磷酸盐对铅镉复合污染土壤的钝化修复研究

通过模拟实验,研究磷酸二氢钾、磷酸二氢钙和磷酸二氢铵3种磷酸盐对铅镉复合污染土壤的钝化效果,采用重金属形态分析和X-射线衍射法(XRD)探讨了钝化剂的修复机制。结果表明:3种磷酸盐处理可使土壤TCLP提取态Pb、Cd含量显著降低,其中磷酸二氢钙钝化效果最好,且随着投加量的增加,在n(P)/n(Pb+Cd)=5∶1时,钝化效率最高,对Pb、Cd的钝化率分别达到69.81%、35.18%。施加磷酸盐可使污染土壤中Pb、Cd从可交换态和碳酸盐结合态向残渣态转化,显著降低Pb、Cd的生物可利用性。X-射线衍射仪(XRD)检测发现,钝化后的土壤中有羟基磷铅矿、磷酸铅、磷酸镉等矿物晶体生成,表明3种磷酸盐对土壤中铅镉的钝化机理主要是生成难溶性磷酸盐沉淀和羟基磷铅镉矿物。     

Assessing the capacity of biochar to stabilize copper and lead in contaminated sediments using chemical and extraction methods

Because of its high adsorption capacity, biochar has been used to stabilize metals when remediating contaminated soils; to date, however, it has seldom been used to remediate contaminated sediment. A biochar was used as a stabilization agent to remediate Cu- and Pb-contaminated sediments, collected from three locations in or close to Beijing. The sediments were mixed with a palm sawdust gasified biochar at a range of weight ratios (2.5%, 5%, and 10%) and incubated for 10, 30, or 60?days. The performance of the different treatments and the heavy metal fractions in the sediments were assessed using four extraction methods, including diffusive gradients in thin films, the porewater concentration, a sequential extraction, and the toxicity characteristic leaching procedure. The results showed that biochar could enhance the stability of heavy metals in contaminated sediments. The degree of stability increased as both the dose of biochar and the incubation time increased. The sediment pH and the morphology of the metal crystals adsorbed onto the biochar changed as the contact time increased. Our results showed that adsorption, metal crystallization, and the pH were the main controls on the stabilization of metals in contaminated sediment by biochar.     

Biotransfer of heavy metals along a soil-plant-insect-chicken food chain：Field study

The study investigated the accumulation and transfer of Pb,Zn,Cu,and Cd along a soil-plant-insect-chicken food chain at contaminated sites.The study site nearing the Pb/Zn mine had been contaminated by heavy metals severely.Cadmium and Pb concentrations steadily declined with increasing trophic level (p<0.01),but concentrations of Zn and Cu slightly increased from plant to insect larva (p>0.05).The concentrations of heavy metals were the highest in chicken muscle,with lower values in liver and blood.Bioaccumulation of Pb was observed in the chicken livers.The eliminations of Pb,Zn,Cu,and Cd via insect and chicken feces avoid metal bioaccumulation in insect and chicken body.These results suggest that the accumulation of heavy metals in specific animal organ of tissues could not be neglected,although transfer of metals to chicken from plant and insect is limited.     

亚氨基二琥珀酸修复重金属污染土壤及环境风险削减评估

以亚氨基二琥珀酸（ISA）为洗脱剂,考察ISA投加量、洗脱液pH值、反应时间和土液比对Cd、Pb和Zn去除率影响,通过Box-Behnken多因素设计法优化最佳洗脱条件,并采用涵盖土壤重金属残留量、浸出浓度和毒性的综合环境风险法评估修复效果.结果表明,ISA对Cd、Pb和Zn去除率随其浓度增加而增加;ISA浓度为50mmol/L时,对矿山污染土壤中Cd、Pb和Zn去除率达到11.83%、34.26%和20.96%;对污染农田土壤中Cd、Pb和Zn去除率达到48.89%、57.08%和81.80%.增加反应时间和洗脱液酸性有助于提高ISA对Cd、Pb和Zn去除率.随土液比减低,Cd、Pb和Zn去除率呈上升趋势.ISA去除Cd、Pb和Zn最佳条件为：ISA浓度70mmol/L、洗脱液pH4.0和反应时间120min,预测矿山土壤和污染农田土壤中Cd、Pb和Zn总去除率最大分别为32.58%和93.16%.ISA大幅度降低水溶态、可交换态和碳酸盐结合态Cd、Pb和Zn残留量,从而削减矿山土壤和污染农田土壤中Cd、Pb和Zn总环境风险达50.81%和87.13%.亚氨基二琥珀酸可有效去除污染土壤中重金属并降低残留重金属的环境风险,是一种潜在材料可用于土壤重金属污染修复.     

亚氨基二琥珀酸修复重金属污染土壤及环境风险削减评估

以亚氨基二琥珀酸（ISA）为洗脱剂,考察ISA投加量、洗脱液pH值、反应时间和土液比对Cd、Pb和Zn去除率影响,通过Box-Behnken多因素设计法优化最佳洗脱条件,并采用涵盖土壤重金属残留量、浸出浓度和毒性的综合环境风险法评估修复效果.结果表明,ISA对Cd、Pb和Zn去除率随其浓度增加而增加;ISA浓度为50mmol/L时,对矿山污染土壤中Cd、Pb和Zn去除率达到11.83%、34.26%和20.96%;对污染农田土壤中Cd、Pb和Zn去除率达到48.89%、57.08%和81.80%.增加反应时间和洗脱液酸性有助于提高ISA对Cd、Pb和Zn去除率.随土液比减低,Cd、Pb和Zn去除率呈上升趋势.ISA去除Cd、Pb和Zn最佳条件为：ISA浓度70mmol/L、洗脱液pH4.0和反应时间120min,预测矿山土壤和污染农田土壤中Cd、Pb和Zn总去除率最大分别为32.58%和93.16%.ISA大幅度降低水溶态、可交换态和碳酸盐结合态Cd、Pb和Zn残留量,从而削减矿山土壤和污染农田土壤中Cd、Pb和Zn总环境风险达50.81%和87.13%.亚氨基二琥珀酸可有效去除污染土壤中重金属并降低残留重金属的环境风险,是一种潜在材料可用于土壤重金属污染修复.     

二甲基苯蒽和苯并(a)芘对小鼠肝脏金属硫蛋白及氧化损伤的诱导作用

观察两种致癌性多环芳烃化合物二甲基苯蒽（DMBA）和苯并（a)芘（BaP）对小鼠肝脏脂质过氧化产物和金属硫蛋白含量的影响。选用雄性C57BL／OLA129小鼠，观察DMBA和BaP各50mg/kg一次腹腔注射染毒后24、48、72和144h后的动物肝脏重量、金属硫蛋白（MT）含量和脂质过氧化程度的变化。MT测定采用镉－血红蛋白亲和分析法；脂质过氧化指标为硫代巴比妥酸测定丙二醛法。结果表明，DMBA和BaP均能引起小鼠肝脏重量增加、MT含量增加和MDA含量增加。随着DMBA和BaP染毒后的时间延长小鼠肝脏的重量不断增加，呈现时间效应关系。小鼠肝脏MT的含量在染毒后24和48h后明显增加1倍。肝脏MDA的含量增加在染毒后24h后达到高峰。本研究观察到DMBA和Bap可以MT增加。MT的增加与MDA的增加呈现一定平行的关。提示MT诱导可能与多环芳烃化合物所致的氧化损伤有关。     

两类典型重金属土壤污染研究

对贵州水城矿务局周围煤矸石污染土壤和Pb、Zn冶炼场污染土壤的重金属污染状况进行了研究和评估。研究结果表明：煤矸石风化形成的土壤有一定的重金属污染，污染程度取决于煤矸石的组成。Pb、Zn土法冶炼造成土地严重污染，在污染土壤中种植的农作物中重金属含量严重超标。重金属在土豆不同部位富集程度各不相同，而且Pb-Cd、PbZn、Zn-Cd在植物体内具有较高的正相性。     

洪湖沉积柱中重金属的历史分布特征及来源

为了解历史上洪湖重金属的含量水平及来源,于2014年12月在洪湖中心位置采集了沉积柱,分析了沉积柱中4种重金属（Cu、Cd、Zn、Pb）的含量,并结合¹³⁷Cs和²¹⁰Pb定年技术得到沉积物中重金属高分辨率年代沉积序列.结果表明：洪湖沉积柱中4种重金属总量介于67.86~189.57mg/kg之间,4种重金属含量的高低为Pb>Zn>Cu>Cd.地累计指数表明Cu和Zn未达到污染级别,而Pb为无污染到中度污染级别,Cd为中度污染到强污染级别.沉积物中重金属含量受洪水和围湖造田的共同影响,新滩水闸建成前,洪水会导致沉积物中重金属含量先降低,随后升高.水闸建成后,洪水会导致洪湖出现内涝致使沉积物中重金属含量升高;围湖造田导致沉积物中重金属含量升高.源解析研究表明,沉积物重金属来源于非点源农业污染、交通活动以及工业废水和生活废水排放.     

贵州省典型污染区土壤重金属的污染特征分析

为了解贵州省不同来源典型污染区土壤重金属的污染特征,为重金属污染防治提供科学依据,对贵阳市、六盘水市、毕节市、都匀市等11个研究区耕地土壤进行调查,采用电感耦合等离子体质谱(ICP-MS)对189个土壤样品的Cr、Cu、Zn、As、Cd和Pb等6种重金属进行测定,并运用聚类分析和主成分分析等方法对结果进行分析。结果表明:开阳县金中镇土壤污染最轻,综合污染因子为0.897,属于磷质石灰岩地球化学背景下Cd较高的土壤类型;处于轻度污染水平的研究区是贵阳市青岩镇二关村、白云区曹官村、花溪区久安乡和清镇市后午;受污灌影响,贵阳市乌当区土壤已处于中度污染水平,特征污染因子是Cd;水城县倮摩村、赫章县野马川、大湾镇安乐村、幸福村和都匀市坝固村分别受到铅锌矿和煤矿开采的影响,属重度污染区,坝固村由于存在独立镉矿床,镉单项污染因子为77.88,综合污染指数达到56.22。主成分分析结果显示,研究区内重金属Cd和Cu是背景值较高的典型元素,Zn、Pb是铅锌矿区污染较重的元素,而Cr和As是外源叠加较严重的重金属元素。研究区内表层土壤以酸性为主,土壤重金属与pH值没有明显相关性,主要受到污染源强度的影响,以污染源为中心,呈现辐射状递减的分布特征。     

乌鲁木齐市大气颗粒物中重金属浓度的分布特征

从2009年7月-2010年4月,在乌鲁木齐市新疆大学设置采样点采集大气PM2.5~10和PM2.5。采用双道原子荧光光谱法分析了样品中的7种重金属元素,对采样期间可吸入颗粒物及重金属的浓度进行了分析,并对重金属的污染水平进行了评价。结果表明:PM2.5质量浓度的日平均值为222μg/m3,超过美国EPA1997年颁布的PM2.5日平均值35μg/m3的6.4倍;PM2.5~10和PM2.5中7种金属元素的浓度从高到低的顺序为Cr>Pb>Mn>Cu>Ni>As>Hg;PM2.5~10和PM2.5中Mn的污染指数Igeo≤1为无污染,Cu污染指数:3≤Igeo≤4为重污染,Ni、Cr、As污染指数:4≤Igeo≤5为重污染至严重污染,Pb、Hg的污染指数:Igeo≥5为严重污染。以Fe作为参考元素计算重金属的富集因子表明,自然来源的Mn具有较小的富集因子,而受工业活动影响的Cr、Pb、Ni、Cu、Hg、As具有较大的富集因子,可以认为大气可吸入颗粒物中重金属的主要来源于工业活动。     

秸秆及生物炭添加对猪粪沼渣施肥水稻重金属积累的影响

秸秆还田在重金属污染稻田中被广泛应用并日益推广,其对土壤中重金属生物有效性和水稻重金属吸收积累产生的影响不容忽视.本研究选用因连续10年以上施用生猪沼渣沼液而导致重金属超标的水稻土,通过盆栽试验研究了不同的秸秆还田方式(直接还田或生物炭还田)与用量(0、1%、2%、4%和8%)对水稻重金属吸收积累的影响.结果表明,长期施用沼渣沼液可导致土壤重金属富集,其中,铜(Cu)、锌(Zn)和镉(Cd)含量高于国家土壤环境质量二级标准;秸秆或生物炭添加提高了水稻根或茎叶中重金属的截留,降低了籽粒中的积累;秸秆还田对于水稻Cu的吸收积累控制效果显著,添加1%、2%、4%和8%的秸秆分别使糙米中的Cu含量降低了35%、51%、64%和71%;生物炭添加对于控制水稻Cd的吸收积累效果显著,1%、2%、4%和8%生物炭添加量分别使水稻Cd的积累降低了21%、33%、36%和35%.对于Zn的吸收积累,两种还田方式均具有显著的控制效果;但在As污染稻田,秸秆直接还田应慎重,因为秸秆添加可显著提高糙米中As的积累.通过对比不同的秸秆还田量对控制糙米中重金属积累的效果,同时考虑该区域重金属的污染状况和还田成本,推荐在该施肥区域实施2%的秸秆直接还田.该研究将为水稻安全生产与农业废弃物循环利用提供理论与实践指导.     

天然黏土联合磷肥对农田土壤镉铅污染原位钝化修复效应研究

为研究天然黏土联合磷肥对农田土壤镉铅污染的原位钝化修复效应,在天津市某地开展了田间示范实验,以油麦菜、油菜和萝卜为模式作物,以海泡石、膨润土和磷肥等作为钝化修复材料,研究其对蔬菜可食部位生物量、镉铅含量和土壤中镉铅形态分布的影响,考察其对土壤镉铅污染的原位钝化修复效果.结果表明:磷肥、海泡石/磷肥复配、膨润土/磷肥复配...     

负载磷酸盐生物质炭材料对重金属复合污染土壤的稳定化机制研究

为探讨负载磷酸盐生物质炭材料对重金属复合污染土壤中共存重金属的稳定化效果和迁移转化特征,以玉米秸秆和小麦秸秆为原材料,负载磷酸盐后在600 °C下无氧热解制备两种生物质炭材料,并将其用于重金属复合污染土壤中进行稳定化批处理试验. 结果表明:负载磷酸盐的玉米秸秆和小麦秸秆生物质炭材料可通过增加土壤中无定形铁、铝氧化物的含量而促进其对Cd的吸附,且负载磷酸盐后玉米秸秆生物质炭材料对土壤中无定形氧化物含量的增幅和游离态氧化物含量的降幅高于小麦秸秆生物质炭;同时,两种生物质炭材料均显著提高了土壤铁的活化度,进而有效控制了土壤重金属的生物有效性. 添加不同比例(如5%、10%和15%)的负载磷酸盐生物质炭均可降低土壤中Pb、Cd、Zn和Cu的迁移风险,并促进Pb的酸可提取态、铁锰结合态向有机结合态和残渣态转化,以及Cd、Zn和Cu的酸可提取态向残渣态转化. 两种负载磷酸盐生物质炭材料均可有效降低重金属的浸出浓度,10%及以上的添加量均可使Pb的浸出浓度降低98%以上. 15%的负载磷酸盐玉米秸秆生物质炭可使Cd和Zn的浸出浓度分别降低89%和47%,而15%的负载磷酸盐小麦秸秆生物质炭可使Cu的浸出浓度降低56%. 研究显示,施用10%~15%的负载磷酸盐生物质炭材料可显著降低重金属复合污染土壤中Pb和Cd的潜在环境风险,对矿区重金属污染土壤的安全利用具有参考和指导意义.      

湘中矿区不同用地类型面源Cd输出负荷的原位实验研究

受污染土壤重金属随降雨径流输出已成为河流、湖泊等水体重金属超标的主要来源之一,近年来日益受到关注.研究表明湘江中下游农田土壤重金属超标问题日益严峻,以镉超标最为严重.研究以湘中矿区Cd超标农业小流域为实验场,选取流域内水稻、旱田、荒草地这3类土地利用模式设置径流小区进行自然降雨水文过程的原位观测.结果表明,雨水pH值由春季到夏季呈升高趋势,径流水相溶解态Cd浓度呈明显的季节性差异,春季显著高于夏季,雨水pH值可显著影响土壤溶解态Cd向径流水相迁移,与径流水相溶解态Cd浓度呈负相关关系.相同降雨条件下,稻田径流水相溶解态Cd浓度显著低于旱田和荒草地,旱田与荒草地Cd面源输出负荷显著高于水稻田,由于降雨量差异,3类土地利用类型溶解态Cd面源输出负荷的季节性规律不明显.本研究可为流域尺度重金属面源输出负荷定量估算以及湘江流域水环境安全与水质预警提供数据支持和科学依据.     

淋洗剂在重金属污染土壤修复中的研究进展

针对镉/铅等一类重金属污染土壤、砷污染土壤,以及镉-铅-砷等复合污染土壤（三类不同重金属污染土壤）,就淋洗剂在污染土壤修复中的选用等问题进行综述.总的来看,对于镉/铅等一类重金属污染土壤,螯合剂的去除率较高.如GLDA（谷氨酸N,N-二乙酸）和柠檬酸等,不仅去除率高,而且环境较友好对于砷污染土壤,复合淋洗剂的去除效果比较显著,如NaOH-EDTA对As的去除率较高对于镉-铅-砷等复合污染土壤,复合淋洗剂则更能发挥其所含各类淋洗剂的优势.如NaOH-H₃PO₄与单一淋洗剂相比,对土壤中多种重金属的去除率均较高.笔者认为,同时对土壤中多种重金属均有较高去除率且二次污染较小的复合淋洗剂将是未来的研究重点.     

Partitioning of heavy metals in the surface sediments of Quanzhou Bay wetland and its availability to Suaeda australis

In order to investigate distributions of heavy metal pollution in Quanzhou Bay wetland, the total concentration and chemical partitioning of a number of heavy metals （Cu, Zn, Cd, Pb, Cr, Hg） in sediments of three sampling sites of Quanzhou Bay wetland and their availability to Suaeda australis were analyzed. The Geoaccumulation Index （Igeo） values reveal that the sediments of three sampling sites may all be considered as moderately contaminated for Pb and Zn, and all sediments might be strongly contaminated with cadmium. The partitioning analyses revealed the measured heavy metals in three sites are bound to the exchangeable fraction at lower concentrations. The measured metals in a considerable amount are bound to the reducible and oxidizable fractions, and a high proportion of the measured heavy metals were distributed in the residual fraction in the sediment samples. The concentrations of Cd in each chemical phase extracted from the sediments are above natural global background levels and should be further investigated because of its toxicity. Suaeda australis has different accumulation abilities for the measured heavy metals. For the root and stem, the bioaccumulation ability assessed by bioaccumulation factor （BAF） for the measured heavy metals follows the decreasing order as： Cu〉Cr〉 Zn〉Cd, Pb, Hg. In the leaf, stronger bioaccumulation ability for Hg is exhibited. The heavy metal concentrations in Suaeda australis roots have positive correlations with their available fractions, while the exchangeable fraction of Cu and Cd might have be more important to both mature plant roots and seedling roots uptake than other fractions; as for Cr, the oxidizable fraction might make a greater contribution to the plant root uptake; as for Zn, the reducible fraction might make so contribution ; and for Pb, the oxidizable fraction might make a significant contribution to the mature plant root uptake, however, the exchangeable fraction might have a significant contribution to the seedling root uptake.     

Effects of several amendments on rice growth and uptake of copper and cadmium from a contaminated soil

Heavy metals in variable charge soil are highly bioavailable and easy to transfer into plants. Since it is impossible to completely eliminate rice planting on contaminated soils, some remediation and mitigation techniques are necessary to reduce metal bioavailability and uptake by rice. This pot experiment investigated the e ects of seven amendments on the growth of rice and uptake of heavy metals from a paddy soil that was contaminated by copper and cadmium. The best results were from the application of limestone that increased grain yield by 12.5–16.5 fold, and decreased Cu and Cd concentrations in grain by 23.0%–50.4%. Application of calcium magnesium phosphate, calcium silicate, pig manure, and peat also increased the grain yield by 0.3–15.3 fold, and e ectively decreased the Cu and Cd concentrations in grain. Cd concentration in grain was slightly reduced in the treatments of Chinese milk vetch and zinc sulfate. Concentrations of Cu and Cd in grain and straw were dependent on the available Cu and Cd in the soils, and soil available Cu and Cd were significantly a ected by the soil pH.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.     

Heavy metal availability and impact on activity of soil microorganisms along a Cu/Zn contamination gradient

All the regulations that define a maximum concentration of metals in the receiving soil are based on total soil metal concentration. However, the potential toxicity of a heavy metal in the soil depends on its speciation and availability. We studied the effects of heavy metal speciation and availability on soil microorganism activities along a Cu/Zn contamination gradient. Microbial biomass and enzyme activity of soil contaminated with both Cu and Zn were investigated. The results showed that microbial biomass was negatively affected by the elevated metal levels. The microbial biomass-C （Cmic）/organic C （Corg） ratio was closely correlated to heavy metal stress. There were negative correlations between soil microbial biomass, phosphatase activity and NH4NO3 extractable heavy metals. The soil microorganism activity could be predicted using empirical models with the availability of Cu and Zn. We observed that 72% of the variation in phosphatase activity could be explained by the NH4NO3-extractable and total heavy metal concentration. By considering different monitoring approaches and different viewpoints, this set of methods applied in this study seemed sensitive to site differences and contributed to a better understanding of the effects of heavy metals on the size and activity of microorganisms in soils. The data presented demonstrate the relationship between heavy metals availability and heavy metal toxicity to soil microorganism along a contamination gradient.     

陕西西部某工业园区采暖期大气降尘重金属特征

为了解陕西省某工业园区采暖期大气降尘重金属元素特征,于2012年11月20日至2013年3月20日,通过被动采样的方式,采集该区域采暖期的大气降尘样品,利用火焰原子吸收分光光度法测定其中重金属元素Cu、Pb、Zn、Cd、Ni、Cr和Fe的含量,并分别计算各元素采暖期的日沉降通量和富集因子.结果表明:研究区采暖期大气降尘量普遍较高,并且受园区人为污染源和道路扬尘影响明显;大气降尘中重金属含量分布不均,位于园区内部点位的重金属含量明显大于上风向点位和对照点;各元素之间也有很大的差异,其中,Fe的含量远高于其他6种元素,Pb、Zn含量次之,Cu、Cd、Ni、Cr的含量较小;从采暖期日沉降通量来看,Fe、Zn、Pb的沉降通量较大,Cu、Cr、Ni、Cd的沉降通量较小.而根据富集因子分析结果可知,Zn、Pb、Cu、Cd主要来自人为源,Fe、Cr、Ni与当地的自然地质背景有关.