# Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan

Zulfiqar Ali Bhatti, Khadija Qureshi, Inamullah Bhatti, Imran Nazir Unar, Mohammad Yar Khuhawar

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Zulfiqar Ali 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, 2017, 36 (4), pp.1037-1048. [hal-01705647](https://hal.science/hal-01705647)

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# 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 RI was 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

As is a hazardous element which is present in ground water in the form of As(III) and As(V). Its presence in the earth's crust is 0.00021%. Illness characteristic of long-term arsenic exposure comes in the form of skin cancer, bladder cancer, inactivation of

an enzyme system in the body, black foot disease, and obesity [1-3]. As contact can also cause other health consequences such as gastrointestinal irritation, diabetes, less number of white and red blood cells, hypertension, blood vessels rupture and abnormal heart beats [4]. Baig

Corresponding Author (E-Mail: zulfiqar.bhatti@faculty.muet.edu.pk)

* Department of Chemical Engineering, Mehran University of Engineering & Technology, Jamshoro.

** Institute of Advanced Research Studies in Chemical Sciences, University of Sindh, Jamshoro.
et. al. [3] performed a study of Gambat town, Sindh and found people suffering from chest infections, pain in the whole body, cramps in legs due to As contamination in water.

Naturally occurring arsenic is known to trickle from contaminated soils. Thus, contact of the general population with arsenic is mainly through the ingestion of groundwater, which comes across As-bearing soils and minerals. Pakistan is suffering from the toxic effects of arsenic as other countries such as Bangladesh, India, Thailand, Taiwan, China, Japan, USA, Canada, Hungary and Ghana [5].

The high level of As species in ground water is due to the dissolution of As compounds coming from the Himalayas through RI and settled down throughout the years and then introduced into ground water by geothermal, hydrological and biochemical factors [6]. In Pakistan, a number of people consume ground water for their drinking, domestic purposes as clean river water is not accessible to them. As toxicity is mostly found in ground water and transported to human beings by ingestion, vegetables, crops, fruits and fishes. The authors in a research showed that the Mancharlake near town Sehwan, Sindh was contaminated with arsenic and the daily intake of As by people is 241-390 µg As/4L [5].

The present study was designed to investigate As in drinking water of Sindh province on both left and right banks of RI.

# 2. MATERIALS AND METHOD

## 2.1 Materials

Ground water samples were collected from various areas of Sindh Province, Pakistan and analyzed in a water quality laboratory, Department of Chemical Engineering, Mehran University of Engineering & Technology, Jamshoro,

Pakistan. All sample bottles (well-stoppered polyethylene plastic) were rinsed with clean water, then filled completely with sample water and tagged properly with a location. Analysis of water samples was performed by using the Arsenic test Kit (Merck, Germany) and AAS (Atomic Absorption Spectrometer). The arsenic kit is a mobile analytical tool that is used in the field to check the arsenic in water. AAS was used to analyze 106 ground water samples, whereas kit method was applied to test 214 ground water samples.

Analytical grade chemicals were used throughout the research work. Distilled water was used during the experiments to prepare all the solutions. Distilled water was prepared in a water quality laboratory by Distilled water machine (Model No. BMS-4CE, Spain). All the glass wares were kept overnight in 5M HNO₃ and then rinsed with deionized water before use. Stock solutions of concentration 1000 ppb As(III) were prepared by mixing arsenic standard solution of 100 mg/L As(III) (Inorganic Venture Company, USA) with distilled water. The stock solutions were used to prepare fresh experimental solutions as per need in clean plastic bottles and were kept away from light to avoid any change in chemical properties [7-9]. For the confirmation of reproducibility, the tests were replicated and the mean values were taken.

## 2.2 Methods

### 2.2.1 Arsenic Kit method

Water samples were analyzed by Arsenic kit (Merck, Germany) by using a calorimetric method with test strips. The arsenic kit reaction bottle was filled to the mark with 60 ml sample water and the analysis was carried out as recommended by the kit manufacturer.

### 2.2.2 Atomic Absorption Spectrometer

Arsenic was analyzed in water samples by AAS (A Analyst 700, Perkin Elmer, USA), at a wavelength of
193.7 nm, by the MHS-15 (Mercury Hydride System) technique. The energy source was the single-element hollow cathode lamp of arsenic working at 7.5 mA. The AAS was attached to a computer and WinLab32 software used to receive and process analytical data. The solution of 1% potassium hydroxide (KOH) was prepared. Then 3% sodium borohydride (NaBH₄) was prepared in 1% KOH solution on Stirrer (Wisd, MSH-20, Korea). The chemicals were weighed using weighing balance (Adventurer, AR 3130, OHAUS, USA). 1.5% HCl (Hydrochloric Acid) was prepared by appropriate dilution of HCl (37%). The arsenic standards were prepared to calibrate the AAS. Then the ASS was used to analyze water samples and the results were obtained by Winlab 32.

### 2.2.3 Technique to Assess Human Health Risk

The HRA of the left bank of RI areas is studied by calculating EDI, THQ and CR. EDI is calculated by using the following equation;

$$EDI = Cm \times \frac{Dw}{Bw} \qquad (1)$$

Where Cm denotes metal concentration (µg/L) in water, Dw is the daily average intake of water (Lit/day, taken as 2 Lit/day), and Bw is the body average weight (kg, taken as 72 kg) [10].

The THQ was obtained by applying the following relationship;

$$THQ = \frac{EDI}{RfD} \qquad (2)$$

Where the oral toxicity reference doseRfD (µg/kg-day) value for arsenic is (3.00E-01) [11].

Following relationship was used to calculate CR;

$$CR = EDI \times CSF \qquad (3)$$

In Equation (3) CSF (µg/kg-day) is Cancer Slope Factor and its value for As is 1.5E+03 (µg/kg-day) [12-13].

## 3. RESULTS AND DISCUSSION

### 3.1 Arsenic kit Method

The As kit is a portable and easy tool method used to analyze As of 24 districts of Sindh Province. Out of 214 ground water samples, 182 were from localities on the left bank and 32 samples from the right bank of RI. All the sample areas were assigned codes as shown in Table 1.

The results of localities on the left bank are reported in Table 1. About 40% of the samples were exceeding the WHO safe limit for As in water, i.e. 10 ppb. The higher As levels were observed in ground water samples of Hala i.e. 10-180 ppb. The other areas with higher As concentrations were Sakrand, Matairi, Nasarpur, Pano Aqil and TMK.

The reasons for higher concentrations in the left bank of RI are the geological presence due to the deposition over the years from the Himalayas, thick population, intense farming, and the areas from where RI passed during the Holocene period such as Tando Allahyar and TMK from where the As ranges from 10-500 ppb [6].

Fig. 1 demonstrates the sample from the right bank of RI. The Dadu district samples showed higher As levels ranging between 0-60 ppb which is inconsistent with the earlier report of As in scalp and hair of children of Dadu district [14]. Apart from the natural deposition of arsenic in ground water other factors for As pollution are coal burning at brick industries, power plants in Jamshoro district [15]. Samples of Jamshoro and Kashmore ranged within permissible limit of 10 ppb.
<table><caption>TABLE 1. GROUND WATER SAMPLE CODES ASSIGNED TO LOCATIONS OF SINDH, PAKISTAN AND ARSENIC KIT RESULTS</caption><thead><tr><td>Code</td><td>Location</td><td>As(ppb)</td><td>Code</td><td>Location</td><td>As(ppb)</td></tr></thead><tbody><tr><td>BD1</td><td>Hand Pump, NabiBuxBhurgri, Badin</td><td>0</td><td>ST3</td><td>Abbasi Village, Sekhat</td><td>40</td></tr><tr><td>BD2</td><td>MuhammadNizamiMalhan, Matli, Badin</td><td>0</td><td>TM1</td><td>Village SaeedPur, Bulri Shah Karim, TMK</td><td>3</td></tr><tr><td>BD3</td><td>NabiBuxBhurgri, Badin</td><td>0</td><td>TM2</td><td>Water Pond, Sajawal Road, TMK</td><td>0</td></tr><tr><td>BD4</td><td>NizamaniOtaq, Matli, Badin</td><td>0</td><td>TA1</td><td>Mosque, Village Talpur, TandoAllahyar</td><td>25</td></tr><tr><td>BD4</td><td>Village Malhan, Matli, Badin</td><td>0</td><td>TA2</td><td>Village Talpur, TandoAllahyar</td><td>0</td></tr><tr><td>DK1</td><td>Ghulab Shah Colony, Dharki</td><td>0</td><td>SR1</td><td>Old Sukkur</td><td>0</td></tr><tr><td>DK2</td><td>Imam Bargah, Dharki</td><td>5</td><td>TM10</td><td>SafeenaShifa, TMK</td><td>30</td></tr><tr><td>DP1</td><td>DaburiWell Water, Diplo</td><td>0</td><td>TM11</td><td>SaqibTalpur, TMK</td><td>5</td></tr><tr><td>DP2</td><td>DileepSaqiHome, Diplo</td><td>0</td><td>TM12</td><td>Tube Well Water (City), TMK</td><td>50</td></tr><tr><td>DP3</td><td>RafiqLangho, Diplo</td><td>0</td><td>TM13</td><td>Village Gaja Mori, TMK</td><td>0</td></tr><tr><td>DP4</td><td>SaqiParo, Diplo</td><td>0</td><td>TM14</td><td>Village GhulamHussainTalpur, TMK</td><td>50</td></tr><tr><td>GK2</td><td>Hand Pump, Yaro Lund, MirpurMathelo, Ghotki</td><td>5</td><td>TM3</td><td>Bus Stop Near Ayobia Hotel, TMK</td><td>60</td></tr><tr><td>GK3</td><td>Motor Water, Yaro Lund, MirpurMathelo, Ghotki</td><td>0</td><td>TM4</td><td>Gaja Mori, Sajawal Road, TMK</td><td>0</td></tr><tr><td>HD1</td><td>House No. 137, Latifabad, Hyderabad</td><td>0</td><td>TM5</td><td>Govt: Girls High School, TMK</td><td>40</td></tr><tr><td>HD2</td><td>House No. 97, Latifabad, Hyderabad</td><td>0</td><td>TM6</td><td>Govt: Girls School, TMK</td><td>5</td></tr><tr><td>HD3</td><td>Hussainabad, Police Colony, Hyderabad</td><td>0</td><td>TM7</td><td>MadarsahJamiatmadinah, TMK</td><td>20</td></tr><tr><td>HD6</td><td>Latifabad, Hyderabad</td><td>0</td><td>TM8</td><td>Majid Ali, Mir Mohalla, TMK</td><td>6</td></tr><tr><td>HD7</td><td>Miyani Road, Hyderabad</td><td>0</td><td>TM9</td><td>SaeedPur, TalukaBulri Shah Karim, TMK</td><td>100</td></tr><tr><td>HD8</td><td>MohsinMemon, Citizen's Colony, Hyderabad</td><td>5</td><td>TB1</td><td>14 KM from GuniChowk, TandoBago</td><td>10</td></tr><tr><td>HD9</td><td>New Wahdat Colony, Hyderabad</td><td>10</td><td>TJ2</td><td>RazaSaeed, Tando Jam</td><td>15</td></tr><tr><td>IK1</td><td>Govt: RO Plant, IslamKot</td><td>0</td><td>TT2</td><td>Warial Khan Khoso, Jhir, Thatta</td><td>0</td></tr><tr><td>IK2</td><td>Private RO Plant, IslamKot</td><td>0</td><td>UK3</td><td>Akripithoro, Umerkot</td><td>10</td></tr><tr><td>IK3</td><td>Village BhabinoBhell, UC SonalBhoh, Thar</td><td>0</td><td>HL1</td><td>Abdul Aziz, KadhMohalla, Hala</td><td>30</td></tr><tr><td>IK4</td><td>Coal Gasification Site, IslamKot, Thar</td><td>0</td><td>HL10</td><td>DargahMakhdomNoh,SalineWater, Pump 2, Hala</td><td>40</td></tr><tr><td>KD1</td><td>Mohammad Din, Kandiaro</td><td>0</td><td>HL11</td><td>DargahMakhdom Noh,Sweet Water, Pump 1, Hala</td><td>60</td></tr><tr><td>JD7</td><td>Liaquat, Ward-2, Jhuddo</td><td>0</td><td>HL12</td><td>DawoodMemonHome, KanarMohalla, Hala</td><td>50</td></tr><tr><td>KP10</td><td>Naib Ali, Tarkowado, Khairpur Mir's</td><td>0</td><td>HL13</td><td>Dr. AR Memon Home, Hala</td><td>35</td></tr><tr><td>KP13</td><td>TarkoWado, Khairpur Mir's</td><td>0</td><td>HL14</td><td>Envious Girls Public School, KadhMohalla, Hala</td><td>50</td></tr><tr><td>KP14</td><td>Tube Well, TalukaNaro, Khairpur</td><td>0</td><td>HL15</td><td>Faiz Mohammad, Hala New</td><td>45</td></tr><tr><td>KP16</td><td>Village Allah Dino Khuhro,Gambat,Khairpur</td><td>45</td><td>HL16</td><td>Fareed Ahmed Home, PirFazalColony, Hala</td><td>180</td></tr><tr><td>KP18</td><td>Wandh, Khairpur Mir's</td><td>10</td><td>HL17</td><td>Fazal, Hala New</td><td>7</td></tr><tr><td>KGM1</td><td>Jamesabad, KotGhulam Mohammad</td><td>0</td><td>HL18</td><td>Govt: Girls High School, KadhMohalla, Hala</td><td>5</td></tr><tr><td>KP3</td><td>HadiBuxLeghari, ThariMirwah, Khairpur</td><td>5</td><td>HL19</td><td>Haji Anwar, Kaka Mohalla, Hala</td><td>40</td></tr><tr><td>KP4</td><td>Hand pump, TalukaNaro, Khairpur</td><td>5</td><td>HL2</td><td>Aftab Ansari, Hala</td><td>25</td></tr><tr><td>KP6</td><td>Jadowahan, Gambat, Khairpur</td><td>25</td><td>HL20</td><td>Haji Faiz Mohammad Home, SiraiMohalla, Hala</td><td>50</td></tr><tr><td>KP8</td><td>Latif colony, Kairpur Mir's</td><td>5</td><td>HL21</td><td>Haji QamarudinHome, Kanar Mohall, Hala</td><td>55</td></tr><tr><td>MT16</td><td>HazoorBux Shop, Khyber Stop, Matairi</td><td>30</td><td>HL22</td><td>Imam Bargah, Hala</td><td>40</td></tr><tr><td>MH1</td><td>Mithi</td><td>0</td><td>HL23</td><td>Imdad Rajput, MohajirChowk, Hala</td><td>25</td></tr><tr><td>MH2</td><td>RO Water, Mithi</td><td>0</td><td>HL24</td><td>JealArbabHome, ArbabMohalla, Hala</td><td>70</td></tr><tr><td>MT10</td><td>Macon-Washy, Matairi</td><td>0</td><td>HL25</td><td>Khair Mohammad, PiniladhoColony, Hala</td><td>30</td></tr><tr><td>MT11</td><td>MatairiCity</td><td>80</td><td>HL26</td><td>Khokhar Fridge Shop, BrohiMohalla, Hala</td><td>10</td></tr><tr><td>MT12</td><td>Matairi City, DargahPardehiPir</td><td>100</td><td>HL27</td><td>MuhammadUsmanHome, Piniladho Colony, Hala</td><td>50</td></tr><tr><td>MT13</td><td>Matairi Sugar Mills Officers Mess, Matairi</td><td>110</td><td>HL28</td><td>MuhammadUsmanHome, PirFazal Colony, Hala</td><td>100</td></tr><tr><td>MT14</td><td>Matairi Sugar Mills RO Plant, Matairi</td><td>120</td><td>HL29</td><td>MuhammadYousuf, TalibMola Road, Hala</td><td>40</td></tr><tr><td>MT15</td><td>Matairi Sugar Mills Supervisor mess, Matairi</td><td>25</td><td>HL3</td><td>Ahmed KhalkaniHome, Kaka Mohalla, Hala</td><td>50</td></tr><tr><td>MT16</td><td>MianpotaMohalla, Matairi</td><td>0</td><td>HL30</td><td>Mohammad Hussain, Kaka Mohalla, Hala</td><td>25</td></tr><tr><td>MT17</td><td>Mir Hassan Mohalla, Matairi</td><td>5</td><td>HL31</td><td>Mohammad Usman, MohajirChowk, Hala</td><td>20</td></tr><tr><td>MT18</td><td>Sekhat, Matairi</td><td>50</td><td>HL32</td><td>Mohammad, Hala New</td><td>25</td></tr><tr><td>MT19</td><td>ShameerJiWari, Matairi</td><td>0</td><td>HL33</td><td>Mosque, Hala New</td><td>50</td></tr><tr><td>MT2</td><td>AbasPir, Highway Road, Matairi</td><td>0</td><td>HL34</td><td>Naseer, Kaka Mohalla, Hala</td><td>30</td></tr><tr><td>MT20</td><td>Village BachalDetho, Near Matairi Sugar Mills</td><td>100</td><td>HL35</td><td>Near Girls College, Hala</td><td>25</td></tr><tr><td>MT21</td><td>Village Bhambra, Matairi</td><td>0</td><td>HL36</td><td>Near Imam Bargah, Hala</td><td>40</td></tr><tr><td>MT22</td><td>Village Shah Alam Shah Wasi, Matairi</td><td>40</td><td>HL37</td><td>Old Hala</td><td>10</td></tr><tr><td>MT23</td><td>Village Vighio, Matairi</td><td>0</td><td>HL38</td><td>Prof. Nafees Ahmed, KashigarMohalla, Hala</td><td>40</td></tr></tbody></table>
Determination of Arsenic and Health Risk Assessment in the Ground Water of Sindh, Pakistan

<table><thead><tr><td>Code</td><td>Location</td><td>As(ppb)</td><td>Code</td><td>Location</td><td>As(ppb)</td></tr></thead><tbody><tr><td>MT3</td><td>BurkatPota, Matairi</td><td>0</td><td>HL39</td><td>Raja Fahad Home, Hala</td><td>90</td></tr><tr><td>MT4</td><td>Canteen, Matairi Sugar Mills</td><td>0</td><td>HL4</td><td>Al Shifa Medical center, KadhMohalla, Hala</td><td>50</td></tr><tr><td>MT5</td><td>Graveyard, Matairi</td><td>30</td><td>HL40</td><td>Raja FahadQureshi Agricultural Farm, Hala</td><td>90</td></tr><tr><td>MT9</td><td>Khyber, Matairi</td><td>0</td><td>HL41</td><td>Rehan home, KashigarMohalla, Hala</td><td>70</td></tr><tr><td>NF3</td><td>Darpa, Tharushah, NausheroFeroz</td><td>0</td><td>HL42</td><td>SaeedMemon, Hala New</td><td>50</td></tr><tr><td>NF4</td><td>KhudaBuxKalhoro, NausheroFeroz</td><td>10</td><td>HL43</td><td>SarfarazQureshi, Mujawar colony, Hala</td><td>10</td></tr><tr><td>NF6</td><td>Tharushah, NausheroFeroz</td><td>0</td><td>HL44</td><td>Shamsudin Book Store, Kanar, Hala</td><td>10</td></tr><tr><td>NF7</td><td>Village Allah Bachayo, NausheroFeroz</td><td>3</td><td>HL45</td><td>Soomar Shah, Hala</td><td>90</td></tr><tr><td>UK9</td><td>Pump Water, Umerkot</td><td>5</td><td>HL46</td><td>Sweet Shop, Hala</td><td>13</td></tr><tr><td>NK1</td><td>Naukot</td><td>0</td><td>HL47</td><td>TahirYasirHome, TalibMola Road, Hala</td><td>150</td></tr><tr><td>NP10</td><td>Ward-6, Nasarpur</td><td>15</td><td>HL48</td><td>TalibMola Colony, Hala</td><td>100</td></tr><tr><td>NP2</td><td>ArainMohallah, Nasarpur</td><td>13</td><td>HL49</td><td>Tariq Road, Hala</td><td>40</td></tr><tr><td>NP3</td><td>Bus Stop, Nasarpur</td><td>80</td><td>HL5</td><td>Alamgir, Kaka Mohalla, Hala</td><td>50</td></tr><tr><td>NP7</td><td>SikanderAlmaniHome, Nasarpur</td><td>40</td><td>HL50</td><td>Tariq, Hala</td><td>20</td></tr><tr><td>NP9</td><td>Ward-4, Nasarpur</td><td>35</td><td>HL51</td><td>Tariq, Hala New</td><td>50</td></tr><tr><td>NF1</td><td>ImdadHome Halani, NausheroFeroz</td><td>60</td><td>HL52</td><td>Zameer, KanarMohalla, Hala</td><td>45</td></tr><tr><td>NF2</td><td>SajadHome Halani, NausheroFeroz</td><td>25</td><td>HL6</td><td>Al-Hafeez Pathology, Hala</td><td>40</td></tr><tr><td>NS3</td><td>Aslam, ShaheedBenazirabad</td><td>0</td><td>HL7</td><td>Allah Bux, ShahnawazMohalla, Hala</td><td>10</td></tr><tr><td>NS4</td><td>Habib College, ShaheedBenazirabad</td><td>50</td><td>HL8</td><td>Arbani Street, Hala</td><td>50</td></tr><tr><td>NS1</td><td>Habib Sugar Mills ShaheedBenazirabad</td><td>0</td><td>HL9</td><td>Cloth Factory, PiniladhoColony, Hala</td><td>40</td></tr><tr><td>PA10</td><td>Village Bhelar, PanoAqil</td><td>35</td><td>DD1</td><td>AB Jamali, Johi, Dadu</td><td>0</td></tr><tr><td>NS2</td><td>Railway station ShaheedBenazirabad</td><td>0</td><td>DD4</td><td>JohiCity, Pump 2, Dadu</td><td>0</td></tr><tr><td>PA5</td><td>Basheerabad, PanoAqil</td><td>90</td><td>DD11</td><td>Water Well, JohiCity, Dadu</td><td>0</td></tr><tr><td>PA6</td><td>Dhandi, PanoAqil</td><td>0</td><td>DD8</td><td>Village Allah Dad, Johi, Dadu</td><td>5</td></tr><tr><td>PA8</td><td>ManderGali, PanoAqil</td><td>10</td><td>DD2</td><td>JohiCity Pump 1, Dadu</td><td>10</td></tr><tr><td>PA9</td><td>Shahi Bazar, PanoAqil</td><td>2</td><td>DD7</td><td>Sample Pump 3, JohiCity, Dadu</td><td>10</td></tr><tr><td>PA1</td><td>Village Sanghi, PanoAqil</td><td>5</td><td>DD3</td><td>JohiCity, Dadu</td><td>60</td></tr><tr><td>PA2</td><td>Village Sultan Pur, PanoAqil</td><td>30</td><td>JC1</td><td>AKColony Jacobabad</td><td>0</td></tr><tr><td>RH2</td><td>Village Abello, Rohri</td><td>0</td><td>JC2</td><td>PaichohaVillage, Jacobabad</td><td>0</td></tr><tr><td>ST1</td><td>Village Abbasi, Sekhat</td><td>80</td><td>JC3</td><td>Village Pandhi, Jacobabad</td><td>0</td></tr><tr><td>SK1</td><td>Seed Plant, MajeedKeerio, Sakrand</td><td>35</td><td>JS2</td><td>SajadAbbasi, Phatak, Jamshoro</td><td>0</td></tr><tr><td>SK2</td><td>Wasomal Stop, MajeedKeerio, Sakrand</td><td>0</td><td>JS3</td><td>Syed YaseenHome, SUECH Society, Jamshoro</td><td>0</td></tr><tr><td>ST2</td><td>Village Abbasi, Sekhat</td><td>50</td><td>JS4</td><td>Village Nawab Khan Khoso, Jamshoro</td><td>0</td></tr><tr><td>SP1</td><td>Society, Shahdadpur</td><td>4</td><td>JS6</td><td>ZABhatti Home, SUECHS, Jamshoro</td><td>0</td></tr><tr><td>SK10</td><td>Jan Mohammad House, Sakrand</td><td>0</td><td>JS1</td><td>OwaisBhatti, Phatak, Jamshoro</td><td>10</td></tr><tr><td>SK11</td><td>KhadimHussainLakho, MajeedKeerio, Sakrand</td><td>5</td><td>KH1</td><td>Haris, Upper Gizri, Clifton, Karachi</td><td>0</td></tr><tr><td>SK12</td><td>Mosque, MajeedKeerio, Sakrand</td><td>0</td><td>KM1</td><td>Hindu Colony, Kashmore</td><td>0</td></tr><tr><td>SK13</td><td>MunawarJamali House, MajeedKeerio, Sakrand</td><td>10</td><td>KM3</td><td>Town, Kashmore</td><td>0</td></tr><tr><td>SK14</td><td>Murtaza Agricultural Farm 1, Sakrand</td><td>5</td><td>KM4</td><td>Village MohdHashim, Kashmore</td><td>0</td></tr><tr><td>SK15</td><td>Murtaza Agricultural Farm 2, Sakrand</td><td>5</td><td>KM2</td><td>Guddu, Kashmore</td><td>10</td></tr><tr><td>SK16</td><td>Qasim Ansari House, MajeedKeerio, Sakrand</td><td>0</td><td>KT1</td><td>Market Kotri</td><td>0</td></tr><tr><td>SK17</td><td>RazzaqKhokhar, MajeedKeerio, Sakrand</td><td>8</td><td>KT2</td><td>Pathan Colony, Kotri</td><td>0</td></tr><tr><td>SK18</td><td>School Road, MajeedKeerio, Sakrand</td><td>0</td><td>LR4</td><td>Hand Pump, Larkana</td><td>0</td></tr><tr><td>SL1</td><td>RasoolBuxTheboHome, Sajawal</td><td>0</td><td>LR9</td><td>Ratodero, Larkana</td><td>2</td></tr><tr><td>SK3</td><td>Animal Hospital, MajeedKeerio, Sakrand</td><td>5</td><td>LR1</td><td>Ali SherKhokhar, Larkana</td><td>5</td></tr><tr><td>SK4</td><td>Anwar, Sakrand</td><td>0</td><td>LR3</td><td>Dhamrah, Larkana</td><td>5</td></tr><tr><td>SK5</td><td>AwaisMugheri home, MajeedKeerio, Sakrand</td><td>25</td><td>SH3</td><td>Akbar Brohi, Shahdadkot</td><td>0</td></tr><tr><td>SK6</td><td>DargahWater, MajeedKeerio, Sakrand</td><td>10</td><td>SH4</td><td>Masan Mohalla, Shahdadkot</td><td>0</td></tr><tr><td>SK7</td><td>Drip No. 1 Water, MajeedKeerio, Sakrand</td><td>3</td><td>SH5</td><td>Saifullah Colony, Shahdadkot</td><td>0</td></tr><tr><td>SK8</td><td>Godown, MajeedKeerio, Sakrand</td><td>50</td><td>SH1</td><td>Shahdadkot</td><td>0</td></tr><tr><td>SK9</td><td>Gulshan-e-Imdad, MajeedKeerio, Sakrand</td><td>0</td><td>SH2</td><td>Tanwary Branch, Shahdadkot</td><td>0</td></tr><tr><td>SR3</td><td>Jamia Mosque, Bander Road, Sukkur</td><td>80</td><td>SR2</td><td>NizamdinBhatti, GarhiYaseen, Shikarpur</td><td>5</td></tr><tr><td>SG2</td><td>Public Handpump, Sarhari, Sanghar</td><td>0</td><td></td><td></td><td></td></tr></tbody></table>
## 3.2 Atomic Absorption Spectrometry

AAS was used to analyze the samples from the left bank of RI and the results are shown in Fig. 2. The Fig. 2 is showing minimum and maximum As concentrations of the studied areas. Eighty-three (83) ground water samples were obtained from various locations of left bank RI. The highest As concentration observed was 204 ppb at Godown, Majeed Keerio in Sakrand, district Shaheed Benazirabad. It was observed that 85% of the studied areas had arsenic above WHO limit, i.e. 10 ppb, whereas, 43% of the analyzed areas reported the level of arsenic above the Pakistan-EPA standard i.e. 50 ppb.

<figure><img src="image_2.png" /><figcaption>FIG. 1. SAMPLES ANALYZED FROM THE AREAS OF THE RIGHT BANK OF RIVER INDUS THROUGH ARSENIC KIT METHOD</figcaption></figure>

<figure><img src="image_3.png" /><figcaption>FIG. 2. ARSENIC IN SINDH SHOWING MINIMUM AND MAXIMUM CONCENTRATIONS WITH (WHO) AND (PAKISTAN- EPA LIMITS)</figcaption></figure>

## 3.3 Comparison of As Kit and AAS

The As kit and AAS results are quite similar as shown by percent standard deviation (% SD (±)) in Table 2. The As kit and AAS (% SD) results are comparable with a research work conducted on As detection of ground water at district Rahim Yar Khan, Punjab, Pakistan in which (4-25 % SD) was observed between kit and AAS results [16].

## 3.4 Contour Mapping

In Fig. 3 Contour plot of As concentration (ppb) in ground water is shown by the map of Sindh province,
Pakistan. The contour map was made by using sample locations (coordinates) on google maps and OriginPro 9 software. The black dots are showing the sampling locations at various regions of Sindh province. The cross-sectional lines show the non-sampling areas in the map. The As concentration is presented in the map by various colors according to the As ranges shown along with the contour map. It is evident from the Fig. 3 that As was found in higher concentrations on the left

bank of RI. The red color highlights the highest As levels at the location MajeedKeerio, SakrandTaluka, district Shaheed Benazirabad. The other higher As contaminations are displayed by orange, yellow, green and cyan colors at Hala, Matairi, TMK and Nasarpur. The authors discussed the ground water samples As (ppb) in district Rahim Yar Khan, Punjab, Pakistan with the help of contour diagrams. They found As levels from 8-118 ppb in ground water of district Rahim Yar

<table><caption>TABLE 2. COMPARISON OF ARSENIC CONCENTRATION ANALYZED WITH KIT METHOD AND ATOMIC ABSORPTION SPECTROMETER</caption><thead><tr><td>Sample Code</td><td>As (ppb) Kit Method</td><td>As (ppb) with AAS</td><td>% Standard Deviation (±)</td></tr></thead><tbody><tr><td>HL4</td><td>50</td><td>37</td><td>9.192</td></tr><tr><td>HL10</td><td>40</td><td>23</td><td>12.020</td></tr><tr><td>HL11</td><td>60</td><td>39</td><td>14.849</td></tr><tr><td>HL12</td><td>50</td><td>34</td><td>11.313</td></tr><tr><td>HL14</td><td>50</td><td>38</td><td>8.485</td></tr><tr><td>HL20</td><td>50</td><td>70</td><td>14.142</td></tr><tr><td>HL21</td><td>55</td><td>40</td><td>10.606</td></tr><tr><td>HL22</td><td>40</td><td>40</td><td>0</td></tr><tr><td>HL24</td><td>70</td><td>43</td><td>19.091</td></tr><tr><td>HL27</td><td>50</td><td>36</td><td>9.899</td></tr><tr><td>HL28</td><td>100</td><td>96</td><td>2.828</td></tr><tr><td>HL41</td><td>70</td><td>51</td><td>13.435</td></tr><tr><td>KP6</td><td>25</td><td>25</td><td>0</td></tr><tr><td>KP16</td><td>46</td><td>45</td><td>0.707</td></tr><tr><td>MT11</td><td>30</td><td>16</td><td>9.899</td></tr><tr><td>MT12</td><td>80</td><td>53</td><td>19.091</td></tr><tr><td>MT14</td><td>110</td><td>98</td><td>8.485</td></tr><tr><td>MT17</td><td>5</td><td>3</td><td>1.414</td></tr><tr><td>NP2</td><td>40</td><td>44</td><td>2.828</td></tr><tr><td>NP3</td><td>35</td><td>35</td><td>0</td></tr><tr><td>NP7</td><td>60</td><td>57</td><td>2.121</td></tr><tr><td>NP10</td><td>80</td><td>75</td><td>3.535</td></tr><tr><td>NF9</td><td>15</td><td>18</td><td>2.121</td></tr><tr><td>NF10</td><td>13</td><td>20</td><td>4.949</td></tr><tr><td>PA5</td><td>30</td><td>20</td><td>7.071</td></tr><tr><td>PA12</td><td>90</td><td>73</td><td>12.020</td></tr><tr><td>SK5</td><td>35</td><td>42</td><td>4.949</td></tr><tr><td>SR3</td><td>25</td><td>20</td><td>3.535</td></tr><tr><td>TM6</td><td>5</td><td>9</td><td>2.828</td></tr><tr><td>TM7</td><td>100</td><td>97</td><td>2.121</td></tr><tr><td>TM9</td><td>15</td><td>2</td><td>9.192</td></tr><tr><td>TM10</td><td>50</td><td>70</td><td>14.142</td></tr><tr><td>LR1</td><td>5</td><td>1</td><td>2.828</td></tr></tbody></table>
Khan, which is located on the left bank of RI [16]. Another study conducted in the Shorabhaji region, northwest of Iran shows the arsenic contents of 1000 ppb. The authors used geochemical contour mapping to determine As and other elements and found As in both metallic and non-metallic forms [17].

## 3.5 Contamination Index ($C_d$)

It is a method to evaluate and anticipate the regions characterized by irregular or toxic contents of elements. This shows the extent of contamination by taking into consideration the number of parameters crossing the upper allowable levels of hazardous elements and concentrations above these levels. The equation of calculating $C_d$ is as follows [18]:

$$C_d = \sum_{i=1}^{n} C_{fi} \qquad (4)$$

Where,

$$C_{fi} = C_{Ai} / C_{Ni} - 1$$

$C_{fi}$ is the contamination factor for i'th component, $C_{Ai}$ is the analytical value of i'th component, and $C_{Ni}$ is the upper allowable concentration of i'th component.

In this study, $C_d$ is studied for As. Contamination index for ground water was in the range between 0-19. 61.5% of the samples were below the permissible limit of WHO guidelines. The ground water on the basis of $C_d$ values may be arranged into four categories; 8.94% of ground water contained $C_d < 1$ showed low contamination, 12.85% were in the range $1 < C_d < 3$ expressing intermediate contamination, 13.97% were within $3 < C_d < 10$ and 2.79% samples resulted in $C_d > 10$ demonstrating the very high contamination. The ground water samples on the left bank

<figure><img src="image_4.png" /><figcaption>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)</figcaption></figure>
<table><caption>TABLE 3. HEALTH RISK ASSESSMENT THROUGH GROUND WATER CONSUMPTION OF REGIONS LOCATED ON LEFT BANK OF RIVER INDUS IN SINDH PROVINCE</caption><thead><tr><th>No.</th><th>Location Code</th><th>Location</th><th>As Contamination (?g/L)</th><th>EDI (?g/kg-day)</th><th>THQ</th><th>CR</th></tr></thead><tbody><tr><td>1.</td><td>HL3</td><td rowspan="12">Hala</td><td>21</td><td>0.583</td><td>1.94E+00</td><td>8.75E+02</td></tr><tr><td>2.</td><td>HL10</td><td>23</td><td>0.638</td><td>2.13E+00</td><td>9.58E+02</td></tr><tr><td>3.</td><td>HL12</td><td>34</td><td>0.944</td><td>3.15E+00</td><td>1.42E+03</td></tr><tr><td>4.</td><td>HL27</td><td>36</td><td>1</td><td>3.33E+00</td><td>1.50E+03</td></tr><tr><td>5.</td><td>HL40</td><td>36</td><td>1</td><td>3.33E+00</td><td>1.50E+03</td></tr><tr><td>6.</td><td>HL4</td><td>37</td><td>1.027</td><td>3.43E+00</td><td>1.54E+03</td></tr><tr><td>7.</td><td>HL14</td><td>38</td><td>1.055</td><td>3.52E+00</td><td>1.58E+03</td></tr><tr><td>8.</td><td>HL11</td><td>39</td><td>1.083</td><td>3.61E+00</td><td>1.63E+03</td></tr><tr><td>9.</td><td>HL21</td><td>40</td><td>1.111</td><td>3.70E+00</td><td>1.67E+03</td></tr><tr><td>10.</td><td>HL22</td><td>40</td><td>1.111</td><td>3.70E+00</td><td>1.67E+03</td></tr><tr><td>11.</td><td>HL24</td><td>43</td><td>1.194</td><td>3.98E+00</td><td>1.79E+03</td></tr><tr><td>12.</td><td>HL41</td><td>51</td><td>1.416</td><td>4.72E+00</td><td>2.13E+03</td></tr><tr><td>13.</td><td>HL20</td><td>70</td><td>1.944</td><td>6.48E+00</td><td>2.92E+03</td></tr><tr><td>14.</td><td>HL28</td><td>96</td><td>2.666</td><td>8.89E+00</td><td>4.00E+03</td></tr><tr><td>15.</td><td>HL47</td><td rowspan="12">Khairpur</td><td>101</td><td>2.805</td><td>9.35E+00</td><td>4.21E+03</td></tr><tr><td>16.</td><td>HL16</td><td>149</td><td>4.138</td><td>1.38E+01</td><td>6.21E+03</td></tr><tr><td>17.</td><td>KP6</td><td>25</td><td>0.694</td><td>2.31E+00</td><td>1.04E+03</td></tr><tr><td>18.</td><td>KP16</td><td>46</td><td>1.277</td><td>4.26E+00</td><td>1.92E+03</td></tr><tr><td>19.</td><td>MT8</td><td rowspan="12">Matiari</td><td>11</td><td>0.305</td><td>1.02E+00</td><td>4.58E+02</td></tr><tr><td>20.</td><td>MT11</td><td>16</td><td>0.444</td><td>1.48E+00</td><td>6.67E+02</td></tr><tr><td>21.</td><td>MT12</td><td>53</td><td>1.472</td><td>4.91E+00</td><td>2.21E+03</td></tr><tr><td>22.</td><td>MT13</td><td>67</td><td>1.861</td><td>6.20E+00</td><td>2.79E+03</td></tr><tr><td>23.</td><td>MT15</td><td>75</td><td>2.083</td><td>6.94E+00</td><td>3.13E+03</td></tr><tr><td>24.</td><td>MT14</td><td>98</td><td>2.722</td><td>9.07E+00</td><td>4.08E+03</td></tr><tr><td>25.</td><td>NP3</td><td rowspan="12">Nasarpur</td><td>35</td><td>0.972</td><td>3.24E+00</td><td>1.46E+03</td></tr><tr><td>26.</td><td>NP2</td><td>44</td><td>1.222</td><td>4.07E+00</td><td>1.83E+03</td></tr><tr><td>27.</td><td>NP9</td><td>56</td><td>1.555</td><td>5.19E+00</td><td>2.33E+03</td></tr><tr><td>28.</td><td>NP7</td><td>57</td><td>1.583</td><td>5.28E+00</td><td>2.38E+03</td></tr><tr><td>29.</td><td>NP6</td><td>66</td><td>1.833</td><td>6.11E+00</td><td>2.75E+03</td></tr><tr><td>30.</td><td>NP10</td><td>75</td><td>2.083</td><td>6.94E+00</td><td>3.13E+03</td></tr><tr><td>31.</td><td>NF4</td><td rowspan="12">Naushahro Feroz</td><td>18</td><td>0.5</td><td>1.67E+00</td><td>7.50E+02</td></tr><tr><td>32.</td><td>NF3</td><td>20</td><td>0.555</td><td>1.85E+00</td><td>8.33E+02</td></tr><tr><td>33.</td><td>PA7</td><td>11</td><td>0.305</td><td>1.02E+00</td><td>4.58E+02</td></tr><tr><td>34.</td><td>PA5</td><td>20</td><td>0.555</td><td>1.85E+00</td><td>8.33E+02</td></tr><tr><td>35.</td><td>PA3</td><td rowspan="12">Pano Aqil</td><td>27</td><td>0.75</td><td>2.50E+00</td><td>1.13E+03</td></tr><tr><td>36.</td><td>PA4</td><td>37</td><td>1.027</td><td>3.43E+00</td><td>1.54E+03</td></tr><tr><td>37.</td><td>PA1</td><td>73</td><td>2.027</td><td>6.76E+00</td><td>3.04E+03</td></tr><tr><td>38.</td><td>SK5</td><td>42</td><td>1.166</td><td>3.89E+00</td><td>1.75E+03</td></tr><tr><td>39.</td><td>SK2</td><td>195</td><td>5.416</td><td>1.81E+01</td><td>8.13E+03</td></tr><tr><td>40.</td><td>SK8</td><td>204</td><td>5.666</td><td>1.89E+01</td><td>8.50E+03</td></tr><tr><td>41.</td><td>ST1</td><td rowspan="12">Sekhat</td><td>18</td><td>0.5</td><td>1.67E+00</td><td>7.50E+02</td></tr><tr><td>42.</td><td>ST1</td><td>49</td><td>1.361</td><td>4.54E+00</td><td>2.04E+03</td></tr><tr><td>43.</td><td>SK3</td><td>20</td><td>0.555</td><td>1.85E+00</td><td>8.33E+02</td></tr><tr><td>44.</td><td>TM14</td><td rowspan="12">Tando Muhammad Khan</td><td>27</td><td>0.75</td><td>2.50E+00</td><td>1.13E+03</td></tr><tr><td>45.</td><td>TM10</td><td>70</td><td>1.944</td><td>6.48E+00</td><td>2.92E+03</td></tr><tr><td>46.</td><td>TM7</td><td>97</td><td>2.694</td><td>8.98E+00</td><td>4.04E+03</td></tr><tr><td>47.</td><td>TP3</td><td>18</td><td>0.5</td><td>1.67E+00</td><td>7.50E+02</td></tr><tr><td colspan="3">Average</td><td>53.702</td><td>1.492</td><td>4.972</td><td>2237.589</td></tr><tr><td colspan="3">Minimum</td><td>11</td><td>0.305</td><td>1.018</td><td>458.333</td></tr><tr><td colspan="3">Maximum</td><td>204</td><td>5.667</td><td>18.889</td><td>8500</td></tr><tr><td colspan="3">Safe Values</td><td>10 (µg/L) (WHO Guideline)</td><td>-</td><td>1</td><td>1 in 10<sup>-6</sup></td></tr></tbody></table>
of RI have elevated C<sub>d</sub> values because of the higher contents of As in ground water. Mahar et. al. [16] also reported that riverine areas of district Rahim Yar Khan, which is located on the border of Sindh and Punjab provinces, Pakistan were contaminated with As and other impurities.

## 3.6 Health Risk Assessment

The HRA of the left bank RI was performed because it was found more contaminated than the right bank in this study. The people of the studied area consume ground water for their drinking, household and farming purposes. The residents of these areas cannot afford mineral water, therefore, they utilize ground water for their daily use. The estimated daily intake EDI (µg/kg-day) for As is given in Table 3.

EDI values ranged from 0.305-5.667 (µg/kg-day) for As. The highest EDI value of 5.66 (µg/kg-day) was observed in the sample of Sakrand district showing the elevated threat level of As contamination to the local people. The higher EDI values of As can be because of municipal waste, leaching of waste materials in the groundwater, use of excess fertilizers and pesticides by farmers.

The THQ indices were calculated to get a health risk assessment. THQ index for As in potable water was in the range from 1.018-18.889. The results show that the THQ is crossing the safe limits, i.e. (THQ should be less than 1) posing a high health risk to the inhabitants of examined areas. Around, 90% population of the left bank RI is utilizing ground water for their domestic and drinking purposes, hence at high health risk because of As contamination which is “carcinogenic to human beings”.

As is the single available element in the periodic table for which there is a cancer slope factor. CR was calculated in the ground water as shown in Table 3. The CR values ranged from 458.333-8500 with an average value of 2237.589 in the ground water of examined region exhibiting elevated risk. It is reported that CR value 1 in 10<sup>6</sup> is significantly considered [12,19]. The results of this study show that the ground water exhibits high risk in the studied areas of Sindh province when compared to USEPA (2010) guidelines. The cancer risk assessment results of this work show the elevated health risk in the observed areas of Sindh.

## 4. CONCLUSIONS

The kit method was used to analyze the 214 ground water samples from the both sides of RI. Then AAS technique was applied to analyze 83 samples from the left bank of RI. The high THQ and CR values for As indicated, that higher intake of As in ground water may pose chronic toxicity and carcinogenic risk to the local inhabitants.

Our results suggest that the ground water from the left bank of RI areas i.e. Sakrand, Hala, Matiari, TMK, Nasarpur and Sukkur is not safe for drinking without proper treatment.

Hence drinking water quality and continuous assessment should be conducted at regular intervals to check the quality of drinking water.

As kit and atomic absorption spectrometer results are quite similar with 0.707-19 % SD. The contour plot of As concentration (ppb) in ground water is shown by the map of Sindh and it is observed that the higher levels of arsenic are present on the left bank of RI. Contamination index was calculated for ground water of Sindh and found in the range between 0-19.
ACKNOWLEDGMENTS

This project is funded by Pakistan-US Science &
Technology Cooperation Program, and Higher Education
Commission, Pakistan. The authors are thankful to
students of the Department of Chemical Engineering,
Mehran University of Engineering & Technology,
Jamshoro, for their help in the ground water sample
collection.

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