添加腐殖酸对猪粪/玉米秸秆厌氧发酵中铜、锌钝化效果的影响

针对畜禽饲料添加蓝矾或称胆矾(CuSO₄·5H₂O)、皓矾(ZnSO₄·7H₂O)等重金属化合物，引起畜禽粪便重金属污染风险，本研究通过构建以猪粪/玉米秸秆为发酵原料、腐殖酸为钝化剂的发酵系统，考察添加腐殖酸对猪粪/玉米秸秆厌氧发酵过程中产气量、重金属(Cu、Zn)形态变化及沼渣光谱特性的影响.结果表明，添加的腐殖酸对猪粪/玉米秸秆厌氧发酵产气具有显著促进作用，添加腐殖酸样本组(编号：F1、 F2、 F3)较未添加组(编号：CK)的累积产气量分别提高了19.81%、 28.44%、50.25%；通过BCR提取法分析沼渣中的Cu、Zn形态动态变化，显示添加腐殖酸有利于Cu、Zn的有效态向稳定态转化，F3中Cu、Zn有效态转化为稳定态的效果最佳；显著性分析表明F3中Cu、Zn的钝化效果最佳，Cu、Zn的钝化效果分别为58.72%、17.95%，显著优于其他处理组；腐殖酸对Cu的钝化效果整体优于Zn;FTIR结果显示，厌氧发酵后各处理组沼渣中碳水化合物、脂肪族化合物等有机物分解、减少，芳香族化合物等腐殖质...     

湘南某矿区菜园土中典型重金属的形态分析

分别运用Tessier连续提取法和Leleyter连续提取法研究湘南某矿区菜园土中Pb,Zn,Cu和Cd的形态分布特征.结果表明：菜园土中Pb,Zn,Cu和Cd的总浓度严重超过国家土壤环境质量标准.Pb,Zn,Cu和Cd的主要形态是残渣态,水溶态和交换态所占比例较小.重金属生物可利用性的研究表明,Pb,Zn,Cu和Cd生物可利用的含量较少;在Tessier方法中,除Cu之外,生物不可利用态是主要形态,其次是潜在生物可利用态,而在Leleyter方法中,潜在生物可利用态是主要形态,其次是生物不可利用态.     

干旱区矿业城市郊区农田土壤重金属有态含量及空间分布特征:以"镍都"金昌市为例

通过野外调查与室内实验分析研究了干旱区典型的矿业城市-金昌市郊农田土壤中重金属Zn、Ni、Cu、Pb、Cd五种重金属的EDTA提取态含量情况,并利用surfer对数据进行了空间插值分析.结果表明,金昌市郊农田土壤中这五种元素的EDTA提取态中,Cu的平均提取含量最高,Ni、Zn、Pb的提取态含量相对比较低,Cd的最低.相关性分析的结果显示,这五种重金属的EDTA提取态含量两两之间均呈显著正相关关系;EDTA提取态含量与其全量之间也均呈正相关关系,但只有Cd和Cu两种元素的相关性达到了显著性水平.空间分析表明,这五种重金属EDTA提取态的含量均在自家咀和马家崖子附近存在高值区.     

可控湿法氧化聚沉工艺对城市污泥中重金属的稳定化影响

采集了长沙市污水厂的剩余污泥（S1）和湿法氧化聚沉工艺处理的深度脱水污泥（S2）,对比分析了处理前后污泥的形貌变化及重金属Zn、Cu、Pb、Cd、Hg和As的形态分布,初步探讨了重金属稳定化机理,对脱水污泥中重金属Zn、Cu、Pb、Cd、Hg和As进行了稳定性评估.结果表明,脱水污泥中重金属的总量均低于我国污泥农用标准中的酸性限值,符合B级污泥泥质要求.处理后,污泥中Zn、Cu、Pb、Cd、Hg和As主要以硫化物有机结合态和残渣态（稳定态）存在,不稳定态在不同程度上向稳定态发生了转变,Cu、Hg的增幅最大,达21.1%.S2中重金属的生物可利用性较S1都有显著的降低,平均降幅达73.1%,S2中重金属的生物可利用性顺序为：Zn〉Pb〉Cu〉Cd〉As〉Hg.污泥经过湿法氧化聚沉工艺处理后,污泥中重金属Zn、Cu、Pb、Cd、Hg和As得到了明显的稳定化,为污泥后续资源化、安全化提供了科学依据.     

钝化剂对好氧高温堆肥处理猪粪重金属含量及形态的影响

采用连续提取法研究猪粪好氧堆肥处理中钝化剂对重金属含量及形态的影响.结果表明:堆肥处理后,猪粪中重金属Zn、Cu、Pb、Cr和As普遍升高,重金属Hg明显降低;堆肥处理能促进猪粪中重金属Zn、Cu、Pb、Cr、As和Hg的形态向活性低的方向转化,降低重金属的生物有效性.在3种重金属钝化剂处理中,沸石处理对降低猪粪中重金属Zn的生物有效性效果最好;海泡石处理对降低猪粪中重金属Cu和Cr的生物有效性效果最好;膨润土处理对降低猪粪中重金属Pb和Hg的生物有效性效果最好.因此沸石、海泡石和膨润土处理有利于降低猪粪施用中的重金属污染风险.     

泉州湾洛阳江河口潮滩表层沉积物中重金属赋存形态分析

对比3种重金属形态提取方法,其中稀HCl法提取率比EDTA法高,改进的BCR四步提取法提取率最高.用改进的BCR法分析泉州湾洛阳江河口潮间带沉积物中重金属的4种形态(弱酸溶态、可还原态、可氧化态和残渣态)的含量.结果表明,大部分金属元素(V、Cr、Co、Ni、Zn、Fe和Cd)主要以残渣态存在,Mn主要以弱酸溶态存在,Pb和Cu则以可还原态存在.各形态与其总量间的相关性分析结果表明,Fe受人类活动的影响相对较小,而Cr、Co、Ni、Pb、Cd和Cu的前三态与其总量之间呈现极显著的正相关,说明它们主要污染源来自人类活动.     

PM10中重金属的提取方法及生物可利用性研究

分别运用模拟生物提取法与化学连续提取法对PM10标准参考样品城市源（NIST-1648A）和工业源（BCR-038）中6种重金属（Cd、Co、Cu、Mn、Ni、Pb）质量分数及赋存形态进行分析。其目标是验证2种提取大气固体颗粒物中重金属方法的有效性,并比较2种方法的优缺点,为将来提取PM10中重金属的方法选取提供依据。模拟生物提取法中,使用Gamble溶液模拟人体肺液对 PM10样品进行溶解,实验方法操作较为简单快捷;化学连续提取法中,不同溶解步骤则可确定重金属的不同赋存形态。在需要快速确定 PM10中某种重金属总量时,应优先使用模拟生物提取法。化学连续提取结果表明,城市源PM10中重金属赋存形态分布没有统一规律,工业源PM10中重金属多以残渣态存在。通过对2种来源的PM10样品中重金属生物可利用性分析,城市源的大气颗粒物对人体的毒性更大,其中标准参考样品城市源 PM10中生物可利用性较高的是重金属Cd（BIBio为61.65%±3.45%;BISE为69.02%±3.82%）和Cu,最低的是重金属Co和Pb;标准参考样品工业源PM10中重金属的生物可利用性最高的是Cd（BIBio为27.66%±1.52%;BISE为15.05%±2.13%）,而Ni、Co和Pb的生物可利用性较低。     

几种萃取剂对土壤中重金属生物有效部分的萃取效果

采用6种萃取剂:pH=7的0.01mol/L CaCl_2、pH=7.3的0.005mol/L DTPA+0.1mol/L TEA(三乙醇胺)+0.01mol/L CaCl_2O.1mol/L NaNO_3、0.43mol/L HOAc、pH=7的0.05mol/L EDTA和pH=4.65的0.5mol/L NH_4OAc+0.02mol/L EDTA浸取液.对污染土壤中的重金属Cu、Zn、Cd、Pb、的进行了萃取,并比较了萃取剂的萃取能力。实验结果表明,HOAc、EDTA以及NH_4OAc-EDTA萃取各种重金属的能力远远大于其它几种萃取剂的萃取能力,是比较理想的萃取剂。     

EGTA淋洗和KH2PO4钝化联合修复重金属污染土壤

为进一步削减螯合淋洗后土壤残留重金属的环境风险,采用淋洗与钝化相结合的方法修复重金属污染土壤.研究了乙二醇双(2-氨基乙基醚)四乙酸(EGTA)淋洗、磷酸二氢钾(KH_2PO_4)钝化及两者联合修复对土壤重金属洗脱率的影响,并分别采用TCLP法和BCR法分析重金属浸出浓度及化学形态分布,构建了涵盖土壤重金属残留量、生物有效性和毒性的环境风险评价方法,对淋洗、钝化及其联合修复效果进行了评价.结果表明,EGTA对Cu和Cd具有较好的洗脱效果,降低了土壤Cu、Zn和Cd浸出浓度,提高了Pb浸出浓度,削减了可还原态Cu残留量、弱酸提取态和可还原态Zn残留量、可还原态Pb残留量以及弱酸提取态、可还原态Cd残留量.随着KH_2PO_4投加量的增加,Pb、Cd和Cu浸出浓度呈下降趋势,Zn浸出浓度先上升后下降.KH_2PO_4对重金属形态分布的影响主要表现为降低弱酸态或可还原态重金属占比,提高残渣态重金属占比.EGTA和KH_2PO_4联合修复显著降低了4种重金属的可还原态残留量和弱酸提取态Pb、Cd残留量,大幅度削减了Cd和Cu的浸出浓度和环境风险.Zn污染土壤宜淋洗修复,Pb污染土壤宜钝化修复,Cd和Cu污染土壤深度修复宜淋洗/钝化联合处理.     

冬氨酸二丁二酸醚(AES)诱导黑麦草提取污染土壤重金属的效应

采用盆栽试验,研究新型生物可降解螯合剂冬氨酸二丁二酸醚(AES)和非降解螯合剂乙二胺四乙酸(EDTA)调控下黑麦草修复重金属污染土壤的效应.黑麦草于含2500 mg Pb·kg-1,500 mg Cu·kg-1,1000 mg Zn·kg-1 和15 mg Cd·kg-1 的土壤中生长45d后,分别施加5 mmol·kg-1 土的AES或EDTA.结果表明,AES和EDTA可以显著提高土壤溶液和黑麦草植株地上部Pb、Zn、Cu和Cd的浓度.EDTA对土壤中Pb的溶解能力和对黑麦草积累重金属的促进作用显著强于AES,前者处理的土壤中水提取态Pb浓度和黑麦草地上部Pb浓度分别达到了15.9 mg·kg-1 和174.1 mg·kg-1,显著高于AES处理的2.6 mg·kg-1 和44.0 mg·kg-1.但AES对黑麦草积累Zn和Cd的促进作用较EDTA明显增强,黑麦草地上部Zn浓度达到了1081.8 mg·kg-1,显著高于EDTA的776.7 mg·kg-1 和对照的389.6 mg·kg-1;地上部Cd浓度为1.57mg·kg-1,高于EDTA的1.06 mg·kg-1 和对照的0.69 mg·kg-1.与对照相比,AES和EDTA对Cu在土壤中的溶解和黑麦草植株中的积累亦有显著的促进作用,但二者处理无极显著差异.结果表明,生物可降解螯合剂AES在诱导植物修复重金属污染土壤尤其是Zn、Cd污染土壤中有很大的应用潜力,且与EDTA相比,环境风险大大降低.     

Soil remediation using in situ immobilisation techniques

The main objective of this study was to investigate the efficiency of different substrates to reduce the extraction of heavy metals concentration in a heavily contaminated soil. Two contaminated soils by Cu and Zn were used to evaluate the effectiveness of eight substrates (calcium carbonate, bentonite, kaolinite, charcoal, manganese oxide, iron oxide, zeolite, phosphate) to reduce metal availability and to study the change of metals speciation in different forms using sequential extraction technique (single step). Sequential extraction technique (single step, 0.11 M acetic acid, HONH₃Cl, H₂O₂+NH₄OAc, Aqua regia) was applied on contaminated soils after and before treatment to evaluate metals speciation. Results indicate that the most effective treatments in decreasing available metal concentrations were calcium carbonate, zeolite and manganese or iron oxide. Metal sequential fractionations indicate that the exchangeable fraction of Cu and Zn in contaminated soils can be transformed into unavailable forms after chemical remediation.     

Remobilization of selected metal ions from Nile sediment (Egypt) according to sequential extraction and metal–EDTA complex

River sediments are basic components of our environment, providing nutrients for living organisms and serving as sinks for deleterious chemical species. The metal contents may be remobilized and released back into waters with changes in environmental conditions, thus affecting living organisms and human activities. This paper aims to determine the effect of a synthetic anthropogenic chelating agent (EDTA) as industrial discharges on the remobilization of several metals (Cu, Zn, Cd, and Pb) in River Nile sediments (at Aswan and Mansoura cities) under different concentrations and pH values, and to investigate the influence of metal–EDTA complexes on this remobilization. For these purposes, sequential extraction and experiments on the effect of pH and metal EDTA complex were carried out on the two representative sediment samples south and north of the River Nile in Egypt. The results of sequential extraction show that most of metal contents present in the residual form (Cu, 11.36–72.34%; Pb, 29.64–66.67%; and Zn, 43.76–50.09% at Aswan and Mansoura, respectively). Non-residual fractions which may be available for the remobilization by EDTA represented anthropogenic (industrial, agriculture, and domestic discharges) and lithiopogenic (metals bound to Fe and Mn oxides) sources. A clear increase was detected for Cu and Zn remobilization from the increase in EDTA concentrations, in contrast, Cd independent of the EDTA concentration and slight influence on Pb content. The remobilization of metals as a function of pH exhibited. The metals were greatly remobilized under the complexing action of EDTA, showing that some of these elements were adsorbed on the sediments. The remobilization rate of metals was dependent upon the added metal–EDTA complex (with the exchange rate being in the order Ca–EDTA>Zn–EDTA>Cd–EDTA>Cu–EDTA>Pb–EDTA), due to the stability constant of the metal–EDTA complex. The results of these experiments showed that heavy metals are greatly remobilized under the complexing action of EDTA when it is present in excess, so all precautions should be taken to prevent any wastewater containing EDTA or any chelating agents discharging directly or indirectly via the River Nile stream because most EDTA remains in the aquatic phase. The ability of this portion to remobilize metals from sediments should be taken into account.     

Electro-remediation of tailings from a multi-metal sulphide mine: comparing removal efficiencies of Pb,Zn, Cu and Cd

Sulphidic mine tailings characterised by high concentrations of heavy metals (Pb 3532?±?97?mg/kg, Zn 8450?±?154?mg/kg, Cu 239?±?18?mg/kg and Cd 14.1?±?0.3?mg/kg) and abundant carbonate (17%) were subjected to eight lab-scale electrodialytic remediation (EDR) experiments to investigate the influence of current density, treatment time and particle size on removal efficiency. Pb and Cu removal improved when increasing current density, while Zn and Cd removal did not. In contrast Zn and Cd removal improved by grinding the tailings, while Pb and Cu removal did not. At the highest current density (1.2?mA/cm²), 94%, 75%, 71% and 67% removal of Pb, Zn, Cu and Cd could be achieved, respectively, on grinded tailings in 28 days. Sequential chemical extraction made before and after EDR revealed larger oxidisable fractions of Zn, Cu and Cd, representing large fractions of sulphides, which was likely to be the main barrier to be removed as efficiently as Pb. This was in accordance with acid/base extraction tests in which Pb showed high solubility at both high and low pH (up to 65% and 86% of extraction, respectively), while considerable extraction of Zn (55%) happened only at low pH; and very limited extraction (<20%) of Cu and Cd occurred at any pH.     

Trace elements in wild grasses: a phytoavailability study on a remediated field

There have been significant efforts to establish a widely usable method for the prediction of trace element bioavailability in soil. In this work, we used extraction with 0.01 M CaCl₂ and 0.05 M ethylenediaminetetraacetic acid (EDTA) to estimate bioavailable concentrations of As, Cd, Cu, Pb, and Zn in a soil moderately contaminated with trace elements 1 and 2 years after the application of three amendments. The experiment took place in a field plot of a soil affected by the toxic spill of the Aznalcóllar mine. Four treatments were established: three with amendments (biosolid compost, sugar beet lime, and a combination of leonardite plus sugar beet lime) and a control without amendment. Trace element concentrations of two representative species in each year (Lamarckia aurea and Poa annua in 2004 and Lamarckia aurea and Bromus rubens in 2005) were analyzed. The results showed a positive effect of the amendments both on soil and vegetation. Trace element concentrations in plants growing in the amended subplots were lower than those in plants from nonamended subplots. As a rule, concentrations of CaCl₂-soluble Cd, Cu, and Zn in soil were positively correlated with trace elements in plants, whereas EDTA extraction was scarcely correlated with plant concentration. For species of grasses, especially L. aurea, CaCl₂ seems to be a more suitable extractant to predict trace element bioavailability in this contaminated soil.     

大气PM_（2.5）中重金属的化学形态分布

运用多级连续提取法,对广州市不同季节不同采样高度大气PM2.5中重金属的化学形态和生物有效性进行分析。研究表明,PM2.5中各重金属元素之间的化学形态分布差异较大,Zn、Cd、As、Mn主要分布在F1（可溶态与可交换态）和F2（碳酸盐态、可氧化态与可还原态）,绝大部分的Pb以F2存在,Ni和Mo主要分布在F1和F3（有机质、氧化物与硫化物结合态）,Cu主要以F2和F3存在,Cr主要分布在F3和F4（残渣态）,Co则4种形态平均分布。采样高度对重金属的化学形态分布影响不大,同一采样期内楼顶与地面样品中同一元素的化学形态分布结果比较一致。两个采样季节重金属的形态百分比存在不同程度的变化,2007年春重金属的不稳定态（F1）比例比2006年秋普遍增加,次稳定态（F2、F3）比例减少。在10种重金属中,Cd、Zn、Pb和As的生物有效性系数高（〉0.7）,属于生物可利用性元素,在环境中的活动性要明显高于其它元素;Mn、Cu、Mo、Co、Ni和Cr元素的生物有效性系数值在0.2～0.6之间,属于潜在生物有效性元素,在环境中比较稳定。     

大气PM2.5中重金属的化学形态分布

运用多级连续提取法,对广州市不同季节不同采样高度大气PM2.5中重金属的化学形态和生物有效性进行分析。研究表明,PM2.5中各重金属元素之间的化学形态分布差异较大,Zn、Cd、As、Mn主要分布在F1(可溶态与可交换态)和F2(碳酸盐态、可氧化态与可还原态),绝大部分的Pb以F2存在,Ni和Mo主要分布在F1和F3(有机质、氧化物与硫化物结合态),Cu主要以F2和F3存在,Cr主要分布在F3和F4(残渣态),Co则4种形态平均分布。采样高度对重金属的化学形态分布影响不大,同一采样期内楼顶与地面样品中同一元素的化学形态分布结果比较一致。两个采样季节重金属的形态百分比存在不同程度的变化,2007年春重金属的不稳定态(F1)比例比2006年秋普遍增加,次稳定态(F2、F3)比例减少。在10种重金属中,Cd、Zn、Pb和As的生物有效性系数高(>0.7),属于生物可利用性元素,在环境中的活动性要明显高于其它元素;Mn、Cu、Mo、Co、Ni和Cr元素的生物有效性系数值在0.2～0.6之间,属于潜在生物有效性元素,在环境中比较稳定。     

The relationship between epilithic periphyton (biofilm) bound metals and metals bound to sediments in freshwater systems

Surficial sediments and epilithic periphyton (biofilm) were sampled from six sites on the River Churnet and five sites on the River Manifold in Staffordshire and analysed for cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn). The sites demonstrated a wide range of sediment trace metal concentrations determined by inductively coupled plasma optical emission spectrometry (ICP-OES) and atomic absorbtion spectroscopy (AAS). Biofilm was removed from the substrate using physical abrasion and 0.005 M ethylenediaminoethanetetra-acetic acid (EDTA) extractant. The European Standards, Measurements and Testing Programmes (BCR) operationally defined geochemical speciation scheme was used to determine the exchangeable, acid soluble fraction of the sediments. Significant positive correlations were determined between the EDTA extractable biofilm and the exchangeable sediment fraction for Cd, Cu and Zn but not for Pb. Natural epilithic periphyton may be a potential metal biomonitor particularly of Cu, Cd and Zn in aquatic systems and provide supporting information in relation to potential sediment toxicity.     

Evaluation of tests to assess the quality of mine-contaminated soils

An acid metal-contaminated soil from the Aljustrel mining area (a pyrite mine located in SW Portugal in the Iberian Pyrite Belt) was subjected to chemical characterisation and total metal quantification (Cd, Cr, Cu, Ni, Pb and Zn). Water-soluble metals were determined and a sequential extraction procedure was used to investigate metal speciation. Two bioavailable metal fractions were determined: a mobile fraction and a mobilisable fraction. Soil ecotoxicity was studied using a battery of bioassays: plant growth test and seed germination with cress (Lepidium sativum L.), earthworm (Eisenia fetida) mortality, E. fetida avoidance behaviour, luminescent inhibition of Vibrio fischeri and Daphnia magna immobilisation. Although the total content of Cu, Zn and Pb in the soil was large (362, 245 and 1,250 mg/kg dry matter, respectively), these metals were mostly structurally bound (87% for Cu, 81% for Zn and 89% for Pb) and, therefore, scarcely bioavailable. Nonetheless, the D. magna immobilization test using soil leachate showed an EC₅₀ (48 h) of 36.3% (v/v), and the luminescent inhibition of V. fischeri presented an EC₂₀ (15 min) of 45.2% and an EC₂₀ (30 min) of 10.7% (v/v), suggesting a considerable toxic effect. In the direct exposure bioassays, E. fetida avoided the mine soil at the highest concentrations (50%, 75% and 100% v/v). At the same soil concentrations, cress showed negligible growth. The results suggest the need to use a battery of toxicity tests, in conjunction with chemical methods, in order to assess the quality of mine-contaminated soils correctly.