Determination of Arsenic and Health Risk Assessment in the Ground

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Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan Zulfiqar Bhatti, Khadija Qureshi, Inamullah Bhatti, Imran Nazir Unar, Mohammad Yar Khuhawar

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Zulfiqar Bhatti, Khadija Qureshi, Inamullah Bhatti, Imran Nazir Unar, Mohammad Yar Khuhawar. Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan. Mehran University Research Journal of Engineering and Technology, Mehran University of Engineering and Technology, Jamshoro, Pakistan, 2017, 36 (4), pp.1037-1048. hal-01705647

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Distributed under a Creative Commons Attribution| 4.0 International License Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan

ZULFIQAR ALI BHATTI*, KHADIJA QURESHI*, INAMULLAH BHATTI*, IMRAN NAZIR UNAR*, AND MOHAMMAD YAR KHUHAWAR** RECEIVED ON 14.02.2017 ACCEPTED ON 29.05.2017 ABSTRACT

As (Arsenic) is one of the lethal element present at the various locations of the world, putting human beings in danger by polluting the water. Arsenic Kit and atomic absorption spectrometer were used to determine As in ground water of Sindh province, Pakistan. Twenty-Four (24) districts both on the left and right bank of RI (River Indus) were analyzed. It was observed from the results that highest As concentration 200 ppb (parts per billion) i.e. above the WHO (World Health Organization) limit (10 ppb) was observed in Sakrand, district Shaheed Benazirabad followed by Hala, Matairi, TMK (Tando Mohammad Khan) and Nasarpur regions. It was further found that ground water of regions on the left bank of RIwas more contaminated than the right bank. Contour map was created using OriginPro and coordinate systems to highlight the elevated arsenic in the studied area. HRA (Health Risk Assessment) of these areas was carried out to calculate EDI (Estimated Daily Intake), TQH (Target Hazard Quotient) and CR (Cancer Risk). 45% of the total ground water samples analyzed were above the permissible limit for As in water and mostly these are located on the left bank of RI.

The local wells in Sindh have never been tested for metal concentration former to use. These results provide baselines for researchers, NGO’s (Non-Governmental Organizations) and government to apply arsenic treatment technologies in those areas.

Key Words: Arsenic, Groundwater, River Indus, Sindh, Atomic Absorption Spectrometer, Health Risk Assessment.

1. INTRODUCTION

s is a hazardous element which is present in an enzyme system in the body, black foot disease, and ground water in the form of As(III) and As(V). obesity [1-3]. As contact can also cause other health AIts presence in the earth’s crust is 0.00021%. consequences such as gastrointestinal irritation, diabetes, Illness characteristic of long-term arsenic exposure comes less number of white and red blood cells, hypertension, in the form of skin cancer, bladder cancer, inactivation of blood vessels rupture and abnormal heart beats [4]. Baig

Corresponding Author (E-Mail: [email protected]) * Department of Chemical Engineering, Mehran University of Engineering & Technology, Jamshoro. ** Institute of Advanced Research Studies in Chemical Sciences, University of Sindh, Jamshoro.

Mehran University Research Journal of Engineering & Technology, Volume 36, No. 4, October, 2017 [p-ISSN: 0254-7821, e-ISSN: 2413-7219] 1037 Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan et. al. [3] performed a study of Gambat town, Sindh and Pakistan. All sample bottles (well-stoppered polyethylene found people suffering from chest infections, pain in the plastic) were rinsed with clean water, then filled completely whole body, cramps in legs due to As contamination in with sample water and tagged properly with a location. water. Analysis of water samples was performed by using the Arsenic test Kit (Merck, Germany) and AAS (Atomic Naturally occurring arsenic is known to trickle from Absorption Spectrometer). The arsenic kit is a mobile contaminated soils. Thus, contact of the general analytical tool that is used in the field to check the arsenic population with arsenic is mainly through the ingestion in water. AAS was used to analyze 106 ground water of groundwater, which comes across As-bearing soils and samples, whereas kit method was applied to test 214 minerals. Pakistan is suffering from the toxic effects of ground water samples. arsenic as other countries such as Bangladesh, India, Thailand, Taiwan, China, Japan, USA, Canada, Hungary Analytical grade chemicals were used throughout the and Ghana [5]. research work. Distilled water was used during the experiments to prepare all the solutions. Distilled water The high level of As species in ground water is due to the was prepared in a water quality laboratory by Distilled dissolution of As compounds coming from the Himalayas water machine (Model No. BMS-4CE, Spain). All the glass through RI and settled down throughout the years and wares were kept overnight in 5M HNO3 and then rinsed then introduced into ground water by geothermal, with deionized water before use. Stock solutions of hydrological and biochemical factors [6]. In Pakistan, a concentration 1000 ppb As(III) were prepared by mixing number of people consume ground water for their drinking, arsenic standard solution of 100 mg/L As(III) (Inorganic domestic purposes as clean river water is not accessible Venture Company, USA) with distilled water. The stock to them. As toxicity is mostly found in ground water and solutions were used to prepare fresh experimental transported to human beings by ingestion, vegetables, solutions as per need in clean plastic bottles and were crops, fruits and fishes. The authors in a research showed kept away from light to avoid any change in chemical properties [7-9]. For the confirmation of reproducibility, that the Mancharlake near town Sehwan, Sindh was the tests were replicated and the mean values were taken. contaminated with arsenic and the daily intake of As by people is 241-390 µg As/4L [5]. 2.2 Methods

The present study was designed to investigate As in 2.2.1 Arsenic Kit method drinking water of Sindh province on both left and right banks of RI. Water samples were analyzed by Arsenic kit (Merck, Germany) by using a calorimetric method with test strips. 2. MATERIALS AND METHOD The arsenic kit reaction bottle was filled to the mark with 60 ml sample water and the analysis was carried out as 2.1 Materials recommended by the kit manufacturer. Ground water samples were collected from various areas 2.2.2 Atomic Absorption Spectrometer of Sindh Province, Pakistan and analyzed in a water quality laboratory, Department of Chemical Engineering, Mehran Arsenic was analyzed in water samples by AAS (A University of Engineering & Technology, Jamshoro, Analyst 700, Perkin Elmer, USA), at a wavelength of

Mehran University Research Journal of Engineering & Technology, Volume 36, No. 4, October, 2017 [p-ISSN: 0254-7821, e-ISSN: 2413-7219] 1038 Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan

193.7 nm, by the MHS-15 (Mercury Hydride System) CR = EDI x CSF (3) technique. The energy source was the single-element In Equation (3) CSF (μg/kg-day) is Cancer Slope Factor hollow cathode lamp of arsenic working at 7.5 mA. The and its value for As is 1.5E+03 (μg/kg-day) [12-13]. AAS was attached to a computer and WinLab32 software used to receive and process analytical data. 3. RESULTS AND DISCUSSION The solution of 1% potassium hydroxide (KOH) was 3.1 Arsenic kit Method prepared. Then 3% sodium borohydride (NaBH4) was prepared in 1% KOH solution on Stirrer (Wisd, MSH-20, The As kit is a portable and easy tool method used to Korea). The chemicals were weighed using weighing analyze As of 24 districts of Sindh Province. Out of 214 balance (Adventurer, AR 3130, OHAUS, USA). 1.5% HCl ground water samples, 182 were from localities on the (Hydrochloric Acid) was prepared by appropriate left bank and 32 samples from the right bank of RI. All dilution of HCl (37%). The arsenic standards were the sample areas were assigned codes as shown in prepared to calibrate the AAS. Then the ASS was used Table 1. to analyze water samples and the results were obtained by Winlab 32. The results of localities on the left bank are reported in Table 1. About 40% of the samples were exceeding the 2.2.3 Technique to Assess Human Health WHO safe limit for As in water, i.e. 10 ppb. The higher Risk As levels were observed in ground water samples of The HRA of the left bank of RI areas is studied by Hala i.e. 10-180 ppb. The other areas with higher As calculating EDI, THQ and CR. EDI is calculated by using concentrations were Sakrand, Matairi, Nasarpur, Pano the following equation; Aqil and TMK.

Dw The reasons for higher concentrations in the left bank EDI = Cm × (1) Bw of RI are the geological presence due to the deposition over the years from the Himalayas, thick population, μ Where Cm denotes metal concentration ( g/L) in water, intense farming, and the areas from where RI passed Dw is the daily average intake of water (Lit/day, taken as during the Holocene period such as Tando Allahyar 2 Lit/day), and Bw is the body average weight (kg, taken and TMK from where the As ranges from 10-500 as 72 kg) [10]. ppb [6].

The THQ was obtained by applying the following Fig. 1 demonstrates the sample from the right bank of relationship; RI. The Dadu district samples showed higher As levels ranging between 0-60 ppb which is inconsistent with EDI THQ = (2) the earlier report of As in scalp and hair of children of RfD Dadu district [14]. Apart from the natural deposition of Where the oral toxicity reference doseRfD (μg/kg-day) arsenic in ground water other factors for As pollution value for arsenic is (3.00E-01) [11]. are coal burning at brick industries, power plants in Jamshoro district [15]. Samples of Jamshoro and Following relationship was used to calculate CR; Kashmore ranged within permissible limit of 10 ppb.

Mehran University Research Journal of Engineering & Technology, Volume 36, No. 4, October, 2017 [p-ISSN: 0254-7821, e-ISSN: 2413-7219] 1039 Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan

TABLE 1. GROUND WATER SAMPLE CODES ASSIGNED TO LOCATIONS OF SINDH, PAKISTAN AND ARSENIC KIT RESULTS As(ppb) Cnode L)ocatio Aes(ppb Cnod Locatio

BnD1 H03and Pump, NabiBuxBhurgri, Badi StT A0bbasi Village, Sekha 4 BnD2 M01uhammadNizamiMalhan, Matli, Badi TKM V3illage SaeedPur, Bulri Shah Karim, TM BnD3 N02abiBuxBhurgri, Badi TKM W0ater Pond, Sajawal Road, TM BnD4 N01izamaniOtaq, Matli, Badi TrA M5osque, Village Talpur, TandoAllahya 2 BnD4 V02illage Malhan, Matli, Badi TrA V0illage Talpur, TandoAllahya DiK1 G01hulab Shah Colony, Dhark SrR O0ld Sukku DiK2 I50mam Bargah, Dhark TKM1 S0afeenaShifa, TM 3 DoP1 D01aburiWell Water, Dipl TKM1 S5aqibTalpur, TM DoP2 D02ileepSaqiHome, Dipl TKM1 T0ube Well Water (City), TM 5 DoP3 R03afiqLangho, Dipl TKM1 V0illage Gaja Mori, TM DoP4 S04aqiParo, Dipl TKM1 V0illage GhulamHussainTalpur, TM 5 GiK2 H53and Pump, Yaro Lund, MirpurMathelo, Ghotk TKM B0us Stop Near Ayobia Hotel, TM 6 GiK3 M04otor Water, Yaro Lund, MirpurMathelo, Ghotk TKM G0aja Mori, Sajawal Road, TM HdD1 H05ouse No. 137, Latifabad, Hyderaba TKM G0ovt: Girls High School, TM 4 HdD2 H06ouse No. 97, Latifabad, Hyderaba TKM G5ovt: Girls School, TM HdD3 H07ussainabad, Police Colony, Hyderaba TKM M0adarsahJamiatmadinah, TM 2 HdD6 L08atifabad, Hyderaba TKM M6ajid Ali, Mir Mohalla, TM HdD7 M09iyani Road, Hyderaba TKM S0aeedPur, TalukaBulri Shah Karim, TM 10 HdD8 M51ohsinMemon, Citizen’s Colony, Hyderaba ToB 104 KM from GuniChowk, TandoBag 1 HdD9 N0ew Wahdat Colony, Hyderaba 12TmJ R5azaSaeed, Tando Ja 1 ItK1 G02ovt: RO Plant, IslamKo TaT W0arial Khan Khoso, Jhirk, Thatt ItK2 P03rivate RO Plant, IslamKo UtK A0kriPithoro, Umerko 1 IrK3 V01illage BhabinoBhell, UC SonalBhoh, Tha HaL A0bdul Aziz, KadhMohalla, Hal 3 IrK4 C00oal Gasification Site, IslamKot, Tha HaL1 D0argahMakhdomNoh,SalineWater, Pump 2, Hal 4 KoD1 M01ohammad Din, Kandiar HaL1 D0argahMakhdom Noh,Sweet Water, Pump 1, Hal 6 JoD7 L02iaquat, Ward-2, Jhudd HaL1 D0awoodMemonHome, KanarMohalla, Hal 5 KsP10 N03aib Ali, Tarkowado, Khairpur Mir’ HaL1 D5r. AR Memon Home, Hal 3 KsP13 T04arkoWado, Khaipur Mir’ HaL1 E0nvious Girls Public School, KadhMohalla, Hal 5 KrP14 T05ube Well, TalukaNaro, Khairpu HwL1 F5aiz Mohammad, Hala Ne 4 KrP16 V5illage Allah Dino Khuhro,Gambat,Khairpu 46HaL1 F0areed Ahmed Home, PirFazalColony, Hal 18 KsP18 W0andh, Khairpur Mir’ 17HwL1 F7azal, Hala Ne KdGM1 J08amesabad, KotGhulam Mohamma HaL1 G5ovt: Girls High School, KadhMohalla, Hal KrP3 H59adiBuxLeghari, ThariMirwah, Khairpu HaL1 H0aji Anwar, Kaka Mohalla, Hal 4 KrP4 H52and pump, TalukaNaro, Khairpu HaL A5ftab Ansari, Hal 2 KrP6 J5adowahan, Gambat, Khairpu 20HaL2 H0aji Faiz Mohammad Home, SiraiMohalla, Hal 5 KsP8 L51atif colony, Kairpur Mir’ HaL2 H5aji QamarudinHome, Kanar Mohall, Hal 5 MiT16 H0azoorBux Shop, Khyber Stop, Matair 32HaL2 I0mam Bargah, Hal 4 MiH1 M03ith HaL2 I5mdad Rajput, MohajirChowk, Hal 2 MiH2 R04O Water, Mith HaL2 J0ealArbabHome, ArbabMohalla, Hal 7 MiT10 M05acon-Washy, Matair HaL2 K0hair Mohammad, PiniladhoColony, Hal 3 MyT11 M0atairiCit 86HaL2 K0hokhar Fridge Shop, BrohiMohalla, Hal 1 MrT12 M0atairi City, DargahPardehiPi 170 HaL2 M0uhammadUsmanHome, PiniLadho Colony, Hal 5 MiT13 M0atairi Sugar Mills Officers Mess, Matair 181 HaL2 M0uhammadUsmanHome, PirFazal Colony, Hal 10 MiT14 M0atairi Sugar Mills RO Plant, Matair 192 HaL2 M0uhammadYousuf, TalibMola Road, Hal 4 MiT15 M5atairi Sugar Mills Supervisor mess, Matair 23HaL A0hmed KhalkaniHome, Kaka Mohalla, Hal 5 MiT16 M00ianpotaMohalla, Matair HaL3 M5ohammad Hussain, Kaka Mohalla, Hal 2 MiT17 M51ir Hassan Mohalla, Matair HaL3 M0ohammad Usman, MohajirChowk, Hal 2 MiT18 S0ekhat, Matair 52HwL3 M5ohammad, Hala Ne 2 MiT19 S03hameerJiWari, Matair HwL3 M0osque, Hala Ne 5 MiT2 A04basPir, Highway Road, Matair HaL3 N0aseer, Kaka Mohalla, Hal 3 MsT20 V0illage BachalDetho, Near Matairi Sugar Mill 150 HaL3 N5ear Girls College, Hal 2 MiT21 V06illage Bhambra, Matair HaL3 N0ear Imam Bargah, Hal 4 MiT22 V0illage Shah Alam Shah Wasi, Matair 47HaL3 O0ld Hal 1 MiT23 V08illage Vighio, Matair HaL3 P0rof. Nafees Ahmed, KashigarMohalla, Hal 4

Mehran University Research Journal of Engineering & Technology, Volume 36, No. 4, October, 2017 [p-ISSN: 0254-7821, e-ISSN: 2413-7219] 1040 Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan

Cnode L)ocatio Aes(ppb Cnod L)ocatio As(ppb MiT3 B09urkatPota, Matair HaL3 R0aja Fahad Home, Hal 9 MsT4 C04anteen, Matairi Sugar Mill HaL A0l Shifa Medical center,KadhMohalla, Hal 5 MiT5 G0raveyard, Matair 30HaL4 R0aja FahadQureshi Agricultural Farm,Hal 9 MiT9 K01hyber, Matair HaL4 R0ehan home,KashigarMohalla, Hal 7 NzF3 D02arpa, Tharushah, NausheroFero HwL4 S0aeedMemon, Hala Ne 5 NzF4 K0hudaBuxKalhoro, NausheroFero 13HaL4 S0arfarazQureshi, Mujawar colony, Hal 1 NzF6 T04harushah, NausheroFero HaL4 S0hamsudin Book Store, Kanar, Hal 1 NzF7 V35illage Allah Bachayo, NausheroFero HaL4 S0oomar Shah, Hal 9 UtK9 P56ump Water, Umerko HaL4 S3weet Shop, Hal 1 NtK1 N07auko HaL4 T0ahirYasirHome, TalibMola Road, Hal 15 NrP10 W5ard-6, Nasarpu 18HaL4 T0alibMola Colony, Hal 10 NrP2 A3rainMohallah, Nasarpu 19HaL4 T0ariq Road, Hal 4 NrP3 B0us Stop, Nasarpu 85HaL A0lamgir, Kaka Mohalla, Hal 5 NrP7 S0ikanderAlmaniHome, Nasarpu 40HaL5 T0ariq, Hal 2 NrP9 W5ard-4, Nasarpu 31HwL5 T0ariq, Hala Ne 5 NzF1 I0mdadHome Halani, NausheroFero 62HaL5 Z5ameer, KanarMohalla, Hal 4 NzF2 S5ajadHome Halani,NausheroFero 26HaL A0l-Hafeez Pathology, Hal 4 NdS3 A07slam, ShaheedBenaziraba HaL A0llah Bux, ShahnawazMohalla, Hal 1 NdS4 H0abib College, ShaheedBenaziraba 58HaL A0rbani Street, Hal 5 NdS1 H09abib Sugar Mills ShaheedBenaziraba HaL C0loth Factory, PiniladhoColony, Hal 4 PlA10 V5illage Bhelar, PanoAqi 31DuD A0B Jamali, Johi, Dad NdS2 R04ailway station ShaheedBenaziraba DuD J0ohiCity, Pump 2, Dad PlA5 B0asheerabad,PanoAqi 91DuD1 W0ater Well, JohiCity, Dad PlA6 D08handi, PanoAqi DuD V5illage Allah Dad, Johi, Dad PlA8 M0anderGali, PanoAqi 12DuD J0ohiCity Pump 1, Dad 1 PlA9 S27hahi Bazar, PanoAqi DuD S0ample Pump 3, JohiCity, Dad 1 PlA1 V53illage Sanghi, PanoAqi DuD J0ohiCity, Dad 6 PlA2 V0illage Sultan Pur, PanoAqi 31JdC A0KColony Jacobaba RiH2 V02illage Abello, Rohr JdC P0aichohaVillage, Jacobaba StT1 V0illage Abbasi, Sekha 83JdC V0illage Pandhi, Jacobaba SdK1 S5eed Plant, MajeedKeerio, Sakran 32JoS S0ajadAbbasi, Phatak, Jamshor SdK2 W03asomal Stop, MajeedKeerio, Sakran JoS S0yed YaseenHome, SUECH Society, Jamshor StT2 V0illage Abbasi, Sekha 54JoS V0illage Nawab Khan Khoso, Jamshor SrP1 S46ociety, Shahdadpu JoS Z0ABhatti Home, SUECHS, Jamshor SdK10 J01an Mohammad House,, Sakran JoS O0waisBhatti, Phatak, Jamshor 1 SdK11 K51hadimHussainLakho, MajeedKeerio, Sakran KiH H0aris, Upper Gizri, Clifton, Karach SdK12 M01osque, MajeedKeerio, Sakran KeM H0indu Colony, Kashmor SdK13 M0unawarJamali House, MajeedKeerio, Sakran 13KeM T0own, Kashmor SdK14 M54urtaza Agricultural Farm 1, Sakran KeM V0illage MohdHashim, Kashmor SdK15 M52urtaza Agricultural Farm 2, Sakran KeM G0uddu, Kashmor 1 SdK16 Q01asim Ansari House, MajeedKeerio, Sakran KiT M0arket Kotr SdK17 R82azzaqKhokhar, MajeedKeerio, Sakran KiT P0athan Colony, Kotr SdK18 S04chool Road, MajeedKeerio, Sakran LaR H0and Pump, Larkan SlL1 R09asoolBuxTheboHome, Sajawa LaR R2atodero, Larkan SdK3 A51nimal Hospital, MajeedKeerio, Sakran LaR A5li SherKhokhar, Larkan SdK4 A03nwar, Sakran LaR D5hamrah, Larkan SdK5 A5waisMugheri home, MajeedKeerio, Sakran 23StH A0kbar Brohi, Shahdadko SdK6 D0argahWater, MajeedKerio, Sakran 14StH M0asan Mohalla, Shahdadko SdK7 D35rip No. 1 Water, MajeedKerio, Sakran StH S0aifullah Colony, Shahdadko SdK8 G0odown,MajeedKeerio, Sakran 51StH S0hahdadko SdK9 G02ulshan-e-Imdad, MajeedKeerio, Sakran StH T0anwary Branch, Shahdadko SrR3 J0amia Mosque, Bander Road, Sukku 82SrR N5izamdinBhatti, GarhiYaseen, Shikarpu SrG2 P0ublic Handpump, Sarhari, Sangha

Mehran University Research Journal of Engineering & Technology, Volume 36, No. 4, October, 2017 [p-ISSN: 0254-7821, e-ISSN: 2413-7219] 1041 Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan

3.2 Atomic Absorption Spectrometry 3.3 Comparison of As Kit and AAS

AAS was used to analyze the samples from the left bank The As kit and AAS results are quite similar as shown by of RI and the results are shown in Fig. 2. The Fig. 2 is percent standard deviation (% SD (±)) in Table 2. The As showing minimum and maximum As concentrations of kit and AAS (% SD) results are comparable with a research the studied areas. Eighty-three (83) ground water samples work conducted on As detection of ground water at district were obtained from various locations of left bank RI. The Rahim Yar Khan, Punjab, Pakistan in which (4-25 % SD) highest As concentration observed was 204 ppb at was observed between kit and AAS results [16]. Godown, Majeed Keerio in Sakrand, district Shaheed Benazirabad. It was observed that 85% of the studied 3.4 Contour Mapping areas had arsenic above WHO limit, i.e. 10 ppb, whereas, 43% of the analyzed areas reported the level of arsenic In Fig. 3 Contour plot of As concentration (ppb) in above the Pakistan-EPA standard i.e. 50 ppb. ground water is shown by the map of Sindh province,

FIG. 1. SAMPLES ANALYZED FROM THE AREAS OF THE RIGHT BANK OF RIVER INDUS THROUGH ARSENIC KIT METHOD

FIG. 2. ARSENIC IN SINDH SHOWING MINIMUM AND MAXIMUM CONCENTRATIONS WITH (WHO) AND (PAKISTAN- EPA LIMITS)

Mehran University Research Journal of Engineering & Technology, Volume 36, No. 4, October, 2017 [p-ISSN: 0254-7821, e-ISSN: 2413-7219] 1042 Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan

Pakistan. The contour map was made by using sample bank of RI. The red color highlights the highest As levels locations (coordinates) on google maps and OriginPro 9 at the location MajeedKeerio, SakrandTaluka, district software. The black dots are showing the sampling Shaheed Benazirabad. The other higher As locations at various regions of Sindh province. The contaminations are displayed by orange, yellow, green cross-sectional lines show the non-sampling areas in and cyan colors at Hala, Matairi, TMK and Nasarpur. the map. The As concentration is presented in the map The authors discussed the ground water samples As by various colors according to the As ranges shown (ppb) in district Rahim Yar Khan, Punjab, Pakistan with along with the contour map. It is evident from the Fig. 3 the help of contour diagrams. They found As levels that As was found in higher concentrations on the left from 8-118 ppb in ground water of district Rahim Yar

TABLE 2. COMPARISON OF ARSENIC CONCENTRATION ANALYZED WITH KIT METHOD AND ATOMIC ABSORPTION SPECTROMETER Sdample Code ASs (ppb) Kit Metho A)s (ppb) with AA % Standard Deviation (± H0L4 57329.19 H0L10 432012.02 H0L11 693914.84 H0L12 543311.31 H0L14 58358.48 H0L20 507214.14 H5L21 504610.60 H0L22 4040 H0L24 734119.09 H0L27 56399.89 H0L28 160 982.82 H0L41 715513.43 K5P6 2520 K6P16 45470.70 M0T11 36199.89 M0T12 835119.09 M0T14 181 958.48 M534T17 1.41 N0P2 44482.82 N5P3 3530 N0P7 67512.12 N0P10 85753.53 N5F9 18112.12 N3F10 10294.94 P0A5 30217.07 P0A12 937012.02 S5K5 32494.94 S5R3 20253.53 T598M6 2.82 T0M7 170 912.12 T5M9 129.19 2 T0M10 507214.14 L518R1 2.82

Mehran University Research Journal of Engineering & Technology, Volume 36, No. 4, October, 2017 [p-ISSN: 0254-7821, e-ISSN: 2413-7219] 1043 Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan

Khan, which is located on the left bank of RI [16]. Where, Another study conducted in the Shorabhaji region, = CAi − northwest of Iran shows the arsenic contents of 1000 Cfi 1 CNi ppb. The authors used geochemical contour mapping to determine As and other elements and found As in th Cfi is the contamination factor for i component, CAi is the both metallic and non-metallic forms [17]. th analytical value of i component, and CNi is the upper allowable concentration of ith component. 3.5 Contamination Index (Cd) In this study, C is studied for As. Contamination index It is a method to evaluate and anticipate the regions d for ground water was in the range between 0-19. 61.5% of characterized by irregular or toxic contents of elements. the samples were below the permissible limit of WHO This shows the extent of contamination by taking into guidelines. The ground water on the basis of C values consideration the number of parameters crossing the upper d may be arranged into four categories; 8.94% of ground allowable levels of hazardous elements and water contained C < 1 showed low contamination, 12.85% concentrations above these levels. The equation of d

were in the range 1< Cd<3 expressing intermediate calculating Cd is as follows [18]: contamination, 13.97% were within 3< Cd<10 and 2.79% n samples resulted in C >10 demonstrating the very high = d Cd Cfi (4) i=1 contamination. The ground water samples on the left bank

FIG. 3. CONTOUR PLOT OF ARSENIC CONCENTRATION (PPB) FROM GROUND WATER IN SINDH PROVINCE, PAKISTAN AT SELECTED SAMPLING LOCATIONS (BLACK DOTS SHOW SAMPLING LOCATIONS, CROSS- SECTIONAL LINES SHOW THE REGIONS FROM WHERE SAMPLES WERE NOT COLLECTED)

Mehran University Research Journal of Engineering & Technology, Volume 36, No. 4, October, 2017 [p-ISSN: 0254-7821, e-ISSN: 2413-7219] 1044 Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan

TABLE 3. HEALTH RISK ASSESSMENT THROUGH GROUND WATER CONSUMPTION OF REGIONS LOCATED ON LEFT BANK OF RIVER INDUS IN SINDH PROVINCE

Neo. Lnocation Cod L)ocatio A)s Contamination (?g/L EQDI (?g/kg-day TRH C 13. HL 231 00.58 12.94E+0 8.75E+0 20. H3L1 2800.63 22.13E+0 9.58E+0 32. H4L1 3400.94 33.15E+0 1.42E+0 47. H6L2 31033.33E+0 1.50E+0 50. H6L4 31033.33E+0 1.50E+0 64. H7L 3710.02 33.43E+0 1.54E+0 74. H8L1 3510.05 33.52E+0 1.58E+0 81. H9L1 3310.08 33.61E+0 1.63E+0 Hala 91. H0L2 4110.11 33.70E+0 1.67E+0 120. H0L2 4110.11 33.70E+0 1.67E+0 141. H3L2 4410.19 33.98E+0 1.79E+0 112. H1L4 5610.41 43.72E+0 2.13E+0 103. H0L2 7410.94 63.48E+0 2.92E+0 184. H6L2 9620.66 83.89E+0 4.00E+0 175. H1L4 150 20.80 93.35E+0 4.21E+0 166. H9L1 184 41.13 13.38E+0 6.21E+0 167. KP 245 00.69 23.31E+0 1.04E+0 Khairpur 168. K6P1 4710.27 43.26E+0 1.92E+0 189. MT 151 00.30 12.02E+0 4.58E+0 210. M6T1 1400.44 12.48E+0 6.67E+0 221. M3T1 5210.47 43.91E+0 2.21E+0 Matiari 232. M7T1 6110.86 63.20E+0 2.79E+0 253. M5T1 7320.08 63.94E+0 3.13E+0 244. M8T1 9220.72 93.07E+0 4.08E+0 235. NP 325 00.97 33.24E+0 1.46E+0 226. N4P 4210.22 43.07E+0 1.83E+0 297. N6P 5510.55 53.19E+0 2.33E+0 Nasarpur 278. N7P 5310.58 53.28E+0 2.38E+0 269. N6P 6310.83 63.11E+0 2.75E+0 300. N5P1 7320.08 63.94E+0 3.13E+0 341. NF 158 00. 12.67E+0 7.50E+0 Naushahro Feroz 332. N0F 2500.55 12.85E+0 8.33E+0 373. PA 151 00.30 12.02E+0 4.58E+0 354. P0A 2500.55 12.85E+0 8.33E+0 335. P7A Pano Aqil 2500.7 23.50E+0 1.13E+0 346. P7A 3710.02 33.43E+0 1.54E+0 317. P3A 7720.02 63.76E+0 3.04E+0 358. SK 462 10.16 33.89E+0 1.75E+0 329. S5K Sakrand 169 51.41 13.81E+0 8.13E+0 480. S4K 260 51.66 13.89E+0 8.50E+0 411. ST 158 00. 12.67E+0 7.50E+0 412. S9T Sekhat 4110.36 43.54E+0 2.04E+0 433. S0K 2500.55 12.85E+0 8.33E+0 444. TM1 257 00.7 23.50E+0 1.13E+0 405. T0M1 Tando Muhammad Khan 7410.94 63.48E+0 2.92E+0 476. T7M 9420.69 83.98E+0 4.04E+0 437. TrP T8harparka 1500. 12.67E+0 7.50E+0 A2verage 523.70 12.49 49.97 2237.58 M1inimum 1508.30 13.01 458.33 M4aximum 270 59.66 108.88 850 S(afe Values 10 μg-10/L) (WHO Guideline) 1 in 1 -6

Mehran University Research Journal of Engineering & Technology, Volume 36, No. 4, October, 2017 [p-ISSN: 0254-7821, e-ISSN: 2413-7219] 1045 Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan

of RI have elevated Cd values because of the higher As is the single available element in the periodic table for contents of As in ground water. Mahar et. al. [16] also which there is a cancer slope factor.CR was calculated in reported that riverine areas of district Rahim Yar Khan, the ground water as shown in Table 3. The CR values which is located on the border of Sindh and Punjab ranged from 458.333-8500 with an average value of provinces, Pakistan were contaminated with As and other 2237.589 in the ground water of examined region exhibiting impurities. elevated risk. It is reported that CR value 1 in 106 is significantly considered [12,19]. The results of this study 3.6 Health Risk Assessment show that the ground water exhibits high risk in the studied areas of Sindh province when compared to The HRA of the left bank RI was performed because it USEPA (2010) guidelines. The cancer risk assessment was found more contaminated than the right bank in this results of this work show the elevated health risk in the study. The people of the studied area consume ground observed areas of Sindh. water for their drinking, household and farming purposes. The residents of these areas cannot afford mineral water, 4. CONCLUSIONS therefore, they utilize ground water for their daily use. The estimated daily intake EDI (μg/kg-day) for As is given The kit method was used to analyze the 214 ground water in Table 3. samples from the both sides of RI. Then AAS technique was applied to analyze 83 samples from the left bank of EDI values ranged from 0.305-5.667 (μg/kg-day) for As. RI. The high THQ and CR values for As indicated, that The highest EDI value of 5.66 (μg/kg-day) was higher intake of As in ground water may pose chronic observed in the sample of Sakrand district showing toxicity and carcinogenic risk to the local inhabitants. the elevated threat level of As contamination to the Our results suggest that the ground water from the left local people. The higher EDI values of As can be bank of RI areas i.e. Sakrand, Hala, Matiari, TMK, Nasarpur because of municipal waste, leaching of waste materials and Sukkur is not safe for drinking without proper in the groundwater, use of excess fertilizers and treatment. pesticides by farmers.

Hence drinking water quality and continuous assessment The THQ indices were calculated to get a health risk should be conducted at regular intervals to check the assessment. THQ index for As in potable water was in quality of drinking water. the range from 1.018-18.889. The results show that the THQ is crossing the safe limits, i.e. (THQ should be less As kit and atomic absorption spectrometer results are than 1) posing a high health risk to the inhabitants of quite similar with 0.707-19 % SD. The contour plot of As examined areas. Around, 90% population of the left bank concentration (ppb) in ground water is shown by the RI is utilizing ground water for their domestic and map of Sindh and it is observed that the higher levels of drinking purposes, hence at high health risk because of arsenic are present on the left bank of RI. Contamination As contamination which is “carcinogenic to human index was calculated for ground water of Sindh and found beings”. in the range between 0-19.

Mehran University Research Journal of Engineering & Technology, Volume 36, No. 4, October, 2017 [p-ISSN: 0254-7821, e-ISSN: 2413-7219] 1046 Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan

ACKNOWLEDGMENTS [7] Zhang, W., Singh, P., Paling, E., and Delides S., “Arsenic Removal from Contaminated Water by Natural Iron This project is funded by Pakistan-US Science & Ores”, Minerals Engineering, Volume 17, No. 4, Technology Cooperation Program, and Higher Education pp. 517-524, 2004.

Commission, Pakistan. The authors are thankful to [8] Zhang, Q.L., Lin, Y., Chen, X., and Gao N.Y., “A Method students of the Department of Chemical Engineering, for Preparing Ferric Activated Carbon Composites Mehran University of Engineering & Technology, Sdsorbents to Remove Arsenic from Drinking Water”, Jamshoro, for their help in the ground water sample Journal of Hazardous Materials, Volume 148, No. 3, pp. 671-678, 2007. collection. [9] Sahin, C.A., Tokgöz, Ý., and Bektaþ, S., REFERENCES “Preconcentration and Determination of Iron and Copper in Spice Samples by Cloud Point Extraction and [1] Kazi, T.G., Arain, M.B., Baig, J.A., Jamali, M.K., Afridi, Flow Injection Flame Atomic Absorption Spectrometry”, H.I., and Jalbani, N., “The Correlation of Arsenic Levels Journal of Hazardous Materials, Volume 181, No. 1, in Drinking Water with the Biological Samples of Skin pp. 359-365, 2010. Disorders”, Science of the Total Environment, Volume 407, No.3, pp. 1019-1026, 2009. [10] Moya, J., Phillips, L., Schuda, L., Wood, P., Diaz, and Lee, A.R., “Exposure Factors Handbook”, US [2] Martínez-Barquero, V., de Marco, G., Martínez-Hervas, Environmental Protection Agency, Washington, 2011. S., Rentero, P., Galan-Chilet, I., and Blesa, S., “Polymorphisms in Endothelin System Genes, Arsenic [11] Rasool, A., Farooqi, A., Xiao, T., Masood, S., and Kamran, Levels and Obesity Risk”, Volume 10, No. 3, pp 1-13, M.A., “Elevated Levels of Arsenic and Trace Metals in 2015. Drinking Water of Tehsil Mailsi, Punjab, Pakistan”, Journal of Geochemical Exploration, Volume 169, [3] Baig, J.A., Kazi, T.G., Shah, A.Q., Afridi, H.I., Khan, S., and Kolachi, N.F., “Evaluation of Toxic Risk Assessment pp. 89-99, 2016. of Arsenic in Male Subjects through Drinking Water in [12] Rasool, A., Xiao, T., Farooqi, A., Shafeeque, M., Masood, Southern Sindh, Pakistan”, Biological Trace Element S., and Ali, S., “Arsenic and Heavy Metal Research, Volume 143, No. 2, pp. 772-786, 2011. Contaminations in the Tube Well Water of Punjab, [4] Abernathy, C.O., Thomas, D.J., and Calderon, R.L., Pakistan and Risk Assessment: A Case Study”, Ecological “Health Effects and Risk Assessment of Arsenic”, The Engineering, Volume 95, pp. 90-100, 2016. Journal of Nutrition, Volume 133, No. 5, [13] USEPARA Forum, “Guidelines for Carcinogen Risk pp. 1536-1538, 2003. Assessment”, 2005. [5] Arain, M., Kazi, T.G., Baig, J.A., Jamali, M., Afridi, H.I., and Shah, A., “Determination of Arsenic Levels in Lake [14] Baig, J.A., Kazi, T.G., Mustafa, M.A., Solangi, I.B., Water, Sediment, and Foodstuff from Selected Area of Mughal, M.J., and Afridi, H.I., “Arsenic Exposure in Sindh, Pakistan: Estimation of Daily Dietary Intake”, Children through Drinking Water in Different Districts Food and Chemical Toxicology, Volume 47, No. 1, of Sindh, Pakistan”, Biological Trace Element Research, pp. 242-248, 2009. pp. 1-12, 2016.

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