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Presented to: Dr. Abida Farooqi

Presented by: Atta Rasool

Faculty of Biological Sciences Quaid-i-Azam University Islamabad

Department of Environmental sceinces

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Water Quality Analysis and Hydrogeological Control on Regional Distribution of Arsenic in Groundwater of Tehsil Mailsi,Punjab.

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ContentsIntroductionMaterials and MethodsResultsConclusionRecommendationsReferences

Arsenic and Water pollution

Geochemical Processes of Arsenic Mobilization

Adsorption and Desorption ProcessPrecipitation and Dissolution ProcessesOxidation and Reduction

Pathways of Contact of heavy metals with organism

There are three principal ways : Atmospheric deposition in water and soil.Drinking contaminated water and crop irrigation.Accumulation in the food web

Impact of Arsenic and heavy metals on the environment It depends on: Environmental availability Toxicity Accumulation phenomena Geochemical transfer Mobility pathways

Arsenic can damage the human nervous system.It is carcinogenic and it can also cause various types of cancer (Apo Saak, 2001).Human common diseases such as carcinogen skin, bladder, kidney, lung, liver Vomiting, Diarrhea, Muscular pain, ,Heart attack and nervous system problems

Status of Pakistan with Respect to Drinking Water Quality

According to a National Conservation Strategy study, about 40% of diseases in Pakistan are water borne.

Report mentions that 25-30% hospital admissions are connected to water-borne bacteria and parasitic conditions (Buszka et al.,1990).

The per capita water availability has dropped from 5,600 m3 to 1,000 m3.

Objectives of the StudyTo determine groundwater quality of the study area by comparing with WHO and EPA standards. Groundwater quality will be accessed by piper plots and stiff diagrams.

To determine irrigation water quality of the study area by comparing with national irrigation quality standards. To determine arsenic concentrations of the groundwater, it is hypothesized that groundwater will be enriched in arsenic because of the presence of arsenic in groundwater in neighboring area, as reported by PCRWR.

ContTo investigate sources of groundwater pollution and to address the possible mechanism of arsenic contamination in the area depending upon the geochemical studies.

To identify possible contamination sources using different statistical techniques.

To calculate health risk assessment under the influence of As contamination in the study area.

Study Area

Sampling Sites

Fig. Sampling points from the study area Mailsi and Sargana.

Sample AnalysisPhysical ParameterspHECTDS

Chemical Parameters

AlkalinityChlorideTotal HardnessCa,Mg, Na, KNitratesSulphatesHeavy MetalsArsenic analysis

Multivariate Statistical Analysis

MVSP and SPSS Statistic software were used for Principle Component analysis Correlation Matrix and Hierarchical cluster analysis.

Arc GIS and Surfer software were used to make distribution maps of Physicochemical parameters and arsenic.

Health Risk AssessmentExposure AssessmentFor this purpose, average daily dose (ADD) of As through drinking water intake is calculated by the following equation: ADD= C IR ED EF/ BW AT

Human Health Risk AssessmentIn this study, both chronic and carcinogenic risk levels were also assessed. Generally, HQ can be calculated by the following formula (US EPA 1998). HQ = ADD/RfDCancer risk (CR) was calculated using the formula: CR=ADD CSF

Physical and Major ion ChemistrySite1.Sargana

Table(3.1):Max,Min and Mean of all physicochemical parameters in SarganaSite2.Mailsi

Table (3.2): Max, Mini and Mean of all physicochemical parameters in MailsiNote: All values are in (mg/L) Except EC (ms/cm)Analytical Results of Drinking Water

Heavy Metal ConcentrationsSite1.Sargana

Parameters Max Mini MeanCd 0.110.0390.075Zn 4.450.1030.769Ni 0.0970.0120.04Fe 2.9180.2671.51Pb 0.230.050.103Mn 0.09610.00240.021Cr 0.0640.0010.0303Co 0.00150.00010.00054Cu 0.2560.00160.0498Table(3.3):Max, Mini and Mean of heavy metal in Sargana area groundwater samplesSite2.Mailsi

Parameters Max Mini MeanCd 0.1110.0460.075

Zn 4.870.02030.751Ni 0.0870.0110.0345Fe 2.520.0460.95Pb 0.20.010.0921Mn 0.08120.00120.0145Cr 0.0610.0070.0283Co 0.00150.00010.0005Cu 0.2730.00440.0489

Table (3.4): Max, Mini and Mean of heavy metal in Mailsi area groundwater samplesNote: All the values are in (mg/L)

Arsenic ConcentrationsTable (3.5): Range of As of Sargana and Mailsi samples Sample localityMaxMinMeanStd. DeviationSargana78714166.4208.5Mailsi82811130.7182.5

Note: The values of Arsenic is in ug/L

Correlations among Physicochemical Parameters

Fig. (3.1)Positive Correlation of SO-24 vs Ca+2,SO-24 vsMg+2,SO4vs Cl- and Na+ vs HCO-3 of both sargana and Mailsi Correlations among Arsenic

Fig.(3.2a) Positive Correlation of As vs HCO-3 ,As vs SO4Fig.(3.2b)Negative Correlation of As vs Fe and As vs Mn

Water Type for Drinking WaterWater type as indicated by Piper plot diagram as shown in Figure. The water Chemistry of the area is Ca-HCO3Na+ type with elevated concentrations of SO4 .Fig . Piper plot for major cations and anions. Circles are symbol for Sargana and Triangles are symbol for Mailsi.The cation profile plotted to the left of the center line and anion profile to the right. Stiff patterns are useful in making a rapid visual comparison between water from different sources as shown in Fig.

Fig. Water quality of drinking water in Sargana and Mailsi by Stiff Diagram.Stiff plot for SARGANA (a)Stiff plot for MAILSI (b)

Spatial Distribution of Arsenic in Drinking water samplesWhen lines ae near, they show rapid change in concentration, while far the lines are change will b gradual.The number of plume indicates concentrated amount of contaminant and variation of values show in legend.The variation of arsenic concentrations in drinkingwater show in 3D arsenic contour map in which dome shape structure which show maximum concentration of arsenic in Mailsi and sargana area.Fig. Arsenic variations in groundwater through contour map.

Fig. Arsenic concentration in groundwater in 3D contour.

Analytical results of irrigation water Physical and Major ion Chemistry Site1.Sargana

Fig: Box-plots showing mean and range of Sargana irrigation water samples

Site2.Mailsi

Fig: Box-plots showing mean and range of Mailsi irrigation water samples

Arsenic Concentrations in Irrigation WaterSargana SiteMailsi Site

Fig: Box-plots showing mean and range of As in Sargana and MailsiSpatial distribution of As in irrigation groundwater

When lines ae near, they show rapid change in concentration, while far the lines are change will b gradual.The number of plume indicates concentrated amount of contaminant and variation of values show in legend.Fig.Spatial distribution of As in irrigation groundwater

Water Quality for IrrigationWater type as indicated by Piper plot diagram as shown in Fig. The water Chemistry of the area is Na-Ca-HCO3-SO4.

IW = Irrigation water and G = GroupFig.Classification of Irrigation water of the study area according to Pipers scheme.The cation profile plotted to the left of the center line and anion profile to the right. cationsare plotted in milliequivalents per liter on the left side of the zero axis in which sodium is dominant in Sargana and Mailsi study area, andanionsare plotted on the right side in which sulphate is dominant in sargana and Mailsi study area in irrigation water samples.

Fig.Water quality of irrigation water in Sargana and Mailsi by Stiff Diagram

Sodium Adsorption Ratio (SAR)The SAR values in Mailsi and Sargana irrigation water samples below the basic guide line value of SAR by (Richard, 1954). Sodium PercentageIt is observed that about 2 samples in Sargana lies between 40 to 60 percent sodium have permissible water class and other samples lies between 60 to 80 percent of sodium the water class is doubtful. 4 samples of mailsi irrigation water lies between 60 to 80 percent sodium.Residual Sodium Carbonate (RSC)According to the US Department of Agriculture, water having more than 2.5 epm of RSC is not suitable for irrigation purposes, 16% samples in sargana area exceeded 2.5 emp and other 84% samples are within limit and in Mailsi irrigation samples RSC below the limit 2.5 emp .The irrigation water of both area is suitable for irrigation the crops on the basis of RSC result in my study as shown in Tables.

Table .Range of irrigation quality parameters of ground water, Sargana.

.Table .Range of irrigation quality parameters of ground water, Maisi

Arsenic Health Risk AssessmentThe calculated result of average daily doze (ADD) in my study area suggest that, where people have consumed drinking water contaminated with As.In my study area the calculated HQ through consumption of As contamination in drinking water was found highest value(76.6) in Mailsi area as compare to the Sargana area HQ values.The results indicate that CR values(3.510-2 mg/kg/day) in drinking water of my study area Mailsi were higher than Sargana except for the 15% people of Mailsi area that showed medium risk, when compared with US EPA approach(1999).as shown in Tables.

Table.Ranges of As,ADD,HQ,CR in drinking water samples of Sargana.

.Table. Ranges of As, ADD, HQ,CR in drinking water samples of Mailsi.

Multivariate Statistical AnalysisHierarchical Cluster AnalysisThe group(G1) include pH ,K ,Ec, Fe, Mn, Cr, Ni, Cu, Pb, Cd and Zn, the second group (G2) include NO3, Mg, Ca and Cl, while the third group (G3) include As,TDS,HCO3,TH,SO4 and Na as shown in Fig. In cluster analysis similar objects fall into the same class and dissimilar group fall into other group (Danielsson et al., 1999) levels of similarity at which observations are merged are used to construct a dendogram (Chen et al., 2007).

Fig.Cluster Analysis of all study parameters in Groundwater samples.

Principle Component Analysis.PCA was employed to compare the compositional patterns between the ground water systems and identification of the factors that influence each one. Eight components of PCA analysis showed 60.2% of the variance on the resulted data of ground water samples as shown in Table.VF1VF2VF3VF4VF5VF6VF7VF8pH0.127-0.137-0.014-0.0190.248-0.0050.1660.303Ec0.416-0.807-0.287-0.027-0.2130.1120.104-0.144TDS0.396-0.805-0.278-0.019-0.2000.1300.083-0.128TH0.9790.1680.0340.1000.0050.0290.0170.015Ca H0.9730.1870.0070.1020.0130.0420.0050.008Mg H0.9620.0930.1240.084-0.023-0.0180.0550.038Ca+20.9730.1870.0070.1020.0130.0420.0050.008Mg+20.9620.0930.1230.084-0.025-0.0190.0560.037HCO3-0.270-0.4780.195-0.3890.2410.315-0.0060.240Cl0.1960.098-0.0990.156-0.3740.248-0.293-0.121SO40.6810.2170.090-0.075-0.140-0.1430.0830.039NO30.1320.404-0.062-0.114-0.0980.149-0.0180.188Na0.0390.162-0.083-0.500-0.018-0.017-0.115-0.122K0.0610.0800.1180.010-0.0280.445-0.3020.047Co0.1030.2600.459-0.3130.2630.2120.090-0.356Cu0.088-0.3130.2040.2780.244-0.1460.192-0.139Mn0.0290.0260.1660.0630.081-0.086-0.184-0.032Cr-0.0060.257-0.590-0.0990.1960.0660.1510.032Fe0.523-0.190-0.379-0.0260.426-0.380-0.465-0.066Pb0.286-0.200-0.013-0.2380.2530.123-0.101-0.102Zn0.2650.1700.036-0.350-0.121-0.2130.193-0.210Ni-0.162-0.0990.1540.4740.3760.2550.034-0.147Cd0.0500.382-0.6330.0100.2310.2630.187-0.037As0.134-0.4510.243-0.1620.033-0.086-0.0180.195Eigenvalue6.1432.6141.5301.1091.0090.8620.6540.526Variability (%)25.59610.8916.3754.6234.2023.5902.7242.191Cumulative %25.59636.48842.86247.48551.68755.27758.00160.192

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Table: PCA. Varimax loading matrix .Clusters of loadings are marked in bold

ConclusionThe current study demonstrates that groundwater from the Mailsi and Sargana areas of Punjab province are heavily contaminated with SO4- , HCO3- , As and heavy metals such as Pb, Cd, Fe, Ni and Zn. The As concentrations showed an increasing trend due to extensive usage of pesticides, fertilizers and wastewater for irrigation purpose. The maximum concentration of As (up to 828 ppb) was recorded in Mailsi. The concentration of calcium and magnesium crossed the permissible limits due to the abundance of calcite and dolomite minerals and rocks in the conducted study. In disparity, the EC values in all samples were above the safe limits (WHO). High concentrations of sulphates were observed in groundwater due to vehicular exhaust, fertilizer and wastewater used for irrigation purpose. In the Tehsil Mailsi samples, negative correlation was observed between dissolved As and Mn, signifying of re-adsorption of As released by dissolution of Mn-oxyhydroxides and As positive correlation with HCO3-. The type of water that predominates in the study area is Na-Ca-HCO3-SO4. The water quality used for irrigation is determined by various parameters including SAR, % Na, RSC and salinity hazard. All the multivariate analysis including CA, PCA showed that high concentration of heavy metals including Pb, Fe, Mn, Cu, Cd, Ni, Ca, K and Na were observed due various anthropogenic sources. These anthropogenic sources were widespread application of pesticides, fertilizers and wastewater for irrigation purpose. Hence, it can be concluded that the groundwater of Tehsil Mailsi and Sargana is not fit for drinking purpose. It is heavily contaminated with various heavy metals and arsenic. The chief sources of these heavy metals and arsenic were vehicular exhaust and agriculture activities. The results of the field survey showed that the current study area had very low literacy rate. Most of the people lacked awareness regarding the status of drinking water quality and its impact on human health.

Recommendations and SuggestionsThere is an urgent need of integrated approach to fight the arsenic contamination in a crises situation and formulation of national action plan for arsenic alleviation. In the rural area some low cost household level filters for treating arsenic contaminated water should be introduced. Although Pakistan Council of Research in Water Resources (PCRWR) in collaboration with UNICEF has developed low cost household level filters for treating arsenic contaminated water called as clay pitcher arsenic removal filter and elevate awareness among arsenic contamination affected communities. The problem related to physical parameters can be easily eliminated by the proper filtration process and removal of sediments. Proper water filtration system for drinking water should be installed in every village of Sargana and Mailsi. Drinking water should always be clean and free of contamination to ensure proper health and wellness.Proper management and monitoring of all water supply pipes and sewage pipes so that in case of any leakage, immediately replacement of pipes is possible as to prevent any serious outbreak.Periodic cleaning of the water tanks should be undertaken so that biological contaminations could be minimized.

Future Prospects of the researchThe study has left some shingle unturned and it has motivated the thinking that it should be extended further in order to get more groundwater samples and cover more area of Tehsil Maillsi for temporal variations in drinking water and irrigation water and discussed different factors affecting these variations. In future, seasonal variations should be checked along with the variation trends in pre and post monsoon seasons because cyclic variation trends of different type depending on different seasons and checked its affect on human health.

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Sheet1ParameterRangeMeanSTDSAR6.3-8.97.51.1RSC(me/L)1.1-6.73.021.8%Na56-6761.84.5

Sheet1ParameterRangeMeanSTDSAR6.01-98.21.12RSC(me/L)0.1-2.31.31.04%Na57-6865.24.2

Sheet1ParametersMinMaxMeanSTDAs(mg/L)0.0180.7870.1660.219ADD(mg/Kg Day)0.00050.0220.00460.0061HQ1.373.315.320.4CR0.00060.0330.00690.0091

Sheet1ParametersMinMaxMeanSTDAs(mg/L)0.0120.8280.1460.202ADD(mg/Kg Day)0.00050.0230.0040.005HQ176.613.418.7CR0.00090.03450.0060.008