Dietary proxies (δ15N, δ13C) as signature of metals and arsenic exposure in birds from aquatic and terrestrial food chains.

In this study, exposure to arsenic (As), lead (Pb), cadmium (Cd), copper (Cu) and zinc (Zn) was investigated in the blood, pectoral muscles and tail feathers of two terrestrial (spotted owlet; Athena brama and bank myna; Acridotheres ginginianus) and two aquatic (cattle egret; Bubulcus ibis and pond heron; Ardeola grayii) bird species inhabiting Pakistan. Food chain specimens, as well as the dietary proxies δ15N and δ13C, were also analyzed to validate potential trophic and dietary transfers of metals and As in birds. Zn was found to be the most prevalent metal in the tissues of birds followed by Pb, As, Cu, and Cd. The bioaccumulation of metals and As was higher in tail feathers reflecting the combined effect of both endogenous and exogenous contamination. Pectoral muscle and blood harbored lower levels of As and metals, indicating less recent exposure through diet. Aquatic birds feeding at higher trophic levels accumulated significantly higher concentrations of metals and As in their tissues (P < 0.05) and, therefore, may be at a greater risk of metal and As toxicity than terrestrial birds. Linear regression model depicts δ15N as a strong predictor of metals and As levels in the tissues of both aquatic and terrestrial birds, followed by the δ13C dietary proxy. All metals in aquatic species, except for Cd, as well as terrestrial species, except for Cu, exhibit bioaccumulative potential through the food chain (Trophic transfer factor: TTFs > 1) indicating potential harmful consequences for birds. Elevated concentrations of metals and As in tissues may cause harmful effects in birds potentially leading to declines in their populations.

Hydrogeochemical and isotopic evaluation of groundwater with elevated arsenic in alkaline aquifers in Eastern Punjab, Pakistan.

Geochemical investigation was carried out for delineating factors responsible for the mobilization of arsenic (As) from aquifer material into the groundwater. Four sites along Ravi River, (Samada, Sarai Chimba, Kot Maiga and Chah Fatehwala), were selected based on the blanket survey. Groundwater-rock interaction and evaporation were the key phenomena controlling groundwater chemistry, as shown by the hydrogeochemical data. Groundwater was predominantly Na-Cl type, with other principle facies being Na-HCO3, Na-Ca-HCO3 and Ca-Mg-Cl. The groundwater As concentration ranged between below detection level (2 µg/L) to 548 µg/L with 59% samples exceeding the World Health Organization (WHO) guidelines for As in drinking water (10 µg/L) and 31% having higher concentrations than the National Environmental Quality Standard (NEQS, 50 µg/L). Moderate to high concentrations of SO4-2 averaged at 244 mg/L and moderate NO3- concentrations averaged at 8 mg/L, together with alkaline pH (7.3-8.8) and high Eh values (113-402 mV) suggest partial oxidizing nature of the aquifers. The values for δ 18O and δ 2H in groundwater varied between -9.14 and -5.51‰, and -56.57 to -39.5‰ respectively, and suggests meteoric origin of the groundwater with some evaporative loss. This effect could be partly responsible for elevated levels of pH and salinity in groundwater. Based on geochemical and isotopic composition of groundwater, desorption of As from metal surfaces under alkaline environment might be the factor causing As enrichment in study area.

Geochemical assessment of metal pollution and ecotoxicology in sediment cores along Karachi Coast, Pakistan.

This paper is an attempt to compare the pollution status in two sediment cores, one from a polluted site (Ghizri Creek) and another from a relatively unpolluted site (Sandspit). Sediment cores (45 cm in length) from coastal locations were characterized in terms of grain size, sediment composition, pH, organic matter, calcium carbonate, and metal element contents. Metal elements, including Al, Ca, Cr, Co Cu, Fe, K, Mg, Mn, Ni, Pb, V, Ti, and Zn, were determined using PIXE. Grain size analysis and sediment composition demonstrated a sandy nature of both cores. Acidic trend in sediment core I was predominant from bottom to top, whereas neutral pH was observed throughout core II. TOC values varied in the range of 1.23-2.68 and 1.14-2.60% in core I and core II, respectively; however, there was an increasing trend in TOC level from bottom to top. The values of enrichment factor for Zn, Cu, Co, Ni, Pb, and Cr were slightly higher in core I than core II. The average geo-accumulation index values for core I and core II showed that sediments were moderately Co- and Pb-polluted but not polluted with Mg, Al, Ca, K, Cr, Cu, Fe, Mn, Ni, Ti, V, and Zn. The degree of contamination was however considerably higher in core I relative to core II. The pollution load index values, although showing an increasing trend from bottom to top in both cores, overall rendered the marine sediment pollution free. The metal toxicology results demonstrated that heavy metal pollution, except Cr, may pose low to moderate risk to marine biota. The sum of toxic unit values however indicated that sediment core I was relatively more polluted than that of core II.

Metal pollution and ecological risk assessment in marine sediments of Karachi Coast, Pakistan.

Concentrations of 12 metals (Fe, Mn, Cr, Mo, Ni, Pb, Se, Sr, U, V, Zn, and Zr) in surface sediments of Karachi Coast, Pakistan were determined to evaluate their distribution and pollution assessment. The measured metals in the sediments were found to be in the range of Fe, 0.84-6.96 %; Mn, 300-1,300 µg/g; Cr, 12.0-319.84 µg/g; Mo, 0.49-2.03 µg/g; Ni, 1.53-58.86 µg/g; Pb, 9.0-49.46 µg/g; Se, 0.25-.86 µg/g; Sr, 192-1185 µg/g; U, 0.19-1.66 µg/g; V, 15.80-118.20 µg/g; Zn, 15.60-666.28 µg/g; and Zr, 44.02-175.26 µg/g. The mean contents of the metal studied were: Fe, 3.07 %, Mn, 0.05 %; Cr, 96.75 µg/g; Mo, 1.34 µg/g; Ni, 31.39 µg/g; Pb, 23.24 µg/g; Se, 0.61 µg/g; Sr, 374.83 µg/g; U, 0.64 µg/g; V, 61.75 µg/g; Zn, 204.75 µg/g; and Zr:76.27 µg/g, and arrangement of the metals from higher to lower mean content in this area is: Fe > Zn > Mn > Sr > Zn > Cr > Zr > V > Ni > Pb > Mo > U > Se. There is no significant correlation among most of these metals, indicating different anthropogenic and natural sources. To assess ecotoxic potential of marine sediments, Numerical Sediment Quality Guidelines were also applied. The concentration of Pb in all the sediments except one was lower than the threshold effect concentration (TECs) showing that there are no harmful effects to marine life from Pb. On the other hand, the concentrations of Cr, Ni, and Zn exceeded TEC in three stations, indicating their potential risk. The degree of pollution in sediments for metals was assessed by calculating enrichment factor (EF) and pollution load index (PLI). The results indicated that sediments of Layari River Mouth Area, Fish Harbour, and KPT Boat Building Area are highly enriched with Cr and Zn (EF > 5). Sediments of Layari River Outfall Zone were moderately enriched with Ni and Pb (EF > 2). The pollution load index was found in the range of 0.98 to 1.34. Lower values of PLI (≤ 1) at most of sampling locations imply no appreciable input from anthropogenic sources. However, relatively higher PLI values (>1) at Layari River Mouth Area, Fish Harbour, and KPT Boat Building Area are attributed to increased human activity in the area.