Microbial catabolic diversity in soils contaminated with hydrocarbons and heavy metals

Understanding indigenous microbial function in contaminated soil is crucial to the successful development and use of bioremediation technologies. We measured the catabolic diversity of indigenous microbial communities in soils with a 30-yr history of Pb, Cr, and hydrocarbon (HC) contamination using a modified substrate-induced respiration method. There were characteristic differences of microbial respirations in the response of highly versus less contaminated soils to the range of organic substrates used. The catabolic response to glucose as compared to succinic acid was approximately 1:5 in less contaminated soils, but 1:25 in highly contaminated soils. In contrast, the response ratio to glucose versus aromatics was about 1:0.4 in less contaminated soils and 1:1 in highly contaminated soils. Principal components analysis (PCA) of the responses confirmed that catabolic diversity differed between highly and less contaminated soils. Univariate analysis also indicated that catabolic diversity was reduced in highly contaminated soils. This catabolic difference was strongly associated with the alteration of microbial community composition. Statistical analyses suggested that the variation in microbial community catabolic diversity was attributed to HCs more than to Pb and Cr.     

块菌中多种重金属及不同形态砷、汞含量分析

目的测定块菌中4种重金属(砷、铅、汞、镉)及无机砷、有机汞含量并进行分析评价。方法采用电感耦合等离子体质谱法(inductively coupled plasma mass spectrometry, ICP-MS)检测块菌种总砷、总汞、铅、镉含量,采用液相-原子荧光光谱联用法(liquid chromatography-atomic fluorescence spectrometry, LC-AFS)检测块菌中无机砷、有机汞含量。结果块菌中无机砷和有机汞含量极低,但铅、镉含量较高。铅的含量为0.8282 mg/kg,镉的含量为0.4040 mg/kg。结论块菌作为一种完全生长在地下的大型真菌,具有较高的重金属吸附富集能力,应加强对此类野生菌的重金属污染物监测。     

Column extraction of heavy metals from soils using the biodegradable chelating agent EDDS

A possible remediation strategy for metal polluted soils is washing with chelants. Here, we compare the efficiency of batch and column extraction of Cu, Zn, and Pb from three soils using the biodegradable chelant EDDS. A total of 53-80% of Cu was extracted in batch and 18-26% in column extraction. For Zn, the extractability was 16-50% in batch and 20-64% in columns and for Pb 25-52 and 18-91%, respectively. Column leaching was therefore equally or better suited for Zn and Pb removal. The longer extraction time in the column resulted in more formations of Fe(III)EDDS by slow dissolution of iron oxides. Zn was uniformly washed from the column, while Cu and Pb were extracted in the top layers and deposited in the bottom layers, presumably by biodegradation of the metal-EDDS complexes and slow dissolution of iron oxides. Between 18 and 42% of the applied EDDS was lost through biodegradation after 7 weeks. In short time experiments, only 6% of EDDS was degraded. Using EDDS concentrations in excess of available heavy metals caused pronounced leaching of organic matter and clogging of the column. Our results prove that heap leaching using EDDS is a promising approach to reduce the heavy metal content of polluted soils.     

Leaching of heavy metals from contaminated soils: an experimental and modeling study

In this paper, we characterize the leaching of heavy metals (Ni, Cu, Zn, Cd, and Pb) from eight contaminated soils over a wide range of pH (pH 0.4-12) using an original approach based on batch pH-static leaching experiments in combination with selective chemical extractions and geochemical modeling. The leached concentrations of the heavy metals are generally much lower than the total concentrations and show a strong pH dependency, resulting in "V-shaped" leaching curves with orders of magnitude changes in solution concentrations. The "multisurface" model used incorporates adsorption to dissolved and solid organic matter (NICA-Donnan), iron/aluminum (hydr)oxide (generalized two-layer model) and clay (Donnan model). These models were applied without modifications, and only the standard set of binding constants and parameters was used (i.e., without any fitting). The model predictions of heavy metal leaching are generally adequate and sometimes excellent. Results from speciation calculations are consistent with the well-recognized importance of organic matter as the dominant reactive solid phase in soils. The observed differences between soils with respect to element speciation in the solid phase correspond to the relative amounts of the reactive surfaces present in the soils. In the solution phase, complexes with dissolved organic matter (DOM) are predominant over most of the pH range. Free metal ions (Me2+) are generally the dominant species below pH 4. The combination of the experimental and modeling approach as used in this study is shown to be promising because it leads to a more fundamental understanding of the pH-dependent leaching processes in soils. The "multisurface" modeling approach, with the selected sorption models, is shown to be able to adequately predict the leaching of heavy metals from contaminated soils over a wide range of conditions, without any fitting of parameters.     

环神农架地区植烟土壤重金属评价及其富集特征

研究了环神农架地区主要植烟土壤91个耕层样品8种重金属元素Cr、Ni、Cu、Zn、As、Cd、Pb、Hg的水平,利用单冈子和内梅罗污染指数法对该区土壤重金属环境质量状况进行了评价,并探讨了该区土壤重金属的富集特征.研究结果显示:环神农架地区土壤重金属元素含量存在较大变异,以Hg和Pb变异最大,变异系数分别为60.22%和59.78%,Ni元素变异最小,变异系数为17.81%.环神农架地Ⅸ植烟土壤Cr、Cu、As、Cd、Pb、Hg含量均符合无公害生产产地标准,Ni和Zn元素分别有3个和2个样品超标,综合污染评价显示供试土壤分别有78%和22%处于清洁和尚清洁水平.以湖北省A层(0～20 cm)土壤元素背景值为基准的研究结果表明,20世纪90年代以来,环神农架地区8种重金属均存在不同程度富集,而As、Pb、Zn、Cd、Ni富集更为明显.     

冀东典型蔬菜种植区设施土壤重金属特征

目的探究冀东典型蔬菜种植区(唐山市和承德市)设施土壤重金属特征。方法对设施大棚进行调查并采集表层土壤样品,检测其重金属,即镉(Cd)、汞(Hg)、砷(As)、铅(Pb)、铬(Cr)、铜(Cu)、锌(Zn)含量,并依据HJ/T 333—2006《温室蔬菜产地环境质量评价标准》进行了土壤质量评价。结果除As外,其他重金属均超过河北省土壤背景值(国家环境保护局),最高为Hg,为背景值的3.46倍。Cd与棚龄呈显著负相关关系(P<0.05)。从地理分布来看,Hg呈现西高东低的分布特征,而As、Pb则呈现南高北低的分布特征。从重金属单项质量指数来看,Cd、Hg、As、Cr、Zn均未超标;Cu、Pb超标率分别为7.37%和22.11%,属轻度污染。从重金属综合质量指数看,3.16%的土壤为超标土壤,属轻度污染,超标率较高的区县为隆化县、乐亭县、滦平县、宽城县和滦南县,重金属综合质量指数与土壤pH呈极显著负相关关系(P<0.01)。结论冀东典型蔬菜种植区设施土壤存在Cu、Pb的轻度污染现象,后续需要对蔬菜中的Cu、Pb进行调查以评估蔬菜产品的安全性。     

Modeling the transport of metals with rate-limited EDTA-promoted extraction and dissolution during EDTA-flushing of copper-contaminated soils

EDTA-flushing of artificially contaminated soils enhanced Cu extraction but also induced mineral dissolution simultaneously. The mobilization and transport of these metal-EDTA complexes was investigated with column experiments. A quantitative transport model was proposed for simulating the experimental breakthrough curves of Cu, Fe, Al, and Ca. The rate-limited EDTA-promoted extraction and dissolution could be described by respective second-order kinetic terms, which were necessary for explaining the time-dependent depletion of extractable metals (sorbed and indigenous) in soils with continuous EDTA-flushing. Simultaneous simulation of extraction of sorbed Cu and dissolution of soil Fe, Al, and Ca is more conceptually accurate than individual modeling of each metal because the latter approach tends to overestimate the concentration of free EDTA during transport and thus underestimate the rate coefficients of EDTA-promoted dissolution. The fitted rate coefficients of Cu were about an order of magnitude larger than those of Fe and Al; these values probably reflect Cu extraction from weakly sorbed fractions and Fe and Al dissolution from amorphous oxides. The apparent retardation of Fe, Al, and Ca transport had to be taken into account by empirical determination, which was attributed to the metal lability in soils and thermodynamics of surface complexation.     

Source analysis of heavy metals and arsenic in organic fractions of municipal solid waste in a mega-city (Shanghai)

Heavy metals and arsenic contamination in municipal solid waste (MSW) and its treatment products has garnered increasing attention. This study investigated the heavy metals and arsenic flows in organic fractions of MSW (OFMSW) in Shanghai, China, through a one-year monitoring program. The OFMSW separated directly from the source (source-separated, pure organic waste), obtained from the treatment facilities were sampled and compared with pure foodstuffs. The heavy metals and arsenic contents in the source-separated OFMSW resembled those in foodstuffs, whereas the OFMSW from the treatment facilities was significantly contaminated with heavy metals and arsenic and failed to meet the government standards for land use. Using flow analysis, > 80% of heavy metals and arsenic were from extrinsic inorganic waste with high ash content that was combined with OFMSW during MSW collection, transfer, transportation, and storage stages. Based on source analysis of heavy metals and arsenic, suggestions for reducing heavy metals and arsenic contents in the current MSW management system in Shanghai are presented.     

2001—2017年我国部分地区蔬菜中砷和重金属累积特征及膳食暴露风险

目的 探讨我国部分地区蔬菜中砷和重金属的累积特征,并分析潜在膳食暴露风险。方法 搜索论文数据库,收集2001—2017年发表文献中蔬菜铜(Cu)、铅(Pb)、镉(Cd)、铬(Cr)、砷(As)及汞(Hg)含量的数据,分析我国根茎类、叶菜类及茄果类蔬菜中As和重金属的污染特性,并采用美国环保署推荐的健康风险评价模型评估蔬菜中砷和重金属的膳食暴露风险。结果 3类蔬菜中Cu、Pb、Cd、Cr、As和Hg均呈非正态分布,变异系数均<10%。根茎类、叶菜类及茄果类蔬菜中Cd、As、Hg的含量均差异有统计学意义(P<0.05),叶菜类和茄果类蔬菜中Pb-Cr含量差异有统计学意义(P<0.05),但3类蔬菜中Cu含量均差异无统计学意义(P>0.05)。根茎类蔬菜中Pb、As和Hg的含量较高,叶菜类蔬菜中Cd含量较高。根茎类和叶菜类蔬菜中Pb-Cd及根茎类蔬菜中Pb-Cr相关性均较强(P<0.01)。3类蔬菜中Cu、Cd、Cr和As污染指数均在安全范围内,而根茎类和叶菜类蔬菜中的Pb和Hg均存在不同程度的污染,但基本属于轻度污染。根茎类和茄果类数值中As和重金属对成人和儿童的风险值均<1.0,但叶菜类蔬菜中Pb对成人和儿童的风险值的第95百分位数分别是1.780和2.020,表明叶菜类蔬菜中的Pb存在潜在的人体非致癌风险。结论 中国蔬菜中Cu、Cd、Cr、As和Hg整体污染较轻,但叶菜类蔬菜中Pb污染应引起重视。     

Hydrophobicity and octanol-water partitioning of trace metals in natural waters

The hydrophobicities of dissolved Al, Cu, Mn, and Pb have been determined in various contaminated natural water samples by 1-octanol extraction and C18 column retention. Octanol extraction varied among the metals studied and between the environments sampled but, in general, was greatest for Pb, whose conditional octanol-water partition coefficient, Dow, exceeded unit value in some samples. In most cases, metal partition into octanol either increased with increasing pH or exhibited a maximum under near-neutral conditions. Although the order and pH-dependence of metal retention by the C18 columns was consistent with these observations, the extent of retention was generally greater than the extent of metal extraction by octanol, possibly because of interferences effected by the C18 column matrix. Speciation calculations and results of controlled experiments employing metals in the presence of model ligands suggest that metals may become hydrophobic either by neutralizing relatively hydrophilic ligands or by combining with ligands that are intrinsically hydrophobic themselves. Given that octanol solubility affords an upper estimate of lipophilicity, the results of this investigation may have important implications regarding our understanding of metal bioavailability and toxicity in natural waters.     

Controls on arsenic speciation and solid-phase partitioning in the sediments of a two-basin lake

Arsenic (As) regeneration from sediments of Spy Pond, a two-basin lake near Boston, MA, continues to result in seasonally elevated As levels despite the several decades that have elapsed since the pond's historical contamination by a pulse input of As. Solid-phase speciation and partitioning of As in the sediments appear to be primary determinants of both potential As regeneration rate and, conversely, the rate at which long-term burial of the pond's As burden will occur. Although iron (Fe) chemistry often controls As speciation in lakes, a higher rate of As regeneration in the south basin, accompanied by the absence of a correlation between regenerated As and Fe in this basin, suggest that additional factors operate to control As cycling in this lake. Solid-phase As speciation was remarkably similar between sediments of the two basins of this lake, about 40% of sedimentary As in upper sediments being in relatively labile (ionically bound and strongly adsorbed) fractions and a larger fraction of As being associated with recalcitrant minerals, likely sulfides. Extraction, X-ray fluorescence, and acid-volatile sulfide data collectively suggest that sedimentary As cycling in both basins is largely controlled by the formation of sulfide minerals. An accounting of the size of sulfur (S) pools supports this conclusion, showing that sufficient S exists in the north basin to control both Fe and As, while the south basin has lower S levels resulting in seasonal accumulation of Fe in the porewater.     

Health risks of heavy metals in sewage‐irrigated soils and edible seeds in Langfang of Hebei province,China

BACKGROUND: Human exposure to heavy metals is attributed to consumption of food crops grown in polluted soil environment. The objective of our study was to assess the health risks of heavy metals in edible seeds of crops grown in sewage‐irrigated soils located in the Langfang of Hebei province, China. Here, heavy metal contents in soils and plants were determined using an internal standard and high‐resolution inductively coupled plasma mass spectrometry. RESULTS: There was a relative buildup of heavy metals in sewage‐irrigated soils in the study area; in particular, all Cr and partial Zn and Cu showed higher concentrations than the limits proposed by the World Health Organization, European Union (EU) and UK. Heavy metal concentrations in edible seeds of plants grown in sewage‐irrigated soils partly exceeded the permissible limits set by the EU, UK and the State Environmental Protection Administration in China. With the exception of Cu, health risk index values of each heavy metal investigated by intake of the edible seeds were less than 1. Here, a health risk index of < 1 is considered safe for human consumption. CONCLUSION: The study indicated that there was a relative absence of health risks associated with the ingestion of sewage‐irrigated edible seeds. Copyright © 2009 Society of Chemical Industry     

Interactions of arsenic and the dissolved substances derived from turf soils

Monosodium methanearsonate (MSMA) is frequently used as an herbicide for the control of weeds in turf grasses at golf courses in Florida. There are concerns about arsenic (As) contamination of local shallow groundwater from the application of MSMA. The distinction between "free" As and colloid-bound/complexed As in soil solution is important for understanding the mobility and bioavailability of As in the environment. In this study, the equilibrium membrane (500 and 3500 Da) dialysis method was employed to determine the "free" and "bound" As in water extracts of five types of golf-course soils containing coated and uncoated sands in various proportions with peat. All samples were evaluated for arsenic species (arsenite, AsIII and arsenate, AsV), dissolved organic matter, and additional constituents (iron, aluminum, and calcium). The impacts of microbial growth were evaluated by conducting experiments with and without the addition of sodium azide for one particular soil type. Results indicate that (1) the presence of peat in the soils plays a significant role in the distribution of As in the dissolved phase of soil solutions; (2) the majority of As present in the soil extracts from soils containing peat was associated with substances of molecular weight (MW) between 500 and 3500 Da; (3) the association of As and dissolved organic matter (DOM) in the soil solution strongly affected As bioavailability, thus determining As transformations via microorganism-mediated processes; and (4) the presence of peat greatly enhanced the release of iron, aluminum, and calcium from soil. Amendment of sand with peat is a common practice at Florida golf courses. However, the addition of peat will alter the properties of the soils, which in turn could affect As transport and transformation. The results of this study are useful for understanding the factors controlling As trapping and transport within porous soil media and in developing comprehensive plans for managing and remediating As contaminated environments, such as golf courses.     

根际-非根际土壤砷形态与三七根部砷赋存形态的相关性研究

本研究选取云南省典型砷污染土壤,以盆栽试验的方式,采用土壤砷形态分级连续浸提法和植物砷形态分级提取法,对三七生长的根际-非根际土壤中砷形态及三七中砷的赋存形态相关性进行研究。结果表明：(1)根际-非根际土壤中各砷形态含量由高到低的总体趋势为：残渣态＞结晶铁锰或铁铝水化氧化物结合态＞无定形和弱结晶铁铝或铁锰水化氧化物结合态＞专性吸附态＞非专性吸附态,残渣态所占比重最大,可达62%～86%。受根部活动的影响,非专性吸附态砷的含量均为根际土＞非根际土。(2)三七根部砷的赋存形态为F_r最高,含量为4.12mg/kg～7.60mg/kg。F_HAc和F_HCl虽迁移活性较弱但其所占的比例却不容忽视,最高可达25%。(3)根际-非根际土壤中不同砷形态与土壤总砷均呈正相关,其中残渣态R^₂=0.976。根际土中活性较强的非专性吸附态砷R^₂=0.499。(4)高砷土壤中砷形态与三七根部砷赋存形态间呈极显著相关,R^₂=0.992。中高砷土壤和中度砷土壤非根际土壤中的砷形态与三七根部砷赋存形态的相关系数较根际土有所升高,具有潜在砷毒害风险。     

重金属复合污染对茶叶重金属、主要生化成分含量及冲泡茶汤浸出率的影响研究

通过土壤盆栽实验,研究四种重金属As、Pb、Cr、Cd复合污染对茶叶重金属含量及主要生化成分含量的影响,同时研究了不同冲泡次数下茶汤中四种重金属的浸出率。结果表明:复合污染条件下,茶叶中重金属积累量显著高于对照,其高低顺序为Pb>Cr>Cd>As,其中,Cd在盆栽土壤中的添加量低于As,但在茶叶中的积累量高于Cd,表明Cd在茶树体内的迁移率高于As。复合污染茶叶中的氨基酸和咖啡碱含量均低于对照,酚氨比值高于对照,从而降低了茶叶品质。四种重金属元素在茶汤中的浸出量均随着冲泡次数的增加而减少,Cd、Cr、Pb和As的总浸出率分别为:18.0%~35.7%、14.8%~26.8%、15.4%~31.9%和13.7%~22.1%,Pb和Cd的浸出率大于Cr和As;四种重金属元素之间的络合作用,会影响重金属在茶叶中的累积量和茶汤中的浸出量。      

Anatomical distribution of heavy metals in the scallop Pecten maximus

This paper studied the anatomical distribution of mercury (Hg), cadmium (Cd), lead (Pb), chromium (Cr), nickel (Ni), arsenic (As), silver (Ag), copper (Cu) and zinc (Zn) in the scallop Pecten maximus and the possible implications in terms of shellfish management. Six organs were analysed: mantle, gills, foot, digestive gland, kidney and gonad. On the basis of their anatomical distribution, two groups of metals were able to be distinguished: the first included Pb, Hg, Ni, Zn and Ag; and the second comprised the four other metals studied. The metals in the first group preferentially accumulated in the kidney (except for Pb), with generally much lower concentrations in the other organs. The metals in the second group accumulated mainly in the digestive gland. As and Cu were included in the second group, but they also had particular inter-organ distribution characteristics. Among the edible organs of the scallop only the adductor muscle contained important proportions of one metal, As (which is very likely accumulated as a non-toxic derivative). A selective evisceration of the metal rich non-edible organs may therefore be considered a reliable measure to be taken with a view to reduce the metal content of scallops used for human consumption. This could be especially relevant for Cd, which is accumulated in high concentrations in the digestive gland.     

核酸适配体检测食品中的重金属研究进展

近些年食品中重金属超标引发很多问题, 严重危害人民群众的生命健康和社会稳定。传统重金属检测方法有原子吸收光谱法, 原子荧光光谱法和X射线荧光光谱法等, 其具有检测灵敏度高, 选择性好, 检测方法成熟等优点, 但是也存在着检测仪器昂贵, 前处理复杂, 检测所需时间长, 不易携带, 不能满足快速、简单、现场测定的实际需要等不足。科研工作者一直在不断探索能够快速, 灵敏, 高效的检测重金属的技术。适配体具有特异性强, 灵敏度高, 稳定性好等优点, 已经成为一种新型识别分子, 被广泛应用于食品中重金属的检测。本文综述了近年来适配体在镉、汞、铅、砷等重金属检测领域的研究, 并对核酸技术在重金属检测方面进行展望。     

微生物法脱除重金属技术的研究进展

工业科技发展带来的负面问题——重金属污染问题日趋突出,严重威胁了生态环境平衡和人体健康,如何缓解重金属污染是目前环保领域关注的焦点问题之一。本文在简介物理、化学和生物法等脱除重金属技术的基础上,综述了生物法中的微生物法,总结了微生物法脱除重金属的显著优势。重点介绍了常见的微生物脱除剂,并分析其作用机理,探讨了国内外利用微生物法处理重金属的应用成果,最后展望了微生物法脱除重金属的未来发展趋势。