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.

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 105C 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%) >4 4-2 2 - 1,12 1,12 - 0,63 0,63 - 0,25 0,25 - 0,112 0,112 - 0,063 < 0,063 total 89 42 52 36 36 13 5 6 279 31,90 15,05 18,64 12,90 12,90 4,66 1,79 2,15 100 residuals- summed share (%) 100,00 68,10 53,05 34,41 21,51 8,60 3,94 2,15 0

Sieving Line Diagramm

100 90 80 70

summed share (%)

60 50 40 30 20 10 0

Mesh Aperture (mm)

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 1000C 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 105C 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 cooled down again in an exsiccator until it reached room temperature. The weight of the crucible with the sample inside was determined. 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 results were as followed:

. Blank Value Sample

pH at 25C 5.85 5.37

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:
. Blank Value Sample Sample corrected Conductivity (S/cm) Temperature 14.2 18.1 162.1 18.2 147.9

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 Bergbaugebude (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 their concentration. Light masses are detected earlier than heavy masses. Before and after the samples a standard (SRM 614) was measured. Following values where measured:
La UP 1 UP 2 LW1 LW2 LW3 LB1 LB2
0,143 0,198 0,133 0,164 0,115 0,047 0,045

Ce
0,197 0,223 0,224 0,180 0,146 0,176 0,056

Nd
0,470 0,185 0,144 0,201 0,170 0,160 0,056

Pr
0,027 0,026 0,018 0,047 -0,062 0,019 0,007

Sm
440,771 482,068 0,019 0,060 0,087 0,043 0,013

Eu
0,002 0,016 0,001 0,015 0,011 0,012 0,036

Gd
11834,335 11549,072 0,090 31,021 2,204 1,833 -0,427

Tb
0,091 0,132 0,022 0,016 -0,086 0,012 0,014

Dy
0,001 -0,361 0,096 0,021 -0,315 0,005 0,083

Ho
< 0,001 0,003 0,013 0,030 0,009 0,004 0,007

Lu
0,337 0,279 0,001 0,001 0,006 -0,145 -0,117

Y
0,008 0,011 0,823 0,827 0,962 0,155 0,118

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 UP1 normalized to chondrites UP1 normalized to Ce_LB1 UP2 normalized to chondrites UP2 normalized to Ce_LB1 LW1 normalized to chondrites LW 1 normalized to Ce_LB1 LW2 normalized to chondrites LW2 normalized to Ce_LB1 LW3 normalized to chondrites LW3 normalized to Ce_LB1 LB1 normalized to chondrites LB 1 normalized to Ce_LB1 LB2 normalized to chondrites LB2 normalized to Ce_LB1
0,604 2,104 0,834 2,904 0,562 1,957 0,693 2,415 0,484 1,687 0,199 0,695

Ce
0,321 1,118 0,364 1,268 0,366 1,275 0,293 1,022 0,239 0,832 0,287 1,000

Nd
1,028 3,582 0,404 1,408 0,315 1,098 0,440 1,532 0,373 1,299 0,349 1,216

Pr
0,295 1,026 0,280 0,975 0,189 0,658 0,501 1,746 0,000 0,000 0,205 0,715

Sm
2978,183 10375,186 3257,214 11347,254 0,127 0,443 0,408 1,422 0,588 2,049 0,293 1,020

Eu
0,035 0,120 0,286 0,997 0,014 0,048 0,261 0,908 0,188 0,656 0,217 0,757

Gd
59469,018 207173,998 58035,537 202180,138 0,451 1,573 155,884 543,057 11,075 38,583 9,213 32,094

Tb
2,522 8,787 3,657 12,741 0,605 2,108 0,447 1,556 0,000 0,000 0,328 1,142

Dy
0,005 0,019 0,000 0,000 0,389 1,354 0,084 0,292 0,000 0,000 0,019 0,068

Ho
0,018 0,064 0,055 0,191 0,235 0,820 0,553 1,927 0,167 0,580 0,073 0,256

Lu
13,688 47,686 11,352 39,547 0,051 0,179 0,032 0,112 0,252 0,878 0,000 0,000

Y
5,187 18,070 6,728 23,440 524,378 1826,791 527,036 1836,051 612,479 2133,711 98,942 344,688

0,189 0,660

0,091 0,316

0,123 0,430

0,080 0,280

0,090 0,314

0,635 2,212

0,000 0,000

0,380 1,325

0,338 1,177

0,125 0,434

0,000 0,000

74,930 261,034

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.

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. The crucible 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:
. Crucible empty Sample Crucible + sample dried (Sdried) Crucible + sample ignited (Signited) Loss on ignition (LOI) LOI in w% Weight (g) 19,8272 3,0415 22,8687 22,8256 0,0431 1,4171

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 1240C 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 follwing:
. Concentration of total (%) Deviation (%) LOI corrected concentration (%)

Na2O MgO Al2O3 SiO2 P2O5 SO3 K2O CaO TiO2 V2O5 Cr2O3 MnO Fe2O3

1,773 1,136 5,703 63,28 0,527 0,3482 0,9569 6,315 0,6001 0,0089 0,3521 0,2343 15,78 97,0145

0,047 0,015 0,043 0,12 0,018 0,0031 0,0035 0,008 0,002 0 0,0008 0,0005 0,03

1,748 1,120 5,622 62,381 0,520 0,343 0,943 6,225 0,592 0,009 0,347 0,231 15,556

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 13.6C and a conductivity of 424 S/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.

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 10,000C 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 optical chamber. 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.

. As Cu Cd Ni Pb Zn

Mean Corrected Intensity -9,2 1702234,2 893 22220,7 8251,1 339082,9

Sequential Extraction

Tl-Species Measurements for receiving the contents of the toxic thallium isotopes 205Tl and 203Tl 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 which 205Tl has the bigger peak and is therefore more abundant. The peak of Li is higher than the peak for Rb. 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. 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 850C. The IR- source produces visible energy and detects the wavelength of the passing gases. The sulphur content was 1,396%. Analysis of particulate matter, pressed powder pellet, XRF Particulate matter was taken from the orange filter in the Ssterfeldstrae 22 that draws in dust from 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 1:100 diluted (ppm) undiluted (ppm) Chondrite (from Mcdonough & Sun (1995) (ppm) Enrichment Factor EF As < 10 1000 Rb < 10

V < 20 2000

Cr < 20 2000

Co < 20 2000

Ni < 20 2000

Cu < 20 2000

Zn 350 35000

56

2650

500

10500

120

310 69,760095 Al

22,0669688 0,46632085 2,47150051 Sr < 10 Zr < 20 1000 2000 Sn < 10 1000

0,1176905 10,2979188 Sb < 20 2000 Pb < 20 2000

1000

13918,67

1,85 333,986555

2,3

7,25

3,82

1650

140

2470

8600 1

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

EF <2 deficiency to minimal enrichment

2-5 5 - 20 20 - 40 > 40

moderate enrichment significant enrichment very high enrichment 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.

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. . 207/206 NBS 981 0,913 Sample A 0,891 NBS 9812 0,914 Sample B 0,86 NBS 9813 0,914 Blank Value 0,883 NBS 9814 0,916

Relative Standard Deviation RSD (%) correction factor correction factor 207/206corrected

0,293

0,138

4,096

0,914/0,913 0,914/0,9135 0,914/0,914 0,914/0,914 0,914/0,914 1,00109529 1,00054735 0,891 0,003 1 1 0,86 0,001 1

0,914/0,915

0,914/0,916

0,998907104 0,99781659 0,882 0,036

As can be seen the corrected isotope ratios of sample A and B dont overlap, so it is certain that the lead does not originate from the same source.