pH值对烧结砖中重金属释放的影响

采用酸消解实验和NEN 7371浸出实验研究了烧结砖中重金属总量和有效释放量,采用pH-dependence实验研究pH对破碎烧结砖样品中重金属(Cr、Ni、As、Cd和Pb)浸出特性的影响,以及烧结砖样品的酸碱缓冲容量。结果表明,烧结砖中重金属的有效释放量低于总量,释放率从大到小依次为CdAsPbNiCr;烧结砖的酸缓冲容量较小,浸出液pH从7.03降到3.64,消耗了29.33 mmol/kg硝酸,碱缓冲容量较大,pH从7.03升到12.40,共消耗256 mmol/kg氢氧化钠溶液,因此在使用烧结砖的过程中要特别注意环境pH;浸提液的酸碱性是影响烧结砖中重金属浸出的重要参数,在实验研究的pH范围内,不同重金属的浸出规律不同。Cr和As的释放受pH影响较小,而Ni和Cd的浸出量随pH的增大而降低,Pb的浸出量在强酸和强碱条件下均较大,当pH在5.59~9.86的范围内浸出量很低。     

柴河铅锌尾矿中重金属铅、锌、镉的迁移特征

采用柱状淋滤实验模拟降水,研究柴河铅锌尾矿中重金属铅(Pb)、锌(Zn)、镉(Cd)的迁移特征。结果表明:无覆土层的尾矿柱(柱1)与含50cm覆土层的尾矿柱(柱2)淋滤液pH均在30d分别出现最低值5.86和6.67;在180d分别出现最高值7.85和7.89。柱1淋滤液中Pb、Zn、Cd最高质量浓度分别为0.053 0、5.980 0、0.009 4mg/L,均超过《地表水环境质量标准》(GB 3838—2002)的Ⅳ类标准规定的限值。柱2淋滤液中Pb、Cd最高浓度符合GB 3838—2002的Ⅳ类标准,Zn最高浓度超过GB 3838—2002的Ⅳ类标准规定的限值。随着淋滤时间延长,柱2淋滤液中Pb、Zn、Cd浓度均低于柱1,说明表层覆土措施可减少尾矿中重金属淋失。经过柱状淋滤实验,柱2中40cm处Pb、Zn、Cd全量相比原覆土分别增加17.47%、23.37%、26.09%,表明下部尾矿层中的重金属可向上部覆土层迁移。     

几种模拟处理方式污泥淋出液重金属与养分特征

为了减少城市污泥重金属对农田的污染,更好地实现污泥农业资源化利用,通过盆栽实验研究不同处理(对照、黑网、附Fe黑网、附Fe黑网+K2SO4及附Fe黑网+玉米)对城市污泥淋出液重金属和养分含量等的影响。结果表明,黑网可降低污泥淋出液的Zn﹑Cd总量,且没有减少污泥淋出液中氮、磷和钾的总量。Fe(OH)3可使淋出液中Zn总量降低,但同时也显著减少了淋出液中的磷总量。K2SO4可降低淋出液中的Cu总量,且促进Fe结合磷的释放。玉米的种植可使污泥的总重降低,同时玉米籽粒和茎叶重金属含量达到饲料标准。综合来看,任何处理每次淋出液的Cu、Zn、Pb、Cd浓度均符合农田灌溉水标准,淋出液氮、磷、钾量占原污泥中氮、磷、钾总量的比例(0.98%～9.88%)远远大于重金属元素(Cu,Zn,Pb,Cd)占原污泥对应重金属总量的比例(0.04%～0.41%),污泥淋出液作为农田灌溉水进行肥水利用将是污泥农业资源化利用的适合途径,同时黑网+玉米处理可能是较理想的污泥综合处理利用方式。     

液/固体系中硅藻土对Pb2+和Cd2+的吸附机制

为了提高硅藻土在重金属废水处理上的应用水平,采用静态吸附实验考察了液/固体系中硅藻土对Pb2＋、Cd2＋的吸附影响因素、吸附等温线和吸附动力学属性。结果表明,随着投加量的减少,离子初始浓度的提高,pH值的增大,吸附作用时间的延长,硅藻土对Pb2＋、Cd2＋吸附量不断上升;硅藻土对Pb2＋、Cd2＋的等温吸附都符合Langmuir模型,硅藻土对Pb2＋、Cd2＋最大吸附量分别为10.428 mg/g和7.916 mg/g,硅藻土对Pb2＋具有更好的吸附能力;Pb2＋具有较低的水合自由能,更容易脱去水膜与硅藻土孔道内的活性基团发生吸附作用;双常数扩散方程可以很好地描述硅藻土对Pb2＋、Cd2＋的吸附动力学属性,硅藻土对Cd2＋有较快的吸附速率。     

模拟酸雨对磷酸二氢钾钝化污染土壤Cu、Cd、Pb和P释放的影响

以磷酸二氢钾(PDP)钝化后的重金属污染土壤为研究对象,通过室内土柱淋溶实验,考察在pH为3.5、4.5和5.6的模拟酸雨作用下土壤Cu、Cd、Pb和P的释放特征。结果表明:PDP处理较对照处理显著增加了淋出液中pH、电导率(EC)和总有机碳(TOC)含量,但不同pH模拟酸雨对对照和PDP处理淋出液pH、EC和TOC含量影响较小。对照处理中,正磷酸盐含量维持在较低水平(0.02~0.13 mg·L~(-1));PDP处理下,正磷酸盐含量在1~3 L和4~12 L分别是《地表水环境质量标准》(GB 3838-2002)五类水标准(总磷含量0.4 mg·L~(-1))的55.1~819倍和9.46~46.6倍,对地表水表现出较大的富营养化风险。PDP处理较对照处理显著降低了淋溶初期淋出液中的Cu、Cd和Pb含量,但是随模拟酸雨pH降低,对照和PDP处理的土壤淋出液中Cu、Pb含量均未表现出显著差异。因此,PDP处理能够显著钝化污染土壤中的Cu、Cd和Pb,但需关注酸雨淋溶下过量磷释放对地表水富营养化的潜在风险。     

辽宁省红透山铜矿区土壤中重金属迁移特征研究

采用柱淋溶实验模拟辽宁省红透山铜矿区土壤中重金属的淋溶迁移特征,研究了淋溶液pH、电导率(EC)和重金属含量的变化及其相关性,分析了重金属在淋溶前后的总量和形态变化,并初步探讨其生态与健康风险.结果表明,在1～3次淋溶中,淋溶液pH迅速下降,土样中的部分酸性物质被快速溶出,在第3次淋溶之后,淋溶液pH缓慢上升;淋溶初期淋溶液EC大幅度、迅速降低,此后随着淋溶次数的增加EC缓慢降低;Fe、Mn、Cu、As、Cd均能从土样中溶出进入淋溶液,其中Fe、Mn、Cu、As的溶出主要在淋溶初期,而Cd除了在初期有所溶出外,在淋溶后期还存在二次溶出释放阶段;淋溶后土样中绝大部分重金属总量均有所下降,各重金属的解吸率为Cd＞As＞Fe＞Cu＞Mn＞Zn,其中以Cd、As含量下降最为明显,而Zn基本未溶出;淋溶前后土样中重金属的活性态(弱酸提取态(BCR-1)、可还原态(BCR-2)、可氧化态(BCR-3))含量发生了不同程度的变化,Fe的活性态含量在淋溶后变化很小,Mn、As的活性态含量在淋溶后有所上升,而Cu、Cd的活性态含量在淋溶后有所下降;随着淋溶的进行,土壤中各重金属的赋存形态发生了一定变化,从而可能引起其生态与健康风险的改变.     

赭石对模拟重金属废水的吸附效果研究

采用模拟重金属废水的正交试验设计,进行赭石对模拟重金属废水的吸附效果研究,探讨pH、赭石加入量和振荡时间等影响因素对吸附效果的影响。结果表明,在一定pH、赭石加入量和振荡时间条件下,赭石对6种重金属（Pb、Cd、Mn、Zn、Cr和Ni）均有较好吸附效果,对Pb、Cd、Mn、Zn和Cr的最大吸附率可达100%,对Ni的吸附率达8963%。处理后废水中重金属达到污水排放标准。各影响因素对Mn、Zn和Cr吸附效率的影响大小表现为：pH＞赭石加入量＞振荡时间,Ni和Cd表现为：赭石加入量＞pH＞振荡时间,Pb表现为：pH＞振荡时间＞赭石加入量。赭石对废水中重金属吸附的最佳条件为赭石加入量40 g/L,pH 10～10.5,振荡时间2 h。     

骨炭对Pb(Ⅱ)的吸附特性

通过间歇实验研究了骨炭对重金属Pb(Ⅱ)的吸附特性。探讨了固液比、pH、离子强度、反应时间、温度及初始浓度等因素的影响。实验结果表明,pH与固液比显著影响去除率,温度与离子强度的影响较小。当温度为20℃,pH=2.5,Pb(Ⅱ)的初始浓度为200 mg/L,固液比为1 g/L时,最大去除率近100%。动力学实验结果表明,骨炭对Pb(Ⅱ)的吸附为快速反应,在30 min内可达到平衡,准二级动力学模型可较好地拟合实验结果。等温吸附实验结果表明,Freundlich模型与Langmuir模型均可较好地拟合等温吸附实验结果。骨炭对Pb(Ⅱ)的吸附机制主要为表面络合反应与分解置换-沉淀反应。     

废物水泥窑共处置产品中Cd释放的pH影响

用高温电炉模拟煅烧试验制取水泥熟料后再制作混凝土,参考EA NEN 7375:2004浸出试验,设定5种不同pH的浸取液对混凝土进行长期浸出试验,研究了pH对水泥窑共处置混凝土中Cd释放量以及释放过程的影响.结果表明:(1)pH为2.00、3.50、5.00、7.35和10.00的浸取液中,Cd的累积释放量分别为0.408 0、0.005 8、0.000 7、0.000 4、0.001 2 mg/kg.在酸性条件下,随pH的增大,Cd的累积释放量减小.在碱性条件下,随pH的增大,Cd的累积释放量增大.(2)pH为7.35的浸取液中,Cd累积释放量的释放曲线与斜率为0.5的直线拟合最佳.pH为7.35的浸取液中,混凝土中Cd的释放机制为扩散控制;pH为2.00和5.00的浸取液中,Cd的释放在前期为扩散控制,后期发生了耗竭作用;pH为3.50和10.00条件下,Cd的释放在前期发生了延滞作用,中期为扩散控制,后期发生了耗竭作用.     

壳聚糖改性对磁性Fe_3O_4吸附去除Pb(Ⅱ)和Cd(Ⅱ)的影响研究

利用壳聚糖改性磁性Fe_3O_4以提高其对重金属Pb(Ⅱ)和Cd(Ⅱ)的吸附性能,考察了改性前后磁性Fe_3O_4对Pb(Ⅱ)、Cd(Ⅱ)的吸附等温线及吸附动力学过程。结果表明,经壳聚糖改性后,壳聚糖-磁性Fe_3O_4比表面积大幅增加,由原来的76.12m2/g增加到142.67m2/g;壳聚糖-磁性Fe_3O_4对Pb(Ⅱ)、Cd(Ⅱ)的吸附性能优于磁性Fe_3O_4;当pH为2.0~7.0时,提高pH有助于促进两种磁性材料对Pb(Ⅱ)和Cd(Ⅱ)的吸附量;两种磁性材料对Pb(Ⅱ)和Cd(Ⅱ)的吸附符合准二级动力学模型,吸附过程属于吸热过程;重复吸附—脱附循环再生5次后,壳聚糖-磁性Fe_3O_4对Pb(Ⅱ)、Cd(Ⅱ)的去除率仍在80%以上,磁性Fe_3O_4对Pb(Ⅱ)、Cd(Ⅱ)的去除率在75%以上,两种磁性材料再生性能较好。     

Heavy metals mobility in full-scale bioreactor landfill: initial stage

Selected heavy metals (HMs) including Cd, Cr, Cu, Ni, Pb and Zn initially released from a full-scale bioreactor landfill were monitored over the first 20 months of operation. At the initial landfill stage, the leachate exhibited high HMs release, high organic matter content (27000-43000gl(-1) of TOC) and low pH (5-6). By the fifth month of landfilling, the methanogenic stage had been established, and HMs release was reduced below the Chinese National Standards. Total released HMs accounted for less than 1% of landfill deposited during the investigated period. Most landfill HMs were inorganic. Fourier-transform infrared (FT-IR) spectra data and model calculations using Visual MINTEQ indicated that humic substances strongly affected the mobility of organic fractions of HMs in the methanogenic landfill. The initial rates of HMs release could be enhanced by recycling the leachate back to bioreactor landfill, but the total quantity released may be reduced by early establishment of methanogenic stage in bioreactor landfill.     

硫酸锰废渣浸出毒性及淋溶特性研究

长沙市兴镇13家硫酸锰厂的生产废渣使当地的生态环境造受到了严重破坏。本文在废渣浸出毒性实验、渣柱淋滤实验以及废渣的全分析基础上,全面地研究了废渣的组成、浸出毒性大小以及在当地酸沉降条件下的淋滤特征,为其安全处置提供了理论基础。研究证明,废渣中重金属种类多、含量高,尤其是锰,高达138800mg/kg。渣的浸出毒性虽未达到国家规定的危险废物鉴别标准,但远超过了《污水综合排放标准》,其衰减可用负指数方程来描述。在酸雨淋溶下,渣中的锰离子会在短时期内大量释放后,维持在一相对较低水平长期释放,对环境威胁巨大。     

Leaching of heavy metals from contaminated soils using EDTA

Ethylenediaminetetraacetic acid (EDTA) extraction of Zn, Cd, Cu and Pb from four contaminated soils was studied using batch and column leaching experiments. In the batch experiment, the heavy metals extracted were virtually all as 1:1 metal-EDTA complexes. The ratios of Zn, Cd, Cu and Pb of the extracted were similar to those in the soils, suggesting that EDTA extracted the four heavy metals with similar efficiency. In contrast, different elution patterns were obtained for Zn, Cd, Cu and Pb in the column leaching experiment using 0.01 M EDTA. Cu was either the most mobile or among the most mobile of the four heavy metals, and its peak concentration corresponded with the arrival of full strength EDTA in the leachate. The mobility of Zn and Cd was usually slightly lower than that of Cu. Pb was the least mobile, and its elution increased after the peaks of Cu and Zn. Sequential fractionations of leached and un-leached soils showed that heavy metals in various operationally defined fractions contributed to the removal by EDTA. Considerable mobilisation of Fe occurred in two of the four soils during EDTA leaching. Decreases in the Fe and Mn oxide fraction of heavy metals after EDTA leaching occurred in both soils, as well as in a third soil that showed little Fe mobilisation. The results suggest that the lability of metals in soil, the kinetics of metal desorption/dissolution and the mode of EDTA addition were the main factors controlling the behaviour of metal leaching with EDTA.     

石灰干化污泥对土壤重金属稳定化处理的效果

以采自湖南省嘉禾县重金属复合污染土壤为研究对象,采用城市污水处理石灰干化污泥作为稳定剂,对污染土壤进行稳定化处理,并采用TCLP和BCR连续提取法对稳定化效果进行分析和评价。研究结果表明,单独使用石灰干化污泥,TCLP浸出浓度随着干化污泥质量分数的增加而显著减少,干化污泥的质量分数为40%时,稳定化率最大为Zn-98.92%、Cd-99.06%、Pb-96.84%;但是干化污泥的高pH值导致稳定后土壤中As的浸出增加。为了恢复植物生长功能,经过亚铁盐和磷酸调节pH后,石灰干化污泥稳定过的土壤pH有效降低,同时亚铁盐和磷酸有利于促进Pb和Zn的稳定效果;但是对Cd的稳定有负面影响;另外,亚铁盐的加入同时可以减少As的浸出浓度。经处理后土壤中重金属形态由不稳定态转为稳定态,使重金属的浸出浓度明显降低,减少了土壤重金属的浸出毒性。该研究结果表明,石灰干化污泥可以作为资源回收利用,应用于重金属污染土壤的修复中,并能改善稳定后土壤适宜植物生长的理化性质。     

Heavy metal availability,bioaccessibility, and leachability in contaminated soil: effects of pig manure and earthworms

A pot experiment and a leaching experiment were conducted to investigate the effects of earthworms and pig manure on heavy metals (Cd, Pb, and Zn) immobility, in vitro bioaccessibility and leachability under simulated acid rain (SAR). Results showed manure significantly increased soil organic carbon (SOC), dissolved organic carbon (DOC), available phosphorus (AP), total N, total P and pH, and decreased CaCl₂-extractable metals and total heavy metals in water and SAR leachate. The addition of earthworms significantly increased AP (from 0.38 to 1.7 mg kg^?1), and a downward trend in CaCl₂-extractable and total leaching loss of heavy metals were observed. The combined earthworm and manure treatment decreased CaCl₂-extractable Zn, Cd, and Pb. For Na₄P₂O₇-extractable metals, Cd and Pb were decreased with increasing manure application rate. Application of earthworm alone did not contribute to the remediation of heavy metal polluted soils. Considering the effects on heavy metal immobilization and cost, the application of 6% manure was an alternative approach for treating contaminated soils. These findings provide valuable information for risk management during immobilization of heavy metals in contaminated soils.

     

施用垃圾堆肥土壤重金属在不同温度和酸雨条件下的淋溶特征

采用淋洗法,研究了垃圾堆肥中重金属在不同温度与模拟酸雨条件下的淋溶特征。结果表明,随着淋洗次数的增加,淋洗液中Cd、Cr、Cu、Ni和Pb的含量都有很大程度的减少。Cd、Cr、Cu和Ni 4种金属在模拟酸雨的情况下淋出量明显高于蒸馏水的情况,增幅都在116%和351%之间,差异显著(P<0.05)或极显著(P<0.01),而酸雨对Pb的淋出影响较小。在酸雨淋洗下,重金属的淋出率在30℃时达到最大,其中Ni随着温度的变化相对较小。而在蒸馏水淋洗下,重金属的淋出率随着温度的变化相对平稳。此外,5种重金属的淋出率明显不同,其中Cr和Ni的淋出率相对较大,Pb最小。     

Use of bone meal amendments to immobilise Pb, Zn and Cd in soil: A leaching column study

The aim of this study is to test the stabilisation of metals in contaminated soils via the formation of low-solubility metal phosphates. Bone apatite, in the form of commercially available bone meal, was tested as a phosphate source on a mine waste contaminated made-ground with high levels of Pb, Zn and Cd. Triplicate leaching columns were set up at bone meal to soil ratios of 1:25 and 1:10, in addition to unamended controls, and were run for 18 months. The columns were irrigated daily with a synthetic rain solution at pH of 2, 3, and 4.4. After 100 days, the leachate Pb, Zn and Cd concentrations of all amended columns were significantly reduced. For 1:10 treatments, release of these metals was suppressed throughout the trial. For 1:25 treatments, Zn and Cd concentrations in the leachates began to increase after 300 days. DTPA and water extractions showed that Pb and Cd were more strongly held in the amended soils. This study concludes that the complexity of soil processes and the small quantities of metals sequestered precluded determination of a metal immobilisation mechanism.     

Residual metal concentrations in soils and leaf accumulations in tobacco a decade following farmland application of municipal sludge

The objectives of this investigation were to examine the long-term residual effects of metal loading through sewage sludge applications on the total vs. diethylene triamine pentacetic acid (DTPA) extractable metal concentrations in soil and leaf accumulations in tobacco. Maryland tobacco (Nicotiana tabacum L.), cv. 'MD 609', was grown in 1983 and 1984 at two sites in Maryland that had been amended in 1972 with dewatered, digested sewage sludge from washington, DC, at rates equal to 0, 56, 112 and 224 mg ha(-1). The metal concentrations in the sludge, in mg kg(-1) dry weight, were: 1300 Zn, 570 Cu, 280 Pb, 45 Ni and 13 Cd. Soil samples collected from the surface horizon and composite leaf samples of cured tobacco were analyzed for total Zn, Cu, Mn, Fe, Pb, Ni and Cd concentrations. The soil samples were also examined for soil pH and DTPA extractable metals. Equations were generated using polynomic and stepwise regression analyses which described the relationships between total vs. DTPA extractable soil metals, and between DTPA soil and soil pH vs. plant metal concentrations, respectively. Significant increases were observed for both total and DTPA extractable metal concentrations for all metals, with all but total Mn and Ni being significant for linear and quadratic effects regarding sludge rates. However, linear relationships were found between DTPA extractable vs. total soil concentrations for all elements except Pb and Ni which were quadratic. Significant increases in plant Zn, Cu, Mn, Ni and Cd and decreases in Fe were observed with increased sludge rates. Plant Pb levels were unaffected by sludge applied Pb. Linear relationships were observed between plant Zn and Cd and DTPA soil metal levels: however, Mn and Cu levels were described by quadratic and cubic relationship, respectively. Relationships between plant Fe and Pb and DTPA extractable concentrations were nonsignificant. Additional safeguards to protect crop contamination from heavy metals such as Cd were discussed.     

污水污泥中重金属污染物的溶出过程研究

污水污泥中污染物尤其是重金属的水体浸出作为重要的二次污染途径备受关注。为了探讨污水污泥中重金属的溶出规律,对上海7个污水处理厂的污水污泥进行了重金属总量分析,并采用水平振荡法对上述污水污泥中重金属进行了溶出动力学研究。结果表明,污水污泥中Cu、Cr和Zn的含量均较高,之后依次是Pb、As、Cd和Hg;污水污泥中重金属溶出动力学过程分为快速反应和慢速反应两个过程,可以用Elovich方程进行模拟;污水污泥中各重金属的溶出负荷差异较大,Cu、Cr和Zn的溶出负荷较大,其他较小,但各重金属相对于污水污泥中重金属总量的溶出百分比差异不大,基本处于10%以下。