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Risk assessment of arsenic in ground water of Larkana city

Risk assessment of arsenic in ground water of Larkana city GeoloGy, ecoloGy, and landscapes, 2018 Vol . 2, no . 1, 8–14 https://doi.org/10.1080/24749508.2018.1438742 INWASCON OPEN ACCESS a,b a b a Abdul Hameed Kori , Mushtaque Ali Jakhrani , Sarfaraz Ahmed Mahesar , Ghulam Qadir Shar , Muhammad b a b Saqaf Jagirani , Abdul Raheem Shar and Oan Muhammad Sahito a b Institute of chemistry, shah abdul latif University, Khairpur, p akistan; national c entre of excellence in analytical chemistry, University of sindh, Jamshoro, pakistan ABSTRACT ARTICLE HISTORY Received 19 July 2017 Water is an essential component for the survival of humans and animals. Due to industrialization, a ccepted 14 o ctober 2017 water is being contaminated with varying polluting agents, arsenic (As) contamination is one of them. An exclusive study was carried out for the determination of As in groundwater of KEYWORDS Larkana city using microwave-assisted digestion followed by atomic absorption spectrometry arsenic; ground water; (AAS). For that purpose, a total of 110 groundwater samples were collected from 10 union atomic absorption councils (UCs) of the city based on global position system (GPS) method. Results revealed spectrophotometer; microwave assisted digestion that maximum concentration of As was found 17.0  μg/L in UC-6, while in UC-1, UC-2 and UC- 10 the concentration of As was found within the permissible limits of WHO. The minimum and maximum mean concentration of As was found 3.59  μg/L and 6.78  μg/L, respectively. Out of 110 ground water samples of Larkana city, 13 samples were found above the permissible limits (~12% of total samples). Hence, water can be used for drinking purpose with caution. 1. Introduction herbicides, crop disinfectant medicine and other anthro- pogenic activates as smelting, mining and an additive Water is an essential component and building block to usage of As to livestock feed for poultry as well as for sustain life. Water is considered economical develop- wood preservative (Haque, Nabi, Baig, Hayat, & Trefry, ment indicator for third world and developed countries. 2008; Jadhav et al., 2015). The contamination of As in Water has essential usages of biochemical reactions in groundwater has become a grave concern of water purity body, drinking, and home usage (Braune & Xu, 2008). in large areas of the world, especially in Bengal. In the Fresh water consists of 3% of the total water on earth and history of mankind, it has been reported that millions very small quantity is used by human beings (Hinrichsen of Bangladeshi peoples suffering from the poison of As & Tacio, 2002). Water resources have dwindled day by in ground water (Kumar & Shah, 2006). In the litera- day and showing negative impact on every walk of life ture, various countries of world such as Australia, USA, due to urbanization, industrialization and agricultural Argentina, Canada, India, Bengal, Mongolia, China as usage (Azizullah, Khattak, Richter, & Häder, 2011; well as Vietnam have highlighted diseases caused by Guven & Akinci, 2011). Recent reports of UNICEF and As contamination in water (Jakhrani, Malik, Sahito, & WHO have revealed 748 million people around the Jakhrani, 2011; Mukherjee & Fryar, 2008). People of world lacking access to safe water resources and over 2.5 Bengal in both parts of India and Bangladesh are exposed billion people suffering shortage of water supply (Supply to As level up to 4 × 10  μg/ (Kumar & Shah, 2006). In & Programme, 2014). another study, Guo et al. (2001) reported highest con- Since water is polluted and contaminated day by centration of As in the region of Chinese Mongolia up day due to anthropogenic activities, waste disposal to 4000 μg/L (Guo et al., 2001). Taiwan inhabitants bore mismanagement, industrial effluent and usage of pes- hazardous quantities of As in their water samples meas- ticides (Soomro, Siyal, Mirjat, & Sial, 2013). Arsenic ured up to 1800 μg/L (Lin, Sung, Chen, & Guo, 2013). (As) is major concern for human health due to its pres- Researchers also pointed out high level of As 3100 μg/L ence in ground water that is used for drinking purpose. in Vietnams water (Berg et al., 2001). Bleak health Mobilization of As in atmosphere has many factors problems were encountered by Pakistani community of such as natural ways like weathering of rocks, eruption of volcanoes and degradation of biological activities infested water of As. Unfortunately, in different parts (Mukherjee & Fryar, 2008). The man-made activities of Pakistan, high quantity of As was spotted in water like combustion of fuel, coal, coke, using insecticides, (Edition, 2011). Water management is poor throughout CONTACT abdul Hameed Kori hameedchemistry97@gmail.com © 2018 The a uthor(s). published by Informa UK limited, trading as Taylor & Francis Group. This is an open a ccess article distributed under the terms of the creative c ommons a ttribution license (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. GEOLOGY, ECOLOGY, AND LANDSCAPES 9 the country, so public health has major threats of water city. Study area is located north of the River Indus and pollution. Pakistan stood at number 80 among 122 positioned between North (6.41 km) and East (3.43Km) countries regarding water quality. Potable water sources with an area of 18.08 km squares and its coordinates are either ground or surface are contaminated and violates 27°33′30″ N 68°12′40″E. All UCs of Larkana are situated WHO set standards (Azizullah et al., 2011). People of in urban area of the city as shown in Figure 1. Sindh bear more burden of As contamination in water, almost 36% common people exposed to higher quanti- 2.2. Sampling ties as reported by Azizullah et al. (2011). To the best of It is always advised to get groundwater sampling by hand our knowledge no report has been published regarding pumps 5  min in order to remove sand and insoluble the quality of water of Larkana city, Sindh, Pakistan. The impurities as well as depth water must be obtained to purpose of this research was to evaluate the potential contain desired elemental quantities (Shar, Shar, Jatoi, hazards of As in groundwater of die ff rent union councils Shar, & Ghouri, 2014). Water was obtained from hand of Larkana using flame atomic absorption spectrometer pumps having depth 80–100 feet. Aer r ft unning water, (FAAS) and to measure the health risks associated with samples were attained. Plastic bottles were used to collect As contamination. 1000 mL water. Ten UCs of Larkana city were selected to acquire water samples of hand pumps and small 2. Material and method motors used in houses to draw water from the ground 2.1. Description of study area with depth 80 to 120 feet as shown in Figure 2(A) and (B). Method of collection of water samples from differ - Larkana city has situated on right bank of River Indus. ent points of Larkana was done with the help of global Larkana is a district of Sindh province, Pakistan. In positioning system (GPS) in 2014. A total of 110 samples Larkana, there are 4 subdivisions and 48 union coun- were obtained from all UCs of Larkana city. Samples cils (UCs). Larkana is a subtropical area, so hot weather were shifted to laboratory to protect them from atmos- is prevalent in summer and cold in winter. Larkana phere and kept at room temperature to avoid their pH temperature has average from 2 to 48 °C with a mean and temperature. Experimental work was carried out for rainfall >240 mm. There are 1.4 million people living in checking of their chemical parameters in the laboratory. the district Larkana, out of which 28.70% are living in Figure 1. Map of sindh province showing larkana district and study area larkana city. Figure 2. Union councils of larkana city ( a ) and water sampling points (B). 10 A. H. KORI ET AL. 2.3. Chemicals and reagents by As contamination in groundwater up to 1900 μg/L (Farooqi, Masuda, & Firdous, 2007). As also causes Standard solution was prepared from reagents purchased hazardous effect for population in northern areas of from Merck (Darmstadt, Germany) and diluted with Pakistan, where 25% people face perilous effect of As de-ionized water for required concentration of ppm (Azizullah et al., 2011). In Sindh, people are suffering solution for detection of As. from 16–36% , exposing high level of As up to 315 μg/L in some areas of groundwater (Jakhrani et al., 2011). 2.4. Instrumentation According to results obtained in current study, max- imum concentration of As was found 17.0  μg/L from This study was conducted using latest techniques of UC-6 and minimum was 0.1 μg/L from UC-10. However analysis such as Modern Atomic absorption spectro- in UC-1, UC-2, and UC-10 the concentration of As was scopic (Perklin A 700) coupled with Mercury Hydride found within the safe limit recommended by WHO System (MHS-15) to measure the contamination of As (10 μg/L). Out of 110 groundwater samples of Larkana in water. This technique provides a simple and precised city, 13 samples found above the permissible limit, which measurement of quantitative and qualitative analysis of was 11.8% (~12%) of total samples as shown in Table 1. metals present in different samples of water (Fisher, Tu, Comparative mean values of As level in ground water & Baldocchi, 2008). of all UCs showed As within safe limit of WHO rec- ommended value, while UC-5 had maximum mean 2.5. Microwave digestion method 6.79 μg/L and UC-1 had minimum mean 3.58 μg/L. Water is being deteriorated and not safe for 500  mL of water samples were put in PTFE flask, then drinking purpose in populous areas of Pakistan like a fl sks were closed and subjected to microwave irradia- Karachi, Lahore, Peshawar and various other cities tion in closed vessel microwave digestion system using due to various anthropogenic activities. In compar- Milestone Ethos D model (Sorisole-Bg, Italy). Digestion ison to the quality of ground water of Larkana city programme of microwave oven was applied at 100  W is much better and safe than other cities of Pakistan (2 min), at 250 W (6 min), at 400 W (5 min), at 550 W specially in Punjab province, where ground water is (8  min) and ventilation for 8  min. The contents of contaminated more and unsafe for people due to high the  a fl sks were cooled and then diluted to 10  mL with concentration of As. Many studies have reported high (0.2 M) HNO . Similarly reagent blanks were also made by concentration of As in different cities such as Dera Gazi same procedure. Microwave digestion method has supe- Khan (1–29  μg/L), Rahim Yar Khan (20–500  μg/L), riority to conventional digestion method because it takes Bahawalpur (0.5–59  μg/L), Muzffargarh (0.01– less time to digest water sample as well as it has less chance 900  μg/L), Multan (0–50  μg/L), Lahore (0–50  μg/L) of evaporation of elements so more accurate extraction of Faisalabad (1.0–23 μg/L) and Sheikhupura (5–76 μg/L) elements from samples than in conventional method. It as shown in Table 2. also uses less acid for digestion (Guven & Akinci, 2011). In comparison to the ground water quality of Larkana city with the cities of Khyber Pakhtunkhwa province 3. Results and discussion is almost identical with the results of present study. In Pakistan, more than 40% population bear the As The level of As in ground water of Peshawar city was contamination in water. Hence, nation of Pakistan has reported in the range of 5–20 μg/L. In another study the more risk exposure of As. More than 20% people liv- level of As in the ground water of Nowshera city was ing in Punjab are suffering from higher pollution of As reported in the range of 0.01–17.58 μg/L as shown in in either ground or surface water sources but tolerate Table 2. The As contamination of ground water quality higher quantity of As in industrial areas (Azizullah et of various cities of Sindh province with Larkana city al., 2011). Part of East Punjab has been most ae ff cted was found comparatively higher and levels are shown Table 1. arsenic (μg/l) level in ground water of different Ucs of larkana city. UCs UC-1 UC-2 UC-3 UC-4 UC-5 UC-6 UC-7 UC-8 UC-9 UC-10 1 4.43 4.83 1.73 5.50 2.23 1.63 2.97 5.57 1.40 2.63 2 4.17 4.38 3.08 8.43 3.63 3.87 3.40 12.0 3.77 3.40 3 5.30 3.93 4.17 5.23 7.0 16.5 4.10 12.0 5.23 4.87 4 6.0 3.48 5.50 14.6 5.43 17.0 4.90 6.0 5.63 5.23 5 3.50 3.19 7.07 9.07 8.23 6.0 3.27 4.80 6.0 4.13 6 2.20 12.0 6.07 2.67 15.6 3.10 2.73 6.77 7.33 4.17 7 3.03 3.70 13.8 3.83 12.3 4.20 2.17 2.97 1.30 3.50 8 2.27 1.50 2.67 5.57 4.70 3.90 3.03 3.30 4.47 2.67 9 4.33 2.80 2.73 0.39 2.63 2.60 0.61 2.63 13.0 3.33 10 2.30 0.20 8.03 0.67 1.90 6.53 11.7 0.28 7.63 4.27 11 1.90 0.10 0.55 0.50 11.0 3.27 1.10 0.54 13.0 2.83 Mean 3.59 3.65 5.04 5.13 6.79 6.24 3.63 5.17 6.25 3.73 s tandard deviation 1.37 3.19 3.71 4.33 4.54 5.38 2.93 3.96 3.91 0.88 GEOLOGY, ECOLOGY, AND LANDSCAPES 11 Table 2. c oncentration of arsenic in different cities of p akistan. Province City As (μg/L) References punjab d era Gazi Khan 1–29 Malana & Khosa, 2011 Rahimyar Khan 20–500 Mahar, Khuhawar, Jahangir, & Baloch, 2015 Muzffargarh 0.01−900 n ickson, Mcarthur, shrestha, Kyaw-Myint, & l owry, 2005 Bhawalpur 0.5−59 a ziz, 2001 Multan 0–50 lahore 0–50 Faisalabad 1.0–23 sheikhupura 5–76 abbas & cheema, 2015 Khyber pakhtunkhwa peshawar 5–20 shakirullah et al., 2004 nowshera 0.01–17.58 Khan et al., 2015 sindh Khairpur 0.24−315.6 Jakhrani, chaudhray, Malik, Mazari, & Jakhrani, 2009 Gambat 0.01–126  Jakhrani et al., 2011 nawab shah 10–200 Kandhro, s amoon, laghari, chandio, & yousfani, 2016 dadu 8–67 Memon et al., 2016 Tando allahayar 0.04–300 Majidano, arain, Bajaj, Iqbal, & Khuhawar, 2010 Matiari 0.05–50 Uqaili et al., 2012 Jamshoro 13−106 Baig et al., 2009 Thatta 10–200 Rubab, naseem, Khan, Husain, & arain, 2014 Karachi 1–80 Rahman, l ee, & Khan, 1997 larkana 0.01–17 c urrent study in Table 2. As contamination in underground water Table 3. arsenic concentration in ground water of different parts of world. of Matiari and Khairpur cities was found in the range of 0.05–50  μg/L and 0.24–315.6  μg/L, respectively. It Country Concentration μg/L Reference was reported that 37% samples showed As contamina- India 2000 Kumar & shah, 2006 Bangladesh 4 × 10 tion >50 μg/L, whereas 15% samples were highly con- Inner Mongolia,china 4000 Guo et al., 2001 taminated with As 315.6 μg/L. In Gambat, the level of Veitnam 3100 Berg et al., 2001 Taiwan 1800 lin et al., 2013 As in hand pump and tube well water was reported in Thailand 114 Kim, chanpiwat, Hanh, the range of 0.01–126 μg/L and 0.01–38 μg/L, respec- Burma 350 phan, & s thiannop- c ambodia 3500 kao, 2011 tively. In Nawab Shah, As concentrations in the ground note: WHo permissible level for as 10 μg/l. water ranged at 10–200  μg/L. These values were too high to bear the burden of contaminants for local pop- ulation. In upper part of Dadu, ground water quality When comparing concentration of As in ground was found polluted with As contamination. The level water of Larkana city with other countries, it has been of As in the water of Dadu was reported in the range found to be much lower level 10 to 17  μg/L in some of 8–67 μg/L. UCs. But it can be deteriorated with passage of time as The ground water quality of Jamshoro was also neighbouring countries of Pakistan such as India and reported with the contamination of As level with 13.0– Bangladesh where people are suffering from too much 106 μg/L. Research also conducted on the ground water contamination of As 2000 μg/L and 4 × 10  μg/L, respec- assessment of Tando Allahyar, Thatta and Karachi, tively, in ground water. In East Asian countries, high where higher concentration of As was reported 0.04– level of As in ground water of Inner Mongolia, Thailand, 300  μg/L, 10–200  μg/L and 1–80  μg/L, respectively. Burma, Vietnam and Cambodia have been reported. The However, one research study was also reported on As contamination in ground water of Asian countries the quality of ground water of Larkana villages where are shown in Table 3. As had found from 0.40–20.0 μg /L (Akhan, Siddqui, & Usmani, 2006). The study concluded that 10% of 3.1. Pearson correlation coefficient ground water samples were exceeded the limit of WHO permissible level and found unsafe for drink- Table 4 shows Pearson correlation among studied UCs of ing purpose. This study also confirms that results of Larkana city. It was observed that UC-1 showed strong our findings are almost identical with the data previ- relation with UC-4, 6 and 8, less strong relation with ously published on the water of Larkana. Furthermore, UC-10 and weak relation with UC-2, while negative rela- these results confirm the worsen situation of ground tion was detected with UC-3, 5, 7 and 9. UC-2 indicated water quality of Punjab and other cities of Sindh prov- strong relation with UC-5 and significant relation with ince, where higher level of As found in ground water UC-3, 4, 8 and 10. It showed negative relation with UC-6, and people has been suffering from various diseases 7 and 9. In UC-3, it was noticed less strong relation with caused by As contamination. However, ground water UC-5, and 10 while weak significant relation with UC- of Larkana city and few cities of Khyber Pakhtunkhwa 4, 6, 7 and negative relation was observed with UC-9. It are comparatively safe and showed lower concentration was noted that UC-4 had strong relation with UC-6 and of As. weak relation with UC-7 and 10, while negative relation 12 A. H. KORI ET AL. Table 4. pearson correlation of arsenic concentration of different Ucs of larkana city. S. No UC-1 UC-2 UC-3 UC-4 UC-5 UC-6 UC-7 UC-8 UC-9 UC-10 Uc-1 1                   Uc-2 .06 1                 Uc-3 −.12 .128 1               Uc-4 .647* .100 .050 1             Uc-5 −.404 .522 * .368 −.137 1           Uc-6 .661* −.085 .113 .563* −.070 1         Uc-7 −.056 −.250 .296 .029 −.380 .318 1       Uc-8 .584* .476 −.151 .485 −.016 .406 −.125 1     Uc-9 −.248 −.236 −.405 −.492 .054 −.105 −.143 −.422 1   Uc-10 .488 .213 .380 .442 .123 .837** .448 .344 −.017 1 * ** notes: c orrelation is significant at the .05 level.; c orrelation is significant at the .01 level. Table 5. arsenic daily intake from drinking water of different Ucs of larkana city S.No UC-1 UC-2 UC-3 UC-4 UC-5 UC-6 UC-7 UC-8 UC-9 UC-10 as mean 3.59 3.65 5.04 5.13 6.79 6.24 3.63 5.17 6.25 3.73 adI 0.21 0.21 0.29 0.30 0.40 0.36 0.21 0.30 0.36 0.22 notes: s afe as daily intake in water 0.66 μg/day. as (μg/l). was spotted with UC -5 and 9. UC-5 had showed weak contaminated water (Memon et al., 2016; Uqaili, relation with UC-9 and 10, while negative relation was Mughal, & Maheshwari, 2012). observed with UC-6, 7 and 8. It was observed that UC-6 had very strong relation with UC-10 and significant 4. Conclusion relation with UC-7 and 8. UC-7 had shown less strong Keeping in view of the results obtained in this study, it relation with UC-10 and observed negative relation with can be concluded that groundwater of Larkana city is UC-8 and 9. It was observed that UC-8 has less strong safe for drinking purpose than other cities of Pakistan relation with UC-10 and less negative with UC-9 . UC-9 and particularly other cities of the province of Sindh, had indicated negative relation with UC-10. Matrix of where As contamination reported higher. Except UC-5 correlation result showed contamination of ground and UC-6, where high concentration of As found which water with As was man-made activities, erosion of bed showed that 27% sample were contaminated than safe rocks, homes, industrial effluent, agricultural runo ff limit recommended by WHO. Therefore, it may cause activities and solid waste dumping (Srinivasamoorthy, health problems for local inhabitants and pose future Vasanthavigar, Chidambaram, Anandhan, & Sarma, complication of Larkana community, if they continue 2011). drinking unsafe water. Hence, it is recommended to Pakistan state and particularly Sindh government to pay 3.2. Human health risk assessment special attention and protect people from contaminated 3.2.1. Arsenic daily intake (ADI) water and improve solid waste management in order to Total As intake was estimated using following formula keep groundwater of Larkana city safe for future as well as reported by Baig et al. (2009). ADI = mean concen- as increase awareness among farmers to use chemicals tration of As in ground water  ×  daily water intake/ (pesticides) sparingly to keep water safe. mean weight of body. The daily water intake and body weight of common people were assumed average 3.0 to 3.5 litres and 65 kg, respectively. The results of the Acknowledgement ADI are reported in Table 5. It was observed that As Abdul Hameed is highly thankful of Institute of Chemistry accumulation in body was found within safe limit in Shah Abdul Latif University, Khairpur, Pakistan that pro- all UCs of Larkana city and values varied from 0.209 to vided chemicals and instrumentations to carry out this work 0.396 μg/day. Hence, people of Larkana city are much for scientific purpose. safer than the other parts of the country, where higher levels of ADI reported (Abbas & Cheema, 2015; Khan, Disclosure statement Rauf, Muhammad, Qasim, & Din, 2016; Khan, Shah, No potential conflict of interest was reported by the authors. Muhammad, Malik, & Shah, 2015). Comparatively UC-5 and UC-6 showed higher ADI values than rest of the studied UCs. The higher ADI values may cause References health problems in future, such as keratosis, black Abbas, M., & Cheema, K. (2015). Arsenic levels in drinking foot disease, hypertension, cardiovascular, diabe- water and associated health risk in District Sheikhupura, tes, and also some typical skin lesion disease, lungs Pakistan. Journal of Animal and Plant Sciences, 25(3), and bladder cancers in local people consuming As 719–724. GEOLOGY, ECOLOGY, AND LANDSCAPES 13 Akhan, F., Siddqui, I., & Usmani, T. (2006). Contamination Jakhrani, M., Malik, K., Sahito, S., & Jakhrani, A. (2011). of arsenic in public water supply scheme of Larkana and Analytical investigation of arsenic and ioron in hand pump Mirpurkhas districts of Sindh. Journal of the Chemical and tube-well groundwater of Gambat, Sindh, Pakistan. Society of Pakistan, 28(2), 131–138. 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Risk assessment of arsenic in ground water of Larkana city

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GeoloGy, ecoloGy, and landscapes, 2018 Vol . 2, no . 1, 8–14 https://doi.org/10.1080/24749508.2018.1438742 INWASCON OPEN ACCESS a,b a b a Abdul Hameed Kori , Mushtaque Ali Jakhrani , Sarfaraz Ahmed Mahesar , Ghulam Qadir Shar , Muhammad b a b Saqaf Jagirani , Abdul Raheem Shar and Oan Muhammad Sahito a b Institute of chemistry, shah abdul latif University, Khairpur, p akistan; national c entre of excellence in analytical chemistry, University of sindh, Jamshoro, pakistan ABSTRACT ARTICLE HISTORY Received 19 July 2017 Water is an essential component for the survival of humans and animals. Due to industrialization, a ccepted 14 o ctober 2017 water is being contaminated with varying polluting agents, arsenic (As) contamination is one of them. An exclusive study was carried out for the determination of As in groundwater of KEYWORDS Larkana city using microwave-assisted digestion followed by atomic absorption spectrometry arsenic; ground water; (AAS). For that purpose, a total of 110 groundwater samples were collected from 10 union atomic absorption councils (UCs) of the city based on global position system (GPS) method. Results revealed spectrophotometer; microwave assisted digestion that maximum concentration of As was found 17.0  μg/L in UC-6, while in UC-1, UC-2 and UC- 10 the concentration of As was found within the permissible limits of WHO. The minimum and maximum mean concentration of As was found 3.59  μg/L and 6.78  μg/L, respectively. Out of 110 ground water samples of Larkana city, 13 samples were found above the permissible limits (~12% of total samples). Hence, water can be used for drinking purpose with caution. 1. Introduction herbicides, crop disinfectant medicine and other anthro- pogenic activates as smelting, mining and an additive Water is an essential component and building block to usage of As to livestock feed for poultry as well as for sustain life. Water is considered economical develop- wood preservative (Haque, Nabi, Baig, Hayat, & Trefry, ment indicator for third world and developed countries. 2008; Jadhav et al., 2015). The contamination of As in Water has essential usages of biochemical reactions in groundwater has become a grave concern of water purity body, drinking, and home usage (Braune & Xu, 2008). in large areas of the world, especially in Bengal. In the Fresh water consists of 3% of the total water on earth and history of mankind, it has been reported that millions very small quantity is used by human beings (Hinrichsen of Bangladeshi peoples suffering from the poison of As & Tacio, 2002). Water resources have dwindled day by in ground water (Kumar & Shah, 2006). In the litera- day and showing negative impact on every walk of life ture, various countries of world such as Australia, USA, due to urbanization, industrialization and agricultural Argentina, Canada, India, Bengal, Mongolia, China as usage (Azizullah, Khattak, Richter, & Häder, 2011; well as Vietnam have highlighted diseases caused by Guven & Akinci, 2011). Recent reports of UNICEF and As contamination in water (Jakhrani, Malik, Sahito, & WHO have revealed 748 million people around the Jakhrani, 2011; Mukherjee & Fryar, 2008). People of world lacking access to safe water resources and over 2.5 Bengal in both parts of India and Bangladesh are exposed billion people suffering shortage of water supply (Supply to As level up to 4 × 10  μg/ (Kumar & Shah, 2006). In & Programme, 2014). another study, Guo et al. (2001) reported highest con- Since water is polluted and contaminated day by centration of As in the region of Chinese Mongolia up day due to anthropogenic activities, waste disposal to 4000 μg/L (Guo et al., 2001). Taiwan inhabitants bore mismanagement, industrial effluent and usage of pes- hazardous quantities of As in their water samples meas- ticides (Soomro, Siyal, Mirjat, & Sial, 2013). Arsenic ured up to 1800 μg/L (Lin, Sung, Chen, & Guo, 2013). (As) is major concern for human health due to its pres- Researchers also pointed out high level of As 3100 μg/L ence in ground water that is used for drinking purpose. in Vietnams water (Berg et al., 2001). Bleak health Mobilization of As in atmosphere has many factors problems were encountered by Pakistani community of such as natural ways like weathering of rocks, eruption of volcanoes and degradation of biological activities infested water of As. Unfortunately, in different parts (Mukherjee & Fryar, 2008). The man-made activities of Pakistan, high quantity of As was spotted in water like combustion of fuel, coal, coke, using insecticides, (Edition, 2011). Water management is poor throughout CONTACT abdul Hameed Kori hameedchemistry97@gmail.com © 2018 The a uthor(s). published by Informa UK limited, trading as Taylor & Francis Group. This is an open a ccess article distributed under the terms of the creative c ommons a ttribution license (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. GEOLOGY, ECOLOGY, AND LANDSCAPES 9 the country, so public health has major threats of water city. Study area is located north of the River Indus and pollution. Pakistan stood at number 80 among 122 positioned between North (6.41 km) and East (3.43Km) countries regarding water quality. Potable water sources with an area of 18.08 km squares and its coordinates are either ground or surface are contaminated and violates 27°33′30″ N 68°12′40″E. All UCs of Larkana are situated WHO set standards (Azizullah et al., 2011). People of in urban area of the city as shown in Figure 1. Sindh bear more burden of As contamination in water, almost 36% common people exposed to higher quanti- 2.2. Sampling ties as reported by Azizullah et al. (2011). To the best of It is always advised to get groundwater sampling by hand our knowledge no report has been published regarding pumps 5  min in order to remove sand and insoluble the quality of water of Larkana city, Sindh, Pakistan. The impurities as well as depth water must be obtained to purpose of this research was to evaluate the potential contain desired elemental quantities (Shar, Shar, Jatoi, hazards of As in groundwater of die ff rent union councils Shar, & Ghouri, 2014). Water was obtained from hand of Larkana using flame atomic absorption spectrometer pumps having depth 80–100 feet. Aer r ft unning water, (FAAS) and to measure the health risks associated with samples were attained. Plastic bottles were used to collect As contamination. 1000 mL water. Ten UCs of Larkana city were selected to acquire water samples of hand pumps and small 2. Material and method motors used in houses to draw water from the ground 2.1. Description of study area with depth 80 to 120 feet as shown in Figure 2(A) and (B). Method of collection of water samples from differ - Larkana city has situated on right bank of River Indus. ent points of Larkana was done with the help of global Larkana is a district of Sindh province, Pakistan. In positioning system (GPS) in 2014. A total of 110 samples Larkana, there are 4 subdivisions and 48 union coun- were obtained from all UCs of Larkana city. Samples cils (UCs). Larkana is a subtropical area, so hot weather were shifted to laboratory to protect them from atmos- is prevalent in summer and cold in winter. Larkana phere and kept at room temperature to avoid their pH temperature has average from 2 to 48 °C with a mean and temperature. Experimental work was carried out for rainfall >240 mm. There are 1.4 million people living in checking of their chemical parameters in the laboratory. the district Larkana, out of which 28.70% are living in Figure 1. Map of sindh province showing larkana district and study area larkana city. Figure 2. Union councils of larkana city ( a ) and water sampling points (B). 10 A. H. KORI ET AL. 2.3. Chemicals and reagents by As contamination in groundwater up to 1900 μg/L (Farooqi, Masuda, & Firdous, 2007). As also causes Standard solution was prepared from reagents purchased hazardous effect for population in northern areas of from Merck (Darmstadt, Germany) and diluted with Pakistan, where 25% people face perilous effect of As de-ionized water for required concentration of ppm (Azizullah et al., 2011). In Sindh, people are suffering solution for detection of As. from 16–36% , exposing high level of As up to 315 μg/L in some areas of groundwater (Jakhrani et al., 2011). 2.4. Instrumentation According to results obtained in current study, max- imum concentration of As was found 17.0  μg/L from This study was conducted using latest techniques of UC-6 and minimum was 0.1 μg/L from UC-10. However analysis such as Modern Atomic absorption spectro- in UC-1, UC-2, and UC-10 the concentration of As was scopic (Perklin A 700) coupled with Mercury Hydride found within the safe limit recommended by WHO System (MHS-15) to measure the contamination of As (10 μg/L). Out of 110 groundwater samples of Larkana in water. This technique provides a simple and precised city, 13 samples found above the permissible limit, which measurement of quantitative and qualitative analysis of was 11.8% (~12%) of total samples as shown in Table 1. metals present in different samples of water (Fisher, Tu, Comparative mean values of As level in ground water & Baldocchi, 2008). of all UCs showed As within safe limit of WHO rec- ommended value, while UC-5 had maximum mean 2.5. Microwave digestion method 6.79 μg/L and UC-1 had minimum mean 3.58 μg/L. Water is being deteriorated and not safe for 500  mL of water samples were put in PTFE flask, then drinking purpose in populous areas of Pakistan like a fl sks were closed and subjected to microwave irradia- Karachi, Lahore, Peshawar and various other cities tion in closed vessel microwave digestion system using due to various anthropogenic activities. In compar- Milestone Ethos D model (Sorisole-Bg, Italy). Digestion ison to the quality of ground water of Larkana city programme of microwave oven was applied at 100  W is much better and safe than other cities of Pakistan (2 min), at 250 W (6 min), at 400 W (5 min), at 550 W specially in Punjab province, where ground water is (8  min) and ventilation for 8  min. The contents of contaminated more and unsafe for people due to high the  a fl sks were cooled and then diluted to 10  mL with concentration of As. Many studies have reported high (0.2 M) HNO . Similarly reagent blanks were also made by concentration of As in different cities such as Dera Gazi same procedure. Microwave digestion method has supe- Khan (1–29  μg/L), Rahim Yar Khan (20–500  μg/L), riority to conventional digestion method because it takes Bahawalpur (0.5–59  μg/L), Muzffargarh (0.01– less time to digest water sample as well as it has less chance 900  μg/L), Multan (0–50  μg/L), Lahore (0–50  μg/L) of evaporation of elements so more accurate extraction of Faisalabad (1.0–23 μg/L) and Sheikhupura (5–76 μg/L) elements from samples than in conventional method. It as shown in Table 2. also uses less acid for digestion (Guven & Akinci, 2011). In comparison to the ground water quality of Larkana city with the cities of Khyber Pakhtunkhwa province 3. Results and discussion is almost identical with the results of present study. In Pakistan, more than 40% population bear the As The level of As in ground water of Peshawar city was contamination in water. Hence, nation of Pakistan has reported in the range of 5–20 μg/L. In another study the more risk exposure of As. More than 20% people liv- level of As in the ground water of Nowshera city was ing in Punjab are suffering from higher pollution of As reported in the range of 0.01–17.58 μg/L as shown in in either ground or surface water sources but tolerate Table 2. The As contamination of ground water quality higher quantity of As in industrial areas (Azizullah et of various cities of Sindh province with Larkana city al., 2011). Part of East Punjab has been most ae ff cted was found comparatively higher and levels are shown Table 1. arsenic (μg/l) level in ground water of different Ucs of larkana city. UCs UC-1 UC-2 UC-3 UC-4 UC-5 UC-6 UC-7 UC-8 UC-9 UC-10 1 4.43 4.83 1.73 5.50 2.23 1.63 2.97 5.57 1.40 2.63 2 4.17 4.38 3.08 8.43 3.63 3.87 3.40 12.0 3.77 3.40 3 5.30 3.93 4.17 5.23 7.0 16.5 4.10 12.0 5.23 4.87 4 6.0 3.48 5.50 14.6 5.43 17.0 4.90 6.0 5.63 5.23 5 3.50 3.19 7.07 9.07 8.23 6.0 3.27 4.80 6.0 4.13 6 2.20 12.0 6.07 2.67 15.6 3.10 2.73 6.77 7.33 4.17 7 3.03 3.70 13.8 3.83 12.3 4.20 2.17 2.97 1.30 3.50 8 2.27 1.50 2.67 5.57 4.70 3.90 3.03 3.30 4.47 2.67 9 4.33 2.80 2.73 0.39 2.63 2.60 0.61 2.63 13.0 3.33 10 2.30 0.20 8.03 0.67 1.90 6.53 11.7 0.28 7.63 4.27 11 1.90 0.10 0.55 0.50 11.0 3.27 1.10 0.54 13.0 2.83 Mean 3.59 3.65 5.04 5.13 6.79 6.24 3.63 5.17 6.25 3.73 s tandard deviation 1.37 3.19 3.71 4.33 4.54 5.38 2.93 3.96 3.91 0.88 GEOLOGY, ECOLOGY, AND LANDSCAPES 11 Table 2. c oncentration of arsenic in different cities of p akistan. Province City As (μg/L) References punjab d era Gazi Khan 1–29 Malana & Khosa, 2011 Rahimyar Khan 20–500 Mahar, Khuhawar, Jahangir, & Baloch, 2015 Muzffargarh 0.01−900 n ickson, Mcarthur, shrestha, Kyaw-Myint, & l owry, 2005 Bhawalpur 0.5−59 a ziz, 2001 Multan 0–50 lahore 0–50 Faisalabad 1.0–23 sheikhupura 5–76 abbas & cheema, 2015 Khyber pakhtunkhwa peshawar 5–20 shakirullah et al., 2004 nowshera 0.01–17.58 Khan et al., 2015 sindh Khairpur 0.24−315.6 Jakhrani, chaudhray, Malik, Mazari, & Jakhrani, 2009 Gambat 0.01–126  Jakhrani et al., 2011 nawab shah 10–200 Kandhro, s amoon, laghari, chandio, & yousfani, 2016 dadu 8–67 Memon et al., 2016 Tando allahayar 0.04–300 Majidano, arain, Bajaj, Iqbal, & Khuhawar, 2010 Matiari 0.05–50 Uqaili et al., 2012 Jamshoro 13−106 Baig et al., 2009 Thatta 10–200 Rubab, naseem, Khan, Husain, & arain, 2014 Karachi 1–80 Rahman, l ee, & Khan, 1997 larkana 0.01–17 c urrent study in Table 2. As contamination in underground water Table 3. arsenic concentration in ground water of different parts of world. of Matiari and Khairpur cities was found in the range of 0.05–50  μg/L and 0.24–315.6  μg/L, respectively. It Country Concentration μg/L Reference was reported that 37% samples showed As contamina- India 2000 Kumar & shah, 2006 Bangladesh 4 × 10 tion >50 μg/L, whereas 15% samples were highly con- Inner Mongolia,china 4000 Guo et al., 2001 taminated with As 315.6 μg/L. In Gambat, the level of Veitnam 3100 Berg et al., 2001 Taiwan 1800 lin et al., 2013 As in hand pump and tube well water was reported in Thailand 114 Kim, chanpiwat, Hanh, the range of 0.01–126 μg/L and 0.01–38 μg/L, respec- Burma 350 phan, & s thiannop- c ambodia 3500 kao, 2011 tively. In Nawab Shah, As concentrations in the ground note: WHo permissible level for as 10 μg/l. water ranged at 10–200  μg/L. These values were too high to bear the burden of contaminants for local pop- ulation. In upper part of Dadu, ground water quality When comparing concentration of As in ground was found polluted with As contamination. The level water of Larkana city with other countries, it has been of As in the water of Dadu was reported in the range found to be much lower level 10 to 17  μg/L in some of 8–67 μg/L. UCs. But it can be deteriorated with passage of time as The ground water quality of Jamshoro was also neighbouring countries of Pakistan such as India and reported with the contamination of As level with 13.0– Bangladesh where people are suffering from too much 106 μg/L. Research also conducted on the ground water contamination of As 2000 μg/L and 4 × 10  μg/L, respec- assessment of Tando Allahyar, Thatta and Karachi, tively, in ground water. In East Asian countries, high where higher concentration of As was reported 0.04– level of As in ground water of Inner Mongolia, Thailand, 300  μg/L, 10–200  μg/L and 1–80  μg/L, respectively. Burma, Vietnam and Cambodia have been reported. The However, one research study was also reported on As contamination in ground water of Asian countries the quality of ground water of Larkana villages where are shown in Table 3. As had found from 0.40–20.0 μg /L (Akhan, Siddqui, & Usmani, 2006). The study concluded that 10% of 3.1. Pearson correlation coefficient ground water samples were exceeded the limit of WHO permissible level and found unsafe for drink- Table 4 shows Pearson correlation among studied UCs of ing purpose. This study also confirms that results of Larkana city. It was observed that UC-1 showed strong our findings are almost identical with the data previ- relation with UC-4, 6 and 8, less strong relation with ously published on the water of Larkana. Furthermore, UC-10 and weak relation with UC-2, while negative rela- these results confirm the worsen situation of ground tion was detected with UC-3, 5, 7 and 9. UC-2 indicated water quality of Punjab and other cities of Sindh prov- strong relation with UC-5 and significant relation with ince, where higher level of As found in ground water UC-3, 4, 8 and 10. It showed negative relation with UC-6, and people has been suffering from various diseases 7 and 9. In UC-3, it was noticed less strong relation with caused by As contamination. However, ground water UC-5, and 10 while weak significant relation with UC- of Larkana city and few cities of Khyber Pakhtunkhwa 4, 6, 7 and negative relation was observed with UC-9. It are comparatively safe and showed lower concentration was noted that UC-4 had strong relation with UC-6 and of As. weak relation with UC-7 and 10, while negative relation 12 A. H. KORI ET AL. Table 4. pearson correlation of arsenic concentration of different Ucs of larkana city. S. No UC-1 UC-2 UC-3 UC-4 UC-5 UC-6 UC-7 UC-8 UC-9 UC-10 Uc-1 1                   Uc-2 .06 1                 Uc-3 −.12 .128 1               Uc-4 .647* .100 .050 1             Uc-5 −.404 .522 * .368 −.137 1           Uc-6 .661* −.085 .113 .563* −.070 1         Uc-7 −.056 −.250 .296 .029 −.380 .318 1       Uc-8 .584* .476 −.151 .485 −.016 .406 −.125 1     Uc-9 −.248 −.236 −.405 −.492 .054 −.105 −.143 −.422 1   Uc-10 .488 .213 .380 .442 .123 .837** .448 .344 −.017 1 * ** notes: c orrelation is significant at the .05 level.; c orrelation is significant at the .01 level. Table 5. arsenic daily intake from drinking water of different Ucs of larkana city S.No UC-1 UC-2 UC-3 UC-4 UC-5 UC-6 UC-7 UC-8 UC-9 UC-10 as mean 3.59 3.65 5.04 5.13 6.79 6.24 3.63 5.17 6.25 3.73 adI 0.21 0.21 0.29 0.30 0.40 0.36 0.21 0.30 0.36 0.22 notes: s afe as daily intake in water 0.66 μg/day. as (μg/l). was spotted with UC -5 and 9. UC-5 had showed weak contaminated water (Memon et al., 2016; Uqaili, relation with UC-9 and 10, while negative relation was Mughal, & Maheshwari, 2012). observed with UC-6, 7 and 8. It was observed that UC-6 had very strong relation with UC-10 and significant 4. Conclusion relation with UC-7 and 8. UC-7 had shown less strong Keeping in view of the results obtained in this study, it relation with UC-10 and observed negative relation with can be concluded that groundwater of Larkana city is UC-8 and 9. It was observed that UC-8 has less strong safe for drinking purpose than other cities of Pakistan relation with UC-10 and less negative with UC-9 . UC-9 and particularly other cities of the province of Sindh, had indicated negative relation with UC-10. Matrix of where As contamination reported higher. Except UC-5 correlation result showed contamination of ground and UC-6, where high concentration of As found which water with As was man-made activities, erosion of bed showed that 27% sample were contaminated than safe rocks, homes, industrial effluent, agricultural runo ff limit recommended by WHO. Therefore, it may cause activities and solid waste dumping (Srinivasamoorthy, health problems for local inhabitants and pose future Vasanthavigar, Chidambaram, Anandhan, & Sarma, complication of Larkana community, if they continue 2011). drinking unsafe water. Hence, it is recommended to Pakistan state and particularly Sindh government to pay 3.2. Human health risk assessment special attention and protect people from contaminated 3.2.1. Arsenic daily intake (ADI) water and improve solid waste management in order to Total As intake was estimated using following formula keep groundwater of Larkana city safe for future as well as reported by Baig et al. (2009). ADI = mean concen- as increase awareness among farmers to use chemicals tration of As in ground water  ×  daily water intake/ (pesticides) sparingly to keep water safe. mean weight of body. The daily water intake and body weight of common people were assumed average 3.0 to 3.5 litres and 65 kg, respectively. The results of the Acknowledgement ADI are reported in Table 5. It was observed that As Abdul Hameed is highly thankful of Institute of Chemistry accumulation in body was found within safe limit in Shah Abdul Latif University, Khairpur, Pakistan that pro- all UCs of Larkana city and values varied from 0.209 to vided chemicals and instrumentations to carry out this work 0.396 μg/day. Hence, people of Larkana city are much for scientific purpose. safer than the other parts of the country, where higher levels of ADI reported (Abbas & Cheema, 2015; Khan, Disclosure statement Rauf, Muhammad, Qasim, & Din, 2016; Khan, Shah, No potential conflict of interest was reported by the authors. Muhammad, Malik, & Shah, 2015). Comparatively UC-5 and UC-6 showed higher ADI values than rest of the studied UCs. The higher ADI values may cause References health problems in future, such as keratosis, black Abbas, M., & Cheema, K. (2015). Arsenic levels in drinking foot disease, hypertension, cardiovascular, diabe- water and associated health risk in District Sheikhupura, tes, and also some typical skin lesion disease, lungs Pakistan. Journal of Animal and Plant Sciences, 25(3), and bladder cancers in local people consuming As 719–724. GEOLOGY, ECOLOGY, AND LANDSCAPES 13 Akhan, F., Siddqui, I., & Usmani, T. (2006). Contamination Jakhrani, M., Malik, K., Sahito, S., & Jakhrani, A. (2011). of arsenic in public water supply scheme of Larkana and Analytical investigation of arsenic and ioron in hand pump Mirpurkhas districts of Sindh. Journal of the Chemical and tube-well groundwater of Gambat, Sindh, Pakistan. Society of Pakistan, 28(2), 131–138. 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Journal

Geology Ecology and Landscapes – Taylor & Francis

Published: Jan 2, 2018

Keywords: Arsenic; ground water; atomic absorption spectrophotometer; microwave assisted digestion

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