Comparison of in vivo and in vitro methodologies for the assessment of arsenic bioavailability in contaminated soils

An in vivo swine assay was utilised for the determination of arsenic (As) bioavailability in contaminated soils. Arsenic bioavailability was assessed using pharmacokinetic analysis encompassing area under the blood plasma-As concentration time curve following zero correction and dose normalisation. In contaminated soil studies, As uptake into systemic circulation was compared to an arsenate oral dose and expressed as relative As bioavailability. Arsenic bioavailability ranged from 6.9+/-5.0% to 74.7+/-11.2% in 12 contaminated soils collected from former railway corridors, dip sites, mine sites and naturally elevated gossan soils. Arsenic bioavailability was generally low in the gossan soils and highest in the railway soils, ranging from 12.1+/-8.5% to 16.4+/-9.1% and 11.2+/-4.7% to 74.7+/-11.2%, respectively. Comparison of in vivo and in vitro (Simplified Bioaccessibility Extraction Test [SBET]) data from the 12 contaminated soils and bioavailability data collected from an As spiked soil study demonstrated that As bioavailability and As bioaccessibility were linearly correlated (in vivo As bioavailability (mgkg(-1))=14.19+0.93.SBET As bioaccessibility (mgkg(-1)); r(2)=0.92). The correlation between the two methods indicates that As bioavailability (in vivo) may be estimated using the less expensive, rapid in vitro chemical extraction method (SBET) to predict As exposure in human health risk assessment.     

In vitro gastro-intestinal method for the assessment of heavy metal bioavailability in contaminated soils

Introduction  

Balya and its associated villages which is a town of the Balikesir region of Turkey have very rich zinc, lead, and manganese mines. These mines have been operating since the thirteenth century and now there is heavy metal contamination in both the soil and natural waters in these areas.     

Effects of oxalate and phosphate on the release of arsenic from contaminated soils and arsenic accumulation in wheat

Oxalate is exuded by plants in the rhizosphere and plays an important role in the soil/root interactions. Phosphate fertilizer is widely used all over the world and may influence the behavior of arsenic (As) in soils. In this study oxalate and phosphate were used as extractants to investigate their effects on the release of As from three As-contaminated soils and the chemical speciation of As. Concentrations of arsenite (As(III)) and arsenate (As(V)) released progressively increased by increasing the concentrations of oxalate or phosphate. The released As(V) content was higher than that of As(III) and the differences between As(V) and As(III) released by oxalate was more obvious than by phosphate. Greenhouse experiment was conducted to evaluate the effects of oxalate and phosphate on As uptake by wheat (Triticum vulgare L.). Addition of oxalate or phosphate resulted in the increase of As accumulation in both wheat root and shoot and the effect of phosphate was more obvious than that of oxalate.     

Distribution, speciation and availability of antimony (Sb) in soils and terrestrial plants from an active Sb mining area

Here, we present one of the first studies investigating the mobility, solubility and the speciation-dependent in-situ bioaccumulation of antimony (Sb) in an active Sb mining area (Xikuangshan, China). Total Sb concentrations in soils are high (527-11,798 mg kg⁻¹), and all soils, including those taken from a paddy field and a vegetable garden, show a high bioavailable Sb fraction (6.3-748 mg kg⁻¹), dominated by Sb(V). Elevated concentrations in native plant species (109-4029 mg kg⁻¹) underpin this. Both chemical equilibrium studies and XANES data suggest the presence of Ca[Sb(OH)₆]₂, controlling Sb solubility. A very close relationship was found between the citric acid extractable Sb in plants and water or sulfate extractable Sb in soil, indicating that citric acid extractable Sb content in plants may be a better predictor for bioavailable Sb in soil than total acid digestible Sb plant content.     

Distribution of antimony in contaminated grassland: 1--Vegetation and soils

Antimony concentrations in surface soils were found to decrease with increasing distance from an antimony smelter. This pattern was also found in moss bags exposed in the same area. At three sites close to the smelter, antimony concentrations in soil and vegetation were much higher than at a rural control site and published background levels. Maximum soil and plant concentrations on a dry weight basis of 1489 mg kg(-1) and 336 mg kg(-1), respectively, were found, compared to background levels of <1 mg kg(-1). Field exposure of grass in pots of uncontaminated soil and a laboratory experiment using soils from near the smelter suggested that the antimony in vegetation was largely due to continued aerial deposition and not to uptake from soil.     

An investigation of inorganic antimony species and antimony associated with soil humic acid molar mass fractions in contaminated soils

The presence of antimony compounds is often suspected in the soil of apple orchards contaminated with lead arsenate pesticide and in the soil of shooting ranges. Nitric acid (1M) extractable Sb from the shooting range (8300 microg kg(-1)) and the apple orchard (69 microg kg(-1)) had considerably higher surface Sb levels than the control site (<1.5 microg kg(-1)), and Sb was confined to the top approximately 30 cm soil layer. Sb(V) was the principal species in the shooting range and the apple orchard surface soils. Size exclusion chromatography-inductively coupled plasma-mass spectrometry (SEC-ICP-MS) analysis of humic acids isolated from the two contaminated soils demonstrated that Sb has complexed to humic acid molar mass fractions. The results also indicate that humic acids have the ability to arrest the mobility of Sb through soils and would be beneficial in converting Sb(III) to a less toxic species, Sb(V), in contaminated areas.     

An uptake and elimination kinetics approach to assess the bioavailability of chromium,copper, and arsenic to earthworms (Eisenia andrei) in contaminated field soils

The aim of this study was to determine the bioavailability of metals in field soils contaminated with chromated copper arsenate (CCA) mixtures. The uptake and elimination kinetics of chromium, copper, and arsenic were assessed in the earthworm Eisenia andrei exposed to soils from a gradient of CCA wood preservative contamination near Hartola, Finland. In soils contaminated with 1480–1590 mg Cr/kg dry soil, 642–791 mg Cu/kg dry soil, and 850–2810 mg Ag/kg dry soil, uptake and elimination kinetics patterns were similar for Cr and Cu. Both metals were rapidly taken up and rapidly excreted by Eisenia andrei with equilibrium reached within 1 day. The metalloid As, however, showed very slow uptake and elimination in the earthworms and body concentrations did not reach equilibrium within 21 days. Bioaccumulation factors (BAF) were low for Cu and Cr (< 0.1), but high for As at 0.54–1.8. The potential risk of CCA exposure for the terrestrial ecosystem therefore is mainly due to As.

     

复合污染土壤中砷和镉的原位固定效果研究

采用人工模拟的砷和镉复合污染土壤研究了不同修复剂对砷和镉固定能力的差异.结果表明,经MgO、CaO这2种碱性药剂处理后4种不同污染浓度的土样中砷和镉的浸出浓度均有所降低,在一定程度上能使2种污染元素达到共同稳定,但土壤pH会随着两者加入量的增加而升高,因此使用时要仔细考虑两者的用量;Al2O3对土样中的砷和镉也有一定的...     

Impact of rhizosphere microorganisms on arsenic (As) transformation and accumulation in a traditional Chinese medical plant

Environmental Science and Pollution Research - Panax notoginseng is an important traditional medicinal plant, but the commercial value is threatened by root-rot disease caused by rhizosphere...     

As(V) and Sb(V) co-adsorption onto ferrihydrite: synergistic effect of Sb(V) on As(V) under competitive conditions

Competitive adsorption of As(V) and Sb(V) at environmentally relevant concentrations onto ferrihydrite was investigated. Batch experiments and XPS analyses confirmed that in a binary system, the presence of Sb(V) exhibited a slight synergistic effect on As(V) adsorption. XPS analyses showed that As(V) and Sb(V) adsorption led to obvious diminishment of Fe–O–Fe and Fe–O–H bonds respectively. At pH of 9, a more significant decrease of Fe–O–Fe was observed in the binary system than that in a single system, indicating that As(V) displayed an even stronger interaction with lattice oxygen atoms under competitive conditions. Basically, ionic strength demonstrated a negligible or positive influence on As(V) and Sb(V) adsorption in binary system. Study of adsorption sequence also indicated that the presence of Sb(V) showed a promotion effect on As(V) adsorption at neutral pHs. Considering that co-contamination of As and Sb in waters has been of great concern throughout the world, our findings contributed to a better understanding of their distribution, mobility, and fate in environment.

     

Organo-modified sericite in the remediation of an aquatic environment contaminated with As(III) or As(V)

The aim of this investigation was to obtain the hybrid material precursor to the naturally and abundantly available sericite, a mica-based clay; the materials were further employed in the remediation of arsenic from aqueous solutions. The study was intended to provide a cost-effective and environmentally benign treatment technology. The hybrid organo-modified sericite was obtained using hexadecyltrimethylammonium bromide (HDTMA) and alkyldimethylbenzylammonium chloride (AMBA) organic surfactants by introducing regulated doses of HDTMA or AMBA. The materials were characterized using infrared and X-ray diffraction analytical data, whereas the surface morphology was discussed by taking its SEM images. These materials were employed to assess the pre-concentration and speciation of As(III) and As(V) from aqueous solutions. The batch reactor data showed that increasing the sorptive concentration (from 1.0 to 15.0 mg/L) and pH (i.e., pH 2.0 to 10.0) caused the percent uptake of As(III) and As(V) to decrease significantly. The kinetic data showed that a sharp initial uptake of arsenic reached its equilibrium state within about 50 min of contact time, and the sorption kinetics followed a pseudo-second-order rate law both for As(III) and As(V) sorption. A 1,000 times increase in the background electrolyte concentration, i.e., NaNO₃, caused a significant decrease in As(III) removal, whereas As(V) was almost unaffected, which inferred that As(III) was adsorbed, mainly by the van der Waals or even by the electrostatic attraction, whereas As(V) was adsorbed chemically and formed “inner-sphere” complexes at the solid/solution interface. The equilibrium state modeling studies indicated that the sorption data fitted well the Freundlich and Langmuir adsorption isotherms. Henceforth, the removal capacity was calculated under these equilibrium conditions. It was noted that organo-modified sericite possessed a significantly higher removal capacity compared to its virgin sericite. Between these two organo-modified sericite, the HDTMA-modified sericite possessed a higher removal capacity compared to the AMBA-modified sericite.     

In vitro and in vivo approaches for the measurement of oral bioavailability of lead (Pb) in contaminated soils: a review

We reviewed the published evidence of lead (Pb) contamination of urban soils, soil Pb risk to children through hand-to-mouth activity, reduction of soil Pb bioavailability due to soil amendments, and methods to assess bioaccessibility which correlate with bioavailability of soil Pb. Feeding tests have shown that urban soils may have much lower Pb bioavailability than previously assumed. Hence bioavailability of soil Pb is the important measure for protection of public health, not total soil Pb. Chemical extraction tests (Pb bioaccessibility) have been developed which are well correlated with the results of bioavailability tests; application of these tests can save money and time compared with feeding tests. Recent findings have revealed that fractional bioaccessibility (bioaccessible compared to total) of Pb in urban soils is only 5-10% of total soil Pb, far lower than the 60% as bioavailable as food-Pb presumed by U.S.-EPA (30% absolute bioavailability used in IEUBK model).     

Organism-induced accumulation of iron, zinc and arsenic in wetland soils

Four year old spruce (Picea abies (L.) Karst.) seedlings were planted in sand pots and supplied with nutrient solution. Three groups were formed, differing only in manganese nutrition (0.5 ppm, 2.5 ppm, 12.5 ppm, respectively). After three months, five individuals of each group were transferred to a dew chamber. For the next seven weeks the trees were sprayed in the evenings, the relative humidity overnight was kept high and the droplets were collected directly from the needles in the mornings. The trees were sprayed with HNO3 (pH 3.4) during the first three weeks to reduce the natural buffering capacity of the needles. After this time, the trees were sprayed with KCl (1 mM) solution, and NaHSO3 was added to the chamber resulting in SO2 concentrations usually between 50 and 150 microg m(-3). Needles and water samples were analysed. Foliar Ca seemed to be only a short-time buffer even under optimal Ca supply. A highly significant influence of managanese supply on manganese in needles and droplets was observed, as well as on sulphate, H+ and calcium concentrations in the droplets. The SO2 flux to trees treated with 12.5 ppm Mn was about twice as high as to trees treated with 0.5 ppm Mn. The conclusion is that this is due to a synergism between manganese leaching and catalysis of the SO2 oxidation by the leached Mn2+ ions. The results suggest a positive feedback between (moderate) acidification of soils and SO2 and NH3 inputs to terrestrial ecosystems.     

Application of an in vivo swine model for the determination of arsenic bioavailability in contaminated vegetables

Considerable information is available in the literature regarding the uptake of arsenic (As) from contaminated soil and irrigation water by vegetables. However, few studies have investigated As speciation in these crops while a dearth of information is available on As bioavailability following their consumption. In this study, the concentration and speciation of As in chard, radish, lettuce and mung beans was determined following hydroponic growth of the vegetables using As-contaminated water. In addition, As bioavailability was assessed using an in vivo swine feeding assay. While As concentrations ranged from 3.0 to 84.2mg As kg(-1) (dry weight), only inorganic As (arsenite and arsenate) was detected in the edible portions of the vegetables. When As bioavailability was assessed through monitoring blood plasma As concentrations following swine consumption of As-contaminated vegetables, between 50% and 100% of the administered As dose was absorbed and entered systemic circulation. Arsenic bioavailability decreased in the order mung beans>radish>lettuce=chard.     

Chemometric evaluation for the relation of BCR sequential extraction method and in vitro gastro-intestinal method for the assessment of metal bioavailability in contaminated soils in Turkey

Introduction  

A chemometric evaluation has been done to classify metal ions in soils and to determine whether or not the gastric and intestinal phases of a physiologically based extraction test bear any relation to any of the phases of the four-stage Community Bureau of Reference (BCR) extraction protocol.     

Fate and bioavailability of arsenic in organo-arsenical pesticide-applied soils. Part-I: incubation study

A laboratory incubation study was conducted to estimate geochemical speciation and in vitro bioavailability of arsenic as a function of soil properties. Two chemically-variant soil types were chosen, based on their potential differences with respect to arsenic reactivity: an acid sand with minimal arsenic retention capacity and a sandy loam with relatively high concentration of amorphous Fe/Al-oxides, considered a sink for arsenic. The soils were amended with dimethylarsenic acid (DMA) at three rates: 45, 225, and 450 mg/kg. A sequential extraction scheme was employed to identify the geochemical forms of arsenic in soils, which were correlated with the "in vitro" bioavailable fractions of arsenic to identify the most bioavailable species. Arsenic bioavailability and speciation studies were done at 0 time (immediately after spiking the soils with pesticide) and after four-months incubation. Results show that soil properties greatly impact geochemical speciation and bioavailability of DMA; soils with high concentrations of amorphous Fe/Al oxides retain more arsenic, thereby rendering them less bioavailable. Results also indicate that the use of organic arsenicals as pesticides in mineral soils may not be a safe practice from the viewpoint of human health risk.     

Assessment of heavy metal bioavailability in contaminated sediments and soils using green fluorescent protein-based bacterial biosensors

A green fluorescent protein (GFP)-based bacterial biosensor Escherichia coli DH5alpha (pVLCD1) was developed based on the expression of gfp under the control of the cad promoter and the cadC gene of Staphylococcus aureus plasmid pI258. DH5alpha (pVLCD1) mainly responded to Cd(II), Pb(II), and Sb(III), the lowest detectable concentrations being 0.1 nmol L(-1), 10 nmol L(-1), and 0.1 nmol L(-1), respectively, with 2h exposure. The biosensor was field-tested to measure the relative bioavailability of the heavy metals in contaminated sediments and soil samples. The results showed that the majority of heavy metals remained adsorbed to soil particles: Cd(II)/Pb(II) was only partially available to the biosensor in soil-water extracts. Our results demonstrate that the GFP-based bacterial biosensor is useful and applicable in determining the bioavailability of heavy metals with high sensitivity in contaminated sediment and soil samples and suggests a potential for its inexpensive application in environmentally relevant sample tests.     

Effects of steel slag amendments on accumulation of cadmium and arsenic by rice (Oryza sativa) in a historically contaminated paddy field

Environmental Science and Pollution Research - Paddy soil contamination by cadmium (Cd) and arsenic (As) is a great concern. Field experiments were conducted to study the effects of steel slag (SS,...     

Interactions of mycorrhizal fungi with Pteris vittata (As hyperaccumulator) in As-contaminated soils

A greenhouse trial was conducted to investigate the role of arbuscular mycorrhizas (AM) in aiding arsenic (As) uptake and tolerance by Pteris vittata (As hyperaccumulator) and Cynodon dactylon (a multi-metal root accumulator). Plants inoculated with lived and killed native mycorrhizas isolated from an As mine site were grown in a sterile and slightly acidic soil. The infectious percentage of mycorrhizas (0 mg/kg As: 26.4%, 50 mg/kg As: 30.3%, 100 mg/kg As: 40.6%) and the average biomass of shoots in infected P. vittata increased (0 mg/kg As: 2.45 g/pot, 50 mg/kg As: 2.48 g/pot, 100 mg/kg As: 10.9 g/pot) according to the increase of As levels when compared to control. The indigenous mycorrhizas enhanced As accumulation (0 mg/kg As: 3.70 mg/kg, 50 mg/kg As: 58.3 mg/kg; 100 mg/kg As: 88.1 mg/kg) in the As mine populations of P. vittata and also sustained its growth by aiding P absorption. For C. dactylon, As was mainly accumulated in mycorrhizal roots and translocation to shoots was inhibited.