Effects of Contaminant Concentration,Aging, and Soil Properties on the Bioaccessibility of Cr(III) and Cr(VI) in Soil

Contaminated soils at numerous U.S. Department of Defense, Department of Energy, and other industrial facilities often contain huge inventories of toxic metals such as chromium. Ingestion of soil by children is often the primary risk factor that drives the need for remediation. Site assessments are typically based solely on total soil-metal concentrations and do not consider the potential for decreased bioaccessibility due to metal sequestration by soil. The objectives of this research are to investigate the effect of soil properties on the bioaccessibility of Cr(III) and Cr(VI) as a function of contaminant concentration and aging. The A and upper B horizons of two well-characterized soils, representative of Cr-contaminated soils in the southeastern United States, were treated with varying concentration of Cr(III) and Cr(VI) and allowed to age. The bioaccessibility of the contaminated soils was measured over a 200-d time period using a physiologically based extraction test (PBET) that was designed to simulate the digestive process of the stomach. The sorption of Cr(III) and Cr(VI) varied significantly as a function of soil type and horizon, and the oxidation state of the contaminant. Solid phase concentrations with Cr(III) were significantly greater than Cr(VI) for any given initial Cr concentration. This is consistent with the mechanisms of Cr(III) vs. Cr(VI) sequestration by the soils, where the formation of Cr(III)-hydroxides can result in the accumulation of large mass fractions of contaminant on mineral surfaces. Overall, Cr bioaccessibility decreased with duration of exposure for all soils and at all solid phase concentrations, with aging effects being more pronounced for Cr(III). The decrease in Cr bioaccessibility was rapid for the first 50 d and then slowed dramatically between 50 and 200 d. In general, the effects of Cr solid phase concentration on bioaccessibility was small, with Cr(III) showing the most pronounced effect; higher solid phase concentrations resulted in a decrease in bioaccessibility. Chemical extraction methods and X-ray Adsorption Spectroscopy analyses suggested that the bioaccessibility of Cr(VI) was significantly influenced by reduction processes catalyzed by soil organic carbon. Soils with sufficient organic carbon had lower Cr bioaccessibility values (～10 to 20%) due to an enhanced reduction of Cr(VI) to Cr(III). In soils where organic carbon was limited and reduction processes were minimal, the bioaccessibility of Cr(VI) dramatically increased (～60 to 70%).     

Heavy metal pollutant induced changes in some biochemical parameters in the freshwater fish Clarias batrachus L

The data on the effects of Hg(II), As(V) and Pb(II) on the biochemical parameters of the freshwater fish. Clarias batrachus L., showed an increased protein content in the liver, kidney, stomach, intestine, testis and ovary, and a decreased content of it in the muscle as compared to control values. A decrease in dry weight and an increase in free amino acid and tissue permeability were recorded in all the organs after treatment with Hg(II), As(V) and Pb(II). In general, the organs were affected by the treatments in the order: Pb(II) greater than As(V) greater than Hg(II) and their effects were pronounced in the liver and kidney, followed by intestine, stomach, muscle, testis and ovary of the species.     

Effects of Particle Size and Redox Potential on Arsenic Fractionation in Soils Irrigated with Arsenate-rich Water

Aging affects arsenic (As) bioaccessibility in soils. This study focuses on the influences of particle size and redox potential on As(V) aging in irrigated soils. The results showed that variation of As fractions in fine particles, except the loosely adsorbed fraction, was larger than that in coarse particles over time. Anoxic conditions decreased the change in As fractions, with the exception of the exchangeable fraction in soils over time, in comparison to the aerobic condition. The aging processes of As(V) in different particle sizes and soils at different redox potentials exhibited several stages. The only significant difference in the aging process of As(V) in different particle sizes was the longer transformation period of the water-soluble fraction into the Fe/Mn/Al oxides-bound fraction in fine particles than in coarse particles. The redox potential had a significant influence on the aging process of As(V) in soils after 10 days of incubation. In terms of As bioaccessibility, anoxic conditions shortened the aging process of As(V) in soils. During the aging process, fine particles and aerobic conditions intensified the decrease in As(V) bioaccessibility in soils in comparison to the coarse particles and anoxic condition.     

Impact of Lipid Content on the Ability of Excipient Emulsions to Increase Carotenoid Bioaccessibility from Natural Sources (Raw and Cooked Carrots)

The influence of lipid concentration on the ability of excipient emulsions to increase carotenoid bioaccessibility from raw and cooked carrots was investigated using a simulated gastrointestinal tract (GIT). Excipient emulsions were fabricated using whey protein as a natural emulsifier and a long chain triglyceride (corn oil) as a digestible lipid. Changes in particle size, charge, and microstructure were determined as the carrot-emulsion mixtures were passed through simulated mouth, stomach, and small intestine. Carotenoid bioaccessibility increased with increasing digestible lipid concentration in the excipient emulsions (from 0 to 8 %). Carotenoid bioaccessibility was higher from boiled carrots than for raw carrots, which was attributed to disruption of plant cell structure facilitating carotenoid release. In conclusion, excipient emulsions are highly effective at increasing carotenoid bioaccessibility from carrots, which can be attributed to the ability of the small lipid droplets to rapidly solubilize the carotenoids.     

Impact of Humin on Soil Adsorption and Remediation of Cd(II), Pb(II), and Cu(II)

In situ immobilization constitutes a promising technology for the mitigation of contaminants, through the reduction of metal bioavailability and mobility. This study investigated the adsorption isotherms and kinetic characteristics of humin extracted from peat soils. We also studied the influences of the pH, ionic strengths, and soluble organic matter concentrations of soil solutions on the adsorptive properties of humin, and compared its ability to detoxify potentially toxic metals in both actual and simulated soil solutions. The study results indicated that humin contains a massive population of oxygen-containing functional groups. Its adsorption capacity for Pb(II) was greater than that for Cu(II), which exceeded that for Cd(II). The adsorption of humin for Pb(II) conformed to the Freundlich model, while the adsorption of humin for Cd(II) and Cu(II) followed the Langmuir model. The adsorption kinetics of humin with respect to potentially toxic metals aligned well with second-order kinetics equations. As the pH was elevated, the potentially toxic metal adsorption by humin increased rapidly. Electrolyte ions and tartaric acids in solution both inhibited the adsorption of potentially toxic metals by humin, and its ability to inactivate potentially toxic metals. This was shown to be improved in actual field soil solutions in contrast to simulated soil solutions.     

Human Health Risk Assessment of Soils Contaminated with Metal(loid)s by Using DGT Uptake: A Case Study of a Former Korean Metal Refinery Site

The human health risk of soils contaminated with As, Pb, Cu, and Zn was evaluated based on pseudo-total concentrations of metal(loid)s, the physiologically based extraction test (PBET), and diffusive gradients in thin films (DGT). Non-carcinogenic (NCR) and carcinogenic (CR) risks exceeded the U.S. Environmental Protection Agency criteria under both the residential and non-residential scenarios. Human bioavailable concentrations (PBET) were much lower than pseudo-total concentrations. The Hazardous Index of NCR (HI (NCR)) for the PBET in the studied soils was 67% and 94% less than that for pseudo-total concentration, respectively, under the non-residential and residential scenarios. Similarly, CR for the PBET was also 65% and 93% less for the two soils. The concentration of metal(loid)s accumulated in the DGT resin was highly correlated with the PBET-extractable concentration (R² > 0.649). Therefore, for both the CR and HI (NCR), the DGT-calculated risk was linearly related to the PBET-calculated risk for the studied soils under both scenarios. The results suggest that DGT uptake and PBET-extracted concentrations are good surrogates for risk estimation and that both J1 and J2 soils require remediation before their use for residential or non-residential purposes.     

Lead fractionation and bioaccessibility in contaminated soils with variable chemical properties

Abstract

The hazard imposed by trace elements within soils is dependent on soil properties and the relative distribution of metal species. Hence, a greenhouse column study was conducted to investigate the geochemical speciation and bioaccessibility of lead (Pb) as a function of soil properties. Four different soil types (Immokalee, Belle Glade, Tobosa and Millhopper series) varying in physico-chemical properties were selected and amended with Pb as Pb(NO₃) at 400, 800, and 1,200 mg kg^?1. A sequential extraction was employed to define the reactive metal pool, which was correlated with Pb bio-accessibility as determined by the physiologically based extraction test. Results show that Pb was mainly distributed in soluble+exchangeable phase in Immokallee (82%) and Millhopper (45%) series, and carbonate and Fe+Mn oxide fractions in Belle Glade (14–74%) and Tobosa (31–64%) series at time zero. With soil aging, Pb underwent chemical transformations in the soils and the majority of added Pb was associated with Fe+Mn oxide fraction (64–81%). Also, Pb bioaccessibility varied widely as a function of soil type and soil aging. Gastric phase (IVG-S) extracted 34–81% and 29–75% and the absorbed intestinal phase (IVG-AI) extracted 12–79% and 12–45% of amended Pb in all the soils at time zero and 6 months, respectively. Among soil types, Tobosa and Belle Glade showed reduced bioaccessibility relative to Immokalee and Millhopper. Statistical analysis revealed that the IVG-S Pb decreases as soil organic matter and cation exchange capacity (CEC) increases and total P decreases. While the Mehlich extractable P and Ca+Mg, total Fe+Al and organic matter predicted the Pb in an intestinal system.     

副溶血性弧菌在动态体外人胃仿生原位消化系统中的存活情况研究

副溶血性弧菌(Vibrio parahaemolyticus)是一种经口摄入感染的食源性致病菌,广泛存在于水产品中,然而其进入人胃后的存活情况尚属研究空白。本研究将浓度为10~7 cfu/g的副溶血性弧菌接种于三文鱼和南美白对虾中,运用体外人胃仿生原位消化系统进行消化模拟,经过120 min后,测定食物排空率、胃部pH值变化及幽门排出食糜中副溶血性弧菌的存活情况。结果显示三文鱼的胃排空滞后时间为60 min,南美白对虾为90 min,模拟消化120 min时,两种食糜均未完全排空。胃部pH值为(1.6±0.1),在食物摄入10 min后大幅上升,随着胃酸的不断分泌及食物的消化分解,其pH值开始下降,并保持在5.41左右。在食品消化120 min进入肠道后,副溶血性弧菌并没有完全被胃酸杀灭,对虾中该菌的存活率为(0.119±0.025)%,而三文鱼中存活率为(0.007±0.005)%。综上所述,副溶血性弧菌可随食物基质的消化分解通过胃排空进入肠道,从而躲避胃酸的杀灭并导致人体患病。     

Biosorption and Desorption of Lead(II) by Hydrilla verticillata

The potential of nonliving biomass of Hydrilla verticillata to adsorb Pb(II) from an aqueous solution containing very low concentrations of Pb(II) was determined in this study. Effects of shaking time, contact time, biosorbent dosage, pH of the medium, and initial Pb(II) concentration on metal-biosorbent interactions were studied through batch adsorption experiments. Maximum Pb(II) removal was obtained after 2 h of shaking. Adsorption capacity at the equilibrium increased with increasing initial Pb(II) concentration, whereas it decreased with increasing biosorbent dosage. The optimum pH of the biosorption was 4.0. Surface titrations showed that the surface of the biosorbent was positively charged at low pH and negatively charged at pH higher than 3.6. Fourier transform infrared (FT-IR) spectra of the biosorbent confirmed the involvement of hydroxyl and C?O of acylamide functional groups on the biosorbent surface in the Pb(II) binding process. Kinetic and equilibrium data showed that the adsorption process followed the pseudo-second-order kinetic model and both Langmuir and Freundlich isothermal models. The mean adsorption energy showed that the adsorption of Pb(II) was physical in nature. The monolayer adsorption capacity of Pb(II) was 125 mg g^?1. The desorption of Pb(II) from the biosorbent by selected desorbing solutions were HNO₃ > Na₂CO₃ > NaOH > NaNO₃.     

Reducing the Leachability and Bioaccessibility of Arsenic in Soils using Supported Nano Titanium Dioxide

We herein report the development and testing of a novel material, namely activated carbon-supported nano titanium dioxide (ACTD) for the immobilization of arsenic in soil. This material, which was prepared using a sol-gel method, effectively reduced the toxicity characteristic leaching procedure (TCLP) leachability and physiologically based extraction test (PBET) bioaccessibility of As(III) in soil samples. Upon processing the soils for 56 d at an ACTD dosage of 0.25 mmol g^?1, the TCLP leachability of As(III) was reduced by 82.7–97.7%, while the bioaccessibility was lowered by 58.6–81.2%. In addition, sequential extraction resulted in an 11.5–96.0% decrease in the mobile-As(III) and the mobilizable-As(III) fractions, but an increase in the residual-As(III) fraction upon treatment with ACTD. These observations indicate that the application of ACTD could result in an 80% reduction in As(III) environmental leaching, thereby confirming that ACTD appears suitable for the treatment of arsenic-contaminated soil.     

Sorption of Cr(VI), Cu(II) and Pb(II) by growing and non-growing cells of a bacterial consortium

This paper reports the sorption of three metallic ions, namely Cr(VI), Cu(II) and Pb(II) in aqueous solution by a consortium culture (CC) comprising an acclimatised mixed bacterial culture collected from point and non-point sources. Metal sorption capability of growing and non-growing cells at initial pH of between 3 and 8 in the 1-100mg/L concentration range were studied based on Q(max) and K(f) values of the Langmuir and linearised Freundlich isotherm models, respectively. Maximal metal loading was generally observed to be dependent on the initial pH. Growing cells displayed significant maximal loading (Q(max)) for Pb(II) (238.09 mg/g) and Cu(II) (178.87 mg/g) at pH 6 and at pH 7 for Cr(VI) (90.91 mg/g) compared to non-growing cells (p < 0.05). At the pH range of 6-8, growing cells showed higher loading capacity compared to non-growing cells i.e. 38-52% for Cr, 17-28% for Cu and 3-17% for Pb. At lower metal concentrations and at more acidic pH (3-4) however, non-growing cells had higher metal loading capacity than growing cells. The metal sorption capacity for both populations were as follows: Pb(II) > Cu(II) > Cr(VI).     

Biosorption of cadmium(II), lead (II) and copper(II) with the filamentous fungus Phanerochaete chrysosporium

The biosorption from artificial wastewaters of heavy metals (Cd(II), Pb(II) and Cu(II)) onto the dry fungal biomass of Phanerochaete chryosporium was studied in the concentration range of 5-500 mg l(-1). The maximum absorption of different heavy metal ions on the fungal biomass was obtained at pH 6.0 and the biosorption equilibrium was established after about 6 h. The experimental biosorption data for Cd(II), Pb(II) and Cu(II) ions were in good agreement with those calculated by the Langmuir model.     

Phytoremediation of lead (Pb) and Arsenic (As) by Melastoma malabathricum L. from Contaminated Soil in Separate Exposure

This study was conducted to investigate the uptake of lead (Pb) and arsenic (As) from contaminated soil using Melastoma malabathricum L. species. The cultivated plants were exposed to As and Pb in separate soils for an observation period of 70 days. From the results of the analysis, M. malabathricum accumulated relatively high range of As concentration in its roots, up to a maximum of 2800 mg/kg. The highest accumulation of As in stems and leaves was 570 mg/kg of plant. For Pb treatment, the highest concentration (13,800 mg/kg) was accumulated in the roots of plants. The maximum accumulation in stems was 880 mg/kg while maximum accumulation in leaves was 2,200 mg/kg. Only small amounts of Pb were translocated from roots to above ground plant parts (TF < 1). However, a wider range of TF values (0.01–23) for As treated plants proved that the translocation of As from root to above ground parts was greater. However, the high capacity of roots to take up Pb and As (BF > 1) is indicative this plants is a good bioaccumulator for these metals. Therefore, phytostabilisation is the mechanism at work in M. malabathricum's uptake of Pb, while phytoextraction is the dominant mechanism with As.     

HG (II)-induced changes in some biochemical parameters in the freshwater fish Clarias batrachus

The data on the effect of Hg(II) on changes of biochemical parameters in the freshwater fish, Clarias batrachus L. showed an increased protein content in the liver, kidney, stomach, intestine, testis and ovary, and a decreased content of it in the muscle over control data. A decrease in DNA, RNA and dry weight and an increase in free amino acids, tissue permeability and the activities of protease and RNase were recorded in all the organs by the treatment with Hg(II). In general, the effect of Hg(II) was maximum in the liver and kidney, followed by the intestine, stomach, muscle, testis and ovary of this species.     

Transfer of Np(V) nitrate from gastrointestinal segments of the adult rat

The transfer of soluble Np(V) nitrate was measured in gastrointestinal segments from adult rats by two procedures: instillation, in segments in which the physico-chemical form of Np might be modified by gastrointestinal factors; and perfusion, in segments in which the luminal state of Np remains constant. These assays allowed accurate measurement of the Np(V) transferred from the intestine to the whole body. The amount measured was proportional to segment length and to the duration of the experiments, which lasted for periods of 0.25 to 2 h. Under these experimental conditions, hourly transfer values were about 2 percent, both per millilitre of Np(V) solution instilled and per 10 cm of jejunum perfused. This flux is very much greater than that which may be deduced from studies in which Np was gavaged into intact rats. Intestinal transfer of Np was constant for Np concentrations ranging from 5 X 10(-12) M to 1 X 10-4) M. Raising the concentration of Np(V) to more than 1 X 10(-4) M reduced its intestinal transfer. Addition of Fe(II) also reduced it. The small intestine was the main site of Np(V) absorption, since the transfer from instilled jejunum was about 20 times that observed from the stomach, and no difference was noted between jejunal and duodenal transfer.     

In-Situ Remediation of Lead–Zinc Polymetallic Mine Contaminated Soils by MnFe2O4 Microparticles

In-situ remediation is a practical approach to remediate soils contaminated with heavy metals. The MnFe₂O₄ microparticles (MM) were prepared for the in-situ remediation of contaminated soils from a lead–zinc polymetallic mine in Inner Mongolia province, China. The effects of MM dosage, pH on remediation efficiency, were determined with static vibration leaching experiment, and the release risk of heavy metals of treated soil was studied by column leaching experiment. The results showed that the leached Cu, Pb, Zn, and As concentration decreased drastically with increasing MM dosage, when the dosage was lower than 10 g/kg. Moreover, the decrease of pH caused increase of leached concentration of Cu, Pb, Zn, but slight decrease of leached As concentration. For the amended soil, concentrations of leached heavy metals were lower than Grade III limit of Chinese Environmental Quality Standards for Ground and Surface water (GB3838-2002) under simulated acid rain leaching condition. In comparison with non-amended soils, the total amount of Cu, Pb, Zn, and As release from amended soils was reduced by 93.6%, 69.2%, 57.0%, and 99.7%, respectively. The MM is a kind of promising amendment for heavy metals contaminated soil.     

Soil–Plant Transfer Factors for Garden Produce from Contaminated Soils: Site Specific versus Generic Estimates for As and Pb

Using publicly available data for contaminated sites, regression relationships between As or Pb concentrations in co-located soils and leaf, root, and fruit vegetables, were developed. The improvement of these regression relationships by additional independent variables known to influence bioavailability of these trace elements in soil (soil pH, available phosphorous, Fe oxide, total Fe, and organic carbon content) was tested. Soil pH, but not plant-available P, decreased unexplained variation in the model for As in leafy vegetables. Iron oxide concentration in soil reduced unexplained variability in As concentrations in root vegetables, but with a positive coefficient thus contradicting its anticipated role as a competitor for As uptake by plants. None of the soil characteristics beyond total Pb concentration reduced variability observed in Pb concentrations in leafy or root vegetables, and there was no model that predicted Pb concentrations in fruit. Predictions of tissue concentration from single-value Plant-Uptake Factors (PUFs) for As in leaf and root vegetables, and for Pb accumulation in root vegetables, deviated more from the observed values than predictions from the regression relationships. The FW PUF determined from this study was within an order of magnitude of that used by the United Kingdom for development of generic soil quality values.     

Accumulation and mobilization of arsenate by Fe(III) polyions trapped in a Ca-polygalacturonate network

The role of Fe(III) stored at the soil–root interface in the accumulation of arsenate and the influence of citric acid on the As(V) mobility were investigated by using Ca-polygalacturonate networks (PGA). The results indicate that in the 2.5–6.2 pH range Fe(III) interacts with As(V) leading to the sorption of As(V) on Fe(III) precipitates or Fe–As coprecipitates. The FT-IR analysis of these precipitates evidenced that the interaction produces Fe(III)–As(V) inner-sphere complexes with either monodentate or bidentate binuclear attachment of As(V) depending on pH.In the 3.0–6.0 pH range, As(V) diffuses freely through the polysaccharidic matrix that was found to exert a negligible reducing action towards As(V). At pH 6.0 citric acid is able to mobilize arsenate from the As–Fe–PGA network through the complexation of the Fe(III) polyions that leads to the release of As(V).     

Assessment of lead availability in soils contaminated by mine spoil

The uptake of lead by two contrasting plant species, radish and red fescue, grown in soils contaminated by mine spoil was investigated. Uptake was found to be poorly correlated either with pH or total Pb concentration in the soils. By contrast, a good correlation was obtained, particularly for red fescue, between Pb uptake and Pb concentration in the solution of equilibrated soil suspensions over a wide range of soil pH, total soil Pb and soil solution Pb concentration.Calculations suggested a similar order of magnitude in the total amounts of Pb taken up by the plants and Pb in the soil solution of the root zone, justifying the latter as a good index of Pb-availability. ei]Section editor: A C Borstlap     

Copper(II) and lead(II) sorption from aqueous solution by non-living Spirogyra neglecta

Dried biomass of Spirogyra neglecta rapidly sorbed the test metals and the process became saturated in 10-20min. Maximum sorption of Pb(II) [116.1mgg(-1)] and Cu(II) [115.3mgg(-1)] occurred at 0.1gl(-1) biomass and 100mgl(-1) metal concentration in the solution. Sorption of Cu(II) and Pb(II) occurred optimally at pH 4.5 and 5.0, respectively. Lead(II) and Cu(II) sorption were lesser from binary metal solution than from single metal solution. Lead(II) more severely inhibited Cu(II) sorption than vice versa thus reflecting greater affinity of Pb(II) for the biomass. NaOH pretreatment slightly enhanced the metal removal ability of the biomass. During repeated sorption/desorption cycles, Pb(II) and Cu(II) sorption decreased by 11% and 27%, respectively, at the end of the fifth cycle due inter alia to 10-15% loss of biomass. Nevertheless, Spirogyra appears to be a good sorbent for removing metals Cu(II) and Pb(II) from wastewaters.