Determining the influence of the physicochemical parameters of urban soils on As availability using chemometric methods: A preliminary study

An initial exploration was conducted using mathematical and statistical methods to obtain relevant information about the determination of the physicochemical parameters capable of controlling As uptake by ryegrass grown on contaminated topsoils.Concentrations of As in the soils were from 10 to 47 mg/kg,mainly in the As(V) form(57%–73%).Concentrations of As in water extracts were very low(61–700 μg/kg).It was suggested that As(Ⅲ) was mainly in the uncharged species and As(V) in the charged species.Chemometric methods revealed that the values of the ratio As(Ⅲ)/As(V) depended on the assimilated-phosphorus,the pseudo-total and water-extractable Fe contents and the soil p H.Arsenic concentrations measured in ryegrass shoots ranged from 119 to 1602 μg/kg.Positive linear correlations were obtained between As in ryegrass shoots and water extractable-As.The transfer coefficient of As correlated well with the ratio assimilated-phosphorus/Fe-oxides.As(Ⅲ)uptake by the shoot of ryegrass was controlled by the organic matter and Fe-oxide contents.     

Polycyclic aromatic hydrocarbon concentrations, compositions, sources, and associated carcinogenic risks to humans in farmland soils and riverine sediments from Guiyu, China

The concentrations of 16 priority polycyclic aromatic hydrocarbons(PAHs) were measured in 23 farmland soil samples and 10 riverine sediment samples from Guiyu, China, and the carcinogenic risks associated with PAHs in the samples were evaluated. Guiyu is the largest electronic waste(EW) dismantling area globally, and has been well known for the primitive and crude manner in which EWs are disposed, such as by open burning and roasting. The total PAH concentrations were 56–567 ng/g in the soils and 181–3034 ng/g in the sediments.The Shanglian and Huamei districts were found to be more contaminated with PAHs than the north of Guiyu. The soils were relatively weakly contaminated but the sediments were more contaminated, and sediments in some river sections might cause carcinogenic risks to the groundwater system. The PAHs in the soils were derived from combustion sources,but the PAHs in the sediments were derived from both combustion and petroleum sources.     

Release and sedimentation behaviors of biochar colloids in soil solutions

The release of biochar colloids considerably affects the stability of biochar in environment. Currently, information on the release behavior and suspension stability of biochar colloids in real soil solutions is scarce. In this study, 20 soils were collected from different districts in China and the release behavior of biochar colloids and their suspension stability in soil solutions were systematically examined. The results showed that both pyrolysis temperature and biomass source had important effects on the formation of biochar colloids in soil solutions. The formation amount of biochar colloids from low pyrolysis temperatures (400 °C) (average amount of 9.33–16.41 mg/g) were significantly higher than those from high pyrolysis temperatures (700 °C) (average amount of less than 2 mg/g). The formation amount of wheat straw-derived biochar colloids were higher than those of rice straw-derived biochar colloids probably due to the higher O/C ratio in wheat-straw biochar. Further, biochar colloidal formation amount was negatively correlated with comprehensive effect of dissolved organic carbon, Fe and Al in soil solutions. The sedimentation curve of biochar colloids in soil solutions is well described by an exponential model and demonstrated high suspension stability. Around 40% of the biochar colloids were maintained in the suspension at the final sedimentation equilibrium. The settling efficiency of biochar colloids was positively correlated with comprehensive effect of the ionic strength and K, Ca, Na, and Mg contents in soil solutions. Our findings help promote a deeper understanding of biochar loss and stability in the soil-water environment.     

Molecular diversity of arbuscular mycorrhizal fungi at a large-scale antimony mining area in southern China

Arbuscular mycorrhizal fungi (AMF) have great potential for assisting heavy metal hyperaccumulators in the remediation of contaminated soils. However, little information is available about the community composition of AMF under natural conditions in soils contaminated by antimony (Sb). The objective of this study was to investigate the characteristics of AMF molecular diversity, and to explore the effects of Sb content and soil properties on the AMF community structure in an Sb mining area. Four Sb mine spoils and one adjacent reference area were selected from around the Xikuangshan mine in southern China. The association of AMF molecular diversity and community composition with the rhizosphere soils of the dominant plant species was studied by Polymerase Chain Reaction-Denaturing Gradient Gel Electrophoresis (PCR-DGGE). Results from all five studied sites showed that the diversity of AMF decreased with increasing Sb concentration. Principal component analysis (PCA) indicated that the AMF community structure was markedly different among these groups. Further redundancy analysis (RDA) showed that Sb contaminationwas the dominating factor influencing the AMF community structure in the Sb mine area. However, the multivariate analysis showed that, apart from the soil Sb content, extractable nitrogen content and organic matter content also attributed to AMF sequence distribution type. Some AMF sequences were only found in the highly contaminated area and these might be ideal candidates for improving phytoremediation efficiency in Sb mining regions. Gene sequencing analysis revealed that most species were affiliated with Glomus, suggesting that Glomus was the dominant AMF genus in the studied Sb mining area.     

Dissimilatory Fe(III) reduction characteristics of paddy soil extract cultures treated with glucose or fatty acids

Dissimilatory Fe(Ⅲ) reduction is a universal process with irreplaceable biological and environmental importance in anoxic environments. Our knowledge about Fe(Ⅲ) reduction predominantly comes from pure cultures of dissimilatory Fe(Ⅲ) reducing bacteria (DFRB). The objective of this study was to compare the effects of glucose and a selection of short organic acids (citrate, succinate, pyruvate, propionate, acetate, and formate) on Fe(Ⅲ) reduction via the anaerobic culture of three paddy soil solutions with Fe(OH)3 as the sole electron acceptor. The results showed significant differences in Fe(Ⅲ) reduction among the three paddy soil solutions and suhstrate types. Bacteria from the Sichuan paddy soil responded quickly to substrate supply and showed higher Fe(Ⅲ) reducing activity than the other two soil types. Bacteria in the Jiangxi paddy soil culture solution could not use propionate as a source of electrons for Fe(Ⅲ) reduction. Similarly, bacteria in the Jilin paddy soil culture could not use succinate effectively. Pyruvate was readily used by cultures from all three paddy soil solutions, thus indicating that there were some similarities in substrate utilization by bacteria for Fe(Ⅲ) reduction. The use of glucose and citrate as substrate for dissimilatory Fe(Ⅲ) reduction indicates important ecological implications for this type of anoxic respiration.     

Water extraction kinetics of metals, arsenic and dissolved organic carbon from industrial contaminated poplar leaves

In industrial areas, tree leaves contaminated by metals and metalloids could constitute a secondary source of pollutants. In the present study, water extraction kinetics of inorganic elements （IE： Pb, Zn, Cd, As, Fe and Mn）, dissolved organic carbon, pH and biological activity were studied for industrial contaminated poplar leaves. Moreover, the distribution of the IE through the size fractions of the associated top soil was measured. High quantities ofMn, Zn and As and polysaccharides were released in the solution from the strongly contaminated leaves. The kinetic of release varied with time and metal type. The solution pH decreased while dissolved organic contents increased with time after 30 days. Therefore, these contaminated leaves could constitute a source of more available organic metals and metalloids than the initial inorganic process particles. However, the distribution of the IE through the size fractions of the top soil suggested that a great part of the released IE was adsorbed, reducing in consequence their transfers and bioavailability. It＇s concluded that mobility/boioavailability and speciation of metals and metalloids released from the decomposition of polluted tree leaves depends on soil characteristics, pollutant type and litter composition, with consequences for environmental risk assessment.     

Effect of struvite and organic acids on immobilization of copper and zinc in contaminated bio-retention filter media

Few studies have been carried out to connect nutrient recovery as struvite from wastewater and sustainable utilization of the recovered struvite for copper and zinc immobilization in contaminated soil. This study revealed the effect of struvite on Cu and Zn immobilization in contaminated bio-retention soil in the presence of commonly exuded plant organic acids. The research hypothesis was that the presence of both struvite and organic acids may influence the immobilization of Cu and Zn in soil. The outcome of this research confirmed that more than 99% of Cu and Zn was immobilized in bio-retention filter media by struvite application. Water-soluble Cu and Zn concentrations of struvite treated soil were less than 1.83 and 0.86 mg/kg respectively, and these concentrations were significantly lower compared to the total Cu and Zn content of 747.05 mg/kg in the contaminated soil. Application of struvite to Cu- and Zn-contaminated soil resulted in formation of compounds similar to zinc phosphate tetrahydrate (Zn₃(PO₄)₂?4H₂O) and amorphous Cu and Zn phases. Struvite was effective in heavy metal remediation in acidic soil regardless of the presence of Ca impurities in struvite and the presence of plant organic acids in soil. Overall, this study revealed that struvite recovered from wastewater treatment plants has potential for use as an amendment for heavy metal remediation in contaminated bio-retention soil.     

Enhanced catalytic degradation process of o-nitrochlorobenzene by palladium-catalyzed Fe0 particles

Over Pd/Fe bimetallic catalyst, o-nitrochlorobenzene（o-NCB）, at a concentration of 20 mg/L in aqueous solutions, is rapidly converted to o-chloroaniline（o-CAN） first, and then quickly dechlorinated to aniline（AN） and Cl^- , without other intermediate reaction products. The aminated and dechlorinated reactions are believed to take place on the surface site of the Pd/Fe. The o-NCB removal efficiency and the next dechlorination rate increase with an increase of bulk loading of palladium and catalysts addition due to the increase of both the surface loading of palladium and the total surface area. These results indicate that reduction, amination and dechlorination of o- NCB by palladium-catalyzed Fe^0 particles, can be designed for remediation of contaminated groundwater.     

Micronutrient dynamics in some wetland soils of south-eastern Nigeria

The inventory of profile distribution of total iron(Fe),zinc(Zn), manganese(Mn) and copper(Cu) were determined in three different soil horizons each of the wetland soils selected form Mbiabet(MB),Nkari(NK)and Nkana(NA) in Ini Local Government Area of Akwa Ibom State.Total Fe ranged between 3.25 and 4.15ppm.The average contents were 3.72,3.91 and 3.62ppm in Mbiabet(MB),Nkari(NK) and Nkana(NA)soils respectively.The total value of Zn also ranged between 2.4 and 4.9 ppm with the average content in each soil being 28.27,17.73and 36.53 ppm respectively.The amount of Fe and Zn in these soil profiles were strongly correlated with the clay content and high levels of organic matter of 3.70%,2.47%and 2.5% respectively.The content clearly reflected a poor drainage conditions.In all the soil profiles Mn and Cu were detected in at least one of the soil horizons.However, Mn and Cu were not detected in the soil horizons at Nkari.Generally , the relative inventory of these micronutrients appeared to be influenced by pH,drainage pattern,organic matter and clay contents of these soils.The inventory of total values of the wetland soils considered are assessed in the light of establishing a baseline information.     

低分子有机酸对高浓度锑砷污染土壤的淋洗效率及机理研究

为研究土壤淋洗技术对锑矿区周边高浓度锑(Sb)、砷(As)污染土壤的修复效果,筛选生物降解性能良好的淋洗剂,以广西河池市南丹县某锑矿区周边高浓度Sb、As污染土壤为研究对象,考察了不同低分子有机酸及淋洗条件(浓度、固液比、淋洗时间和淋洗级数)对Sb、As淋洗效率的影响,利用Wenzel连续形态提取法比较淋洗前后土壤中Sb、As形态变化,并结合扫描电子显微镜-X射线能量色散谱(SEM-EDS)、X射线光电子能谱(XPS)等分析方法初步探索了淋洗去除土壤Sb、As的反应机理.结果表明：由于草酸(oxalic acid,OA)具有较强的酸性及还原性,其对Sb、As的淋洗效率最高,且在最佳淋洗条件下Sb、As淋洗效率分别可达91.18%、97.63%.高浓度污染土壤中Sb、As主要以铁铝氧化物结合态形式存在,占Sb、As总量的70%以上;OA淋洗后,土壤中结合态、残渣态的Sb、As向吸附态Sb、As转化. OA淋洗去除Sb、As的反应机理主要包括三方面：(1) OA的含氧官能团与Sb、As含氧阴离子竞争土壤颗粒中铁(氢)氧化物表面的吸附位点,发生配位交换,从而解吸出Sb、As;(2) OA的有...     

沸石负载纳米零价铁去除水中Sb(Ⅲ)和Sb(Ⅴ)的研究

锑矿开采和含锑化合物的应用在一定程度上会造成环境锑污染的加重,对人体健康和生态系统带来风险,为缓解这一现象,采用液相还原负载的方式制备沸石负载纳米零价铁(Z-ZVI)复合材料,探究其对Sb(Ⅲ)和Sb(Ⅴ)的去除效果;采用扫描电子显微镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)对反应前后复合材料进行表征,并探究不同材料配比、溶液初始pH及无机阴离子对Sb(Ⅲ)和Sb(Ⅴ)吸附效率的影响.结果表明：(1)沸石负载后的纳米零价铁(Z-ZVI)具有较高的比表面积(54.54 m²/g)和反应活性,能够有效吸附、还原高价锑.(2)在pH=7、1.0 g/L Z-ZVI的条件下,反应4 h对20 mg/L Sb(Ⅲ)和Sb(Ⅴ)的吸附率分别达到88%和62%,吸附过程符合准二级动力学方程和Freundlich等温吸附模型.(3)Sb(Ⅲ)的去除率受pH变化的影响不大,但Sb(Ⅴ)的去除率随初始pH的升高而下降,溶液反应终点pH相比初始pH均有所上升.(4)XRD和XPS表征发现,Sb的去除过程中同时存在吸附和还原作用,Fe⁰氧化过程中...     

起爆药污染场地土壤中锑的环境风险评估

为研究起爆药污染场地土壤中Sb（锑）的环境风险,利用微波消解原子荧光光度法、Tessier逐级提取法、TCLP（toxicity characteristic leaching procedure）毒性浸出法及SBET（simplied bioaccessibility extraction test）方法,分析了某起爆药场地表层土壤中Sb的价态、形态、浸出水平和生物可给性及其对人体健康风险水平和地下水环境风险水平的影响.结果表明:①土壤中w（TSb）为26.7~4 255.0 mg/kg,是GB 36600-2018《土壤环境质量建设用地土壤污染风险管控标准》中第一类用地筛选值的1.33~212.75倍,最大值超过相应管制值的10.82倍.土壤样品中Sb主要以Sb5+存在,w（Sb5+）在w（TSb）中的占比达65.57%~95.46%.②土壤中不同形态Sb的比例由高到低依次为残渣态（38.05%~94.22%）、铁锰氧化物结合态（0.01%~31.80%）、有机结合态（0.32%~21.55%）、碳酸盐结合态（0.01%~11.16%）和可交换态（0.42%~3.70%）.土壤中w（可交换态Sb）与CEC（阳离子交换量）呈负相关,w（铁锰氧化物结合态Sb）与w（Fe）、w（Mn）均呈正相关.③土壤中Sb的浸出浓度为0.22~35.49 μg/L,并随土壤中w（砂粒）、w（TSb）、w（碳酸盐结合态Sb）和w（可交换态Sb）的增大而升高,随CEC的增大而降低.④土壤中Sb的生物可给性范围在8.03%~67.69%之间,w（Fe）和w（OM）的增加能够降低Sb的生物可给性.⑤基于Sb生物可给性健康风险水平和基于Sb价态健康风险水平的结果分别是以w（TSb）为暴露浓度计算的传统风险评估模型预测结果的8.00%~67.69%和62.00%~77.01%,土壤中Sb的实际浸出浓度较常规模型（三相平衡耦合地下水稀释模型）预测值低3~5个数量级.研究显示,充分考虑Sb在起爆药污染场地土壤中的赋存特征能够降低常规风险评估方法的保守性.      

次生铁矿物及其与环境中锑的相互作用研究进展

我国锑矿资源丰富,锑矿资源开发利用过程导致锑进入表生环境并富集。锑作为人体非必需重金属,具有高化学毒性,是国际公认优先控制金属污染物。次生铁矿物在形成过程中和成矿后能以共沉淀、吸附等方式固定有害金属,但又易受环境因子变化的影响,重新释放被固定的有害金属,对有害金属的环境行为和归宿有着重要影响。本文面向我国锑污染现状,立足于常见次生铁矿物的基本结构和表面过程,以次生铁矿物相转变为切入点,论述了次生铁矿物与锑的相互作用机理,总结了环境pH、溶解性有机物、Fe(II)、微生物及环境温度等外界因素作用下次生铁矿物对锑环境行为的作用规律,以期从矿物学角度厘清环境因素-次生铁矿物-锑之间的微观作用机制,为表生环境锑污染的环境风险评价和修复治理提供理论指导。     

疏水改性石灰对土壤中高浓度硝基苯的强化固定

石灰是一种常见的应用于污染土壤固化稳定化的水硬性胶结材料,但对于紧急事故情况下释放到土壤中的高浓度毒性有机物的固定能力十分有限.为了增强石灰对于毒性有机物的定向捕获的固定能力,本研究用硬脂酸对石灰进行疏水改性,并通过分散性实验、粒度测试、扫描电镜测试、红外光谱测试和接触角测试对改性前后的石灰进行表征.然后用改性石灰对硝基苯含量为8163 mg·kg~(-1)的污染土壤进行固化稳定化实验,测试在固化稳定化过程中硝基苯的挥发率和浸出率.结果表明,与不添加石灰的空白组和只添加30%未改性石灰的对照组相比,添加20%的改性石灰和10%的未改性石灰,可分别减少94.44%和88.46%的硝基苯挥发量,99.10%和88.11%的酸浸出条件下的硝基苯浸出量,及98.51%和59.74%的水浸出条件下的硝基苯浸出量.经硬脂酸疏水改性后的石灰可作为定向捕获快速固定土壤中高浓度毒性有机物的固化剂.     

3种耐锑土壤细菌的筛选及对锑的吸附研究

从湖南省冷水江锡矿山尾渣土壤中筛选分离出3株具有较高锑耐性的细菌,通过宏观吸附结合X射线光电子能谱（XPS）,阐明3株细菌对Sb（Ⅲ）和Sb（Ⅴ）的吸附机制.根据生理生化指标和16S rDNA序列同源性对比,鉴定出1株革兰氏阴性菌和2株革兰氏阳性菌,分别为人苍白杆菌（Ochrobactrum anthropi）、芽孢杆菌（Bacillus sp.）及蜡状芽孢杆菌（Bacillus cereus）.3株细菌都呈杆状,且都能在高锑含量营养液中良好生长.3株细菌对锑的等温吸附符合Langmuir模型,对锑的最大吸附量约为11.0~14.3 mg·g^-1,其中,蜡状芽孢杆菌对锑的吸附能力高于其它两株细菌,3株细菌对Sb（Ⅲ）的吸附量略高于Sb（Ⅴ）.XPS结果表明,细菌表面的羧基和氨基在锑吸附过程中发挥主导作用.本研究结果对于理解土壤微生物吸附固定锑机制及其在土壤修复中的应用有重要意义.     

土壤锑胁迫下赤子爱胜蚓在个体和细胞水平的毒性效应

随着锑(Sb)矿的开采,Sb及其化合物对矿区周围生物暴露风险增大,Sb污染研究在国内外日益受到重视. 为阐明矿区Sb污染土壤对周边生物的毒性效应,本文通过向人工土壤添加焦锑酸钾(KSbO₆H₆)模拟受污染土壤,分别探究了Sb对土壤无脊椎模式生物——赤子爱胜蚓(Eisenia fetida)存活、Sb富集、总蛋白、抗氧化系统酶、丙二醛(malondialdehyde, MDA)的影响,并利用生物标志物响应指数(biomarker response index, BRI)对Sb胁迫下蚯蚓的毒性效应进行综合评价. 结果表明:①蚯蚓死亡率与土壤Sb浓度和暴露时间剂量效应关系明显,经计算蚯蚓56 d LC₅₀为4 380.37 mg/kg. ②蚯蚓对Sb仅有少量吸收,最高处理组(12 800 mg/kg)在暴露56 d后Sb富集量仅为213 mg/kg. ③超氧化物歧化酶(superoxide dismutase, SOD)、过氧化物酶(peroxidase, POD)、MDA在暴露28 d内呈现先升高后降低的倒“U”型变化,过氧化氢酶(catalase, CAT)总体呈现“上升—下降—上升—下降”的变化趋势;总蛋白随时间和处理水平增加呈现不断下降趋势. ④在暴露期间共计24个含Sb处理组中,20个处理受到中等及以下水平健康影响,仅有4个处理组BRI小于2.5,属于严重健康影响. 研究显示,总蛋白、SOD、CAT、POD、MDA均对Sb比较敏感,Sb对赤子爱胜蚓的毒性效应不强,该研究结果可为我国土壤Sb污染提供关键毒理学数据.      

Molecular diversity of arbuscular mycorrhizal fungi at a large-scale antimony mining area in southern China

Arbuscular mycorrhizal fungi (AMF) have great potential for assisting heavy metal hyperaccumulators in the remediation of contaminated soils. However, little information is available about the community composition of AMF under natural conditions in soils contaminated by antimony (Sb). The objective of this study was to investigate the characteristics of AMF molecular diversity, and to explore the effects of Sb content and soil properties on the AMF community structure in an Sb mining area. Four Sb mine spoils and one adjacent reference area were selected from around the Xikuangshan mine in southern China. The association of AMF molecular diversity and community composition with the rhizosphere soils of the dominant plant species was studied by Polymerase Chain Reaction-Denaturing Gradient Gel Electrophoresis (PCR-DGGE). Results from all five studied sites showed that the diversity of AMF decreased with increasing Sb concentration. Principal component analysis (PCA) indicated that the AMF community structure was markedly different among these groups. Further redundancy analysis (RDA) showed that Sb contamination was the dominating factor influencing the AMF community structure in the Sb mine area. However, the multivariate analysis showed that, apart from the soil Sb content, extractable nitrogen content and organic matter content also attributed to AMF sequence distribution type. Some AMF sequences were only found in the highly contaminated area and these might be ideal candidates for improving phytoremediation efficiency in Sb mining regions. Gene sequencing analysis revealed that most species were affiliated with Glomus, suggesting that Glomus was the dominant AMF genus in the studied Sb mining area.