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Determination of PCDDs and PCDFs in soil samples from Salzburg, Austria
Chemosphere, Vol.25,No.3, pp 283-291, 1992 Printed in Great Brilain
0045-6535/92 $5.00 + 0.00 Pergamon PressLtd.
DETERMINATION OF PCDDs AND PCDFs IN SOIL SAMPLES FROM SALZBURG,AUSTRIA
R.Boos*, A.Himsl, F.Wurst, T.Prey~d K.Scheidl 1 G. Sperka and O.Gl~serz IForschungsgesellschaft Technischer Umweltschutz (FTU) Shuttleworthstr. 4-8, A-1210 Vienna, Austria 2 Amt der Salzburger Landesregierung, Referat fiir Umweltschutz Michael-Pacher-Str.36, A - 5010 Salzburg (Received in Germany 14 May 1992; accepted 9 June 1992) ABSTRACT In 1990/91, a soil-sampling survey was conducted in the federal state of Salzburg, Austria, to determine the levels of concentration of PCDDs and PCDFs in rural, urban, and industrial sites. Background sampling was performed in undisturbed Alpine settings. The analyses were carried out isomer specifically to express the concentrations in TCDDequivalents (TE) as defined by FHO/Berlin and NATO/CCMS. INTRODUCTION While PCDD/PCDF emissions by such combustion sources as the municipal waste incinerators are regulated by the "Clean Air Act for Steam Boilers" (1-2), and numerous data on emissions have been collected, levels of these compounds in Austrian soils are not regulated, and information on soil pollution is limited to certain areas (3-8). The objective of this research was to evaluate the situation of soil pollution with PCDD/Fs at defined points in the federal state of Salzburg, to assess the actual situation and to derive information about supposed sources for further investigations. This study (9-10) was instigated and funded by the Government of the federal state of Salzburg (Department of Environmental Protection). Major studies in several countries indicate that PCDD/Fs are ubiquitous in industrial, urban, and rural areas (11-16), and the encountered profiles often display a typical pattern that is characterised by similar levels of PCDDs and PCDFs; PCDD amounts increase from tetra to octa homologues, while PCDF homologue concentrations remain at similar levels. Background levels are about 1 ng TEQ/kg, while contaminated sites can show up to 29/zg TEQ/kg. An unambiguous assignment to a specific source is rarely possible. A comparison of different studies is hampered by differences in sampling depths, and sometimes by a lack of isomer-specific data. * Author t o whom correspondence shoutd be addressed.
283
284
EXPERIMENTAL
Sampling 24 soil samples were taken in October 1990, April 1991 and October 1991. The sites were chosen because of the vicinity of potential sources, but remote background areas were also included in the survey. As far as possible, undisturbed soil was selected, but in conurbation areas this is difficult to achieve. The position of the sites chosen are indicated in Fig. 1. Brief descriptions of sampling sites are given in Tab, i. Detailed descriptions of soil characteristics were made by the Federal Institute of Soil Management. Sampling was performed by taking a series of 30cm-deep, 4cm-diameter cores on the periphery of a circle, whose centre was establised by cartography. For analysis, only the upper 10cm were taken. The total sample sizes was at least 500g.
Fig. 1: Soil sampling locations
285
Tab. 1: Sample site description ....
ii i
No~
Site descrip~on
Potential souree~ : :
1 2
urban outskirts, meadow urban soil, park area
3
urban traffic island
4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
urban outskirts, meadow 1 urban outskirts, meadow 1 urban outskirts, meadow urban outskirts, meadow urban outskirts, park area industrial area, meadow industrial area, meadow industrial area, meadow rural area, meadow rural area, meadow rural area, meadow rural area, meadow urban outskirts, meadow urban outskirts, meadow industrial area, meadow rural area, meadow urban outskirts, meadow urban outskirts, meadow urban outskirts, meadow rural area, meadow industrial area
urban immission area urban immission area, earlier small hospital waste incinerator (5Ore) urban immission area, high volume of trajfic (0,5m) urban immission area urban immission area urban immission area urban immission area urban immission area, street at 3-5m small cable processing plant small cable processing plant small cable processing plant diffuse immissions diffuse immissions diffuse immissions, highway at 110m diffuse immissions, highway at 200m upstream steel foundry, road at 150m downstream steel foundry, road at 50m various industrial plants, urban immissions Alpine background, no neighbouring sources secondary aluminium smelter, highway at 300m secondary aluminium smelter, highway at 300m diffuse immissions highway at 0,5m metal smelter and processing plant
1 Same location (sampling of No.4 on 10/90 and No.5 on 4/91)
CLEAN-UP
Soil samples were dried at 20oc to constant weight in the dark, manually sieved through a 2mm mesh sieve, and homogenised. The fraction < 2mm was spiked prior to extraction with known amounts of all 13C12-2,3,7,8-substituted PCDDs and PCDFs (Cambridge Isotopes Laboratories), with the exception of 2,3,4,6,7,8-HxCDF. All solvents used were nanograde (Mallinckrodt) or p.a. (Merck). Silica gel and basic alumina were purchased from Bio-Rad and ICN-Biomedicals,
respectively.
Samples
were
extracted
using
286
toluene in a soxhlet extractor for 48 hours. The cleanup includes a KOH-extraction to separate the chlorinated phenols, followed by H2SO4- and H20-liquid/liquid-extraction. The chromatographic cleanup system consists of a multilayer column (acid- and base-treated silicas) and a basic alumina column. The extracts were eventually cleaned further by gel-permeation-chromatography on Bio-Beads SX-3.
HIGH-RESOLUTION GAS CHROMATOGRAPHY/MASS SPECTROMETRY GC/MS analysis was carried out by splitless injection of 2 ~1 of extract on an HP-Ultra-2 (length 50m; i.d. 0.20 mm; 0.11 tzm film thickness) and an SP 2331 (length 60m; i.d. 0.25 ram; 0.20 /~m film thickness) fused silica capillary column for the isomer-specific analysis. Helium was used as the carrier gas. Column temperatures were programmed as follows: 120°C (4 min. isothermal), 16°C/rain. to 250°C (SP 2331)or 120°C (4 min. isothermal), 25°C/min. to 240°C, 4°C/rain. to 320°C (U 2). All samples were analyzed on a Carlo Erba QMD-1000 mass spectrometer in electron impact (El) ionization mode (70 eV, 250°C), using the Selected Ion Monitoring (SIM) mode. Identification and quantification was carried out by monitoring two masses ([M] + and [M +2] +, eventually [M +2-COC1] + and [M +4] +), and comparing the peak areas of the native isomers with the areas of the corresponding isotope labeled internal standards, assuming the same response for labeled and unlabeled isomers. Positive identification was made when the following criteria were fulfilled: correct retention time ( + / - 3 sec), signal-to-noise ratio >3: 1, and correct isotope ratio (+/-15%). Recovery rates of the added 13C-marked congeners should be > 50 and < 110%. The limits of detection were between 0,6 and 1,5 pg/g. RESULTS AND DISCUSSION The PCDD/PCDF data are summarized in the following tables. They are quoted in ppt (ng/kg dry weight) and 2,3,7,8-tetrachloredibenzo-p-dioxin Toxic Equivalents (TEQ) were calculated using the NATO/CCMS (17) and the FHO/Berlin (18) factors (column A). In the case of undetectable levels, the congener was also assumed present at 50% of the detection limit (column B).
A series of PCDD/Fs have been identified in all samples, however the levels were found to vary greatly between background locations and source-related samples. The congener group profile for the mean concentration of all samples is shown in Fig.2. A sharp increase from the tetra to the octa PCDD congeners is generally observed, while the PCDF-congener concentrations are in the same order of magnitude. O8CDD had the greatest abundance of PCDDs; the most toxic 2,3,7,8T4CDD was not detected in any sample. Higher levels of PCDDs than PCDFs are observed, and deviations from this mean profile may be due to the impact of a particular unidentified source and would require a detailed local investigation. In the case of samples 20 and 21 similarities with other samples (stack gas, filter dust, spruce needles) in the profile of chlorohomologues, the PCDD/PCDF-ratio, and the isomer-specific distribution of compounds of the same degree of chlorination make a source-soil correlation probable.
287
Tab.2: Summary of PCDD a n d PCDF data for all samples No.
ng/kg
1 2 3 4 5 6 7 8 9 10 11 12 13
104.9 151.6 770.2 1.154.8 475.1 453.4 1.403.6 150.4 302.8 269.9 270.0 129.6 43.2
14
76.1
15 16 17 18 19 20 21 22 23 24
58.6 79.3 117.8 158.6 19.1 183.9 265.5 204.1 261.3 810.3
ng TEQ (NATO)/kg
ng TE (FHO)/kg
A
B
A
3.2 2.8 8.6 5.9 2.8 4.4 5.4 3.2 5.0 7.6 4.3 3.8 1.7 1.6 1.9 2.0 2.5 4.1 1.3 3.5 6.0 4.3 3.8 12.5
2.2 1.7 8.5 5.7 2.3 3.8 5.6 2.4 4.6 7.2 4.2 3.2 0.8 0.9 1.1 1.1 2.0 3.1 0.1 3.2 5.6 4.3 3.6 9.6
2.3 1.8 8.3 5.2 1.8 3.9 4.5 2.2 4.0 6.9 3.5 3.0 0.8 0.6 0.9 1.0 1.8 3.7 0.1 2,8 5.3 3.6 3.1 11.5
B 3.1 2.6 8.9 6.2 3.0 4.4 6.2 3.1 5.3 7.6 4.7 3.9 1.7
1.9 1.9 1.9 2.4 3.6 1.3 3.7 6.2 4.8 4.1 10.5
A: undetectable congeners assumed as zero B: undetectable congeners assumed as 50% of detection limit
Fig.2: Mean ~ D D / P C D F concentrations of all samples expressed as ng/kg
160140120- - 100-
80--6040--20 0 T4CDD/F
PSCI~D/F
H6CDD/F ~c, molooe
H7GDD/F
OSCDD/F
288
Highly variable levels of PCDDs and PCDFs were found within a 2-hectare area situated in the outskirts of a major city (No.4-7). The variability is apparent in samples 4 and 5, which were taken at the same location 6 months apart and may be due to the past application of settling basin contents.
If the results are grouped with regard to the potential sources (Fig.3), it is evident, that no clearcut relationships can be obtained. Rural areas generally show lower PCDD/F-contents, but long range atmospheric deposition may contribute considerably in exposed locations (sample 12). The TEQ-figures are generally in the low ppt-range. Compared with the limits proposed by the FHO, 6 samples contain PCDD/F amounts over 5 ng TE (FHO)/kg, a limit which restricts the cultivation of certain vegetables, but none are over 40 ng TE (FHO)/kg, which would exclude the cultivation of any plants. Including in the calculation 50% of the detection limit, 7 samples would exceed the lower limit.
Fig.3: D~dbution of PCDD/Fswith regard~ potenfi~urces expressed as ng ~ (~0)/~
........
121 I~ wb.....
~ i~strio~zed ~eo
1(}
1 2 34587822
9101t161"1'18202t24 s a m p l e NO.
12131415
23
19.5 10.5 65.0
12.2 7.3
H7CDD
3.0 1.7
15.3 11.3 n.n.
12.1
65.1
H7CDF 1,2,3,4,6,7,8-H7CDF
O8CDF
Total content PCDF
Total content PCDD/F
1,2,3,4,7,8,9-H7CDF
104.9
6.4 2.2 n.n. 1.9
1,2,3,7,8,9-H6CDF 2,3,4,6,7,8-H6CDF
1 2,3,4,7,9-H6CDF 1;2,3,8,7,8-HTCDF
20.3
2.6 1.7
17.4
P5CDF 1,2,3,7,8-P5CDF + 1,2,3,4,8-P5CDF 2,3,4,7,8-P5CDF
H6CDF 1,2,3,4,7,8-H6CDF +
17.6
n.n. n.n.
T4CDF 2,3,7,8-T4CDF
151.6
56,3
10.2
15.8 9.8 0.5
3.3 2.1 n.n. n.n.
12.7
n.n. n.n.
95.3
19.4
39.8
O8CDD
10.8 n.n. n.n. n.n.
Total content PCDD
1,2,3,4,6,7,8-H7CDD
8.2 n.n. n.n. n.n.
H6CDD 1,2,3,4,7,8-H6CDD 1 2 3,6,7,8-H6CDD 112;3,7,8,9-H6CDD
n.n. n.n.
n.n. n.n.
n.n. n.n.
2
1,2,3,7,8-P5CDD
,
P5CDD
,
n.n. n.n.
,
T4CDD 2,3,7,8-T4CDD
,,
Tab.3: PCDD und PCDF concentrations (ng/kg)
770.2
260.8
30.1
57.5 38.8 2.9
11.3 4.3 n.n. n.n.
61.9
6.5 2.7
67.0
44.3 3.0
509.4
304.7
115.4 84.3
53.0 3.2 5.6 1.6
36.3 4.6
n,n. n.n.
3
1154.8
132.7
27.2
28.8 15.9 1.4
2.7 3.6 n.n. 1.8
27.5
4.2 2.2
28.7
20.5 6.1
1022.1
892.3
t02.1 57.7
25.4 1.5 3.3 3.0
2.3 n.n.
n.n. n.n.
4 ,,
5
475.1
71.6
26.1
25.3 12.4 0.5
1.3 2.1 n.n. 2.5
13.6
2.6 n.n.
6.6
n.n. n.n.
304.8
328.4
65.4 45.5
8.9 n.n. 1.1 n.n.
0.8 n.n.
n.n. n.n.
,
35.3 17.2 48.5
125.5 40,9 2.3 44.1 4.7 3.3 33.9
22.5 10.6 40.8
80.6 11.6 1.3 8.1 1.5 1.3 21.8
1022.O
356.7 1283.7
453.4
96.7
20.9
28.1 16.6 1.8
7.1 2.9 n.n. 2.8
28.4
3.3 1.6
19.3
n.n. n.n.
269.8
62.2 38.9
177.7
269.9
30.1 177.3
302.8
13.3 69.8 150.4
45.6
139.9 1403,6
12.8
29.3 18.5 4.1
28.3 19.0 1.8
15.0 12.0 n.n. 61.6 26.2 4.2
5.2 4.0 n.n. 5.5
14.0 5.2 1.2 3.2
42.5
13.4 5.3
64.1
28.4 3.8
92.2
29.4
27.9 13.8
21.6 0.8 1.8 1.6
6.3 n.n.
7.0 n.n.
i 0
3.6 1.9 n.n. 5.4 2.5 1.5 n.n. 3.9
29.7
1.7 n.n.
3.0
n.n. n.n.
197.1 121.8
3.9 4.6
2.0
38.7
5.9 n.n. 25.7 n.n. n.n. n.n.
19.2 n.n. 2.4 n.n.
5.5 1.1 16.1 n.n. n.n. n.n.
9
6.2 n.n.
8
1.2 B.a.
,, 9.8 n.n.
n.n. n.n.
7 n.n. n.n.
n.n, n.n.
6
270.0
144.8
3.5
17.4 12.7 n.n.
3.2 2.9 n.n. 5.0
28.7
2.3 2.8
39.3
55.9 2,2
125.2
57.2
33.4 16.2
20.3 n.n. 1.8 1.6
8.5 n.n.
5.8 n.n,
11 , , i,, ,,~
i2
129.6
75.7
10.9
13.5 13,5 n.n.
5.1 3.2 2.8 4.1
32.7
2.7 1.7
18.6
n.n. n.n.
53.9
19.2
20.0 10.8
14.7 1.1 1.1 n.n.
n.n. n.n.
n.n. n.n.
:,i,
xO
oo
290
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REFERENCES 1. Luftreinhaltegesetz ffir Kesselanlagen - LRG-K. BGB1. Nr. 380/1988 2. Luftreinhalteverordnung ffir Kesselanlagen - LRV-K. BGB1. Nr. 19/1989 and Novelle BGB1.Nr. 134/1990 3. Arbeitsgemeinschaft Technischer Umweltschutz und Technisches Bfiro Dr.J.Lueger (1989): Bericht iiber die Bodenbelastung im Gemeindegebiet Steyregg. 4. Wurst et al.: Bestimmung yon PCDD und PCDF in Proben aus dem Wiener Stadtgebiet, im Auftrag der Umweltschutzabteilung der Stadt Wien (MA 22 - 2028/87) 5. Umweltbundesamt 1990: Montanwerke Brixlegg - Wirkungen auf die Umwelt. Monographien Bd.25. Wien. 6. Riss A.,Hagenmaier H.,Weberruss U.,Schlatter C.,Wacker R., 1990: Comparison of PCDD/PCDF levels in soil, grass, cow's milk, human blood and spruce needles in an area of PCDD/PCDF contamination through emissions from a metal reclamation plant. Chemosphere 21/12,pp1451-1456. 7. Riss A.,Hagenmaler H.,Rotard W., 1990: Wirkungen von Dioxin-emissionen auf Boden, Griinlandaufwuchs und Kuhmilch - Fallstudie anhand einer Metallrfickgewinnungsanlage in Osterreich. In VDI-Berichte 837. Dfisseldorf. 8. Riss A., Weiss P., Hartl W., Hagenmaier H., 1990: PCDD/PCDF and PCB in soils of an industrialized area (Linz/Upper Austria). In: Hutzinger O., Fiedler H. (ed.): Organohalogen Comounds, Vol 4, Dioxin '90 - EPRI-Seminar Bayreuth. 421-423. 9. Boos et al (FTU), 1991: Bericht fiber die Bestimmung von polychlorierten Dibenzodioxinen und Dibenzofuranen in Bodenproben des Landes Salzburg.Forschungsgesellschaft Technischer Umweltschutz 1991. 10. Boos et al (FTU), 1991: Bericht fiber die Bestimmung von polychlorierten Dibenzodioxinen und Dibenzofuranen in zwei Feststoffproben. Forschungsgesellschaft Technischer Umweltschutz 1991. 11. Creaser C., Fernandes A., A1-Haddad A., Harrad S., Homer R.,Skett P., Cox E., 1989: Survey of background levels of PCDDs & PCDFs in UK soils. Chemosphere, Vol. 18, Nos. 1-6, pp 767-776. 12. Birmingham B., 1990: Analysis of PCDD and PCDF patterns in soil samples: use in the estimation of the risk of exposure. Chemosphere, Vol.20, Nos.7-9, pp 807-814. 13. Pearson R.G., McLaughlin D.L., McIlveen W.D., 1990: Concentrations of PCDD and PCDF in Ontario soils from the vicinity of refuse and sewage sludge incinerators and remote rural and urban locations. Chemosphere, Vol.20, Nos. 10-12, pp 1543-1548. 14. Ministerium f/Jr Umwelt, Raumordnung und Landwirtschaft des Landes NordrheinWestfalen, 1991: Chloraromaten - Herkunft und Transfer. 15. Landtag yon Baden-Wfirtemberg, 1990: 10.Wahlperiode, Drucksache 10/3011 vom 05.03.1990. 16. Hagenmeier, H., 1990: Importance of Sources, Levels in Air, Sewage Sludge and Water. Health Effects and Safety Assessments of Dioxins und Furans, January 15-17, Karlsruhe, Germany. Proceedings, 356ff. 17. NATO-CCMS report No. 178 (1988) International toxicity equivalency factor (I-TEF) method for risk assessment for complex mixtures of dioxins and related compounds. 18. Umweltbundesamt, 1984: Bericht "Sachstand Dioxine" November 84, 262-266. Umweltbundesamt, Bismarckplatz 1, 1000 Berlin 33.
0045-6535/92 $5.00 + 0.00 Pergamon PressLtd.
DETERMINATION OF PCDDs AND PCDFs IN SOIL SAMPLES FROM SALZBURG,AUSTRIA
R.Boos*, A.Himsl, F.Wurst, T.Prey~d K.Scheidl 1 G. Sperka and O.Gl~serz IForschungsgesellschaft Technischer Umweltschutz (FTU) Shuttleworthstr. 4-8, A-1210 Vienna, Austria 2 Amt der Salzburger Landesregierung, Referat fiir Umweltschutz Michael-Pacher-Str.36, A - 5010 Salzburg (Received in Germany 14 May 1992; accepted 9 June 1992) ABSTRACT In 1990/91, a soil-sampling survey was conducted in the federal state of Salzburg, Austria, to determine the levels of concentration of PCDDs and PCDFs in rural, urban, and industrial sites. Background sampling was performed in undisturbed Alpine settings. The analyses were carried out isomer specifically to express the concentrations in TCDDequivalents (TE) as defined by FHO/Berlin and NATO/CCMS. INTRODUCTION While PCDD/PCDF emissions by such combustion sources as the municipal waste incinerators are regulated by the "Clean Air Act for Steam Boilers" (1-2), and numerous data on emissions have been collected, levels of these compounds in Austrian soils are not regulated, and information on soil pollution is limited to certain areas (3-8). The objective of this research was to evaluate the situation of soil pollution with PCDD/Fs at defined points in the federal state of Salzburg, to assess the actual situation and to derive information about supposed sources for further investigations. This study (9-10) was instigated and funded by the Government of the federal state of Salzburg (Department of Environmental Protection). Major studies in several countries indicate that PCDD/Fs are ubiquitous in industrial, urban, and rural areas (11-16), and the encountered profiles often display a typical pattern that is characterised by similar levels of PCDDs and PCDFs; PCDD amounts increase from tetra to octa homologues, while PCDF homologue concentrations remain at similar levels. Background levels are about 1 ng TEQ/kg, while contaminated sites can show up to 29/zg TEQ/kg. An unambiguous assignment to a specific source is rarely possible. A comparison of different studies is hampered by differences in sampling depths, and sometimes by a lack of isomer-specific data. * Author t o whom correspondence shoutd be addressed.
283
284
EXPERIMENTAL
Sampling 24 soil samples were taken in October 1990, April 1991 and October 1991. The sites were chosen because of the vicinity of potential sources, but remote background areas were also included in the survey. As far as possible, undisturbed soil was selected, but in conurbation areas this is difficult to achieve. The position of the sites chosen are indicated in Fig. 1. Brief descriptions of sampling sites are given in Tab, i. Detailed descriptions of soil characteristics were made by the Federal Institute of Soil Management. Sampling was performed by taking a series of 30cm-deep, 4cm-diameter cores on the periphery of a circle, whose centre was establised by cartography. For analysis, only the upper 10cm were taken. The total sample sizes was at least 500g.
Fig. 1: Soil sampling locations
285
Tab. 1: Sample site description ....
ii i
No~
Site descrip~on
Potential souree~ : :
1 2
urban outskirts, meadow urban soil, park area
3
urban traffic island
4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
urban outskirts, meadow 1 urban outskirts, meadow 1 urban outskirts, meadow urban outskirts, meadow urban outskirts, park area industrial area, meadow industrial area, meadow industrial area, meadow rural area, meadow rural area, meadow rural area, meadow rural area, meadow urban outskirts, meadow urban outskirts, meadow industrial area, meadow rural area, meadow urban outskirts, meadow urban outskirts, meadow urban outskirts, meadow rural area, meadow industrial area
urban immission area urban immission area, earlier small hospital waste incinerator (5Ore) urban immission area, high volume of trajfic (0,5m) urban immission area urban immission area urban immission area urban immission area urban immission area, street at 3-5m small cable processing plant small cable processing plant small cable processing plant diffuse immissions diffuse immissions diffuse immissions, highway at 110m diffuse immissions, highway at 200m upstream steel foundry, road at 150m downstream steel foundry, road at 50m various industrial plants, urban immissions Alpine background, no neighbouring sources secondary aluminium smelter, highway at 300m secondary aluminium smelter, highway at 300m diffuse immissions highway at 0,5m metal smelter and processing plant
1 Same location (sampling of No.4 on 10/90 and No.5 on 4/91)
CLEAN-UP
Soil samples were dried at 20oc to constant weight in the dark, manually sieved through a 2mm mesh sieve, and homogenised. The fraction < 2mm was spiked prior to extraction with known amounts of all 13C12-2,3,7,8-substituted PCDDs and PCDFs (Cambridge Isotopes Laboratories), with the exception of 2,3,4,6,7,8-HxCDF. All solvents used were nanograde (Mallinckrodt) or p.a. (Merck). Silica gel and basic alumina were purchased from Bio-Rad and ICN-Biomedicals,
respectively.
Samples
were
extracted
using
286
toluene in a soxhlet extractor for 48 hours. The cleanup includes a KOH-extraction to separate the chlorinated phenols, followed by H2SO4- and H20-liquid/liquid-extraction. The chromatographic cleanup system consists of a multilayer column (acid- and base-treated silicas) and a basic alumina column. The extracts were eventually cleaned further by gel-permeation-chromatography on Bio-Beads SX-3.
HIGH-RESOLUTION GAS CHROMATOGRAPHY/MASS SPECTROMETRY GC/MS analysis was carried out by splitless injection of 2 ~1 of extract on an HP-Ultra-2 (length 50m; i.d. 0.20 mm; 0.11 tzm film thickness) and an SP 2331 (length 60m; i.d. 0.25 ram; 0.20 /~m film thickness) fused silica capillary column for the isomer-specific analysis. Helium was used as the carrier gas. Column temperatures were programmed as follows: 120°C (4 min. isothermal), 16°C/rain. to 250°C (SP 2331)or 120°C (4 min. isothermal), 25°C/min. to 240°C, 4°C/rain. to 320°C (U 2). All samples were analyzed on a Carlo Erba QMD-1000 mass spectrometer in electron impact (El) ionization mode (70 eV, 250°C), using the Selected Ion Monitoring (SIM) mode. Identification and quantification was carried out by monitoring two masses ([M] + and [M +2] +, eventually [M +2-COC1] + and [M +4] +), and comparing the peak areas of the native isomers with the areas of the corresponding isotope labeled internal standards, assuming the same response for labeled and unlabeled isomers. Positive identification was made when the following criteria were fulfilled: correct retention time ( + / - 3 sec), signal-to-noise ratio >3: 1, and correct isotope ratio (+/-15%). Recovery rates of the added 13C-marked congeners should be > 50 and < 110%. The limits of detection were between 0,6 and 1,5 pg/g. RESULTS AND DISCUSSION The PCDD/PCDF data are summarized in the following tables. They are quoted in ppt (ng/kg dry weight) and 2,3,7,8-tetrachloredibenzo-p-dioxin Toxic Equivalents (TEQ) were calculated using the NATO/CCMS (17) and the FHO/Berlin (18) factors (column A). In the case of undetectable levels, the congener was also assumed present at 50% of the detection limit (column B).
A series of PCDD/Fs have been identified in all samples, however the levels were found to vary greatly between background locations and source-related samples. The congener group profile for the mean concentration of all samples is shown in Fig.2. A sharp increase from the tetra to the octa PCDD congeners is generally observed, while the PCDF-congener concentrations are in the same order of magnitude. O8CDD had the greatest abundance of PCDDs; the most toxic 2,3,7,8T4CDD was not detected in any sample. Higher levels of PCDDs than PCDFs are observed, and deviations from this mean profile may be due to the impact of a particular unidentified source and would require a detailed local investigation. In the case of samples 20 and 21 similarities with other samples (stack gas, filter dust, spruce needles) in the profile of chlorohomologues, the PCDD/PCDF-ratio, and the isomer-specific distribution of compounds of the same degree of chlorination make a source-soil correlation probable.
287
Tab.2: Summary of PCDD a n d PCDF data for all samples No.
ng/kg
1 2 3 4 5 6 7 8 9 10 11 12 13
104.9 151.6 770.2 1.154.8 475.1 453.4 1.403.6 150.4 302.8 269.9 270.0 129.6 43.2
14
76.1
15 16 17 18 19 20 21 22 23 24
58.6 79.3 117.8 158.6 19.1 183.9 265.5 204.1 261.3 810.3
ng TEQ (NATO)/kg
ng TE (FHO)/kg
A
B
A
3.2 2.8 8.6 5.9 2.8 4.4 5.4 3.2 5.0 7.6 4.3 3.8 1.7 1.6 1.9 2.0 2.5 4.1 1.3 3.5 6.0 4.3 3.8 12.5
2.2 1.7 8.5 5.7 2.3 3.8 5.6 2.4 4.6 7.2 4.2 3.2 0.8 0.9 1.1 1.1 2.0 3.1 0.1 3.2 5.6 4.3 3.6 9.6
2.3 1.8 8.3 5.2 1.8 3.9 4.5 2.2 4.0 6.9 3.5 3.0 0.8 0.6 0.9 1.0 1.8 3.7 0.1 2,8 5.3 3.6 3.1 11.5
B 3.1 2.6 8.9 6.2 3.0 4.4 6.2 3.1 5.3 7.6 4.7 3.9 1.7
1.9 1.9 1.9 2.4 3.6 1.3 3.7 6.2 4.8 4.1 10.5
A: undetectable congeners assumed as zero B: undetectable congeners assumed as 50% of detection limit
Fig.2: Mean ~ D D / P C D F concentrations of all samples expressed as ng/kg
160140120- - 100-
80--6040--20 0 T4CDD/F
PSCI~D/F
H6CDD/F ~c, molooe
H7GDD/F
OSCDD/F
288
Highly variable levels of PCDDs and PCDFs were found within a 2-hectare area situated in the outskirts of a major city (No.4-7). The variability is apparent in samples 4 and 5, which were taken at the same location 6 months apart and may be due to the past application of settling basin contents.
If the results are grouped with regard to the potential sources (Fig.3), it is evident, that no clearcut relationships can be obtained. Rural areas generally show lower PCDD/F-contents, but long range atmospheric deposition may contribute considerably in exposed locations (sample 12). The TEQ-figures are generally in the low ppt-range. Compared with the limits proposed by the FHO, 6 samples contain PCDD/F amounts over 5 ng TE (FHO)/kg, a limit which restricts the cultivation of certain vegetables, but none are over 40 ng TE (FHO)/kg, which would exclude the cultivation of any plants. Including in the calculation 50% of the detection limit, 7 samples would exceed the lower limit.
Fig.3: D~dbution of PCDD/Fswith regard~ potenfi~urces expressed as ng ~ (~0)/~
........
121 I~ wb.....
~ i~strio~zed ~eo
1(}
1 2 34587822
9101t161"1'18202t24 s a m p l e NO.
12131415
23
19.5 10.5 65.0
12.2 7.3
H7CDD
3.0 1.7
15.3 11.3 n.n.
12.1
65.1
H7CDF 1,2,3,4,6,7,8-H7CDF
O8CDF
Total content PCDF
Total content PCDD/F
1,2,3,4,7,8,9-H7CDF
104.9
6.4 2.2 n.n. 1.9
1,2,3,7,8,9-H6CDF 2,3,4,6,7,8-H6CDF
1 2,3,4,7,9-H6CDF 1;2,3,8,7,8-HTCDF
20.3
2.6 1.7
17.4
P5CDF 1,2,3,7,8-P5CDF + 1,2,3,4,8-P5CDF 2,3,4,7,8-P5CDF
H6CDF 1,2,3,4,7,8-H6CDF +
17.6
n.n. n.n.
T4CDF 2,3,7,8-T4CDF
151.6
56,3
10.2
15.8 9.8 0.5
3.3 2.1 n.n. n.n.
12.7
n.n. n.n.
95.3
19.4
39.8
O8CDD
10.8 n.n. n.n. n.n.
Total content PCDD
1,2,3,4,6,7,8-H7CDD
8.2 n.n. n.n. n.n.
H6CDD 1,2,3,4,7,8-H6CDD 1 2 3,6,7,8-H6CDD 112;3,7,8,9-H6CDD
n.n. n.n.
n.n. n.n.
n.n. n.n.
2
1,2,3,7,8-P5CDD
,
P5CDD
,
n.n. n.n.
,
T4CDD 2,3,7,8-T4CDD
,,
Tab.3: PCDD und PCDF concentrations (ng/kg)
770.2
260.8
30.1
57.5 38.8 2.9
11.3 4.3 n.n. n.n.
61.9
6.5 2.7
67.0
44.3 3.0
509.4
304.7
115.4 84.3
53.0 3.2 5.6 1.6
36.3 4.6
n,n. n.n.
3
1154.8
132.7
27.2
28.8 15.9 1.4
2.7 3.6 n.n. 1.8
27.5
4.2 2.2
28.7
20.5 6.1
1022.1
892.3
t02.1 57.7
25.4 1.5 3.3 3.0
2.3 n.n.
n.n. n.n.
4 ,,
5
475.1
71.6
26.1
25.3 12.4 0.5
1.3 2.1 n.n. 2.5
13.6
2.6 n.n.
6.6
n.n. n.n.
304.8
328.4
65.4 45.5
8.9 n.n. 1.1 n.n.
0.8 n.n.
n.n. n.n.
,
35.3 17.2 48.5
125.5 40,9 2.3 44.1 4.7 3.3 33.9
22.5 10.6 40.8
80.6 11.6 1.3 8.1 1.5 1.3 21.8
1022.O
356.7 1283.7
453.4
96.7
20.9
28.1 16.6 1.8
7.1 2.9 n.n. 2.8
28.4
3.3 1.6
19.3
n.n. n.n.
269.8
62.2 38.9
177.7
269.9
30.1 177.3
302.8
13.3 69.8 150.4
45.6
139.9 1403,6
12.8
29.3 18.5 4.1
28.3 19.0 1.8
15.0 12.0 n.n. 61.6 26.2 4.2
5.2 4.0 n.n. 5.5
14.0 5.2 1.2 3.2
42.5
13.4 5.3
64.1
28.4 3.8
92.2
29.4
27.9 13.8
21.6 0.8 1.8 1.6
6.3 n.n.
7.0 n.n.
i 0
3.6 1.9 n.n. 5.4 2.5 1.5 n.n. 3.9
29.7
1.7 n.n.
3.0
n.n. n.n.
197.1 121.8
3.9 4.6
2.0
38.7
5.9 n.n. 25.7 n.n. n.n. n.n.
19.2 n.n. 2.4 n.n.
5.5 1.1 16.1 n.n. n.n. n.n.
9
6.2 n.n.
8
1.2 B.a.
,, 9.8 n.n.
n.n. n.n.
7 n.n. n.n.
n.n, n.n.
6
270.0
144.8
3.5
17.4 12.7 n.n.
3.2 2.9 n.n. 5.0
28.7
2.3 2.8
39.3
55.9 2,2
125.2
57.2
33.4 16.2
20.3 n.n. 1.8 1.6
8.5 n.n.
5.8 n.n,
11 , , i,, ,,~
i2
129.6
75.7
10.9
13.5 13,5 n.n.
5.1 3.2 2.8 4.1
32.7
2.7 1.7
18.6
n.n. n.n.
53.9
19.2
20.0 10.8
14.7 1.1 1.1 n.n.
n.n. n.n.
n.n. n.n.
:,i,
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290
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291
REFERENCES 1. Luftreinhaltegesetz ffir Kesselanlagen - LRG-K. BGB1. Nr. 380/1988 2. Luftreinhalteverordnung ffir Kesselanlagen - LRV-K. BGB1. Nr. 19/1989 and Novelle BGB1.Nr. 134/1990 3. Arbeitsgemeinschaft Technischer Umweltschutz und Technisches Bfiro Dr.J.Lueger (1989): Bericht iiber die Bodenbelastung im Gemeindegebiet Steyregg. 4. Wurst et al.: Bestimmung yon PCDD und PCDF in Proben aus dem Wiener Stadtgebiet, im Auftrag der Umweltschutzabteilung der Stadt Wien (MA 22 - 2028/87) 5. Umweltbundesamt 1990: Montanwerke Brixlegg - Wirkungen auf die Umwelt. Monographien Bd.25. Wien. 6. Riss A.,Hagenmaier H.,Weberruss U.,Schlatter C.,Wacker R., 1990: Comparison of PCDD/PCDF levels in soil, grass, cow's milk, human blood and spruce needles in an area of PCDD/PCDF contamination through emissions from a metal reclamation plant. Chemosphere 21/12,pp1451-1456. 7. Riss A.,Hagenmaler H.,Rotard W., 1990: Wirkungen von Dioxin-emissionen auf Boden, Griinlandaufwuchs und Kuhmilch - Fallstudie anhand einer Metallrfickgewinnungsanlage in Osterreich. In VDI-Berichte 837. Dfisseldorf. 8. Riss A., Weiss P., Hartl W., Hagenmaier H., 1990: PCDD/PCDF and PCB in soils of an industrialized area (Linz/Upper Austria). In: Hutzinger O., Fiedler H. (ed.): Organohalogen Comounds, Vol 4, Dioxin '90 - EPRI-Seminar Bayreuth. 421-423. 9. Boos et al (FTU), 1991: Bericht fiber die Bestimmung von polychlorierten Dibenzodioxinen und Dibenzofuranen in Bodenproben des Landes Salzburg.Forschungsgesellschaft Technischer Umweltschutz 1991. 10. Boos et al (FTU), 1991: Bericht fiber die Bestimmung von polychlorierten Dibenzodioxinen und Dibenzofuranen in zwei Feststoffproben. Forschungsgesellschaft Technischer Umweltschutz 1991. 11. Creaser C., Fernandes A., A1-Haddad A., Harrad S., Homer R.,Skett P., Cox E., 1989: Survey of background levels of PCDDs & PCDFs in UK soils. Chemosphere, Vol. 18, Nos. 1-6, pp 767-776. 12. Birmingham B., 1990: Analysis of PCDD and PCDF patterns in soil samples: use in the estimation of the risk of exposure. Chemosphere, Vol.20, Nos.7-9, pp 807-814. 13. Pearson R.G., McLaughlin D.L., McIlveen W.D., 1990: Concentrations of PCDD and PCDF in Ontario soils from the vicinity of refuse and sewage sludge incinerators and remote rural and urban locations. Chemosphere, Vol.20, Nos. 10-12, pp 1543-1548. 14. Ministerium f/Jr Umwelt, Raumordnung und Landwirtschaft des Landes NordrheinWestfalen, 1991: Chloraromaten - Herkunft und Transfer. 15. Landtag yon Baden-Wfirtemberg, 1990: 10.Wahlperiode, Drucksache 10/3011 vom 05.03.1990. 16. Hagenmeier, H., 1990: Importance of Sources, Levels in Air, Sewage Sludge and Water. Health Effects and Safety Assessments of Dioxins und Furans, January 15-17, Karlsruhe, Germany. Proceedings, 356ff. 17. NATO-CCMS report No. 178 (1988) International toxicity equivalency factor (I-TEF) method for risk assessment for complex mixtures of dioxins and related compounds. 18. Umweltbundesamt, 1984: Bericht "Sachstand Dioxine" November 84, 262-266. Umweltbundesamt, Bismarckplatz 1, 1000 Berlin 33.