Environ Sci Pollut Res (2015) 22:2757–2764 DOI 10.1007/s11356-014-3493-4
RESEARCH ARTICLE
Screening for potentially hazardous PRTR chemicals in the Lake Biwa-Yodo River basin of Japan using a one-box multimedia model B. H. A. K. T. Ariyadasa & Akira Kondo & Yoshio Inoue
Received: 25 January 2014 / Accepted: 20 August 2014 / Published online: 11 September 2014 # Springer-Verlag Berlin Heidelberg 2014
Abstract A system is needed to predict the behavior, fate, and occurrence of environmental pollutants for effective environmental monitoring. Available monitoring data and computational modeling were used to develop a one-box multimedia model based on the mass balance of the emitted chemicals. Eight physiochemical phenomena in the atmosphere, soil, water, and sediment were considered in this model. This study was carried out in the Lake Biwa-Yodo River basin which provides multiple land uses and also the natural water resource for nearly 13 million of population in the region. Annual emissions for 214 nonmetallic compounds were calculated using the chemical emission data on Japanese pollutant release and transfer registry and used for executing the model simulations for 1997, 2002, and 2008 as input data. The calculated chemical concentrations by the model for all the environmental media were analyzed to determine trends in concentration over this study span. The majority of the chemicals decreased in concentration over time. Among the 214 nonmetallic chemical pollutants, 36 chemicals did not decrease in concentration and were in the top 10 % for concentration on average. Of these 36 pollutants, 7 occur in all 4 environmental media and pose a potential health risk at humans in the Lake Biwa-Yodo River basin. Responsible editor: Philippe Garrigues Electronic supplementary material The online version of this article (doi:10.1007/s11356-014-3493-4) contains supplementary material, which is available to authorized users. B. H. A. K. T. Ariyadasa (*) : A. Kondo : Y. Inoue Graduate School of Engineering, Osaka University, PO Box. 565–0871, Yamadaoka 2-1, Suita, Osaka, Japan e-mail: [email protected] A. Kondo e-mail: [email protected] Y. Inoue e-mail: [email protected]
Keywords Chemical pollutants . Environmental health risk . Environmental modeling . Lake Biwa-Yodo River basin . One-box multimedia model . PRTR Abbreviations PRTR Pollutant release and transfer registry LBYRB Lake Biwa-Yodo River basin
Introduction When chemical pollution in the environment reaches a threshold level, these chemicals begin to damage the environment and the health of humans, plants, and animals. In most cases, these chemicals receive attention after the damage has become apparent. The case of Minamata disease caused by methylmercury poisoning in Kumamoto, Japan (Harada 1995), and Itai disease due to cadmium poisoning in Toyoma prefecture, Japan (Inaba et al. 2005) seems to be localized incidents but proved the awareness of those pollutants were raised after the damage was done. In most countries, environmental monitoring is carried out to elucidate the status of these chemicals in the environment and to enable better management practices, but environmental monitoring is challenging when the pollutants or geographical areas affected are unknown. Thus, alternative data sources and mathematical and computational modeling may be used to produce environmental-modeling tools to increase the efficiency of environmental monitoring and environmental management, ultimately helping to protect the environment. In 1991, Mackay used a level-III multimedia model based on fugacity to evaluate the fate of organic chemicals (Mackay and Paterson 1991). In 2001, a multicompartmental, multibasin fugacity model was used to describe the fate of polychlorinated biphenyls in the Baltic Sea (Wania et al.
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2001). Recently, we used a one-box multimedia model to evaluate the lead and mercury concentrations in the Lake Biwa-Yodo River basin (LBYRB) in Japan (Kondo et al. 2013; Ariyadasa et al. 2014). Most of these environmentalmodeling studies focus on a particular chemical (Kondo et al. 2013) or on smaller chemical groups and on a particular environmental medium (Mackay and Paterson 1991; Wania et al. 2001). Usually, the studies describe the fate (−changes in concentration) of these chemicals but the extended applications of environmental modeling as a tool to facilitate mitigation of environmental pollution was absent. Objectives The main objective of this study was to identify the chemicals posing a health risk based on the environmental emission data provided in the Pollutant Release and Transfer Registry (PRTR) in the LBYRB by using a one-box multimedia model. For that reason, we studied the behavior and the fate of a much wider chemical group to provide better insight of the status of these pollutants and to prevent environmental pollution proactively.
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by the Kizu and Katsura Rivers, becomes the Yodo River, and flows to Osaka bay. The Lake Biwa-Yodo River system provides water to nearly 13 million people in the region (Sudo et al. 2002).
One-box multimedia model The one-box multimedia model (OBMM) is a mathematical model developed to interpret the behaviors and fates of chemicals in the atmosphere, soil, water, and sediment. Figure 2 diagrammatically explains the OBMM including the chemical behaviors and environmental media considered in this study (Kondo et al. 2013). The study site is considered a three-dimensional, concealed compartment, and the OBMM is based on the mass balance of the chemicals. Once the emissions data for a given chemical pollutant are input to the OBMM, the model calculates the concentration of the pollutant in each of the above environmental media, considering the following chemical phenomena:
Pollutant release and transfer registry The Pollutant Release and Transfer Registry was established in Japan under the supervision of the Japanese Ministry of Environment in 1996. Under this system, businesses and industrial facilities must report the quantity of chemicals they release to the atmosphere, public water bodies, land (on-site) and landfills (on-site), and transfer for further processing (as sewage or off-site) annually. These data are publically available as registered PRTR data (mainly submitted by businesses and facilities as point-source emissions) and nonregistered PRTR data (estimated by the Japanese Ministry of Environment as non-point-source emissions). These PRTR data were downloaded from the PRTR data page of the PRTR Information Plaza website and used in this study as the data source to calculate the annual emission data used in the model simulations (referred to PRTR data page, PRTR Information Plaza website, http://www2.env.go.jp/chemi/prtr/ prtrinfo/e-index.html). Lake Biwa-Yodo River basin The LBYRB is located in the Kinki region of Japan, on the main Island as shown in the Fig. 1. It lies between the latitudes 34.65~35.69° N and the longitudes 136.15~136.51° E. This study area is composed of six prefectures as follows: Hyogo, Kyoto, Mie, Nara, Osaka, and Shiga. It was selected as the study site due to its multiple land-use patterns (residential, agricultural, and industrial). It contains the largest water body in Japan, Lake Biwa, which covers 630.77 km2. The Seta River starts from the southern tip of Lake Biwa and is joined
(a) Emission of various chemicals to the atmosphere, soil, and water. This phenomenon is mainly affected by anthropogenic activities. Natural emission and inflow of chemicals via soil erosion also can occur (Seinfeld and Pandis 2006). Emission is the main process by which chemicals enter the three-dimensional compartment considered in the OBMM. (b) Degradation is the natural decay, accumulation into/consumption by living organisms, and conversion of various chemicals into other compounds in the environment (Seinfeld and Pandis 2006). Conversion (or breaking down into other chemical compounds) is a process of emission into the OBMM, but degradation is mainly the process that removes chemicals from the OBMM. (c) Advection is the chemical transport in the atmosphere (Seinfeld and Pandis 2006). (d) Sedimentation mainly occurs in water. Suspended solids (SS) in the water settle to the bottom of the water body due to gravity, and these SS can adsorb chemicals and facilitate their transportation into the sediment at the bottom of the water body (Seinfeld and Pandis 2006). (e) Resuspension is the reverse process whereby the chemicals are released into the water from the sediments (Seinfeld and Pandis 2006). (f) Dry deposition is the process whereby chemicals in the atmosphere are collected or deposited onto soil or a water body via gravitation, interception, impaction, diffusion, and turbulence (Seinfeld and Pandis 2006).
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Fig. 1 The Lake Biwa-Yodo River basin and the diagrammed emission sources
(g) Wet deposition occurs when atmospheric hydrometeors such as rain or snow scavenge the chemicals from the atmosphere and deposit them on soil or a water body (Seinfeld and Pandis 2006). (h) Atmospheric mixing is a process where the atmosphere is divided into the upper mixing layer and lower mixing layers relative to the atmospheric mixing height, which changes from 200 to 1,000 m above sea level during the day. The exchange of chemicals between these two layers is a natural process (Kondo et al. 2013).
Fig. 2 Diagrammatic explanation of the one-box multimedia model with the chemical behaviors and environmental media of interest
Main equation The main equation of the OBMM was developed by considering the following variables: 1. Emission of chemicals into the atmosphere, soil, and water 2. Degradation of chemicals in all four environmental media 3. Transport of chemicals by advection in the atmosphere 4. Dry and wet deposition of chemicals in the atmosphere 5. Sedimentation and resuspension of chemicals in water
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According to the OBMM, the concentration of a particular chemical pollutant in a particular environmental medium at a particular time can be interpreted by the summation of the emission flux, degradation flux, advection flux, sedimentation/deposition flux, and mass-transfer flux between environmental media at equilibrium. Equation (1) expresses the main equation of the mass balance for a particular chemical pollutant (e.g., chemical A): dM
i=dt ¼
MN X
f eq− i; jþ f emi− iþ f ad− iþ
j¼1
MN X j¼1
f dprs− i; jþ
MN X
f deg− i; j ð1Þ
j¼1
Where i,j is the environmental medium, MN is the number of media, Mi is the gross mass of A in media i (mol), feq_ij is the mass-transfer flux of A at equilibrium (mol s−1), femi is the emission flux of A (mol s−1), fad is the advection flux of A (mol s−1), fdprs is the deposition flux of A, and fdeg is the degradation flux of A. Detailed equations are provided in Appendix A of the supplementary data. These differential equations were solved using Runge–Kutta technique by the computer program coded with Fortran code.
Methodology Annual emissions amounts in LBYRB for 214 nonmetallic PRTR chemicals were calculated using the PRTR data. Depending on the constant data availability, annual emission amounts for the years of 1997, 2002, and 2008 were calculated and fed into the OBMM for simulations while providing reasonable study span. Separate OBMM simulation runs were carried out for each year to evaluate the calculated concentrations of these chemicals in each of the atmosphere, soil, water, and sediment. The calculated results were compared with the available published monitoring data to validate the concentrations calculated by the OBMM. Scenarios were developed to screen the potentially hazardous PRTR chemicals by using the trends in their calculated concentration, calculated concentration levels, and the occurrences in multiple environmental media. Screened PRTR chemicals were qualitatively analyzed for health risks using the health-risk categories set by the United States Department of Labor. For better comprehension, the methodology will be described in three main steps: emissions-data calculation, OBMM simulation runs, and screening of the chemicals. Emissions-data calculation Annual emissions for 214 nonmetallic PRTR chemicals were calculated using PRTR data. These calculations were carried out as separate processes because the emissions and quantities
of chemicals transferred are available as registered PRTR data and nonregistered PRTR data. Registered PRTR data The registered PRTR data provide the emissions and quantities of chemicals transferred per year by compound, area, and industry. The locations of the emission sources were provided as addresses in the PRTR system. The emissions and transfer data for the 214 nonmetallic chemicals were collected for the 6 prefectures (Hyogo, Kyoto, Mie, Nara, Osaka, and Shiga). Then, the geocoding service developed by the Center for Spatial Information Science, Tokyo University was used to select the emission sources of these chemicals within each study site, and their emissions were summed to calculate the emission of each pollutant from the registered PRTR data (Center for Spatial Information Science, Tokyo University, Japan, http://www.csis.u-tokyo.ac.jp/english/index.html). Nonregistered PRTR data The nonregistered PRTR data include the diffuse or nonpoint-source emissions estimated for businesses that are smaller in size or product volume, nonlisted industries, households, and mobile sources. These data are delimited by emissions to the atmosphere, water, landfills, and soil. Emissions to landfills and soil were negligible and thus were not considered in the calculation of nonregistered emissions in this study. As these data were provided by region, estimation was required to calculate the total emissions in the LBYRB. The population ratio of the LBYRB to the Kinki region was assumed to be representative to the ratio of emissions between LBYRB and to that of Kinki region. Total emissions from nonregistered PRTR into the LBYRB were estimated based on the above assumption for the respective 214 nonmetallic PRTR chemicals. After the total emissions from both registered PRTR data and nonregistered PRTR data for LBYRB were calculated, they were summed to obtain the total emissions of the 214 nonmetallic PRTR chemicals in the study site. One-box multimedia model stimulations Calculated emissions were input to the OBMM together with the other required chemical properties to calculate the concentrations of the chemicals in the atmosphere, soil, water, and sediment. Tables S1 and S2 in the Appendix A of the supplementary data provide parameters used in the OBMM calculations and the chemical properties required for the OBMM calculations, respectively. Simulations were carried out separately for 1997, 2002, and 2008 in a similar manner. These calculations were carried out with the conditions of chemicals observe mass conservation and mixes perfectly within the environmental media and between the environmental media
Nondecreasing concentration trends
Highest calculated concentrations
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Occur in all media
Potentially hazardous chemicals
Fig. 3 Diagrammatic explanation of the screening scenarios
they are in nonequilibrium state. Time steps of the calculations were set to 6 min. Screening of the chemicals Calculated concentrations (or results) of the OBMM from 1997 to 2008 were analyzed and screening scenarios were developed to identify the potentially hazardous PRTR chemicals as shown in the Fig. 3. Screening scenarios were developed based on the following criteria. & &
&
For possessing nondecreasing changes of the calculated concentration over the time span of the study For possessing the highest calculated concentrations in each environmental media among the 214 chemicals (upper 10 % of the chemicals listed descending on their averaged concentrations) For their occurrence in all four environmental media
Results and discussion Calculated concentrations of the 214 nonmetallic PRTR chemicals for the years of 1997, 2002, and 2008 were plotted against their representative PRTR number. Figure 4 shows the Fig. 4 Calculated concentrations in the atmosphere for the 214 nonmetallic PRTR chemicals obtained from the OBMM simulations for 1997, 2002, and 2008
Calculated concentration levels in Atmosphere (log 10) (mg m-3)
Environ Sci Pollut Res (2015) 22:2757–2764 1997
2002
2008
1.0E+00
Decreasing concentration trends Nondecreasing concentration trends
1.0E-10
1.0E-20 90 84 85 96 97 Chemicals` PRTR reference number
Atmosphere Soil Water Sediment
55/214 69/214 72/214 65/214
Fig. 5 Explanation of the concentration trends and the number of chemicals showing the nondecreasing concentration trends in each media
calculated concentrations for the atmosphere while the calculated concentrations for the soil, water, and sediments are shown in the Fig. S5 in the Appendix B of the supplementary data. These calculated concentrations for 214 nonmetallic chemicals in the atmosphere varied from 4.30×10−15 to 2.64 × 10 − 0 3 mg m − 3 (1997), 2.66 × 10 − 1 7 to 1.88 × 10 − 0 6 mg m − 3 (2002), and 8.12 × 10 − 2 2 to 5.45 × 10−07 mg m−3 (2008). In the soil, these calculated concentrations varied from 5.02×10−17 to 8.39×10−05 mg g−1 (1997), 1.63×10−18 to 1.97×10−05 mg g−1 (2002), and 2.56×10−21 to 9.64×10−06 mg g−1 (2008), while in water they ranged from 6.44×10−15 to 5.12×10−03 mg L−1 (1997), 4.58×10−16 to 2.53 × 10−04 mg L−1 (2002), and 2.52 × 10−16 to 9.22 × 10−05 mg L−1 (2008). Similarly in the sediments, calculated concentrations varied from 4.79×10−18 to 3.71×10−06 mg g−1 (1997), 2.53×10−18 to 2.08×10−07 mg g−1 (2002), and 1.84× 10−18 to 7.81×10−08 mg g−1 (2008). The calculated results were compared with the available published data of the observed environmental concentrations of these nonmetallic chemicals to validate the accuracy of the OBMM calculations. For an example, the total annual emission amounts of glyoxal (PRTR no. 65) in the LBYRB were 2.4×105, 6.61×101, and 1.08×101 kg for the respective years of 1997, 2002, and 2008. For the year 1997, the calculated concentrations of glyoxal were 5.49×10−10 mg m−3 for the atmosphere, 7.33 × 10 −09 mg g −1 for the soil, 2.18 × 10−05 mg L−1 for water, and 1.63×10−08 mg g−1 for sediment. For 2002 and 2008, the calculated glyoxal concentrations in
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Soil 13 Chemicals with Highest 10% of the avg. calculated concentration
Chemicals with nondecreasing concentration
Water 26
Sediment 19
Fig. 6 Numbers of chemical pollutants showing both properties of the nondecreasing concentration trends and highest averaged calculated concentration in each environmental medium
the atmosphere were 1.46×10−06 and 4.93×10−07 mg m−3 while the observed glyoxal concentration in the atmosphere around Tokyo was reported as 4.06×10−08 mg m−3 (Ortiz et al. 2006, Kawamura et al. 2013). Atrazine (PRTR no. 75) is an antifouling compound and a herbicide which was observed 58.8 ng L−1 in water at a fishery harbor in Kobe, Japan (Liu et al. 1999) and the calculated concentration of atrazine in water in 1997 was 2.98×10−1 ng L−1. Another study using OBMM in 2007 to evaluate health risks found 33 hazardous chemicals in the atmosphere and 109 in the water (Kawashima et al. 2007). Similar chemicals were identified by Kawashima and this study, supporting the reliability of the results calculated by OBMM. However, it was difficult to validate all calculated concentrations of the chemicals studied in this study due to the lack of monitoring data. When the calculated concentrations of this group of 214 nonmetallic chemicals were observed, the range of the concentrations was decreasing from 1997, 2002, to 2008. The highest calculated concentrations for the atmosphere were 2.60×10−3, 1.88×10−6, and 5.54×10−7 mg m−3 for the years 1997, 2002, and 2008, respectively, and they were decreased along with the study span from 1997, 2002, and 2008. Similarly, the highest calculated concentrations were decreasing from 8.39×10−5, 1.97×10−5, and 9.64×10−6 mg g−1 in soil; 5.12×10−3, 2.53×10−4, and 9.22×10−5 mg L−1 in water, and 3.71 × 10−6, 2.08 × 10−7, and 7.81 × 10−8 mg g−1 in
sediment. To confirm these data, these 214 chemicals were analyzed individually for their changes in concentration along the study span. While majority of these chemicals showed a decreasing concentration trends from 1997 to 2008, some chemicals exhibited nondecreasing trends. Of the 214 chemicals, 55 chemicals in the atmosphere, 69 in soil, 72 in water, and 65 in sediment exhibited nondecreasing concentration trends as shown in Fig. 5. The average calculated concentrations for the three OBMM runs were obtained for these 214 chemical compounds in each of the environmental media. They were arranged in descending order; the chemicals with the highest 10 % average calculated concentrations were selected, and their relationships to the chemicals with nondecreasing concentration trends were observed. Figure 6 shows the number of chemicals that showed both the properties of nondecreasing concentration trends and occurred within the 10 % of the chemicals with highest averaged calculated concentration in each environmental medium. Considering the number of chemicals shown in Fig. 6 possessing both of the abovementioned properties in each media, 75 chemicals were expected to be identified, but only 36 chemicals were observed. This suggested the occurrence of chemicals in multiple environmental media. Seven of these 36 chemicals were identified to occur in all 4 environmental media and they are listed in Table 1. Chemicals with nondecreasing concentration trends, among the highest 10 % of the averaged calculated concentrations, and occurring in multiple environmental media (not occurring in all four environmental media) are listed in Table S4 provided in Appendix C of the supplementary data. Table S5 given in Appendix C lists the chemicals those only occupy one environmental media while showing the nondecreasing concentration trends and the highest 10 % of the averaged calculated concentrations, and Table S6 lists the remaining nonmetallic PRTR chemicals considered in this study of those concentrations were decreasing along with the study span. As these seven chemicals are increasing in concentration and present in relatively high concentrations, their health-risk
Table 1 Identified potentially hazardous chemical pollutants occurring in all environmental media PRTR no.
CAS no.
Chemicals name
MW (Da)
HC (atm m3 mol−1)
DC (log 10)
Solubility (g L−1)
DR (Air) (m2 s−1)
DR(Water) (m2 s−1)
65 90 146 179 238 239 300
107-22-2 122-34-9 3347-22-6 1746-01-6 86-30-6 100-02-7 552-30-7
Glyoxal Simazine Dith ian on dioxins (TCDD) N-Nitros odiphenylamine p-Nitrophenol 1,2,4-Benzenstricarboxylicanhydride
58.0 201.7 296.3 322.0 198.2 139.1 192.1
3.33×10−9 9.42×10−10 1.32×10−11 3.20×10−05 1.21×10−6 4.51×10−10 1.28×10−10
2.10 2.15 2.84 7.17 3.13 1.91 1.95
8.00×102 6.20×10−3 1.40×10−4 2.00×10−7 3.51×10−2 1.45×10−1 1.04×100
1.23×10−5 5.79×10−6 5.24×10−6 5.60×10−6 5.86×10−6 7.58×10−6 6.54×10−6
1.48×10−9 6.18×10−10 5.58×10−10 6.10×10−10 6.26×10−10 8.53×10−10 7.23×10−10
MW molecular weight, DC distribution coefficient, HC Henry’s coefficient, DR diffusion rate Ref. NIST Chemistry WebBook (http://webbook.nist.gov/chemistry/)
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potential was qualitatively studied using the Health Hazard Criteria of the Occupational Safety and Health Administration, United State Department of Labor (United States Department of Labor, http://www.osha.gov/pls/ oshaweb/owadisp.show_document?p_table= STANDARDS&p_id=10100). The health risk and the adverse effects of the chemical substances are categorized into ten main categories: acute toxicity, aspiration hazard, carcinogenicity, germ-cell mutagenicity, reproductive toxicity, skin corrosion/ irritation, respiratory or skin irritation, serious eye damage/eye irritation, specific target-organ toxicity (single exposure), and specific target-organ toxicity (repeated/prolonged exposure). A diagrammatical explanation of the relationships among these seven chemicals, their calculated concentrations in the different environmental media, and their adverse health effects is shown in Fig. 7. As the potential of sediments to directly affect human health is comparatively negligible, sediment is not shown in Fig. 7. Three axes show the average calculated concentrations of the seven chemicals from Table 1 for water, atmosphere, and soil. In water, dioxins (tetrachlorodibenzodioxin; TCDD) were present at the minimum average calculated concentration (2.62× 10−6 mg L−1), while glyoxal was present at the highest averaged calculated concentration (1.22×10−4 mg L−1). In the atmosphere, the calculated concentrations of these chemicals varied from 4.33×10−8 to 9.41×10−7 mg m−3, while in soil, it varied from 2.03×10−8 to 9.79×10−6 mg g−1.
Fig. 7 Summary of the calculated concentrations and qualitative health risks of the chemical pollutants identified in water, the atmosphere, and soil
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The qualitative health risks posed by these seven chemicals are shown in Fig. 7. Dioxins pose five categories of health risks: carcinogenicity, skin corrosion/irritation, respiratory or skin sensation, serious eye damage/eye irritation, and specific target-organ toxicity (repeated/ prolonged exposure; Bertazzi et al. 2000 and Kogevinas 2001). Simazine poses risks of carcinogenicity, germ-cell mutagenicity, reproductive toxicity, and specific targetorgan toxicity (repeated/prolonged exposure; IARC Monographs on the Evaluation of Carcinogenic Risk to Humans, http://monographs.iarc.fr/ENG/Monographs/ vol73/mono73-25.pdf and Zorrilla et al. 2010). Glyoxal (Kielhorn et al. 2004), dithianon (Paolini et al. 1997 and Toxicology Data Network, http://toxnet.nlm.nih.gov/cgibin/sis/search/a?dbs±hsdb:@term±@DOCNO±1583), and p-nitrophenol (Edwards and Tchounwou 2005) pose three categories of health risk. These results support our findings of 7 potentially hazardous chemicals among the 214 nonmetallic PRTR chemicals that were initially considered in this study. Environmental monitoring can be carried out for these seven identified chemicals and thus we can confirm their present status in the environment and eventually those details can be used to control and mitigate the adverse effects they are posing on our environment. This way we can use the findings of this study to proactively protect our environment.
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Conclusion The one-box multimedia model was used to identify hazardous chemicals in LBYRB. Initially, 214 nonmetallic chemicals were selected from among the PRTR chemicals, and their emissions were estimated for 1997, 2002, and 2008 using PRTR data. These data were input to the OBMM to calculate chemical concentrations in the atmosphere, soil, water, and sediment. The calculated results were validated using the published monitoring data. Trends in the calculated concentrations over time were analyzed from 1997 to 2008. Scenarios were developed to select the chemicals with trends deviating from the majority and with the highest concentrations, and 36 chemical compounds were selected. Seven of these 36 chemicals (glyoxal, simazine, dithianon, Nnitrosodiphenylamine, dioxins, p-nitrophenol, and 1,2,4benzenetricarboxylic anhydride) occur in all 4 environmental media and were identified as potentially hazardous; the associated risks should be thoroughly studied in the future. The lack of monitoring data was a weakness in validating the concentrations calculated from the OBMM. More monitoring data would allow us to increase the accuracy, reliability, and adaptability of this model to diverse study sites.
Conflict of interest We would like to declare that we do not have any conflicts of interests.
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RESEARCH ARTICLE
Screening for potentially hazardous PRTR chemicals in the Lake Biwa-Yodo River basin of Japan using a one-box multimedia model B. H. A. K. T. Ariyadasa & Akira Kondo & Yoshio Inoue
Received: 25 January 2014 / Accepted: 20 August 2014 / Published online: 11 September 2014 # Springer-Verlag Berlin Heidelberg 2014
Abstract A system is needed to predict the behavior, fate, and occurrence of environmental pollutants for effective environmental monitoring. Available monitoring data and computational modeling were used to develop a one-box multimedia model based on the mass balance of the emitted chemicals. Eight physiochemical phenomena in the atmosphere, soil, water, and sediment were considered in this model. This study was carried out in the Lake Biwa-Yodo River basin which provides multiple land uses and also the natural water resource for nearly 13 million of population in the region. Annual emissions for 214 nonmetallic compounds were calculated using the chemical emission data on Japanese pollutant release and transfer registry and used for executing the model simulations for 1997, 2002, and 2008 as input data. The calculated chemical concentrations by the model for all the environmental media were analyzed to determine trends in concentration over this study span. The majority of the chemicals decreased in concentration over time. Among the 214 nonmetallic chemical pollutants, 36 chemicals did not decrease in concentration and were in the top 10 % for concentration on average. Of these 36 pollutants, 7 occur in all 4 environmental media and pose a potential health risk at humans in the Lake Biwa-Yodo River basin. Responsible editor: Philippe Garrigues Electronic supplementary material The online version of this article (doi:10.1007/s11356-014-3493-4) contains supplementary material, which is available to authorized users. B. H. A. K. T. Ariyadasa (*) : A. Kondo : Y. Inoue Graduate School of Engineering, Osaka University, PO Box. 565–0871, Yamadaoka 2-1, Suita, Osaka, Japan e-mail: [email protected] A. Kondo e-mail: [email protected] Y. Inoue e-mail: [email protected]
Keywords Chemical pollutants . Environmental health risk . Environmental modeling . Lake Biwa-Yodo River basin . One-box multimedia model . PRTR Abbreviations PRTR Pollutant release and transfer registry LBYRB Lake Biwa-Yodo River basin
Introduction When chemical pollution in the environment reaches a threshold level, these chemicals begin to damage the environment and the health of humans, plants, and animals. In most cases, these chemicals receive attention after the damage has become apparent. The case of Minamata disease caused by methylmercury poisoning in Kumamoto, Japan (Harada 1995), and Itai disease due to cadmium poisoning in Toyoma prefecture, Japan (Inaba et al. 2005) seems to be localized incidents but proved the awareness of those pollutants were raised after the damage was done. In most countries, environmental monitoring is carried out to elucidate the status of these chemicals in the environment and to enable better management practices, but environmental monitoring is challenging when the pollutants or geographical areas affected are unknown. Thus, alternative data sources and mathematical and computational modeling may be used to produce environmental-modeling tools to increase the efficiency of environmental monitoring and environmental management, ultimately helping to protect the environment. In 1991, Mackay used a level-III multimedia model based on fugacity to evaluate the fate of organic chemicals (Mackay and Paterson 1991). In 2001, a multicompartmental, multibasin fugacity model was used to describe the fate of polychlorinated biphenyls in the Baltic Sea (Wania et al.
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2001). Recently, we used a one-box multimedia model to evaluate the lead and mercury concentrations in the Lake Biwa-Yodo River basin (LBYRB) in Japan (Kondo et al. 2013; Ariyadasa et al. 2014). Most of these environmentalmodeling studies focus on a particular chemical (Kondo et al. 2013) or on smaller chemical groups and on a particular environmental medium (Mackay and Paterson 1991; Wania et al. 2001). Usually, the studies describe the fate (−changes in concentration) of these chemicals but the extended applications of environmental modeling as a tool to facilitate mitigation of environmental pollution was absent. Objectives The main objective of this study was to identify the chemicals posing a health risk based on the environmental emission data provided in the Pollutant Release and Transfer Registry (PRTR) in the LBYRB by using a one-box multimedia model. For that reason, we studied the behavior and the fate of a much wider chemical group to provide better insight of the status of these pollutants and to prevent environmental pollution proactively.
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by the Kizu and Katsura Rivers, becomes the Yodo River, and flows to Osaka bay. The Lake Biwa-Yodo River system provides water to nearly 13 million people in the region (Sudo et al. 2002).
One-box multimedia model The one-box multimedia model (OBMM) is a mathematical model developed to interpret the behaviors and fates of chemicals in the atmosphere, soil, water, and sediment. Figure 2 diagrammatically explains the OBMM including the chemical behaviors and environmental media considered in this study (Kondo et al. 2013). The study site is considered a three-dimensional, concealed compartment, and the OBMM is based on the mass balance of the chemicals. Once the emissions data for a given chemical pollutant are input to the OBMM, the model calculates the concentration of the pollutant in each of the above environmental media, considering the following chemical phenomena:
Pollutant release and transfer registry The Pollutant Release and Transfer Registry was established in Japan under the supervision of the Japanese Ministry of Environment in 1996. Under this system, businesses and industrial facilities must report the quantity of chemicals they release to the atmosphere, public water bodies, land (on-site) and landfills (on-site), and transfer for further processing (as sewage or off-site) annually. These data are publically available as registered PRTR data (mainly submitted by businesses and facilities as point-source emissions) and nonregistered PRTR data (estimated by the Japanese Ministry of Environment as non-point-source emissions). These PRTR data were downloaded from the PRTR data page of the PRTR Information Plaza website and used in this study as the data source to calculate the annual emission data used in the model simulations (referred to PRTR data page, PRTR Information Plaza website, http://www2.env.go.jp/chemi/prtr/ prtrinfo/e-index.html). Lake Biwa-Yodo River basin The LBYRB is located in the Kinki region of Japan, on the main Island as shown in the Fig. 1. It lies between the latitudes 34.65~35.69° N and the longitudes 136.15~136.51° E. This study area is composed of six prefectures as follows: Hyogo, Kyoto, Mie, Nara, Osaka, and Shiga. It was selected as the study site due to its multiple land-use patterns (residential, agricultural, and industrial). It contains the largest water body in Japan, Lake Biwa, which covers 630.77 km2. The Seta River starts from the southern tip of Lake Biwa and is joined
(a) Emission of various chemicals to the atmosphere, soil, and water. This phenomenon is mainly affected by anthropogenic activities. Natural emission and inflow of chemicals via soil erosion also can occur (Seinfeld and Pandis 2006). Emission is the main process by which chemicals enter the three-dimensional compartment considered in the OBMM. (b) Degradation is the natural decay, accumulation into/consumption by living organisms, and conversion of various chemicals into other compounds in the environment (Seinfeld and Pandis 2006). Conversion (or breaking down into other chemical compounds) is a process of emission into the OBMM, but degradation is mainly the process that removes chemicals from the OBMM. (c) Advection is the chemical transport in the atmosphere (Seinfeld and Pandis 2006). (d) Sedimentation mainly occurs in water. Suspended solids (SS) in the water settle to the bottom of the water body due to gravity, and these SS can adsorb chemicals and facilitate their transportation into the sediment at the bottom of the water body (Seinfeld and Pandis 2006). (e) Resuspension is the reverse process whereby the chemicals are released into the water from the sediments (Seinfeld and Pandis 2006). (f) Dry deposition is the process whereby chemicals in the atmosphere are collected or deposited onto soil or a water body via gravitation, interception, impaction, diffusion, and turbulence (Seinfeld and Pandis 2006).
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Fig. 1 The Lake Biwa-Yodo River basin and the diagrammed emission sources
(g) Wet deposition occurs when atmospheric hydrometeors such as rain or snow scavenge the chemicals from the atmosphere and deposit them on soil or a water body (Seinfeld and Pandis 2006). (h) Atmospheric mixing is a process where the atmosphere is divided into the upper mixing layer and lower mixing layers relative to the atmospheric mixing height, which changes from 200 to 1,000 m above sea level during the day. The exchange of chemicals between these two layers is a natural process (Kondo et al. 2013).
Fig. 2 Diagrammatic explanation of the one-box multimedia model with the chemical behaviors and environmental media of interest
Main equation The main equation of the OBMM was developed by considering the following variables: 1. Emission of chemicals into the atmosphere, soil, and water 2. Degradation of chemicals in all four environmental media 3. Transport of chemicals by advection in the atmosphere 4. Dry and wet deposition of chemicals in the atmosphere 5. Sedimentation and resuspension of chemicals in water
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According to the OBMM, the concentration of a particular chemical pollutant in a particular environmental medium at a particular time can be interpreted by the summation of the emission flux, degradation flux, advection flux, sedimentation/deposition flux, and mass-transfer flux between environmental media at equilibrium. Equation (1) expresses the main equation of the mass balance for a particular chemical pollutant (e.g., chemical A): dM
i=dt ¼
MN X
f eq− i; jþ f emi− iþ f ad− iþ
j¼1
MN X j¼1
f dprs− i; jþ
MN X
f deg− i; j ð1Þ
j¼1
Where i,j is the environmental medium, MN is the number of media, Mi is the gross mass of A in media i (mol), feq_ij is the mass-transfer flux of A at equilibrium (mol s−1), femi is the emission flux of A (mol s−1), fad is the advection flux of A (mol s−1), fdprs is the deposition flux of A, and fdeg is the degradation flux of A. Detailed equations are provided in Appendix A of the supplementary data. These differential equations were solved using Runge–Kutta technique by the computer program coded with Fortran code.
Methodology Annual emissions amounts in LBYRB for 214 nonmetallic PRTR chemicals were calculated using the PRTR data. Depending on the constant data availability, annual emission amounts for the years of 1997, 2002, and 2008 were calculated and fed into the OBMM for simulations while providing reasonable study span. Separate OBMM simulation runs were carried out for each year to evaluate the calculated concentrations of these chemicals in each of the atmosphere, soil, water, and sediment. The calculated results were compared with the available published monitoring data to validate the concentrations calculated by the OBMM. Scenarios were developed to screen the potentially hazardous PRTR chemicals by using the trends in their calculated concentration, calculated concentration levels, and the occurrences in multiple environmental media. Screened PRTR chemicals were qualitatively analyzed for health risks using the health-risk categories set by the United States Department of Labor. For better comprehension, the methodology will be described in three main steps: emissions-data calculation, OBMM simulation runs, and screening of the chemicals. Emissions-data calculation Annual emissions for 214 nonmetallic PRTR chemicals were calculated using PRTR data. These calculations were carried out as separate processes because the emissions and quantities
of chemicals transferred are available as registered PRTR data and nonregistered PRTR data. Registered PRTR data The registered PRTR data provide the emissions and quantities of chemicals transferred per year by compound, area, and industry. The locations of the emission sources were provided as addresses in the PRTR system. The emissions and transfer data for the 214 nonmetallic chemicals were collected for the 6 prefectures (Hyogo, Kyoto, Mie, Nara, Osaka, and Shiga). Then, the geocoding service developed by the Center for Spatial Information Science, Tokyo University was used to select the emission sources of these chemicals within each study site, and their emissions were summed to calculate the emission of each pollutant from the registered PRTR data (Center for Spatial Information Science, Tokyo University, Japan, http://www.csis.u-tokyo.ac.jp/english/index.html). Nonregistered PRTR data The nonregistered PRTR data include the diffuse or nonpoint-source emissions estimated for businesses that are smaller in size or product volume, nonlisted industries, households, and mobile sources. These data are delimited by emissions to the atmosphere, water, landfills, and soil. Emissions to landfills and soil were negligible and thus were not considered in the calculation of nonregistered emissions in this study. As these data were provided by region, estimation was required to calculate the total emissions in the LBYRB. The population ratio of the LBYRB to the Kinki region was assumed to be representative to the ratio of emissions between LBYRB and to that of Kinki region. Total emissions from nonregistered PRTR into the LBYRB were estimated based on the above assumption for the respective 214 nonmetallic PRTR chemicals. After the total emissions from both registered PRTR data and nonregistered PRTR data for LBYRB were calculated, they were summed to obtain the total emissions of the 214 nonmetallic PRTR chemicals in the study site. One-box multimedia model stimulations Calculated emissions were input to the OBMM together with the other required chemical properties to calculate the concentrations of the chemicals in the atmosphere, soil, water, and sediment. Tables S1 and S2 in the Appendix A of the supplementary data provide parameters used in the OBMM calculations and the chemical properties required for the OBMM calculations, respectively. Simulations were carried out separately for 1997, 2002, and 2008 in a similar manner. These calculations were carried out with the conditions of chemicals observe mass conservation and mixes perfectly within the environmental media and between the environmental media
Nondecreasing concentration trends
Highest calculated concentrations
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Occur in all media
Potentially hazardous chemicals
Fig. 3 Diagrammatic explanation of the screening scenarios
they are in nonequilibrium state. Time steps of the calculations were set to 6 min. Screening of the chemicals Calculated concentrations (or results) of the OBMM from 1997 to 2008 were analyzed and screening scenarios were developed to identify the potentially hazardous PRTR chemicals as shown in the Fig. 3. Screening scenarios were developed based on the following criteria. & &
&
For possessing nondecreasing changes of the calculated concentration over the time span of the study For possessing the highest calculated concentrations in each environmental media among the 214 chemicals (upper 10 % of the chemicals listed descending on their averaged concentrations) For their occurrence in all four environmental media
Results and discussion Calculated concentrations of the 214 nonmetallic PRTR chemicals for the years of 1997, 2002, and 2008 were plotted against their representative PRTR number. Figure 4 shows the Fig. 4 Calculated concentrations in the atmosphere for the 214 nonmetallic PRTR chemicals obtained from the OBMM simulations for 1997, 2002, and 2008
Calculated concentration levels in Atmosphere (log 10) (mg m-3)
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2002
2008
1.0E+00
Decreasing concentration trends Nondecreasing concentration trends
1.0E-10
1.0E-20 90 84 85 96 97 Chemicals` PRTR reference number
Atmosphere Soil Water Sediment
55/214 69/214 72/214 65/214
Fig. 5 Explanation of the concentration trends and the number of chemicals showing the nondecreasing concentration trends in each media
calculated concentrations for the atmosphere while the calculated concentrations for the soil, water, and sediments are shown in the Fig. S5 in the Appendix B of the supplementary data. These calculated concentrations for 214 nonmetallic chemicals in the atmosphere varied from 4.30×10−15 to 2.64 × 10 − 0 3 mg m − 3 (1997), 2.66 × 10 − 1 7 to 1.88 × 10 − 0 6 mg m − 3 (2002), and 8.12 × 10 − 2 2 to 5.45 × 10−07 mg m−3 (2008). In the soil, these calculated concentrations varied from 5.02×10−17 to 8.39×10−05 mg g−1 (1997), 1.63×10−18 to 1.97×10−05 mg g−1 (2002), and 2.56×10−21 to 9.64×10−06 mg g−1 (2008), while in water they ranged from 6.44×10−15 to 5.12×10−03 mg L−1 (1997), 4.58×10−16 to 2.53 × 10−04 mg L−1 (2002), and 2.52 × 10−16 to 9.22 × 10−05 mg L−1 (2008). Similarly in the sediments, calculated concentrations varied from 4.79×10−18 to 3.71×10−06 mg g−1 (1997), 2.53×10−18 to 2.08×10−07 mg g−1 (2002), and 1.84× 10−18 to 7.81×10−08 mg g−1 (2008). The calculated results were compared with the available published data of the observed environmental concentrations of these nonmetallic chemicals to validate the accuracy of the OBMM calculations. For an example, the total annual emission amounts of glyoxal (PRTR no. 65) in the LBYRB were 2.4×105, 6.61×101, and 1.08×101 kg for the respective years of 1997, 2002, and 2008. For the year 1997, the calculated concentrations of glyoxal were 5.49×10−10 mg m−3 for the atmosphere, 7.33 × 10 −09 mg g −1 for the soil, 2.18 × 10−05 mg L−1 for water, and 1.63×10−08 mg g−1 for sediment. For 2002 and 2008, the calculated glyoxal concentrations in
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Soil 13 Chemicals with Highest 10% of the avg. calculated concentration
Chemicals with nondecreasing concentration
Water 26
Sediment 19
Fig. 6 Numbers of chemical pollutants showing both properties of the nondecreasing concentration trends and highest averaged calculated concentration in each environmental medium
the atmosphere were 1.46×10−06 and 4.93×10−07 mg m−3 while the observed glyoxal concentration in the atmosphere around Tokyo was reported as 4.06×10−08 mg m−3 (Ortiz et al. 2006, Kawamura et al. 2013). Atrazine (PRTR no. 75) is an antifouling compound and a herbicide which was observed 58.8 ng L−1 in water at a fishery harbor in Kobe, Japan (Liu et al. 1999) and the calculated concentration of atrazine in water in 1997 was 2.98×10−1 ng L−1. Another study using OBMM in 2007 to evaluate health risks found 33 hazardous chemicals in the atmosphere and 109 in the water (Kawashima et al. 2007). Similar chemicals were identified by Kawashima and this study, supporting the reliability of the results calculated by OBMM. However, it was difficult to validate all calculated concentrations of the chemicals studied in this study due to the lack of monitoring data. When the calculated concentrations of this group of 214 nonmetallic chemicals were observed, the range of the concentrations was decreasing from 1997, 2002, to 2008. The highest calculated concentrations for the atmosphere were 2.60×10−3, 1.88×10−6, and 5.54×10−7 mg m−3 for the years 1997, 2002, and 2008, respectively, and they were decreased along with the study span from 1997, 2002, and 2008. Similarly, the highest calculated concentrations were decreasing from 8.39×10−5, 1.97×10−5, and 9.64×10−6 mg g−1 in soil; 5.12×10−3, 2.53×10−4, and 9.22×10−5 mg L−1 in water, and 3.71 × 10−6, 2.08 × 10−7, and 7.81 × 10−8 mg g−1 in
sediment. To confirm these data, these 214 chemicals were analyzed individually for their changes in concentration along the study span. While majority of these chemicals showed a decreasing concentration trends from 1997 to 2008, some chemicals exhibited nondecreasing trends. Of the 214 chemicals, 55 chemicals in the atmosphere, 69 in soil, 72 in water, and 65 in sediment exhibited nondecreasing concentration trends as shown in Fig. 5. The average calculated concentrations for the three OBMM runs were obtained for these 214 chemical compounds in each of the environmental media. They were arranged in descending order; the chemicals with the highest 10 % average calculated concentrations were selected, and their relationships to the chemicals with nondecreasing concentration trends were observed. Figure 6 shows the number of chemicals that showed both the properties of nondecreasing concentration trends and occurred within the 10 % of the chemicals with highest averaged calculated concentration in each environmental medium. Considering the number of chemicals shown in Fig. 6 possessing both of the abovementioned properties in each media, 75 chemicals were expected to be identified, but only 36 chemicals were observed. This suggested the occurrence of chemicals in multiple environmental media. Seven of these 36 chemicals were identified to occur in all 4 environmental media and they are listed in Table 1. Chemicals with nondecreasing concentration trends, among the highest 10 % of the averaged calculated concentrations, and occurring in multiple environmental media (not occurring in all four environmental media) are listed in Table S4 provided in Appendix C of the supplementary data. Table S5 given in Appendix C lists the chemicals those only occupy one environmental media while showing the nondecreasing concentration trends and the highest 10 % of the averaged calculated concentrations, and Table S6 lists the remaining nonmetallic PRTR chemicals considered in this study of those concentrations were decreasing along with the study span. As these seven chemicals are increasing in concentration and present in relatively high concentrations, their health-risk
Table 1 Identified potentially hazardous chemical pollutants occurring in all environmental media PRTR no.
CAS no.
Chemicals name
MW (Da)
HC (atm m3 mol−1)
DC (log 10)
Solubility (g L−1)
DR (Air) (m2 s−1)
DR(Water) (m2 s−1)
65 90 146 179 238 239 300
107-22-2 122-34-9 3347-22-6 1746-01-6 86-30-6 100-02-7 552-30-7
Glyoxal Simazine Dith ian on dioxins (TCDD) N-Nitros odiphenylamine p-Nitrophenol 1,2,4-Benzenstricarboxylicanhydride
58.0 201.7 296.3 322.0 198.2 139.1 192.1
3.33×10−9 9.42×10−10 1.32×10−11 3.20×10−05 1.21×10−6 4.51×10−10 1.28×10−10
2.10 2.15 2.84 7.17 3.13 1.91 1.95
8.00×102 6.20×10−3 1.40×10−4 2.00×10−7 3.51×10−2 1.45×10−1 1.04×100
1.23×10−5 5.79×10−6 5.24×10−6 5.60×10−6 5.86×10−6 7.58×10−6 6.54×10−6
1.48×10−9 6.18×10−10 5.58×10−10 6.10×10−10 6.26×10−10 8.53×10−10 7.23×10−10
MW molecular weight, DC distribution coefficient, HC Henry’s coefficient, DR diffusion rate Ref. NIST Chemistry WebBook (http://webbook.nist.gov/chemistry/)
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potential was qualitatively studied using the Health Hazard Criteria of the Occupational Safety and Health Administration, United State Department of Labor (United States Department of Labor, http://www.osha.gov/pls/ oshaweb/owadisp.show_document?p_table= STANDARDS&p_id=10100). The health risk and the adverse effects of the chemical substances are categorized into ten main categories: acute toxicity, aspiration hazard, carcinogenicity, germ-cell mutagenicity, reproductive toxicity, skin corrosion/ irritation, respiratory or skin irritation, serious eye damage/eye irritation, specific target-organ toxicity (single exposure), and specific target-organ toxicity (repeated/prolonged exposure). A diagrammatical explanation of the relationships among these seven chemicals, their calculated concentrations in the different environmental media, and their adverse health effects is shown in Fig. 7. As the potential of sediments to directly affect human health is comparatively negligible, sediment is not shown in Fig. 7. Three axes show the average calculated concentrations of the seven chemicals from Table 1 for water, atmosphere, and soil. In water, dioxins (tetrachlorodibenzodioxin; TCDD) were present at the minimum average calculated concentration (2.62× 10−6 mg L−1), while glyoxal was present at the highest averaged calculated concentration (1.22×10−4 mg L−1). In the atmosphere, the calculated concentrations of these chemicals varied from 4.33×10−8 to 9.41×10−7 mg m−3, while in soil, it varied from 2.03×10−8 to 9.79×10−6 mg g−1.
Fig. 7 Summary of the calculated concentrations and qualitative health risks of the chemical pollutants identified in water, the atmosphere, and soil
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The qualitative health risks posed by these seven chemicals are shown in Fig. 7. Dioxins pose five categories of health risks: carcinogenicity, skin corrosion/irritation, respiratory or skin sensation, serious eye damage/eye irritation, and specific target-organ toxicity (repeated/ prolonged exposure; Bertazzi et al. 2000 and Kogevinas 2001). Simazine poses risks of carcinogenicity, germ-cell mutagenicity, reproductive toxicity, and specific targetorgan toxicity (repeated/prolonged exposure; IARC Monographs on the Evaluation of Carcinogenic Risk to Humans, http://monographs.iarc.fr/ENG/Monographs/ vol73/mono73-25.pdf and Zorrilla et al. 2010). Glyoxal (Kielhorn et al. 2004), dithianon (Paolini et al. 1997 and Toxicology Data Network, http://toxnet.nlm.nih.gov/cgibin/sis/search/a?dbs±hsdb:@term±@DOCNO±1583), and p-nitrophenol (Edwards and Tchounwou 2005) pose three categories of health risk. These results support our findings of 7 potentially hazardous chemicals among the 214 nonmetallic PRTR chemicals that were initially considered in this study. Environmental monitoring can be carried out for these seven identified chemicals and thus we can confirm their present status in the environment and eventually those details can be used to control and mitigate the adverse effects they are posing on our environment. This way we can use the findings of this study to proactively protect our environment.
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Conclusion The one-box multimedia model was used to identify hazardous chemicals in LBYRB. Initially, 214 nonmetallic chemicals were selected from among the PRTR chemicals, and their emissions were estimated for 1997, 2002, and 2008 using PRTR data. These data were input to the OBMM to calculate chemical concentrations in the atmosphere, soil, water, and sediment. The calculated results were validated using the published monitoring data. Trends in the calculated concentrations over time were analyzed from 1997 to 2008. Scenarios were developed to select the chemicals with trends deviating from the majority and with the highest concentrations, and 36 chemical compounds were selected. Seven of these 36 chemicals (glyoxal, simazine, dithianon, Nnitrosodiphenylamine, dioxins, p-nitrophenol, and 1,2,4benzenetricarboxylic anhydride) occur in all 4 environmental media and were identified as potentially hazardous; the associated risks should be thoroughly studied in the future. The lack of monitoring data was a weakness in validating the concentrations calculated from the OBMM. More monitoring data would allow us to increase the accuracy, reliability, and adaptability of this model to diverse study sites.
Conflict of interest We would like to declare that we do not have any conflicts of interests.
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