残留药剂对土壤As、Hg、Cd、Pb浸出测试干扰及消除方法

固化/稳定化是应用最广泛的重金属污染土壤修复技术,但残留药剂在浸出测试过程对土壤二次修复导致的验收假达标风险未引起充分重视.本研究分别采用Fe₂（SO₄）₃、Na₂S和KH₂PO₄修复As、Hg、Cd-Pb污染土壤,探究不同养护反应时间、药剂混合均匀度和投加量等工艺条件下土壤重金属浸出浓度差异,验证液相二次修复干扰效应的发生,并考察Cu²⁺和Al³⁺等竞争剂对土壤残留KH₂PO₄药剂干扰的消除效果,提出最佳的残留药剂消除方法.结果表明,分别投加6.7%的Fe₂（SO₄）₃、6.7%的Na₂S和3.3%的KH₂PO₄修复含As、Cd和Pb土壤时,土壤中各重金属浸出浓度从第0 d起分别持续小于0.05、0.5和1.6 mg·L^-1,稳定化效率分别保持在99%、83%~99%和97%~98%.投加0.0008%的Na₂S修复土壤Hg时,Hg浸出浓度自第0 d起随养护反应时间显著下降,稳定化效率维持在78%~88%.虽然修复后土壤中Hg浸出浓度随药剂混合均匀度增加而显著下降,As、Cd、Pb浸出浓度在混合均匀度为67%和33%时相较混合均匀度为100%时均无显著变化（1.7% Fe₂（SO₄）₃修复组除外）,但均小于无二次反应理论值.此外,Cu²⁺能与Pb²⁺竞争浸出液中的残留PO₄^3-减弱干扰效应,当Cu²⁺优化投加量为5.7%、11.3%、14.2%时,混合均匀度67%处理组Pb浸出浓度分别升至理论值的51%、72%、84%,混合均匀度33%处理组Pb浸出浓度则分别升至理论值的38%、71%、81%.而Al³⁺无法与Pb²⁺竞争PO₄^3-,甚至对土壤Pb具有显著活化效果.Cu²⁺对Pb也具有一定的活化效果,因此,需控制Cu²⁺投加量以寻求活化效果与优化作用的最佳平衡点.     

Release of Pb adsorbed on graphene oxide surfaces under conditions of Shewanella putrefaciens metabolism

In this study, Pb(II) was used as a target heavy metal pollutant, and the metabolism of Shewanella putrefaciens (S. putrefaciens) was applied to achieve reducing conditions to study the effect of microbial reduction on lead that was preadsorbed on graphene oxide (GO) surfaces. The results showed that GO was transformed to its reduced form (r-GO) by bacteria, and this process induced the release of Pb(II) adsorbed on the GO surfaces. After 72 hr of exposure in an S. putrefaciens system, 5.76% of the total adsorbed Pb(II) was stably dispersed in solution in the form of a Pb(II)-extracellular polymer substance (EPS) complex, while another portion of Pb(II) released from GO-Pb(II) was observed as lead phosphate hydroxide (Pb₁₀(PO₄)₆(OH)₂) precipitates or adsorbed species on the surface of the cell. Additionally, increasing pH induced the stripping of oxidative debris (OD) and elevated the content of dispersible Pb(II) in aqueous solution under the conditions of S. putrefaciens metabolism. These research results provide valuable information regarding the migration of heavy metals adsorbed on GO under reducing conditions due to microbial metabolism.     

Bio-remediation of acephate–Pb(II) compound contaminants by Bacillus subtilis FZUL-33

Removal of Pb~(2+)and biodegradation of organophosphorus have been both widely investigated respectively. However, bio-remediation of both Pb~(2+)and organophosphorus still remains largely unexplored. Bacillus subtilis FZUL-33, which was isolated from the sediment of a lake, possesses the capability for both biomineralization of Pb~(2+)and biodegradation of acephate. In the present study, both Pb~(2+)and acephate were simultaneously removed via biodegradation and biomineralization in aqueous solutions.Batch experiments were conducted to study the influence of p H, interaction time and Pb~(2+)concentration on the process of removal of Pb2+. At the temperature of 25°C, the maximum removal of Pb~(2+)by B. subtilis FZUL-33 was 381.31 ± 11.46 mg/g under the conditions of p H 5.5, initial Pb~(2+)concentration of 1300 mg/L, and contact time of 10 min. Batch experiments were conducted to study the influence of acephate on removal of Pb~(2+)and the influence of Pb2+on biodegradation of acephate by B. subtilis FZUL-33. In the mixed system of acephate–Pb2+, the results show that biodegradation of acephate by B. subtilis FZUL-33 released PO43+, which promotes mineralization of Pb2+. The process of biodegradation of acephate was affected slightly when the concentration of Pb2+was below 100 mg/L. Based on the results, it can be inferred that the B. subtilis FZUL-33 plays a significant role in bio-remediation of organophosphorus-heavy metal compound contamination.     

氧化木糖无色杆菌(Achromobacte rxylosoxidans)LAX2对Cu、Pb和Cd复合污染土壤的生物矿化修复研究

我国土壤重金属复合污染较为突出,是目前亟待解决的土壤环境问题之一.本文研究了一株氧化木糖无色杆菌LAX2对Cu、Pb和Cd共存体系的生物矿化作用及其复合污染土壤的矿化修复作用.结果表明,菌株LAX2的发酵液、无菌发酵液和菌体细胞对3种重金属的去除能力大小顺序均为Pb~(2+)Cd~(2+)Cu~(2+).X-射线衍射、扫描电镜、红外光谱和能谱分析表明,3种重金属共存时菌株LAX2发酵液可诱导形成PbCO_3和CdCO_3晶体,而Cu不能单独成矿,混合矿物晶体呈长杆状.菌株LAX2发酵液能够明显降低黑钙土和白浆土中Cu、Pb和Cd的有效态含量,矿化修复30 d后,黑钙土中Cu、Pb、Cd的有效态含量分别降低了48.0%、71.4%、62.8%,白浆土中Cu、Pb、Cd的有效态含量分别降低了42.0%、63.2%、53.6%;碳酸盐结合态和铁锰氧化物结合态含量明显增加,可交换态和有机物结合态含量明显降低.矿化修复后的土壤中重金属的浸出毒性随修复时间的增长而降低,黑钙土中Cu、Pb、Cd浸出量分别降低了90.3%、93.2%、92.8%,白浆土中Cu、Pb、Cd浸出量分别降低了82.5%、86.1%、84.3%.以上结果说明,菌株LAX2可通过碳酸盐矿化作用固定土壤中的复合重金属,且在相同条件下对黑钙土的修复效果好于白浆土.     

不同阴离子对水溶性磷酸盐稳定污染土壤中重金属的影响

在重金属污染土壤中加入磷酸盐是稳定重金属的有效方法.本研究的目的是探讨不同阴离子对水溶性磷酸盐稳定污染土壤铅、镉和锌的影响.在重金属复合污染土壤(全铅、镉和锌的含量分别为2337、21.4和391 mg·kg^-1)中按P:Pb=2:1 (mol:mol)加入磷酸二氢钙,之后按P:阴离子=3:1或3:2 (mol:mol)加入盐酸、氯化钠、硫酸、硫酸钠或氟化钠,并设置只加磷酸盐、不加其它试剂的对照,培养55 d,之后测定土壤性质.结果表明,与对照相比,HCl处理、2HCl处理、NaCl处理和2NaCl处理土壤DTPA-Pb含量下降比例依次为5.72%、9.29%、6.38%和8.80%(p<0.05),加入硫酸、硫酸钠的处理土壤DTPA-Pb含量与对照无显著差异(p>0.05),而加入氟化钠的处理升高4.70%(p<0.05).加入盐酸或氯化钠的处理土壤镉有效性显著高于对照(升高5.24%~12.8%)(p<0.05),其它处理对DTPA-Cd含量无显著影响(p>0.05).各处理对土壤DTPA-Zn含量和pH影响较小,但均引起土壤电导率明显升高.以上结果表明,氯离子可促进水溶性磷酸盐对土壤铅的稳定,但可促进镉有效性.氯磷酸铅的生成是加氯情况下磷酸盐稳定铅的重要机制.     

Field demonstration of in situ immobilization of soil Pb using P amendments

A long-term field-scale demonstration project on the feasibility of using P to immobilize Pb in a Pb-contaminated urban soil was conducted. Phosphate was applied at an average rate of 3040 mg P/kg soil based on a P/Pb molar ration of 4.0, with four treatments: T₀, no P application; T₁, H₃PO₄ only; T₂, 1/2 H₃PO₄+1/2 CaH₂PO₄; and T₃, 1/2 H₃PO₄+1/2 phosphate rock. Soil samples were collected and analyzed 220 days after the P applications. For all P treatments, toxicity characteristic leaching procedure (TCLP) extractable Pb levels in surface soils (0-10 cm) were reduced to below 5.0 mg Pb/l, with T₂ also effective in reducing the TCLP Pb level in subsurface soils (10-30 cm, <4.63 mg/l). Sequential extraction analysis indicates that P was effective in transforming soil Pb from non-residual fractions to a residual fraction. Such a transformation was mainly through dissolution of Pb associated with carbonate fraction and precipitation of pyromorphite-like minerals, which were confirmed using X-ray diffraction (XRD). Among these three treatments, T₃ was the most effective in reducing Pb mobility and minimizing P and Pb leaching in the soil. Our research clearly demonstrates that P amendments were effective in immobilizing Pb in contaminated soil.     

不同供磷水平对四种超富集植物生长及吸收重金属的影响

本论文通过水培试验研究了以KH2PO4作为磷(P)源在不同浓度(0~45.52 mg·L-1)和以Ca3(PO4)2作为磷(P)源在22.76 mg·L-1对Zn/Cd超富集植物东南景天Sedum alfredii、Zn/Cd/Ni超富集植物遏蓝菜Noccaea caerulescens(两个品种)和Ni超富集植物庭荠属Alyssum murale在20 mg·L-1(Zn)、18 mg·L-1(Ni)、10 mg·L-1(Pb)和0.5 mg·L-1(Cd)胁迫下的生长和吸收重金属的影响.试验结果表明严重缺磷的无磷和磷酸钙源处理显著抑制了这些超富集植物的生长,但4种超富集植物的地上部生物量在11.38、22.76、45.52 mg·L-13个磷水平处理之间均无显著差异.正常营养液的供磷水平(22.76 mg·L-1),S.alfredii对Zn/Cd和N.caerulescen 1号对Zn/Cd/Ni的吸收累积达到最大值,而高浓度的磷素供应(45.52 mg·L-1)显著抑制了这两种植物对相应元素的吸收;A.murale对Ni/Cd/Pb的吸收累积均在高浓度的磷素供应(45.52 mg·L-1)获得最大;增加磷的供应对N.caerulescen 1号吸收累积Zn/Ni/Cd/Pb产生了不同的效应.这些超富集植物提取重金属的最佳供P水平因植物种类而不同.     

镁改性硅藻土回收废水氮磷产物对水中Pb2+和Zn2+的去除

通过使用镁改性硅藻土回收废水中的氮磷营养素,优化制备了一种复合材料（D-MAP）,并将其用于废水中重金属Pb²⁺和Zn²⁺的去除.研究探讨了材料投加量、反应时间、反应温度和溶液初始pH等因素对Pb²⁺和Zn²⁺在D-MAP上吸附的影响.D-MAP吸附去除Pb²⁺和Zn²⁺的最优条件为：D-MAP投加量分别为0.25 g·L^-1和0.30 g·L^-1,Pb²⁺和Zn²⁺初始浓度分别为300 mg·L^-1和60 mg·L^-1,溶液初始pH为5.0.在此条件下,其对Pb²⁺和Zn²⁺去除率分别可达78.67%和89.66%.动力学和热力学的结果表明,D-MAP对Pb²⁺和Zn²⁺的吸附更符合准二级动力学模型;其吸附等温线可用Langmuir模型描述,吸附是自发吸热的过程.Langmuir等温拟合结果指出,D-MAP对Pb²⁺和Zn²⁺的最大吸附容量分别为901.0 mg·g^-1和206.2 mg·g^-1.使用SEM/EDS、XRD和FT-IR等手段对吸附Pb²⁺和Zn²⁺前后的吸附剂进行表征,结果表明,D-MAP是一种鸟粪石-硅藻土复合材料,可通过与Pb²⁺和Zn²⁺生成Pb₁₀（PO₄）₆（OH）₂和Zn₃（PO₄）₂·2H₂ O去除废水中Pb²⁺和Zn²⁺.D-MAP对Pb²⁺和Zn²⁺的去除效果随着pH的增加而增加,且最终产物形态随pH不同产生变化.     

Effects of EDTA and plant growth-promoting rhizobacteria on plant growth and heavy metal uptake of hyperaccumulator Sedum alfredii Hance

Phytoremediation is a cost-effective and environment-friendly strategy for decontaminating heavy-metal-contaminated soil. However, the practical use of phytoremediation is constrained by the low biomass of plants and low bioavailability of heavy metals in soil. A pot experiment was conducted to investigate the effects of the metal chelator ethylenediaminetetraacetic acid (EDTA) and EDTA in combination with plant growth-promoting rhizobacteria (Burkholderia sp. D54 or Burkholderia sp. D416) on the growth and metal uptake of the hyperaccumulator Sedum alfredii Hance. According to the results, EDTA application decreased shoot and root biomass by 50% and 43%, respectively. The soil respiration and Cd, Pb, Zn uptake were depressed, while the photosynthetic rate, glutathione and phytochelatin (PC) contents were increased by EDTA application. Interestingly, Burkholderia sp. D54 and Burkholderia sp. D416 inoculation significantly relieved the inhibitory effects of EDTA on plant growth and soil respiration. Compared with the control, EDTA + D416 treatment increased the Cd concentration in shoots and decreased the Pb concentration in shoots and roots, but did not change the Zn concentration in S. alfredii plants. Furthermore, EDTA, EDTA + D54 and EDTA + D416 application increased the cysteine and PC contents in S. alfredii (p < 0.05); among all tested PCs, the most abundant species was PC2, and compared with the control, the PC2 content was increased by 371.0%, 1158.6% and 815.6%, respectively. These results will provide some insights into the practical use of EDTA and PGPR in the phytoremediation of heavy-metal-contaminated soil by S. alfredii.     

Immobilization of lead in anthropogenic contaminated soils using phosphates with/without oxalic acid

Understanding the effects of oxalic acid (OA) on the immobilization of Pb(II) in contaminated soils by phosphate materials, has considerable benefits for risk assessment and remediation strategies for the soil. A series of phosphate amendments with/without oxalic acid were applied to two anthropogenic contaminated soils. We investigated the immobilization of Pb(II) by KH₂PO₄, phosphate rock (PR), activated phosphate rock (APR) and synthetic hydroxyapatite (HAP) at different phosphate:Pb (P:Pb) molar ratios (0, 0.6, 2.0 and 4.0) in the presence/absence of 50 mmol oxalic acid/kg soil, respectively. The effects of treatments were evaluated using single extraction with deionized water or CaCl₂, Community Bureau of Reference (BCR) sequential extraction and toxicity characteristic leaching procedure (TCLP) methods. Our results showed that the concentration of water extractable, exchangeable and TCLP-Pb all decreased with incubation time. The concentration of water-extractable Pb after 120 days was reduced by 100% when soils were amended with APR, HAP and HAP + OA, and the TCLP-Pb was < 5 mg/L for the red soil at P:Pb molar ratio 4.0.Water-soluble Pb could not be detected and the TCLP-Pb was < 5 mg/L at all treatments applied to the yellow-brown soil. BCR results indicated that APRwasmost effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pbmolar ratio 4.0 at the beginning of incubation. Oxalic acid activated phosphates, and so mixing insoluble phosphates with oxalic acid may be a useful strategy to improve their effectiveness in reducing Pb bioavailability.     

磷酸盐、腐殖酸与粉煤灰联合钝化处理模拟铅镉污染土壤

本研究利用过磷酸钙、腐殖酸、粉煤灰及其复配组合钝化处理人工模拟Pb、Cd污染土壤,并采用CaCl_2浸取法、三乙三胺五乙酸(DTPA)浸取法以及BCR形态分级实验评价钝化效果,利用X射线衍射仪(XRD)和扫描电子显微镜能谱(SEMEDS)分析土壤表面微观形态与结构,进一步探究其钝化机制.结果表明,除了腐殖酸单一处理,其他不同钝化处理均能降低土壤CaCl_2和DTPA提取态Pb、Cd含量,其中先添加过磷酸钙和腐殖酸,然后再添加粉煤灰的联合处理实验组效果最佳.土壤pH值与CaCl_2、DTPA提取态Pb含量存在微弱的正相关关系,与CaCl_2、DTPA提取态Cd含量存在负相关关系,速效磷含量与二者都存在显著的负相关关系,说明速效磷含量是控制土壤Pb、Cd活性的主要因素.施用磷酸盐、腐殖酸和粉煤灰可以促进Pb、Cd由活性较高的弱酸提取态向活性低的残渣态转化,从而有效降低Pb、Cd的迁移能力.XRD和SEM-EDS分析表明,过磷酸钙钝化重金属的机制主要是通过离子交换作用将重金属转化为难溶的Ca-重金属混合磷酸盐,3种钝化剂联合作用机制主要通过溶解/沉淀以及表面吸附作用将重金属转化为稳定的磷酸铅沉淀[Pb_3(PO_4)_2]或者混合重金属矿物[PbFe_3(SO_4)(PO_4)(OH)_6],从而有效钝化重金属.     

Immobilization of lead in anthropogenic contaminated soils using phosphates with/without oxalic acid

Understanding the effects of oxalic acid (OA) on the immobilization of Pb(II) in contaminated soils by phosphate materials, has considerable benefits for risk assessment and remediation strategies for the soil. A series of phosphate amendments with/without oxalic acid were applied to two anthropogenic contaminated soils. We investigated the immobilization of Pb(II) by KH₂PO₄, phosphate rock (PR), activated phosphate rock (APR) and synthetic hydroxyapatite (HAP) at different phosphate:Pb (P:Pb) molar ratios (0, 0.6, 2.0 and 4.0) in the presence/absence of 50 mmol oxalic acid/kg soil, respectively. The effects of treatments were evaluated using single extraction with deionized water or CaCl₂, Community Bureau of Reference (BCR) sequential extraction and toxicity characteristic leaching procedure (TCLP) methods. Our results showed that the concentration of water extractable, exchangeable and TCLP-Pb all decreased with incubation time. The concentration of water-extractable Pb after 120 days was reduced by 100% when soils were amended with APR, HAP and HAP + OA, and the TCLP-Pb was <5 mg/L for the red soil at P:Pb molar ratio 4.0. Water-soluble Pb could not be detected and the TCLP-Pb was <5 mg/L at all treatments applied to the yellow-brown soil. BCR results indicated that APR was most effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pb molar ratio 4.0 at the beginning of incubation. Oxalic acid activated phosphates, and so mixing insoluble phosphates with oxalic acid may be a useful strategy to improve their effectiveness in reducing Pb bioavailability.     

Optimized production of a novel bioflocculant M-C11 by Klebsiella sp. and its application in sludge dewatering

The optimized production of a novel bioflocculant M-C11 produced by Klebsiella sp. and its application in sludge dewatering were investigated. The optimal medium carbon source,nitrogen source, metal ion, initial pH and culture temperature for the bioflocculant production were glucose, NaNO3, MgSO4, and pH 7.0 and 25°C, respectively. A compositional analysis indicated that the purified M-C11 consisted of 91.2% sugar, 4.6% protein and 3.9% nucleic acids（m/m）. A Fourier transform infrared spectrum confirmed the presence of carboxyl, hydroxyl,methoxyl and amino groups. The microbial flocculant exhibited excellent pH and thermal stability in a kaolin suspension over a pH range of 4.0 to 8.0 and a temperature range of 20 to 60°C.The optimum bioflocculating activity was observed as 92.37% for 2.56 mL M-C11 and 0.37 g/L CaCl2 dosages using response surface methodology. The sludge resistance in filtration（SRF）decreased from 11.6 × 1012 to 4.7 × 1012m/kg, which indicated that the sludge dewaterability was remarkably enhanced by the bioflocculant conditioning. The sludge dewatering performance conditioned by M-C11 was more efficient than that of inorganic flocculating reagents,such as aluminum sulfate and polymeric aluminum chloride. The bioflocculant has advantages over traditional sludge conditioners due to its lower cost, benign biodegradability and negligible secondary pollution. In addition, the bioflocculant was favorably adapted to the specific sludge pH and salinity.     

干热河谷林地燥红土固碳特征及"新固定"碳表观稳定性

全球气候变化背景下,森林土壤固碳能力及所固定碳的稳定性受到极大关注.基于土壤密度分组和酸水解技术,对比研究了1991年营造的大叶相思(Acacia auriculiformis)林不同阶段(1991、1997、2003和2010年)土壤及其物理和生化组分中有机碳密度.结果表明,造林19 a后林地表层(0～15 cm)和亚表层(15～30 cm)土壤有机碳密度分别为1.40 kg.m-2和0.99kg.m-2.研究期内(1991～2010年)表层和亚表层土壤平均固碳速率分别为37.89 g.(m2.a)-1和16.84 g.(m2.a)-1,且土壤呈现加速固碳特征.2003年林地表层重组有机碳分配比例为71.44%,显著高于2010年(67.99%).2003年林地表层或亚表层轻组顽固性碳指数显著高于重组,但均随林龄的增加而降低,尤其是轻组顽固性碳指数.2003～2010年间燥红土"新固定"碳中57%～70%受物理保护,33%～49%为生化稳定性碳.研究揭示出干热河谷人工林燥红土具备较大的固碳能力.受物理保护碳的生化稳定性低于非保护碳,其稳定性均随林龄的增加而降低.     

复合污染对Pb2+在固定床系统中的动态吸附过程影响及机制

针对复合污染体系对污染物处理效果的影响问题,以限氧裂解法制备的污泥基生物炭（SSB）为吸附剂,探索其在不同污染体系下的吸附性能变化.基于污泥基生物炭构建固定床系统,研究连续流条件下复合污染体系（Zn2+、NH₄+、H₂PO₄-）对Pb2+在固定床动态吸附行为的影响,对比不同体系下系统运行参数的变化.结果表明:①不同复合体系均对SSB的Pb2+吸附效果产生抑制作用,其影响大小为NH₄+ > Zn2+ > H₂PO₄-.而三元/四元复合污染体系中,H₂PO₄-的加入会减弱复杂体系对Pb2+的吸附抑制作用.②固定床系统中,不同复合体系对吸附穿透曲线参数的影响顺序为Pb2+-Zn2+-NH₄+-H₂PO₄- > Pb2+-Zn2+-H₂PO₄- > Pb2+-Zn2+-NH₄+ > Pb2+-NH₄+-H₂PO₄-.③固定床系统动态吸附量（q_d）与传质区长度（H）的变化分析均显示,复合污染体系会降低固定床吸附性能.④数据拟合结果表明,相比于Yoon-Nelson模型,Thomas模型能更好地描述Pb2+在复合体系中的动态吸附过程,但复合污染会限制动态吸附模型的应用,导致模型预测不准确.研究显示,复合污染体系会显著影响吸附剂在连续流状态下的吸附性能,有选择地处理特定污染物可以减少复合污染体系对净化效果的干扰.      

丁基黄药对选矿区土壤吸附铅镉的影响

选矿废水排放和尾矿库溢流等会将大量残留的选矿药剂带入选矿区周边土壤和水环境.采用批处理实验,研究了不同pH、初始丁基黄药（PBX）、Pb²⁺和Cd²⁺浓度下,PBX对某铅锌选矿区土壤吸附Pb²⁺和Cd²⁺的影响;并通过BCR连续提取,研究了不同浓度PBX处理后土壤中铅镉形态变化.结果表明,PBX明显抑制了土壤对Pb²⁺和Cd²⁺的吸附.PBX浓度为40mg·L^-1时,土壤对Pb²⁺和Cd²⁺的吸附量分别由未经PBX处理时的3540 mg·kg^-1和387mg·kg^-1降至3085 mg·kg^-1和100mg·kg^-1.无论是否添加PBX,土壤对Pb²⁺和Cd²⁺的吸附动力学过程可用准二级动力学模型拟合,表明Pb²⁺和Cd²⁺在土壤上的吸附是以化学吸附为主.PBX与Pb²⁺、Cd²⁺形成疏水性难溶络合物以及在土壤表面存在竞争吸附是降低土壤Pb²⁺和Cd²⁺吸附量的主要原因,表明PBX能增加Pb²⁺和Cd²⁺在土壤中的迁移性.PBX对土壤Pb²⁺和Cd²⁺吸附的抑制作用随初始Pb²⁺和Cd²⁺浓度的增大而减弱,随初始PBX浓度及溶液pH值的增大而加强,Freundlich方程能较好描述其等温吸附特征.低含量PBX （100mg·kg^-1）下土壤中可交换态和可还原态镉含量有所增加,可导致土壤中镉的活化;但PBX可降低土壤中可交换态和可还原态铅含量,且随PBX含量升高,铅活性降低效果越显著,这与Pb （C₄H₉OCS₂）₂的络合能力比Cd （C₄H₉OCS₂）₂强有关.研究结果表明应加强选矿废水中残留药剂对土壤中铅镉等重金属潜在生态风险的防控.     

氧化铜纳米颗粒(CuO NPs)对土壤环境因子与砷生物有效性的影响

氧化铜纳米颗粒（CuO NPs）可以通过农药和肥料施用、意外泄露或污水灌溉进入As污染农田土壤,从而对土壤环境因子和As生物有效性产生影响.本试验选取两种不同类型土壤（安徽宿松黄棕壤和黑龙江海伦黑土）进行人工As污染,添加不同浓度的CuO NPs,探究90 d淹水-落干过程中CuO NPs对As污染农田环境因子和As生物有效态的影响.结果表明,CuO NPs进入土壤后12 h内快速溶解产生Cu²⁺,且在黄棕壤中的溶解速度较黑土迅速.CuO NPs可在短时间内降低土壤pH,提高土壤氧化还原电位（E_h）,降低土壤电导率（EC）,但随着培养时间增加土壤EC逐渐提高.一定时间内CuO NPs在两种类型土壤中可降低51.0%~82.5%土壤浸出液中的As和15.7%~66.5%的As生物有效性,减少淹水时Fe （II）的含量.但在土壤落干时期产生一定的“纳米效应”从而促进了Fe （II）的产生.研究表明,CuO NPs进入As污染农田改变了土壤环境因子,一定时间内降低了土壤As生物有效性.     

Colonization of Penicillium oxalicum SL2 in Pb-contaminated paddy soil and its immobilization effect on soil Pb

Penicillium oxalicum SL2 (SL2) is a previously screened Pb-tolerant fungus that can promote crops growth. The relationship between SL2 colonization and Pb immobilization was studied to provide a theoretical basis for microbial remediation of Pb-contaminated paddy soil. In this study, green fluorescent protein (GFP) labeled SL2 was inoculated into different Pb-contaminated paddy soils (S1-S6). The Pb extracted from the soil by HNO₃, EDTA and CaCl₂ were used to characterize the available Pb. The results showed that the colonization of SL2 was divided into lag phase (0-7 days), growth phase (7-30 days), and mortality phase (30-90 days). SL2 colonized well in sandy soils rich in clay and total phosphorus with initial pH of 4.5-7.0. In addition, SL2 increased soil pH and decreased soil Eh, which was beneficial to immobilize Pb. In different soils, the highest percentages of CaCl₂-Pb, EDTA-Pb, and HNO₃-Pb immobilized by SL2 were 34.34%-40.53%, 17.05%-20.11%, and 7.39%-15.62%, respectively. Pearson correlation analysis showed that the percentages of CaCl₂-Pb and EDTA-Pb immobilized by SL2 were significantly positively correlated with the number of SL2 during the growth phase. SL2 mainly immobilized Pb in the growth phase and a higher peak number of SL2 was beneficial to the immobilization of Pb.     

Methane and nitrous oxide fluxes from four tundra ecotopes in Ny-Ålesund of the High Arctic

During the summers of 2008 and 2009, net methane（CH4） and nitrous oxide（N2O） fluxes were investigated from 4 tundra ecotopes： normal lowland tundra（LT）, bird sanctuary tundra（BT）, the tundra in an abandoned coal mine（CT） and the tundra in scientific bases（ST） in Ny-Alesund of the High Arctic. Tundra soils in CT（184.5 ± 40.0 μg CH4/（m2·hr）） and ST（367.6 ± 92.3 μg CH4/（m2·hr）） showed high CH4 emissions due to the effects of human activities, whereas high CH4 uptake or low emission occurred in the soils of LT and BT.The lowland tundra soils（mean,-4.4-4.3 μg N2O/（m2·hr）） were weak N2 O sources and even sinks. Bird activity increased N2 O emissions from BT with the mean flux of7.9 μg N2O/（m2·hr）. The mean N2 O fluxes from CT（45.4 ± 10.2 μg N2O/（m2·hr）） and ST（78.8 ± 18.5 μg N2O/（m2·hr）） were one order of magnitude higher than those from LT and BT, indicating that human activities significantly increased N2 O emissions from tundra soils. Soil total carbon and water regime were important factors affecting CH4 fluxes from tundra soils. The N2 O fluxes showed a significant positive correlation with ammonia nitrogen（NH4＋-N） contents（r = 0.66, p 〈 0.001） at all the observation sites, indicating that ammonia nitrogen（NH4＋-N） content acted as a strong predictor for N2 O emissions from tundra soils. The CH4 and N2O fluxes did not correspond to the temperature variations of soil at 0-15 cm depths.Overall our results implied that human activities might have greater effects on soil CH4 and N2O emissions than current climate warming in Ny-Alesund, High Arctic.     

农地土壤重金属Pb和Cd有效性测定方法的筛选与评价

作物重金属累积主要受土壤中重金属有效性的制约,由于土壤种类和污染特征的差异,目前尚无公认的有效态测定方法.为筛选建立适宜土壤铅（Pb）和镉（Cd）有效性评价的方法,本文选择重庆市4种性质差异较大的典型农地土壤：酸性紫色土、中性紫色土、石灰性黄壤和钙质紫色土,系统比较了氯化钙（CaCl₂）、醋酸铵（NH₄OAc）、盐酸（HCl）、乙二胺四乙酸二钠盐（EDTA）和二乙基三胺五乙酸（DTPA）这5种化学提取方法与梯度扩散薄膜技术（DGT）对供试土壤Pb和Cd的提取能力,并以黑麦草为指示植物开展盆栽试验,探讨不同提取剂提取量与植物Pb和Cd累积能力的相关性,进而综合评价不同方法的适宜性.结果表明,不同提取方法对Pb和Cd的提取量存在明显差异：酸性紫色土和石灰性黄壤中以HCl-Pb提取态含量最高,中性紫色土和钙质紫色土中则以EDTA-Pb提取态含量最高;除钙质紫色土以EDTA-Cd提取态含量最高外,其余3种土壤则是以HCl-Cd提取态含量最高.考虑提取量与植物吸收量之间的相关关系,在相同类型土壤上,可选择除CaCl₂外的5种提取方法作为Pb的评价方法,Cd则是6种提取方法均较适合.在不同类型土壤中,EDTA-Pb提取态和DGT-Cd提取态含量与黑麦草地上部Pb和Cd含量相关性最高,相关系数分别为0.941和0.919,说明EDTA提取适用于不同类型土壤间Pb生物有效性的比较与评价,而Cd则以DGT技术最好,化学提取剂中以HCl较为适宜.