HYDROGEOLOGIC AND SOILS INVESTIGATION FOR BENDIX PLIGHT SYSTEMS DIVISION SOUTH HONTROSE, PENNSYLVANIA VOLUME II - APPENDICES I January 1985 I I I Environmental Resources Management, Inc. 999 West Chester Pike I West Chester, Pennsylvania 19382 BR300073
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HYDROGEOLOGIC AND SOILS INVESTIGATIONFOR
BENDIX PLIGHT SYSTEMS DIVISIONSOUTH HONTROSE, PENNSYLVANIA
VOLUME II - APPENDICES
I January 1985
III
Environmental Resources Management, Inc.999 West Chester Pike
I West Chester, Pennsylvania 19382
BR300073
The ERM Group
TABLE OF CONTENTS
Section 1, Appendix A - Boring Logs and Data from ChesterEngineers Reports
Section 2, Appendix B - EPA Analytical Methods
Section 3, Appendix C - ERM Well, Boring, and Trench Logs
Section 4, Appendix D - Analytical Data
IIIII .4R300071!
IVIIIII
The ERM Group
APPENDIX A
I BORING LOGS AND DATA FROMCHESTER ENGINEERS REPORTS
IIIIIII
flR300075
TABLE I 1-4 v JII SUMMARY OF FIELD PERMEABILITY DATA
I Monitoring Permeability Well Depth Screen LengthWell cm/seed) feet feet
I MW-1 1.5 x 10"6 31.5 5.0
MW-2 2.7 X 10~6 40.0 5.0
I MW-3 1.1 x 10"5 31.5 5.0
. MW-4 2.3 X 10~3 50.0 5.0
' MW-5 1.8 X 10~6 30.0 5.0
I MW-6 (2) 200.0 20.0
' MW-7 2.4 X, 10"& 26.0 5.01 1 • • ' "•>•'
MW-8 4.8 x 10 5 22.0 5.0
MW-9 9.6 x 10"6 20.0 5.0
» MW-10 8.8 x 10~4 20.0 15.0
I MW-11 8.3 x 10"5' 13.0 10.0
MW-12 8.4 X 10"s 15*0 15.0
I MW-13 1.5 X 10~4. 20.0 15.0 1
MW-14 1.6 x 10"3 20.0 15.0 . ,
I MW-15 9.0 X 10"4 20.0 15.0 '
• MW-16 1.7 x 10~3 18.0 15.0 I
NOTES; (1) Tests conducted as Hvorslev slug tests. . I
I (2) Could not obtain rise in water table, permeabilitynot determined. .i i
i i, BENDIX CORP. ^-S II 3238-12/10-83 11-14 ' L
, AR300076 ,[
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8"TO? BENUTX AVTATTOM rrWPfiRJTfrWA* uriNTp E pwv«
Total Organic Halogens, pg/L Cl 49 11 22 44 238,000
• Unless otherwise noted, analyses are in accordance with methods and procedures outlined and approved by the Environmental /Protection Agency and conform to quality assurance protocol.
I* "Less-than" «> values are indicative ol the detection limit.
Ann Arbor • Atlanta • Chadds Ford • Dallas • Kingston • Nashvillai
• Unltss otherwise noted, analyses are m accordance with methods and procedures outlined and approved by theProtection Agency and conform to Quality assurance protocol.
• "Less-than" «( values are indicative of (he detection limit.
Ann Arbor • Atlanta • Chadds Ford • Dallas • Kingston • Nashvillest rj '*'•'' - i onwnouu i 20
• Unless otherwise noted, analyses are in accordance with methods and procedures outlined and approved by the EnvironmentalProtection Agency and conform to Quality assurance protocol.
• "Less-than" «) values are indicative of the detection limit. fl D Q H fl I 9 I
Ann Arbor • Atlanta • Chadds Ford • Dallas • Kingston • Nashville
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1.2 This is a purge and trap gas 136.1. When this method is used tochromatographic method applicable to analyze unfamiliar samples for any orthe determination of the compounds all of the compounds above, compoundlisted above in municipal and industrial . • identification should be supported by atdischarges as provided under 40 CFR least one additional qualitative
technique. This method describes contamination under the conditions of suspected, human or mammaliananalytical conditions for a second gas the analysis by running laboratory carcinogens: carbon tetrachloride,chromatographic column that can be " reagent blanks as described in Section chloroform, 1,4-dichlorobenzene, andused to confirm measurements made 8.5. The use of non-TFS plastic tubing, vinyl chloride. Primary standards ofwith the primary column. Method 624 non-TFE thread sealants, or flow these toxic compounds should beprovides gas chromatograph/mass controllers with rubber components in prepared in a hood. A NIOSH/MESAspectrometer (GC/MS) conditions the purging device should be avoided. approved toxic gas respirator should beappropriate for the qualitative and •» « c i w • worn when the analyst handles highquantitative confirmation of results for J-* Samples can be contaminated by conc8ntrations of these toxicmost of the parameters listed above. dlf'u!!on of v<?lat'" Or9an'« (particu- compounds.larly f luorocarbons and methylene1.3 The method detection limit (MDL, chloride) through the septum seal into 5. Apparatus and Materialsdefined in Section 12.1 )I1) for each the sample during shipment andparameter is listed in Table 1. The MDL storage. A field reagent blank prepared 5.1 Sampling equipment, for discretefor a specific wastewater may differ from reagent water and carried through sampling.from those listed, depending upon the the sampling and handling protocol can g 1 1 Vial—25 mL capacity or lamernature of interferences in the sample serve as a check on such equipped with a screw cap with hole inmatnx- contamination. center (pierce jj 307 5 or equivalent).1.4 Any modification of this method, 3.3 Contamination by carry-over can Detergent wash, rinse cap with tap andbeyond those expressly permitted, occur whenever high level and low distilled water, and dry at 105 °Cshall be considered as major modifies- level samples are sequentially analyzed. before use.tions subject to application and To reduce carry-over, the purging SJ2 Septum - Tef lon-f aced siliconeapproval of alternate test procedures device and sample syringe must be (Pierce #12722 or equivalent)under 40 CFR 136.4 and 138.5. rinsed with reagent water between Detergent wash, rinse with tap and1.5 This method is restricted to use S - -*' »H «mn£ i« distilled water' and dry at 105 °C for. . . . unusually conconiraivu sarnuio 19 **•*• K««. .» K f.*** •.«.*nv nt iindnr tnfl un*>rv/ismn of anAlv^f^ .. . ... ... .. wno noui uoioro uso.oy or unasr in» supervision oi analysis encountered, it should be followed byexperienced in the operation of a purge an anaiysis of reagent water to check 5.2 Purge and trap device-Theand trap system and a gas chrornato- for cross contamination. For samples purge and trap device consists of threegraph and in the interpretation of containing large amounts of water- separate pieces of equipment: thechromatograms. Each analyst must soluble materials, suspended solids. sample purger, trap, and the desorber.demonstrate the ability to generate nign boi|jng compounds or high Several complete devices are nowacceptable results with this method organohalide levels, it may be neces- commercially available.usmgthe procedure descnbed in sary to wash out the purging device . , , _Sectlon 8-2- with a detergent solution, rinse it with ?f' Jh9 "mpl* purger must be2. Summary of Method I SS SX iX X ^2.1 An inert gas is bubbled through a trap and other parts of the Jystem are "*** 9aseous head sPa« b«ween the5-mL water sample contained in a also subject to contamination; there- watfr c°lumn f"d tn? traP, ™« have aspecially-designed purging chamber at fore, frequent bakeout and purging of total volume °\less than 1 ™- Theambient temperature. The halocarbons the entire system may be required. P"'98 "* mu* pas? :tn™U9/? fhe wa'erare efficiently transferred from the A o * *„ column as finely divided bubbles with aaqueous phase to the vapor phase. The 4- SafetV t?Tn ?he u?% asr!iiTsTbe\!itto
4* 1 Tho toxicity or carcinogenicity of ducod no more than 5 mm from ths83cn rsagsnt used in this msthod h33 b3so of tho wdtdr column* Th0 S3mpl0
>,.„.* »« **MI, .h.H «,ith th. inort not been Precisely defined; however. purger. illustrated in Figure 1, meetsheated and backflushed with the inert each cnemical compound should be these design criteriagas to desorb the halocarbons onto a treated as a potential health hazard. ^se design cntena.gas chromatographic column. The gas From this vi8wpoint. exposure to these 5'2:2 f *«» mus5 b? at'?a« 25 mchromatograph is temperature pro- chemicals must be reduced to the cm, 'onfl and have an inside diameter ofgrammed to separate the halocarbons ,owest ibla ,9vfl| b whatever at least 0.105 inch. The trap must bewhich are then detected with a halide- means avai|able. The laboratory is ***«* "contain the followingspecific detector.(2.3» responsible for maintaining a current rr"rwmum lengths of adsorbents: 1.02.2 The method provides an optional awareness file of OSHA regulationsgas chromatoqraphic column that may regarding the safe handling of theS heipTuTSoLg the compound," chemicals specified in this method. A SSETCS" " "m oSaof interest from interferences that may reference file of material data handling ^ 5 <rf'««iii chaTcoal Secocc... sheets should also be made available to ^.7 gm or coconut cnarcoausecOCCUf' all personnel involved in the chemical 8.3. ).f it is not necessary to analyze1 tnterterencas a"a'vsi«- Additional references to for d.chlorod, luroromethane. the char-3. Interferences laboratory safety are available and coal can be ehminated and the polymer3 1 Impurities in the purge gas and have been identified<*-8> for the infor- S8.cVon Ien9'hened to 15 cm. Thej. i impurmes m me puiao yoao< u _ati._ _f th_ -.,a|uet minimum specifications for the trap areorganic compounds out-gassing from mation of the analyst. illusnatBd in Fiaura lthe plumbing ahead of the trap account iwwwatwi in n8u.« *.for the majority of contamination 4.2 The following parameters 5.2.3 The desorber must be capableproblems. The analytical system must covered by this method have been ten- of rapidly heating the trap to 180 °C.be demonstrated to be free from tatively classified as known or The polymer section of the trap should
SOI-2 July 1382
not be heated higher than 1 80 °C and 6.1.1 Reagent water can be generated the flask, then re weigh. Be sure thatthe remaining sections should not by passing tap water through a carbon the drops fall directly into the alcoholexceed 220 °C. The desorber design, filter bed containing about 1 Ib. oft without contacting the neck of theillustrated in Figure 2, meets these activated carbon (Filtrasorb-300 or flask.criteria. equivalent (Calgon Corp.)).
6.5.2.2 Gases— To prepare standards5.2.4 The purge and trap device may 6. 1.2 A water purification system for any of the six halocarbons that boilbe assembled as a separate unit or be (Millipore Super-Q or equivalent) may below 30 °C (bromomethane, chloro-coupled to a gas chromatograph as be used to generate reagent water. ethane chloromethane, dichlorodi-illustrated in Figures 3 and 4. ft f 3 , ^ be fluoromethane . trichlorofluoromethane.6.3 Gas chromatograph- An analyti- prepared by boiling water for 1 S Y'"*1 chloride), Ml a 5-mL valved gas-cal system complete with a tempera- minutes. Subsequently, while maintain- tl9nt ?y""fle* * *he referencfture programmable gas chromatograph ing the temperature at 90 °C. bubble a **nd'rj!ll [„? "X Jl h!,.suitable for on-column injection and all contaminant-free inert gas through the the "eedle to 5 fJ ' T Lrequired accessories including syringes, water for one hour. While still hoi alco ho1 meniscus. Slowly introduce theanalytical columns, gases, detector? transfer the water to a narrow mouthand strip-chart recorder. A data system screw-cap bottle and seal with a ne q.ul e ^ ,is recommended for measuring peak Teflon-lined septum and cap. dissolve Into the methv' alcohol>-areas- 6.2 Sodium thiosulf ate -(ACS) 6-6-3 Reweigh. dilute to volume.5.3. 1 Column 1 -8 ft long x 0. 1 in Granular. stopper, then mix by inverting the flaskID stainless steel or glass, packed with _ , _ „ . , several times. Calculate the concentre-1 % SP- 1 000 on Carbopack B (60/80 6-3 Trap Matena's tion in micrograms per microliter from .mesh) or equivalent. This column was e 3. 1 Coconut charcoal (6/1 0 mesh *** net gain in weiSht- W"6" compoundused to develop the method perfor- sieved to 26 mesh). (Barnaby Chaney, *>"<** ? assayed to * 96* or 8reatcr-mance statements in Section 12. CA-580-26 lot * M-2649 or the weight can be used without correc-Guidelines for the use of alternate equivalent). tion to calculate the concentration ofcolumn packings are provided in the stock standard. Commercially pre-Section 10.1. 6.3.2 2,6-Diphenylene oxide pared stock standards can be used at
polymer— Tenax, (60/80 mesh), any concentration if they are certified5.3.2 Column 2— 6 ft long x 0.1 in chromatographic grade or equivalent. by the manufacturer or by an indepen-ID stainless steel or glass, packed with dent source.chemically bonded n-octane on Porasil- 6-3-3 Methyl silicone packing -3%
-x C (100/1 20) mesh or equivalent. OV-1 on 60/80 mesh Chromosorb-W e.S.4 Transfer the stock standard* , . „ « - .. ^ or equivalent. solution into a Teflon-sealed screw-cap
5.3.3 Detector- Electrolytic conduc- eg.,..., « /fio m«h bottle. Store, with minimal headspace,tivity or microcoulometric. These types *-*-4 Silica gel-35/60 mesh, at - in to -2O«C and nroteet fromof detectors have proven effective in Davison. grade-1 5 or equivalent. « 1 ° to - 20 C and Protect f romthe analysis of wastewaters for the 64 Methyl Alcohol-Pesticide quality fparameters listed in the scope. The or equivalent 5.5.5 Prepare fresh standards weeklyelectrolytic conductivity detector was ' for the six gases and 2-chloroethylvinylused to develop the method perfor- 6.5 Stock standard solutions— Stock ether. All other standards must bemance statements fnd MDL listed in standard solutions may be prepared replaced after one month, or sooner ifTables 1 and 2. Guidelines for the use from pure standard materials or comparison with check standardsof alternate detectors are provided In purchased as certified solutions. indicate a problem.Section 10.1. Prepare stock standard solutions In
methyl alcohol using assayed liquids or 6.6 Secondary dilution standards -if eas cylinders as appropriate. Because Using stock standard solutions, prepare
w t - V,, «f the *oxicitV of some of the secondary dilution standards in methylapplicable to the purging device. organohalides, primary dilutions of alcohol that contain the compounds of6.6 Micro syringes- 25 ftL, 0.006 in these materials should be prepared in a interest, either singly or mixed together.ID needle. hood. A NIOSH/MESA approved toxic The secondary dilution standards
gas respirator should be used when the should be prepared at concentrations6.6 Syringe valve- 2-way, with Luer analyst handles high concentrations of such that the aqueous calibrationends (three each). such materials. standards prepared in Sections 7.3.1K t eurinn0 R mi a*« ttnht with *. j-« «. u „ „ . , ,_ . or 7-4.1 wi" bracket the working range*hut <£F XT J , ,P'aCe "*out9-8 ml of methyl of the flnalytical system. Secondaryshut-off valve. alcohol into a 10-mL ground glass dilution standards should be stored6.8 Bottle-16-mL, screw cap, with stoppered volumetric flask. Allow the with minimal headspace and should beTeflon cap liner. flask to 8tand- ""stoppered, for about checked frequently for signs of degrad-
10 minutes or until all alcohol wetted ation or evaporation especially iust6.9 Balance-Analytical, capable of surfaces have dried. Weigh the flask to prior to preparinS caiibration standardsaccurately wetghma 0.0001 g. the nearest 0.1 mg. from tnem. Quf eorrtrol cneck6. Reagents 5.5.2 Add the assayed reference standards that can be used to
material: determine the accuracy of calibration6.1 Reagent water—Reagent water is ' standards will be available from thedefined as a water in which an 6.6.2.1 Liquids—Using a 100-,uL U.S." Environmental Protection Agency,interferes is not observed at the MDL syringe. Immediately add two or more Environmental Monitoring and Supportof the parameters of interest. • drops of assayed reference material to Laboratory, in Cincinnati. Ohio.
601.3 JUfy1S82 A R 30 01
7. Calibration or calibration factor must be prepared response for any parameter varies fromfor that parameter. the predicted response by more than
7.1 Assemble a purge and trap device ±10%, the test must be repeatedthat meets the specifications in Section /••* Internal standard calibration usjng a fresn calibration standard5.2. Condition the trap overnight at procedure. To use this approach, the Alternatively, a new calibration curve1 80 °C by backf lushing with an inert analyst must select one or more internal mijst be prepared for that compoundgas flow of at least 20 mUmin. Prior to standards that are similar in analytical ^use, daily condition traps 1 0 minutes behavior to the compounds of interest. 8. Quality Controlwhilebackflushingat180°C. The analyst must further demonstrate _ , _ . . .
that the measurement of the internal 8.1 Each laboratory that uses this7.2 Connect the purge and trap standard is not affected by method or method is required to operate a formaldevice to a gas chromatograph. The matrix interferences. Because of these quality control program. The minimumgas chromatograph must be operated limitations, no internal standard can be requirements of this program consist ofusing temperature and flow rate param- suggested that is applicable to all an initial demonstration of laboratoryeters equivalent to those in Table 1 . samples. The compounds recommended capability and the analysis of spikedCalibrate the purge and trap-gas for uso as surrogate spikes in Section samples as a continuing check onchromatographic system using either 3.7 have been used successfully as performance. The laboratory is requiredthe external standard technique internal standards, because of their to maintain performance records to(Section 7.3) or the internal standard generally unique retention times. define the quality of data that istechnique (Section 7.4). generated. Ongoing performance
. 7.4. 1 Prepare calibration standards checks must be compared with estab-7.3 External standard calibration at a mjnjmurn of three concentration lished performance criteria to determineprocedure: levels for each parameter of interest as if the results of analyses are within7.3. t Prepare calibration standards described in Section 7 .3. 1 . accuracy and precision limits expectedat a minimum of three concentration , . _ _ •,.•,.• of th8 metnod'
*" Before performing anyi oo 5< ~ usi"9 <he procedures described in a"alyses. the analyst must demonstrate
Sections 65 and 8.8. It is recom- the ability to generate acceptable
«——•—«•..concentration near, but above, the standard compound. The addition of ai>2 |n recognition of the rapidmethod detection limit (See Table 1 ) 1 °»tL.of S advances that are occurring in chroma-. . Mand the other concentrations should *ampls. <» cal'bration standafd would tography, the analyst is permitted cer- , Jcorrespond to the expected range of D" 8('ulvalent to 3O na/L. tain options to improve the separations — r<*-concentrations found in real samples or 7,4,3 Analyze each calibration stand- ** lower the cost of measurements.should define the working range of the ard< according to Section 1 0. adding Eacn tima such modifications are madedetector. These aqueous standards can 1 o UL of internal standard spiking solu- to tne method, the analyst is requiredbe stored up to 24 hours, if held in tion directly to the syringe (Section to reP°at *• Procedure in Section 8.2.sealed vials with zero headspace as , 0.4). Tabulate peak height or area a. 1.3 The laboratory must spike anddescribed in Section 9.2. If not so responses against concentration for analyze a minimum of 1 0% of allstored, they must be discarded after eacn compound and internal standard, samples to monitor continuing labora-one hour. and calculate response factors (RF) for tory performance. This procedure is7.3.2 Analyze each calibration each compound using equation 1 . described in Section 8.4.standard according to Section 1 0, and Eq. , RF , (A,Ci$)/l AitC.) 8.2 To establish the ability to generatetabulate peak height or area responses whera: acceptable accuracy and precision, theversus the concentration in the A . Response for tha parameter to analyst must perform the followingstandard. The results can be used to be measured. operationsprepare a calibration curve for each A;, - Response for the internalcompound. Alternatively, if the ratio of standard. a-2- 1 Select a representative spikeresponse to concentration (calibration c^ m Concentration of the internal concentration for each compound to befactor) is a constant over tha working standard. measured. Using stock standards,range (<1 0% relative standard devia- c, » Concentration of the prepare a quality control check sampletion. RSD), linearity through the origin parameter to be measured. concentrate in methyl alcohol 500can be assumed and the average ratio times more concentrated than theor calibration factor can be used in If the RF value over the working range selected concentrations. Qualityplace of a calibration curve. *« a constant (-si 0% RSD), the RF can control check sample concentrates., , _ _. . . ... .. be assumed to be invariant and the appropriate for use with this method.7.3.3 The working calibration curve average RF can be used for calculations, will be available from the U S.or calibration factor must be verified on Alternatively, the results can be used Environmental Protection Agencyeach working day by the measurement to p|Ot a calibration curve of response Environmental Monitoring and Supportof one or more cal.brat.on standards. If ratjos. A Ai$, vs. RF. Laboratory. Cincinnati, Ohio 45288.the response for any parameter varies .from the predicted response by more 7.4.4 The working calibration curve 3.2.2 Using a syringe, add 1 0 pL of ^than ± 1 0%. the test must be repeated or RF must be verified on each working the check sample concentrate to each \ ****~using a fresh calibration standard. day by the measurement of one or of a minimum of four 5-mL aliquots ofAlternatively, a new calibration curve more calibration standards. If tha reagent water. A representative waste-
\601-4 July 1992
•AR300I3C
water may be used in place of the 8.4 The laboratory is required to and reference standard analyzed.reagent water, but one or more addi- collect a portion of their samples in Prepare a fresh surrogate spiking
"~N tional aliquots must be analyzed to duplicate to monitor spike recoveries. solution on a weekly basis.I determine background levels, and the The frequency of spiked sample
spike level must exceed twice the analysis must be at least 10% of all 9. Sample Collection,background level for the test to be samples or one sample per month. Preservation, and Handlingvalid. Analyze the aliquots according to whichever is greater. One aliquot of thethe method beginning in Section 10. sample must be spiked and analyzed as 9.1 All samples must be iced or
described in Section 8.2. If the refrigerated from the time of collection5.2.3 Calculate the average percent recovery for a particular parameter until extraction. If the sample containsrecovery, (R), and the standard devia- does not fall within the control limits free or combined chlorine, add sodiumtion of the percent recovery (s), for the for method performance, the results thiosulfate preservative (10 mg/40 mLresults. Wastewater background cor- reported for that parameter in all is sufficient for up to 5 ppm CI2) to therections must be made before R and s samples processed as part of the same empty sample bottle just prior tocalculations are performed. set must be qualified as described in shipping to the sampling site. USEPA
•' Section 11.3. The laboratory should methods 330.4 and 330.5 may be8.2.4 Using Table 2, note the average monitor the frequency of data so used for measurement of residualrecovery (X) and standard deviation (p) qualified to ensure that it remains at or chlorine. Field test kits are availableexpected for each method parameter. below 5%. for this purpose.Compare these to the calculated valuesfor Rands. If s=>2por |X-R|=»2p. 8-6 Each day, the analyst must 9.2 Grab samples must be collectedreview potential problem areas and demonstrate through the analysis of in glass containers having a totalrepeat the test. reagent water, that interferences from volume of at least 25 mL. Fill the
' the analytical system are under control, sample bottle just to overflowing in8.3 The analyst must calculate B- l( lc r..nm_onHo,« »hat *K» such a manner that no air bubbles passmethod performance criteria and define *£JJ*<!S!SS£2«2nL throuflh the sample as the bottle isthe performance of the laboratory for a'ory •y ^ f being filled. Seal the bottle so that no
' each spike concentration and parameter SSE 'jS air bubbles are 'rapped in it. Ifbeing measured. method. The specif ic practices that are preservative has been added, shakeg measured. most productive depend upon the vigorously for one minute. Maintain the
1 5.2.5 The U.S. Environmental needs of the laboratory and the nature hermetic seal on the sample bottle until; Protection Agency plans to establish ' SS !£ftSS!!5 'ime <* ana|Ysis-analyzed to monitor the precision of
the sampling technique. When doubt 9.3 All samples must be analyzedexists over the identification of apeak within 14 days of collection.
q'u 10. Sample Extraction andwjtn § djssimi|ar column, specific Qas Chromatographyelement detector, or mass spectrom-
r« H m i n r * . eter must be used. Whenever possible. 10.1 Table 1 summarizes thecontrol limts for method performance. tne |aboratory shou|d perform analysis recommended operating conditions forUpper Control Limit (UCL) « R + 3s of standard reference materials and the gas chromatograph. Included in thisLower Control Limit (LCD - R - 3s participate in relevant performance Table are estimated retention times and
evaluation studies. method detection limits that can bewhere R and s are calculated as in achieved by this method. An exampleSection 8.2.3. The UCL and LCL can 8.7 The analyst should maintain of the separations achieved by Columnbe used to construct control charts'7' constant surveillance of both the per- 1 js shown in Figure 5. Other packedthat are useful in observing trends in formance of the analytical system end columns, chromatographic conditions,performance. The control limits above the effectiveness of the method in or detectors may be used if themust be replaced by method perfor- dealing with each cample matrix by requirements of Section 8.2 are met.mance criteria as they become available spiking each sample, standard andfrom the U.S. Environmental Protection blank with surrogate halocarbons. A 10.2 Calibrate the system daily asAgency. combination of bromochlqromethane, described in Section 7.
2-bromo-l-chloropropane. and 10 3 Adiust the ourae oas (nitroaen5.3.2 The laboratory must develop 1,4-dichlorobutane Is recommended to *"Uf w raTto O mll/rnin0and maintain separate accuracy state- encompass the range of the tempera- Attach tne t jn,et to tne ,ments of laboratory performance for ture program used in this method. From device and set the device to Duraewastewater samples. An accuracy stock standard solutions Prepared as 0 t'n . , , d «t*hstatement for the method is defined as above add a volume to give 7600 M £ , device sample IntroductionR ± s. The accuracy statement should of each surrogate to 45 mL of reagent needlebe developed by the analysis of four water contained in a 50-mL volumetricaliquots of wastewater as described in flask, mix and dilute to volume (15 10.4 Allow sample to come toSection 8.2.2, followed by the calcu- ngffiL], If the internal standard calibre- ambient temperature prior to introduc-lation of R and s. Alternately, the tion procedure is being used, the ing it to the syringe. Remove theanalyst may use four wastewater data surrogate compounds may be added plunger from a 5-mL syringe and attachpoints gathered through the require- directly to the internal standard spiking a closed syringe valve. Open the samplement for continuing quality control in solution (Section 7.4.2). Add 10 n\. of bottle (or standard) and carefully pourSection 8.4. The accuracy statements this surrogate spiking solution directly . the sample into the syringe barrel toshould be updated regularly.*7' into the 5-mL syringe with every sample just short of overflowing. Replace the
601-5 July 19S2 BR3UUI3I
syringe plunger and compress the retention time for a compound can be used to measure concentration levelssample. Open the syringe valve and used to calculate a suggested window above 1 000 x MDL.vent any residual air while adjusting the size; however, the experience of the , .sample volume to 5.0 mL. Since this analyst should weigh heavily in the "'3 '" a Sll?9le 'aboratory (Monsantoprocess of taking an aliquot destroys interpretation of chromatograms. Research), using reagent water andthe validity of the sample for future , _ , , u w t „ u wastewaters spiked at or near back-analysis the analyst should fill a 1 0. 1 1 If the response for the peak ground levels, the average recoveriessecond syringe at this time to protect axceeds the worki"? range of the presented in Table 2 were obtained<9».against possible loss of data Add system, prepare a dilution of the The standard deviation of the measure-1 0.0 fit of the surrogate spiking solu- sample with reagent water from the ment in percent recovery is alsotion (87) and 1 O.O L of the internal allc'uot '" th« second sV""3e and included in Table 2<9i.standard spiking solution (Section reanalyze. 124 The u<s< Environmenta,7.4.2), if applicable, through the valve 11. Calculations Protection Agency is in the process ofbore, then close the valve. conducting an interlaboratory method105 Attach tha svrinaa-svrinaa 11-1 Determine the concentration of study to fully define the performance10.5 Attach the syringe-syringe individual compounds in the sample. of this methodvalve assembly to the syringe valve on K onnwm«noa.the purging device. Open the syringe 11.1.1 If the external standardvalves and inject the sample into the calibration procedure is used, calculatepurging chamber. the concentration of material from the• A a /»• u u i j t peak response using the calibration1 0.8 Close both valves and purge the calibration factor determinedsample for 1 1 .0 * .1 minutes at in Section J32ambient temperature. References
,s..,.A.ys ^ f nse factw RR deter. 2. Bellar> T< A.. and Lichtenberg, J.J.
and begin to temperature program the . rf . s tj 743 d equation 2. Journal American Water Worksgas chromatograph. Introduce the minea '" s>8Cllon •*•» ana «q"™°" "• Associationi 55, 739, ( 1 974).trapped materials to the GC column by Eq. 2. 3. Bellar, T.A., and Lichtenberg, JJ.rapidly heating the trap to 1 80 °C Concentration jig/L - (AsCis>/(A,,)(RF) "Semi-Automated Headspace Analysiswhile backf lushing the trap with an where: of Drinking Waters and Industrialinert gas between 20 and 60 mL/min A, * Response for the parameter to Waters for Purgeable Volatile Organicfor four minutes. If rapid heating of the be measured. Compounds," Proceedings fromtrap cannot be achieved, the gas A,, - Response for tha internal Symposium on Measurement ofchromatographic column must be used standard. Organic Pollutants in Water andas a secondary trap by cooling it to C, * Concentration of the internal Wastewater, American Society for30 °C (subambient temperature, if poor standard. Testing and Materials, STP 688. C.E.peak geometry or random retention mirronram. Van Hall, editor. 1 978.time problems persist) instead of the 1 1 •* RfP°rt results in micrograms "Carcinogens- Working Withinitial I nrnnram t omn«r ati ir » of 45 °C P9r >tBr. When duplicate and Spiked -V y«W"°«*"» »»t»wng winm.t.al program temperature of 45 C. £ £ J Carcinogens." Department o Health.,% r. ,.„_., i. . . _ . , , _u j rvHt=i«»rf^iththj,«mnUr»«.,it« Education, and Welfare, Public Health10.8 Wh,le the trap is be.ng desorbed obtained w.th the sample results. g ^ Cemw fw Djsease Coninto the gas chromatograph, empty the , ., 3 For samp|es processed as part National Institute for Occupationalpurging chamber using the sample in- of a S8t whera tflt spjked samp|e Saf 8ty and Hea|th ,,,30,, No>troduction syringe. Wash the chamber recovery fa||8 outsida of the contro| 77-206, Aug. 1 977.with two 5-mL flushes of reagent ,jmits whicn wera estab|isned according 5. "OSHA Safety and Health Stand-water- to Section 8.3. data for the affected ards. General Industry," (29 CFR109 After desorbing the sample for parameters must be labeled as suspect. 1 9 1 0). Occupational Safety andfour minutes recondition the trap by , 2 Method performance SS Sl l ™*'returning the purge and trap device to (Revised, January. 1 379).the purge mode. Wait 1 5 seconds then 12.1 Tha method detection limit 6. "Safety in Academic Chemistryclose the syringe valva on the purging (MDU is defined as the minimum Laboratories. American Chemicaldevice to begin gas flow through the concentration of a substance that can Society Publication. Committee ontrap. The trap temperature should be be measured and reported with 99% , SZIju !7' * , -'°?« rmaintained at 1 80 °C. After approxl- confidence that the value is above '• Har«b°ok f or A"a'vtical QuahtVmately seven minutes turn off the trap zero.n» The MDL concentrations listed f a™™ in. Wa*e_r and Was,te.w-at8r, „heater and open the syringe valve to jn Table 1 were obtained using reagent Laboratories. EPA-6OO/4-79-0 1 9,stop the gas flow through the trap. water.o» Similar results were achieved ". <S: Environmental Protection Agency,When cool the trap is ready for the USjng representative wastewaters. Tha Environmental Mcjnitormg and Supportnext sample. MDL actually achieved in a given Laboratory -Cincinnati. Ohio 45288,
10.10 Thewidthoftheretention SS """!"*time window used to make identifies- FAS) and 330.5 (Spectrophotometnc,tions should be based upon measure- 1 2.2 This method is recommended DPD) for Chlorine, Total Residual," ^ments of actual retention time variations for use in the concentration range from Methods for Chemical Analysis of Water Lof standards over the course of a day. the MDL up to 1 000 x MDL. Direct and Wastes, EPA 600/4-79-020. U.S. — -Three times the standard deviation of a aqueous injection techniques should be Environmental Protection Agency,
SOI -6 July 1992
AR300I32
Environmental Monitoring and Support Table 1. Chromatographic Conditions and Method Detection LimitsLaboratory—Cincinnati, Ohio 45268,March 1979. Retention Time Method9. "EPA Method Validation Study 23. _______tmin-1_______ Detection LimitMethod 601 (Purgeable Halocarbons)," Parameter____________Column 1____Column 2______>jg/I____Report for EPA Contract 68-03-2856 chloromethane 1.50 5.28 0.08(In preparation). Bromomethane 2.17 7.05 1.18
Dichlorodifluoromethane 2.62 nd 1.81Vinyl chloride 2.67 5.28 0.18Ch/oroethane 3.33 8.68 0.52Methylene chloride - 5.25 10.1 0.25Trichlorofluoromethane 7.18 nd nd1,1-Dichloroethene 7.93 7.72 0.131,1-Dichloroethane 9.30 12.6 O.07trans-1,2-Dichloroethene 10.1 9.38 0.10Chloroform 10.7 12.1 0.051,2-Dichloroethane 11.4 15.4 0.031,1,1-Trichioroethane 12.6 13.1 0.03Carbon tetrachloride 13.0 14.4 0.12Bromodichloromethane 13.7 14.6 0.1O1,2'DicMoropropane 14.9 16.6 O.04trans-1,3-Dichloropropehe 15.2 16.6 0.34Trichloroethene 15.8 13.1 0.12Dibromochloromethane 16.5 16.6 0.091.1,2-Trichloroethane 16.5 18.1 0.02cis-1,3-Dichloropropene 16.5 18.0 0.202-Chloroethylvinyl ether 18.0 nd 0.13Bromoform 19.2 19.2 0.201,1,2,2-Tetrachloroethane 21.6 nd 0.03Tetrachloroethene 21.7 15.0 0.03Chloroberuene 24.2 18.8 O.251,3-Dichlorobemene 34.0 22.4 0.321.2-Dichlorobemene 34.9 23.5 0.151,4-Dichlorobenzene______35.4______22.3_______0.24nd m not determinedColumn t conditions: Carbopack B 60/80 mesh coated with 1 % SP- 1OOO packed inan 8 ft x 0. t in ID stainless steel or glass column with helium carrier gas et 40mUmin flow rate. Column temperature held at 45*C for 3 min. then programmedat 8°C/min. to 220° end held for 15 min.
Column 2 conditions: Porasil-C 100/120 mesh coated with n-octane packedin a 6 ftx 0.1 in ID stainless steel or glass column with helium carrier gas at 40 mUminflow rate. Column temperature held at 50°C for 3 min then programmed at6 °C/min to 170 ° and held for 4 min.
601.7 j iSS2 AR300I33
Tabla 2. Single Operator Accuracy and PrecisionAverage Standard Spike NumberPercent Deviation Range of Matrix -./-
Figure 4. Schematic of purge and trap device — desorb mode
Column: 1% SP-1000 on Carbopack-8Program: 45°C-3 minutes, 8*'/minute to 220°CDetector: Hall 700-A electrolytic conductivity
•"• Z Q-• 114 5 ii
__•_____t •
02 4 S a 10 12 14 16 18 20 22 24 26 28 30 32 34 3S
Retention time, minutes
Flgure 3. Gas chromatogram ofpurgeabte halocarbons
601-10 July 1992
AR300I.36
vvEPA
United States Environmental Monitoring andEnvironmental Protection . Support LaboratoryAgency ' > Cincinnati OH 45268•__________ _________________'___ . . ffci. '••••._______.____________________________-^^
Research and Development ,
Test Method
Purgeable Aromatics—Method 602
1. Scope and Application1.1 This method covers the determi-nation of various purgeable aromatics.The following parameters may bedetermined by this method:Parameter__________________STORET No.__________CAS No.Benzene 34030 71-43-2Chlorobenzene 34301 108-90-71,2-Oichlorobenzene 34536 95-50-11,3-Dichlorobenzene 34566 841-73-1
I Toluene 34010 108-88-31.2 This is a purge and trap gas 1.4 Any modification of this method,chromatographic method applicable to beyond those expressly permitted,
{ the determination of the compounds shall be considered as major modifica-listed above in municipal and industrial tiorts subject to application anddischarges as provided under 40 CFR approval for alternate test procedures136.1. When this method is used to under 40 CFR 136.4 and 136.5analyze unfamiliar camples for any or .--... ^ -•. • "..all of the compounds above, compound *-5 This method Is restricted to useIdentifications should be supported by bv or .""der the euPerv.s.on of analysts
i at least one additional qualitative experienced in the operation,of a purgetechnique. This method describes and trap system and a gas chromato-analytical conditions for a second gas graph and in the interpretation ofchromatographic column that can be chromatograms. Each analyst mustused to confirm measurements made demonstrate the ability to generatewith the primary column. Method 624 acceptable resute wrth this methodprovides gas chromatograph/mass using the procedure described inspectrometer (GC/MS) conditions Section 8.2.appropriate for the qualitative andquantitative confirmation of results for 2. Summary of Methodall of the parameters listed above. „. ,, ........ -, _ ..2.1 An inert gas is bubbled through a1.3 The method detection limit (MDL, 6-mL water sample contained in adefined in Section 12.1 <'») for each specially-designed purging chamber atparameter is listed in Table 1. The MDL ambient temperature. The aromaticsfor a specific wastewater may differ are efficiently transferred from the
V j from these listed depending upon the aqueous phase to the vapor phase. Thev--x nature of interferences in the cample vapor is swept through a eorbent trap
matrix. where the aromatics are trapped. After
£02-1 July 1982AR300I37
purging is completed, the trap is heated treated as a potential health hazard. 5.2.2 The trap must be at least 25and backflushed with the inert gas to From this viewpoint, exposure to these cm long and have an inside diameter ofdesorb the aromatics onto a gas chemicals must be reduced to the at least 0.105 inch.chromatographic column. The gas lowest possible level by whatever 5.2 2. 7 The trap is packed with 1 cmchromatograph is temperature pro- means available. The laboratory is of metny| sj|jcor,e and 23 cm "grammed to separate the aromatics responsible for maintaining a current 2 6.dipheny|ena oxida po|yrner 3Swhich are then detected with a photo- awareness file of OSHA regulations shown in Figure 2 This trap was usedionization detector '2.3>. ' regarding the safe handling of the deve, th. me;hod perforrnanca_ . - . chemicals specified in this method. A .»,..—..».;. o-M\n* 1 •»2.2 The method provides an opt,onal referenct fi£ of materia| data hand|jng statements m Sect,on 12.gas chromatographic column that may sheets shou)d also be made avai|ab|a to 5.2.2.2 Alternatively, either of thebe helpful in resolving the compounds a,( personne| involved in the chemical two traps described in Method 601of interest from interferences that may ana|ysj$. Additional references to may be used, although water vapor willoccur. laboratory safety are available and preclude the measurement of low3 Interferences have been identifiedU-ai for the concentrations of benzene.
information of the analyst. 5.2.3 The desorber must be capable3.1 mpunt.es .n the purge gas and ,rtlUuuiM naram.tar« „„ „ of rapidly heating the trap to 180 °C.organic compounds out-gassing from 4.2 The following parameters covered Tha noh»mar *Mtien of tr»the plumbing ahead of the trap account by this method have been tentatively Sff& T Afor the majority of contamination classified as known or suspected. «J £JjJJ scions shoud noproblems. The analytical system must human or mammalian carcinogens: exceed 200 °C The desorber designbe demonstrated to be free from benzene and 1,4-dichlorobenzene. illustrated in Figure 2. meets thesecontamination under the conditions of rnmary standards ot these toxic criteriathe analysis by running laboratory compounds should be prepared in areagent blanks as described in Section hood. An NIOSH/MESA approved toxic 5.2.4 The purge and trap device may8.5. Tha use of non-TFE plastic tubing, gas respirator should be worn when the be assembled as a separate unit or benon-TFE thread sealants, or flow analyst handles high concentrations of coupled to a gas chromatograph ascontrollers with rubber components in these toxic compounds. illustrated in Figures 3. 4, and 5.the purging device should be avoided. _ M«*«ri,i. 5-3 Gas chromatograph-Analytical3.2 Samples can be contaminated by 5< Apparatus and Materials sy,tem complete with a temperaturediffusion of volatile organics through programmable gas chromatographthe septum seal into the sample during 3.1 Sampling equipment, for discrete suitable for on-column injection and allshipment and storage. A field reagent sampling. required accessories including syringes,blank prepared from reagent water and .-.„,,--, ^ , analytical columns, gases, detector,carried through the sampling and 3- *•' Vial- 25-mL capacity or larger, and stripchart recorder. A data systemhandling protocol can serve as a check equipped with a screw cap with hole in is recommended for measuring peakon such contamination/ «nt«r 'Pierca *13.075 of aqulvalant). areas.Detergent wash, rinse with tap and3.3 Contamination by carry-over can distilled water, and dry at 105 °C 5-3-* Column 1 - 6 ft long x 0.082occur whenever high level and low before use. in ID stainless steel or glass, packedlevel samples are sequentially with 5% SfM 20° and 1 -75%analyzed. To reduce carry-over, the S. 1.2 Septum—Teflon-faced silicone Bentone-34 on Supelcoport (100/120purging device and sample syringe (Pierce #12722 or equivalent). mesh) or equivalent. This column wasmust be rinsed with reagent water Detergent wash, rinse with tap and used to develop the method perfor-between sample analyses. Whenever distilled water, and dry at 105 °C for mance statements and the MDLs listedan unusually concentrated sample is one hour before use. in Tables 1 and 2. Guidelines for theencountered, it should be followed by us* of alternate column packings arean analysis of reagent water to check s-* *»8» and tra.P device-The provided in Section 10.1..for cross contamination. For samp.es . 1 ^ 3.3.2 Column 2-8 ft .ong x 0.1 incontaining large amounts of water- JJP«tiSS ratTXTe desorber «> stainless steel or glass, packed withsoluble materials, suspended solids, "Jjjj SSSirSinS?e now 5* 1.2.3-Tris(2-cvanoethoxy)ProPanehigh boiling compounds or high fjmmeSJ available °" Chromosorb W-AW (60/80 mesh)aromatic levels, it may be necessary to commercially avaiiawe. or equivalent.wash out the purging device with a _ _ , _. .,__,. _,„_„ _,,., »,.detergent solution, rinse it with distilled *2:' J™ ™£*Z3 ZZ?. ith 3'3'3 °«tector- Photoionizationwater, and then dry it in an oven at des'9"ed *? !S?ta !l"** detector <n-nu Systems. Inc. Model105 °C between analyses. The trap awater column at least 3 cm deep. p,.5. ,02 or equivalent). This typ* ofandI othar panl10 TtheTsystem are also ™* 9as8OUS head s,?a" batwee!:th(> detector has been proven effective inLSect« li!; n . rsr ± 1 Kt"STa *•anaivsi$°f™«™*«**»*•frequent bakeout and purging of the J± J Jlli tllS.. Parameters listed in the scope, andentire system may be required. purs* gas T * pi"J i J I was used to develop the performancesystem may oerequ column as finely divided bubbles with a statements in Section 12! Guidelines4. Safety diameter of less than 3 mm at the for the use of alternate detectors are
^ or.g.n. The purge gas must be mtro- provided in Section 10.1.4.1 The toxicity or carcinogenicity of duced no more than 5 mm from theeach reagent used in this method has base of tha water column. The sample 5.4 Syringes—5-mL glassnot been precisely defined; however. purger, illustrated in Figure 1, meets hypodermic with Luerlok tip (twoeach chemical compound should be these design criteria. if applicable to the purge device.
502-2 HR300138
6.5 Micro syringes- 2 5 j/L, 0.006 in flask to stand, unstoppered, for about 7.2 Connect the purge and trapID needle. 1 0 minutes or until all alcohol wetted device to a gas chromatograph. The
-2-vuiiv with i nor surfaces have dried. Weigh the flask to gas chromatograph must be operated2way'wlthLuer the nearest 0.1 mg. using temperature and flow rate
--,,,. ,rtrt . . parameters equivalent to those in Table6.7 Bottle- 1 5-mL ccrew-cap with f'6'L lL two « ™ *nn« of 1 ' Calibrate the pur0e and trap-BasTeflon cap liner. immediately add two or more drops of chromatographic system using either
P "»V«d reference matenal to the flask, the extern*, £andayrd techniq«e6.8 Balance- Analytical, capable of then reweigh. Be sure that the drops (SectJon 7 3} 0{ tne jnterna, standar<Jaccurately weighing 0.0001 g. 'all directly into the alcohol without techniaue (Section 74)
contacting the neck of the flask. ' ' '6. Reagents . 7.3 External standard calibration
6.6.3 Reweigh, dilute to volume, nrocedure-6.1 Reagent water— Reagent water is stopper, then mix by inverting the flaskdefined as a water in which an inter- several times. Calculate the concentre- 7.3. / Prepare calibration standards'f erent is not observed at the MDL of tion in micrograms per microliter from at a minimum of three concentrationthe parameters of interest. the net gain in weight. When compound levels for each parameter by carefullyK i * a - L, purity is certified at 96% or greater, adding 20.0 fil of one or more second-!,lr.« ,t H * -I . the we'flht can be used without correc- ary dilution standards to 1 00. 600, orgenerated by .Passing tap water tjon to calcu|ate the concentration of 1 000 mL of reagent water. A 25-/iLIK« tfli i"h ?°n*- f ' ?' "ntainin9 the stock standard. Commercially syringe with a 0 006 inch ID needle/CH. K-ffti? • C, °,o , prepared stock standards can be used, should be used for this operation. One(Filtrasorb-300 or equivalent (Calgon ^ any eoncentration, if they are of the external standards should be at a10 P.M. certified by the manufacturer or by an concentration near, but above, the6.1. 2 A water purification system independent source. MDL (see Table 1 ) and the other(Millipore Super-Q or equivalent) may 664 Transfer the stock standard concentrations should correspond tobe used to generate reagent water. f0Lion inS a Teflon lealed Sew can the exPected ran8e of concentrationssolution into 8 ' "ion-sealed screw-cap found jn rea| samples or should definee. 1.3 Reagent water may also be bottle. Store at 4 °C and protect from the working ranfle of thc detector.prepared by boiling water for 15 I'flht. These aqueous standards must beminutes. Subsequently, while main- 666 A|| 8tandards must be rep|aced prepared fresh daily.taking the temperature at 90 «C, after one month, or sooner if compari- -,- Ana)tf.e _ach Mlibrlltionbubble a contaminant-free nert gas «„ uh _h,w.i, *t.n*arric innate . 7-3-2 Analyze each calibrationthrough the water for one hour. While £££? Che<* standards indicate a standard according to Section 1 0, andctill hot, transfer the water to a narrow ProDiem- tabulate peak height or area responsesmouth screw-cap bottle and seal with a 6.7 Secondary dilution standards— versus the concentration in theTeflon-lined septum and cap. Using stock standard solutions, prepare standard. The results can be used to«<> e ^ w, » ,.-c. secondary dilution standards in methyl prepare a calibration curve for eache.Z sodium thiosuitate-(ACS) alcohol that contain the compounds of compound. Alternatively, if the ratio ofGranular. Interest, either singly or mixed response to concentration (calibration6.3 Hydrochloric acid (1+1)- Add together. The secondary dilution factor) is a constant over the working50 mL of concentrated HCI to 50 mL standards should be prepared at «nge ( : -=1 0% relative standard devia-of reaaent water concentrations such that the aqueous *on, RSD), linearity through the origin
calibration standards prepared in can be assumed and the average ratio6.4 Trap Materials Sections 7.3.1 or 7.4.1 will bracket or calibration factor can be used inG 4 1 2 6-Oiphenylene oxide *** worWng range of the analytical P'ace of a calibration curve.polymer-Tenax, (60/80 mesh) chroma- «ystem- Secondary solution standards ?33 ^ workfna calibration curvetographic grade or equivalent. mu?t e *J°1[ed wit? "rf "eadspace or ca|ibration f actor must be verif ied on** I J K , -,. wn,* •""• *h«UJd be =h8cked fre"uent'y f<>r each worki da b the measurement6.4.2 Me«\V 'cone-3% OV-1 on s,gns of degrada, on or evaporation, Of one or more calibration standards. IfChrpmosorb-W (60/80 mesh) or especially just prior to preparing ^ „ e for parameter varieset»uivalent- calibration standards from them from the predicted response by more
l be Alternatively, a new calibration curve6.6 Stock standard solutions-Stock available from the U.S. Environmental or calibration factor must be preparedstandard solutions may be prepared Protection Agency, Environmental for tnat parameter.from pure standard materials or Monitoring and Support Laboratory, in **purchased as certified solutions. Cincinnati. Ohio, 7.4 Internal standard calibrationPrepare stock standard solutions in _ ^ procedure. To use this approach, themethyl alcohol using assayed liquids. 7. Calibration analyst must select one or moreBecause benzene and 1 ,4-dichloro- < internal standards that are similar inbenzene are suspected carcinogens, 7- 1 Assemble a purge and trap analytical behavior to the compoundsprimary dilutions of these materials- device that meets the specifications in of interest. The analyst must furthershould be prepared in a hood Section 5.2. Condition the trap over- demonstrate that the measurement of
' night at 1 80 °C by backflushing with the internal standard is not affected by6*. 6. 1 Place about 9.8 mL of methyl an inert gas flow of at least 20 ml/min. method or matrix interferences.alcohol into a 1 0-mL ground glass Prior to use, daily condition traps 1 0 . Because of these limitations, nostoppered volumetric flask. Allow the minutes while backflushing at 1 80 °C. internal standard can be suggested that
602-3 July 1982
AR3uGI39
is applicable to all samples. The an initial demonstration of laboratory results. Wastewater background cor-compound, a ,a,a-trif luorotoluene, capability and the analysis of spiked rections must be made before R and srecommended as a surrogate spiking samples as a continuing check on calculations are performed. x*compound in Section 8.7 has been performance. The laboratory is required .....used successfully as an internal to maintain performance records to * *•* Usm9 Tabl8 2, note the ,standard. define the quality of data that is average recovery (X) and standard \^/
generated. Ongoing performance checks delation (p) expected for each method7.4. 1 Prepare calibration standards must ba compared witn established parameter. Compare these to theat a minimum of three concentration performance criteria to determine if the calculated values for R and s. If s =»2plevels for each parameter of interest as rasults of anarysas ar. witnin accuracy or |X - R| =» 2p. review potentialdescribed in Section 7.3.1 . and pr8CjSj0n |imjts expected of the problem areas and repeat the test.7.4.2 Prepare a spiking solution con- method. 3.2.5 The U.S. Environmentaltaining each of the internal standards a , y Befort perforrning any analyses. Protection Agency plans to establishusing the procedures described in Sec- the ana|yst must demonstrate the performance criteria for R and s basedtions 8.8 and 6.7. It is recommended abi|JW to generate acceptable accuracy UP°" tha results of interlaboratorythat the secondary dilution standard be and VTW^mn witn this method. This testir>9- When thav become available,prepared at a concentration of 1 5 u.g/mL abj|jtv j$ e$tab|ished as described in tne$B criteria must be met before anyof each internal standard compound. Section 8 2. samples may be analyzed.The addition of 1 0 u.L of this standardto 5.0 mL of sample or calibration 8. 1.2 In recognition of the rapid 8-3 ""• analyst must calculatestandard would be equivalent to advances that are occurring in chroma- method performance criteria and define30 /ug/L. tography. the analyst is permitted the performance of the laboratory for
„,.,., certain options to improve the each spike concentration and parameter7.4.3 Analyze each calibration separations or lower the cost of being measured.
LSS S S' measurements. Each time such a 3. , calculate upper and lowersolStten dSecSv to "to swing. ™difica'i°I?» ara mad* to tha rnathod- control limits for method performance:solution directly to tne syringe ^ analyst is required to repeat the
I as indicated in Section 1 0.4. Tabulate procedure in Section 3 2 Upper Control Limit (UCL) - R -I- 3speak height or area responses against Lower Control Limit (LCD - R - 3sconcentration for each compound and 8. 1.3 The laboratory must spike and
1 internal standard, and calculate analyze a minimum of 1 0% of all where R and s are calculated as inresponse factors (RF) for each com- samples to monitor continuing Section 8.2.3pound using equation 1 . laboratory performance. This procedure Th§ UCL and LCL cgn bB used to
Eq. 1 RF - (A.Cj.WAi.C.) to described in Section 8'4' construct control charts'" that are use- / *' where: 8-2 To establish the ability to ful in observing trends in performance, x /» A, - Response for the parameter to generate acceptable accuracy and The control limits above must be N —
be measured. precision, the analyst must perform the replaced by method performanceAJ, m Response for tha internal following operations. criteria as they become available from
1 standard » <. . . , , •,_ the U.S. Environmental Protection
measured. Using stock standards. A3. 2 The laboratory must developC, - Concentration of the prepare a quality control check sample and maintain separate accuracy state-
parameter to be measured. concentrate in methyl alcohol 500 ments of laboratory performance forIf the RF value over the working range times more concentrated than tha wastewater samples. An accuracyis a constant ( -«1 0% RSD), the RF selected concentrations. Quality statement tor the method is defined as
I can be assumed to be invariant and the control check sample concentrates, R ± s. The accuracy statement shouldaverage RF can be used for calculations, appropriate for use with this method. b« developed by the analysis of fourAlternatively, the results can be used will be available from the U.S. aliquots of wastewater as described into plot a calibration curve of response Environmental Protection Agency. Section 8.2.2. followed by theratios A JA*. vs RF Environmental Monitoring and Support calculation of H and s. Alternately, the
' Laboratory, Cincinnati, Ohio 45268. analyst may use four wastewater data7.4.4 The working calibration curve points gathered through the requirementor RF must b» verified on each working 3.2.2 Using a syringe, add 1 0 wL of for continuing quality control in Sectionday by the measurement of one or the check sample concentrate to each 3.4. The accuracy statements shouldmore calibration standards. If the of a minimum of four 5-mL aliquots of be updated regularly<7>.response for any parameter varies from reagent water. A representative waste-^predicted response by more than water may b. used in place of the± 1 0%. the test must be repeated reagent water, but one or more addi-using a fresh calibration standard. tional aliquots must be analyzed toAlternatively, a new calibration curve determine background levels, and the vbt VB% of allmust be prepared for that compound. spike level must exceed twice the »«8. Quality Control n whichever is greater. On. aliquot of the
*h. mothnH haninninn in Qiwtinn i n sample must be spiked and analyzed as8.1 Each laboratory that uses this the method beginning ,n Section 1 0. described in Section 8.2. If the -method is required to operate a formal 3.2.3 Calculate the average percent recovery for a particular parameter \ Lquality control program. Tha minimum recovery, (R). and the standard devia- does not fall within the control limits ~~r~'requirements of this program consist of tion of the percent recovery (s), for the for method performance, the results
6O2-4 July 1992
AR3UOUO
reported for that parameter in all to measure residual chlorine<8». Field 10.6 Close both valves and purge thesamples processed as part of the same Test Kits are available for this purpose. sample for 12.0 ± 0.1 minutes at
-v set must be qualified as described in Knn , , . ambient temperature.J Section 11.3. The laboratory should 9'* Collect about 500 mL sample in ,.,.....,„.T monitor the frequency of data so 8 clean container. Adjust the pH of the 10.7 After the 12-minute purge time,
V ./' qualified to ensure that it remains at or 8amP|e to about 2.by adding 1+1 HCI d.sconnect the purge chamber from the"~" below 5% whlle 8t|rring gently. Fill the sample trap. Dry the trap by maintaining a flow
bottle in such a manner that no air of 40 mL/min of dry purge gas through8.6 Each day, the analyst must . bubbles pass through the sample as the jt for six minutes. See Figure 4. A drydemonstrate through the analysis of bottle is being filled. Seal the bottle so purger should be inserted into thereagent water, that interferences from that no air bubbles are entrapped in it. device to minimize moisture in the gas.the analytical system are under control. Maintain the hermetic seal on the Attach the trap to the chromatograph,fi fi it •« r.r.«mmj, H H th.« *h. sample bottle until time of analysis. adjust the device to the desorb mode.8.6 It is recommended that the r and begin to temperature program thelaboratory adopt additional quality 9.3 All samples must be analyzed gas chromatograph. Introduce theassurance practices for use with this within 14 days of collection-^) trapped materials to the GC column bymethod. The specific practices that are Samnla Extraction and rapidly heating the trap to 180 »Cmost Productive depend upon the ™- r? _!n™V"5j 8"d while backflushing the trap with an
j needs of the laboratory and the nature Gas Chromatography inert gas between 20 and 60 mL/minof the samples. Field duplicates may be «Ummari™s the for tour minutes. If rapid heating—•»—<"—— -J *•— —__r*— **-,— n-Af»it>tAn ftl • V* I I Bute I »UmfTianZe$ InC . . . . . 9
* When doubt recommended operating conditions for cannot be achieved the gas" , Jgak the gas chromatograph. Included in this SS rm eo itto
rif COnTiriTio iOry ji « • >•. .a < ^IO Q^ /ci irSflfnhiOjnt fflfnrtArflf nr^ if nnnr' method detection limits that cfln hp ^ ^* isuDarnuieni tcrnpcraiure, u pour
element detector, or mass spectrometer ." ^ S" nitialVogram temperature of 50 «C.must be used Whenever possible the ' shown in Figure o. other packed r " *laboratory should perform analysis of columns, chromatographic conditions, 10.8 While the trap is being desorbedstandard reference materials and or detectors may be used if the onto the t3C column, empty the
S££. rnt pcrformance requirements are met< ySSSSSS SSevaluation stuoies. 10.2 Calibrate the system daily as chamber with two 5-mL flushes of8.7 The analyst should maintain described in Section 7. reagent water.constant surveillance of both the per- 10.3 Adjust the purge gas (nitrogen 10.9 After deserting the sample forformance of the analytical system and or helium) flow rate to 40 mL/min. four minutes, recondition the trap bythe effectiveness of the method in Attach the trap inlet to the purging returning the purge and trap device todealing with each sample matrix by device, and set the device to purge. the purge mode. Wait 15 seconds thenspiking each sample, standard and open the syringe valve located on the close the syringe valve on the purgingblank with surrogate compounds (e.g. purging device sample introduction device to begin gas flow through theo.o.a.-trifluorotoluene). From stock needle. trap. The trap temperature should bestandard solutions prepared as above, ,AJ. ... maintained at 180 "C. After approxi-add a volume to give 7500/jg of each ™ Allow sample to come to mately seven minutes, turn off the trapsurrogate to 45 mL of organic-free fTi! L .mpf • PB ir*f°duc- heater and open the syringe valve towater contained in a 60-mL volumetric ing rt into the syringe. Remove the stop the gas flow through the trap.flask, mix and dilute to volume (15 plunger from a 6-mL syringe and attach When co", thfl |$ read f thflng/juU. If the internal standard calibra- a closed syringe valve. Open the next sampletion procedure is being used, the sample bottle (or standard) and care- Th-'-wts „* th- »*„„*„„surrogate compounds may be added f"»V pour the sample Into the syringe \OM The width of the retentiondirectly to tneintemal standard spiking barrel to just short of overflowing. time window used to make identifica-solution (Section 7.4.2). Dose 10 «uL Replace the syringe plunger and tions should be based upon measure-of this surrogate spiking, solution compress the sample. Open the syringe ""ents of actual retention time variations•Sirectly intotheTs-mL.syringe with valve and vent any residual air while of standards over the course of a day.every sample and reference standard adjusting the sample volume to 5.0 Three times the standard deviation of aanalyzed Prepare a fresh surrogate mL Since this process of taking an retention time for a compound can bespiking solution on a weekly basis. aliquot destroys the validity of the used to calculate a suggested window
' sample for future analysis, the analyst size; however, the experience of thea c. r.1-r»«n-r.*««« should fill a second syringe at this time analyst should weigh heavily in the». bampie collection, to protect agajn$t possible loss of data, interpretation of chromatograms.Preservation, and Handling Add 10.0 ML of the surrogate spiking 10.11 if the response for the peakfi 1 The tamoles must be iced or solution (Section 8.7) and 10.0 fiL of . exceeds the working range of the«Vlrteerated fTom Jhe time of?ollection the internal standard 8pikin° solution «V«em. prepare a dilution of thercTrigcraiCu TroiTi ine lime OT collection !€«.«»**«•» A oi it *M»«|I*«*IHIA »!*••«*• .«*i« ... • * . *until extraction. If the sample contains |£ J ? Ihln £* t£ «. sample with reagent water from thefree or combined chlorine, add sodium the valve bore'then close the valve' *W«in th* «cond synnge andthiosurfate preservative (10 rng/40 mL 10.6 Attach the syringe-syringe reanalyze.is sufficient for up to E ppm Clj) to the valve assembly to the syringe valve on 11. Calculationsempty sample bottles just prior to the purging device. Open the syringeshipping to the sampling site. USEPA valves and inject the sample into the - 11.1 Determine the concentration ofMethods 330.4 or 330.5 may be used- purging chamber. individual compounds in the sample.
602-5 July 1582
AR300IM
11.1.1 If the external standard call- References. bration procedure is used, calculate the• concentration of material from the peak 1 • See Appendix A.
response using the calibration curve or 2. Bellar, T.A., and Lichtenberg, J. J.calibration factor determined in Section Journal American Water Works7.3.2. Association, 66, 739. (1974).
. ., 3. Bellar, T.A., and Lichtenberg. J.J.1 1. 1.2 If the internal standard call- "Semi- Automated Headspace Analysisbration procedure was used, calculate of Drjnking Waters and Industrialthe concentration in the sample using Waters for Purgeable Volatile Organicthe response factor (RF) determined in Compurids," Proceedings of Sym-Section 7 .4. 3 and equation 2 . posium on Measurement of Organic£_ 2 Pollutants in Water and Wastewater.Concentration pg/L - (A.Ci.WAj.HRF) American Society for Testing andwhere: Matenals, STP 688, C.E. Van Hall,A, - Response for the parameter to editor, 1978. ....,.._
be measured. 4. "Carcinogens-Working withA,, - Response for the internal Carcinogens," Department of Health,
standard Education, and Welfare, Public HealthCj, - Concentration of the internal Service. Center for Disease Control.
standard. National Institute for OccupationalSafety and Health. Publication No.
11.2 Report results in micrograms 77-206. August 1 977.per liter. When duplicate and spiked 5. "OSHA Safety and Healthsamples are analyzed, report all data Standards, General Industry." (29 CFRobtained with the sample results. 1910). Occupational Safety and
Health Administration, OSHA 2206,11.3 For samples processed as part (Revised January 1 97 6).of 9 set where the spiked sample 6. "Safety in Academic Chemistryrecovery falls outside of the control Laboratories," American Chemicallimits which were described in Section Society Publication, Committee on8.3, data for the affected parameters Safety, 3rd Edition, 1 979.must be labeled as suspect. 7. "Handbook for Analytical Quality
Control in Water and Wastewater12. Method Performance Laboratories." EPA-600/4.79.01 9,
U.S. Environmental Protection Agency.12.1 The method detection limit Office of Research and Development,(MDL) is defined as the minimum con- Environmental Monitoring and Support
1 centration of a substance that can ba Laboratory, Cincinnati. Ohio 45268.measured and reported with 99% March 1979.confidence that the value is above 8. "Methods 330.4 (Titrimetric, DPD-zerol'l. Tha MDL concentrations listed FAS) and 330.5 (Spectrophotometric,in Table 1 were obtained using reagent DPW for Chlorine. Total Residual."water<9». Similar results were achieved Methods for Chemical Analysis of
- using representative wastewaters. Water and Wastes, EPA 600/4-79-020.U.S. Environmental Protection Agency.
I 12.2 This method has been demon- Office of Research and Development,strated to be applicable for the concen- Environmental Monitoring and Supportnation range from the MDL up to 1 000 Laboratory. Cincinnati, Ohio 45268.x MDL<9>. Direct aqueous injection March 1 979.
i techniques should be used to measure 9. "EPA Method Validation Study 24,concentration levels above 1 000 x Method 802 (Purgeabla Aromatics)."
' MDL Report for EPA Contract 68-03-2858(In preparation).
i 12.3 In a single laboratory (Monsanto] Research), using reagent water and( wastewaters spiked at or near
background levels, tha average< recoveries presented in Table 2 were| obtained*9'. Tha standard deviation of' tha measurement in percent recovery is
also included In Table 2.
! 12.4 The Environmental Protectioni Agency is in the process of conducting
an intartaboratory method study tofully define the performance of this
i method.
502-5 July 1992
4R300U2
\
Table 1. Chromatographic Conditions end Method Detection Limits•fk
Retention Time Method'______tmin->________ Detection Limit
1.75% Bentone-34 packed in a 6 ft. x 0.065 in ID stainless steel column withhelium carrier gas at 36 cc/min flow rate. Column temperature held at 50"C for 2min. then programmed at 6°C/min to 90"Cfora final hold.
Column 2 conditions: Chromosorb W-AW 60/80 mesh coated with 5%1,2,3-Tris(2-cyanoethyoxy)propane packed in a 6 ft. x 0.055 in ID stainlesssteel column with helium carrier gas at 30 cc/min flow rate. Column temperatureheld at 40"C for 2 min then programmed at 2 °C/min to 100°C fora final hold.
Table 2. Single Operator Accuracy and PrecisionAverage Standard Spike NumberPercent Deviation Range of Matrix
4-6' Same as above, damp, firm, slight odor. .-.._.(I1) loose f/c subangular GRAVEL, dense, saturated, -strong odor *
6-8' Dk. brown clayey SILT and f/c subrounded GRAVEL ....dense, damp, strong odor.
8-10 r Same as above ——dense, damp, slight odor. .— ~
N.B. Samples 2-4', 6-8' and 8-10' submitted for volatileorganic analysis.
The ERM Group
BACKHOE TRENCH LOGS
BT-1 0 to 4 ft Red brown fine sandy and clayey siltwith coarse subangular gravel. Highlymottled. Medium dense. Slight odor.
4 to 7 ft Same, with numerous large sandstoneslabs up to 2 feet in diameter. Odor-ous.
BT-2 0 to 2.5 ft Red-brown clayey silt with some sand andfine to medium gravel. Seeps at 1.5feet. Highly mottled. No odor.
2.5 to 5 ft Red-brown silt and fine to medium gravelwith large sandstone slabs up to 2 feetin diameter. Highly mottled. Someseepage zones. No odor.
5 to 7 ft Brown silty clay/clayey silt with somegravel and sandstone slabs. Dense. Noodor.
^BT-3 0 to 3 ft Yellow-brown sandy and clayey silt withtrace of fine to medium gravel. Looseto medium firm. Some wet areas. Noodor.
3 to 5 ft Red-brown silt and fine to medium gravelwith sandstone slabs up to 8 inches indiameter. Highly mottled. Dense. Noodor.
5 to 8 ft Same, with increased mottling andmoderate odor.
BT-4 0 to 1.5 ft Brown coarse sandy silt fill. No odor.
1.5 to 2 ft Black fill. Odorous, with seepage atbottom. Water oily.
2 to 5 ft Red-brown silt and fine to medium gravelwith some large sandstone slabs. Highlymottled. Some seeps. Dense.
5 to 7 ft Red-brown silt with fine to coarsegravel. Fewer sandstone slabs. Dense.Dry. Slight odor. , >
AR3002U
The ERM Group
BT-5 0 to 3 ft Yellow-brown silt with some sand andfine to medium gravel. Highly mottled.Wet. Loose to medium firm. No odor.
3 to 4 ft Red-brown silt with sand, fine to mediumgravel, and large sandstone slabs. Wet.Highly mottled. No odor.
4 to 6 ft Red-brown silt with trace of clay andsome fine to medium gravel and sandstoneslabs. Mottled. Dense. No odor.
BT-6 0 to 1 ft Soil
1 to 1.5 ft Yellow-brown silt with fine to mediumgravel. Looks like fill. Mottled.Moist. Loose. No odor.
2.5 to 4.5 ft Red-brown silt with fine to mediumgravel and sandstone boulders. Highlymottled. Moist. Medium dense. Plasticpipeline at 4.5 feet. Pipeline backfillwet.
4.5 to 5 ft Red-brown silt with some fine to mediumgravel and few sandstone slabs. Verydense. Dry.
BT-7 0 to .5 ft Soil
.5 to 1.5 ft Black soil and metal fill. Odorous.Crossed former drain pipe at 1.5 feet.Pipe backfill saturated. Water collect-ed in pit.
1.5 to 3.5 ft Red clayey silt with fine to mediumgravel. Loose. Looks like fill.Odorous at west end of pit. East end,large sandstone boulders. Looks likefill.
BT-8 0 to .5 ft Miscellaneous fill. Railroad ties.
.5 to 1.0 ft Black odorous fill.
1.0 to 4 ft Red-brown silt and fine to mediumgravel. Dense. Appears to be natural.Odorous. Some wet zones.
BT-9 0 to 4 ft Large flat sandstone boulders with somesilt. Fill.
&R3G02I5
..,« cftM Group
4 to 5 ft Gray clayey sand and gravel. Appears tobe fill. Wet. Strong odor.
BT-10 0 to 1 ft Miscellaneous fill.
1 to 2 ft Black oily fill. Odorous.
2 to 3 ft Brown clayey fill.
3 ft Gray gravel and silt fill. Strong odor.
BT-11 0 to 3 ft Large flat sandstone boulders with somesilt. Fill. Slight odor.
3 to 5 ft Brown silt and gravel. Appears to befill. Slight odor.
BT-12 0 to 3.5 ft Large flat sandstone boulders. Fill.
3.5 to 5 ft Gray clayey and silty gravel. Lookslike fill. Slight odor.
BT-13 0 to 1.5 ft Old railroad bed fill. Wood, ties,brick. Silty soil.
1.5 to 2.5 ft Red-brown silt and gravel fill. Slightodor.