Sorption and bioavailability of arsenic in selected Bangladesh soils

The bioavailability of arsenic (As) in the soil environment is largely governed by its adsorption–desorption reactions with soil constituents. We have investigated the sorption–desorption behaviour of As in four typical Bangladeshi soils subjected to irrigation with As-contaminated groundwater. The total As content of soils (160 samples) from the Laksham district ranged from <0.03 to approximately 43 mg kg⁻¹. Despite the low total soil As content, the concentration of As in the pore water of soils freshly irrigated with As-contaminated groundwater ranged from 0.01 to 0.1 mg l⁻¹. However, when these soils were allowed to dry, the concentration of As released in the pore water decreased to undetectable levels. Remoistening of soils to field moisture over a 10-day period resulted in a significant (up to 0.06 mg l⁻¹) release of As in the pore water of soils containing >10 mg As kg⁻¹ soil, indicating the potential availability of As. In soils containing <5 mg As kg⁻¹, As was not detected in the pore water. A comparison of Bangladeshi soils with strongly weathered long-term As-contaminated soils from Queensland, Australia showed a much greater release of As in water extracts from the Australian soils. However, this was attributed to the much higher loading of As in these Australian soils. The correlation of pore water As with other inorganic ions (P, S) showed a strongly significant (P < 0.001) relationship with P, although there was no significant relationship between As and other inorganic cations, such as Fe and Mn. Batch sorption studies showed an appreciable capacity for both As^V and As^III sorption, with As^V being retained in much greater concentrations than As^III.     

Interaction effects of lead on bioavailability and pharmacokinetics of arsenic in the rat

Arsenic (As) and lead (Pb) are common contaminants found in mine waste materials. For an evidence-based risk assessment, it is important to better understand the potential interaction of mixed contaminants; and this interaction study was investigated in an in vivo rat model. Following co-administration of a fixed dose of As^V as in sodium arsenate and different doses of Pb as lead acetate to Sprague–Dawley rats, blood arsenic concentration and bioavailability decreased. A decrease in As blood concentration when lead was co-administered was observed with increasing lead doses. Pharmacokinetic parameters for As in the blood showed faster absorption and elimination of this metalloid in the presence of Pb. The elimination half-life of As decreased from 67 days in As solo group to 27–30 with doses of Pb. Bioavailability of As was also decreased by 30–43 % in the presence of Pb. Decreased urinary excretion of Pb and tissue accumulation were also observed. It indicates lower absorption of As when co-administered with Pb. A probable explanation for these findings is that As co-administration with Pb could have resulted in the formation of less soluble lead arsenate. However, such an interaction between As and Pb could only explain about one-third of the variation when real mine waste materials containing both of these elements were administered to rats. This suggests that other effects from physical and chemical parameters could contribute to the bioavailability of arsenic in complex real environmental samples.     

污染土壤中铅、砷的生物可给性研究进展

土壤铅、砷污染已成为重要的环境问题,并可对人体健康造成严重危害。对食物链途径的有效控制使得从口部无意摄入的土壤铅、砷对人体,特别是对儿童铅、砷摄入总量的贡献率越来越大,甚至成为主要来源。土壤中铅、砷直接进入人体的消化系统并可被人体胃肠道溶解出的部分称为其生物可给性。有效、准确地判定土壤中铅、砷的生物可给性已经成为解决儿童铅、砷中毒的关键科学问题。因此,有关土壤中铅、砷的生物可给性及其在人体健康风险评价中的应用受到了越来越多的关注。文章综述了污染土壤中铅、砷生物可给性的研究方法及各方法的优缺点,并从土壤性质、模拟胃肠条件等方面分析了影响土壤中铅、砷生物可给性的主要因素和存在的问题,还进一步论述了土壤中铅、砷生物可给性在人体健康风险评价中的应用。最后,提出了今后该领域应重点加强土壤铅、砷生物可给性的标准参考物、模拟胃肠条件的优化以及土壤铅、砷生物可给性在人体健康风险评价中的应用等方面的研究。以期充分发挥铅、砷等环境污染物的生物可给性研究方法的潜力,更好地为控制土壤污染、保护人类健康服务。     

A sensitive spectrophotometric method for the determination of arsenic in environmental samples

We developed a cost-effective and sensitive spectrophotometric method for the determination of arsenic at trace level using a new reagent, leuco malachite green. Here we show that, arsenic reacts with potassium iodate in acidic conditions to liberate iodine, and the liberated iodine selectively oxidizes leuco malachite green to malachite green dye. We studied the Beer’s law at 617 nm, which showed linearity over the concentration range 0.09–0.9 μg ml⁻¹ of arsenic. We show that the molar absorptivity, Sandell’s sensitivity and detection limit of the method are 6.1 × 10⁴ l mol⁻¹ cm⁻¹, 0.0012 μg cm⁻² and 0.025 μg ml⁻¹, respectively. We applied the developed method for the determination of arsenic in environmental samples.     

Distribution of arsenic compounds in Plantaginaceae and Cyperaceae plants growing in contaminated soil

The ability of plant species to accumulate arsenic (As) species in the biomass from As-contaminated soils is variable. Among the plants widely grown at the As-contaminated locations, Plantaginaceae and Cyperaceae families belong to the frequent ones. In this study, the ability of Plantago lanceolata (Plantaginaceae) and three wetland plant species representing the family Cyperaceae (Carex praecox, Carex vesicaria, and Scirpus sylvaticus) naturally occurring in the soils with an elevated As in the Czech Republic were investigated. The plants were cultivated under controlled conditions in an As-contaminated soil reaching 735?mg?kg^?1 of the total As. The total As in plants reached up to 8.3?mg?kg^?1 in leaves, and up to 155?mg?kg^?1 in roots of C. praecox. Dominant As compounds were arsenite and arsenate with a small abundance of dimethylarsinic acid (DMA) in all the plant species. In Cyperaceae, small percentages of arsenobetaine (AB) and arsenocholine (AC) were detected, suggesting the ability of these plants to transform As into less toxic compounds. Moreover, the important role of As(V) sequestration on iron plaque on the root surface of Cyperaceae was confirmed. In this context, root washing with oxalic acid partially disrupted the iron plaque for the better release of arsenate.     

Probabilistic health risk assessment for ingestion of seafood farmed in arsenic contaminated groundwater in Taiwan

Seafood farmed in arsenic (As)-contaminated areas is a major exposure pathway for the ingestion of inorganic As by individuals in the southwestern part of Taiwan. This study presents a probabilistic risk assessment using limited data for inorganic As intake through the consumption of the seafood by local residents in these areas. The As content and the consumption rate are both treated as probability distributions, taking into account the variability of the amount in the seafood and individual consumption habits. The Monte Carlo simulation technique is utilized to conduct an assessment of exposure due to the daily intake of inorganic As from As-contaminated seafood. Exposure is evaluated according to the provisional tolerable weekly intake (PTWI) established by the FAO/WHO and the target risk based on the US Environmental Protection Agency guidelines. The assessment results show that inorganic As intake from five types of fish (excluding mullet) and shellfish fall below the PTWI threshold values for the 95th percentiles, but exceed the target cancer risk of 10^?6. The predicted 95th percentile for inorganic As intake and lifetime cancer risks obtained in the study are both markedly higher than those obtained in previous studies in which the consumption rate of seafood considered is a deterministic value. This study demonstrates the importance of the individual variability of seafood consumption when evaluating a high exposure sub-group of the population who eat higher amounts of fish and shellfish than the average Taiwanese.     

土壤重金属化学形态的生物可利用性评价

重金属化学形态是近年来土壤化学、植物营养和环境科学研究领域的一个热点和难点,利用重金属的化学形态分布和含量变化来评价重金属的生物可利用性,有利于全面研究重金属的危害性和治理重金属污染土壤。结果表明,水溶态和交换态的重金属易被生物吸收利用,而残留态重金属一般不被生物利用,其它形态如碳酸盐结合态、铁锰氧化物结合态和有机物结合态的生物可利用性主要取决于外界环境的变化。     

石灰氮对镉污染土壤中镉生物有效性的影响

以石灰作对比,在大田条件下研究了不同石灰氮用量对镉污染土壤中镉生物有效性的影响。结果表明,一定量石灰或石灰氮处理均能显著提高酸性土壤的pH值,降低污染土壤中有效态镉质量分数及水稻茎叶和糙米中的镉质量分数。与不施改良剂的对照相比,石灰施用量达到1 200 kg.hm-2时土壤pH值显著提高,土壤有效态镉质量分数降低12.6%（P〈0.05）,水稻茎叶和糙米中镉质量分数分别降低25.5%（P〈0.05）和28.3%（P〈0.05）;石灰氮施用量达到600 kg.hm-2时,土壤pH值显著高于对照,土壤有效态镉质量分数较对照降低10.9%（P〈0.05）,水稻茎叶和糙米中镉质量分数分别降低36.8%（P〈0.05）和33.0%（P〈0.05）。等量条件下（600 kg.hm-2）石灰氮对降低土壤镉有效性及水稻累积镉的效果相对优于石灰处理。因此,石灰氮与石灰一样可用于酸性重金属污染土壤的修复与改良,是一种极具潜力的土壤改良剂。     

An anticlastogenic in vivo micronucleus assay for tea

Common use of antimutagens and anticarcinogens in everyday life is an effective measure for preventing human cancer and genetic diseases. Antioxidant properties of tea have vast potential as protective agents against diverse toxic effects. The present study was aimed to evaluate the role of aqueous clonal tea extracts (green tea, oolong tea and black tea) in modulating the genotoxic damage induced by cyclophosphamide (CP), a commonly used chemotherapeutic drug and a well-known mutagen and clastogen. All the three tea extracts at 1 and 2% concentration did not increase the frequency of micronucleated polychromatic erythrocytes (MPE) in bone marrow cells of mice when administered individually. The tea extracts decreased the micronuclei (MN) induced by CP. Therefore, regular intake of tea may improve the antioxidant status in in vivo and thereby reduce the risk of cancer and coronary heart disease.     

An assessment of sampling,preservation, and analytical procedures for arsenic speciation in potentially contaminated waters

This study was undertaken to ascertain optimal methods of sampling, preserving, separating, and analyzing arsenic species in potentially contaminated waters. Arsenic species are readily transformed in nature by slight changes in conditions. Each species has a different toxicity and mobility. The conventional field sampling method using filters of 0.45 μm in size could overestimate the dissolved arsenic concentrations, as passing suspended particles that can act as a sink or source of arsenic depending on the site condition. For arsenic species in neutral pH and iron-poor waters, the precipitation can be stable for up to 3 days without any treatment, but for longer periods, a preservative, such as phosphoric acid, is required. Also, the analytical procedure must be selected carefully because the levels and hydride generation efficiencies of arsenic in different species can vary, even for the same amount of arsenic. For arsenic speciation in samples that also include organic species, a hybrid high-performance liquid chromatography (HPLC) column and inductively coupled plasma mass spectrometry (ICP-MS) gave the best resolution and lowest detection limits. However, the procedure using a solid phase extraction (SPE) cartridge can be used economically and conveniently for analyzing samples containing only inorganic arsenic species, such as groundwater, especially that related to mine activity.     

Assessment of relative bioavailability of heavy metals in soil using in vivo mouse model and its implication for risk assessment compared with bioaccessibility using in vitro assay

There is limited study to simultaneously determine the relative bioavailability of heavy metals such as Cd, Pb, Cu, Cr(VI), and Ni in soil samples. In the present study, the bioaccessibility of heavy metals using in vitro assay was compared with the relative bioavailability of heavy metals using in vivo mouse model. The bioaccessibility of heavy metals ranged from 9.05 ± 0.97 % (Cr) to 42.8 ± 3.52 % (Cd). The uptake profile of heavy metals in soil and solution samples in mouse revealed that the uptake kinetics could be fitted to a two-compartment model. The relative bioavailability of heavy meals ranged from 34.8 ± 7.0 % (Ni) to 131 ± 20.3 % (Cu). Poor correlation between bioaccessibility and relative bioavailability of heavy metals was observed (r ² = 0.11, p > 0.05). The relative bioavailability of heavy metals was significantly higher than the bioaccessibility of heavy metals (p < 0.05). The present study indicated that the in vitro digestion method should be carefully employed in risk assessment.     

Concentration of arsenic in water, sediments and fish species from naturally contaminated rivers

Arsenic (As) may occur in surface freshwater ecosystems as a consequence of both natural contamination and anthropogenic activities. In this paper, As concentrations in muscle samples of 10 fish species, sediments and surface water from three naturally contaminated rivers in a central region of Argentina are reported. The study area is one of the largest regions in the world with high As concentrations in groundwater. However, information of As in freshwater ecosystems and associated biota is scarce. An extensive spatial variability of As concentrations in water and sediments of sampled ecosystems was observed. Geochemical indices indicated that sediments ranged from mostly unpolluted to strongly polluted. The concentration of As in sediments averaged 6.58 μg/g ranging from 0.23 to 59.53 μg/g. Arsenic in sediments barely followed (r = 0.361; p = 0.118) the level of contamination of water. All rivers showed high concentrations of As in surface waters, ranging from 55 to 195 μg/L. The average concentration of As in fish was 1.76 μg/g. The level of contamination with As differed significantly between species. Moreover, the level of bioaccumulation of As in fish species related to the concentration of As in water and sediments also differed between species. Whilst some fish species seemed to be able to regulate the uptake of this metalloid, the concentration of As in the large catfish Rhamdia quelen mostly followed the concentration of As in abiotic compartments. The erratic pattern of As concentrations in fish and sediments regardless of the invariable high levels in surface waters suggests the existence of complex biogeochemical processes behind the distribution patterns of As in these naturally contaminated ecosystems.     

Automated method for the determination of total arsenic and selenium in natural and drinking water by HG-AAS

A multicommutated flow system was designed and evaluated for the determination of total arsenic and selenium by Hydride Generation Atomic Absorption Spectrometry (HG-AAS). It was applied to the determination of arsenic and selenium in samples of natural and drinking water. Detection limits were 0.46 and 0.08 μg l⁻¹ for arsenic and selenium, respectively; sampling frequency was 120 samples h⁻¹ for arsenic and 160 samples h⁻¹ for selenium. Linear ranges found were 1.54–10 μg l⁻¹ (R = 0.999) for arsenic and 0.27–27 μg l⁻¹ (R = 0.999) for selenium. Accuracy was evaluated by spiking various water samples and using a reference material. Recoveries were in the range 95–116%. Analytical precision (s _r (%), n = 10) was 6% for both elements. Compared with the Standard Methods, APHA, 3114B manual method, the system consumes at least 10 times less sample per determination, and the quantities of acid and reducing agent used are significantly lower with a reduction in the generation of pollutants and waste. As an additional advantage, the system is very fast, efficient and environmentally friendly for monitoring total arsenic and selenium levels in waters.     

Effects of carbon nanotube and biochar on bioavailability of Pb,Cu and Sb in multi-metal contaminated soil

This study examined the effects of carbon nanotube and biochar on the bioavailability of Pb, Cu and Sb in the shooting range soils for developing low-cost remediation technology. Commercially available multi-walled carbon nanotube (MWCNT) and biochar pyrolyzed from soybean stover at 300 °C (BC) at 0.5, 1 and 2.5% (w w^?1) were used to remediate the contaminated soil in an incubation experiment. Both DTPA (bioavailable) and TCLP (leaching) extraction procedures were used to compare the metal/loid availability and leaching by the amendments in soil. The addition of BC was more effective in immobilizing mobile Pb and Cu in the soil than that in MWCNT. The BC reduced the concentrations of Pb and Cu in the soil by 17.6 and 16.2%, respectively. However, both MWCNTs and BC increased Sb bioavailability by 1.4-fold and 1.6-fold, respectively, in DTPA extraction, compared to the control. The toxicity characteristic leaching procedure (TCLP) test showed that the leachability of Pb in the soil amended with 2.5% MWCNT was 1.3-fold higher than that the unamended soil, whereas the BC at 2.5% decreased the TCLP-extractable Pb by 19.2%. Precipitation and adsorption via electrostatic and π–π electron donor–acceptor interactions were postulated to be involved in the interactions of Pb and Cu with surfaces of the BC in the amended soils, whereas ion exchange mechanisms might be involved in the immobilization of Cu in the MWCNT-amended soils. The application of BC derived from soybean stover can be a low-cost technology for simultaneously immobilizing bioavailable Pb and Cu in the shooting range soils; however, neither of amendments was effective in Sb immobilization.     

Gypsum addition to soils contaminated by red mud: implications for aluminium, arsenic, molybdenum and vanadium solubility

Red mud is highly alkaline (pH 13), saline and can contain elevated concentrations of several potentially toxic elements (e.g. Al, As, Mo and V). Release of up to 1 million m³ of bauxite residue (red mud) suspension from the Ajka repository, western Hungary, caused large-scale contamination of downstream rivers and floodplains. There is now concern about the potential leaching of toxic metal(loid)s from the red mud as some have enhanced solubility at high pH. This study investigated the impact of red mud addition to three different Hungarian soils with respect to trace element solubility and soil geochemistry. The effectiveness of gypsum amendment for the rehabilitation of red mud-contaminated soils was also examined. Red mud addition to soils caused a pH increase, proportional to red mud addition, of up to 4 pH units (e.g. pH 7 → 11). Increasing red mud addition also led to significant increases in salinity, dissolved organic carbon and aqueous trace element concentrations. However, the response was highly soil specific and one of the soils tested buffered pH to around pH 8.5 even with the highest red mud loading tested (33 % w/w); experiments using this soil also had much lower aqueous Al, As and V concentrations. Gypsum addition to soil/red mud mixtures, even at relatively low concentrations (1 % w/w), was sufficient to buffer experimental pH to 7.5–8.5. This effect was attributed to the reaction of Ca²⁺ supplied by the gypsum with OH^? and carbonate from the red mud to precipitate calcite. The lowered pH enhanced trace element sorption and largely inhibited the release of Al, As and V. Mo concentrations, however, were largely unaffected by gypsum induced pH buffering due to the greater solubility of Mo (as molybdate) at circumneutral pH. Gypsum addition also leads to significantly higher porewater salinities, and column experiments demonstrated that this increase in total dissolved solids persisted even after 25 pore volume replacements. Gypsum addition could therefore provide a cheaper alternative to recovery (dig and dump) for the treatment of red mud-affected soils. The observed inhibition of trace metal release within red mud-affected soils was relatively insensitive to either the percentage of red mud or gypsum present, making the treatment easy to apply. However, there is risk that over-application of gypsum could lead to detrimental long-term increases in soil salinity.     

叶面喷施铈硅复合溶胶抑制生菜砷积累效应研究

采用水热合成法,利用正硅酸乙酯和硝酸铈分别制备了二氧化硅和二氧化铈溶胶。通过土培盆栽试验,在广东省汕头市莲花山钨矿区砷污染土壤上种植意大利生菜,研究了叶面喷施不同浓度二氧化硅、二氧化铈以及不同掺杂比的铈硅复合溶胶对生菜地上部生物量、叶绿素含量、砷含量以及生菜地上部砷积累量的影响。结果表明：叶面喷施不同浓度铈、硅溶胶及不同掺杂比的铈硅复合溶胶均可以缓解生菜砷毒害,表现为生菜的地上部鲜重升高了9%～58.8%,砷含量降低了23%～48%。叶面喷施低浓度的二氧化铈掺杂5mmol·L-1二氧化硅复合溶胶可以增加生菜叶片叶绿素含量,进一步提高二氧化硅缓解生菜砷毒害效果。其中以叶面喷施5mmol·L-12%铈掺杂二氧化硅复合溶胶生菜地上部鲜重最高为对照的1.6倍;砷含量最低为对照的51.4%。叶面喷施铈、硅复合溶胶不仅可以降低生菜可食用部位砷浓度,而且可以减少生菜地上部吸收积累砷总量,从而降低了砷通过食物链对人体健康的危害。与传统土壤施用硅肥相比,叶面施用硅溶胶具有经济高效的优点,为土壤砷污染控制提供了一种新的选择。     

叶面喷施硒硅复合溶胶抑制水稻砷积累效应研究

砷是一种毒性较强的类金属元素,稻米砷污染是近年来环境科学关注的难点和热点问题。为了控制稻米对砷的吸收积累,利用水热合成法制备了一系列浓度硒掺杂硅复合溶胶。采用盆栽和大田试验结合的方法,研究了硒掺杂纳米硅溶胶对水稻（Oryza sativa L.）砷吸收积累的影响。结果显示,叶面喷施硒掺杂纳米硅溶胶可以有效缓解水稻砷毒害,增加稻米硒含量,抑制稻米砷积累。盆栽试验结果表明：叶面喷施质量分数1%的硒掺杂纳米硅溶胶（1%Se-Si处理）后,水稻籽粒干质量比对照增加了43.8%,砷含量下降了46%,硒含量由对照的0.050 mg·kg-1增加到0.272 mg·kg-1。且与喷施亚硒酸钠相比（1%Se处理）,喷施硒掺杂纳米硅溶胶更有利于水稻生长,抑制稻米砷积累。与喷施硒质量分数1%的亚硒酸钠（1%Se处理）相比,喷施质量分数1%的硒掺杂纳米硅溶胶（1%Se-Si处理）后,水稻籽粒干质量增加了65.4%,砷含量下降了33.1%。大田试验结果也表明：叶面喷施硒硅复合溶胶可以显著抑制稻米砷积累,且随着硒掺杂量的增加,稻米砷含量显著降低、硒含量显著增加;硒的最佳掺杂量质量分数为0.5%,叶面喷施这种硒掺杂硅溶胶,稻米总砷质量分数由对照的0.25 mg·kg-1下降到0.14 mg·kg-1,稻米中硒的质量分数为0.26 mg·kg-1,符合富硒大米标准。砷污染稻田上,叶面喷施硒硅复合溶胶不仅使稻米砷含量达标,而且可以生产出富硒大米。因此,叶面喷施硒硅复合溶胶可能是治理稻米砷污染的新途径。     

表面活性剂洗脱污染土壤中多氯联苯(PCBs)的研究与应用

多氯联苯(PCBs)为一类在环境中广泛分布且难以降解的持久性有机污染物。利用表面活性剂亲油和亲水的两亲特性．将多氯联苯从土壤中洗脱出来，从而修复受污染土壤是当前环境研究的热点之一。文章综述了近年来国内外使用表面活性剂溶液修复多氯联苯污染土壤的研究进展。表面活性剂对土壤中多氯联苯的洗脱作用主要是：(1)表面活性剂通过减小液一固之间的表面张力，将阻塞在土壤孔隙中的多氯联苯分散到溶液中来；(2)表面活性剂通过形成胶束，促使多氯联苯从土壤中重新分配到疏水的胶束核中。洗脱效果与表面活性剂种类、性质、质量浓度及土壤成份有关，通常非离子型表面活性剂效果较好，对多氯联苯的洗脱可达86％。含多氯联苯洗脱液可利用生物降解、紫外光照射及焚烧等方法进行后续处理。     

Correction to: Effects of carbon nanotube and biochar on bioavailability of Pb,Cu and Sb in multi-metal contaminated soil

Environmental Geochemistry and Health - Unfortunately, in the original publication of the article, Prof. Yong Sik Ok’s affiliation was incorrectly published. The author’s affiliation is...