Arsenic stability and mobilization in soil at an amenity grassland overlying chemical waste (St. Helens, UK)

A 6.6 ha grassland, established on a former chemical waste site adjacent to a residential area, contains arsenic (As) in surface soil at concentrations 200 times higher than UK Soil Guideline Values. The site is not recognized as statutory contaminated land, partly on the assumption that mobility of the metalloid presents a negligible threat to human health, groundwater and ecological receptors. Evidence for this is evaluated, based on studies of the effect of organic (green waste compost) and inorganic (iron oxides, lime and phosphate) amendments on As fractionation, mobility, plant uptake and earthworm communities. Arsenic mobility in soil was low but significantly related to dissolved organic matter and phosphate, with immobilization associated with iron oxides. Plant uptake was low and there was little apparent impact on earthworms. The existing vegetation cover reduces re-entrainment of dust-blown particulates and pathways of As exposure via this route. Minimizing risks to receptors requires avoidance of soil exposure, and no compost or phosphate application.     

Extraction of arsenic in a synthetic arsenic-contaminated soil using phosphate

An environment-friendly and cost-effective extraction method has been studied for the removal of arsenic from contaminated soil. A yellow-brown forest soil was contaminated with arsenic(V) and used as a model soil. Among various potassium and sodium salts, potassium phosphate was most effective in extracting arsenic, attaining more than 40% extraction in the pH range of 6–8 with minimum damage to the soil properties. Exchange mechanism is proposed for the extraction of arsenic from soil by phosphate. Sequential extraction shows that phosphate is effective in extracting arsenic of Al- and Fe-bound forms. Arsenic of residual form was not extracted. Arsenic was efficiently extracted by phosphate solution of pH 6.0 at 300 mM phosphate concentration and at 40°C.     

High-level arsenite removal from groundwater by zero-valent iron

The objectives of this study were to conduct batch and column studies to (i) assess the effectiveness of zero-valent iron for arsenic remediation in groundwater, (ii) determine removal mechanisms of arsenic, and (iii) evaluate implications of these processes with regard to the stability of arsenic and long-term remedial performance of the permeable reactive barrier (PRB) technology. A high concentration arsenic solution (50 mg l(-1)) was prepared by using sodium arsenite (arsenic (III)) to simulate groundwater at a heavily contaminated Superfund site in the USA. Batch studies indicate that the removal of arsenic is a two-step reaction with fast initial disappearance of arsenite followed by a slow subsequent removal process. Flow-through columns were conducted at a flow rate of 17 ml h(-1) under reducing conditions for 6.6 mo. Kinetic analysis suggested that arsenic removal behaves as a zero-order reaction at high arsenic concentrations. Arsenic removal rate constants decreased with time and arsenic breakthrough was observed in the column study. Arsenic removal capacity of zero-valent iron was determined to be approximately 7.5 mg As/g Fe. Carbonate green rust was identified from the analysis of surface precipitates; arsenite uptake by green rust may be a major mechanism responsible for arsenic remediation by zero-valent iron. Analysis of HCl-extractable arsenic from iron samples indicated that approximately 28% of arsenic was in the form of arsenate suggesting that a surface oxidation process was involved in the arsenic removal with zero-valent iron.     

Synthetic zeolites as amendments for sewage sludge-based compost

The effects of incorporating a synthetic zeolite (Zeolite P) in a range of concentrations (0.1-1.0 w:w) into an experimental horticultural compost, derived from sewage sludge, have been investigated. The impact of zeolite treatment on time-related changes of the labile zinc, copper, iron and manganese pools within the compost was compared to lime incorporation (5% w:w) and to a proprietary unamended peat-based compost. Addition of 0.5% and 1.0% zeolite significantly reduced labile zinc over a 90 day period. The highest zeolite treatment was more effective than liming; 0.5% zeolite was as effective as lime. Plant growth trials measuring transfer of metals to ryegrass (Lolium perenne L. cv Elka) in successive harvests demonstrated that both 1.0% zeolite and 5% lime treatment caused significant reduction in total metal transfer from soil-plant over a 116 day growth period. It is concluded that the use of synthetic zeolite as an amendment for compost of this type significantly reduces potential for soil metal mobility and soil-plant transfer.     

A methodological approach for the identification of arsenic bearing phases in polluted soils

A methodological approach is used to characterize arsenic pollution in three soils and to determine arsenic speciation and association with solid phases in three polluted soils. HPLC-ICP-MS was used for arsenic speciation analysis, SEM-EDS and XRD for physical characterization of arsenic pollution, and sequential chemical extractions to identify arsenic distribution. Arsenic was concentrated in the finest size fractions also enriched in iron and aluminium. Total arsenic concentrations in soils are close to 1%. Arsenic was mainly present as arsenate, representing more than 90% of total arsenic. No crystallised arsenic minerals were detected by XRD analysis. SEM-EDS observations indicated arsenic/iron associations. Modified Tessier's procedure showed that arsenic was mainly extracted from amorphous iron oxide phase. The results of this methodological approach lead to predict the formation of iron arsenates in the case of one of the studied soils while arsenic sorption on iron amorphous (hydr)oxides seemed to be the determinant in the two other soils.     

The applicability of compost,zeolite and calcium oxide in assisted remediation of acidic soil contaminated with Cr(III) and Cr(VI)

Environmental Science and Pollution Research - The effect of soil amendments, i.e., compost, zeolite, and calcium oxide, on the chemical properties of soil contaminated with Cr(III) and Cr(VI) and...     

Heavy metal immobilization by chemical amendments in a polluted soil and influence on white lupin growth

The effects of chemical amendments (zeolite, compost and calcium hydroxide) on the solubility of Pb, Cd and Zn in a contaminated soil were determined. The polluted soil was from the Southwest Sardinia, Italy. It showed very high total concentrations of Pb (19663 mgkg(-1) d.m.), Cd (196 mgkg(-1) d.m.) and Zn (14667 mgkg(-1) d.m.). The growth and uptake of heavy metals by white lupin (Lupinus albus L., cv. Multitalia) in amended soils were also studied in a pot experiment under greenhouse conditions. Results showed that the amendments increased the residual fraction of heavy metals in the soils, and decreased the heavy metals uptake by white lupin compared with the unamended control. Among the three amendments, compost and Ca(OH)2 were the most efficient at reducing Pb and Zn uptake, while zeolite was the most efficient at reducing Cd uptake by the plants. White lupin growth was better in amended soils than in unamended control. The above ground biomass increased with a factor 1.8 (soil amended with zeolite), 3.6 (soil amended with compost) and 3.1 (soil amended with Ca(OH)2) with respect to unamended soil. The roots biomass increased with a factor 1.4 (soil amended with zeolite), 5.6 (soil amended with compost) and 4.8 (soil amended with Ca(OH)2). Results obtained suggest that the soil chemical treatment improved the performance of crops by reducing bioavailability of metals in the soils. However it would be therefore interesting to find a suitable mixture of these amendments to contemporarily immobilize the three main pollutants in the polluted soils.     

Effect of external iron and arsenic species on chelant-enhanced iron bioavailability and arsenic uptake in rice (Oryza sativa L.)

This study was conducted to investigate the effect of external iron status and arsenic species on chelant-enhanced iron bioavailability and arsenic uptake. Rice seedlings (Oryza sativa L.) were used as model plant, and were grown in artificially contaminated sandy soils irrigated with Murashige and Skoog (MS) culture solution. Arsenate uptake in roots and shoots of rice seedlings were affected significantly (p > 0.05) while dimethylarsinic acid (DMAA) was not by the additional iron and chelating ligand treatments. Regardless of iron concentrations in the soil solution, HIDS increased arsenic uptake for roots more than EDTA and EDDS. Chelating ligands and arsenic species also influenced iron uptake in rice roots. Irrespective of arsenic species, HIDS was found to be more effective in the increase of iron bioavailability and uptake in rice roots compared to other chelants. There was a significant positive correlation (r = 0.78, p < 0.05) between arsenate and iron concentrations in the roots of rice seedlings grown with or without additional iron indicating that arsenate inhibit iron uptake. In contrast, there was no correlation between iron and DMAA uptake in roots. Poor correlation between iron and arsenic in shoots indicated that iron uptake in shoots was neither affected by additional iron nor by arsenic species. Compared to the control, chelating ligands increased iron uptake in shoots of rice seedlings significantly (p < 0.05). Regardless of additional iron and arsenic species, iron uptake in rice shoots did not differed among EDTA, EDDS, and HIDS treatments.     

Effect of in situ soil amendments on arsenic uptake in successive harvests of ryegrass (Lolium perenne cv Elka) grown in amended As-polluted soils

Several iron-bearing additives, selected for their potential ability to adsorb anions, were evaluated for their effectiveness in attenuation of arsenic (As) in three soils with different sources of contamination. Amendments used were lime, goethite (alpha-FeOOH) (crystallised iron oxide) and three iron-bearing additives, iron grit, Fe(II) and Fe(III) sulphates plus lime, applied at 1% w/w. Sequential extraction schemes conducted on amended soils determined As, Cu, Zn and Ni fractionation. Plant growth trials using perennial ryegrass (Lolium perenne var. Elka) assessed shoot As uptake. This was grown in the contaminated soils for 4 months, during which time grass shoots were successively harvested every 3 weeks. Goethite increased biomass yields, but clear differences were observed in As transfer rates with the various iron oxides. In conclusion, whilst Fe-oxides may be effective in situ amendments, reducing As bioavailability, their effects on plant growth require careful consideration. Soil-plant transfer of As was not completely halted by any amendment.     

Effects of compost and phosphate amendments on arsenic mobility in soils and arsenic uptake by the hyperaccumulator,Pteris vittata L

Chinese brake fern (Pteris vittata L.), an arsenic (As) hyperaccumulator, has shown the potential to remediate As-contaminated soils. This study investigated the effects of soil amendments on the leachability of As from soils and As uptake by Chinese brake fern. The ferns were grown for 12 weeks in a chromated-copper-arsenate (CCA) contaminated soil or in As spiked contaminated (ASC) soil. Soils were treated with phosphate rock, municipal solid waste, or biosolid compost. Phosphate amendments significantly enhanced plant As uptake from the two tested soils with frond As concentrations increasing up to 265% relative to the control. After 12 weeks, plants grown in phosphate-amended soil removed >8% of soil As. Replacement of As by P from the soil binding sites was responsible for the enhanced mobility of As and subsequent increased plant uptake. Compost additions facilitated As uptake from the CCA soil, but decreased As uptake from the ASC soil. Elevated As uptake in the compost-treated CCA soil was related to the increase of soil water-soluble As and As(V) transformation into As(III). Reduced As uptake in the ASC soil may be attributed to As adsorption to the compost. Chinese brake fern took up As mainly from the iron-bound fraction in the CCA soil and from the water-soluble/exchangeable As in the ASC soil. Without ferns for As adsorption, compost and phosphate amendments increased As leaching from the CCA soil, but had decreased leaching with ferns when compared to the control. For the ASC soil, treatments reduced As leaching regardless of fern presence. This study suggest that growing Chinese brake fern in conjunction with phosphate amendments increases the effectiveness of remediating As-contaminated soils, by increasing As uptake and decreasing As leaching.     

Effect of chemical amendments on the concentration of cadmium and lead in long-term contaminated soils

The availability of metal in contaminated soil can be reduced by the addition of soil amendments. The objectives of this study are to study the effects of applying different soil amendments on the concentration of Cd and Pb in soil solution, DTPA or EDTA extractable Cd and Pb, and the uptake of Cd and Pb by wheat (Triticum vulgare) when growing in long-term Cd and Pb-contaminated soils, more than 20 years. The soil amendments, including check, compost, zinc oxide, calcium carbonate, calcium carbonate mixed with zinc oxide, and calcium carbonate mixed with compost, were conducted in a four replicates pot cultural study. The amended soils were incubated for six months under 60% of water holding capacity. Following incubation, wheat was grown for four months in greenhouse. Analyses of Cd concentration demonstrated a significant decrease in soil solution concentration and DTPA or EDTA extractable in soils amended with calcium carbonate or calcium carbonate mixed with ZnO (or compost) (p<0.01). These amendments can significantly reduce the Cd concentration in the grain, leaf and stem, or reduce the total Cd uptake in all parts of wheat species grown in highly contaminated soil amended with calcium carbonate or calcium carbonate mixed with ZnO (or compost) (p<0.01). The concentration of Cd in soil solution and extracted with DTPA or EDTA can predict the Cd concentration in wheat, especially for soil solution.     

Arsenic contamination in wood mice (Apodemus sylvaticus) and bank voles (Clethrionomys glareolus) on abandoned mine sites in southwest Britain

Arsenic can be highly toxic to mammals but there is relatively little information on its transfer to and uptake by free-living small mammals. The aim of this study was to determine whether intake and accumulation of arsenic by wild rodents living in arsenic-contaminated habitats reflected environmental levels of contamination and varied between species, sexes and age classes. Arsenic concentrations were measured in soil, litter, wood mice (Apodemus sylvaticus) and bank voles (Clethrionomys glareolus) from six sites which varied in the extent to which they were contaminated. Arsenic residues on the most contaminated sites were three and two orders of magnitude above background in soil and litter, respectively. Arsenic concentrations in the stomach contents, liver, kidney and whole body of small mammals reflected inter-site differences in environmental contamination. Wood mice and bank voles on the same sites had similar concentrations of arsenic in their stomach contents and accumulated comparable residues in the liver, kidney and whole body. Female bank voles, but not wood mice, had significantly higher stomach content and liver arsenic concentrations than males. Arsenic concentration in the stomach contents and body tissues did not vary with age class. The bioaccumulation factor (ratio of arsenic concentration in whole body to that in the diet) in wood mice was not significantly different to that in bank voles and was 0.69 for the two species combined, indicating that arsenic was not bioconcentrated in these rodents. Overall, this study has demonstrated that adult and juvenile wood mice and bank voles are exposed to and accumulate similar amounts of arsenic on arsenic-contaminated mine sites and that the extent of accumulation depends upon the level of habitat contamination.     

Arsenic accumulation in duckweed (Spirodela polyrhiza L.): a good option for phytoremediation

Some unavoidable drawbacks of traditional technologies have made phytoremediation a promising alternative for removal of arsenic from contaminated soil and water. In the present study, the potential of an aquatic macrophyte Spirodela polyrhiza L. for phytofiltration of arsenic, and the mechanism of the arsenic uptake were investigated. The S. polyrhiza L. were grown in three test concentrations of arsenate and dimethylarsinic acid (DMAA) (i.e. 1.0, 2.0 and 4.0microM) with 0 (control), 100 or 500microM of phosphate. One control treatment was also set for each test concentrations of arsenic. The PO(4)(3-) concentration in control treatment was 0.02microM. When S. polyrhiza L. was cultivated hydroponically for 6d in culture solution containing 0.02microM phosphate and 4.0microM arsenate or DMAA, the arsenic uptake was 0.353+/-0.003micromolg(-1) and 7.65+/-0.27nmolg(-1), respectively. Arsenic uptake into S. polyrhiza L. was negatively (p<0.05) correlated with phosphate uptake when arsenate was applied to the culture solutions owing to similar in the sorption mechanism between AsO(4)(3-) and PO(4)(3-), and positively (p<0.05) correlated with iron uptake due to adsorption of AsO(4)(3-) onto iron oxides. Thus, the S. polyrhiza L. accumulates arsenic by physico-chemical adsorption and via the phosphate uptake pathway when arsenate was added to the solutions. These results indicate that S. polyrhiza L. would be a good arsenic phytofiltrator. In contrast, DMAA accumulation into S. polyrhiza L. was neither affected by the phosphate concentration in the culture nor correlated (p>0.05) with iron accumulation in plant tissues, which indicates that S. polyrhiza L. uses different mechanisms for DMAA uptake.     

污泥堆肥施用于草坪草栽培:Zn和Cu的分布特征简

为了探索污泥堆肥中重金属在土壤-植物系统中的积累与转移特性,通过温室盆栽实验,分析了污泥堆肥对草坪草高羊茅、黑麦草和白三叶生物量积累的情况,研究了污泥堆肥中Zn和Cu在植物和土壤中的分布特征。结果表明,污泥堆肥施用可以有效促进3种草坪草的积累生物量,在0~6 kg/m²的污泥堆肥施用量范围内,草坪草的生物量积累随着施用量的增加而提高。土壤中Zn和Cu的含量随污泥堆肥施加量的增加而增大,85%以上的Zn和Cu残留在土壤中。污泥堆肥中的Zn和Cu均可以被植物吸收,随着污泥堆肥施用量的增加,草坪草对Zn和Cu的吸收量增大,但当污泥堆肥施用量超过一定阈值时,草坪草吸收Zn和Cu不再增加,甚至减少;对于不同的草坪草,这一阈值有所不同。植物对Zn和Cu的吸收量只占土壤中Zn和Cu减少量的5%左右。根据生物富集系数（BCF）的计算结果推测,污泥堆肥的施用对土壤环境的影响大于对植物体内累积Zn和Cu的影响。     

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.     

污泥堆肥施用于草坪草栽培：Zn和Cu的分布特征

为了探索污泥堆肥中重金属在土壤一植物系统中的积累与转移特性,通过温室盆栽实验,分析了污泥堆肥对草坪草高羊茅、黑麦草和白三叶生物量积累的情况,研究了污泥堆肥中Zn和Cu在植物和土壤中的分布特征。结果表明,污泥堆肥施用可以有效促进3种草坪草的积累生物量,在0～6kg／m2的污泥堆肥施用量范围内,草坪草的生物量积累随着施用量的增加而提高。土壤中Zn和Cu的含量随污泥堆肥施加量的增加而增大,85％以上的Zn和Cu残留在土壤中。污泥堆肥中的Zn和Cu均可以被植物吸收,随着污泥堆肥施用量的增加,草坪草对Zn和Cu的吸收量增大,但当污泥堆肥施用量超过一定阈值时,草坪草吸收zn和cu不再增加,甚至减少;对于不同的草坪草,这一阈值有所不同。植物对zn和cu的吸收量只占土壤中zn和cu减少量的5％左右。根据生物富集系数（BCF）的计算结果推测,污泥堆肥的施用对土壤环境的影响大于对植物体内累积zn和Cu的影响。     

Bioaccumulation and the soil factors affecting the uptake of arsenic in earthworm, Eisenia fetida

To better understand arsenic (As) bioaccumulation, a soil invertebrate species was exposed to 17 field soils contaminated with arsenic due to mining activity. Earthworms (Eisenia fetida) were kept in the soils for 70 days under laboratory conditions, as body burden increased and failed to reach equilibrium in all soils. After 70 days of exposure, XANES spectra determined that As was biotransformed to a highly reduced form. Uptake kinetics for As was calculated using one compartment model. Stepwise multiple regression suggested that sorbed As in soils are bioaccessible, and uptake is governed by soil properties (iron oxide, sulfate, and dissolved organic carbon) that control As mobility in soils. As in soil solution are highly related to uptake rate except four soils which had relatively high chloride or phosphate. The results imply that uptake of As is through As interaction with soil characteristics as well as direct from the soil solution. Internal validation showed that empirically derived regression equations can be used for predicting As uptake as a function of soil properties within the range of soil properties in the data set.     

The effects of chemical remediation treatments on the extractability and speciation of cadmium and lead in contaminated soils

Two rural soils contaminated by cadmium (Cd) and lead (Pb) were used to evaluate the effect of different chemical treatments on changes in speciation and extractability of Cd and Pb, and in phytoavailability to wheat. Triplicates of seven chemical treatments were tested to compare and evaluate the remediation techniques for contaminated soils using pot experiments. Treatments applied were calcium carbonate, a high quantity of phosphate salt, hog composts, iron oxide, manganese oxide, zeolite, and unamended control. Wheat (Triticum aestivum) was planted in the different amended soils for a further one month to evaluate the effectiveness of treatments on uptake of Cd and Pb by the wheat shoots. Results indicated that addition of calcium carbonate, manganese oxide, or zeolite reduces the extractability of Cd or Pb in both soils, and significantly reduce the uptake of Cd and Pb by wheat shoots. Changes in the extractability and metal sequential fractionations indicate that the exchangeable (or available) form of Cd and Pb in two soils can be transformed into unavailable forms after these amendments.     

Effects of plant arsenic uptake and heavy metals on arsenic distribution in an arsenic-contaminated soil

This study examined the effects of heavy metals and plant arsenic uptake on soil arsenic distribution. Chemical fractionation of an arsenic-contaminated soil spiked with 50 or 200mg kg(-1) Ni, Zn, Cd or Pb was performed before and after growing the arsenic hyperaccumulator Pteris vittata L for 8weeks using NH(4)Cl (water-soluble plus exchangeable, WE-As), NH(4)F (Al-As), NaOH (Fe-As), and H(2)SO(4) (Ca-As). Arsenic in the soil was present primarily as the recalcitrant forms with Ca-As being the dominant fraction (45%). Arsenic taken up by P. vittata was from all fractions though Ca-As contributed the most (51-71% reduction). After 8weeks of plant growth, the Al-As and Fe-As fractions were significantly (p<0.01) greater in the metal-spiked soils than the control, with changes in the WE-As fraction being significantly (p=0.007) correlated with plant arsenic removal. The plant's ability to solubilize soil arsenic from recalcitrant fractions may have enhanced its ability to hyperaccumulate arsenic.     

Induction of PAH-catabolism in mushroom compost and its use in the biodegradation of soil-associated phenanthrene

This paper describes the induction of phenanthrene-catabolism within Phase II mushroom compost resulting from its incubation with (1) phenanthrene, and (2) PAH-contaminated soil. Respirometers measuring mineralization of freshly added 14C-9-phenanthere were used to evaluate induction of phenanthrene-catabolism. Where pure phenanthrene (spiked at a concentration of 400 mg kg(-1) wet wt.) was used to induce phenanthrene-catabolism in compost, induction was measurable, with maximal mineralization observed after 7 weeks phenanthrene-compost contact time. Where PAH-contaminated soil was used to induce phenanthrene-catabolism in un-induced compost, induction was observed after 5 weeks soil-compost contact time. Microcosm-scale amelioration of soil contaminated with 14C-phenanthrene (aged in soil for 516 days prior to incubation with compost) indicated that both induced (using pure phenanthrene) and uninduced Phase II mushroom composts were equally able to promote degradation of this soil-associated contaminant. After 111 days incubation time, 42.7 +/- 6.3% loss of soil-associated phenanthrene was observed in the induced-compost soil mixture, while 36.7 +/- 2.9% loss of soil-associated phenanthrene was observed in the uninduced-compost soil mixture. These results are notable as they indicate that while pre-induction of phenanthrene-catabolism within compost is possible, it does not significantly increase the extent of degradation when the compost is used to ameliorate phenanthrene-contaminated soil. Thus, compost could be used directly in the amelioration of contaminated land i.e. without pre-induction of catabolism.