Irshad Bibi

Unraveling Health Risk and Speciation of Arsenic from Groundwater in Rural Areas of Punjab, Pakistan.

This study determined the total and speciated arsenic (As) concentrations and other health-related water quality parameters for unraveling the health risk of As from drinking water to humans. Groundwater samples (n = 62) were collected from three previously unexplored rural areas (Chichawatni, Vehari, Rahim Yar Khan) of Punjab in Pakistan. The mean and median As concentrations in groundwater were 37.9 and 12.7 µg·L−1 (range = 1.5–201 µg·L−1). Fifty three percent groundwater samples showed higher As value than WHO safe limit of 10 µg·L−1. Speciation of As in groundwater samples (n = 13) showed the presence of inorganic As only; arsenite (As(III)) constituted 13%–67% of total As and arsenate (As(V)) ranged from 33% to 100%. For As health risk assessment, the hazard quotient and cancer risk values were 11–18 and 46–600 times higher than the recommended values of US-EPA (i.e., 1.00 and 10−6, respectively). In addition to As, various water quality parameters (e.g., electrical conductivity, Na, Ca, Cl−, NO3−, SO42−, Fe, Mn, Pb) also enhanced the health risk. The results show that consumption of As-contaminated groundwater poses an emerging health threat to the communities in the study area, and hence needs urgent remedial and management measures.

Chromium speciation, bioavailability, uptake, toxicity and detoxification in soil-plant system: A review

Chromium (Cr) is a potentially toxic heavy metal which does not have any essential metabolic function in plants. Various past and recent studies highlight the biogeochemistry of Cr in the soil-plant system. This review traces a plausible link among Cr speciation, bioavailability, phytouptake, phytotoxicity and detoxification based on available data, especially published from 2010 to 2016. Chromium occurs in different chemical forms (primarily as chromite (Cr(III)) and chromate (Cr(VI)) in soil which vary markedly in term of their biogeochemical behavior. Chromium behavior in soil, its soil-plant transfer and accumulation in different plant parts vary with its chemical form, plant type and soil physico-chemical properties. Soil microbial community plays a key role in governing Cr speciation and behavior in soil. Chromium does not have any specific transporter for its uptake by plants and it primarily enters the plants through specific and non-specific channels of essential ions. Chromium accumulates predominantly in plant root tissues with very limited translocation to shoots. Inside plants, Cr provokes numerous deleterious effects to several physiological, morphological, and biochemical processes. Chromium induces phytotoxicity by interfering plant growth, nutrient uptake and photosynthesis, inducing enhanced generation of reactive oxygen species, causing lipid peroxidation and altering the antioxidant activities. Plants tolerate Cr toxicity via various defense mechanisms such as complexation by organic ligands, compartmentation into the vacuole, and scavenging ROS via antioxidative enzymes. Consumption of Cr-contaminated-food can cause human health risks by inducing severe clinical conditions. Therefore, there is a dire need to monitor biogeochemical behavior of Cr in soil-plant system.

Remediation of arsenic-contaminated water using agricultural wastes as biosorbents

ABSTRACT Arsenic (As) contamination of groundwater reservoirs is a global environmental and health issue given to its toxic and carcinogenic nature. Over 170 million people have been affected by As due to the ingestion of As-contaminated groundwater. Conventional methods such as reverse osmosis, ion exchange, and electrodialysis are commonly used for the remediation of As-contaminated water; however, the high cost and sludge production put limitations on their application to remove As from water. This review critically addresses the use of various agricultural waste materials (e.g., sugarcane bagasse, peels of various fruits, wheat straw) as biosorbents, thereby offering an eco-friendly and low-cost solution for the removal of As from contaminated water supplies. The effect of solution chemistry such as solution pH, cations, anions, organic ligands, and various other factors (e.g., temperature, contact time, sorbent dose) on As biosorption, and safe disposal methods for As-loaded biosorbents to reduce secondary As contamination are also discussed.

Phosphate-assisted phytoremediation of arsenic by Brassica napus and Brassica juncea: Morphological and physiological response

ABSTRACT In this study, we examined the potential role of phosphate (P; 0, 50, 100 mg kg−1) on growth, gas exchange attributes, and photosynthetic pigments of Brassica napus and Brassica juncea under arsenic (As) stress (0, 25, 50, 75 mg kg−1) in a pot experiment. Results revealed that phosphate supplementation (P100) to As-stressed plants significantly increased shoot As concentration, dry biomass yield, and As uptake, in addition to the improved morphological and gas exchange attributes and photosynthetic pigments over P0. However, phosphate-assisted increase in As uptake was substantially (up to two times) greater for B. napus, notably due to higher shoot As concentration and dry biomass yield, compared to B. juncea at the P100 level. While phosphate addition in soil (P100) led to enhanced shoot As concentration in B. juncea, it reduced shoot dry biomass, primarily after 50 and 75 mg kg−1 As treatments. The translocation factor and bioconcentration factor values of B. napus were higher than B. juncea for all As levels in the presence of phosphate. This study demonstrates that phosphate supplementation has a potential to improve As phytoextraction efficiency, predominantly for B. napus, by minimizing As-induced damage to plant growth, as well as by improving the physiological and photosynthetic attributes.

Chromium(VI) sorption efficiency of acid-activated banana peel over organo-montmorillonite in aqueous solutions

ABSTRACT In the present study, we examined sorption of chromate (Cr(VI)) to acid-activated banana peel (AABP) and organo-montmorillonite (O-mont) as a function of pH, initial Cr(VI) concentration at a sorbent dose of 4 g L−1 and at 20 ± 1°C in aqueous solutions. In sorption edge experiments, maximum Cr(VI) removal was obtained at pH 3 after 2 hours by AABP and O-mont (88% and 69%). Sorption isotherm data showed that the sorption capacity of AABP was higher than O-mont (15.1 vs. 6.67 mg g−1, respectively, at pH 4). Freundlich and Langmuir models provided the best fits to describe Cr(VI) sorption onto AABP (R2 = 0.97) and O-mont (R2 = 0.96). Fourier transform infrared spectroscopy elucidated that for AABP mainly the –OH, –COOH, –NH2, and for O-mont intercalated amines and –OH surface functional groups were involved in Cr(VI) sorption. The scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM-EDX) analyses, although partly, indicate that the (wt. %) proportion of cations (e.g., Ca, Mg) in AABP decreased after Cr(VI) sorption. This may be due to ion exchange of chromite (Cr(III)) (produced from Cr(VI) reduction) with cationic elements in AABP. Also, Cr(VI) desorption (using phosphate solution) from AABP was lower (29%) than that from O-mont (51%) up to the third regeneration cycle. This bench scale comparative study highlights that the utilization of widely available and low-cost acid-activated biomaterials has a greater potential than organo-clays for Cr(VI) removal in aqueous media. However, future studies are warranted to precisely delineate different mechanisms of Cr(VI) sorption/reduction by acid-activated biomaterials and organo-clays.

Arsenic Uptake, Toxicity, Detoxification, and Speciation in Plants: Physiological, Biochemical, and Molecular Aspects

Environmental contamination with arsenic (As) is a global environmental, agricultural and health issue due to the highly toxic and carcinogenic nature of As. Exposure of plants to As, even at very low concentration, can cause many morphological, physiological, and biochemical changes. The recent research on As in the soil-plant system indicates that As toxicity to plants varies with its speciation in plants (e.g., arsenite, As(III); arsenate, As(V)), with the type of plant species, and with other soil factors controlling As accumulation in plants. Various plant species have different mechanisms of As(III) or As(V) uptake, toxicity, and detoxification. This review briefly describes the sources and global extent of As contamination and As speciation in soil. We discuss different mechanisms responsible for As(III) and As(V) uptake, toxicity, and detoxification in plants, at physiological, biochemical, and molecular levels. This review highlights the importance of the As-induced generation of reactive oxygen species (ROS), as well as their damaging impacts on plants at biochemical, genetic, and molecular levels. The role of different enzymatic (superoxide dismutase, catalase, glutathione reductase, and ascorbate peroxidase) and non-enzymatic (salicylic acid, proline, phytochelatins, glutathione, nitric oxide, and phosphorous) substances under As(III/V) stress have been delineated via conceptual models showing As translocation and toxicity pathways in plant species. Significantly, this review addresses the current, albeit partially understood, emerging aspects on (i) As-induced physiological, biochemical, and genotoxic mechanisms and responses in plants and (ii) the roles of different molecules in modulation of As-induced toxicities in plants. We also provide insight on some important research gaps that need to be filled to advance our scientific understanding in this area of research on As in soil-plant systems.

Arsenic removal by Japanese oak wood biochar in aqueous solutions and well water: Investigating arsenic fate using integrated spectroscopic and microscopic techniques

In this study, we examined the sorption of arsenite (As(III)) and arsenate (As(V)) to Japanese oak wood-derived biochar (OW-BC) in aqueous solutions, and determined its efficiency to remove As from As-contaminated well water. Results revealed that, among the four sorption isotherm models, Langmuir model showed the best fit to describe As(III) and As(V) sorption on OW-BC, with slightly greater sorption affinity for As(V) compared to As(III) (QL=3.89 and 3.16mgg-1; R2=0.91 and 0.85, respectively). Sorption edge experiments indicated that the maximum As removal was 81% and 84% for As(III)- and As(V)-OW-BC systems at pH7 and 6, respectively, which decreased above these pH values (76-69% and 80-58%). Surface functional groups, notably OH, COOH, CO, CH3, were involved in As sequestration by OW-BC, suggesting the surface complexation/precipitation and/or electrostatic interaction of As on OW-BC surface. Arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy indicated that 36% of the added As(III) was partially oxidized to As(V) in the As(III) sorption experiment, and in As(V) sorption experiment, 48% of As(V) was, albeit incompletely, reduced to As(III) on OW-BC surface. Application of OW-BC to As-contaminated well water (As: 27-144μgL-1; n=10) displayed that 92 to 100% of As was depleted despite in the presence of co-occurring competing anions (e.g., SO42-, CO32-, PO43-). This study shows that OW-BC has a great potential to remove As from solution and drinking (well) water. Overall, the combination of macroscopic sorption data and integrated spectroscopic and microscopic techniques highlight that the fate of As on biochar involves complex redox transformation and association with surface functional moieties in aquatic systems, thereby providing crucial information required for implication of biochar in environmental remediation programs.

Influence of groundwater and wastewater irrigation on lead accumulation in soil and vegetables: Implications for health risk assessment and phytoremediation

ABSTRACT The current study evaluated the effect of groundwater and wastewater irrigation on lead (Pb) accumulation in soil and vegetables, and its associated health implications. A pot experiment was conducted in which spinach (Spinacia oleracea), radish (Raphanus sativus), and cauliflower (Brassica oleracea) were irrigated with groundwater and wastewaters containing varying concentrations of Pb. Lead contents were measured in wastewaters, soils and root and shoot of vegetables. We also measured health risk index (HRI) associated with the use of vegetables irrigated by wastewaters. Results revealed that Pb contents in groundwater and wastewater samples (range: 0.18–0.31 mg/L) were below the permissible limits (0.5 mg/L) set by the Food and Agriculture Organization (FAO). Application of Pb-containing groundwater and wastewater increased Pb concentration in soil and vegetables. Lead concentrations in all soils ranged from 10 to 31 mg/kg and were below the permissible limits of 300 mg/kg set by the European Union. Significant Pb enrichment was observed in the soils whereby all types of vegetables were grown and assessed for Pb risk. Our data showed that Pb contents, in all three vegetables (21–28 mg/kg DW), were higher than the permissible Pb limit of FAO (5 mg/kg Dry Weight (DW)). The HRI values were > 1.0 for radish and cauliflower. It is proposed that Vehari city wastewater/groundwater must be treated prior to its use for irrigation to avoid vegetable contamination by Pb, and as such for reducing Pb-induced human health risk.

A critical review of selenium biogeochemical behavior in soil-plant system with an inference to human health

Selenium (Se) is an essential trace element for humans and animals, although controversial for different plant species. There exists a narrow line between essential, beneficial and toxic levels of Se to living organisms which greatly varies with Se speciation, as well as the type of living organisms. Therefore, it is crucial to monitor its solid- and solution-phase speciation, exposure levels and pathways to living organisms. Consumption of Se-laced food (cereals, vegetables, legumes and pulses) is the prime source of Se exposure to humans. Thus, it is imperative to assess the biogeochemical behavior of Se in soil-plant system with respect to applied levels and speciation, which ultimately affect Se status in humans. Based on available relevant literature, this review traces a plausible link among (i) Se levels, sources, speciation, bioavailability, and effect of soil chemical properties on selenium bioavailability/speciation in soil; (ii) role of different protein transporters in soil-root-shoot transfer of Se; and (iii) speciation, metabolism, phytotoxicity and detoxification of Se inside plants. The toxic and beneficial effects of Se to plants have been discussed with respect to speciation and toxic/deficient concentration of Se. We highlight the significance of various enzymatic (catalase, peroxidase, superoxide dismutase, ascorbate peroxidase, glutathione peroxidase) and non-enzymatic (phytochelatins and glutathione) antioxidants which help combat Se-induced overproduction of reactive oxygen species (ROS). The review also delineates Se accumulation in edible plant parts from soils containing low or high Se levels; elucidates associated health disorders or risks due to the consumption of Se-deficient or Se-rich foods; discusses the potential role of Se in different human disorders/diseases.

The evaluation of arsenic contamination potential, speciation and hydrogeochemical behaviour in aquifers of Punjab, Pakistan

In this study, we tested 123 groundwater wells from five different areas of Punjab, Pakistan for arsenic (As) contamination level and species, as well as delineated hydrogeochemical behaviour of As in aquifers. Results revealed that 75% and 41% of the groundwater wells exceeded the safe As limit of World Health Organisation (WHO, 10 μg L-1) and Pakistan-EPA (50 μg L-1), respectively. Arsenite (As(III)) and arsenate (As(V)) spanned 0-80% and 20-100% of total As (1.2-206 μg L-1), respectively. The mean As content (5.2 μg L-1) of shallow wells at 9-40 m depth did not exceed the WHO safe limit, representing a safe aquifer zone for pumping of groundwater compared to deeper wells at 41-90 m (51 μg L-1) and >90 m (23 μg L-1) depths. Piper-plot elucidated that the aqueous chemistry was dominated with Na-SO4, Na-Ca-SO4, Na-Mg-SO4 type saline water. Principal component analysis grouped As concentration with well depth, pH, salinity, Fe and CO3, exhibiting that these hydrogeochemical factors could have potential role in controlling As release/sequestration into the aquifers of study area. Geochemical modeling showed positive saturation indices only for iron (Fe) oxide-phases, indicating Fe oxides as the major carriers of As. Overall, this study provides insights to tackle emerging As threat to the communities in Punjab, Pakistan, as well as help develop suitable management/mitigation strategies - based on the baseline knowledge of As levels/species and factors governing As contamination in the study area.