25/pkg......... 1731-25Vial, zeroing.........................................................................1 ....................... each....... 21228-00

132


OPTIONAL REAGENTSDescription Unit Cat. No.Hydrochloric Acid Standard Solution, 6.0 N (1:1) .................................. 500 mL ...........884-49Phosphate Pretreatment Powder Pillows ....................................................50/pkg .......14501-66Phosphate Standard Solution, Voluette ampul,

50 mg/L as PO43-, 10 mL .....................................................................16/pkg ...........171-10

Phosphate Standard Solution, 50 mg/L as PO43-....................................... 500 mL ...........171-49

Phosphate Standard Solution, 1 mg/L as PO43-......................................... 500 mL .........2569-42

Sodium Chloride, ACS ................................................................................454 g ...........182-01Sodium Hydroxide Standard Solution, 5.0 N .............................. 100 mL* MDB .........2450-32Water, demineralized........................................................................................4 L ...........272-56

OPTIONAL APPARATUSAccuVac Snapper Kit .....................................................................................each .......24052-00Cylinder, graduated, mixing, 25 mL, tall .......................................................each .......20886-40pH Indicator Paper, 1 to 11 pH.............................................................5 rolls/pkg ...........391-33pH Meter, EC10, portable ..............................................................................each .......50050-00Pipet, 2 mL serological...................................................................................each ...........532-36Pipet, TenSette, 1.0 to 10.0 mL ..................................................................... each .......19700-10Pipet Tips, for 19700-10 TenSette Pipet ....................................................50/pkg ...... 21997-96Pipet Tips, for 19700-10 TenSette Pipet ................................................1000/pkg ...... 21997-28Pipet, TenSette, 0.1 to 1.0 mL TenSette Pipet ................................................each .......19700-01Pipet Tips, for 19700-01.............................................................................50/pkg .......21856-96Pipet Filler, safety bulb...................................................................................each .......14651-00Spoon, measuring, 0.1 g .................................................................................each ...........511-00Thermometer, -20 to 105 °C...........................................................................each .........1877-01

OPTIONAL 25 ML ANALYSIS ITEMSPhosVer 3 Phosphate Reagent Set for 25 mL samples (100 tests) ..................................2125-99Pour-Thru Cell Assembly Kit (for 25 mL reagents only) ..............................each ...... 45215-00Sample Cell, 25 ml matched pair ....................................................................pair .......20950-00


* Larger sizes available.

133

134

Method 8051

SULFATE (0 to 70 mg/L) For water, wastewater, and seawater

SulfaVer® 4 Method* (Powder Pillows or AccuVac Ampuls), USEPA accepted for reporting wastewater analysis**


* Adapted from Standard Methods for the Examination of Water and Wastewater.** Procedure is equivalent to USEPA method 375.4 for wastewater.

1. A User-Entered Calibration is necessary to obtain the most accurate results. See User Calibration section of this procedure. Program 680 can be used directly for process control or applications where a high degree of accuracy is not needed.

Note: The nature of turbidimetric tests and reagent lot variation necessitate user calibration for best results.

2. Enter the appropriate stored program number for sulfate (SO4

2-) powder pillows.

Press: 6 8 0 ENTER

or

9 ? ? ENTER


Dial nm to 450

Note: The Pour-Thru cell cannot be used with this procedure.


450 nm


then: mg/L SO42-

Note: For greater accuracy, perform a user calibration for each new lot of SulfaVer 4 Sulfate Reagent Powder Pillows; see User Calibration following these steps.

4. Fill a clean sample cell with 25 mL of sample.

Note: Filter highly turbid or colored samples. Use filtered sample in this step and Step 7.

Choose Desired Program Accuracy ? ?

or

450 nm

135

SULFATE, continued

5. Add the contents of one SulfaVer 4 Sulfate Reagent Powder Pillow to the sample cell (the prepared sample). Swirl to dissolve.

A white turbidity will develop if sulfate is present.

Accuracy is not affected by undissolved powder.



Allow the cell to stand undisturbed.

7. When the timer beeps, the display will show: mg/L SO4

2-

Fill a second sample cell with 25 mL of sample (the blank).


9. Press: ZERO


Zeroing. . .

then: 0. mg/L SO42-

10. Within five minutes after the timer beeps, place the prepared sample into the cell holder. Close the light shield.

11. Press: READ


Reading. . .

then the results in mg/L SO4


Note: Clean the sample cells with soap and a brush.

136

SULFATE, continued


1. A User-Entered Calibration is necessary to obtain the most accurate results. See User Calibration Section at the back of this procedure. Program 685 can be used directly for process control or applications where a high degree of accuracy is not needed.

Note: The nature of turbidimetric tests and reagent lot variation necessitate user calibration for best results.

2. Enter the appropriate stored program number for sulfate (SO4

2-) AccuVac Ampls.

Press: 6 8 5 ENTER

or

9 ? ? ENTER


Dial nm to 450


450 nm


then: mg/L SO42- AV


Note: Filter highly turbid or colored samples. Use filtered sample in this step and Step 5.

5. Fill a SulfaVer 4 Sulfate AccuVac Ampul with sample.

Note: Keep tip immersed until the ampul fills completely.


Note: A white turbidity will develop if sulfate is present.




Note: Allow the ampul to stand undisturbed.



Choose Desired Program Accuracy ? ?

or

450 nm

137

SULFATE, continued

Sampling and StorageCollect samples in clean plastic or glass bottles. Samples may be stored up to28 days by cooling to 4 °C (39 °F) or lower. Warm to room temperaturebefore analysis.



b) Snap the neck off a Sulfate Voluette Ampule Standard Solution, 2500 mg/L SO4

2- .

c) Use a TenSette Pipet to add 0.1, 0.2 and 0.3 mL of standard to the three 25-mL samples. Mix thoroughly. For AccuVac Ampuls, transfer to clean, dry 50-mL beakers.

d) Analyze each sample as described above. The sulfate concentration should increase 10 mg/L for each 0.1 mL of standard added.



mg/L SO42- AV


10. Press: ZERO


Zeroing. . .

then: 0. mg/L SO42- AV

11. Within five minutes after the timer beeps, place the AccuVac Ampul into the cell holder. Close the light shield.

12. Press: READ


Reading. . .

then the results in mg/L SO4


138

SULFATE, continued

139

Standard Solution MethodCheck the accuracy of the test by using the Sulfate Standard Solution,50 mg/L, listed under Optional Reagents. Or, prepare this solution bypipetting 1.0 mL of the contents of a Voluette Ampule Standard forSulfate (2500 mg/L) into a 50-mL volumetric flask. Dilute to volumewith demineralized water.

Substitute this standard for the sample and proceed with the test asdescribed in the procedure. The mg/L SO4

2- reading should be 50 mg/L.

User CalibrationFor most accurate results, the use of a user-calibrated program is highlyrecommended. The Hach stored programs 680 and 685 are intended forprocess control samples or other applications where a high degree ofaccuracy is not necessary.

A one-time setup program for sulfate is required. A sulfate programtemplate is pre-programmed into memory to make the process easier.After the setup is complete, the calibration can be entered for each new lotof reagents used or as necessary.

Standard PreparationA new calibration should be performed for each new lot of SulfaVer 4Sulfate Reagent as follows:

Prepare standards of 10, 20, 30, 40, 50, and 60 mg/L sulfate by pipetting 1,2, 3, 4, 5, and 6 mL of a 1000-mg/L Sulfate Standard Solution into 100-mLvolumetric flasks. Dilute to the mark with demineralized water. Mix well.

Initial Setup of Sulfate ProgramNote: The templates within User Program cannot be run directly. They must be copied into a usable program number (greater than 950) as in step c and d. Then, calibrate the program. The preprogrammed calibration (680 or 685) may be suitable for process control.

a) Press SHIFT USER PRGM. Use the UP arrow key to scroll to Copy Program. Press ENTER.

b) Scroll to or enter the template number for sulfate [906, 907 (AV)]. Press ENTER.

c) Scroll to or enter the desired user program number for sulfate (>950). Press ENTER. Record the program number for reference.

d) The display will show: Program Copied. Press EXIT. The program is now ready to be calibrated.

SULFATE, continued

User Calibration of Sulfate ProgramNote: The standards must be run through the test procedure just prior to recording the calibration absorbance values. The instrument lamp should be in the Constant ON mode.

a) Press SHIFT USER PRGM. Use the UP arrow to scroll to Edit Program. Press ENTER.

b) Scroll to or enter the program number for sulfate (from step c in Setup). Press ENTER.

c) Rotate the wavelength dial until the small display shows 450 nm.

d) Scroll down to Calibration Table. Press ENTER. The first concentration point will be displayed.

e) Press ENTER to display the absorbance value of the first concentration point. Place the blank solution in the cell holder. Close the light shield. Press ZERO.

f) Place the first developed standard solution (10 mg/L SO42-) in the

cell holder. Close the light shield. Press ENTER to accept the absorbance reading.

g) The second concentration point will be displayed. Press ENTER to display the stored absorbance value of the second concentration. Place the second developed standard solution (20 mg/L sulfate) in the cell holder. Close the light shield. Press READ to display the absorbance value of the standard solution.

h) Press ENTER to accept the absorbance reading. The next concentration point will then be displayed.

i) Repeat steps g and h as necessary for the remaining standards. There are 6 standards in addition to the blank.

j) When finished reading the absorbance values of the standards, press EXIT. Scroll down to Force Zero. Press ENTER to change the setting. Change to ON by pressing the arrow key, then press ENTER.

k) Scroll down to Calib Formula. Press ENTER twice or until only the 0 in F(0) is flashing. Press DOWN arrow to select F3 (cubic calibration). Press ENTER to select F3.

Note: Alternative calibration fits may also be used if appropriate.

l) Press EXIT twice. The display will show Store Changes?. Press ENTER to confirm.

m) Press EXIT. The program is now calibrated and ready for use. Start with step 2 of the iconed test procedure.

140

SULFATE, continued

141

Precision In a single laboratory, using a standard solution of 50 mg/L sulfate and tworepresentative lots of powder pillows with the DR/2010 Spectrophotometer,a single operator obtained a standard deviation of ±0.9 mg/L sulfate.

In a single laboratory, using a standard solution of 50 mg/L sulfate and tworepresentative lots of AccuVac Ampuls with the DR/2010 Spectorphotometer,a single operator obtained a standard deviation of ±2.2 mg/L sulfate.

Estimated Detection Limit (EDL)The EDL for program 680 is 7 mg/L SO4

2-. The EDL is the calculatedlowest average concentration in a demineralized water matrix that isdifferent from zero with a 99% level of confidence. For more informationon derivation and use of Hach’s estimated detection limit, see Section I ofthe DR/2010 Spectrophotometer Procedures Manual.

The EDL for program 685 is 7 mg/L SO42-. The EDL is the calculated

lowest average concentration in a demineralized water matrix that isdifferent from zero with a 99% level of confidence. For more informationon derivation and use of Hach’s estimated detection limit, see Section I ofthe DR/2010 Spectrophotometer Procedures Manual.

InterferencesThe following interfere at levels above those concentrations listed:

Summary Of MethodSulfate ions in the sample react with barium in the SulfaVer 4 SulfateReagent and form insoluble barium sulfate turbidity. The amount ofturbidity formed is proportional to the sulfate concentration.

Calcium 20,000 mg/L as CaCO3

Chloride 40,000 mg/L as Cl-

Magnesium 10,000 mg/L as CaCO3

Silica 500 mg/L as CaCO3

SULFATE, continued

142


Description Per Test Units Cat. No.SulfaVer 4 Sulfate Reagent Powder Pillows .................. 1 pillow............ 100/pkg....... 12065-99

REQUIRED REAGENTS (Using AccuVac Ampuls)SulfaVer 4 Sulfate AccuVac Ampuls ............................. 1 ampul.............. 25/pkg....... 25090-25

REQUIRED APPARATUS (Using Powder Pillows)Sample Cell, 25 mL, matched pair ......................................2 ....................... each....... 20950-00Brush....................................................................................1 ....................... each........... 690-00

REQUIRED APPARATUS (Using AccuVac Ampuls)Adapter, AccuVac Vial.........................................................1 ....................... each....... 43784-00Beaker, 50-mL .....................................................................1 ....................... each........... 500-41Vial, zeroing.........................................................................1 ....................... each....... 21228-00

OPTIONAL REAGENTSSulfate Standard Solution, 50 mg/L..........................................................500 mL......... 2578-49Sulfate Standard Solution, 1000 mg/L......................................................500 mL....... 21757-49Sulfate Standard Solution, Voluette Ampule, 2500 mg/L, 10 mL............. 16/pkg....... 14252-10Water, demineralized ........................................................................................4L........... 272-56

OPTIONAL APPARATUSAccuVac Snapper Kit..................................................................................... each....... 24052-00Ampule Breaker Kit....................................................................................... each....... 21968-00Cylinder, Graduated Mixing, 25 mL.............................................................. each....... 20886-40Filter Paper, folded, 12.5 cm.................................................................... 100/pkg......... 1894-57Flask, volumetric, 50 mL, Class A ................................................................ each....... 14574-41Flask, volumetric, 100 mL, Class A .............................................................. each....... 14574-42Funnel, poly, 65 mm ...................................................................................... each......... 1083-67Pipet, TenSette, 0.1 to 1.0 mL........................................................................ each....... 19700-01Pipet, Tips, for 19700-01 Pipet .................................................................. 50/pkg....... 21856-96Pipet, Volumetric, 1.00 mL, Class A ............................................................. each....... 14515-35Pipet, Volumetric, 2.00 mL, Class A ............................................................. each....... 14515-36Pipet, Volumetric, 3.00 mL, Class A ............................................................. each....... 14515-03Pipet, Volumetric, 4.00 mL, Class A ............................................................. each....... 14515-04Pipet, Volumetric, 5.00 mL, Class A ............................................................. each....... 14515-37Pipet, Volumetric, 6.00 mL, Class A ............................................................. each....... 14515-06Pipet, Filler, saftey bulb ................................................................................. each....... 14651-00


Method 8195

TURBIDITY (0 to 999 NTU) For water and wastewater

Using the 2100P Turbidimeter

1. Collect a representative sample in a clean container. Fill a 2100P sample cell to the line (about 15 mL), taking care to handle the sample cell by the top. Cap the cell. (See Section 2.3 Measurement Techniques of the 2100P Turbidimeter Instrument Manual for more information about collecting a representative sample).

2. Wipe the cell with a soft, lint-free cloth to remove water spots and fingerprints.

3. Apply a thin film of silicone oil. Wipe with a soft cloth to obtain an even film over the entire surface.

4. Press: I/O. The instrument will turn on. Place the instrument on a flat, sturdy surface. Do not hold the instrument while making measurements.

Note: The instrument automatically shuts off after 5.5 minutes if no keystrokes occur. To resume operation, press I/O.

143

TURBIDITY, continued

Sampling and StorageCollect samples in clean plastic or glass bottles. Analyze samples as soon aspossible after collection. Samples may be stored for 7 days by cooling to 4 °C(39 °F) or lower. Warm samples to room temperature before analyzing.

Accuracy CheckRefer to the 2100P Turbidimeter Instrument Manual for calibrationprocedures and formazin standard preparation.

5. Put the sample cell in the instrument cell compartment so the diamond or orientation mark aligns with the raised orientation mark in front of the cell compartment. Close the lid.

6. Select manual or automatic range selection by pressing:

RANGE

When the instrument is in automatic range selection the display will show:

AUTO RNG

7. Select signal averaging mode by pressing:

SIGNAL AVERAGE


SIG AVGwhen the instrument is using signal averaging. Use signal average mode if the sample causes a noisy signal (display changes constantly).

Note: The instrument defaults to the last operating mode selected. If automatic range mode and signal averaging were used on the previous measurements, these options will automatically be selected for subsequent samples.

8. Press: READThe display will show:

- - - -

then: the turbidity in

NTU

Record the turbidity after the lamp icon turns off.

Note: Refer to the 2100P Turbidimeter Instrument Manual for degassing procedure if air bubbles are present.

144

TURBIDITY, continued

Summary of MethodTurbidity occurs in most surface waters as the result of suspended clay,slit, finely divided organic and inorganic matter, plankton and othermicroorganisms. The turbidity test measures an optical property of thewater sample that results from the scattering and absorbing of light by theparticulate matter present. The amount of turbidity measured depends onsuch variables as size, shape and refractive index of the particles.

REQUIRED REAGENTS AND APPARATUSDescription Units Cat. No.Sample Cells, 1 inch, with cap .....................................................................6/pkg .......24347-06Silicone Oil, 15 mL ........................................................................................each .........1269-36Turbidimeter, Portable, 2100P........................................................................each .......46500-00

OPTIONAL REAGENTS AND APPARATUSDescription Units Cat. No.Batteries, AA................................................................................................4/pkg .......19380-04Carrying Case, for 2100P...............................................................................each .......46506-00Formazin Turbidity Standard, 4000 NTU ................................................ 168 mL .........2461-14Gelex Standards Set (w/3 sample cells) .........................................................each .......24641-05Instrument Manual, 2100P .............................................................................each .......46500-88StablCal™ Standards for 2100P, bulk solutions ............................................each .......26594-00Standard Methods for the Examination

of Water and Wastewater, 19th Edition.......................................................each .......22708-00

Related Products For the most precise turbidity measurements, the Hach Model 2100P PortableTurbidimeter, or Model 2100AN Turbidimeter are recommended. Theseinstruments are true nephelometers that meet all the performancerequirements for turbidity measurements described in APHA StandardMethods, the USEPA Methods of Chemical Analysis of Water and Wastes andthe Federal Register.


145

146

GENERAL INFORMATION

147

At Hach Company, customer service is an important part of every product we make.

With that in mind, we have compiled the following information for your convenience.

148

HOW TO ORDER

By Phone:6:30 a.m. to 5:00 p.m. MSTMonday through Friday800-227-HACH (800-227-4224)

By Mail:Hach Company World HeadquartersP. O. Box 389Loveland, Colorado 80539-0389 U.S.A.

By FAX:970-669-2932 (Hach Loveland)

Information Required:

• Hach account number (if available)

• Billing address

• Shipping address

• Your name and phone number

• Purchase order number

• Catalog number

• Brief description or model number

• Quantity and size

Technical and Customer ServiceHach Technical and Customer Service Department personnel are eager toanswer questions about our products and their use and to take your orders.Specialists in analytical methods, they are happy to put their talents towork for you. Call 1-800-227-4224.

149

International Customers:Hach maintains a network of dealers and distributors throughout theworld. Obtain assistance from a nearby Hach distributor or:

Hach Company World HeadquartersP. O. Box 389Loveland, Colorado, U.S.A. 80539Telex: 160840Telephone: (1) (970) 669-3050FAX: (1) (970) 669-2932

Information presented on these pages applies only to Hach productsmanufactured for use within the United States.Exportation of theseproducts renders these terms void.

Prices and TermsPrices are subject to change without notice. All prices are FOB from theshipping point (usually Ames, Iowa). Hach offers instant credit up to $200 onNet 30 Day terms. Larger orders are subject to credit review. Customers maysend remittance with orders or we can ship C.O.D. if preferred.

Claims and ReturnsWe take extreme care to fill, check, re-check and pack orders properly. Iferrors or damages should occur, please report details to our LovelandCustomer Service Department and to the carrier immediately. Be sure tokeep all containers and packing materials.

AUTHORIZATION MUST BE OBTAINED from Hach when returning itemsfor any reason. Call 1-800-227-4224 toll free. ALL “FREIGHTCOLLECT” SHIPMENTS OR MERCHANDISE RETURNEDWITHOUT PROPER AUTHORIZATION FROM HACH WILL BEREFUSED.

HOW TO ORDER, continued

150

WarrantyHach warrants its products to be of high quality, to be free of materialdefects on the date of shipment and to be as specified. Full warrantyinformation is on the back of Hach invoices.

Limits of UsageOur chemicals and reagents are offered for laboratory and manufacturinguse ONLY. They may not be used as drugs, cosmetics or food additives.

MSDSHach Material Safety Data Sheets, among the most complete andinformative in the industry, provide comprehensive safety data essential forday-to-day operations and safety training.

An MSDS accompanies all Hach chemical products including test kits. For anadditional $15.00 per item, we will print MSDSs on your own forms.

Label InformationLabels on Hach chemicals and reagents supply the following information:

• Product Name — Printed in French, German, Italian and Spanish as well as English is printed on all but the smallest-size labels.

• Hach Catalog Number — Makes reordering easy and helps match the appropriate MSDS.

• Storage Information and Lot Numbers — Lot numbers made up of letters and numbers indicate an extended shelf life; a four-digit number indicates items should be rotated and checked with a standard to confirm performance. The lot number is essential if you call for technical assistance or with questions about reagent performance.

ShipmentOur experienced warehouse staff packages your orders for safe arrival.Unless we are instructed otherwise, the best and most efficient mode oftransportation is selected. Motor freight shipments will be sent freightcollect unless you specify otherwise at the time you order.

If you have questions about methods for shipment and availability ofspecial packaging, please ask when you place your order.


151

Trademarks of Hach Company

NewsletterNews & Notes for the Analyst, Hach’s informative newsletter, containsupdates on federal regulations, in-depth discussions of chemicalreactions, application notes and information about new products. ContactHach for your free subscription.

AccuVac® NitriVer®

AluVer® PermaChem®

BariVer® PhosVer®

BoroVer® PocketPal™

CalVer® PourRite™

ChromaVer® Ratio™

CuVer® RoVer®

CyaniVer® StablCAL™

Digesdahl® StillVer®

DithiVer® SulfaVer®

FerroVer® TanniVer®

FerroZine® TenSette®

Hach Logo® Test ‘N Tube™

Hach One® TitraStir®

HexaVer® TitraVer®

LeadTrak® ToxTrak

ManVer® UniVer®

MolyVer® Voluette®

NitraVer® ZincoVer®


152

If Hach account number is not known, leave the space blank.

Most chemicals and apparatus are sold separately (“each”), but others are sold in units. Powder pillows, for example, are available in packages of 100. To purchase 100 powder pillows, order 1 unit, not 100 pillows. Be sure to order the number of units (packages) you need.

Include all numbers given in the products listing.

A one- or two-word description of the item.

If more than one size of an item is offered, state the size you want.

Your shipping charge goes here. Figure your simplified freight fee using the information in “Simplified Freight Charges” on the preceding pages.

Check one box. Tax exempt status must be substantiated with documentation identifying your tax exempt number. If taxable, sales tax will be added to

MAIL ORDER FORMSend order to: HACH COMPANY, P.O. Box 608, Loveland, CO 80539-0608

Use this convenient form, your own purchase orders, or for PROMPT PHONESERVICE CALL 1-800-227-4224. If ordering by phone, please have informationrelated to items 1 - 4 (below) ready.

Check box if “Ship To” information is identical to “Bill To”.

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HACH COMPANYWORLD HEADQUARTERSP.O. Box 389Loveland, Colorado 80539-0389Telephone: (970) 669-3050FAX: (970) 669-2932

FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING:Call 800-227-4224

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Basic Water Quality Laboratory Procedures Manual.pdf

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