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Contents lists available at SciVerse ScienceDirect

Journal of Hazardous Materials

jou rn al h om epage: www.elsev ier .com/ loc ate / jhazmat

nvironmental arsenic contamination and its health effects in a historic goldining area of the Mangalur greenstone belt of Northeastern Karnataka, India

ipankar Chakraborti a,∗, Mohammad Mahmudur Rahmana,b, Matthew Murrill a, Reshmi Dasa,iddayyac, S.G. Patild, Atanu Sarkare, Dadapeer H.J. f, Saeed Yendigeri f, Rishad Ahmedf, Kusal K. Dasf

School of Environmental Studies (SOES), Jadavpur University, Kolkata 700032, IndiaCentre for Environmental Risk Assessment and Remediation (CERAR), University of South Australia, Mawson Lakes Campus, Mawson Lakes, Adelaide, South Australia, SA 5095,ustraliaCollege of Agriculture, Bheemarayanagudi 585287, Yadgir, Karnataka, IndiaUniversity of Agricultural Sciences, Raichur 584102, Karnataka, IndiaDivision of Community Health and Humanities, Faculty of Medicine, Memorial University, St John’s, Newfoundland and Labrador A1B 3V6, CanadaAl Ameen Medical College & Hospital, Bijapur 586108, Karnataka, India

i g h l i g h t s

First report of chronic human arsenic toxicity in any historic gold mining area.Highly elevated arsenic in topsoil as well as groundwater used for drinking.Prevalence of arsenical skin lesions comparable to other severe areas in South Asia.Integration of clinical, analytical chemical, and environmental research.

r t i c l e i n f o

rticle history:eceived 26 November 2011eceived in revised form8 September 2012ccepted 2 October 2012vailable online xxx

eywords:rsenicroundwaterreenstoneold mine

a b s t r a c t

This report summarizes recent findings of environmental arsenic (As) contamination and the consequenthealth effects in a community located near historic gold mining activities in the Mangalur greenstonebelt of Karnataka, India. Arsenic contents in water, hair, nail, soil and food were measured by FI-HG-AAS.Elemental analyses of soils were determined by ICP-MS (inductively coupled plasma-mass spectrometry).Of 59 tube-well water samples, 79% had As above 10 �g L−1 (maximum 303 �g L−1). Of 12 topsoil samples,six were found to contain As greater than 2000 mg kg−1 possibly indicating the impact of mine tailingson the area. All hair and nail samples collected from 171 residents contained elevated As. Arsenical skinlesions were observed among 58.6% of a total 181 screened individuals. Histopathological analysis ofpuncture biopsies of suspected arsenical dermatological symptoms confirmed the diagnosis in three outof four patients. Based on the time-course of As-like symptoms reported by the community as well asthe presence of overt arsenicosis, it is hypothesized that the primary route of exposure in the study area

arnatakarsenical skin lesions

was via contaminated groundwater; however, the identified high As content in residential soil couldalso be a significant source of As exposure via ingestion. Additional studies are required to determinethe extent as well as the relative contribution of geologic and anthropogenic factors in environmentalAs contamination in the region. This study report is to our knowledge one of the first to describe overtarsenicosis in this region of Karnataka, India as well as more broadly an area with underlying greenstone

ing ac

geology and historic min

. Introduction

Please cite this article in press as: D. Chakraborti, et al., Environmental arseof the Mangalur greenstone belt of Northeastern Karnataka, India, J. Hazar

Chronic arsenic (As) exposure through ingestion can causeevere adverse effects on human health, especially via the

∗ Corresponding author at: Jadavpur University, School of Environmental StudiesSOES), Chemical Engineering Building, Kolkata, West Bengal 700032, India.el.: +91 33 2414 6233; fax: +91 33 2414 6266.

E-mail address: dcsoesju@gmail.com (D. Chakraborti).

304-3894/$ – see front matter © 2012 Elsevier B.V. All rights reserved.ttp://dx.doi.org/10.1016/j.jhazmat.2012.10.002

tivity.© 2012 Elsevier B.V. All rights reserved.

consumption of contaminated groundwater [1–5]. Epidemiologi-cal and experimental evidence is furthermore mounting that inutero or early life exposure to As may affect fetal developmentor increase rates of several malignant and non-malignant dis-eases [6,7]. Arsenic with a naturally low average crustal abundance(1.7 mg kg−1) is substantially concentrated in certain sediments

nic contamination and its health effects in a historic gold mining aread. Mater. (2012), http://dx.doi.org/10.1016/j.jhazmat.2012.10.002

adsorbed to hydrous iron oxides or in the form of sulfide-bearingminerals [8]. The natural dispersion of As in the environment isgoverned by a combination of region and site-specific biogeochem-ical and hydrological factors [9,10]. The mining of gold and base

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ARTICLEAZMAT-14624; No. of Pages 8

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etals, frequently associated with sulfide mineralization, has ineveral settings induced or exacerbated localized As contamination11–13]. Historically active mines abandoned with little rehabilita-ion are particularly notorious for the pollution of the surroundingoil and groundwater with toxic elements [14–16]. Elevated Asn biomarkers, such as urine and toenails, has been reported inormer or current gold mining areas in Australia [17,18], Ghana19], Canada [20], France [21], Slovakia [22] and Brazil [23]. In areasf historic mining activity however, the relative contribution andnteraction of anthropogenic and natural processes in environmen-al As contamination are known to vary greatly depending on theocality and a host of related factors [24,25].

In the present study area in a northeastern region of Kar-ataka, India, factors impacting the natural secondary geochemicalispersion of As in groundwater and soil have been found to

nclude: topography, water table depth, drainage, soil type, andnderlying geology [26]. This area also has several historic goldines with some presently active and many abandoned [27]. An

nderstanding of the nature of the source, mobilization, and dis-ribution of environmental As in the region as well as the extentf human exposure to this contamination is essential to effectiveitigation efforts and future planning. The purpose of the present

tudy was the assessment of environmental (groundwater, soil,nd food) and human biomarker As levels as well as the healthffects of As in a community with previously reported arsenicosisases.

The earliest cases of groundwater As contamination in Kar-ataka were identified in villages of the greenstone belts of Yadgiristrict, a district recently created in late 2009 from a southernegion of Gulbarga district. Studies conducted by UNICEF and Gov-rnment of Karnataka (GOK) [28,29] discovered several villages

Please cite this article in press as: D. Chakraborti, et al., Environmental arseof the Mangalur greenstone belt of Northeastern Karnataka, India, J. Hazar

ith well water supplies containing As exceeding the World Healthrganization (WHO) guideline value (10 �g L−1). One of these stud-

es hypothesized that local gold mining might be a contributingactor to As contamination [30].

ig. 1. Location of the surveyed villages and local historic gold mining activities [27] in Yadfter the creation of Yadgir district in 2009 (dark red), Yadgir district (medium red), and

33,41] located within Yadgir and Raichur districts, respectively; the border between theorkings within the Mangalur greenstone belt. (For interpretation of the references to co

PRESSous Materials xxx (2012) xxx– xxx

The occurrence of arsenicosis and As-related cancers in KiradalliTanda village was first identified in early July 2009. Several patientsfrom the community were admitted to the DISTRICT Hospital,Gulbarga with dermatological symptoms. Attending physicianssuspected As in drinking water could be the cause and carriedout further investigations. Water samples were collected by GOKfrom the community and As levels were found up to 160 �g L−1;these reports along with cases of the adverse health impacts werepublished in a regional daily newspaper [31,32].

2. Materials and methods

2.1. Study area and timeline

Kiradalli Tanda (16◦37′7.9′′N, 76◦36′47.3′′E) is a small village(total population 535) situated in a remote region of Yadgir districtin Karnataka, India. Traces of arsenopyrite are noticed in and aroundvillages such as Godryal and Heggandoddi and specifically in theproximity of abandoned gold mines. Kiradalli Tanda is situatedin the Mangalur greenstone belt (16◦30′ to 16◦44′N, 76◦32′30′′ to76◦40′E), one of the four Archean greenstone belts (Kolar, Ramagiri,Hutti-Maski and Mangalur) of the gold-bearing eastern province(Fig. 1) of the Dharwar Craton [33].

The Mukangavi (Mangalur) gold mine is located 4 km south ofKiradalli Tanda and was in operation between 1887 and 1913 andwas reclaimed in 1980 to resume mining operations. The mine wasclosed in 1994 primarily due to heavy water inflow into the mininggalleries [27] and remains closed to this day. Following the newspa-per publication of possible arsenicosis in Kiradalli Tanda, an initialsurvey of the community, consisting of patient interviews as wellas the collection of 12 groundwater and a small number of hair and

nic contamination and its health effects in a historic gold mining aread. Mater. (2012), http://dx.doi.org/10.1016/j.jhazmat.2012.10.002

nail samples, was conducted in July 2009. With the identification ofelevated As levels in groundwater and biological samples, a moredetailed survey with a complete medical team was organized inSeptember 2009.

gir district, Karnataka, India. (A) Karnataka State (gold), India; (B) Gulbarga district,Raichur district (pink), Karnataka; (C) Mangalur and Hutti-Maski greenstone beltsse two districts is the Krishna River; (D) surveyed villages and historic gold minelour in this figure legend, the reader is referred to the web version of this article.)

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Fig. 2. Locations and levels of As in water and soil samples collected from KiradalliTanda and the surrounding communities during the second more detailed surveyof the study area in September 2009. Two groundwater samples, which are notplotted, were collected without spatial information: Kiradalli Tanda (144 �g/L) andG

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present but not in use; water from this well was found to havean As content of 245 �g L−1. While the villagers of Kiradalli Tandaappeared to have used this dug-well for many years, we areunaware of when it became As-contaminated. During our surveys

Table 1Summary of recent groundwater quality surveys investigating As contamination inGulbarga, Yadgir, and Raichur districts, Karnataka.

Present study GOK (2008) GOK (2008)

Districts sampled Yadgir and Raichur Gulbarga Raichurn 59 464 316Arsenic concentration (�g L−1)<3 3 (5.2%) 264 (56.9%) 237 (75.0%)3–10 10 (17.2%) 175 (37.7%) 3 (0.9%)>10–50 28 (48.3%) 16 (3.4%) 52 (16.5%)>50–100 11 (19.0%) 5 (1.1%) 18 (5.7%)>100–200 4 (6.9%) 3 (0.6%) 3 (0.9%)>200–300 2 (3.4%) 0 (0%) 2 (0.6%)

owdigeri (13 �g/L).

.2. Sampling and analysis

Water samples from tube-wells and dug-wells as well as sam-les of food grains and soil were collected from Kiradalli Tandand the surrounding communities. Water samples were collectedn acid pre-washed 10 ml polyethylene bottles. Immediately afterample collection, a drop of nitric acid (1:1) was added as preser-ative. Soil samples (n = 12) were collected from residential areasn and around Heggandoddi, Kiradalli, Kiradalli Tanda, Jainapurnd Gowdigeri (Fig. 2). Additionally, spot sampling of groundwaterources was conducted in Raichur district (Fig. S1 in Supplemen-ary Material).

A medical camp was organized in Kiradalli Tanda in September009 to assess recent As exposure and consequent health effects.ach individual visiting the camp was thoroughly screened forrsenicosis symptoms by dermatologists and other medical person-el. Hair and nail samples as well as other general information werelso collected from these individuals during personal interviews.uncture biopsies of suspected As-related cancers were collectedrom willing patients and histopathological analysis was performedt Al Ameen Medical College. We were unable to analyze urineamples, which indicate recent As exposure, as individuals wereeluctant to submit urine.

All samples except punch biopsies were analyzed at SOES fors using FI-HG-AAS. The total concentration of As in the water

arsenite and arsenate) was measured after potassium bromatexidation [34]. For hair, nail, soil and food samples, total Asas determined after teflon-bomb digestion. Sample collection,rocessing, digestion of samples, analytical procedures and detailsf the instrumentation including the flow-injection system haveeen reported earlier [34–38]. Additionally, six soil samples were

Please cite this article in press as: D. Chakraborti, et al., Environmental arseof the Mangalur greenstone belt of Northeastern Karnataka, India, J. Hazar

lso analyzed at CERAR – University of South Australia by ICP-MSinductively coupled plasma-mass spectrometry) (Agilent 7500ce)ollowing microwave digestion (CEM Microwave Accelerated

PRESSus Materials xxx (2012) xxx– xxx 3

Reaction System 5, MARS5) in order to assess the levels of As andother elements in the soil samples.

2.3. Quality assurance and quality control

For quality control, inter-laboratory tests were performed onwater, hair, food grain and soil samples as reported in earlier publi-cations [34,37–39]. USEPA standardized water reference materialswere also analyzed as reported previously [38]. National Institute ofStandard and Technology (NIST) standard reference material (SRM)2711 (Montana soil) was used to validate the results of As and otherelements in soil. NIST 1643e (trace elements in water), NIST 2709(San Joaquin Soil), SRM GBW 07601 (human hair, China) and NIST1568a (rice) were routinely analyzed to validate the results duringanalysis of water, soil, hair and food grain samples [34]. Spikes andduplicates were also analyzed.

2.4. Statistical analysis

Descriptive statistics were calculated for the baseline charac-teristics of the affected population. All statistical analyses wereperformed using SPSS. Spearman two-tailed p value of <0.05 wasconsidered to be statistically significant.

3. Results and discussion

3.1. Water analysis

During community interviews, elderly residents recalled thatdug-wells were the primary source for all water needs over 20 yearsago. Due to endemic guinea worm disease, hand-pumps and deeptube-wells were installed in the districts of Gulbarga, Raichur, andBijapur through the Guinea Worm Eradication Programme startingin 1984 [40]. Community members also reported that skin lesionssimilar to those diagnosed by the medical team as arsenical firstappeared roughly 15 years ago.

The first column of Table 1 shows the distribution of As inwater sources in the present survey. Arsenic concentration in thehand tube-well thought to be the main source of contaminationin Kiradalli Tanda was 303 �g L−1 in July 2009, and many vil-lagers reported using this source for an extended time period. Thesource was abandoned after our initial survey, and an alterna-tive groundwater source supplied by pipeline was installed thatcontained 63 �g L−1 of As. The primary large dug-well used bythe community before the installation of other sources is, still

nic contamination and its health effects in a historic gold mining aread. Mater. (2012), http://dx.doi.org/10.1016/j.jhazmat.2012.10.002

>300–400 1 (1.7%) 0 (0%) 0 (0%)>400–500 0 (0%) 0 (0%) 0 (0%)>500 0 (0%) 1 (0.2%) 1 (0.3%)

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Table 2Concentration of As and other elements (mg kg−1) in soils measured by ICP-MS. Variation of As concentration of the same samples measured at SOES laboratory by FI-HG-AASmethod is within the 10% error margin on the reported values by the two methods.

Soil ID GPS location Na Mg Al K Ca Cr Mn Fe Co Ni Cu Zn As Pb

1. Heggandoddi village soil N16◦ 35.858′ , E76◦ 38.049′ 286 12,086 17,149 5007 34,241 88 6039 35,016 26 53 73 157 5884 302. Jainapur village soil N16◦ 36.960′ , E76◦ 37.026′ 230 12,188 17,534 5031 29,143 89 689 38,165 33 58 82 92 9136 343. Kiradalli Tanda village soil N16◦ 37.132′ , E76◦ 36.788′ 272 12,232 17,615 5002 36,576 87 656 35,390 27 52 72 90 6711 304. Jainapur village soil 4 N16◦ 36.813′ , E76◦ 37.408′ 81 4134 23,494 2235 4886 88 962 45,250 30 77 80 63 334 6

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5. Jainapur village soil 5 N16◦ 36.878′ , E76◦ 37.313′ 81 3652 33,66. Jainapur village soil 6 N16◦ 36.746′ , E76◦ 37.493′ 117 6442 24,0

n Kiradalli Tanda, the local Public Health Engineering Departmentas informed about the presence of arsenicosis patients, and they

uickly arranged As-safe water for the village initially by tankernd later through a newly dug bore-well. Furthermore, the localanchayat Raj and Health Departments arranged for regular medi-al follow-up visits to the community by physicians from a nearbyospital.

In separate surveys in 2008, Zilla Panchayat Groundwaterivision, Government of Karnataka and Department of Mines &eology, Government of Karnataka in collaboration with UNICEF

28,29] also analyzed hand tube-well water samples in Gulbargand Raichur districts, respectively (Table 1). It is important to notehat the sampling methodologies significantly differed betweenhe present study and the GOK–UNICEF surveys. In the presenttudy, the majority of collected groundwater samples were concen-rated around an area in Yadgir district with identified As-relatedealth effects. The larger GOK–UNICEF studies systematically sur-eyed a large number of communities within Gulbarga (Shorapuraluka only) and Raichur districts. The GOK–UNICEF surveys iden-ified not only areas with considerably higher As outside ofiradalli Tanda but also an additional five villages in Gulbargand 10 villages in Raichur with drinking water As concentration50 �g L−1. Furthermore, these surveys identified a total of 14 addi-ional villages in Gulbarga and 39 in Raichur with drinking waters > 10 �g L−1. It is not known whether these contaminated waterupplies continue to be used and importantly whether individ-als from these areas have been screened for As-related healthffects.

.2. Soil samples

During recent inspection (July 2012) of the Mukangavi mine site,ne shaft was observed measuring about 150 m with two drives ofbout 450 m in length and 1.5 m in width on the north and southides of the shaft. The shaft and drives are filled with loose exca-ated material. Only a small heap of material, not a large amountf tailings, was observed near the shaft. The host rock has beenescribed previously as amphibolites crossed by quartz stringers

Please cite this article in press as: D. Chakraborti, et al., Environmental arseof the Mangalur greenstone belt of Northeastern Karnataka, India, J. Hazar

ith sulphides, including pyrite, pyrrhotite and arsenopyrite. Addi-ionally, the ore zone was estimated at 1.5–2 mega ton, and as of996, three lodes had been identified with over 600 m in lengthccessible to mining [41].

able 3rsenic concentrations in hair and nail samples of individuals from Kiradalli Tanda.

Hair (�g kg−1)

n P10 P50 P90

Gender Male 87 903 2168 4158

Female 83 900 2062 5262

Age quartiles (Yrs) 1st (up to 18) 43 582 1001 1764

2nd (19–28) 43 974 1920 4413

3rd (29–42) 42 1305 2877 4246

4th (43–75) 42 1689 3007 6027

10, P50, and P90 are the 10th, 50th, and 90th percentiles, respectively.

1814 4984 112 1185 50,383 27 91 75 61 313 102532 7648 107 762 44,397 30 76 93 92 99 9

The study area is located within the command area of the UpperKrishna Project (UKP), an irrigation development project initiatedin 1965, consisting of dams on the Krishna River as well as canalsand associated irrigation schemes that aimed to develop irrigationpotential in the Upper Krishna River Basin, including the districtsof Raichur and Gulbarga [42]. Water table fluctuation followingthe hydrologic changes from the UKP likely resulted in the fil-tration of water through soil and fractures of amphibolite andassociated minerals in the parental rock or the remnants of exca-vated mining material. It is hypothesized that this contributed tothe release of these minerals into the groundwater due to disin-tegration, leachification, and chemical decomposition of As fromarsenopyrite associated with amphibolites.

Table 2 reports the concentrations of As and other elementsof six topsoil samples (analyzed by ICP-MS) collected from themore densely populated areas of Heggandoddi, Jainapur, KiradalliTanda (samples 1–3) and the outskirts of Jainapur village (sam-ples 4–6). These residential samples (samples 1–3 of Table 2) wereall found to exceed 2000 mg kg−1 with a maximum concentrationof 9136 mg kg−1 possibly indicating the presence of mine tailings.The analysis for As of four additional soil samples, also from theresidential areas of these three villages revealed three sampleswith elevated levels of As (range: 2203–4264 mg/kg) much greaterthan the typical background level of 5–10 mg kg−1 in soil [10].Three samples collected from Gowdigeri village had As levels wellwithin the background levels in soil. This community is fartheraway from known historic gold mining activity than the other sur-veyed villages and was also found to contain significantly lowergroundwater As concentrations (Fig. 2). Based on this limited spa-tial information, variable natural geochemical dispersion as wellas historic mining activities appear to have resulted in heteroge-neous local environmental As contamination; however, additionaland more detailed groundwater and soil studies are needed todetermine the nature and extent of the source and mobilizationof As.

3.3. Food grains

nic contamination and its health effects in a historic gold mining aread. Mater. (2012), http://dx.doi.org/10.1016/j.jhazmat.2012.10.002

Fourteen samples of local staple foods (pearl millet or bajra andpigeon pea or red gram/arhar) were collected from in and aroundKiradalli Tanda village and analyzed for As. The agricultural culti-vations in this area are on the sides of hillocks where the average

Nail (�g kg−1)

Max Min n P10 P50 P90 Max Min

6265 456 87 1236 3390 5922 8213 6966976 464 83 1237 3196 6748 9815 9202965 456 43 941 2032 2981 3265 6966321 795 43 1857 3005 6077 7726 10296162 1007 42 3021 4073 7155 8213 24026976 1025 42 2980 4341 7026 9815 2062

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Table 4Age distribution of individuals screened and identified with arsenical skin lesions.

Age wise distribution of population No. of people who came to the medical camp and were screened No. of people having arsenical skin lesions

Age range (Yrs) No. of people

>25 216 94 (43.5% of 216) 85 (90.4%)20–25 60 42 (70% of 60) 20 (47.6%)<20 259 45 (17.4% of 259) 1 (2.2%)

Total 535 181 (33.8% of 535) 106 (58.6%) of 181 population screened

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ig. 3. Comparative prevalence of dermatologic symptoms of individuals of KiradaM, spotted melanosis; WM, whole body melanosis; LM, leucomelanosis (white-speratosis palm; SKS, spotted keratosis sole; DKS, diffuse keratosis sole; DK, dorsal ker

s concentration of soil is 4.5 mg kg−1. As the hillside agriculturallots are above the groundwater table and the topology of the landesults in the drainage of rainwater down from these slopes to thealleys, As and other heavy metals were expected to be flushed fromhe soil and only minimally enter into the food supply. Arsenic con-entrations of the food grains ranged between 12 and 112 �g kg−1,onsiderably lower than the recommended upper limit of As in rice1000 �g kg−1) [43].

.4. Hair and nail samples

Elevated As levels in hair and nail samples are an indicator ofxposure over the last 3–18 months, depending on the growth

Please cite this article in press as: D. Chakraborti, et al., Environmental arseof the Mangalur greenstone belt of Northeastern Karnataka, India, J. Hazar

ate and what section of hair or nail is analyzed. For individualsith no known As exposure, concentrations of As in hair generally

ange from 20 to 200 �g kg−1 and in nails from 20 to 500 �g kg−1

4]. Of 170 samples, 100% of both hair and nails were found to

Fig. 4. Histopathological section showing, (A) thickened epiderm

da screened for arsenicosis (age quartiles). Abbreviations: DM, diffuse melanosis; pigmentation alongside black-spotted); SKP, spotted keratosis palm; DKP, diffuse; SB, suspected Bowen’s Disease; SC, suspected skin cancer; MM, mucous melanosis.

exceed the upper limit of unexposed individuals (Table 3). Of the170 individuals that provided samples, 43 were below 18 years ofage. Despite having an elevated level of biological As, many arenot showing arsenical skin lesions and are possibly sub-clinicallyaffected. Arsenic concentration between genders was highly similarfor both hair (p = 0.937) and nail samples (p = 0.927). The spearmancorrelation (necessitated due to skewed distributions) was posi-tive and strong between age and As concentrations in the collectedsamples of hair (r = 0.682, p < 0.0001) and nail (r = 0.685, p < 0.0001).Arsenic levels of these biomarkers strongly correlated with eachother (r = 0.937, p < 0.0001). The high levels of As in the hair and nailsof the children from the study area after the drinking water sourcehas been changed indicate that besides drinking water there exists

nic contamination and its health effects in a historic gold mining aread. Mater. (2012), http://dx.doi.org/10.1016/j.jhazmat.2012.10.002

some other source of As. It is possible that the extremely high con-centrations of As in the residential soil may be a significant sourceof As for small children as well as other community members viaingestion.

is (10×) and (B) Bowen’s disease (carcinoma in situ) (45×).

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ARTICLEAZMAT-14624; No. of Pages 8

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Based on the time-course of As-like symptoms reported by theommunity as well as the presence of overt arsenical symptomsn recent surveys, we are hypothesizing that the primary routef exposure in the study area was via contaminated groundwatersed for drinking. Arsenical symptoms were reported by the elderlyesidents of Kiradalli Tanda as emerging first around 15 years ago,orresponding with the drilling of tube-wells and a transition inhe drinking water supply source. As mining operations at Mukan-avi gold mine were resumed from 1980 to 1994, it is possible thathese activities or naturally present soil As in high concentrationsere however the major factors in the emergence of arsenicosis.nlike contaminated groundwater, we are unaware of residentialuman exposure to As-contaminated soil leading to overt arseni-osis, notably dermatological symptoms as in the present study.eports have been published though on increased As biomarker

evels with soil exposure [17] as well as contaminated soil beingssociated with decreased weeks of gestation for newborns [44] orignificant increased risks of multiple types of cancer [45,46].

.5. Clinical investigations

A total of 181 individuals were screened for symptoms ofhronic As toxicity and complete demographic information wasollected for 171. High rates of arsenicosis were identified with8.6% of screened individuals presenting with at least one relatedymptoms (Table 4). Dermatological symptoms were not found toe significantly different between genders with the exception ofucous membrane melanosis, which was only observed in eight

emales; we are uncertain whether As alone is responsible for this.he majority of dermatological symptoms were found to sharplyncrease with increasing age quartiles, reaching a similar preva-ence in the oldest two quartiles where individuals were 29 yearsnd older (Fig. 3). Table 5 presents the clinical details of 12 patientsaving pre-cancer (Bowen’s disease), gangrene (amputated) andon-healing ulcer. Punch biopsies were performed for the sus-ected cancers of four willing adult arsenicosis patients. Somelinically suspected carcinoma patients refused biopsy. Among theour completed histopathological reports, two samples showeduclear atypia, mitosis and disarray in cellular arrangement andyperchromatic nuclei.

From histopathological observations, three patients were foundo have confirmed arsenical keratosis and one patient was con-rmed with features highly consistent with Bowen’s disease (initu carcinoma). The pathological analysis of the suspected Bowen’sisease biopsy revealed an epidermis composed of keratinizedtratified squamous epithelium which is thickened. The base-ent membrane is intact and there is no evidence of infiltration

Fig. 4A). Furthermore, there was moderate hyperkeratosis, mod-rate acanthosis with focal dyskeratosis and keratin plugging. Theells exhibited cellular as well as nuclear atypia throughout theull thickness of the epidermis and were arranged in a ‘windblownppearance’. The cells appeared large and round having hyper-hromatic nuclei containing prominent nucleoli with moderateosinophilic cytoplasm. The cells also exhibited mild-moderateleomorphism with disoriented maturation order (Fig. 4B). Sincehe health effects of chronic As exposure take years to manifestossibly as carcinomas, further detailed histopathological evalua-ion is needed in this population to rule out other non-melanomakin cancers.

Most residents of Kiradalli Tanda village are primarily dailyage laborers. There was no history of loss of appetite among the

linically examined group. There is no apparent nutritional defi-

Please cite this article in press as: D. Chakraborti, et al., Environmental arsenic contamination and its health effects in a historic gold mining areaof the Mangalur greenstone belt of Northeastern Karnataka, India, J. Hazard. Mater. (2012), http://dx.doi.org/10.1016/j.jhazmat.2012.10.002

iency in the community; however, additional study is requiredo assess the prevalence of malnutrition in the area, which maylay a significant role in the occurrence of arsenicosis [47]. Whensked about deceased family members and skin lesions similar to Ta

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HAZMAT-14624; No. of Pages 8

D. Chakraborti et al. / Journal of Hazardous Materials xxx (2012) xxx– xxx 7

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Fig. 5. Characteristics of three individuals from

rsenicosis, 12 individuals were named that had died with compa-able symptoms in the last 10 years. Furthermore, four individualsho had skin lesions and died of cancer in the last 5 years were also

eported. Death certificates for these individuals, however, couldot be obtained. Fig. 5 shows the dermatological symptoms of threeevere arsenicosis patients with associated photographs.

. Conclusions

Elevated biomarker As levels in communities with underlyingreenstone geology as well as historic gold mining activity haveeen reported previously [17–23]. This study report, however, is tour knowledge one of the first to describe overt arsenicosis in suchn area as well as in this region of Karnataka, India. In the presenttudy, 106 of the 181 (58.6%) individuals of Kiradalli Tanda villagecreened for arsenical symptoms presented with at least one skinesion specifically related to chronic As toxicity. Of these individualsncluding children, 94.5% volunteered for hair and nail analysis with00% of these found to have elevated As levels in these samples.his evidence indicates that those without identified symptoms areotentially sub-clinically affected.

While groundwater contamination is hypothesized to be theain route of As exposure, the presence of highly elevated As lev-

ls in soil samples from the area warrants further investigation ofther possible significant routes of exposure as well as their rela-ive contributions to toxicity. The historic gold mine workings ofhe Mangalur belt may be a significant contributor to localized pol-ution in this and other similar regions in Karnataka. Consequently,dditional studies to determine, temporal variation, the nature ofs mobilization, particularly whether previous and ongoing mining

Please cite this article in press as: D. Chakraborti, et al., Environmental arseof the Mangalur greenstone belt of Northeastern Karnataka, India, J. Hazar

ctivities are playing a role, are crucial in guiding efforts to identifyt-risk communities and remedy the effects of this contamination.

If historic gold mining has played a role in contamination,ncreasing interest in the reopening of previously closed mines

dalli Tanda suffering from chronic As toxicity.

[48] and the prospecting of new regions in the Mangalur belt andaround Karnataka [49] should be conducted along with sound mon-itoring and assessment of the environment and the health effectsresulting from its degradation. As the GOK–UNICEF surveys identi-fied many additional communities with elevated groundwater As,environmental contamination appears to be more widespread thanthe present study area. Both medical screening and regular waterquality analysis programs should be continued or organized in theregion immediately.

Ethical committee permission

Ethical approval for this study was obtained from the Institu-tional Ethical Committee of Al-Ameen Medical College, Karnataka,India as per the ethical guidelines for Biomedical Research onhuman participants by the Indian Council for Medical Research [50].Informed consent was obtained from the participants before thestudy started.

Competing interests

None declared.

Acknowledgements

Thanks to the Hamdard National Foundation, India for the award

nic contamination and its health effects in a historic gold mining aread. Mater. (2012), http://dx.doi.org/10.1016/j.jhazmat.2012.10.002

to Dipankar Chakraborti of INR 5 million to continue As researchwork in India. The authors would also like to thank Prof. Ravi Naidu,Director, CERAR, Australia for the opportunity to use the microwavedigestion and ICP-MS for soil analysis.

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ARTICLEAZMAT-14624; No. of Pages 8

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ppendix A. Supplementary data

Supplementary data associated with this article can beound, in the online version, at http://dx.doi.org/10.1016/j.hazmat.2012.10.002.

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