The principal object of the current study was to estimate total arsenic and its inorganic speciation in different origins of surface water (n=480) and groundwater (n=240) of Sindh, Pakistan. This study provided a description based on the evaluation of physico-chemical parameters of collected water samples and possible distribution of As with respect to its speciation. The concentration of total inorganic As (iAs) and its species (As(3+) and As(5+)) for the surface and underground water was reported in terms of basic statistical parameters, principal component analysis, cluster analysis, metal-to-metal correlations and linear regression analyses. The chemical correlations were observed by PCA, which were used to classify the samples by CA, based on the PCA scores. Standard addition method confirmed the accuracy; the recoveries of As(3+) and iAs were found to be >98%. The concentration of As(5+) in the water samples was calculated by the difference of the total inorganic arsenic and As(3+). The results revealed that the groundwater of the understudied area was more contaminated as compared to the surface water samples. The mean concentration of As(3+) and As(5+) in the surface water and groundwater samples were in the range 3.0 to 18.3 and 8.74-352 microg/L, respectively.
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