Health risk estimate for groundwater and soil contamination in the Slovak Republic a convenient tool for identification of risk areas

Health risk estimate for groundwater and soil contamination in the Slovak Republic a convenient tool for identification of risk areas 1 Fajčíková K., 1 Cvečková V., 1 Rapant S. www.geology.sk 1 State Geological Institute of D. Štúr, Mlynská dolina 1, 817 04 Bratislava, Slovak Republic katarina.fajcikova@geology.sk

Origin of this research has gone with new idea to find mechanism for map visualization of quantitative assessment of health risks from contamination of geological environment in the Slovak Republic by combining international principles and methodology of health risk assessment with methodological procedures used in environmental geochemistry that would be easy to understand and usefull in decision make process

Objective of the work was based on this idea and includes: Quantitative estimation of health risk to residents living in the Slovak Republic of exposure to contaminated groundwater (adult population) and soils (adult and child population) Identification of potential risk areas within the country based on map visualization.

Background of the work Identification and characterization of: distribution of chemicals in groundwater and soils, contamination of geological environment and sources of contamination, Within environmental-geochemical mapping programme in the Slovak Republic at: national level Geochemical Atlases of the Slovak Republic at the scale 1:1 000 000, regional level environmental-geochemical maps of selected regions at the scale 1:50 000.

Sources of groundwater and soil contamination in the Slovak Republic: www.geology.sk Background of the work Main geogenic (natural) sources specific rock types and associated mineralization occurrences and ore deposits (e.g. hydrothermal vein mineralization associated with granitoids and metamorphic rocks, lowsulphide mineralization associated with Neogene volcanics, Paleozoic sediment-hosted mineralizations) Increased groundwater and soil contents of potentially toxic elements: As, Pb, Zn, Cu, Hg, Sb Main anthropogenic sources Mining activities, Metallurgy, Agriculture, Waste industry, Other industrial activities (chemical industry, refineries etc.), Transport etc. Increased groundwater and soil contents of various chemical elements / components: As, Cd, Hg, Pb, Ni, Fe, Mn, Al, Zn, Cu, Cr, NO 3-, SO 2-4, NH 4+ etc. Geogenic-anthropogenic sources (e.g. historical mining areas)

Background of the work Output: Environmental geochemical regionalization of the Slovak Republic (Rapant et al. 2004)

Background of the work Data source for health risk estimate for groundwater and soil contamination in the Slovak Republic Datasets of 20 339 groundwater samples and 10 738 soil samples were transformed in mean values of respective chemical elements and components for single administrative units of the Slovak Republic (municipalities, districts, regions) based on grid data interpolation - calculation of arithmetic means for grid cells falling into bounds of every single administrative unit GROUNDWATER (n=20 339) ph MIN ChSK Mn Ca+Mg Li Na K Ca Mg Sr Fe Mn NH 4 7.33 629.75 2.18 3.5 0.019 20.34 11.10 93.56 28.29 0.36 0.17 0.12 0.10 F Cl SO 4 NO 2 NO 3 PO 4 HCO 3 SiO 2 Cr Cu Zn As Cd 0.13 32.96 79.32 0.11 38.76 0.20 303.85 18.21 0.0013 0.0026 0.2673 0.0019 0.0010 Se Pb Hg Ba Al Sb Note: Data except of ph in mg.l -1 0.0010 0.0014 0.0001 0.0747 0.0297 0.0009 SOILS (n=10 738) Al As B Ba Be Bi Ca Cd Ce Co Cr Cu F 5.90 12.45 65.03 392.78 1.39 0.41 1.46 0.60 64.65 11.77 87.55 26.15 330.98 Fe Hg K Mg Mn Mo Na Ni P Pb Sb Se Sn 2.71 0.24 1.70 0.87 0.08 0.68 0.85 29.29 0.07 29.62 3.69 0.16 4.71 Sr V W Zn ph H2O ph KCl carbonates Note: macrocomponents in %, microcomponents in mg.kg -1 101.38 79.07 0.92 75.79 6.26 5.52 2.45

Background of the work Example for surface distribution of arsenic in groundwater in municipalities of the Slovak Republic

Background of the work Example for surface distribution of arsenic in soils in municipalities of the Slovak Republic

Health risk estimate US EPA methodology www.geology.sk Data evaluation Mean values for Slovak municipalities for following contaminants with defined toxicity data were included in calculation of health risk estimates: Groundwater As, Ba, Cd, Cu, F, Hg, Mn, NO3, Pb, Sb, Se, Zn Soils - As, B, Ba, Be, Cd, Cu, F, Hg, Mn, Mo, Ni, Pb, Sb, Se, Zn ADD = Exposure assessment Groundwater and soil contents (C) specific value, Other exposure data model values for (US EPA) Exposure route - ingestion C CR ED EF BW AT CHRONIC RISK CANCER RISK Risk characterization HQ = ADD RfD Toxicity assessment (IRIS database) HI CR = ADD Chronic effects: principle of REFERENCE DOSE (RfD) was applied ( existence of safe dose) Carcinogenic effects: principle of cancer slope factor (CSF) was applied ( no dose is safe ) = HQi CSF RISC Workbench software used for calculations

Input exposure parameters were following: for adult population www.geology.sk Health risk estimate Analyzed media Parameter Value Unit Reference BW Body weight 70 kg US EPA, 1991 AT* Averaged exposure period - cancer risk 25 550 day US EPA, 1989a Groundwater AT* Averaged exposure period - chronic risk 25 550 day US EPA, 1989a CW Groundwater concentration of chemical Specific locally mg l -1 IR Daily water intake 2 l day -1 US EPA, 1989b EF Exposure frequency 365 day year -1 US EPA, 1989a ED Exposure duration 70 year US EPA, 1989a Soils AT* Averaged exposure period - chronic risk 23360 day US EPA, 1989a CS Soil concentration of chemical Specific locally mg kg -1 IR Daily soil intake 50 mg day -1 US EPA, 1991 FI Fraction ingested from contaminated source 1 - US EPA, 1991 EF Exposure frequency 40 day year -1 US EPA, 1999b ED Exposure duration 64 year US EPA, 1991 CF Conversion factor 10-6 kg mg -1 US EPA, 1989a

Health risk estimate Input exposure parameters were following: for child population Analyzed media Parameter Value Unit Reference BW Body weight 15 kg US EPA, 1991 AT* Averaged exposure period - Chronic risk 2190 day US EPA, 1989a Soils CS Soil concentration of chemical Specific locally mg kg -1 IR Daily soil intake 100 mg day -1 US EPA, 1991 FI Fraction ingested from contaminated source 1 - US EPA, 1991 EF Exposure frequency 120 day year -1 US EPA, 1999b ED Exposure duration 6 year US EPA, 1991 CF Conversion factor 10-6 kg mg -1 US EPA, 1989a

Health risk estimate Database of Integrated Risk Information System (IRIS) was used for definition of input toxicity parameters: Chronic risk: reference doses Cancer risk: Arsenic as known human carcinogen - cancer slope factor for arsenic 1.5 mg.kg -1 -day Element RfD Confidence As 0.0003 medium B 0.2 high Ba 0.2 medium Be 0.002 low-medium Cd gw 0.0005 high Cd soil 0.001 high Cu 0.04 - F 0.06 high Hg 0.0003 - Mn 0.14 medium Mo 0.005 medium Ni 0.02 medium NO 3 1.6 high Pb 0.0036 - Sb 0.0004 low Se 0.005 high Zn 0.3 medium - high

Classification used for health risk estimate interpretation and map visualization CHRONIC RISK Risk level 1 2 3 4 CANCER RISK HQ <0.1 >0.1<1 >1<4 >4 Chronic risk no risk low medium high Note: The same classification used for Hazard Index (HI) www.geology.sk Health risk estimate Risk level 1 2 3 4 5 No. of cases per population <1 per 1000 000 inhabitants >1 per 1000 000 inhabitants <1 per 100 000 inhabitants >1 per 100 000 inhabitants <1 per 10 000 inhabitants >1 per 10 000 inhabitants <1 per 1 000 inhabitants >1 per 1 000 inhabitants Cancer risk very low low medium high very high

Interpretation of health risk estimates in map and table form was performed for all administrative units of the Slovak Republic municipalities, districts and regions Example for arsenic in groundwater in Slovak districts / regions District/Region C As HQ adult Chronic risk ELCR Cancer risk Bratislavský 0.0025 2.32E-01 1 1.04E-04 4 Bratislava I 0.0011 1.01E-01 1 4.55E-05 1-3 Bratislava II 0.0009 8.68E-02 1 3.90E-05 1-3 Bratislava III 0.0015 1.41E-01 1 6.36E-05 1-3 Bratislava IV 0.0012 1.12E-01 1 5.02E-05 1-3 Bratislava V 0.0009 8.14E-02 1 3.66E-05 1-3 Malacky 0.0031 2.89E-01 1 1.30E-04 4 Pezinok 0.0024 2.26E-01 1 1.02E-04 4 Senec 0.0022 2.05E-01 1 9.23E-05 1-3 Trnavský 0.0012 1.11E-01 1 5.00E-05 1-3 Total No. of evaluated administrative units: 2883 municipalities, 79 districts, 8 regions. Dunajská Streda 0.0012 1.12E-01 1 5.04E-05 1-3 Galanta 0.0014 1.36E-01 1 6.13E-05 1-3 Hlohovec 0.0007 6.71E-02 1 3.02E-05 1-3 Piešťany 0.0008 7.16E-02 1 3.22E-05 1-3 Senica 0.0015 1.40E-01 1 6.30E-05 1-3 Skalica 0.0015 1.38E-01 1 6.21E-05 1-3 Trnava 0.0008 8.09E-02 1 3.64E-05 1-3 Trenčiansky 0.0044 4.22E-01 1 1.90E-04 4 Bánovce nad Bebravou 0.0011 9.99E-02 1 4.49E-05 1-3 All results are available on the website www.geology.sk/geohealth

Chronic risk estimate for groundwater contamination Health risk estimate for chronic disease occurrence due to groundwater ingestion by adult population of the Slovak Republic MUNICIPALITIES (As, Ba, Cd, Cu, F, Hg, Mn, NO3, Pb, Sb, Se, Zn) expressed in the form of maximum of hazard quotient (HQ) HQ 0 20 40 km regional city boundary of municipalities boundary of districts boundary of regions state boundary Risk level 1 2 3 4 HQ <0.1 >0.1<1 >1<4 >4 Chronic risk no risk low medium high No. of municipalities 589 2198 79 17 Main results: chronic risk was documented in 17 municipalities, arsenic and antimony were defined to share the significant part of total risk level

Chronic risk estimate for groundwater contamination Health risk estimate for chronic disease occurrence due to groundwater ingestion by adult population of the Slovak Republic MUNICIPALITIES (As, Ba, Cd, Cu, F, Hg, Mn, NO3, Pb, Sb, Se, Zn) HI ( Σ HQ) 0 20 40 km regional city boundary of municipalities boundary of districts boundary of regions state boundary Risk level 1 2 3 4 HI <0.1 >0.1<1 >1<4 >4 Chronic risk no risk low medium high No. of municipalities 1 2686 176 20 Main results: high chronic risk was documented in 20 municipalities, arsenic and antimony were defined to share the significant part of total risk level, the summary effect of calculation of hazard index is reflecting mainly in classification of municipalities in lowland areas (Suthern part of the Slovak Republic) into category of medium chronic risk

Chronic risk estimate for groundwater contamination Health risk estimate for chronic disease occurrence due to groundwater ingestion by adult population of the Slovak Republic MUNICIPALITIES ARSENIC groundwater 0 20 40 km regional city boundary of municipalities boundary of districts boundary of regions state boundary Risk level 1 2 3 4 HQ <0.1 >0.1<1 >1<4 >4 Chronic risk no risk low medium high No. of municipalities 1809 1036 29 9 Main results: medium to high chronic risk was documented mainly in highly contaminated areas with geogenic or geogenic-anthropogenic sources of contamination (ore deposit and mineralized occurrences, associated historical mining activities ), medical-geochemical research made in the region of Spišsko-gemerské rudohorie revealed the negative impact of high As groundwater contents and health status of inhabitants.

Chronic risk estimate for groundwater contamination Health risk estimate for chronic disease occurrence due to groundwater ingestion by adult population of the Slovak Republic MUNICIPALITIES ANTIMONY groundwater Risk level Chronic risk 0 20 40 km regional city 1 <0.1 no risk 2 >0.1<1 low boundary of municipalities boundary of districts 3 >1<4 medium boundary of regions 4 >4 high state boundary HQ No. of municipalities 2796 66 15 6 Main results: medium to high chronic risk was documented mainly in highly contaminated areas with geogenic or geogenic-anthropogenic sources of contamination (ore deposit and mineralized occurrences), medical-geochemical research made in the region of Spišsko-gemerské rudohorie revealed the negative impact of high Sb groundwater contents and health status of inhabitants.

Chronic risk estimate for soil contamination Health risk estimate for chronic disease occurrence due to soil ingestion by child population of the Slovak Republic MUNICIPALITIES (As, B, Ba, Be, Cd, Cu, F, Hg, Mn, Mo, Ni, Pb, Sb, Se, Zn) expressed in the form of maximum of hazard quotient (HQ) HQ 0 20 40 km regional city boundary of municipalities boundary of districts boundary of regions state boundary Risk level 1 2 3 4 HQ <0.1 >0.1<1 >1<4 >4 Chronic risk no risk low medium high No. of municipalities 2479 392 10 2 Main results: the majority of Slovak municipalities were classified into the category of no or low chronic risk.

Chronic risk estimate for soil contamination Health risk estimate for chronic disease occurrence due to soil ingestion by child population of the Slovak Republic MUNICIPALITIES (As, B, Ba, Be, Cd, Cu, F, Hg, Mn, Mo, Ni, Pb, Sb, Se, Zn) HI ( Σ HQ) 0 20 40 km regional city boundary of municipalities boundary of districts boundary of regions state boundary Risk level 1 2 3 4 HI <0.1 >0.1<1 >1<4 >4 Chronic risk no risk low medium high No. of municipalities 1717 1140 22 4 Main results: medium to high chronic risk was documented in 26 municipalities, arsenic, antimony and lead were defined to share the main part of total risk level, the territory of the Slovak Republic is from the point of view of soil contamination by other evaluated contaminants at no risk.

Chronic risk estimate for soil contamination Health risk estimate for chronic disease occurrence due to soil ingestion by child population of the Slovak Republic MUNICIPALITIES ARSENIC soils 0 20 40 km regional city boundary of municipalities boundary of districts boundary of regions state boundary Risk level 1 2 3 4 HQ <0.1 >0.1<1 >1<4 >4 Chronic risk no risk low medium high No. of municipalities 2500 372 10 0 Main results: medium risk levels were documented only in 10 municipalities from highly contaminated areas by geogenic or geogenic-anthropogenic sources of contamination

Chronic risk estimate for soil contamination Health risk estimate for chronic disease occurrence due to soil ingestion by child population of the Slovak Republic MUNICIPALITIES ANTIMONY soils Chronic risk 0 20 40 km 1 no risk regional city boundary of municipalities boundary of districts boundary of regions state boundary Risk level 2 3 4 HQ <0.1 >0.1<1 >1<4 >4 low medium high No. of municipalities 2810 67 6 0 Main results: medium risk levels were documented only in 6 municipalities from highly contaminated area by geogenic or geogenic-anthropogenic sources of contamination

Cancer risk estimate for groundwater contamination Health risk estimate for carcinogenic disease occurrence due to groundwater ingestion by adult population of the Slovak Republic - MUNICIPALITIES ARSENIC groundwater 0 20 40 km Risk level No. of cases per population Cancer risk No. of municipalities regional city boundary of municipalities boundary of districts boundary of regions state boundary 1-3 4 5 <1 per 10 000 inhabitants low-medium 2534 >1 per 10 000 inhabitants <1 per 1 000 inhabitants >1 per 1 000 inhabitants high very high 330 19 Main results: high to very high risk was defined for more than 300 municipalities, because of many samples with arsenic contents below the detection limit 0.0005 mg.l -1 (the exact contents are not known) the first 3 risk categories were unified into one category of low to medium risk

Cancer risk estimate for soil contamination Health risk estimate for carcinogenic disease occurrence due to soil ingestion by population (additive model) of the Slovak Republic - MUNICIPALITIES ARSENIC soils 0 20 40 km regional city boundary of municipalities boundary of districts boundary of regions state boundary Risk level 1 2 3 4 5 No. of cases per population <1 per 1000 000 inhabitants >1 per 1000 000 inhabitants <1 per 100 000 inhabitants >1 per 100 000 inhabitants <1 per 10 000 inhabitants >1 per 10 000 inhabitants <1 per 1 000 inhabitants >1 per 1 000 inhabitants Cancer risk very low low medium high very high No. of municipalities 0 2736 Main results: medium to high risk was defined for about 150 municipalities located in areas with a.) historical minining activities with ore deposit occurence, b.) area with anthropogenic contamination (depositions due to As-rich coal burning by power plant) 142 5 0

Conclusions - Presented approach of health risk estimate based on national and regional geochemical data represents a convenient tool for identification of risk areas, It is easily comprehensible for decision makers and can serve as basis for future works focused on detail studies of health risks. - Increased risk levels, both for chronic as well as in case of arsenic also carcinogenic diseases were identified mainly in highly contaminated areas with dominant geogenic or geogenicanthropogenic source of contamination (historical mining areas). - The results of health risk estimation indicate that arsenic and antimony pose the highest chronic risk in some areas in the case of groundwater as well as soils. - Health risk estimation for soil contamination has highlighted the significance of exposure through soil ingestion in case of child population while for adults it is negligible.

Some additional remarks / uncertainties: Expression of chronic risk estimate for groundwater and soil contamination in the form of maximum value of hazard quotient instead of summmary hazard index is probably more objective way how to define risk levels (in this way we exclude the case when sum of no or low risk values result in one high risk value). So far realized medical geochemical researches in some of highly contaminated areas confirmed the existence of risk in regions identified as risk areas through the approach of model quantification of health risk. Advantage of this approach is fast, visual and comprehensible visualization of risk areas for decision makers, disadvantage of this approach lies in data interpolation local contamination partially spread out into non-contaminated areas. There is still need to identify potential health risks associated with other elements that are essential at certain levels but have negative health effects at excess or deficit contents (e.g. macro-elements - Ca, Mg; Zn, Se etc.). This issue is dealed with within the running project GEOHEALTH, for more information about the project please go to the website www.geology.sk/geohealth.

The research staff of this project would like to invite you to the: SEGH 2015 31 th INTERNATIONAL CONFERENCE of THE SOCIETY FOR ENVIRONMENTAL GEOCHEMISTRY AND HEALTH THE LINKING BEETWEN ENVIRONMENT AND HEALTH June/July 2015, State Geological Institute of Dionyz Stur, Bratislava, Slovak Republic Organized by The International European Association Society for Geochemistry and Health in collaboration with the Slovak association of Geochemists and project GEOHEALTH research staff For additional information please visit: www.geology.sk/geohealth/conference

THANK YOU FOR YOUR ATTENTION Acknowledgement This research has been performed within the project LIFE10 ENV/SK/000086 The impact of geological environment on health status of residents of the Slovak Republic financially supported by the EU s funding instrument for the environment Life+ programme.