Integrated Approach to Hydrogeochemical Assessment of Groundwater Quality in Major Industrial Zone of Punjab, Pakistan.

Groundwater contamination with arsenic (As) is a significant concern in Pakistan's Punjab Province. This study analyzed 69 groundwater samples from Faisalabad, Gujranwala, Lahore, and Multan to understand hydrogeochemistry, health impacts, contamination sources, and drinking suitability. Results revealed varying as concentrations across districts, with distinctive cation and anion orders. Faisalabad exhibited Na+ > Mg2+ > Ca2+ > K+ > Fe2+ for cations and SO42- > Cl- > HCO3- > NO3- > F- for anions. Gujranwala showed Na+ > Ca2+ > Mg2+ > K+ for cations and HCO3- > SO42- > Cl- > NO3- > F- for anions. In Lahore, demonstrated: Na+ > Ca2+ > Mg2+ > Fe > K+ for cations and HCO3- > SO42- > Cl- > NO3- > F- for anions. Multan indicated K+ > Ca2+ > Mg2+ > Na+ > Fe for cations and HCO3- > SO42- > Cl- > F- > NO3- ) for anions. Hydrochemical facies were identified as CaHCO3 and CaMgCl types. Principal Component Analysis (PCA), highlighted the influence of natural processes and human activities on groundwater pollution. Water Quality Index (WQI) result reveal that most samples met water quality standards. The carcinogenic risk values for children exceeded permissible limits in all districts, emphasizing a significant cancer risk. The study highlights the need for rigorous monitoring to mitigate (As) contamination and protect public health from associated hazards.

Human Health and Ecological Risks Associated with Total and Bioaccessible Concentrations of Cadmium and Lead in Urban Park Soils.

This study investigated the total and bioaccessible concentrations of cadmium (Cd) and lead (Pb) in urban soils and their associated human health and ecological risk. Total and bioaccessible metal concentrations were found within the safe limits except for Cd, surpassing the State Environmental Protection Administration (SEPA) China limit in 9.5% of parks. Bioaccessible concentrations were higher in the gastric (G) phase than the intestinal (I) phase, while Cd showed more bioaccessibility compared to Pb. Bioaccessible concentrations reduced Hazard Quotient (HQing) values by 2-22 times and 0-2 times for children and adults, respectively, while hazard index (HI) declined by 1.7 times, and the mean total bioaccessible risk of Pb decreased by 20.8 times. Further, the study revealed a low level of contamination factor (CF < 1) and a low degree of contamination (CD < 6), and Potential Ecological Risk Index (PERI) values for all the cities were less than 150, indicating low ecological risk.

Biochar supplementation regulates growth and heavy metal accumulation in tomato grown in contaminated soils.

Biochar application has recently gained increased attention to reclaim heavy metal degraded soils. In this context, the present study investigated the effects of biochar on the growth regulation and heavy metal accumulation in tomato grown on contaminated soils. A two-factorial design with factor A including three treatments with mine (contaminated soil) and garden soil in the following ratio viz., T1 = 1:2, T2 = 1:1, and T3 = 2:1, and garden soil only as control; whereas factor B consists of biochar amendments at three levels viz., B1 (3%), B2 (6%), and B3 (9%). Our results revealed significant negative effects of heavy metal-contaminated soil on plant growth, and besides resulted heavy metal accumulation in tomato fruit. Tomato plants showed maximum reduction of growth in T3 followed by T2, and lowest in T1, a similar pattern was found for accumulation of heavy metals in the fruit. However, the application of biochar reduced the bioavailability and accumulation of heavy metals in the tomato fruit, as well as improved plant growth in contaminated soils. Overall, among the three biochar treatments, B2 was determined as the optimum level for improved growth coupled with reduced heavy metal accumulation in the tomato fruit. Besides, biochar application decreased the daily intake of metals and human health risk index values, thus alleviating the health risk. Hence, the present study demonstrated a positive role of biochar in reclaiming heavy metal-contaminated soils and in increasing the plant growth.

Methyl mercury concentrations in seafood collected from Zhoushan Islands, Zhejiang, China, and their potential health risk for the fishing community: Capsule: Methyl mercury in seafood causes potential health risk.

Seafood is an important exposure route for mercury, especially methyl mercury (MeHg). Therefore, we quantified MeHg concentrations in 69 species of seafood including fish, crustaceans and mollusks collected from Zhoushan Islands, China. MeHg concentrations ranged from <0.0020-0.2098 µg/g and did not exceed the threshold limit of 1 µg/g in all sampled species, However, MeHg concentrations significantly differed among fish species (0.0085-0.2098 mg kg-1), crustaceans (<0.002-0.0221 mg kg-1) and mollusks (<0.002-0.1389 mg kg-1). The trophic magnification factor (TMF) was determined on the basis of the trophic level (TL). The TL values for fish, crustaceans and mollusks were above 3 when the TMF values were >1. The daily dietary intake and hazard quotient for MeHg were calculated to estimate exposure and health risk through seafood consumption by local inhabitants. The calculated HQ was lower than 1, thus indicating that the exposure was below the risk threshold of related chronic diseases. However, higher MeHg concentrations in fish species such as Scoliodon sorrakowah and Auxis thazard are concerning and may pose health risk through continuous consumption by local inhabitants.

Contamination of soil with potentially toxic metals and their bioaccumulation in wheat and associated health risk.

The present study was conducted to investigate the concentrations of potential toxic metals (PTMs) in agricultural soil (n = 25) and their bioaccumulation in wheat crop (n = 25) collected from alongside the Kurram River, Pakistan. The highest concentrations of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn in soil samples were 0.16, 19.5, 14.7, 46.5, 13.5, 14.5, 14.0, and 19.7 mg kg-1, respectively. In the edible tissues of cultivated wheat crop, the highest concentrations of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn were 0.15, 10.00, 8.75, 22.25, 11.00, 11.25, 10.50, and 7.50 mg kg-1, respectively. The selected PTM concentrations in soil samples were observed within their respective permissible limits set by the Food and Agriculture Organization (FAO) and State Environmental Protection Administration (SEPA) China, while in wheat crops, the Cr and Pb concentrations were above the permissible limits of both FAO and SEPA China. The results showed that the orders of PTMs were Fe > Zn > Cr > Cu > Ni > Pb > Mn in soil and Fe > Ni > Mn > Pb > Cr > Cu > Zn in wheat. The highest PTM concentrations were reported in the sample collected near dumping sites. The results of different soil pollution indices including geo-accumulation index (Igeo), contamination factor (CF), and enrichment factor (EF) indicated that the soil of the study area was moderately to severely contaminated. The ADI values of wheat crops were less than 1, while the HQ varied among different PTMs with the highest value of 2.118 for Pb, and the lowest for Zn (0.007). The results indicated that anthropogenic intervention has made a substantial contribution to soil contamination with PTMs and subsequent uptake by wheat, which may exert potential human health risk.

Environmental and health impacts of industrial wastewater effluents in Pakistan: a review.

In developing countries, one of the most severe modern-day dilemmas is the management of industrial wastewater. In these countries, industrial wastewater effluents are directly discharged into the natural drain, a sewer system, an internal septic tank or a nearby field. Some of these industrial wastewater effluents are inadequately treated or untreated before being discharged. In recent years, in developing countries, urbanization and industrial activities have led to environmental deterioration. This paper was designed to review the health and environmental impacts of inadequately treated or untreated industrial wastewater effluents in Pakistan. The quality of industrial wastewater effluents is responsible for the degradation of the receiving water bodies. This is due to the reason that inadequately treated or untreated industrial wastewater effluents may cause eutrophication in the receiving water bodies and also form a favorable condition for toxin-producing waterborne pathogens. In order to comply with the wastewater guidelines and legislations, there is a need for proper treatment before discharge. In order to minimize the risk to the environment and public health, there is a need for proper treatment processes for industrial wastewater effluents. To achieve unpolluted discharge of industrial wastewater into the receiving water bodies, regular monitoring, proper and suitable treatment, careful planning and appropriate legislation are recommended.

Concentrations, dietary exposure, and human health risk assessment of heavy metals in market vegetables of Peshawar, Pakistan.

The present study was carried out to assess heavy metal concentrations in ready-to-eat vegetables (RTEs) collected from open markets. Samples of RTEs including lettuce, coriander, and carrot were collected from five different local markets of Peshawar, Pakistan including Industrial estate, Board, Agriculture University, Firdos, and Hashtnaghri on four different dates, i.e., 21st March, 04th April, 19th April, and 05th May, 2016. The samples were analyzed through atomic absorption spectrophotometer to see the amount of heavy metals present in them. The elements studied were cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), and lead (Pb). Maximum Cd, Cr, Cu, Ni, and Pb concentrations in samples collected from different markets were 0.68, 5.28, 12.31, 7.61, and 25.04 mg kg-1, respectively, whereas maximum Cd, Cr, Cu, Ni, and Pb concentrations in RTEs collected at different dates were 0.59, 4.08, 14.85, 7.23, and 21.97 mg kg-1, respectively. The mean Cd, Cr, and Pb concentrations exceeded the permissible limits, while Cu and Ni were found within the limits set by FAO/WHO in all studied RTEs. The daily dietary intake and hazard quotient (HQ) showed great variations. The HQ was found > 1 for Pb in all studied vegetables, while it was < 1 for Cd, Cr, Cu, and Ni with few exceptions. It can be concluded from the study that heavy metal concentrations were above the permissible toxicity levels and their continuous consumption may cause several health issues.

The effects of biochar and rice husk on adsorption and desorption of cadmium on to soils with different water conditions (upland and saturated).

Hard wood derived biochar (BCH) and rice husk (RCH) were applied to soils having upland and saturated conditions to investigate their effects on adsorption and desorption of Cd by conducting incubation and batch experiments. The results obtained from the experiments indicated that BCH increased Cd sorption by 59-71% onto saturated soil (SS), while by 57-84% onto upland soil (US). The application of RCH also increased the sorption of Cd onto the soils under both water conditions but the increases were less as compared to BCH. With RCH application, 21-41% increases in sorption of Cd on SS and 38-54% on US soils were observed. The Langmuir equation fitted sorption of Cd better than Freundlich with R2 > 0.95 for all selected treatments. Both electrostatic and non-electrostatic mechanisms played their important roles in the adsorption of Cd in the amended soils. BCH enhanced non-electrostatic adsorption as compared to RCH and thus control and induced greater specific adsorption capacity. High desorption percentage of pre-adsorbed Cd on soils were observed both with and without amendments. Decreases in desorption percentage of pre-adsorbed Cd on both soils were observed with BCH with a highest decrease on SS (39%). The application of selected amendments into different soils increased Cd adsorption of soils through both electrostatic and non-electrostatic mechanisms and the contribution of both the mechanisms varied with types of amendments and soil conditions. BCH material showed promising results in Cd adsorption as compared to RCH for different selected soils and conditions but cost-benefit analysis is needed in field condition.

The influence of various organic amendments on the bioavailability and plant uptake of cadmium present in mine-degraded soil.

Mining of minerals and precious elements leads to land degradation that need to be reclaimed using environmentally friendly and cost effective techniques. The present study investigated the potential effects of different organic amendments on cadmium (Cd) bioavailability in mining-degraded soil and its subsequent bioaccumulation in tomato and cucumber. The selected organic geosorbents (hard wood biochar (HWB), bagasse (BG), rice husk (RH), and maize comb waste (MCW)) were added at application rates of 3% and 5% to chromite mine-degraded soil containing Cd. Tomato and cucumber plants were then grown in the soil, and the roots, shoots, leaves, and fruits of each plant were analysed for Cd concentration, biomass production, and chlorophyll content. The results indicated that the different organic materials have variable effects on physiochemical characteristics of vegetables and Cd bioavailability. The biochar amendment significantly (P < 0.01) increased chlorophyll contents (20-40%) and biomass (40-63%), as did RH to a lesser extent (increase of 10-18% in chlorophyll content and 3-45% in biomass). Among the amendments, HWB was the most effective at reducing Cd bioavailability, wherein significant decreases were observed in Cd uptake by fruits of tomato (24-30%) and cucumber (36-54%). The higher application rate of 5% was found to be more effective for mitigation of Cd mobility and bioaccumulation in plants grown in mine degraded soil. The study results indicate that effective use of organic amendments, especially HWB, can significantly reduce Cd levels in vegetables, improve food quality, and reduce human-health risk while increasing biomass production.

Removal of potentially toxic elements from aqueous solutions and industrial wastewater using activated carbon.

Water contamination with potentially toxic elements (PTEs) has become one of the key issues in recent years that threatens human health and ecological systems. The present study is aimed at removing PTEs like cadmium (Cd), chromium (Cr), copper (Cu) and lead (Pb) from aqueous solutions and industrial wastewater using activated carbon (AC) as an adsorbent through different batch and column experiments. Results demonstrated that the removal of PTEs from aqueous solutions was highly pH dependent, except for Cr, and the maximum removal (>78%) was recorded at pH 6.0. However, maximum Cr removal (82.8%) was observed at pH 3.0. The adsorption reached equilibrium after 60 min with 2 g of adsorbent. Coefficient (R2) values suggested by the Langmuir isotherm model were 0.97, 0.96, 0.93 and 0.95 for Cd, Cr, Cu and Pb, respectively, indicating the fit to this model. In column experiments, the maximum removal of PTEs was observed at an adsorbent bed height of 20 cm with the optimal flow rate of 3.56 mL/min. Furthermore, PTEs removal by AC was observed in the order of Cu > Cd > Pb > Cr. Findings from this study suggest that AC could be used as a promising adsorbent for simultaneously removing several PTEs from wastewaters.

Appraisement, source apportionment and health risk of polycyclic aromatic hydrocarbons (PAHs) in vehicle-wash wastewater, Pakistan.

Vehicle-wash wastewater (VWW) contains elevated concentrations of different petrochemicals including polycyclic aromatic hydrocarbons (PAHs), a carcinogenic group of organic compounds. This study investigates the discharge of PAHs present in the untreated wastewater of vehicle-wash stations (VWS) located in district Peshawar, Pakistan. The data obtained was being novel with the detection of 16 USEPA PAHs (both individuals and total) and compared with earlier studies and international standards. The ∑16PAHs in wastewater from light vehicle-wash stations (LVWS) and heavy vehicle-wash stations (HVWS) ranged from 245-429µg/l and 957-1582µg/l, respectively. A significant difference (p<0.01) was observed in PAHs discharged from LVWS and HVWS. The projected ∑16PAHs discharge from both HVWS (92% of total generated PAHs) and LVWS (8%) was about 5109.9 g per annum. According to PAH diagnostic ratios, PAHs were both petrogenic (chrysene/benz(a)anthracene, low molecular weight/high molecular weight) and pyrogenic (phenanthrene/anthracene, fluoranthene/pyrene, fluoranthene/fluoranthene+pyrene) in origin. The highest toxic equivalent quotient (TEQ) value was shown by benzo(a)pyrene (21.6µg/l) followed by dibenz(ah)anthracene (9.81µg/l) in wastewater from HVWS. However, in LVWS the case was reversed with highest value (7.54µg/l) for dibenz(ah)anthracene followed by benzo(a)pyrene (3.54µg/l). The lowest TEQ value was indicated for phenanthrene (0.007µg/l) in wastewater of LVWS, while pyrene showed the lowest value (0.007µg/l) in wastewater of HVWS. The results indicated that VWS contribute significant amount of PAHs each year, which is of great concern regarding water quality, ecological and human health risk. This is the first systematic and comprehensive research related with generation of PAHs load per day, week, month and annum from VWS, their source apportionment and health effects in Pakistan.

Soil contamination with cadmium, consequences and remediation using organic amendments.

Cadmium (Cd) contamination of soil and food crops is a ubiquitous environmental problem that has resulted from uncontrolled industrialization, unsustainable urbanization and intensive agricultural practices. Being a toxic element, Cd poses high threats to soil quality, food safety, and human health. Land is the ultimate source of waste disposal and utilization therefore, Cd released from different sources (natural and anthropogenic), eventually reaches soil, and then subsequently bio-accumulates in food crops. The stabilization of Cd in contaminated soil using organic amendments is an environmentally friendly and cost effective technique used for remediation of moderate to high contaminated soil. Globally, substantial amounts of organic waste are generated every day that can be used as a source of nutrients, and also as conditioners to improve soil quality. This review paper focuses on the sources, generation, and use of different organic amendments to remediate Cd contaminated soil, discusses their effects on soil physical and chemical properties, Cd bioavailability, plant uptake, and human health risk. Moreover, it also provides an update of the most relevant findings about the application of organic amendments to remediate Cd contaminated soil and associated mechanisms. Finally, future research needs and directions for the remediation of Cd contaminated soil using organic amendments are discussed.

Occurrence, enantiomeric signature and ecotoxicological risk assessment of HCH isomers and DDT metabolites in the sediments of Kabul River, Pakistan.

Hexachlorocyclohexane (HCH) isomers and dichlorodiphenyltrichloroethane (DDT) metabolites were analyzed in sediments of three different depths (0-10, 10-20 and 20-30 cm) collected from Kabul River, Pakistan, in February 2014. The occurrence levels, enantiomer fractions and potential ecological risk of these organochlorine pesticides (OCPs) were evaluated. The total concentrations of ∑HCHs and ∑DDTs in surface sediments ranged from 4.9-23.9 ng g-1 and from 6.4-18.8 ng g-1 (dry weight basis), respectively. The vertical contamination profile of DDTs was found in order of 20-30 cm >10-20 cm >0-10 cm, indicated that the residue levels of DDTs gradually decreased after it was banned. The ratios of ß-HCH/HCHs ranged from 0.04 to 0.73 (69 % of samples below 0.5) suggesting the fresh input of HCHs, while isomeric ratios of α-HCH/γ-HCH (ranged from 0.02 to 7.94), with 76 % of samples less than 3, indicating the cocktail use of technical grade HCH and lindane in the study area. The ratio of (DDE + DDD)/DDTs (ranged from 0.42 to 0.90) indicated long-term biodegradation of parent DDT. The enantiomer of α-HCH was generally racemic or close to racemic for most of the samples, with enantiomeric fraction (EF) value <0.5 for some of the samples indicated the preferential biodegradation of (+)-α-HCH enantiomer, while for o,p'-DDT the EF values >0.5 indicated the depletion of (-)-o,p'-DDT enantiomer in most of the samples. According to sediment quality guidelines (SQGs), HCH contamination is the main concern for ecotoxicological risk in Kabul River.

Health risk assessment from contaminated foodstuffs: a field study in chromite mining-affected areas northern Pakistan.

This study aimed to investigate the potential health risk associated with toxic metals in contaminated foodstuffs (fruits, vegetables, and cereals) collected from various agriculture fields present in chromite mining-affected areas of mafic and ultramafic terrains (northern Pakistan). The concentrations of Cr, Ni, Zn, Cd, and Pb were quantified in both soil and food samples. The soil samples were highly contaminated with Cr (320 mg/kg), Ni (108 mg/kg), and Cd (2.55 mg/kg), which exceeded their respective safe limits set by FAO/WHO. Heavy metal concentrations in soil were found in the order of Cr>Ni>Pb>Zn>Cd and showed significantly (p < 0.001) higher concentrations as compared to reference soil. The integrated pollution load index (PLI) value was observed greater than three indicating high level of contamination in the study area. The concentrations of Cr (1.80-6.99 mg/kg) and Cd (0.21-0.90 mg/kg) in foodstuffs exceeded their safe limits, while Zn, Pb, and Ni concentrations were observed within their safe limits. In all foodstuffs, the selected heavy metal concentrations were accumulated significantly (p < 0.001) higher as compared to the reference, while some heavy metals were observed higher but not significant like Zn in pear, persimmon, white mulberry, and date-plum; Cd in pear, fig and white mulberry; and Pb in walnut, fig, and pumpkin. The health risk assessment revealed no potential risk for both adults and children for the majority of heavy metals, except Cd, which showed health risk index (HRI) >1 for children and can pose potential health threats for local inhabitants. Graphical Abstract Heavy metals released from chromite mining lead to soil and foodstuff contamination and human health risk.

Tissue distribution of HCH and DDT congeners and human health risk associated with consumption of fish collected from Kabul River, Pakistan.

Distribution of hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT) congeners in tissues of four different fish species and their associated potential health risks to local consumers are presented in this paper. The average ∑(HCHs+DDTs) concentration in Glyptothorax punjabensis (214ngg(-1) wet weight (ww)) (carnivores) was found higher than Tor putitora (155ngg(-1) ww) (herbivores). The distribution of ∑(HCHs+DDTs) in all fish tissues was found in order of liver>muscle>stomach>gills. The profile of congeners (ß-HCH/∑HCH from 0.29-0.47) indicated that all selected fish species were contaminated with HCH because of its recent usage in the study area. Furthermore, DDT profile ((DDE+DDD)/∑DDT from 0.61-0.78) showed that fish contamination with DDT originated from past usage and long-time degradation mechanism. The average estimated daily dietary intake of ∑HCHs (15.0ngkg(-1) day(-1)) was higher than ∑DDTs (12.5ngkg(-1) day(-1)) by the local consumers via fish consumption. On the basis of both 50th and 95th percentile exposure levels, the carcinogenic hazard ratios for DDT and its congeners were exceeded one (safe limit) for all fish species, indicating a great potential cancer risk for local consumers with life time consumption of contaminated fish collected from Kabul River.

Toxic metal interactions affect the bioaccumulation and dietary intake of macro- and micro-nutrients.

The present study was conducted to evaluate the effects of heavy metals (cadmium (Cd), lead (Pb) and Cd-Pb mix) on bioaccumulation of different nutrients. Three plant species including potato, tomato and lettuce were grown in pots containing soil contaminated with Cd, Pb and Cd-Pb mix at four different levels. The edible portions of each plant were analysed for Cd, Pb and different macro- and micro-nutrients including protein, vitamin C, nitrogen (N), phosphorous (P), potassium (K), iron (Fe), manganese (Mn), calcium (Ca) and magnesium (Mg). Results indicated significant variations in selected elemental concentrations in all the three plants grown in different treatments. The projected daily dietary intake values of selected metals were significant (P < 0.001) for Fe, Mn, Ca and Mg but not significant for protein, vitamin C, N and P. The elemental contribution to Recommended Dietary Allowance (RDA) was significant for Mn. Similarly, Fe and Mg also showed substantial contribution to RDA, while Ca, N, P, K, protein and vitamin C showed the minimal contribution for different age groups. This study suggests that vegetables cultivated on Cd and Pb contaminated soil may significantly affect their quality, and the consumption of such vegetables may result in substantial negative effects on nutritional composition of the consumer body. Long term and continuous use of contaminated vegetables may result in malnutrition.

The uptake and bioaccumulation of heavy metals by food plants, their effects on plants nutrients, and associated health risk: a review.

Heavy metal contamination is a globally recognized environmental issue, threatening human life very seriously. Increasing population and high demand for food resulted in release of various contaminants into environment that finally contaminate the food chain. Edible plants are the major source of diet, and their contamination with toxic metals may result in catastrophic health hazards. Heavy metals affect the human health directly and/or indirectly; one of the indirect effects is the change in plant nutritional values. Previously, a number of review papers have been published on different aspects of heavy metal contamination. However, no related information is available about the effects of heavy metals on the nutritional status of food plants. This review paper is focused upon heavy metal sources, accumulation, transfer, health risk, and effects on protein, amino acids, carbohydrates, fats, and vitamins in plants. The literature about heavy metals in food plants shows that both leafy and nonleafy vegetables are good accumulators of heavy metals. In nonleafy vegetables, the bioaccumulation pattern was leaf > root ≈ stem > tuber. Heavy metals have strong influence on nutritional values; therefore, plants grown on metal-contaminated soil were nutrient deficient and consumption of such vegetables may lead to nutritional deficiency in the population particularly living in developing countries which are already facing the malnutrition problems.