Quantitative-spatial assessment of the risks associated with high Pb loads in soils around Lavrio, Greece a b c A. Korre *, S. Durucan , A. Koutroumani Environmental and Mining Engineering Research Group, Department of Environmental Science and Technology, Imperial College of Science, Technology and Medicine, Royal School of Mines, Prince Consort Road, London SW7 2BP, UK Abstract The advantages of quantitative environmental risk assessment techniques over the more commonly used qualitative approach is widely accepted. Yet, correct implementation of quantitative risk assessment is a difficult task, given the present state of understanding of the environmental processes. One important parameter related to the level of risk is the extent and geographic spread of pollutants. Geographic Information Systems (GIS) provide a very powerful and highly flexible tool that increases the sophistication of the risk assessment methodology. Through spatial representation, the estimated risk becomes more comprehensive, thus facilitating the decision making process. In addition, valuable qualitative information can be incorporated into the risk assessment procedure with the help of GIS. This paper illustrates a methodology which incorporates a probabilistic risk assessment model within a GIS. The case study utilised to illustrate the methodology is a large industrial area around a number of decommissioned minerals production and processing sites with known high heavy metal loads at Lavrio, Greece. The spatial distribution of Pb concentration in soils was derived from 425 soil samples collected over a total area of 120 km2. A risk assessment model was constructed to simulate and assess the risk associated with high Pb loads in soils in the study area. The methodology consists of a typical exposure assessment model, constructed for adult and child populations. The Pb exposure for both populations is compared with relevant Reference Dose levels providing hazard quotients. The results of the quantitative risk assessment study are analysed and presented in the form of GIS maps covering the study area. a Fax: 44(0)20 7594 47354. E-mail: [email protected] * Corresponding Author b Fax: 44(0)20 7594 47354. E-mail: [email protected] c Fax: 44(0)20 7594 47354. E-mail: [email protected] 1 1. Introduction An increasing number of environmental concerns stem from the problem of land contamination, the most important being its effects on human health. Effective interaction between science, policy and public demand accelerates the development in this field. Risk assessment defines the balance between these forces. While risk may be defined as a combination of the consequence of a negative effect and the probability of that effect to occur (Vegter and Ferguson, 1998), risk assessment is the systematic process for identifying, describing, analysing and quantifying the risk associated with hazardous substances, processes, activities or events. In the field of contaminated land research, risk assessment has so far been used mainly for comparative and priority setting purposes. Within the context of comparative risk analysis, risk is used as an indicator, not as an absolute quantitative measure describing the environmental or human health impact of soil and groundwater contamination. It is often argued that, in contaminated soils, the measurement of the adverse effects can easily be performed. However, due to the difficulties of performing experiments and because of the need for the prediction of future exposure, this is not always easily achieved (Ferguson et al., 1998). In order to generalise the risk assessment procedure, Covello and Merkhofer (1993) have proposed an integrated methodology which consists of 4 distinct steps as follows: release assessment, exposure assessment, consequence assessment, and risk estimation. This methodology, as used by many others before (NCR, 1983; 1994; USEPA, 1995; Petts et al., 1997), was adopted as the basis for risk assessment model development in the study reported in this paper. Characterisation of uncertainties in risk assessment is a well-researched area, particularly through the use of probabilistic uncertainty analysis for the release and exposure factors. However, uncertainty analysis in consequence modelling has not equally advanced yet (Suter, 1993; Finley and Paustenbach, 1994; USEPA, 1995; 1997; Ferguson et al., 1998). The need to incorporate the uncertainty in the risk estimation process has given the incentive for 2 many researchers to use a more complex probabilistic risk assessment methodology, as opposed to the simpler deterministic risk assessment approach (Moore and Elliot, 1996; Richardson, 1996; Covello and Merkhofer, 1993). The work presented in this paper illustrates how a spatial release assessment model (geostatistical analysis) coupled with a probabilistic exposure assessment model (MonteCarlo approach) can be used to quantify risk from Pb exposure in soils within a geographic database environment (GIS). 2. Risk assessment methodology In risk assessment for contaminated land, the release assessment step involves the identification and monitoring of the source, and the use of statistical analysis and modelling techniques to quantify the sources of risk. In their previous research, the authors have developed a methodology incorporating statistical, geostatistical and spatial analysis tools to identify and quantify the sources of soil contamination (Korre, 1997; Korre and Durucan 1999). The exposure assessment process entails the description of the exposure’s characteristics, identification of the exposure routes, and description of the exposed population and the analysis of all the critical variables of the exposure scenario. The exposure assessment model described below was constructed so as to fulfil these requirements. In the model, the pathways of the contaminants to humans were restricted to exposure to total Pb contained in the soil. The default values of exposure frequency, exposure duration and human body characteristics, as suggested by Petts et al. (1997), were used for the pathways under examination. Currently, the exposure model does not incorporate spatially referenced population data, therefore, the spatial referencing of the risk estimates were built upon the spatial distribution of total Pb concentration of soils established at the release assessment stage. In general, the exposure routes that are related to soil exposure are direct soil ingestion and dermal exposure to soil. It is known from literature that dermal absorption is considered significant in the case of organic substances and organometallic compounds, but is negligible in the case of heavy metals (Veerkamp, 1994). Therefore, only the ingestion pathway was investigated. Equation 1 was used to calculate the Chronic Daily Intake (CDI) of Pb deriving from the pathway of direct ingestion of contaminated soil, 3 Chronic Daily Intake CS IR CF FI EF ED BW AT (1) where CS is the Pb concentration in soil (mg/kg), IR is the ingestion rate of soil from all sources (mg/day), CF is a conversion factor (10-6 kg/mg), FI is the fraction ingested from the site as a fraction of the total from all sources (in range 0.0 – 1.0), EF is the exposure frequency (days/yr), ED is the exposure duration (yrs), BW is the body weight (kg) and AT is averaging time (days). For non-cancer risks AT = ED * 365. The above equation takes into consideration the bioavailability of the heavy metal. For the current study, the fraction of Pb absorbed into the blood stream after ingestion was considered maximum and was set to one. This represents a ‘worst-case’ scenario, which increases the influence of the pathway. In a previous study of the bioavailability of Pb via the ingestion pathway Veerkamp (1994) used 0.3 for the bioavailable fraction of Pb, however, the value commonly used in commercial risk assessment models is one. Due to the uncertainty inherent in the exposure model parameters (body weight, ingestion rate, exposure frequency, etc.) used for the target groups, a stochastic approach was followed for the estimation of exposure in the risk assessment model. The authors have generated probability distributions for each exposure model parameter and have performed a Monte Carlo-type random sampling technique to estimate the mean Chronic Daily Intake for each estimation. The U.S. EPA generic Reference Dose (RfD) is a commonly used estimate of exposure for the human population, including sensitive sub-populations, that is likely to be without an appreciable risk of deleterious effects during lifetime (IRIS, 1988; Petts et al., 1997). Several RfD values for Pb exist in the literature. At the consequence assessment step, the authors have utilised both the U.S. EPA RfD value of 0.1 mg kg-1 day-1 (Petts et al., 1997) and the Aid for Evaluating the Redevelopment of Industrial Sites (AERIS) RfD value of 0.0035 mg kg-1 day-1 (AERIS, 1991) for comparing the estimates of exposure calculated in the exposure assessment step. The first RfD is a generic reference level (employed for different routes of exposure) which has the maximum value found in the literature, while the second one is the smallest oral exposure RfD found in the literature. No specific RfD values are available for children, therefore, the same values were used to evaluate child exposure. In this study, the carcinogenic effects of exposure to Pb was not considered due to the lack of quantified carcinogenic effects and the absence of comparative measures for Pb. The U.S. 4 EPA Integrated Risk Information System (IRIS) database (IRIS, 1988) suggests that the human evidence available thus far is inadequate to refute or demonstrate any potential carcinogenicity for humans from Pb exposure. According to the same source, quantifying cancer risk due to Pb involves many uncertainties some of which may be unique to Pb. Age, health, nutritional state, body burden, and exposure duration affect the rate of absorption, release, and excretion of Pb. In addition, current knowledge of Pb pharmacokinetics indicates that an estimate derived by standard procedures would not truly describe the potential risk. The results of the release, exposure and consequence assessment steps were integrated to provide a quantitative estimate of the likelihood of risk. The exposure model output for each of the estimation points was a probability distribution for the Chronic Daily Intake. For the risk estimation step, the exposure estimates were compared with the RfD, providing a number of exceeding counts in the form of a Hazard Quotient. The number of counts of these exposure distributions exceeding the RfD chosen as reference in the consequence assessment step was used to provide a quantitative measure of risk. Finally, in order to address the uncertainty entailed in the approach, the probability distribution for the CDI was fit to a standard probability distribution and the Confidence Levels around the mean of the distributions generated were calculated and compared with the selected RfD value. After the completion of the risk assessment stage, a sensitivity test on the model parameters was carried out. The single parameter perturbation technique was utilised to examine the sensitivity of the Chronic Daily Intake exposure model to variations in 7 of the model parameters. For this purpose, the parameter in question was kept constant at its minimum value for 10 respective runs of the model and the mean CDI was calculated for the recorded outcomes. The same was repeated for the maximum value of the same parameter and equation 2 was used to calculate the Sensitivity Index. Sensitivity Index 1 CDI min CDI max (2) The closer to zero the calculated SI is, the smaller the correlation between the input parameter under investigation and the resultant Chronic Daily Intake. If the sensitivity index of a parameter was found to be close to one, the parameter was labelled as sensitive and its variance was expected to have a significant effect on the resultant CDI. 5 The spatial referencing of the Pb distribution obtained at the release assessment stage provided the basis for the calculation of spatially referenced quantitative risk estimates to humans from Pb consumption due to direct ingestion of soil. Once the risk estimates are introduced into a spatial database such as a GIS, the additional quantitative and qualitative geographic information can be used for further analysis and interpretation of the results. 3. Geological, mining and environmental background to the Lavrio old mine site, Greece The Lavrio old mine site is situated at the SE of the Attiki peninsula, about 60 km from Athens. The region is hilly and dry. A fault running along the Legraina valley northwards divides the area into two sections. The eastern region, where the small dispersed ore bodies are found, is commonly known as the metalliferous Lavrio. The silver bearing structures around Lavrio were known and exploited since the 6th century BC. Many million tons of rich Pb and Ag ore were mined, resulting in the exhaustion of a large proportion of the rich deposits. By the end of the Peloponnesian War in 389 BC, only the large reserves of poor and deeper ore deposits were left unexploited. Brief flickerings of mining activity continued until the first century AD. After that Lavrio lapsed into inactivity and oblivion, to revive again only during the last century. Enormous heaps of waste from mining and metallurgical work carried out over many centuries and several million tons of tailings and slag, some recovered from the beaches of Lavrio, were sufficiently rich in metals that the latter day miners re-processed them for many years. 1864 marked the beginning of the revival of the mines, and an era of high profits for the French company Serpieri-Roux de Fraissinet and its successors (Marinos and Petrascheck, 1956). All mining activities in the area ceased in the mid-sixties and the ore processing at the plant north of the city of Lavrio stopped in 1986. The primary ore comprises of 2 groups, the Fe-Mn ore and the mixed sulphides which frequently exist together or alternate. The mixed sulphide minerals are pyrite, sphalerite and Ag-bearing galena. The Fe-Mn formation consists mainly of manganiferous ankerite and rhodochrosite, with barite, fluorspar and quartz, subsequently oxidised into limonite, pyrolousite etc. There are also smaller proportions of other related minerals with As, Bi, Cu, Ni and Co. The widely dispersed ore bodies and the sporadic mining all over Lavrio district induced widely spread high heavy metal loads in the area. The port and the city of Lavrio, situated at the east coast of the peninsula, has been developed around and on the mining and 6 processing waste materials (Fig.1). Epidemiological studies in the area have shown a high blood Pb burden in school age children which was associated with mental retardation, slower response rate and increased sickliness (Lavrio Health Centre, 1989; Makropoulos et al., 1991; 1992; Eikmann et al., 1991; Stavrakis et al., 1994; Kafourou et al., 1997). Fig. 1. Urban development around the old mine tailings dumps in Lavrio Previous research on soil pollution assessment and remediation in the Lavrio area include the work carried out by Korre and Durucan (1995, 1999), Demetriades et al. (1997), Korre (1997, 1999a, b), Durucan and Korre (1997) and the contaminated soil remediation research by Kontopoulos et al. (1995a, b, 1996). Recently, a deterministic risk assessment study based on the source-pathway-target principle aimed to identify targets for rehabilitation and assess environmental risks around the Pb smelter north of the city of Lavrio (Kontopoulos et al., 1998). After determining the sources of contamination -i.e. flotation tailings dam, pyritic tailings dump, smelter-off gas tunnel, contaminated soils, stored chemicals- the contaminants’ concentrations were estimated and compared to the Canadian standards for industrial areas. Subsequently, pathways to human targets were indicated. The outcome of this study was an assessment of the probability and magnitude of the consequences, and hence of the risk to humans using simpler linguistic descriptors (high, medium, low, negligible). The magnitude of harm from 7 the predicted exposure to the target was further assessed using similar linguistic descriptors (severe, moderate, mild, negligible). Based on the estimation of the probability and magnitude, the risk was rated from high to near zero. In another study, dealing with hazard and exposure assessment in the area, the IEUBK and HESP exposure assessment models were applied to the Lavrio urban area (Tristan et al., 2000). 4. Risk assessment related to high lead levels in soils around the Lavrio old mine site The risk assessment study presented in this paper covers an area of approximately 120 km2 at the south-eastern corner of Lavreotiki peninsula (Fig. 2). The natural setting and the current and historical mining activities at Lavrio indicate a complex exposure scenario, with multiple-sources and multiple pathways. Due to the significance of Pb and its known negative health effects in the area, the authors have selected the total Pb concentration in soil for the initial spatial-quantitative risk assessment study presented here. Some 425 samples of 1kg average weight were collected from the upper 4-5 cm of soil using a rectangular sampling pattern (400500 m). The total soil metal concentrations were analysed by ICP – AES after digestion with HNO3 and HClO4 acid at Imperial College. Chemical analysis yielded the concentration of 24 elements in the soil samples, including Pb (Korre, 1999a, b). Statistical and spatial analysis tools were utilised in order to combine the quantitative information obtained from the chemical analysis of the soil samples with the site-specific qualitative information. The primary analysis focused on identifying the levels and correlation between the elements determined. Through geostatistical analysis, the spatial distribution of each element in the study area was estimated (Korre, 1997). This provided a new grid of estimated values for each element, along with estimation errors and the coordinates of each data point, in a 250250 m grid. Geographical data (e.g. elevation, roads, housing, land use) and the geology of the area were entered into a GIS database along with the heavy metal load estimates. Simultaneous site surveys carried out during the sampling process provided site-specific information relating to the type of vegetation and human activities near the sampling points. 8 Fig.2. Risk assessment study area around Lavrio. Further analysis of the original data aimed at understanding the physical processes driving the pollution in the area. Dominant processes which controlled the redistribution of elements in the area were explored using principal component and factor analysis. In order to distinguish and quantify the multiple coexisting sources of pollution in the area, a 9 methodology utilising canonical correlation analysis and geostatistical analysis was developed (Korre, 1999a; b; Korre and Durucan, 1999). Canonical correlation statistical analysis enabled the authors to distinguish the natural background from the human induced soil contamination. Finally, the coupling of statistical analysis tools with geostatistics and GIS tools allowed the spatial assessment of both soil contamination and its sources (Korre, 1999b). The geographic database held in GIS served as the host environment for additional spatial operations such as spatial referencing between quantitative and qualitative information (geology, topographic relief, human activities) and for the graphical representation of the results. The GIS system that was used to form the spatial database for the geographical interpretation of the heavy metal levels was ARC/INFO (Environmental Systems Research Institute Inc., 1990). It is recognised that the natural ore occurrence in the area induces elevated levels of heavy metals, including Pb. However, the contribution of human activities over and above the background values is undoubted. A GIS map of Pb distribution in the area (Fig.3) illustrates that areas with an estimated concentration of 500 ppm and below are very limited. The measured maximum values were well in excess of normal levels -approximately 70 ppm for non-polluted soils and non-mineralised parent rocks in the area. The maximum concentrations were found to correlate well with the spread of mining and processing activities. It was also possible to identify the bays where waste material had been disposed in the sea (Korre, 1997). The ordinary kriging estimates of Pb concentration in the soil were utilised as the basis for the release assessment step. The Chronic Daily Intake of Pb deriving from the pathway of direct ingestion of contaminated soil was estimated for two population groups using equation 1. These were male adults who, due to their profession, experience maximum exposure to soil (e.g. gardeners, farmers) and children of 1-6 years old. The main exposure parameters and their mean values used for each target group are presented in Table 1. 10 Fig. 3. Estimated Pb levels in the study area. 11 Table 1. The mean values and probability distributions used for the main parameters in the exposure model. Exposure Assessment Parameter Adult value Child value Distribution Body Weight (kg) 70 16 Normal Ingestion Rate (mg/day) 100 200 Normal Exposure Duration (yrs) 30 10 Normal Exposure Frequency (days/yr) Fraction Ingested Conversion Factor (kg/mg) 300 Normal 0.0 – 1.0 Uniform 10-6 Uniform The mean values listed in Table 1 were used for each parameter and the probability distributions obtained from 1,000 trials were generated performing a Monte Carlo-type random sampling so as to cater for uncertainty inherent in the model parameters. In order to remain consistent with the choice of RfD in the consequence assessment step, the mean values utilised for the model parameters during the exposure assessment stage were those suggested by the U.S. EPA (Petts et al., 1997) except for FI and EF. In the case of fraction ingested (FI), the whole range of values (0.0 to 1.0) was used. Also, instead of using the U.S. EPA ‘reasonably maximum’ exposure frequency (EF) of 350 days per year, a normal distribution with a mean of 300 was judged to be more realistic. The choice of statistical distribution used to randomly sample each parameter was based on the recommendations of previous researchers (Finley et al., 1994). The standard deviations utilised for generating the distributions of all other parameters (apart from the uniform distribution generated for the Conversion Factor) was 10% of the respective mean. The fit of the resulting 1000 values to the desired distribution was tested before use in the exposure model. Random combinations of 1000 trials generated for each parameter were submitted to the direct ingestion model together with one concentration estimate for each estimation point in a regular 250250 metres grid. The 1000 values of CDI calculated for each estimation point were then used to describe statistically the exposure to Pb in the study area for the adult and child populations. The x-y co-ordinates of the Pb concentration values provided the spatial reference for the CDI statistical distributions. At this stage of the exposure assessment procedure, the CDI estimates for each of the target groups were compared with the RfD values of 0.1 mg kg-1 day-1 and 0.0035 mg kg-1 day-1 by initially calculating the number of exceeding counts out of the 1000 for each estimation 12 point. The outcome for each estimation point was then introduced to the GIS database. The spatial representation of the results yielded a comprehensive picture of the risk to human health, from direct ingestion of soil, encountered by the population under investigation. To provide a measure of the uncertainty entailed in the model, confidence levels around the mean CDI for each estimation point needed to be established in order to provide a confidence level for the exceedence of the mean above the selected RfD. For this purpose the CDI distributions were transformed to match a standard statistical distribution and were tested for 3 different levels of exposure -high, medium and low. In order to achieve representativeness, the exposure distributions were regenerated after 10,000 trials. After a series of transformations (i.e. normal, lognormal, beta) the exposure distributions generated were found to resemble best the truncated normal distribution. This was consistent with the fact that the estimated distribution approximated closely the experimental exposure distribution for high levels of exposure. The 95%, 90% and 80% confidence levels around the CDI means were calculated for each point and the corresponding study area was classified in one of 4 classes indicating the significance of the corresponding risk. Finally, the model parameters were tested by applying the single perturbation sensitivity analysis technique to evaluate their effect on the model outcome. The model results were recorded for 10 runs each, using the minimum and maximum parameter values in question and the relevant sensitivity index calculated using equation 2. Table 2 presents the minimum, maximum and default mean values of the parameters considered, as well as the sensitivity indices calculated. The results have revealed that the most sensitive parameters were the fraction ingested (FI) and the concentration (CS). The wide ranges considered for the fraction ingested (FI) (0.01.0) and for the Pb concentrations (CS) (125-33,503 ppm) were responsible for the high sensitivity of these parameters. The ingestion rate (IR), exposure duration (ED), exposure frequency (EF) and the conversion factor (CF) represented a medium level of sensitivity, and their increase resulted in an increase in the resultant CDI. On the other hand, body weight (BW) appeared to be a rather insensitive parameter, increase of which caused a decrease in the value of the resultant CDI. 13 Table 2. Exposure parameters considered in the sensitivity analysis and the sensitivity indices calculated. Upper Limit Sensitivity Index 33503.6 0.969 70 90 0.166 19.5 30 38.6 0.578 EF (days/year) 217 300 384.9 0.588 IR (mg/day) 65 100 128.7 0.496 FI 0.0002 0.0 - 1.0 0.968 0.999 CF (kg/mg) 710-7 110-6 1.2810-6 0.456 Parameter Lower Limit Default Value (mean) CS (mg/kg) 125 2994.433 BW (kg) 50.6 ED (yrs) a a arithmetic mean as calculated from the measured concentrations for all estimation points 5. Results and discussion The exposure to Pb calculated in the exposure assessment step for both adult and child target groups is depicted in Fig. 4 and Fig. 5 respectively. Topographical and other general geographic characteristics of the area, valuable in appreciating the significance of the risk on the exposed population are also provided in these maps. Further spatial data included in the maps show the nature of mining activity in the study area. 14 Fig. 4. Mean exposure to Pb for the adult population in Lavrio. 15 Fig. 5. Mean exposure to Pb for the child population in Lavrio. 16 The characteristic differences in the parameters of the exposure pathways for the two target groups (i.e. body weight, ingestion rate) control the differences in the resultant exposures. Indeed, child exposure is one to two orders of magnitude higher than adult exposure for all the estimation points. The patterns guiding the high exposure areas are uniformly followed for both populations, being dictated by the metal concentration patterns shown in Fig. 3. The highest exposure means are observed around the city of Lavrio, at a wide area south of the village Agios Konstantinos (Kamariza) and in the NW direction, following the occurrence of ore deposits and mining activities. The actual risk estimates for the target groups studied were calculated in the form of counts and exceedence rates above the selected RfD values. For the adult population, the probability of exposure to levels higher than the U.S. EPA RfD of 0.1 mg kg-1 day-1 was found to be zero for all estimated points. Fig. 6 illustrates the spatial distribution of exceedence counts with respect to the 0.0035 mg kg-1 day-1 AERIS RfD. The highlighted areas of high exceedence coincide with the areas of high exposure means, as can be seen by comparing Fig. 4 with Fig. 6. For the child population on the other hand, there are areas of high exceedence counts above both the 0.1 mg kg-1 day-1 and the 0.0035 mg kg-1 day-1 as shown in Fig. 7 and Fig. 8. With respect to the AERIS RfD, alarmingly high exceedence levels are observed over a very wide section of the peninsula. Yet, when compared with the U.S. EPA RfD value of 0.1 mg kg-1 day-1, the area of high exceedence levels is limited to the region around the city of Lavrio, Agios Konstantinos and two relatively smaller regions to the NW and south of the peninsula. 17 Fig. 6. Exceedence counts for Pb exposure above the 0.0035 mg kg-1 day-1 RfD for the adult population. 18 Fig. 7. Exceedence counts for Pb exposure above the 0.1 mg kg-1 day-1 RfD for the child population. 19 Fig. 8. Exceedence counts for Pb exposure above the 0.0035 mg kg-1 day-1 RfD for the child population. 20 The uncertainty inherent in the risk assessment methodology selected was assessed by determining the confidence around the mean of the exposure distributions established for each estimation grid point. This confidence was expressed with respect to the selected RfD. Risk ratings were attributed to different cases of the relationship between the mean and the Reference Dose such that, areas where the mean exposure exceeds the Reference Dose were rated 4, posing significant risk which stems from high exposure levels; areas where the mean is smaller than the Reference Dose but is within the 80% confidence level from the mean were rated 3; areas where the mean is smaller than the Reference Dose but is within the 90% confidence level from the mean were rated 2; areas where the mean is smaller than the Reference Dose but is within the 95% confidence level from the mean were rated 1; all other areas where the Reference Dose is higher than the mean and lie outside the confidence levels were rated 0, corresponding to low risk levels. Fig. 9 and Fig. 10 illustrate examples of these ratings for the adult and child populations in relation to the 0.0035 mg kg-1 day-1 AERIS RfD and 0.1 mg kg-1 day-1 U.S. EPA RfD respectively. 21 Fig. 9 Exceedence rates for Pb exposure above the 0.0035 mg kg-1 day-1 RfD for the adult population. 22 Fig. 10 Exceedence rates for Pb exposure above the 0.1 mg kg-1 day-1 RfD for the child population. 23 The confidence levels around the mean did not have a significant effect on the final outcome for any of the adult or child rate calculations. This can be seen by comparing Fig. 6 with Fig. 9 and Fig. 7 with Fig. 10. Indeed, for the majority of the estimated points, the selected RfD was either much lower than the mean of the distribution, or was significantly higher. The areas where the Reference Dose was found to be within the 80% Confidence Level from the mean were very limited. Apart from giving a comprehensive picture of the harmful exposure’s spatial distribution in the area, GIS maps provided the means to consider qualitative spatial information in the assessment of the results. Indeed, the comparison of the risk maps with the road network and the dwellings’ map of Fig. 2 shows that wide areas of high estimated RfD exceedence are not easily accessed or are situated far from villages and are mostly covered by forest land. Yet, concern for the human health is raised for the areas in close proximity to villages such as Agios Konstantinos (Kamariza) and for the town of Lavrio, as well as for any households randomly located around the mining and smelting areas. It is clear that high exceedence and consequently the high risk probability concurs with high heavy metal concentrations. The pattern of exceedence was the same for all 3 cases examined. Yet, the effect of the selection of the Reference Dose was significant. 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