Sources of Arsenic and Fluoride in Highly Contaminated Soils Causing Groundwater Contamination in Punjab,Pakistan

Highly contaminated groundwater, with arsenic (As) and fluoride (F⁻) concentrations of up to 2.4 and 22.8 mg/L, respectively, has been traced to anthropogenic inputs to the soil. In the present study, samples collected from the soil surface and sediments from the most heavily polluted area of Punjab were analyzed to determine the F⁻ and As distribution in the soil. The surface soils mainly comprise permeable aeolian sediment on a Pleistocene terrace and layers of sand and silt on an alluvial flood plain. Although the alluvial sediments contain low levels of F, the terrace soils contain high concentrations of soluble F⁻ (maximum, 16 mg/kg; mean, 4 mg/kg; pH > 8.0). Three anthropogenic sources were identified as fertilizers, combusted coal, and industrial waste, with phosphate fertilizer being the most significance source of F⁻ accumulated in the soil. The mean concentration of As in the surface soil samples was 10.2 mg/kg, with the highest concentration being 35 mg/kg. The presence of high levels of As in the surface soil implies the contribution of air pollutants derived from coal combustion and the use of fertilizers. Intensive mineral weathering under oxidizing conditions produces highly alkaline water that dissolves the F⁻ and As adsorbed on the soil, thus releasing it into the local groundwater.     

Inorganic arsenic speciation in soil and groundwater near in-service chromated copper arsenate-treated wood poles

The environmental impact of chromated copper arsenate (CCA)-treated utility poles is linked to the possible soil and groundwater contamination with arsenic. The objective of the present study was to determine the arsenic speciation in soil and groundwater near in-service CCA-treated poles. Arsenite (As[III]) and arsenate (As[V]) concentrations were determined in 29 surface and subsurface soil samples collected near eight CCA-treated wood poles. Temporal variability of total arsenic concentrations and inorganic arsenic speciation was also assessed in groundwater at two sites through four sampling events over a 19-month period. Arsenic speciation was carried out by a solvent extraction method using ammonium pyrrolidine dithiocarbamate-methyl isobutyl ketone, and total arsenic was quantified by inductively coupled plasma/atomic emission spectrometry/hydride generation. Average arsenic concentrations in surface soils immediately adjacent to utility poles ranged from 153+/-49 to 410+/-150 mg/kg but approached background levels (below 5 mg/kg) within 0.50 m from the poles. A positive correlation was found between surface soil As concentration and total Fe content. In subsurface samples (0.50 m), arsenic levels were generally high in sandy soils (up to 223+/-32 mg/kg), moderate in clayey soils (up to 126+/-26 mg/kg), and relatively lower in organic soils (up to 56+/-24 mg/ kg). Arsenic(V) was the predominant arsenic species in surface (>78%) and subsurface soils (>66%). Total arsenic concentrations in groundwater below the clayey site were high and varied widely over time (79-390 microg/L), with 30 to 68% as As(III). Below the utility pole located on the organic site with a high Fe content, lower total arsenic levels (12-33 microg/L) were found, with As(III) ranging from 0 to 100%.     

Analysis of Arsenic Concentrations and Correlation in Water, Soil and Aurum by Neutron Activation Analysis Technique: A Case Study in Bagerhat, Bangladesh

Arsenic concentrations were measured in water, soil and arum (vegetables) samples using the Neutron Activation Analysis method and a correlation between arsenic concentrations in the samples was investigated. The case study at Bagerhat, Bangladesh revealed that almost all the water samples were contaminated by a hazardous level of arsenic that exceeding the World Health Organization recommended value of 0.05 mg/L for Bangladesh. Arsenic concentration of all the water samples ranged from 0.09 to 0.87 mg/L. The concentrations in soil and aurum samples were found to be in the range of 2.22–35.21 and 0.07–0.73 mg/kg, respectively. A positive correlation between arsenic concentrations in soil and water samples was observed. Aurum sample was found to be contaminated by arsenic to a harmful level if the corresponding water sample was also highly contaminated.     

Arsenic Status and Distribution in Soils at Disused Cattle Dip in South Africa

The status and the distribution of arsenic in soils from a disused cattle dip were determined. Elevated total arsenic levels (1,033–1,369 mg/L) were detected in the soils. Significant difference (p < 0.05) between the values for the soils obtained from the contaminated sites and control site (0.15 mg/L) was observed. The level of total arsenic decreased with increase in depth. The peak total arsenic (1,369 mg/L) was obtained at 0 cm depth, indicating the abundance of arsenic at the surface despite the fact that the dip has been out of use for a long time. The total arsenic recorded for different depths were significantly higher than the trigger value of 40 mg/kg. The distribution of arsenic in the different phases showed that arsenic was mostly bound to the residual fractions (52%) and Fe and Al hydroxides (21%). The distribution of arsenic in the order phases was in the following order: exchangeable (14%), carbonates (10%) and soluble (3%).     

Arsenic Concentrations in Soils Impacted by Dam Failure of Coal-Ash Pond in Zemianske Kostolany,Slovakia

In this study, the concentrations of arsenic were determined in the soils around old coal-ash pond. The soils in the study area were severely contaminated with arsenic after dam failure of the coal-ash pond. The mean concentrations of arsenic in soils collected from three sampling depths of 0–20, 20–40 and >40 cm were 173, 155 and 426 μg/g, respectively, exceeding greatly the Dutch intervention threshold for this element. Arsenic concentrations were positively correlated with total iron and aluminium contents in the soils (r = 0.73, p < 0.001 and r = 0.72, p < 0.001, respectively), indicating that oxyhydroxides of iron and aluminium may control the distribution of arsenic in these soils. Ammonium nitrate extractant was used to mimic availability of arsenic for plant uptake from the soils. Between 0.05 and 6.21% of the total soil arsenic were extracted using a single extraction test and a significant positive correlation between soil leachate pH and arsenic extractability (r = 0.70, p < 0.01) was observed. This suggested that soil pH might play a role in the bioavailability of arsenic.     

Identification of Sesbania sesban (L.) Merr. as an Efficient and Well Adapted Phytoremediation Tool for Cd Polluted Soils

A pot experiment was carried out to assess Cd uptake and accumulation efficiency of Sesbania sesban. Plants were grown in soil spiked with 25, 50, 100, 150, 200, 250, and 300 mg/kg Cd. After 120 days, plants were harvested and analyzed for Cd content. A steady increase in Cd accumulation with increasing metal concentration in soil was observed for all treatments. Accumulation of Cd was greatest in roots (86.7 ± 6.3 mg/kg), followed by stem (18.59 ± 1.9 mg/kg), and leaf (3.16 ± 1.1 mg/kg). Chlorophyll content declined with increasing Cd concentration, while proline and protein content increased as compared to control. At higher Cd levels, root, shoot length, and biomass were all significantly reduced (p ≤ 0.001). An increase in total protein along with greater A₂₅₀/A₂₈₀ value suggested an increase in metal-protein complexes. Considering the rapid growth, high biomass, accumulation efficiency, and adaptive properties, this plant could be used as a valuable tool for the phytoremediation of Cd contaminated soils.

     

Transfer of Copper,Lead and Zinc in Soil–Grass Ecosystem in Aspect of Soils Properties,in Poland

The total metal concentrations in soil samples from polluted area (roadside soils) ranged from 13.87 to 195.76 mg/kg for Cu; 13.56–310.17 mg/kg for Pb and 18.43–894.11 mg/kg for Zn and they were, respectively about 5, 2 and 13 times above the corresponding values in soil samples from country area. The mean values of EDTA-extractable concentrations in soil samples at unpolluted sites were: 2.47 mg/kg for Cu, 6.33 mg/kg for Pb and 4.94 mg/kg for Zn. The highest concentrations of Cu, Pb and Zn in grass were measured in soils from polluted area. Higher values of proportions of EDTA-extractable metals (24% for Cu, 40% for Pb and 38% for Zn) indicate that anthropogenic metals were more mobile and bioavailable than the same metals in soils from unpolluted area (20, 16 and 20% for Cu, Pb and Zn, respectively). The availability of Cu, Pb and Zn are affected by soil properties such as pH, organic matter content and cation exchange capacity. Correlation between the EDTA-extractable forms concentrations of metals and the total concentration in the various soils was observed. The coefficients of determination (R²) varied between 0.809 for Cu; 0,709 for Pb and 0.930 for Zn in polluted soils and they are higher than corresponding values in unpolluted soils.     

Toxicological Responses of Red-Backed Salamander (Plethodon cinereus) Exposed to Aged and Amended Soils Containing Lead

The use of lead in military and civilian small arms projectiles is widely acknowledged to have resulted in high soil lead concentrations at many small arms ranges. These ranges are often adjacent to wildlife habitat or have become habitat when no longer used. To assess the potential toxicity of lead to terrestrial amphibians in contaminated areas, we exposed 100 red-backed salamanders (Plethodon cinereus) to either a control soil or one of four soil treatments amended with lead acetate for 28 days. Analytical mean soil concentrations were 14 (control), 553, 1700, 4700, and 9167 mg Pb/kg soil dry weight. An additional 60 salamanders were also exposed for 28 days to one of six field-collected soil samples from a small arms range and a skeet range. The field soil concentrations ranged from 11 (background) to 16,967 mg Pb/kg soil dry weight. Food consisted of uncontaminated flightless Drosophila melanogaster. Salamander survival was reduced in amended soil treatments of 4700 and 9167 mg/kg by 15% and 80%, respectively. Inappetence was observed at 4700 and 9167 mg/kg and growth decreased in the 9167 mg/kg treatment. Total white blood cells decreased 32% at 4700 mg/kg compared to controls and were 22% lower in the 9167 mg/kg treatment. In contrast, survival was 100% for all field-collected soils with no hematological effects. At 16,967 mg/kg there was evidence of soil avoidance and decreased growth. These data suggest marked differences in toxicity and bioavailability of the lead-amended soil in contrast to the field-collected soil containing lead.     

Effect of soil properties on lead bioavailability and toxicity to earthworms

Soil properties are important factors modifying metal bioavailability to ecological receptors. Twenty-one soils with a wide range of soil properties (USA; http://soils.usda.gov/technical/classification/taxonomy/) were amended with a single concentration of Pb (2,000 mg/kg) to determine the effects of soil properties on Pb bioavailability and toxicity to earthworms. Earthworm mortality ranged from 0 to 100% acute mortality following exposure to the same total concentration of Pb (2,000 mg/kg) in amended field soils. Internal Pb concentrations in earthworms ranged from 28.7 to 782 mg/kg, with a mean of 271 mg/kg. Path analysis was used to partition correlations in an attempt to discern the relative contribution of each soil property. Results of path analysis indicated that pH was the most important soil property affecting earthworm mortality (p < 0.01) and internal Pb (p < 0.05). Soil pH was related inversely to mortality and internal Pb, soil solution Pb, and Pb bioavailability. The most important soil property modifying reproduction was amorphous iron and aluminum oxides (FEAL). Because FEAL is rich in pH-dependent cation-exchange sites, several soil properties, including pH, FEAL, and cation-exchange capacity, have a causal effect on Pb adsorption and soluble Pb. Path analysis is useful for assessing contaminated soils with a wide range of soil properties and can assist in ecological risk assessment and remediation decisions for contaminated sites. Soil properties are important factors modifying metal bioavailability and toxicity and should be considered during the ecological risk assessment of metals in contaminated soils.     

Arsenic speciation in the earthworms Lumbricus rubellus and Dendrodrilus rubidus

Two species of earthworm, Lumbricus rubellus Hoffmeister and Dendrodrilus rubidus (Savigny) collected from an arsenic-contaminated mine spoil site and an uncontaminated site were investigated for total tissue arsenic concentrations and for arsenic compounds by liquid chromatography-mass spectrometry (LC-MS) and liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). For L. rubellus, whole-body total tissue arsenic concentrations were 7.0 to 17.0 mg arsenic/ kg dry weight in uncontaminated soil and 162 to 566 mg arsenic/kg dry weight in contaminated soil. For D. rubidus, whole-body tissue concentrations were 2.0 to 5.0 mg arsenic/kg dry weight and 97 to 321 mg arsenic/kg dry weight, respectively. Arsenobetaine was the only organic arsenic species detected in both species of earthworms, with the remainder of the extractable arsenic being arsenate and arsenite. There was an increase in the proportion of arsenic present as arsenobetaine in the total arsenic burden. Lumbricus rubellus and D. rubidus have similar life styles, both being surface living and litter feeding. Arsenic speciation was found to be similar in both species for both uncontaminated and contaminated sites, with dose-dependent formation of arsenobetaine. When L. rubellus and D. rabidus from contaminated sites were incubated in arsenic-free soils, the total tissue burden of arsenic diminished. Initially, L. rubellus from the tolerant populations (from the contaminated site) eliminated arsenic in the first 7 d of exposure before accumulating arsenic in tissues, whereas nontolerant populations (from the uncontaminated site) accumulated arsenic linearly. The tolerant and nontolerant L. rubellus eliminated tissue arsenic linearly over 21 d when incubated in uncontaminated soil.     

Arsenic in Air and Soil in the Vicinity of the Central Gas Station Molve,Croatia

Spatial and temporal distribution of arsenic levels in soil during the 9 year monitoring period was investigated on four different soil types in the area of the gas borehole system Podravina in Croatia. Arsenic levels in the PM₁₀ particle fraction were measured periodically at the same locations for 3 years. Arsenic levels in soil significantly depended on soil types. Elevated levels were found on gleysol vertic, at two sampling sites, with values exceeding 30 mg/kg of arsenic in soil. Arsenic levels in air were low and they were not significantly different between sampling sites, suggesting that gas borehole activities have no influence on arsenic levels in the environment.     

Risk from Winter Vegetables and Pulses Produced in Arsenic Endemic Areas of Nadia District: Field Study Comparison With Market Basket Survey

Arsenic contaminated groundwater uses for irrigation potentially lead the incidence of arsenic into food chain. In present study we examined total arsenic concentrations in 32 types of vegetables and 7 types of pulses. Range of total arsenic concentration in edible parts of vegetables collected from grown fields was 0.114–0.910 mg/kg. Highest arsenic values were in spinach 0.910 mg/kg. Vegetable samples were grouped into leafy, non-leafy-fruity, root-tubers. 18 common types of vegetables and pulses were collected through market basket survey, total arsenic were approximately 100 mg lower than those observed for the vegetables collected from the fields.     

Arsenic contamination in New Orleans soil: Temporal changes associated with flooding

The flooding of New Orleans in late August and September 2005 caused widespread sediment deposition in the flooded areas of the city. Post-flood sampling by US EPA revealed that 37% of sediment samples exceeded Louisiana corrective screening guidelines for arsenic of 12 mg/kg, but there was debate over whether this contamination was pre-existing, as almost no pre-flood soil sampling for arsenic had been done in New Orleans. In this study, archived soil samples collected in 1998-1999 were location-matched with 70 residential sites in New Orleans where post-flood arsenic concentrations were elevated. Those same locations were sampled again during the recovery period 18 months later. During the recovery period, sampling for arsenic was also done for the first time at school sites and playgrounds within the flooded zone. Every sample of sediment taken 1-10 months after the flood exceeded the arsenic concentration found in the matched pre-flood soils. The average difference between the two sampling periods was 19.67 mg/kg (95% CI 16.63-22.71) with a range of 3.60-74.61 mg/kg. At virtually all of these sites (97%), arsenic concentrations decreased substantially by 18 months into the recovery period when the average concentration of matched samples was 3.26 mg/kg (95% CI 1.86-4.66). However, 21 (30%) of the samples taken during the recovery period still had higher concentrations of arsenic than the matched sample taken prior to the flooding. In addition, 33% of samples from schoolyards and 13% of samples from playgrounds had elevated arsenic concentrations above the screening guidelines during the recovery period. These findings suggest that the flooding resulted in the deposition of arsenic-contaminated sediments. Diminution of the quantity of sediment at many locations has significantly reduced overall soil arsenic concentrations, but some locations remain of concern for potential long-term soil contamination.     

Dietary Intake of Total and Inorganic Arsenic by Adults in Arsenic-Contaminated Area of Ron Phibun District, Thailand

Ron Phibun District, approximately 800 km south of Bangkok, is the site of tin mines operated almost 100 years ago. As a result of mining activities, arsenic contaminated the soil and groundwater of the district. The specific aim of this study was to estimate the dietary intakes of total and inorganic arsenic in 20 adults (10 males and 10 females) residing in Ron Phibun District by a duplicate food approach for 7-consecutive days. The weekly intake rates of inorganic arsenic ranged from 5.54 to 13.3 μg/kg BW for males and 6.11–12.1 μg/kg BW for females.     

Removal of Selenium from Se Enriched Natural Soils by a Consortium of Bacillus Isolates

Four bacterial strains designated as SNTP-1, NS-2 to NS-4 were isolated from selenium contaminated soils of Nawanshahr-Hoshiarpur region of Punjab, India, by enrichment technique and a consortium was developed using these isolates. The isolates were observed to be belonging to Bacillus sp. In soil microcosm, complete removal was observed by the consortium in selenite augmented soils while the rate of removal with consortia in selenate treatment was 72% after 120 days. Population survival of isolates showed stability at lower treatments and decline at higher levels of Se enrichment. The consortium can, thus, be used for removal of Se contaminated sites.     

Effect of Bauxite Mineralized Soil on Residual Metal Levels in Some Post Harvest Food Crops in Jamaica

The concentrations of nine residual metals in some Jamaican foods were determined using inductively coupled plasma mass spectrometry technique. Cadmium concentration was highest in yellow yam (0.21 mg/kg). Sweet potato had the highest concentrations of lead (0.31 mg/kg), arsenic (0.70 mg/kg) and mercury (0.35 mg/kg). Samples from Grove Place exceeded the regulatory limits of 0.1 mg/kg for cadmium, lead and arsenic and 0.05 mg/kg for mercury. Significant correlations were found between soil and agricultural produce concentrations for cadmium and lead (r² ≥ 0.5). These results suggest that the elements were available in soluble forms in the soil for absorption by food crops.     

Phytotoxicity and phytoaccumulation of trivalent and hexavalent chromium in brake fern

A recently recognized hyperaccumulator plant, Chinese brake fern (Pteris vittata), has been found to extract very high concentration of arsenic from arsenic-contaminated soil. Chromium usually is a coexisting contaminant with arsenic in most contaminated soils. The potential application of ferns for phytoremediation of chromium(III)- and chromium(VI)-contaminated soils and their phytotoxicity to ferns has not been studied before. In this study, chromium distribution and phytotoxicity at the plant and cellular levels of brake ferns were studied using chemical analyses and scanning electron microscopy. The results show a higher phytotoxicity of Cr from Cr(VI)-contaminated soil to Chinese brake fern than from Cr(III)-contaminated soil. Phytotoxicity symptoms included significant decreases both in fresh biomass weight and relative water content (RWC), and also in leaf chlorosis during the late stage of growing. At higher concentrations (500 mg/kg Cr[VI] and 1,000 mg/kg Cr[III] addition), plants showed reduction in the number of palisade and spongy parenchyma cells in leaves. Compared with other plant species reported for phytoremediation of Cr(VI)-contaminated soil, brake fern took up and accumulated significant amounts of Cr (up to 1,145 mg/kg in shoots and 5,717 mg/kg in roots) and did not die immediately from phytotoxicity. Our study suggests that Chinese brake fern is a potential candidate for phytoremediation of Cr(VI)-contaminated soils, even though plants showed severe phytotoxic symptoms at higher soil Cr concentrations.     

Presence of Polycyclic Aromatic Hydrocarbons (PAHs) in Top Soils from Rural Terrains in Mexico City

A soil survey was carried out to determine the levels and sources and concentrations of 16 polycyclic aromatic hydrocarbons in 2 semi-rural terrains in Mexico City (Tlahuac and Milpa Alta) during 2008–2009. PAH determination was made by Soxhlet extraction and chromatographic clean-up with final analysis by gas chromatography with a flame ionization detector. The concentrations in Tlahuac were 9.13 mg/kg (dry season) and 11.22 mg/kg (wet season) and in Milpa Alta were 11.43 mg/kg (dry season) and 35.77 mg/kg (wet season). The variation of total PAH concentrations are due to environmental and anthropogenic conditions within Mexico City and also the addition of compost to the soils. According to Mexican regulations BaP, DaA, BbF and Ind were within the permissible limit (2 mg/kg) for agricultural and residential soils and BkF was close to the limit (8 mg/kg). The total PAH concentrations do however surpass the permissible European limit of 1,000 μg/kg and there is probably some risk to human health, in spite of measures aimed at decreasing contamination in Mexico City. Long term monitoring of soils will be necessary.     

Simple and Sensitive Method for Determination of Imidacloprid Residue in Soil and Water by HPLC

A rapid, sensitive and reliable HPLC method was developed and validated for the determination of imidacloprid residue in water at different pH and in soil. Quantification was performed by reversed phase HPLC system equipped with UV detector. The limit of quantification (LOQ) was found to be 0.02 mg/kg in soil and 0.02 mg/L in water. The limit of detection (LOD) was 0.006 mg/kg in soil and 0.006 mg/L in water. Recoveries for imidacloprid were 95.18%, 94.66%, 95.27% and 94.78% in black, red, sandy loam and clay soils, respectively. Recoveries for imidacloprid from water were 96.86%, 86.14%, and 92.34% at pH values of 4, 7, and 9, respectively.     

Redistribution of Fractions of Zinc,Cadmium, Nickel,Copper, and Lead in Contaminated Calcareous Soils Treated with EDTA

Effect of ethylene diamine tetraacetic acid (EDTA) on the fractionation of zinc (Zn), cadmium (Cd), nickel (Ni), copper (Cu), and lead (Pb) in contaminated calcareous soils was investigated. Soil samples containing variable levels of contamination, from 105.9 to 5803 mg/kg Zn, from 2.2 to 1361 mg/kg Cd, from 31 to 64.0 mg/kg Ni, from 24 to 84 mg/kg Cu, and from 109 to 24,850 mg/kg Pb, were subjected to EDTA treatment at different dosages of 0, 1.0, and 2.0 g/kg. Metals in the incubated soils were fractionated after 5 months by a sequential extraction procedure, in which the metal fractions were experimentally defined as exchangeable (EXCH), carbonate (CARB), Mn oxide (MNO), Fe oxide (FEO), organic matter (OM), and residual (RES) fractions. In contaminated soils without EDTA addition, Zn, Ni, Cu, and Pb were predominately present in the RES fraction, up to 60.0%, 32.3%, 41.1%, and 36.8%, respectively. In general, with the EDTA addition, the EXCH and CARB fractions of these metals increased dramatically while the OM fraction decreased. The Zn, Ni, Cu, and Pb were distributed mostly in RES, OM, FEO, and CARB fractions in contaminated soils, but Cd was found predominately in the CARB, MNO, and RES fractions. The OM fraction decreased with increasing amounts of EDTA. In the contaminated soils, EDTA removed some Pb, Zn, Cu, and Ni from MNO, FEO, and OM fractions and redistributed them into CARB and EXCH fractions. Based on the relative percent in the EXCH and CARB fractions, the order of solubility was Cd > Pb > Ni > Cu > Zn for contaminated soils, before adding of EDTA, and after adding of EDTA, the order of solubility was Pb > Cd > Zn > Ni > Cu. The risk of groundwater contamination will increase after applying EDTA and it needed to be used very carefully.