Praktikumsprotokoll IEG 2013 Mueller281614

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Inorganic EnvironmentalGeochemistryPractical Course Report

by Simon Müller

matriculation number 281614

[email protected]



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Contents 1. Introduction

2. Grain size distribution

3. Sample Preparation

4. pH-Value Determination

5. Electrical Conductivity

6. REE-Analyses with LA-ICP-MS

7. Loss on ignition

8. Fused Disc for XRF

9. Ion-selective Electrode (ISE)

10. Determination of elements in solution (ICP-OES/MS)

11. Sequential Extraction

12. Tl-Species

13. Sulphur measurement

14. Analysis of particulate matter, pressed powder pellet, XRF

15. Analysis of Pb-isotope ratios, data interpretation, acid neutralization capacity



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1. Introduction

In the practical course for “Inorganic Environmental Geochemistry” construction material from the

city of Stolberg was investigated geochemically. The following descriptions of the experiments and

their results occur in chronologically sorted succession.

2. Grain size distribution

In order to determine the grain size distribution, the sample was grain sieved after DIN ISO 11464

(DIN-HB 2.4a). As preparation the sample had been dried at 105°C to lose all adsorbed water. At first

non-soil-materials like roots, twigs and anthropogenic substances were sorted out. Then

aggregations of grains were broken up in a small agate mortar and the total sample was weighed.

After that the whole sample was sieved with a sieving tower consisting of individual sieves with

different mesh apertures (Tab. 1). The smallest fraction (<0.063mm) was collected in a bowl. It was

not further separated because it would have required considerable additional expenses. Using

vibration (~10min) the single grain size fractions were separated. Each fraction was weighed

subsequently after some waiting time for the dust to settle. The results are shown in Tab. 1 and as a

grain size distribution curve in Fig. 1.

mesh aperture (mm) residuals - (g) residuals - share (w%)residuals- summed share

(%)

> 4 89 31,90 100,00

4 - 2 42 15,05 68,10

2 - 1,12 52 18,64 53,05

1,12 - 0,63 36 12,90 34,41

0,63 - 0,25 36 12,90 21,51

0,25 - 0,112 13 4,66 8,60

0,112 - 0,063 5 1,79 3,94

< 0,063 6 2,15 2,15

total 279 100 0



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3. Sample Preparation

The fraction <2mm was now prepared for further investigation. To get representative results the

fraction was milled in a rotating disc mill. Before that the mill was cleaned with laboratory grade sea

sand (SiO2) and water. To accelerate the drying procedure, ethanol was used.

As mill material of choice wolfram-carbide and agate were available. Wolfram carbide would have

increased the values of the milled sample of e.g. wolfram, carbon and also cobalt and tantal. In an

investigation of heavy metals that would have been a disadvantage. Because agate just increases the

SiO2 content, it was chosen. In respect to the brittleness of agate only 7g at once (ca.10g in total) of

the fraction of <2mm was milled for not longer than 30sec until its rigidity was flour-like.

A ceramic crucible was roasted at 1000°C for 10min in a muffle furnace. The roasted crucible was

kept in an exsiccator. The cooled down crucible was then weighed (19.8272g).

Following this, the sample was dried at 105°C for 24h to lose the adsorptive bound water. At a higher

temperature also the water structurally bound to clay minerals would have been lost. The crucible

0

10

20

30

40

50

60

70

80

90

100

s u m m e d s h a r e ( % )

Mesh Aperture (mm)

Sieving Line Diagramm



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cooled down again in an exsiccator until it reached room temperature. The weight of the crucible

with the sample inside was determined.

4. pH-Value Determination

The pH-value of the soil-sample was determined after DIN 19 684 part 1. At first a 0.01 M CaCl2

solution was prepared by mixing 0.147 g CaCl2 with 100ml of distilled water. Then 10g of air dried

sample was admixed with 25ml of the solution. The mixture was stirred intensively and then left to

stand for one hour. Before the measurement the solution was stirred again and then filtrated. The

same procedure was conducted for a solution without the sample to detect the blank value. The

measuring itself was carried out on the filtrate with a calibrated single-rod measuring cell. The resultswere as followed:

. pH at 25°C

Blank Value 5.85

Sample 5.37

5. Electrical Conductivity

The electrical Conductivity measurement was conducted after DIN ISO 11265. Therefore 20g of the

air dried sample were mixed with 100ml of distilled water (conductivity <0.2 mS/m) in a 250ml bottle

and then stirred with a horizontal-shaker with 180 movements per minute for half an hour. After that

the suspension was filtrated and the conductivity measured. Once more a blank value was

determined after the same procedure that was subtracted from the sample value to get the real

conductivity (Sample corrected) of the soil:

. Conductivity (µS/cm) Temperature

Blank Value 14.2 18.1

Sample 162.1 18.2

Sample corrected 147.9



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6. REE-Analyses with LA-ICP-MS

Rare earth element contents in general and gadolinium contents in particulary of 3 different samples

were measured. The first sample (UP) was a urine sample taken after ingesting a Gd-DTPA-complex,

the second a sinter of dust containing tap water from the Bergbaugebäude (LW) and the third

sample a sinter from the Landesbad Quelle (LB).

The measurements were conducted with LA-ICP-MS (laser inductively coupled plasma mass

spectrometry). Thereby the sample becomes ionized in a plasma. The plasma consists of argon,

electrons and argon ions and has a temperature of about 10,000 K. The sample injected into this

plasma evaporates and its solved solids vaporize and break up into their atoms, which get ionized.

These ions are extracted out of the plasma into a mass spectrometer, in our case a quadrupole.

Based on their mass-to-charge ratio (m/z) the ions are detected proportionally to theirconcentration. Light masses are detected earlier than heavy masses. Before and after the samples a

standard (SRM 614) was measured. Following values where measured:

Previously by the calcutaion of the values the underground was subtracted. This underground could

be estimated too high, so some values are negative. These values have to be equalized to zero.

These values where normalized to the values of chondrites from McDonough & Sun (1995), and then

again normalized to the Ce-value of the sample LB1.

La Ce Nd Pr Sm Eu Gd Tb Dy Ho Lu Y

UP 1 0,143 0,197 0,470 0,027 440,771 0,002 11834,335 0,091 0,001 < 0,001 0,337 0,008

UP 2 0,198 0,223 0,185 0,026 482,068 0,016 11549,072 0,132 -0,361 0,003 0,279 0,011

LW1 0,133 0,224 0,144 0,018 0,019 0,001 0,090 0,022 0,096 0,013 0,001 0,823

LW2 0,164 0,180 0,201 0,047 0,060 0,015 31,021 0,016 0,021 0,030 0,001 0,827

LW3 0,115 0,146 0,170 -0,062 0,087 0,011 2,204 -0,086 -0,315 0,009 0,006 0,962

LB1 0,047 0,176 0,160 0,019 0,043 0,012 1,833 0,012 0,005 0,004 -0,145 0,155

LB2 0,045 0,056 0,056 0,007 0,013 0,036 -0,427 0,014 0,083 0,007 -0,117 0,118

La Ce Nd Pr Sm Eu Gd Tb Dy Ho Lu Y

UP1 normalized to

chondrites0,604 0,321 1,028 0,295 2978,183 0,035 59469,018 2,522 0,005 0,018 13,688 5,187

UP1 normalized to

Ce_LB12,104 1,118 3,582 1,026 10375,186 0,120 207173,998 8,787 0,019 0,064 47,686 18,070

UP2 normalized to

chondrites 0,834 0,364 0,404 0,280 3257,214 0,286 58035,537 3,657 0,000 0,055 11,352 6,728

UP2 normalized to

Ce_LB12,904 1,268 1,408 0,975 11347,254 0,997 202180,138 12,741 0,000 0,191 39,547 23,440

LW1 normalized to

chondrites0,562 0,366 0,315 0,189 0,127 0,014 0,451 0,605 0,389 0,235 0,051 524,378

LW 1 normalized to

Ce_LB11,957 1,275 1,098 0,658 0,443 0,048 1,573 2,108 1,354 0,820 0,179 1826,791

LW2 normalized to

chondrites0,693 0,293 0,440 0,501 0,408 0,261 155,884 0,447 0,084 0,553 0,032 527,036

LW2 normalized to

Ce_LB12,415 1,022 1,532 1,746 1,422 0,908 543,057 1,556 0,292 1,927 0,112 1836,051

LW3 normalized to

chondrites0,484 0,239 0,373 0,000 0,588 0,188 11,075 0,000 0,000 0,167 0,252 612,479

LW3 normalized to

Ce_LB11,687 0,832 1,299 0,000 2,049 0,656 38,583 0,000 0,000 0,580 0,878 2133,711

LB1 normalized to

chondrites0,199 0,287 0,349 0,205 0,293 0,217 9,213 0,328 0,019 0,073 0,000 98,942

LB 1 normalized to

Ce_LB1 0,695 1,000 1,216 0,715 1,020 0,757 32,094 1,142 0,068 0,256 0,000 344,688

LB2 normalized to

chondrites 0,189 0,091 0,123 0,080 0,090 0,635 0,000 0,380 0,338 0,125 0,000 74,930

LB2 normalized to

Ce_LB1 0,660 0,316 0,430 0,280 0,314 2,212 0,000 1,325 1,177 0,434 0,000 261,034



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As a result we can say how much more or less than Ce is a REE element in our samples enriched in

the samples in comparison to the earth crust. We can see that Gd of course in our urine samples are

much more enriched in comparison to the earth crust than other elements in all the samples. But it is

also 4 times more enriched in comparison to the Ce value of LB1. You can get similar information in

different intensities for all investigated elements from the table above, in comparison to the earth

crust and then as a ratio to Ce.

7. Loss on ignition

The preparation for this experiment is described in the section “Preparation of sample”. Continuing

this proceeding the crucible including the sample is annealed in a muffle furnace for 120min. Thecrucible is cooling down in the deactivated furnace and thereafter in an exsiccator until it reached

room temperature. Then the crucible with the sample is weighed again and the L.O.I. can be

calculated:

. Weight (g)

Crucible empty 19,8272

Sample 3,0415

Crucible + sample dried (Sdried) 22,8687

Crucible + sample ignited (Signited) 22,8256Loss on ignition (LOI) 0,0431

LOI in w% 1,4171

8. Fused Disc for XRF

For the creation of the fused disc 0.5000g of the sample was merged with 5.000g Fluxana (66%

lithiumtetraborat/ 34% lithiummetaborat) as a disintegration agent to a homogenous mass. The

purpose of Fluxana is to make the sample more easily to melt and to attenuate it. The blend was

carried over into a platinum crucible with 1.5mL of a solution of 10% lithiumiodide. The purpose of

this solution is to increase the surface tension. Now the crucible was heated three times for five

minutes at 1240°C in a resistance furnace. In that time the furnace was brandished so the sample

was homogenized. The cooled down disc has to be kept in an exsiccator.

The results of the XRF and the LOI corrected values are following:



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.

Concentration of total

(%)Deviation (%)

LOI corrected concentration

(%)

Na2O 1,773 0,047 1,748

MgO 1,136 0,015 1,120

Al2O3 5,703 0,043 5,622

SiO2 63,28 0,12 62,381

P2O5 0,527 0,018 0,520

SO3 0,3482 0,0031 0,343

K2O 0,9569 0,0035 0,943

CaO 6,315 0,008 6,225

TiO2 0,6001 0,002 0,592

V2O5 0,0089 0 0,009

Cr2O3 0,3521 0,0008 0,347

MnO 0,2343 0,0005 0,231

Fe2O3 15,78 0,03 15,556

97,0145

9. Ion-selective Electrode (ISE)

A waste water sample (no excreta) was taken from the basement of the laboratory. Organo-leptic

(odor, color, cloudiness and depth of visibility) and physico-chemical examinations (temperature,

conductivity) were undertaken. The sample was odorless and colorless. The depth of visibility lasted

to the ground (42cm) and the water had a very weak cloudiness. A content of ions of 286mg/l, a

temperature of 13.6°C and a conductivity of 424 µS/cm were detected.

At first the electrode was calibrated with 10, 30 and 50ppm Cl in 100ml.

Then 1ml of ISA (Ionic Strength Adjuster) was put to 25ml of the sample. The ISA (natriumnitrate) is

added to maintain a constant ionic strength, such that the total ionic strength is independent of the

of the analyte (in our case Cl) concentration.

In the sample a concentration of 42.5 mg/l of Cl was measured. Chloride is the most abundant ion

and in relation to the conductivity a higher content was expected. Therefore other ions like most

likely nitrate had to be present. Nitrate is common in waste waters with organic content.



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10. Determination of elements in solution (ICP-OES/MS)

The fused disc was now solved and transferred to a graduated flask with a volume of 500ml. The flask

was then filled up to 500ml with 0.5 M HNO3. So 0.5g of initial sample weight were thinned to 500ml

of sample preparation volume. After filtration about 10ml were filled into a polystyrene tube. With

this ICP-OES (inductively coupled plasma optical emission spectrometry) measurements were

undertaken.

ICP is explained in the section “LA-ICP-MS, REE-Analyses”. The gas the plasma is created with was

argon. It has a temperature of 10,000°C and a current of 15l/min. 1.5ml/min of the sample are

injected. When the molecules of the sample are broken up into their atoms which lose electrons and

recombine again with them, they give off radiation at characteristic wavelength (color) of the

elements involved. The intensities of the light of different wavelengths are measured within a opticalchamber. These intensities are compared to preciously measured intensities of known

concentrations of the elements. Therefore a 1ppm, a 5ppm and a 10ppm standard is measured

ahead of the sample to construct a calibration line. The elements measured were As, Cu, Cd, Ni, Pb

and Zn. In the following results the blank value is already subtracted from the mean corrected

intensities.

.

Mean Corrected

Intensity

As -9,2

Cu 1702234,2

Cd 893

Ni 22220,7

Pb 8251,1

Zn 339082,9

11. Sequential Extraction

In the following the corrected results of the sequential extraction are seen, of every of the 6

fractions.



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12. Tl-Species

Measurements for receiving the contents of the toxic thallium isotopes205

Tl and203

Tl were

conducted on the ICP-MS, as well as for other cations like Li, K, Rb and Na. Of these, Na is the one

with the by far highest peak, followed by K. The K peak though is superposed by the steady intensity

signal of Argon, that forms the plasma of the ICP-MS. 205Tl and 203Tl both form two peaks each at

which205

Tl has the bigger peak and is therefore more abundant. The peak of Li is higher than the

peak for Rb.

13. Sulphur measurement

For the sulphur measurements a LECO S-200 microprocessor was used. It is about an induction

furnace. Its core is an induction coil. For this analysis a ceramic crucible is filled with iron chips, 0.1g

sample material and Lecocel II flux.

As Cu Cd Ni Pb Zn Fe Tl Co Cr

mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/LSample A I-II

corrected 0,58 0,83 0,02 0,11 34,77 21,19 18,93 0 0,05 0,02

Sample B I-II

corrected 0,57 0,47 -0,01 0,09 84,02 32,97 29,3 0 0,049 -0,01

Sample A III-IV

corrected 0,27 0,46 0 0 20,34 13,75 26,2 0 0,019 0

Sample B III-IV

corrected 0,28 0,56 0 0 18,42 21,12 39,46 0 0,019 0

Sample A V-VI

corrected 0,76 0,51 0,00 0,15 9,32 12,34 49,99 0,00 0,04 0,23

Sample B V-VI

corrected 0,66 0,26 0 0,12 14,24 9 32,9 0 0,039 0,17

resid. F A KWA

corrected 5,23 6,14 0,17 1,58 308,8 511,46 109,88 0 0,749 3,41

resid F B KWA

corrected 5,79 4,47 0,18 1,69 394,3 514,92 116,09 0 0,719 3,01

Sample A total KWA

corrected 19,86 37,24 0,72 19,1 946,7 1145,94 2512,91 0 2,749 10,08

Sample B total KWA

corrected 18,45 47,80 0,69 6,10 959,70 1104,97 2462,93 0,00 3,00 9,66

ST A1 24-26

corrected 0 4,56 0 0,32 1,08 13,21 162,3 0 0,11 3,02

ST B1 24-26

corrected 0 4,47 0 0,39 1,02 12,59 151,11 0 0,09 2,67

ST A2 24-26

corrected 0 5,55 0 0,4 1,16 14,38 161,89 0 0,11 3,14

ST B2 24-26

corrected 0,02 3,58 0 0,28 0,88 11,81 147,74 0 0,08 2,19

ST A3 63 corrected 0,01 2,74 0 0,26 0,96 11,9 169,99 0 0,09 3,26

ST B3 63 corrected 0,03 3,73 0,00 0,30 1,19 9,36 139,94 0,00 0,09 2,64

Nr.Probenbezeichn

ung



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Oxygen is running through the oven and the analyst. After the cleaning of the incoming oxygen it is

conducted onto the ceramic crucible. During the process of combustion the atmospheric gases CO

and SO2 are formed. The CO is converted into CO2 and the SO2 attains to a cellulose sink. During the

process of combustion the sulphur components are oxidized to form SO2. The infrared cell is a

chrome nickel wire which is heated to 850°C. The IR- source produces visible energy and detects the

wavelength of the passing gases.

The sulphur content was 1,396%.

14. Analysis of particulate matter, pressed powder pellet, XRF

Particulate matter was taken from the orange filter in the Süsterfeldstraße 22 that draws in dustfrom outside. 0.1g particulate matter was thinned with 9.9g quartz in a small mortar until they are

combined to a homogenous mass. This 1:100 attenuation was necessary because the heavy metal

content would have been too high for the detection device.

The thinned sample was combined with 2ml of adhesive. The adhesive consists of a 5% elvacite

solution in which the elvacite is solved in acetone. The sample and the adhesive were mixed until all

the acetone had escaped and the mixture was a powder again. The powder was filled into an

aluminium cup and covered with a Mylar-sheet. This is important to ensure an even surface for the

pressed powder pellet and to prevent contamination. The powder was no compressed with a

pressure of 15t for 30sec to a pellet. At such a high pressure the adhesive precipitates and the

powder becomes solid. The XRF measurements were now done with a SpectroX-LAB 2000 device.

In Tab. the results of the XRF measurements, the calculated undiluted values and the corresponding

EF values pictured in a color-code are listed.

Sample A2 V Cr Co Ni Cu Zn

1:100 diluted (ppm) < 20 < 20 < 20 < 20 < 20 350

undiluted (ppm) 2000 2000 2000 2000 2000 35000

Chondrite (from

Mcdonough & Sun

(1995) (ppm) 56 2650 500 10500 120 310

Enrichment Factor EF 22,0669688 0,46632085 2,47150051 0,1176905 10,2979188 69,760095

As Rb Sr Zr Sn Sb Pb Al

< 10 < 10 < 10 < 20 < 10 < 20 < 20

1000 1000 1000 2000 1000 2000 2000 13918,67



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1,85 2,3 7,25 3,82 1650 140 2470 8600

333,986555 268,64136 85,2241555 323,494831 0,37446977 8,82678753 0,50030375 1

EF

< 2 deficiency to minimal enrichment

2 - 5 moderate enrichment

5 - 20 significant enrichment

20 - 40 very high enrichment

> 40 extremely high enrichment

It can be seen that Zn, As, Rb, Sr and Zr are extremely high enriched in the investigated particulate

matter. A major source of Zn in the cities is the abrasion of tires which consist for 1 w% of Zn. The

enrichment of As can derive from incineration processes. A possible source of the very high enriched

V is the firing of oil. The still significant enriched Cu can come from the soot of diesel vehicles and SB

from the abrasion of brakes. All these enrichments indicate road traffic. Co, Cr, Ni, Sn and Pb are only

moderately to minimally enriched.

15. Analysis of Pb-isotope ratios, data interpretation, acid neutralization capacity

Two different Pb-samples (Sample A and Sample B) were investigated via ICP-MS for their Pb-isotope

ratios to find out whether they come from the same source or not. Therefore their corrected

207/206 ratio with its error margin is calculated and compared to each other for overlaps. As

preparation the lead was solved in 0.5 M HNO3.

The measurement of a sample as well as the blank value is encircled with the measurements of the

standard for calculating the correction factor. As standard NBS 981 was used which has a known

207/206 ratio of 0,914.

. NBS 981 Sample A NBS 9812 Sample B NBS 9813 Blank Value NBS 9814

207/206 0,913 0,891 0,914 0,86 0,914 0,883 0,916



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Relative

Standard

Deviation RSD

(%)

0,293 0,138 4,096

correction

factor0,914/0,913 0,914/0,9135 0,914/0,914 0,914/0,914 0,914/0,914 0,914/0,915 0,914/0,916

correction

factor1,00109529 1,00054735 1 1 1 0,998907104 0,99781659

207/206corrected 0,891 ±

0,003

0,86 ±

0,0010,882 ± 0,036

As can be seen the corrected isotope ratios of sample A and B don’t overlap, so it is certain that the

lead does not originate from the same source.

Praktikumsprotokoll IEG 2013 Mueller281614

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