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Human and environmental biomonitoring of polychlorinated biphenyls and hexachlorobenzene in Saxony, Germany based on the German Environmental Specimen Bank
International Journal of Hygiene and Environmental Health 215 (2012) 220–223
Contents lists available at SciVerse ScienceDirect
International Journal of Hygiene and Environmental Health journal homepage: www.elsevier.de/ijheh
Short communication
Human and environmental biomonitoring of polychlorinated biphenyls and hexachlorobenzene in Saxony, Germany based on the German Environmental Specimen Bank Marchela Pandelova a,∗ , Karl-Werner Schramm a,b a b
Helmholtz Zentrum München, German Research Center for Environmental Health, Institute of Ecological Chemistry, Ingolstädter Landstrasse 1, 85764 Neuherberg, Germany TUM, Wissenschaftszentrum Weihenstephan für Ernährung und Landnutzung, Department für Biowissenschaften, Weihenstephaner Steig 23, 85350 Freising, Germany
a r t i c l e
i n f o
Keywords: PCB HCB Human biomonitoring Pine shoots Ecosurveillance Germany
a b s t r a c t The objective of the present study was to investigate the principle relationships between concentrations in human and environmental matrices of polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) in short distance comparable areas within Saxony, Germany by employing the data of the German Environmental Specimen Banking (ESB). Examples supporting this idea were presented by selecting data on blood plasma collected from students in University of Halle and pine shoots, egg matter of city pigeons, earthworm, and roe deer liver. Similar pattern for PCB 138 and PCB 180 was found for the human plasma and pine shoots samples during investigated years and the human data followed the corresponding environmental levels with some delay of approximately two years. However, PCB 153 that was the prevailing congener did not manifest this relationship. In addition, the correlation of the ratios of concentrations (human/environmental concentration) to some physicochemical constants such as molecular weight (MW), octanol–water partition coefficient (log Kow ), Henry’s law constant (KH ), and sorption partition coefficient (log Koc ) of HCB, PCB 138, PCB 153, and PCB 180 were studied. The resulted negative slopes with all constants in case of blood plasma/city pigeons egg matter pairs suggested that the accumulation of lipophilic compounds is more pronounced in pigeon eggs than in human blood. © 2011 Elsevier GmbH. All rights reserved.
Introduction Due to the hydrophobic and lipophilic nature of polychlorinated biphenyls (PCBs) and their resistance to degrade, these compounds bioaccumulate in the environment and are widely found in humans. Other persistent organic pollutants (POPs) such as hexachlorobenzene (HCB) and organochlorine pesticides were also widely used throughout the developed world. Although the HCB production was banned in Germany in 1993, some levels still exist in the environment and these chemicals are a matter of concern (Wang et al., 2010). In environmental health, biological monitoring of pollutant concentration in human tissue and fluids are used frequently for better assessment of exposure from multiple sources and routes. In Germany, the Human Biomonitoring Commission of the German Federal Environment Agency established scientifically based criteria for the application for human biomonitoring in 1992 (Wilhelm et al., 2003; Schulz et al., in press; Angerer et al., 2011). In this study, the levels of HCB, PCB 138, PCB 153, and PCB 180 in blood plasma and different environmental matrices collected in short
∗ Corresponding author. Tel.: +49 89 3187 2932; fax: +49 89 3187 3371. E-mail address: [email protected] (M. Pandelova). 1438-4639/$ – see front matter © 2011 Elsevier GmbH. All rights reserved. doi:10.1016/j.ijheh.2011.11.005
distance comparable areas within Saxony, Germany areas were investigated. For human risk management, human biomonitoring data can be interpreted using the recently developed concept of biomonitoring equivalents (BE) using toxicokinetic data. In this regard, methodologies such as toxicokinetic models allowed to estimate the biomarker concentrations based on physico-chemical properties (Boogaard et al., 2011). Consequently, the bioconcentration ratios (human/environmental concentration) as a function of some physicochemical constants were studied. Materials and methods Investigated human and environmental samples The investigated human data encompassed blood plasma sampled between 1995 and 2008 from students from University of Halle with an even number of female and male at the age of 20–29. Furthermore, different environmental samples were studied such as (1) pine shoots from the nature park Dübener Heide sampled during 1993, 1995, 1997, 1999–2004; (2) and (3) egg matter of city pigeons from the residential use areas in Halle and Leipzig sampled during 1997, 2000–2008, and 2000–2008, respectively; (4) and (5) earthworm (Lumbricus terrestris) from park areas of Halle and
blood plasma (μg/L fw)
A
0.8 0.6 0.4 0.2 0 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
blood plasma (μg/L fw)
pine shoots (μg/kg dw)
1.5
A
1 0.5 0 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
0.4
pine shoots (μg/kg dw)
blood plasma (μg/L fw)
A
0.3 0.2 0.1 0 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
PCB138 concentration level
pine shoots (μg/kg dw)
1
PCB153 concentration level
1.2
PCB180 concentration level
PCB180 concentration level
PCB153 concentration levels
PCB138 concentration level
M. Pandelova, K.-W. Schramm / International Journal of Hygiene and Environmental Health 215 (2012) 220–223
221
pine shoots (μg/kg dw) blood plasma (μg/L fw) *adapted with 2 years
1.2
B
1
0.8 0.6 0.4 0.2 0 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004
pine shoots (μg/kg dw) blood plasma (μg/L fw) *adapted with 2 years
1.5
B
1 0.5 0 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004
pine shoots (μg/kg dw) blood plasma (μg/L fw) *adapted with 2 years
0.4
B
0.3 0.2 0.1 0 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004
Fig. 1. PCB 138, PCB 153 and PCB 180 level in human blood plasma during 1995–2006 and pine shoots during 1993–2004 sampled from Halle and nature park Dübener Heide, respectively (A). Human data adapted by shifting by two years back (B).
Leipzig sampled during 2000–2008 and 1999–2008, respectively; (6) roe deer liver from nature park Dübener Heide sampled during 1995 and 1999–2008. These human and environmental data were selected due to the short distance between collected samples of approximately 60 and 40 km within nature park Dübener Heide–Halle and Leipzig–Halle, respectively. The number of the species used is presented in Table 1, whereas additional biometric and anamnestic parameters are given elsewhere (Federal Environment Agency). Determination of PCB and HCB Detailed information on clean-up procedure and instrumental parameters for analyzing environmental and human samples are given elsewhere (Federal Environment Agency). Hexachlorobenzene (HCB) and polychlorinated biphenyls (PCB 138, PCB 153, PCB 180) were identified and quantified in g/L fw, ng/g fw, ng/g fw and ng/g fw for blood plasma, egg matter of city pigeons, earthworm and roe deer liver, respectively. Pines shoots samples were homogenized and grinded powder in sub-samples of approx. 10 g in the vapor phase above liquid nitrogen (Rappolder et al., 2007). Analysis for PCB was performed only and the results were presented in ng/g dw. The concentration levels of investigated species are presented in Table 2.
Evaluation of the data The pair of human and environmental data within sampled year and compound were identified. In all cases, the human data were from the blood plasma sampled from Halle whereas the environmental data varied between the above mentioned matrices. The arithmetic mean (Federal Environment Agency) pair data within investigated years and within compound were divided such as human/environmental concentration, named as bioconcentration ratios. Consequently, the mean and standard deviation of resulted ratios within compound were calculated. In order to find a relationship between these ratios and the physicochemical properties for certain compounds, the molecular weight (MW), octanol–water partition coefficient (log Kow ), Henry’s law constant (KH ), and sorption partition coefficient (log Koc ) constants were identified (Mackay et al., 1992). The used physicochemical properties were MW: 284.8, 360.9, 360.9, 395 g/mol (Baker et al., 2000); log Kow (1): 5.5, 6.5, 6.5, 6.7 (Oliver, 1987); Kow (2): 5.5, 6.7, 6.8, 7.2 (Ballschmiter and Wittlinger, 1991); KH : 139, 69, 13.4, 102 Pa m3 mol−1 at 298 K (Ballschmiter and Wittlinger, 1991), log KOC : 5.8, 7.6, 7.2, 7.30 (Oliver, 1987a) for HCB, PCB 138, PCB 153 and PCB 180, respectively. Finally, the linear correlation and slopes and y-intercepts were studied and discussed.
Table 1 Number species used. Species (n)
1993
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
Pine shoots Human blood plasma Egg matter of city pigeons Earthworm Roe deer liver
15
15 97
77
15 90 20
91
15 88
15 98 31 857 11
15 65 20 850 11
15 117 32 890 11
15 104 40 953 10
15 105 20 857 9
15 102 40 756 12
15 106 40 727 6
15 108 75 978 13
15 106 50 782 11
2
4
222
M. Pandelova, K.-W. Schramm / International Journal of Hygiene and Environmental Health 215 (2012) 220–223
Table 2 Concentration levels of PCB 138, PCB 153, PCB 180, and HCB in pine shoots, human blood plasma, egg matter of city pigeons, earthworm, and roe deer liver, respectively.
PCB 138 Pine shoots (ng/g dw) Blood plasma (g/L fw) Egg matter of city pigeons (ng/g fw) Earthworm (ng/g fw) Roe deer liver (ng/g fw) PCB 153 Pine shoots (ng/g dw) Blood plasma (g/L fw) Egg matter of city pigeons (ng/g fw) Earthworm (ng/g fw) Roe deer liver (ng/g fw) PCB 180 Pine shoots (ng/g dw) Blood plasma (g/L fw) Egg matter of city pigeons (ng/g fw) Earthworm (ng/g fw) Roe deer liver (ng/g fw) HCB Blood plasma (g/L fw) Egg matter of city pigeons (ng/g fw) Earthworm (ng/g fw) Roe deer liver (ng/g fw)
1993
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
0.44
0.36 0.62
0.79
0.29 0.84 1.73
0.65
0.48 0.76
0.32 0.30
0.23 0.65 1.39 1.75 0.19 0.20 0.20
0.22 0.82 1.18 1.22 0.23 0.21 0.31
0.14 0.50 1.48 0.85 0.22 0.19 0.43
0.15 0.60 0.84 0.88 0.78 0.22 0.70
0.14 0.50 0.65 0.37 0.30 0.22 0.93
0.46 1.61 1.38 0.77 0.28 0.43
0.37 0.73 0.46 0.32 0.19 0.30
0.42 1.05 1.34 0.19 0.22 0.20
0.34 0.71 0.65 0.37 0.21 0.21
1.17 0.42 1.36 1.81 0.19 0.21 0.61
0.56 0.51 1.25 1.21 0.24 0.21 0.21
0.56 0.49 1.51 1.15 0.23 0.19 0.59
0.36 0.30 0.82 0.84 0.26 0.22 0.71
0.31 0.31 0.62 0.38 0.23 0.23 0.89
0.35 0.29 1.59 1.28 0.40 0.29 0.74
0.28 0.94 0.91 0.26 0.23 0.57
0.26 1.44 1.29 0.19 0.22 0.31
0.25 0.97 0.74 0.23 0.22 0.45
0.22
0.19 0.26 0.82 1.10 0.06 0.07 0.33
0.12 0.18 0.79 0.77 0.08 0.07 0.19
0.12 0.32 0.99 0.59 0.07 0.06 0.36
0.04 0.18 0.55 0.57 0.16 0.07 0.45
0.08 0.20 0.31 0.31 0.07 0.07 0.60
0.07 0.15 0.78 0.95 0.16 0.09 0.36
0.14 0.53 0.46 0.07 0.06 0.26
0.14 1.01 0.59 0.08 0.07 0.17
0.13 0.54 0.43 0.08 0.07 0.22
0.12
0.20
0.21 0.18 0.23 0.71 0.26 0.25
0.21 0.13 0.19 0.95 0.29 0.40
0.18 0.23 0.16 0.88 0.40 0.63
0.17 0.35 0.50 0.83 0.52 0.85
0.14 0.29 0.10 0.86 0.29 0.82
0.15 0.15 0.18 1.07 0.22 0.29
0.12 0.52 0.31 0.21 0.04 0.53
0.13 0.15 0.17 0.66 0.26 0.36
0.12 0.12 0.24 0.59 0.20 0.29
Halle Leipzig Halle Leipzig 0.19 0.87
0.69 0.53
0.53
Halle Leipzig Halle Leipzig
0.47 0.51 2.01
0.47
0.33 0.33 0.20
0.17 0.32
0.32
Halle Leipzig Halle Leipzig
0.12 0.33 0.77
0.25
0.10 0.16 0.51
Halle Leipzig Halle Leipzig
0.40
0.31 0.48
0.19
0.28 0.30
0.20
Results and discussion The PCB results of blood plasma and pine shoots sampled from Halle and nature park Dübener Heide, respectively during 1995–2008 are shown in Fig. 1A. Similar pattern was found for both type samples during investigated years whereas the human data followed the corresponding environmental levels with some delay. Thus, the human data curve was additionally adapted by shifting it by two years back as shown in Fig. 1B. Consequently, fairly good relationship was found for both blood plasma and pine shoots samples in regard to PCB 138 and PCB 180. However, PCB 153 that was the prevailing congener did not manifest such dependence. The results of the mean and standard deviation for HCB, PCB 138, PCB 153 and PCB 180 based on human/environmental data (bioconcentration ratios) are presented in Table 3. Since Halle has been an industrial city since the nineteenth century, somewhat lower bioconcentration ratios were found for this area compared to the human/environmental ratios regarding Leipzig. In addition, the linear regression coefficient and related slope and y-intercepts as a function of MW, log Kow (1), log Kow (1), KH , and log Koc are shown in Table 4.
0.22
0.08
Particularly, in case of blood plasma/city pigeons egg matter pairs negative slopes were found for the correlations with all constants in both locations. Since the octanol–water partition coefficient (Kow ) and sorption partition coefficient (log Koc ) as well as the Henry’s constant (KH ) are used to calculate the transport and fate of chemicals in the environment or eco-system, the results here suggest that the accumulation of lipophilic compounds is more pronounced in pigeon eggs than in human blood. In case of blood plasma/earthworm pair the opposite behavior was exhibited, but also with strikingly similar slopes and y-intercepts for the two different locations. However, the exposure to earthworm from uncontaminated soils to contaminated soils concerning metal bioavailabilities and chemical pollutants in soils has provided meaningful integration data and usefulness for biomonitoring purposes (Corp and Morgan, 1991; Calisi et al., 2011). Moreover, fairly good relationship was demonstrated for the dependence of the ratios concerning egg matter of city pigeons and earthworm in the park areas in Halle, respectively to the log Kow , log Koc and MW constants. Another study has found a significant positive correlation between the sum of PCB concentrations in blue tit eggs and great tit eggs, suggesting similar exposure pathways, mechanisms
Table 3 Mean and standard deviation values of the bioconcentration (human/environmental) ratios. Bioconcentration ratios
Blood plasma/egg matter of city pigeons Blood plasma/earthworm Blood plasma/roe deer liver from Dübener Heide park
Residential use areas in Halle Residential use areas in Leipzig Park areas in Halle Park areas in Leipzig 0.8 ± 0.6
PCB 138
PCB 153
PCB 180
HCB
Mean ± STD
Mean ± STD
Mean ± STD
Mean ± STD
0.5 0.6 1.7 2.2 0.8
± ± ± ± ±
0.2 0.2 1.0 0.7 0.6
0.3 0.3 1.3 1.3 0.7
± ± ± ± ±
0.1 0.1 0.6 0.5 0.5
0.2 0.2 1.8 2.1 0.6
± ± ± ± ±
0.1 0.1 0.9 0.8 0.7
0.8 0.8 0.2 0.8
± ± ± ±
0.4 0.4 0.1 0.7
−2.4x + 8.0 −2.3x + 8.1 1.1x + 5.6 1.1x + 5.2 0.70 0.55 0.93 0.78 7.4x + 1.5 −40.6x + 151.7 −50.6x + 157.8 −33.0x + 174.2 −63.1x + 235.6 0.77 0.02 0.04 0.12 0.40 −3.3x + 136.0 −2.6x + 7.7 −2.6x + 7.8 1.0x + 5.3 0.9x + 5.1 0.00 0.94 0.89 0.91 0.66 5.0x + 2.8 −1.9x + 7.1 −1.9x + 7.2 0.8x + 5.3 0.7x + 5.2 0.42 0.91 0.82 0.94 0.70 4.2x + 3.1 −161.3x + 422.7 −164.9x + 429.6 64.9x + 270.3 58.8x + 255.3 0.54 Blood plasma/egg matter of city pigeons Blood plasma/earthworm Blood plasma/roe deer liver from Dübener Heide park
Residential use areas in Halle Residential use areas in Leipzig Park areas in Halle Park areas in Leipzig 0.37
R
0.89 0.86 0.93 0.71 300x + 128.5
log KOC
R2 R2
KH (Pa m3 mol−1 )
y R y
2 2
MW (g/mol) Bioconcentration ratios
Table 4 Linear regression coefficients and y-intercepts as a function of the ratios and Kow constants.
log Kow (1)
y
R
2
log Kow (2)
y
y
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223
of accumulation and maternal transfer of PCBs (Van den Steen et al., 2010). No linear correlations were found for the blood plasma/roe deer liver ratio in regard to all physicochemical constants here studied except log Koc . Also no correlation was observed for KH , for all cases. Although the data set is poor with respect to the number of chemicals, the study shows some very interesting and also promising general relationships between environmental data and human biomonitoring data. It seems worth to extend the number of chemicals in the data set investigated and also to mine other data with respect to the approach followed here. Acknowledgements The authors would like to thank Dr. Schröter-Kermani for provided support in this study. The study was financially supported by the European Union network INTARESE (EU-Contract No. 0183852) within WP 2.2. Biomonitoring. References Angerer, J., Aylward, L.L., Hays, S.M., Heinzow, B., Wilhelm, M., 2011. Human biomonitoring assessment values: approaches and data requirements. Int. J. Hyg. Environ. Health 214, 348–360. Baker, J.R., Mihelcic, J.R., Shea, E., 2000. Estimating Koc for persistent organic pollutants: limitations of correlations with Kow. Chemosphere 41, 813–817. Ballschmiter, K., Wittlinger, R., 1991. Interhemisphere exchange of hexachlorocyclohexanes, haxachlorobenzenes, polychlorobiphenyls, and 1,1,1-trichloro-2,2-bis (p-chlorophenyl)ethane in the lower troposhere. Environ. Sci. Technol. 25, 1103–1111. Boogaard, P.J., Hays, S.M., Aylwar, L.L., 2011. Human biomonitoring as a pragmatic tool to support health risk management of chemicals – Examples under the EU REACH programme. Regul. Toxicol. Pharmacol. 59, 125–132. Calisi, A., Lionetto, M.G., Schettino, T., 2011. Biomarker response in the earthworm Lumbricus terrestris exposed to chemical pollutants. Sci. Total. Environ. 409, 4456–4464. Corp, N., Morgan, A.J., 1991. Accumulation of heavy metals from polluted soils by the earthworm Lumbricus rubellus: can laboratory exposure of ‘control’ worms reduce biomonitoring problems? Environ. Pollut. 74, 39–52. Federal Environment Agency (Umweltbundesamt). German Environmental Specimen Bank. Available at http://www.umweltprobenbank.de/de. Mackay, D., Shiu, W.Y., Ma, K.C., 1992. Illustrated Handbook of Physical–Chemical Properties and Environmental Fate for Organic Chemicals, vol. 1. Monoaromatic Hydrocarbons, Chlorobenzenes and PCBs. ISBN 0-87371-513-6. Oliver, B.G., 1987. Partitioning relationship for chlorinated organics between water and particulates in the St. Clair, Detroit and Niagara Rivers. In: Kaiser, K.L.E. (Ed.), QSAR in Environmental Toxicology – II. D. Reidel Publ. Co., Dordrecht, Holland, pp. 251–260. Oliver, B.G., 1987a. Bio-uptake of chlorinated hydrocarbons from laboratoryspiked and field sediments by oligochaete worms. Environ. Sci. Technol. 21, 785–790. Rappolder, M., Schröter-Kermani, C., Schädel, S., Waller, U., Körner, W., 2007. Temporal trends and spatial distribution of PCDD, PCDF, and PCB in pine and spruce shoots. Chemosphere 67, 1887–1896. Schulz, C., Wilhelm, M., Heudorf, U., Kolossa-Gehring, M., in press. Update of the reference and HBM values derived by the German Human Biomonitoring Commission. Int. J. Hyg. Environ. Health. Van den Steen, E., Pinxten, R., Covaci, A., Carere, C., Eeva, T., Heeb, P., Kempenaers, B., Lifjeld, J.T., Massa, B., Norte, A.C., Orell, M., Sanz, J.J., Senar, J.C., Sorace, A., Eens, M., 2010. The use of blue tit eggs as a biomonitoring tool for organohalogenated pollutants in the European environment. Sci. Total Environ. 408, 1451–1457. Wang, G., Lu, Y., Han, J., Luo, W., Shi, Y., Wang, T., Sun, Y., 2010. Hexachlorobenzene sources, level and human exposure in the environment of China. Environ. Int. 36, 122–130. Wilhelm, M., Ewers, U., Schulz, C., 2003. Revised and new reference values for some persistent organic pollutants (POPs) in blood for human biomonitoring in environmental medicine. Int. J. Hyg. Environ. Health 206, 223–229.
Contents lists available at SciVerse ScienceDirect
International Journal of Hygiene and Environmental Health journal homepage: www.elsevier.de/ijheh
Short communication
Human and environmental biomonitoring of polychlorinated biphenyls and hexachlorobenzene in Saxony, Germany based on the German Environmental Specimen Bank Marchela Pandelova a,∗ , Karl-Werner Schramm a,b a b
Helmholtz Zentrum München, German Research Center for Environmental Health, Institute of Ecological Chemistry, Ingolstädter Landstrasse 1, 85764 Neuherberg, Germany TUM, Wissenschaftszentrum Weihenstephan für Ernährung und Landnutzung, Department für Biowissenschaften, Weihenstephaner Steig 23, 85350 Freising, Germany
a r t i c l e
i n f o
Keywords: PCB HCB Human biomonitoring Pine shoots Ecosurveillance Germany
a b s t r a c t The objective of the present study was to investigate the principle relationships between concentrations in human and environmental matrices of polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) in short distance comparable areas within Saxony, Germany by employing the data of the German Environmental Specimen Banking (ESB). Examples supporting this idea were presented by selecting data on blood plasma collected from students in University of Halle and pine shoots, egg matter of city pigeons, earthworm, and roe deer liver. Similar pattern for PCB 138 and PCB 180 was found for the human plasma and pine shoots samples during investigated years and the human data followed the corresponding environmental levels with some delay of approximately two years. However, PCB 153 that was the prevailing congener did not manifest this relationship. In addition, the correlation of the ratios of concentrations (human/environmental concentration) to some physicochemical constants such as molecular weight (MW), octanol–water partition coefficient (log Kow ), Henry’s law constant (KH ), and sorption partition coefficient (log Koc ) of HCB, PCB 138, PCB 153, and PCB 180 were studied. The resulted negative slopes with all constants in case of blood plasma/city pigeons egg matter pairs suggested that the accumulation of lipophilic compounds is more pronounced in pigeon eggs than in human blood. © 2011 Elsevier GmbH. All rights reserved.
Introduction Due to the hydrophobic and lipophilic nature of polychlorinated biphenyls (PCBs) and their resistance to degrade, these compounds bioaccumulate in the environment and are widely found in humans. Other persistent organic pollutants (POPs) such as hexachlorobenzene (HCB) and organochlorine pesticides were also widely used throughout the developed world. Although the HCB production was banned in Germany in 1993, some levels still exist in the environment and these chemicals are a matter of concern (Wang et al., 2010). In environmental health, biological monitoring of pollutant concentration in human tissue and fluids are used frequently for better assessment of exposure from multiple sources and routes. In Germany, the Human Biomonitoring Commission of the German Federal Environment Agency established scientifically based criteria for the application for human biomonitoring in 1992 (Wilhelm et al., 2003; Schulz et al., in press; Angerer et al., 2011). In this study, the levels of HCB, PCB 138, PCB 153, and PCB 180 in blood plasma and different environmental matrices collected in short
∗ Corresponding author. Tel.: +49 89 3187 2932; fax: +49 89 3187 3371. E-mail address: [email protected] (M. Pandelova). 1438-4639/$ – see front matter © 2011 Elsevier GmbH. All rights reserved. doi:10.1016/j.ijheh.2011.11.005
distance comparable areas within Saxony, Germany areas were investigated. For human risk management, human biomonitoring data can be interpreted using the recently developed concept of biomonitoring equivalents (BE) using toxicokinetic data. In this regard, methodologies such as toxicokinetic models allowed to estimate the biomarker concentrations based on physico-chemical properties (Boogaard et al., 2011). Consequently, the bioconcentration ratios (human/environmental concentration) as a function of some physicochemical constants were studied. Materials and methods Investigated human and environmental samples The investigated human data encompassed blood plasma sampled between 1995 and 2008 from students from University of Halle with an even number of female and male at the age of 20–29. Furthermore, different environmental samples were studied such as (1) pine shoots from the nature park Dübener Heide sampled during 1993, 1995, 1997, 1999–2004; (2) and (3) egg matter of city pigeons from the residential use areas in Halle and Leipzig sampled during 1997, 2000–2008, and 2000–2008, respectively; (4) and (5) earthworm (Lumbricus terrestris) from park areas of Halle and
blood plasma (μg/L fw)
A
0.8 0.6 0.4 0.2 0 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
blood plasma (μg/L fw)
pine shoots (μg/kg dw)
1.5
A
1 0.5 0 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
0.4
pine shoots (μg/kg dw)
blood plasma (μg/L fw)
A
0.3 0.2 0.1 0 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
PCB138 concentration level
pine shoots (μg/kg dw)
1
PCB153 concentration level
1.2
PCB180 concentration level
PCB180 concentration level
PCB153 concentration levels
PCB138 concentration level
M. Pandelova, K.-W. Schramm / International Journal of Hygiene and Environmental Health 215 (2012) 220–223
221
pine shoots (μg/kg dw) blood plasma (μg/L fw) *adapted with 2 years
1.2
B
1
0.8 0.6 0.4 0.2 0 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004
pine shoots (μg/kg dw) blood plasma (μg/L fw) *adapted with 2 years
1.5
B
1 0.5 0 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004
pine shoots (μg/kg dw) blood plasma (μg/L fw) *adapted with 2 years
0.4
B
0.3 0.2 0.1 0 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004
Fig. 1. PCB 138, PCB 153 and PCB 180 level in human blood plasma during 1995–2006 and pine shoots during 1993–2004 sampled from Halle and nature park Dübener Heide, respectively (A). Human data adapted by shifting by two years back (B).
Leipzig sampled during 2000–2008 and 1999–2008, respectively; (6) roe deer liver from nature park Dübener Heide sampled during 1995 and 1999–2008. These human and environmental data were selected due to the short distance between collected samples of approximately 60 and 40 km within nature park Dübener Heide–Halle and Leipzig–Halle, respectively. The number of the species used is presented in Table 1, whereas additional biometric and anamnestic parameters are given elsewhere (Federal Environment Agency). Determination of PCB and HCB Detailed information on clean-up procedure and instrumental parameters for analyzing environmental and human samples are given elsewhere (Federal Environment Agency). Hexachlorobenzene (HCB) and polychlorinated biphenyls (PCB 138, PCB 153, PCB 180) were identified and quantified in g/L fw, ng/g fw, ng/g fw and ng/g fw for blood plasma, egg matter of city pigeons, earthworm and roe deer liver, respectively. Pines shoots samples were homogenized and grinded powder in sub-samples of approx. 10 g in the vapor phase above liquid nitrogen (Rappolder et al., 2007). Analysis for PCB was performed only and the results were presented in ng/g dw. The concentration levels of investigated species are presented in Table 2.
Evaluation of the data The pair of human and environmental data within sampled year and compound were identified. In all cases, the human data were from the blood plasma sampled from Halle whereas the environmental data varied between the above mentioned matrices. The arithmetic mean (Federal Environment Agency) pair data within investigated years and within compound were divided such as human/environmental concentration, named as bioconcentration ratios. Consequently, the mean and standard deviation of resulted ratios within compound were calculated. In order to find a relationship between these ratios and the physicochemical properties for certain compounds, the molecular weight (MW), octanol–water partition coefficient (log Kow ), Henry’s law constant (KH ), and sorption partition coefficient (log Koc ) constants were identified (Mackay et al., 1992). The used physicochemical properties were MW: 284.8, 360.9, 360.9, 395 g/mol (Baker et al., 2000); log Kow (1): 5.5, 6.5, 6.5, 6.7 (Oliver, 1987); Kow (2): 5.5, 6.7, 6.8, 7.2 (Ballschmiter and Wittlinger, 1991); KH : 139, 69, 13.4, 102 Pa m3 mol−1 at 298 K (Ballschmiter and Wittlinger, 1991), log KOC : 5.8, 7.6, 7.2, 7.30 (Oliver, 1987a) for HCB, PCB 138, PCB 153 and PCB 180, respectively. Finally, the linear correlation and slopes and y-intercepts were studied and discussed.
Table 1 Number species used. Species (n)
1993
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
Pine shoots Human blood plasma Egg matter of city pigeons Earthworm Roe deer liver
15
15 97
77
15 90 20
91
15 88
15 98 31 857 11
15 65 20 850 11
15 117 32 890 11
15 104 40 953 10
15 105 20 857 9
15 102 40 756 12
15 106 40 727 6
15 108 75 978 13
15 106 50 782 11
2
4
222
M. Pandelova, K.-W. Schramm / International Journal of Hygiene and Environmental Health 215 (2012) 220–223
Table 2 Concentration levels of PCB 138, PCB 153, PCB 180, and HCB in pine shoots, human blood plasma, egg matter of city pigeons, earthworm, and roe deer liver, respectively.
PCB 138 Pine shoots (ng/g dw) Blood plasma (g/L fw) Egg matter of city pigeons (ng/g fw) Earthworm (ng/g fw) Roe deer liver (ng/g fw) PCB 153 Pine shoots (ng/g dw) Blood plasma (g/L fw) Egg matter of city pigeons (ng/g fw) Earthworm (ng/g fw) Roe deer liver (ng/g fw) PCB 180 Pine shoots (ng/g dw) Blood plasma (g/L fw) Egg matter of city pigeons (ng/g fw) Earthworm (ng/g fw) Roe deer liver (ng/g fw) HCB Blood plasma (g/L fw) Egg matter of city pigeons (ng/g fw) Earthworm (ng/g fw) Roe deer liver (ng/g fw)
1993
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
0.44
0.36 0.62
0.79
0.29 0.84 1.73
0.65
0.48 0.76
0.32 0.30
0.23 0.65 1.39 1.75 0.19 0.20 0.20
0.22 0.82 1.18 1.22 0.23 0.21 0.31
0.14 0.50 1.48 0.85 0.22 0.19 0.43
0.15 0.60 0.84 0.88 0.78 0.22 0.70
0.14 0.50 0.65 0.37 0.30 0.22 0.93
0.46 1.61 1.38 0.77 0.28 0.43
0.37 0.73 0.46 0.32 0.19 0.30
0.42 1.05 1.34 0.19 0.22 0.20
0.34 0.71 0.65 0.37 0.21 0.21
1.17 0.42 1.36 1.81 0.19 0.21 0.61
0.56 0.51 1.25 1.21 0.24 0.21 0.21
0.56 0.49 1.51 1.15 0.23 0.19 0.59
0.36 0.30 0.82 0.84 0.26 0.22 0.71
0.31 0.31 0.62 0.38 0.23 0.23 0.89
0.35 0.29 1.59 1.28 0.40 0.29 0.74
0.28 0.94 0.91 0.26 0.23 0.57
0.26 1.44 1.29 0.19 0.22 0.31
0.25 0.97 0.74 0.23 0.22 0.45
0.22
0.19 0.26 0.82 1.10 0.06 0.07 0.33
0.12 0.18 0.79 0.77 0.08 0.07 0.19
0.12 0.32 0.99 0.59 0.07 0.06 0.36
0.04 0.18 0.55 0.57 0.16 0.07 0.45
0.08 0.20 0.31 0.31 0.07 0.07 0.60
0.07 0.15 0.78 0.95 0.16 0.09 0.36
0.14 0.53 0.46 0.07 0.06 0.26
0.14 1.01 0.59 0.08 0.07 0.17
0.13 0.54 0.43 0.08 0.07 0.22
0.12
0.20
0.21 0.18 0.23 0.71 0.26 0.25
0.21 0.13 0.19 0.95 0.29 0.40
0.18 0.23 0.16 0.88 0.40 0.63
0.17 0.35 0.50 0.83 0.52 0.85
0.14 0.29 0.10 0.86 0.29 0.82
0.15 0.15 0.18 1.07 0.22 0.29
0.12 0.52 0.31 0.21 0.04 0.53
0.13 0.15 0.17 0.66 0.26 0.36
0.12 0.12 0.24 0.59 0.20 0.29
Halle Leipzig Halle Leipzig 0.19 0.87
0.69 0.53
0.53
Halle Leipzig Halle Leipzig
0.47 0.51 2.01
0.47
0.33 0.33 0.20
0.17 0.32
0.32
Halle Leipzig Halle Leipzig
0.12 0.33 0.77
0.25
0.10 0.16 0.51
Halle Leipzig Halle Leipzig
0.40
0.31 0.48
0.19
0.28 0.30
0.20
Results and discussion The PCB results of blood plasma and pine shoots sampled from Halle and nature park Dübener Heide, respectively during 1995–2008 are shown in Fig. 1A. Similar pattern was found for both type samples during investigated years whereas the human data followed the corresponding environmental levels with some delay. Thus, the human data curve was additionally adapted by shifting it by two years back as shown in Fig. 1B. Consequently, fairly good relationship was found for both blood plasma and pine shoots samples in regard to PCB 138 and PCB 180. However, PCB 153 that was the prevailing congener did not manifest such dependence. The results of the mean and standard deviation for HCB, PCB 138, PCB 153 and PCB 180 based on human/environmental data (bioconcentration ratios) are presented in Table 3. Since Halle has been an industrial city since the nineteenth century, somewhat lower bioconcentration ratios were found for this area compared to the human/environmental ratios regarding Leipzig. In addition, the linear regression coefficient and related slope and y-intercepts as a function of MW, log Kow (1), log Kow (1), KH , and log Koc are shown in Table 4.
0.22
0.08
Particularly, in case of blood plasma/city pigeons egg matter pairs negative slopes were found for the correlations with all constants in both locations. Since the octanol–water partition coefficient (Kow ) and sorption partition coefficient (log Koc ) as well as the Henry’s constant (KH ) are used to calculate the transport and fate of chemicals in the environment or eco-system, the results here suggest that the accumulation of lipophilic compounds is more pronounced in pigeon eggs than in human blood. In case of blood plasma/earthworm pair the opposite behavior was exhibited, but also with strikingly similar slopes and y-intercepts for the two different locations. However, the exposure to earthworm from uncontaminated soils to contaminated soils concerning metal bioavailabilities and chemical pollutants in soils has provided meaningful integration data and usefulness for biomonitoring purposes (Corp and Morgan, 1991; Calisi et al., 2011). Moreover, fairly good relationship was demonstrated for the dependence of the ratios concerning egg matter of city pigeons and earthworm in the park areas in Halle, respectively to the log Kow , log Koc and MW constants. Another study has found a significant positive correlation between the sum of PCB concentrations in blue tit eggs and great tit eggs, suggesting similar exposure pathways, mechanisms
Table 3 Mean and standard deviation values of the bioconcentration (human/environmental) ratios. Bioconcentration ratios
Blood plasma/egg matter of city pigeons Blood plasma/earthworm Blood plasma/roe deer liver from Dübener Heide park
Residential use areas in Halle Residential use areas in Leipzig Park areas in Halle Park areas in Leipzig 0.8 ± 0.6
PCB 138
PCB 153
PCB 180
HCB
Mean ± STD
Mean ± STD
Mean ± STD
Mean ± STD
0.5 0.6 1.7 2.2 0.8
± ± ± ± ±
0.2 0.2 1.0 0.7 0.6
0.3 0.3 1.3 1.3 0.7
± ± ± ± ±
0.1 0.1 0.6 0.5 0.5
0.2 0.2 1.8 2.1 0.6
± ± ± ± ±
0.1 0.1 0.9 0.8 0.7
0.8 0.8 0.2 0.8
± ± ± ±
0.4 0.4 0.1 0.7
−2.4x + 8.0 −2.3x + 8.1 1.1x + 5.6 1.1x + 5.2 0.70 0.55 0.93 0.78 7.4x + 1.5 −40.6x + 151.7 −50.6x + 157.8 −33.0x + 174.2 −63.1x + 235.6 0.77 0.02 0.04 0.12 0.40 −3.3x + 136.0 −2.6x + 7.7 −2.6x + 7.8 1.0x + 5.3 0.9x + 5.1 0.00 0.94 0.89 0.91 0.66 5.0x + 2.8 −1.9x + 7.1 −1.9x + 7.2 0.8x + 5.3 0.7x + 5.2 0.42 0.91 0.82 0.94 0.70 4.2x + 3.1 −161.3x + 422.7 −164.9x + 429.6 64.9x + 270.3 58.8x + 255.3 0.54 Blood plasma/egg matter of city pigeons Blood plasma/earthworm Blood plasma/roe deer liver from Dübener Heide park
Residential use areas in Halle Residential use areas in Leipzig Park areas in Halle Park areas in Leipzig 0.37
R
0.89 0.86 0.93 0.71 300x + 128.5
log KOC
R2 R2
KH (Pa m3 mol−1 )
y R y
2 2
MW (g/mol) Bioconcentration ratios
Table 4 Linear regression coefficients and y-intercepts as a function of the ratios and Kow constants.
log Kow (1)
y
R
2
log Kow (2)
y
y
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of accumulation and maternal transfer of PCBs (Van den Steen et al., 2010). No linear correlations were found for the blood plasma/roe deer liver ratio in regard to all physicochemical constants here studied except log Koc . Also no correlation was observed for KH , for all cases. Although the data set is poor with respect to the number of chemicals, the study shows some very interesting and also promising general relationships between environmental data and human biomonitoring data. It seems worth to extend the number of chemicals in the data set investigated and also to mine other data with respect to the approach followed here. Acknowledgements The authors would like to thank Dr. Schröter-Kermani for provided support in this study. The study was financially supported by the European Union network INTARESE (EU-Contract No. 0183852) within WP 2.2. Biomonitoring. References Angerer, J., Aylward, L.L., Hays, S.M., Heinzow, B., Wilhelm, M., 2011. Human biomonitoring assessment values: approaches and data requirements. Int. J. Hyg. Environ. Health 214, 348–360. Baker, J.R., Mihelcic, J.R., Shea, E., 2000. Estimating Koc for persistent organic pollutants: limitations of correlations with Kow. Chemosphere 41, 813–817. Ballschmiter, K., Wittlinger, R., 1991. Interhemisphere exchange of hexachlorocyclohexanes, haxachlorobenzenes, polychlorobiphenyls, and 1,1,1-trichloro-2,2-bis (p-chlorophenyl)ethane in the lower troposhere. Environ. Sci. Technol. 25, 1103–1111. Boogaard, P.J., Hays, S.M., Aylwar, L.L., 2011. Human biomonitoring as a pragmatic tool to support health risk management of chemicals – Examples under the EU REACH programme. Regul. Toxicol. Pharmacol. 59, 125–132. Calisi, A., Lionetto, M.G., Schettino, T., 2011. Biomarker response in the earthworm Lumbricus terrestris exposed to chemical pollutants. Sci. Total. Environ. 409, 4456–4464. Corp, N., Morgan, A.J., 1991. Accumulation of heavy metals from polluted soils by the earthworm Lumbricus rubellus: can laboratory exposure of ‘control’ worms reduce biomonitoring problems? Environ. Pollut. 74, 39–52. Federal Environment Agency (Umweltbundesamt). German Environmental Specimen Bank. Available at http://www.umweltprobenbank.de/de. Mackay, D., Shiu, W.Y., Ma, K.C., 1992. Illustrated Handbook of Physical–Chemical Properties and Environmental Fate for Organic Chemicals, vol. 1. Monoaromatic Hydrocarbons, Chlorobenzenes and PCBs. ISBN 0-87371-513-6. Oliver, B.G., 1987. Partitioning relationship for chlorinated organics between water and particulates in the St. Clair, Detroit and Niagara Rivers. In: Kaiser, K.L.E. (Ed.), QSAR in Environmental Toxicology – II. D. Reidel Publ. Co., Dordrecht, Holland, pp. 251–260. Oliver, B.G., 1987a. Bio-uptake of chlorinated hydrocarbons from laboratoryspiked and field sediments by oligochaete worms. Environ. Sci. Technol. 21, 785–790. Rappolder, M., Schröter-Kermani, C., Schädel, S., Waller, U., Körner, W., 2007. Temporal trends and spatial distribution of PCDD, PCDF, and PCB in pine and spruce shoots. Chemosphere 67, 1887–1896. Schulz, C., Wilhelm, M., Heudorf, U., Kolossa-Gehring, M., in press. Update of the reference and HBM values derived by the German Human Biomonitoring Commission. Int. J. Hyg. Environ. Health. Van den Steen, E., Pinxten, R., Covaci, A., Carere, C., Eeva, T., Heeb, P., Kempenaers, B., Lifjeld, J.T., Massa, B., Norte, A.C., Orell, M., Sanz, J.J., Senar, J.C., Sorace, A., Eens, M., 2010. The use of blue tit eggs as a biomonitoring tool for organohalogenated pollutants in the European environment. Sci. Total Environ. 408, 1451–1457. Wang, G., Lu, Y., Han, J., Luo, W., Shi, Y., Wang, T., Sun, Y., 2010. Hexachlorobenzene sources, level and human exposure in the environment of China. Environ. Int. 36, 122–130. Wilhelm, M., Ewers, U., Schulz, C., 2003. Revised and new reference values for some persistent organic pollutants (POPs) in blood for human biomonitoring in environmental medicine. Int. J. Hyg. Environ. Health 206, 223–229.