On-site environmental water analyses by ICP-MS

The Science of the Total Environment 172 (1995) 133-144

ELSEVIER

n-site environmental water analyses by ICP-MS M.J. Duane*, S. Facchetti JRC, Environment Institute, Ispra @‘a), l-21020, Italy Received 12 December 1994; accepted 12 February 1995

Abstract ICP-MS analyseson drinking and vadosewaterswere performed on-site at a disusedindustrial/mining site in the former DDR. The results indicate the viability of performing on-site analysesof matrix samplesfor heavy metals while maintainingprecisionand accuracybetter than other conventionaltechniquessuchaspotentiometric stripping analysis(PSA). The precision,on a NIST 1643~water standardrun frequently during the campaign,is better than 2% in most cases.Duplicate and triplicate runs performed on three samplesprove precisioncomparablewith, if not better, than conventionaltechniquesand home-basedlaboratories.‘Hot spot’ identification of heavy metal anomalies were located quickly and the environmental assessment report was accomplishedwithin hours of the first sample being analysed.Polluted water samplesare notablefor their high Zn (maximum12000ppb), Mn (maximum656ppb), Ni (maximum126ppb), Co (29.8ppb), As (maximum22.5ppb), Sb (maximum54.9ppb) and Pb (maximum184ppb). Keywords:

ICP-MS analyses;Water; On-site

1. Introduction On-site chemical analysis is becoming increasingly important due to current knowledge on migration and toxicity of inorganic chemicals in the vadose zone, coupled with increased public awareness due to frequent legislation directives from Bruxelles. Field investigations for site characterization of toxic chemicals have many advantages over stationary laboratories since

*Corresponding author, Department of Geology, University of Natal, Private bag X10, Dalbridge 4014, South Africa.

transportation time is reduced and sample integrity is maintained. In caseswhere toxic spillages flow into aquifers which feed large domestic reservoirs and, where follow-up legal action may be pending, preventive measures can be made on the spot. Furthermore, on-site analysis of many samplesin a short time allows a directional investigation of ‘hot spots’ in the hinterland. In response to this demand the European Advanced Mobile Analytical Laboratory (AMAL) was established in the Eureka Project EU 674 to serve the needs of on-site investigations of polluted industrial sites. The AMAL combines the latest analytical techniques for inorganic and or-

004%9697/95/$09.50 0 1995 Elsevier Science BV. All rights reserved. SSDZ 0048-9697(95)04783-W

134

hf.1 Duane, S. Facclaetti /T&e Science of the Total Environment 172 (1995) 133-144

ganic analysis with new methods of sample collecting, sample processing and data transfer. It consists of four vehicles, one for sample collection and three for sample processing and sample analysis. One of the aims of the project is to compare the use of the latest analytical techniques for environmental analysis such as ICP-MS (inductively coupled mass spectrometer), solidphase microextraction GC MS (gas chromatography mass spectrometer), and membrane inlet mass spectrometry. ICP-MS is a relatively new powerful technique for the determination of metals in aqueous solution 111. It uses a plasma to ionise sample components which its quadruple discriminates according to mass. Sample introduction is done by direct aspiration of small liquid volumes. The determination time is rapid allowing replicate analysis, external and internal standardization and quality control procedures in line with the U.S. Environmental Protection Agency (EPA) guidelines [2]. A distinct advantage of the ruggedised, mobile ICPMS (Fisons P Qe instrument) is its capability for transport in the field (bolted to floor by steel screws), simultaneous multielement determinations through peak hopping, either as single masses or as isotope ratios and its high dynamic range (0.1 ppb to 1000 ppm). This article describes a number of advances in the analysis of water on-site at a disused industrial site by comparing a ruggedised ICP-MS with a portable PSA (potentiometric analyser). 2. Experimental 2.1. Sampling sites

The area investigated lies between the Harz Mountains in the northwest and the old mining areas of Gera-Ronneburg to the south of the former DDR. A group of 29 water samples were collected from drainages close to a large early 20th Century industrial and mining site. The sampling sites are of the following categories: operative public wells, artesian wells, samples from aqueducts, abandoned shallow domestic wells and piezometers (see caption to Table 1). The water samples contain constituents that are extremely complex mixtures of organic and inorganic com-

pounds encountered in toxic waste dumps, drinking wells and rivers draining the industrial and mining site. 2.2. Trace element analysis

The optimum concentration range of the modified FISONS P Qe MS depends on the analytes but can be considered to be in the range of 0.001 to 1 mg/l. Higher concentrations may be determined through sample dilution. The precision has been tested measuring the mass calibration elements in standard solutions made in deionized water (resistivity greater than 18 mn) and also from real environmental samples in the field. Detection limits for a tune solution of Be-Al-CoIn-Pb-Bi-LJ are as follows: Be 0.3 ppb, Al 0.4 ppb, Co 0.09 ppb, In 0.09 ppb, Pb 0.006 ppb, Bi 0.1 ppb and Pb 0.07 ppb. Results indicate that the precision is in the range of 2-10% or better in terms of coefficient of variation (c.v.%). Method interferences are caused by contaminants in the water, reagents, glassware and sample processing hardware but these are generally monitored by method blanks and adjusted accordingly. A peristaltic pump was used for sample delivery (A Gilson Minipuls 3) and flow rate adjusted to 22.8 ml/h to remove gas bubbles from the sample delivery tubing. Deionised water and certified nitric acid (Merck Suprapure) were used routinely for both blanks and samples (1% for most samples without matrix). The sample injection times were 3 min plus a 1-min wash between samples as well as standards. Concentration calculations were done using the external standard method. Correction for signal instability was made using the internal standard method added in the same (100 ppb) concentration to blank, standard and samples. 2.3. Analytical quality assurance

The system used here mirrors the method of the U.S. E.P.A. [2] where a blank and 3 standards was run before the samples. Blanks are again inserted before the first sample and after the last sample was analysed to monitor memory effects and changes to the internal standard. Of importance to rigorous QJQ, requirements we repeated the 50 and 100 ppb standards which were

M.J. Duane,

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172 (1995)

run as samples subsequent to all environmental samples.

cycles are compared sponse is obtained.

2.4. Instrumental modijication and vehicle conditions in the field

3. Results

The Fisons P Qe model (350 kg) was modified to account for instabilities experienced with the first prototype in 1993. The truck conditions were considered in the upgrade of the instrument to take account of such factors as vibrations (rubber attachments to panels), shortened gas lines (to prevent moisture containment within the PFTE lines and hence shorter purge times), water pipelagging to maintain the low temperature required for stability during measurement and adverse weather conditions (temperature held constant by air-conditioning). The following outlines the important modifications and running conditions: Water supply cooler 1Zstage multiplier E.T.P

Neslab CFT 875 chiller (86 kg) 6°C during measurement Stabilities on a tune solution of Be-Mg-In-Co-Bi-Eu-U circa 3% R.S.D.over a 4-h period.

Auxiliary gas flow (Ar 99.9% purity) 14l/min Nebuliser pressure 35.0 psi. Data acquisition parameters DAC intervals between channels is 15, dwell time (ms) 1500, acquisition time 30-60 s. 3 measurements per sample.

Other minor, but significant changes were made to the environment of the truck itself such as strict control of personnel entry during measurement of the samples, a constant ‘room’ temperature of 18°C was maintained by air-conditioning and RF, together with ozone emissions expelled by air extractor with fan (800 m3/hr). A diesel powered generator maintained the current required to run the ICP-MS facility which requires 45 A single phase. The PSA instrument used in the mobile laboratory is the Radiometer TRACELAB. The technique uses an electrolytic cycle to oxidise and reduce the ions present in a liquid using a Hg film-plated electrode. The signals from the two

133-144

and an EMF/current

135

re-

The performance characteristics of the modified P Qe under field conditions are shown in Table 1. A NIST 1643~ water standard was periodically run (seven times in all) over 2 weeks of on-site investigations to establish the reliability of the data collected on the aqueous environmental samples. For Be we obtained a value of 21.4 + 0.9 for the mean and 1.3 S.D. (Standard Deviation). This compares with 23.2 + 2.2 ppb for the certified standard. For V a mean of 29.2 + 3.5 and S.D. of 1.7. The certificate value is 31.4 f 2.8 ppb. For Cr a mean of 18.8 rt 0.4 and a S.D. of 0.7. This compares with 19.0 + 0.6 for the certificate value. The mean obtained for Mn is 35.5 + 0.8 with a S.D. of 2.5. This compares with 35.1 f 2.2 ppb for the certificate result. For Ni the mean is 58.03 + 1.0 and a S.D. of 2.7. This compares with 60.6 + 7.3 ppb for the certificate result. For Co the mean is 23.8 + 0.3 and a S.D. of 1.6. This compares with a value of 23.5 + 0.8 ppb for the certificate result. For Zn a mean value of 56.1 f 0.7 and a S.D. of 5. This compares with a certificate value of 73.9 + 0.9 ppb, considerably lower than expected. This result was obtained many times during routine analyses of NIST 1643~ (at Ispra) using alternative in-house mass spectrometers (PQ 2). Cu has a mean of 19.4 + 0.3 and a S.D. of 1.2. This compares with 22.3 + 2.8 ppb for the certificate value. As values have a mean of 69.2 + 0.9 ppb with a S.D. of 8.6, compared to a certificate value of 82.1 f 1.2 ppb. Cd results have a mean value of 10.4 $: 0.09 and a S.D. of 1.0 compared to 12.2 + 1 ppb value for the certificate result. Pb has a mean value of 29.5 + 0.5 ppb with a S.D. of 1.2. This compares with 35.3 & 0.9 ppb for the certificate result. Overall, with the exception of Pb and As (also Zn, which is questioned since we consistently find a lower value of 56 ppb) the values agree within error. Sample numbers and results for environmental water samples are also shown in Table 1 and

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histograms for the ICP-MS data are presented in Fig. 1. Both duplicate (samples ALR-154, ALR155, ALR-156, ALR-157 and ALR-158) and triplicate results (ALR-126, ALR-127 and ALR-128) are reported. For ALR-126 the means for all elements range from 0.027 ppb to 16.8 ppb. The standard deviations are below 1 except for Cr

Table 1 ICP-MS results

for standards

NIST 1643 c Elements

MST

Be V Cr Mn Ni co Zn CU As Cd Sb Pb

23.4 31.6 20.4 41 62.1 23.8 58.6 21.2 79.6 8.2 0.01 29.7

ppb ppb mb mb mb wb mb ppb wb ppb ppb ppb

Elements wb ppb ppb ppb ppb ppb ppb ppb mb ppb mb ppb

Elements Be V Cr Mn Ni co Zn CU As Cd Sb Pb

1

NBT

Be V Cr Mn Ni co Zn CU As Cd Sb Pb

ppb ppb ppb wb ppb ppb ppb ppb ppb mb wb ppb

and water

samples

Uncert

NIST

1.2 3.5 0.4 0.8 1.6 0.7 1.3 0.6 1.2 0.13 0.01 0.3

19.9 31.2 18.5 33.8 59.9 25.7 62.6 20.3 76.7 12.3 0.01 28.7

6

22.4 28.8 18.5 34.8 55.4 22.8 51.8 18.3 60.7 9.6 0.003 27.6

2

from

172 (1995) 133-144

(1.4). This sample is considered to be a non-polluted water and serves as a background determination to the other results below. A similar pattern emerges for sample ALR-127 and ALR-128 with SD. below 2% in most cases. Be concentrations are below 1 ppb and will not be considered further except in the discussion

the Advanced

Mobile

Analytical

Laboratory

(AMAL)

on site

Uncert

NIST 3

(PQe) Uncert

NIST 4

Uncert

NIST

0.7 0.4 0.5 0.9 1.3 0.4 1 0.4 1.6 0.2 0.05 1

22 26.5 18.8 35.3 60.2 26.2 62.6 20.3 78.7 12.1 0.01 28.7

0.7 8 0.5 1 1.3 0.4 1 0.4 1.6 0.2 0.14 1.03

20.3 28.6 18.5 33.9 56.3 22.6 51.7 18.5 62.9 9.7 0.02 29.9

1.6 3.8 0.9 0.6 0.5 0.1 0.3 0.2 0.3 0.05 0.01 0.34

21.9 28.9 18.6 35 57.2 23.1 52.3 18.5 63.1 9.8 0.03 31.2

0.9 3.2 0.2 0.2 0.6 0.2 0.6 0.1 0.4 0.07 0.01 0.16

cert

Uncert

Uncert

MST

0.4 2.9 0.3 1.2 0.8 0.3 0.2 0.2 0.2 0.2 0.003 0.2

20.2 28.6 18.4 34.4 55.1 22.3 53.3 18.5 63 9.9 0.01 30.6

7

5

Uncert

Uncert

Mean

Std. dev.

MST

1.1 2.7 0.3 1.2 1.1 0.2 0.2 0.09 0.9 0.07 0.02 0.2

21.4 29.2 18.8 35.5 58.0 23.8 56.1 19.4 69.2 10.2 0.01 29.5

1.3 1.7 0.7 2.5 2.7 1.6 5.0 1.2 8.9 1.5 0.01 1.2

23.2 31.4 19 35.1 60.6 23.5 73.9 22.3 82.1 12.1

2.2 2.8 0.6 2.2 7.3 0.8 0.9 2.8 1.2 1

35.3

0.9

ALR-105

Uncert

ALR-106

Uncert

m-107

Uncert

ALR-108

Uncert

ALR-109

Uncert

0.02 0.4 2.5 1.20 22.5 0.12 11.9 5.4 0.26 0.14 0.003 0.5

0.01 0.5 0.12 1.9 0.6 0.01 0.1 0.03 0.02 0.03 0.01 0.03

0.02 0.7 1.6 3.1 5.9 0.22 8.8 0.9 0.6 0.09 0.01 0.04

0.004 0.04 0.06 0.08 0.13 0.01 0.2 0.01 0.02 0.11 0.02 0.01

0.5 0.5 2 656.3 89.7 4.3 67.3 0.4 1.9 0.14 0.01 0.02

0.01 0.01 0.07 4.8 0.9 0.03 1.4 0.01 0.05 0.03 0.007 0.4

0.02 0.4 1.5 1.44 7.9 0.4 6.8 0.8 1.1 0.07 0.02 0.7

0.002 0.02 0.09 3.9 0.3 0.01 0.15 0.02 0.03 0.04 0.01 0.01

0.03 0.5 1.9 208 50.1 1 7.2 0.3 4.5 0.12 0.002 1.3

0.02 0.01 0.13 4.7 0.8 0.01 0.04 0.04 0.05 0.16 0.04 0.02

Table

1

wb wb ppb ppb ppb ppb wb mb ppb ppb mb wb

Elements Be V Cr Mn Ni co Zn cu As Cd Sb Pb

ppb ppb ppb wb ppb ppb ppb ppb ppb ppb mb ppb

Elements Be V Cr Mn Ni co Zn CU As Cd Sb Pb

ppb ppb mb ppb ppb mb wb ppb ppb ppb wb ppb

Elements Be V Cr Mn Ni co Zn CLl As Cd Sb Pb

S. Facchetti

Science of the Total Environment

172 (1995)

133-144

ALR-110

Uncert

ALR-111

Uncert

ALR-112

Uncert

ALR-113

Uncert

ALR-114

Uncert

0.09 0.6 5.4 31.7 40.4 1.7 6.8 1.6 0.9 2.2 0.07 0.04

0.08 0.04 0.2 0.3 0.4 0.02 0.08 0.2 2 0.09 0.04

0.02 0.5 4.9 27.2 12.5 0.6 41.7 1.2 0.08 1.4 0.001 0.05

0.1 0.004 0.22 0.72 0.3 0.01 0.8 0.04 0.09 2.6 0.02 0.02

0.03 2.4 4.5 60.8 17.9 0.8 51.0 2.8 0.6 0.16 0.07 2.2

0.01 0.06 0.1 0.77 0.1 0.02 0.7 0.05 0.01 0.4 0.02 0.03

0.02 1.1 2.1 2.2 11.5 1.5 13.6 1.9 0.6 0.1 0.1 0.13

0.02 0.6 0.3 0.2 0.4 0.1 0.7 0.1 0.04 0.02 0.01 0.01

0.02 0.33 3.3 215 25.2 0.24 70.8 8.9 0.5 0.04 10.01 1.4

0.001 0.08 0.2 5 0.2 0.01 0.8 0.1 0.02 0.03 0.01 0.02

ALR-115

Uncert

ALR-118

Uncert

ALR-119

Uncert

ALR-120

Uncert

ALR-121

Uncert

0.04 1.4 5.5 7.2 5.6 0.7 1017 3.5 0.9 0.3 0.25 1.3

0.02 1.3 0.4 0.7 0.1 0.01 15 0.02 0.06 0.1 0.04 0.04

0.1 0.5 3 4.6 4.5 0.4 11.9 2.9 0.9 0.06 0.2 0.03

0.01 0.01 0.1 0.2 0.1 0.01 0.7 0.01 0.04 0.002 0.03 0.01

0.03 2.8 9.7 62.6 21.8 1.2 37.2 6.3 1.1 0.08 0.09 0.27

0.01 2 0.25 0.9 0.4 0.05 0.3 0.07 0.01 0.05 0.01 0.01

0.01 0.6 5.5 38.2 25.4 0.9 195 0.6 0.6 0.05 0.003 0.001

0.01 0.6 0.005 0.6 0.5 0.04 0.9 0.04 0.01 0.03 0.02 0.001

0.08 1.95 9.8 40.7 16.9 1.4 134.1 5.2 1 0.13 0.13 0.36

0.01 2 0.32 1.4 0.6 0.08 1.7 0.07 0.05 0.01 0.04 0.02

(Continued)

Elements Be V Cr Mn Ni co Zn CU As Cd Sb Pb

/The

131

M.J. Duane,

ALR-122

Uncert

ALR-123

Uncert

ALR-124

Uncert

ALR-125

Uncert

0.04 0.8 5.5 14.3 2.9 0.7 35 4.9 0.5 0.1 0.12 0.12

0.01 0.8 0.05 0.2 0.17 0.02 0.4 0.04 0.03 0.07 0.03 0.01

0.02 1.2 8.2 172 10.1 1.3 252 2.4 0.7 0.07 0.09 0.75

0.01 2 0.5 0.8 0.08 0.02 0.62 0.04 0.08 0.02 0.02 0.01

0.01 0.74 2.4 4.4 5.7 0.5 191.3 1.5 0.3 0.4 0.03 0.001

0.005 0.9 0.2 0.3 0.08 0.01 2.7 0.04 0.04 0.02 0.003 0.001

0.9 2.8 5.8 52 47.9 4.6 778 7.6 1.1 0.3 0.23 46.5

0.001 1.6 0.03 0.5 0.13 0.03 4.5 0.13 0.01 0.02 0.01 0.2

ALR-126 mb ppb ppb mb mb ppb ppb ppb ppb ppb ppb mb

0.04 0.9 4.7 2.4 4.4 0.5 16.6 2.95 0.3 0.1 0.04 0.02

(1)

Uncert 0.01 1 0.17 0.2 0.2 0.01 1.4 0.04 0.09 0.08 0.07 0.02

ALR-126 0.08 1 2.3 2.2 4.5 0.5 17.2 3.3 0.3 0.01 0.06 0.06

(2)

Uncert 0.06 0.7 0.1 0.08 0.2 0.02 0.1 0.1 0.02 0.07 0.03 0.01

AIR-I 0.07 0.98 2.3 2.1 4.32 0.5 16.6 3.3 0.3 0.04 0.06 0.07

26 (3)

Uncert 0.01 0.5 0.09 0.01 0.05 0.002 0.2 0.03 0.02 0.03 0.04 0.03

Mean 0.06 0.96 3.10 2.23 4.41 0.5 16.8 3.2 0.3 0.05 0.05 0.05

Std. dev. 0.02 0.05 1.4 0.2 0.09 0.01 0.35 0.2 0.01 0.05 0.01 0.03

138

M.J. Duane,

Table

1

ALR-127 ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb

ALR-128

Elements ppb ppb ppb ppb ppb wb wb wb ppb ppb ppb wb

Elements

ALR-155

Be V CT Mh Ni Co Zn Cu As Cd Sb Pb

0.03 1.6 4.1 84.3 106 29.8 513 6.4 3.4 0.17 53 70.9

ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb

(1)

0.01 0.6 2.6 6 1.3 0.25 5.5 2.1 0.5 0.07 0.19 0.01

wb ppb ppb ppb ppb ppb mb ppb ppb ppb ppb ppb

Be V Cr Mn Ni co Zn CU As Cd Sb Pb

(1)

0.01 1.5 3.4 7 3.1 0.6 35.4 1.5 0.6 0.02 0.01 0.5

Elements Be V Cr Mn Ni co Zn CU As Cd Sb Pb

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172 (1995) 133-144

(Continued)

Elements Be V Cr Mn Ni co Zn CU As Cd Sb Pb

S. Facchetti

Uncert

AL,R-127

0.01 1 0.04 0.1 0.1 0.02 0.13 0.003 0.02 0.03 0.02 0.01

0.01 1.5 1.9 6.5 3 0.6 37.7 1.6 0.6 0.08 0.2 0.5

Uncert

ALR-128

0.01 0.7 0.09 0.05 0.09 0.002 0.07 0.04 0.02 0.09 0.03 0.01

0.03 0.001 0.6 0.01 0.1 0.01 0.1 0.02 0.04 0.04 0.01 0.01

(2)

(2)

ALR-138

Uncert

ALR-154

0.1 5.7 21.4 55.8 126.4 22.9 160.2 20.1 2.1 1.8 0.1 137.2

0.001 4 0.4 0.9 1.9 0.5 2.1 0.2 0.2 0.05 0.01 1.1

0.34 4.3 9.1 73.9 49.1 5 133.7 13.3 22.5 0.26 0.2 75.7

(1)

Uncert

ALR-155

0.02 0.9 0.14 1.4 1.9 0.5 7.5 0.12 0.09 0.05 0.13 0.6

0.004 1.5 1.1 81 106 28.9 539 6.8 3.3 0.22 55 74

(2)

Uncert

ALR-127

0.01 0.5 0.04 0.07 0.09 0.01 0.5 0.01 0.08 0.11 0.05 0.05

0.04 1.5 1.8 6.2 2.9 0.5 37.1 1.6 0.6 0.004 0.15 0.4

Uncer

ALzR-128

0.002 0.2 0.05 0.01 0.01 0.01 0.02 0.05 0.04 0.02 0.01 0.01

0.01 0.5 0.9 5.2 1.3 0.3 5.6 2.4 0.5 0.03 0.15 0.2

(1)

(3)

(3)

Uncert

ALR-154

0.01 1.7 0.03 2.3 0.9 0.1 1.6 0.13 0.09 0.03 0.01 0.3

0.26 3.3 4.7 67.8 48.1 4.8 14.3 13.7 21.3 0.2 0.22 78

Uncert

Mean

ALR-156

0.05 0.4 0.03 1.9 1.9 0.4 7.7 0.13 0.07 0.07 0.4 0.7

0.02 1.6 2.6 83 106 29.4 526 6.6 3.4 0.2 54 72.2

0.04 2.9 11.1 95 13.1 1.2 11572 26.2 0.9 0.2 0.8 178.8

(1)

Uncert

Mean

Std. dev.

0.004 0.5 0.05 0.2 0.1 0.03 0.5 0.02 0.03 0.04 0.02 0.008

0.02 1.5 2.4 6.6 3.0 0.6 36.7 1.6 0.6 0.04 0.12 0.5

0.02 0.01 0.9 0.4 0.1 0.06 1.2 0.06 0.01 0.04 0.01 0.1

Uncert

Mean

Std. dev.

0.004 0.3 0.04 0.16 0.1 0.01 0.1 0.9 0.01 0.05 0.01 0.01

0.02 0.37 1.37 3.74 0.90 0.19 3.73 1.51 0.35 0.05 0.12 0.07

0.01 0.32 1.1 3.3 0.7 0.2 3.2 1.3 0.3 0.02 0.1 0.1

(2)

Uncert

Mean

0.02 1.03 0.31 0.71 0.09 0.02 2.6 0.2 0.2 0.04 0.01 0.11

0.3 3.8 6.9 70.9 48.6 4.9 138 13.5 21.9 0.23 0.21 76.8

Uncert

ALR-156(2)

Uncert

Mean

0.03 2.1 0.04 0.8 0.09 0.02 56.6 0.2 0.3 0.1 0.05 0.8

0.007 2.6 8.1 92.5 12.9 1.13 12315 24.04 0.9 0.12 0.9 184.1

0.01 1.5 0.2 0.4 0.05 0.007 212.3 0.07 0.3 0.17 0.01 0.23

0.02 2.8 9.6 94 13 1.2 11944 25 0.9 0.2 0.9 182

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139

Table 1 (Continued) Elements

ALR-157 (1)

Uncert

ALR-X7(2)

Uncert

Mean

ALR-158(l)

Uncert

ALR-158 (2)

Uncert

Mean

Be V Cr Mn Ni Co Zn Cu As Cd Sb Pb

0.002 0.73 3.9 3.1 2.04 0.41 8.8 0.6 0.3 0.09 0.02 0.3

0.02

0.07

0.8

0.6

0.3

0.2

0.01 0.2 0.003

0.04 0.7 2.1

0.09

2.9 1.8 0.3

0.31 0.05

3 1.9 0.4 9.3 0.7 0.3 0.06

0.01 0.01

0.01 0.31

0.003 1.4 0.2 1.2 0.2 0.04 0.3 0.06 0.02 0.05 0.06 0.02

0.07 0.96 0.9 44.7 1.8 0.5 85 4.9 0.4 0.03 0.07 0.14

0.04 0.3 0.08 0.5 0.05

0.009 0.09 0.003 0.05 0.08

0.004 1.12 6.9 46.4 2.3 0.6 78.9 4.6 0.4 0.05 0.03

0.04 1.04 3.9 45.6 2.1 0.6 82 4.8 0.4 0.04 0.05 0.14

ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb

0.07

0.01 0.3 0.05

0.09 0.2 0.07 0.04

9.8 0.7 0.3 0.02

0.001 0.32

0.14

0.01 0.7 0.03 0.02 0.07 0.1 0.01

All samples were acidified on sampling day with nitric acid (Suprapure Merck). Sample numbers ALR 105 to ALR 158 are environmental water samples. ALR-105 = operative public well, ALR 106 = spring, ALR-107 = artesian well, ALR-108 = sample from surface well, ALR-109 = water table sampled at 25 m, ALR-110 = artesian well feeding aqueduct, ALR 111 = sample from aqueduct, ALR 112 = non-artesian abandoned well, ALR 113 = abandoned well, ALR 114 = artesian well, ALR 115 = domestic farm well, ALR 118 = abandoned domestic well, ALR 119 = abandoned domestic well, ALR 120 = abandoned domestic well, ALR 121 = abandoned domestic well, ALR 122 = abandoned domestic well, ALR 123 = fountain on roadway, ALR 124 = abandoned domestic well, ALR 125 = abandoned domestic well, ALR 126 = abandoned well, ALR 127 = abandoned domestic well, ALR 128 = abandoned well, ALR 138 = sampling depth with drilling at 11 m, ALR 154 = monitoring piezometer sampled at 13 m, ALR 155 = monitoring piezometer, water depth at 13.75 m, ALR 156 = monitoring piezometer on water table at 4.3 m, ALR 157 = spring, ALR 158 = abandoned domestic well.

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M.J. Duane, S. Facchetti /The Science of the Total Environment 172 (1995) 133-144

140

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h4.J. Duane,

S. Facchetti

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Science of the Total Environment

172 (1995) ALR-114

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141

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MI. Duane, S. Facchetti / The Science of the Total Environment 172 (1995) 133-144

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Science of the Total Environment

below. V is less than 5 ppb but sample AIR-138 has 5.7 ppb. Cr is mostly below 10 ppb for all samples except ALR-138 (21.4 ppb) and AIR-156 (9 ppb). Mn concentrations are variable but one sample AIR-107 has a value of 656 ppb. Samples AIR-105, 108, 109, 114, and 123 have more than 100 ppb Mn. Samples ALR-112, 119, 128, 138, 154,155, and 156 have more than 50 but less than 100 ppb. Ni concentrations are low except 2 samples with more than 100 ppb (AIR-138 and ALR155), along with two samples with more than 50 ppb (AIR 107, 109). AIR-155 and AIR-156 have the highest concentrations of Zn (12769.0 ppb), while sample AIR-115 has more than 1000 ppb Zn concentration. Two samples have more than 500 ppb (AIR125, 155) and seven samples have more than 100 ppb (AIR-120, 122, 124, 125, 138, 154). ALR-156 has more than 20 ppb Cu but the remaining samples have less than 10 ppb. The samples have in general low As concentrations except AIR-154 (22 ppb) and the remaining samples have less than 5 ppb. Cd values are low less than 2 ppb. Sb values are low except for AIR-155 (53 ppb). Pb concentrations are mostly low except in the following samples: ALR-156 has 180 ppb and AIR-138 has a concentration of 137 ppb Pb. AIR-154 and-155 have more than 70 ppb. The remaining samples have less than 2 ppb. Potentiometric stripping analyses were performed in parallel with our study in order to compare the elements Zn, Cu, Cd and Pb and the results for 23 samples are shown in Table 2 and comparative plots in Fig. 2. Measurement errors are in the range lo-20% with detection limits as follows: Cu (1 ppb), Cd (0.1 ppb), Pb (0.5 ppb), Zn (1 ppb), and Ni (1 ppb). The results for Cd and Pb show poor correlation (Y = 0.06 and Y = 0.03, respectively) but a good result was obtained for Zn yielding a high correlation (Y = 0.9). Correlation between the techniques is also poor for Cu (r = 0.34). For Ni the correlation is high (Y = 0.69). This method does successfully locate the highly anomalous samples AIR-121, 122, 123, 124, 125 and a second anomalous group from AIR-154, 155, 156, and 138 but the measurements do not compare for precision and accuracy with the ICP-MS results.

172 (1995) 133-144

143

4. Discussion In the Freiberg region the metallurgical industry is the main cause of the technogenic input of heavy-metal aerosols. High levels of Pb, Zn, Cd, and As occur in the immediate vicinity of non-ferrous metallurgical complexes [3]. Typically the anthropogenic/industrial loading in stream drainages in eastern Germany appears to be caused by direct discharge of residential, industrial and mining runoffs which results in multielement anomalies [4]. High contrast anomalies of the element Zn, Pb, Cr and As occur in residential as well as disused industrial sites. In the catchment area of the mining industry, stream waters typically contain the anomalous association Zn-Mn-Ni-Pb-Sb with values ranging from 10 to 30 times the regional geochemical background [4]. Stream drainages in our survey locality drain an old lignite mine and associated spoil heaps together with the products of coking coal such as tars. The source of heavy metals in our samples are therefore from two possible sources: the first from the regional mineralised veins that carry minerals with an association of Mo-Cu-Zn-Co-NiAs-Mn-V (in 1984 surface waters of these mining districts were loaded with electrolytes to the highest degree anywhere in Germany [41). The second potential source is the tar that was dumped into shallow (less than 10 m) pits close to aquifers. Enriched concentrations of V, Ni, Cu and Co have been noted in a variety of naturally occurring organic substances including crude oils, asphalts, and organic matter in sedimentary rocks, and their high stability suggests that they occur as porphyrin-type tetrapyrrole complexes or mixedligand tetradentates [5] and [61. The sources of V, Ni, and Co in the organic matter of sedimentary rocks are two-fold: the endemic metals in the living matter from which the organic accumulation was derived, and dissolved metals in the interstitial waters of the sediments from which the organic matter is deposited [5]. Multivariate statistics performed on the environmental water analyses reveal three distinct groups, a V-Pb-CrCu group, a Ni-Co group and a Be-Cd-As group suggesting a fundamental mineralogical aspect to the water anomalies.

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Today there are nearly 20 EEC directives related to protection of the aquatic environment. Directives exist which set quality standards related to specific use of water and on control of discharges to receiving waters. Examples of such Directives are Council Directive 76/464/EEC on pollution caused by certain dangerous substances discharged into the aquatic environment and Council Directive 88/280/EEC on the limit values for discharges of certain dangerous substances. Substances which could have a harmful effect on groundwater are Zn, Cu, Ni, Cr, Pb, Se, As, Sb, MO, Ti, Sn, Ba, Be, Bi, U, V, Co, Tl, Te, and Ag [5]. The maximum admissible concentrations (MAC) for EU drinking potable water [8] have been exceeded in some samples by 3-4 orders of magnitude in 50% of the samples analysed. The EEC MAC for Mn is 50 ppb, As 50 ppb, Cd 5 ppb, Cr 50 ppb, Ni 50 ppb, Pb 50 ppb (in running water), and Sb 10 ppb. Guidelines apply only for Cu (100 ppb at pump stations and 3000 ppb at the tap) and Zn (100 ppb at pumping stations and 5000 ppb at the tap). In Germany the MAC’s for drinking water are the same EU states [9] except for As (40 ppb) and Pb (40 ppb). ‘Hot spot’ sites near the inhabited area were located rapidly and assessment of the entire waterway was possible within days of the first analysis using the ICP-MS on-site. Although ICP-AES may share features such as the same dynamic range and simultaneous multielement detection, its sensitivity for many elements such as heavy metals is inadequate for direct measurement in the majority of surface waters [l], and is unlikely to migrate into the mobile laboratory for detailed surveys. In conclusion, increased awareness of water as a valuable commodity and the proliferation of studies on surface waters has spurred the scientific community to examine its capability in the analysis of surface and ground waters for a wide range of chemicals. The ICP-MS plays a major role in such analysis, producing data at sub-ppb to ppm levels for most metals which cannot be

172 (1995) 133-144

achieved with conventional methods such as PSA. Good duplicate and triplicate data were produced in this Eureka Project 674 illustrating the viability of transportable ICP-MS in the field conditions. Acknowledgements We would like to express our thanks to our colleagues from, the Danish FORCE Institute who performed the PSA analyses on site. We would also like to thank Fisons Instruments (UK) for providing the ruggedised ICP-MS for the duration of the Eureka Project 674. Thanks are also extended to Dr. Sabbioni for useful comments on the manuscript. References [II

G.E.M. Hall, Capabilities of production-oriented laboratories in water analysis using ICP-ES and ICP-MS. J. Geochem. Exp., 49, (1993) 89-121. I21 United States Environmental Protection Agency, Quality Assurance/Quality Control Guidance for Removal Activities: Sampling QA/QC Plan and Data Validation Procedures. Interim Final (1990). EPA/540/G-90/004. [31 B. Voland, Charakter und Genese anthropogener Veranderungen der Geochemie der Landschaft-ein Beitrag zur Umweltgeochemie (1985). Thesen zur Habilschrift. Bergakademie Freiburg. [41 M. Birke and U. Rauch, Environmental aspects of the regional geochemical survey in the southern part of East Germany. J. Geochem. Explor., 49 (1993) 35-61. [51 M.Langer, EC legislation covering the Protection of Groundwater. Eurocourse on Technologies for Environmental Clean-up: Soils and Groundwater. Ispra, Italy 1988. [61 M.D. Lewan and J.B. Maynard, Factors controlling enrichment of vanadium and nickel in the bitumen of organic sedimentary rocks. Geochim. Cosmochim. Acta, 46 (1982) 2547-2560. [71 D.A.C. Manning, Base metal transport in composite petroleum-brine systems. Abstracts, 28th International Geological Congress, (1989) Washington, D.C. 2. 181 Council Directive relating to the quality of drinking water intended for human consumption. Official Journal of the European Communities, 80/778/EEC 11-24. Dl M. Leiterer and U. Munch, Determination of heavy metals in groundwater samples-ICP-MS analysis and evaluation. Fresenius J. Anal. Chem., 350 (1994) 204-209.