纳米零价铁与黑曲霉发酵液联用对砷锑污染土壤的淋洗修复

土壤砷 (As) 、锑 (Sb) 污染对生态环境和人体健康有着潜在的风险,采用黑曲霉发酵液 (FB) 与纳米零价铁 (nZVI) 联用淋洗修复As、Sb污染土壤。通过振荡淋洗实验,探究nZVI强化FB淋洗去除As、Sb的效果及不同条件下对As、Sb淋洗效率的影响。结果表明,制备的FB对污染土壤中As和Sb有着较好的去除效果,去除率可达84.1%和71.8%;nZVI对FB去除As、Sb有强化作用,在nZVI质量浓度为0.1 g·L⁻¹、pH为1和淋洗时间为60 min的条件下,其淋洗效果最佳,对As、Sb淋洗效率可达96.6%和95.6%,修复后的土壤达到《土壤环境质量 建设用地土壤污染风险管控标准 (试行) 》 (GB 36600-2018) 二类用地标准。nZVI-FB对土壤中As、Sb的解吸动力学符合拟二级动力学方程。nZVI-FB能够有效的提取土壤中As、Sb的铁铝氧化物结合态。本研究结果可为As、Sb复合污染土壤的淋洗修复提供参考。     

The chemistry and behaviour of antimony in the soil environment with comparisons to arsenic: A critical review

This article provides a critical review of the environmental chemistry of inorganic antimony (Sb) in soils, comparing and contrasting findings with those of arsenic (As). Characteristics of the Sb soil system are reviewed, with an emphasis on speciation, sorption and phase associations, identifying differences between Sb and As behaviour. Knowledge gaps in environmentally relevant Sb data for soils are identified and discussed in terms of the limitations this imposes on understanding the fate, behaviour and risks associated with Sb in environmental soil systems, with particular reference to mobility and bioavailability.     

Assessment and distribution of antimony in soils around three coal mines, Anhui, China

Thirty-three soil samples were collected from the Luling, Liuer, and Zhangji coal mines in the Huaibei and Huainan areas of Anhui Province, China. The samples were analyzed for antimony (Sb) by inductively coupled plasma-optical emission spectrometry (ICP-OES) method. The average Sb content in the 33 samples was 4 mg kg(-1), which is lower than in coals from this region (6.2 mg kg(-1)). More than 75% of the soils sampled showed a significant degree of Sb pollution (enrichment factors [EFs] 5-20). The soils collected near the gob pile and coal preparation plant were higher in Sb content than those collected from residential areas near the mines. The gob pile and tailings from the preparation plant were high in mineral matter content and high in Sb. They are the sources of Sb pollution in surface soils in the vicinity of coal mines. The spatial dispersion of Sb in surface soil in the mine region shows that Sb pollution could reach out as far as 350 m into the local environment conditions. Crops in rice paddies may adsorb some Sb and reduce the Sb content in soils from paddyfields. Vertical distribution of Sb in two soil profiles indicates that Sb is normally relatively immobile in soils.     

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.     

Assessment and Distribution of Antimony in Soils around Three Coal Mines,Anhui, China

ABSTRACT

Thirty-three soil samples were collected from the Luling, Liuer, and Zhangji coal mines in the Huaibei and Huainan areas of Anhui Province, China. The samples were analyzed for antimony (Sb) by inductively coupled plasma-optical emission spectrometry (ICP-OES) method. The average Sb content in the 33 samples was 4 mg kg^?1, which is lower than in coals from this region (6.2 mg kg^?1). More than 75% of the soils sampled showed a significant degree of Sb pollution (enrichment factors [EFs] 5–20). The soils collected near the gob pile and coal preparation plant were higher in Sb content than those collected from residential areas near the mines. The gob pile and tailings from the preparation plant were high in mineral matter content and high in Sb. They are the sources of Sb pollution in surface soils in the vicinity of coal mines. The spatial dispersion of Sb in surface soil in the mine region shows that Sb pollution could reach out as far as 350 m into the local environment conditions. Crops in rice paddies may adsorb some Sb and reduce the Sb content in soils from paddyfields. Vertical distribution of Sb in two soil profiles indicates that Sb is normally relatively immobile in soils.

IMPLICATIONS This work was carried out to analyze the pollution situation and environmental distribution of Sb in three important mines in Anhui Province of China. A detailed concentration analysis of Sb was used to indicate the anthropogenic source of human operation such as coal mining and depositing, coal cleaning, and electricity generation by coal power plants in the mine region. The investigation provides special useful information on the environmental behavior characteristics of Sb for environmental scientists and policy-makers.     

Antimony sorption at gibbsite-water interface

Antimony (Sb) is extensively used in flame retardants, lead-acid batteries, solder, cable coverings, ammunition, fireworks, ceramic and porcelain glazes and semiconductors. However, the geochemical fate of antimony (Sb) remained largely unexplored. Among the different Sb species, Sb (V) is the dominant form in the soil environment in a very wide redox range. Although earlier studies have examined the fate of Sb in the presence of iron oxides such as goethite and hematite, few studies till date reported the interaction of Sb (V) with gibbsite, a common soil Al-oxide mineral. The objective of this study was to understand the sorption behavior of Sb (V) on gibbsite as a function of various solution properties such as pH, ionic strength (I), and initial Sb concentrations, and to interpret the sorption-edge data using a surface complexation model. A batch sorption study with 20 g L⁻¹ gibbsite was conducted using initial Sb concentrations range of 2.03-16.43 μM, pH values between 2 and 10, and ionic strengths (I) between 0.001 and 0.1 M. The results suggest that Sb (V) sorbs strongly to the gibbsite surface, possibly via inner-sphere type mechanism with the formation of a binuclear monodentate surface complex. Weak I effect was noticed in sorption-edge data or in the isotherm data at a low surface coverage. Sorption of Sb (V) on gibbsite was highest in the pH range of 2-4, and negligible at pH 10. Our results suggest that gibbsite will likely play an important role in immobilizing Sb (V) in the soil environment.     

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.     

Antimony mobility in Japanese agricultural soils and the factors affecting antimony sorption behavior

The mobility of antimony (Sb) in Japanese agricultural soils was studied by radiotracer experiments using 124Sb tracer. The soil-solution distribution coefficients (Kd) of Sb were measured for 110 soil samples. These Kds ranged from 1 to 2065 L kg(-1); the geometric mean was 62 L kg(-1) excluding one extremely high value, 2065 L kg(-1). Experimental measurement of Kd showed a decrease with both increasing pH and increasing phosphate concentration. The latter suggested that one aspect of the Sb sorption phenomena in Japanese soil was influenced by specific adsorption of anions such as phosphate. However, other aspects could not be explained by this specific adsorption mechanism, because only 20-40% of soil-sorbed Sb could be extracted by phosphate solution.     

Antimony bioavailability in mine soils

Five British former mining and smelting sites were investigated and found to have levels of total Sb of up to 700 mg kg(-1), indicating high levels of contamination which could be potentially harmful. However, this level of Sb was found to be biologically unavailable over a wide range of pH values, indicating that Sb is relatively unreactive and immobile in the surface layers of the soil, remaining where it is deposited rather than leaching into lower horizons and contaminating ground water. Sb, sparingly soluble in water, was unavailable to the bacterial biosensors tested. The bioluminescence responses were correlated to levels of co-contaminants such as arsenic and copper, rather than to Sb concentrations. This suggests that soil contamination by Sb due to mining and smelting operations is not a severe risk to the environment or human health provided that it is present as immobile species and contaminated sites are not used for purposes which increase the threat of exposure to identified receptors. Co-contaminants such as arsenic and copper are more bioavailable and may therefore be seen as a more significant risk.     

The effects of heavy metal contamination on the soil arthropod community of a shooting range

Soils in clay pigeon shooting ranges can be seriously contaminated by heavy metals. The pellets contained in ammunition are composed of Pb, Sb, Ni, Zn, Mn and Cu. The total concentrations of these metals in soils, and the effects of their increasing levels on the arthropod community were investigated at seven sampling sites in a clay pigeon shooting range and compared with two controls. Research revealed that the spatial distribution of Pb and Sb contamination in the shot-fall area was strongly correlated with the flight path of the pellets. Ordination obtained through Redundance Analysis showed that Collembola, Protura and Diplura were positively correlated with major detected contaminants (Pb, Sb), while Symphyla showed a negative correlation with these pollutants. Determination of the soluble lead fraction in soil, and of its bioaccumulation in the saprophagous Armadillidium sordidum (Isopoda) and the predator Ocypus olens (Coleoptera), showed that a significant portion of metallic Pb from spent pellets is bioavailable in the soil and can be bioaccumulated by edaphic organisms, entering the soil trophic network, but without biomagnification.     

Geogenic Distribution of Arsenic (As) and Antimony (Sb) in Soils of the Murcia Region in Spain

The objective of this study was to determine the As and Sb contents in soils from the Murcia Region of Spain and the possible relationship between the mineralogical composition, soil properties, and As and Sb concentrations. In this study, 490 samples were selected from areas with different characteristics in order to study As and Sb variability. Results show that As and Sb concentrations are positively correlated with the phyllosilicate and quartz content but negatively correlated with the calcite content. The generic reference level (GRL) for these elements was determined according to the Spanish legislation. Established GRL values vary according to the established mineralogical groups, suggesting that GRL has to be determined considering the lithological characteristics of the study area.     

Evaluation of different amendments to stabilize antimony in mining polluted soils

Soil pollution with antimony is of increasing environmental concern worldwide. Measures for its control and to attenuate the risks posed to the ecosystem are required. In this study the application of several iron and aluminium oxides and oxyhydroxides as soil amendments was evaluated in order to assess their feasibility to stabilize Sb in mining polluted soils. Mine soils with different pollution levels were amended with either goethite, ferrihydrite or amorphous Al oxide at various ratios (0–10%). The effectiveness of such treatments was assessed by both batch and column leaching tests. The use of ferrihydrite or amorphous Al oxide proved to be highly effective to stabilize Sb. Immobilization levels of 100% were found when doses of 5% ferrihydrite or 10% amorphous Al oxide were applied, regardless of the soil Sb load. Column leaching studies also showed a high Sb leaching reduction (>75%) when soils were amended with 1% ferrihydrite or 5% amorphous Al oxide. Moreover, such treatments proved to simultaneously immobilize As and Pb in a great extent when soils were also polluted with such toxic elements.     

Mobility of metals and metalloids in a multi-element contaminated soil 20 years after cessation of the pollution source activity

Knowledge of trace element concentrations and mobility is important in the ecotoxicological assessment of contaminated soils. We analysed soil pore water under field conditions to provide new insights into the mobility of residual contaminants in the surface 50cm of a highly contaminated woodland soil. Cadmium and Zn were highly mobile in the acidic soil, concentrations increasing with depth in soil pore water, showing considerable downward mobility. High levels of surface organic matter restricted the solubility of Cu, Pb and Sb, with highest concentrations being found close to the surface. Dissolved organic carbon in pore water had a strong influence on mobility of Cu, Zn, Pb and Sb. Elevated As had moved from the organic surface horizons but was largely immobilised in deeper layers and associated with Fe and Al oxides. The measured differential mobility of pollutants in the present study is highly relevant to protection of groundwater and other receptors.     

Food crop accumulation and bioavailability assessment for antimony (Sb) compared with arsenic (As) in contaminated soils

Field samples and a 9-week glasshouse growth trial were used to investigate the accumulation of mining derived arsenic (As) and antimony (Sb) in vegetable crops growing on the Macleay River Floodplain in Northern New South Wales, Australia. The soils were also extracted using EDTA to assess the potential for this extractant to be used as a predictor of As and Sb uptake in vegetables, and a simplified bioaccessibility extraction test (SBET) to understand potential for uptake in the human gut with soil ingestion. Metalloids were not detected in any field vegetables sampled. Antimony was not detected in the growth trial vegetable crops over the 9-week greenhouse trial. Arsenic accumulation in edible vegetable parts was <10 % total soil-borne As with concentrations less than the current Australian maximum residue concentration for cereals. The results indicate that risk of exposure through short-term vegetable crops is low. The data also demonstrate that uptake pathways for Sb and As in the vegetables were different with uptake strongly impacted by soil properties. A fraction of soil-borne metalloid was soluble in the different soils resulting in Sb soil solution concentration (10.75?±?0.52 μg L^–1) that could present concern for contamination of water resources. EDTA proved a poor predictor of As and Sb phytoavailability. Oral bioaccessibility, as measured by SBET, was <7 % for total As and <3 % total Sb which is important to consider when estimating the real risk from soil borne As and Sb in the floodplain environment.     

Contents and Leachability of Heavy Metals (Pb,Cu, Sb,Zn, As) in Soil at the Pantex Firing Range,Amarillo, Texas

ABSTRACT

Pantex firing range soil samples were analyzed for Pb, Cu, Sb, Zn, and As. One hundred ninety-seven samples were collected from the firing range and vicinity area. There was a lack of knowledge about the distribution of Pb in the firing range, so a random sampling with proportional allocation was chosen. Concentration levels of Pb and Cu in the firing range were found to be in the range of 11-4675 and 13-359 mg/kg, respectively. Concentration levels of Sb were found to be in the range of 1-517 mg/kg. However, the Zn and As concentration levels were close to average soil background levels. The Sn concentration level was expected to be higher in the Pantex firing range soil samples. However, it was found to be below the neutron activation analysis (NAA) detection limit of 75 mg/kg.

Enrichment factor analysis showed that Pb and Sb were highly enriched in the firing range with average magnitudes of 55 and 90, respectively. Cu was enriched ~6 times more than the usual soil concentration levels. Tox-icity characteristic leaching procedure (TCLP) was carried out on size-fractionated homogeneous soil samples. The concentration levels of Pb in leachates were found to be ~12 times higher than the U.S. Environmental Protection Agency (EPA) regulatory concentration level of 5 mg/L. Sequential extraction (SE) was also performed to characterize Pb and other trace elements into five different fractions. The highest Pb fraction was found with organic matter in the soil.     

Contents and leachability of heavy metals (Pb, Cu, Sb, Zn, As) in soil at the Pantex firing range, Amarillo, Texas.

Pantex firing range soil samples were analyzed for Pb, Cu, Sb, Zn, and As. One hundred ninety-seven samples were collected from the firing range and vicinity area. There was a lack of knowledge about the distribution of Pb in the firing range, so a random sampling with proportional allocation was chosen. Concentration levels of Pb and Cu in the firing range were found to be in the range of 11-4675 and 13-359 mg/kg, respectively. Concentration levels of Sb were found to be in the range of 1-517 mg/kg. However, the Zn and As concentration levels were close to average soil background levels. The Sn concentration level was expected to be higher in the Pantex firing range soil samples. However, it was found to be below the neutron activation analysis (NAA) detection limit of 75 mg/kg. Enrichment factor analysis showed that Pb and Sb were highly enriched in the firing range with average magnitudes of 55 and 90, respectively. Cu was enriched approximately 6 times more than the usual soil concentration levels. Toxicity characteristic leaching procedure (TCLP) was carried out on size-fractionated homogeneous soil samples. The concentration levels of Pb in leachates were found to be approximately 12 times higher than the U.S. Environmental Protection Agency (EPA) regulatory concentration level of 5 mg/L. Sequential extraction (SE) was also performed to characterize Pb and other trace elements into five different fractions. The highest Pb fraction was found with organic matter in the soil.     

Abiotic reduction of antimony(V) by green rust (Fe(4)(II)Fe(2)(III)(OH)(12)SO(4).3H(2)O)

Green rust (Fe(4)(II)Fe(2)(III)(OH)(12)SO(4).3H(2)O) is an intermediate phase in the formation of iron (oxyhydr)oxides such as goethite, lepidocrocite, and magnetite. It is widely considered that green rust occurs in many soil and sediment systems. Green rust has been shown to reduce sorbed Se(VI), Cr(VI), and U(VI). In addition, it is also reported that green rust does not reduce As(V) to As(III). In this study, we have investigated for the first time the interaction between Sb(V) and green rust using XAFS and HPLC-ICP-MS. Most of the added Sb(V) was adsorbed on green rust, and Sb(III), a reduced form, was observed in both solid and liquid phases. Thus, it was shown that green rust has high affinity for Sb(V), and that Sb(V) was reduced to more toxic Sb(III) by green rust despite the high stability of the Sb(V) species even under reducing condition as reported in previous studies. Therefore, green rust can be one of the most important reducing agents for Sb(V), which can influence the Sb mobility in suboxic environments where green rust is formed.     

Migration and leaching risk of extraneous antimony in three representative soils of China: Lysimeter and batch experiments

Antimony (Sb) distribution, solubility and mobility onto natural soils of China were studied in lysimeter and batch experiments as a function of physicochemical properties of the soil. An outdoor lysimeter experiment investigated the leaching and migration of Sb in the soils with Sb-polluted topsoil and unpolluted subsoil over a 5 month period. Soil solutions were collected by suction cups installed at different depth of lysimeters, and leachates were regularly collected and analyzed for Sb concentrations. The majority of the added Sb was retained in the topsoil layers, but small portions were moved to the sub-layers. Sb concentrations in the soil solutions and leachates ranged from 0–755.5 (6.38 ± 54 on average) μg l⁻¹ and 0–0.45 (smaller than the detection limit) μg l⁻¹ respectively, indicating the low solubility of Sb in the soils. Batch experiments were performed in order to determine the sorption capacity and the partition coefficient (K_d). Freundlich isotherm described properly the equilibrium experimental data and results show that the K_d values for Primosol, Isohumosol, Ferrosol equal to 22.5, 87.8, 704 L kg⁻¹, respectively. These results showed the strong capacity of the soils to retain Sb, and prevent it being leached down the profile. The mobilizable Sb was in the order: Primosol > Isohumosol > Ferrosol. Sb migration in the soils was mainly associated with the exchangeable, carbonate-bound, and metal–organic complex-bound fractions. Health risk assessment indicates that Sb leaching from Ferrosol will not harm to human health through groundwater under the test conditions, while it has certain health risks from the Isohumosol and Primosol.     

蒌蒿(Artemisia selengensis)根际耐镉产酸细菌的筛选鉴定及其生物学特性

根际细菌的筛选研究有助于构建有效的植物-微生物联合修复体系.采用稀释平板法从蒌蒿根际土壤中分离耐Cd产酸的根际细菌,并对菌株Pb2+、Cu2+和Sb3+的耐受性,分泌吲哚乙酸(IAA)、铁载体、解磷特性及对土壤中Cd的活化效果进行了测定,基于形态特性、生理生化测定和16S rDNA 序列分析对目标菌株进行了分类鉴定.结果表明,从蒌蒿根际土壤中分离到能耐50 mg/L镉浓度且产酸能力较强的根际细菌1株T3,菌株T3对Pb2+、Cu2+和Sb3+均具一定的耐受性,能分泌一定量的IAA和铁载体,但不具解磷特性,能明显增加土壤中有效态镉的含量,经鉴定可初步确定为芽孢杆菌属(Bacillus sp.).为进一步研究其在蒌蒿修复镉污染土壤中的作用奠定了基础.     

Probing the distribution and contamination levels of 10 trace metal/metalloids in soils near a Pb/Zn smelter in Middle China

The horizontal and vertical distribution patterns and contamination status of ten trace metal/metalloids (Ag, Bi, Co, Cr, Ge, In, Ni, Sb, Sn, Tl) in soils around one of the largest Chinese Pb–Zn smelter in Zhuzhou City, Central China, were revealed. Different soil samples were collected from 11 areas, including ten agricultural areas and one city park area, with a total of 83 surface soil samples and six soil cores obtained. Trace metal/metalloids were determined by inductively coupled plasma–mass spectrometry after digestion by an acid mixture of HF and HNO₃. The results showed that Ag, Bi, In, Sb, Sn, and Tl contents decreased both with the distance to the Pb–Zn smelter as well as the soil depth, hinting that these elements were mainly originated from the Pb–Zn smelting operations and were introduced into soils through atmospheric deposition. Soil Ge was influenced by the smelter at a less extent, while the distributions of Co, Cr, and Ni were roughly even among most sampling sites and soil depths, suggesting that they were primarily derived from natural sources. The contamination status, as revealed by the geo-accumulation index (I _geo), indicated that In and Ag were the most enriched elements, followed by Sb, Bi, and Sn. In general, Cr, Tl, Co, Ni, and Ge were of an uncontaminated status.