用分级方法评估土壤对重金属的缓冲能力

研究了不同Cd,Zn,Cu和Pb负荷对5种土壤(油黄泥土、棕红壤、红壤、石砂土和紫砂土)中的重金属形态的影响,分析了不同土壤对重金属的缓冲作用及其影响因素.结果表明,未污染土壤中的重金属主要以残余态为主,占土壤重金属总量的51%以上.随着土壤重金属负荷的提高,土壤中交换态重金属的比例增大,残余态比例下降,有效性提高,对重金属的缓冲作用下降.由于Cd,Zn,Cu和Pb本身的特性不同,土壤中各组分与Cd,Zn,Cu和Pb的结合方式及程度不同.当外源重金属进入土壤后,土壤对重金属的缓冲性为:Pb>Cu>Zn Cd,酸性土壤和砂质土壤的缓冲能力较低.当重金属加入量较低时,重金属优先向氧化物结合态和有机质结合态转化;而当加入量较高时,向交换态和碳酸盐结合态转化的比例增加.土壤pH下降可使交换态Cd,Zn,Cu和Pb的比例递增,降低土壤对重金属的缓冲性,增加了重金属对环境影响的风险.      

新河污灌区土壤中重金属的形态分布和生物有效性研究

通过野外采样调查和实验分析,对北京市新河污灌区土壤中Cu、Pb、Zn、Cd 4种重金属的含量、形态分布和生物有效性进行了研究.首次尝试运用体外消化法研究了土壤中重金属的生物有效性问题,并与经典的Tessier五步连续提取法的结果进行了对比.结果发现,新河污灌区土壤中,Cd的浓度超过国家二级标准,Cu、Pb、Zn的浓度未超标.土壤中Cu、Pb、Zn主要以残渣态存在,Cd主要以有机结合态存在,且Cd的可交换态比例最高,生物有效性也最高.体外消化法分析得到的重金属生物有效性成分的含量要比利用化学形态分析法分析得到的高,但Cu、Pb、Zn、Cd 4种重金属的生物有效性排序是相同的,即Cd＞Zn＞Pb＞Cu.两种方法提取的重金属含量之间有相关关系.     

生物淋滤联合类Fenton反应去除污染土壤中重金属的效果

针对我国南方地区广泛存在的土壤重金属污染问题,以广东韶关铅锌矿周边污染农田土壤为研究对象,探讨利用生物淋滤方法与生物淋滤联合类Fenton反应对土壤Cu、Zn、Cd和Pb的去除效果,并采用序列化学提取(SEC)方法,分析不同处理对土壤中4种重金属形态分布的影响.结果表明,经12 d生物淋滤Cu、Zn、Cd和Pb的去除率分别达到66.5%、55.1%、72.8%和35.6%,其中无机结合态重金属去除效果最好,固相中剩余重金属主要以稳定的残渣态形式存在.2 d生物淋滤联合类Fenton反应在优化的H_2O_2浓度(5 g·L-1)下,对上述4种重金属的去除率分别为55.6%、50.6%、60.7%和30.5%,低于12 d生物淋滤处理,但显著高于H_2SO_4酸化、2 d生物淋滤、化学Fenton反应等对照处理.生物淋滤联合类Fenton反应可以实现原土壤中残渣态、有机结合态和无机结合态等较稳定态重金属的有效去除,使处理后土壤中4种重金属Cu、Zn、Cd和Pb的含量分别低于50、200、0.3和250 mg·kg~(-1)的标准限值.该方法兼具生物淋滤高去除效率和Fenton反应快速处理等优势,对于修复重金属Cu、Zn、Cd和Pb等复合污染的土壤具应用前景.     

好氧高温堆肥处理对猪粪中重金属形态的影响

用 Tessier 连续提取法研究了好氧高温堆肥处理对猪粪中重金属结合形态变化的影响.结果表明,经过好氧堆肥处理,猪粪中 Pb、Cu、Zn、Ni、Cr、Cd、As 的总浓度升高;碳酸盐结合态 Ni、Zn 的浓度降低,其余 Pb、Cu、Cr、Cd 的浓度都升高;硫化物及有机结合态、残渣态重金属的浓度普遍升高,仅有硫化物及有机结合态 As 和 Zn 的浓度下降;可交换态 Cu、Zn、Cr、As 的浓度显著降低.堆肥处理可以降低可交换态和碳酸盐交换态 Pb、Ni、Cu、Cr、Zn、As 和铁锰氧化物结合态 Pb、Cu、Cr、As 的分配系数,因此可以降低猪粪中重金属的有效性.堆肥处理有利于降低猪粪土地利用中重金属污染的风险.     

黔西土法炼锌区Pb、Zn、Cd地球化学迁移特征

黔北土法炼锌致使Pb、Zn、Cd在土壤和水体大量积累,危及到整个生态系统.以小流域为例,探索了废渣、土壤、水体的Pb、Zn、Cd地球化学形态及其迁移性.结果表明,冶炼废渣的Pb、Zn、Cd含量分别为4 632、 8 968、 58 mg·kg^-1;污染土壤Pb、Zn、Cd含量分别达到234、 400、 9.6 mg·kg^-1.废弃地的地球化学形态分析表明,污染土壤的Pb、Zn、Cd可交换态含量较高,具有较大迁移性和生物有效性,相对而言,废渣中Pb、Zn、Cd具有很低的生物有效性和迁移性,交换态含量低于0.2%.冶炼区的地表水受到严重的Pb、Zn、Cd污染,地下水重金属含量未超出三类水体的质量标准.在地表水体中,可溶态的Pb、Zn、Cd含量少,主要以悬浮态存在,表明了河流重金属污染主要来自于沿岸水土流失.     

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.      

典型平原地区生活垃圾焚烧厂周边土壤重金属赋存形态分布特征及生物有效性评价

为考察并掌握典型平原地区生活垃圾焚烧厂周边土壤中重金属Cd、Cr、Cu、Pb、Ni和Zn的污染现状,以上海市某生活垃圾焚烧厂为例,研究其周边土壤中重金属赋存形态分布特征及生物有效性,采用Tessier连续提取法结合电感耦合等离子体发射光谱检测分析表层土壤中目标重金属总量及形态分布,并利用风险评估编码法（RAC）评价其生态风险水平.结果表明:研究区域土壤中Pb和Zn主要以Fe-Mn氧化物结合态和残渣态为主（>80%）;Cr、Cu和Ni则以残渣态为主（>60%）;Cd虽以残渣态为主（>50%）,但与其他重金属相比,其碳酸盐结合态占比相对较高.生物有效性分析结果显示,Cr、Cu和Ni以惰性态为主,生物有效性低,而潜在可利用态Cd、Pb和Zn占比较高,存在较高的释放风险.土壤中各重金属潜在生态风险水平由高到低依次为Cd > Zn > Pb > Cu > Ni > Cr,其中,Cu、Pb和Zn处于低风险水平,Cr和Ni处于无风险水平,而Cd处于中等风险水平.研究显示,该垃圾焚烧厂周边土壤中重金属已存在不同程度的污染累积,其中,潜在可利用态Cd的占比较高,已达中等风险水平,应引起重视.      

几种有机物料对设施菜田土壤Cd、Pb生物有效性的影响

利用风化煤、草炭和生物炭这3种有机物料,采集陕西关中地区设施菜田土壤,通过2014~2015年两季盆栽模拟试验,研究了3种有机物料在设施菜田土壤重金属Cd、Pb单一和复合污染条件下对Cd、Pb生物有效态等赋存形态的影响,探究风化煤、草炭和生物炭对设施菜田重金属Cd、Pb污染土壤修复的可行性.结果表明,风化煤显著降低了复合污染土壤中Cd有效态含量,达11.9%(P0.05),并使Pb有效态含量显著降低达83.5%以上(P0.05);对Cd、Pb的交换态、碳酸盐结合态和铁锰氧化物结合态之和分别降低了26.4%~34.4%和12.0%~34.5%.草炭显著降低了复合污染土壤中Cd有效态含量18.9%(P0.05),分别显著降低了Pb单一和Cd、Pb复合污染土壤中Pb有效态含量2.7%和7.2%(P0.05),对Pb交换态、碳酸盐结合态和铁锰氧化物结合态三者之和分别降低了15.8%和14.6%.生物炭提高了土壤p H 0.03~0.08个单位,分别降低了Cd有效态、Pb有效态含量4.7%~15.0%和1.0%~6.8%,Pb交换态、碳酸盐结合态和铁锰氧化物结合态之和降低了11.9%~66.6%.风化煤、草炭和生物炭使番茄地上部对Cd的累积量显著降低15.0%~38.0%(P0.05),使复合污染条件下番茄地上部对Pb的累积量显著降低17.9%~30.0%(P0.05).番茄Cd含量与土壤中Cd交换态含量呈现极显著正相关关系(P0.01).番茄Pb含量与Pb交换态、碳酸盐结合态、铁锰氧化物结合态三者含量之和呈现极显著正相关关系(P0.01).综合来看,风化煤、草炭和生物炭这3种有机物料可以通过改变设施菜田土壤p H值和对重金属的吸附、络合等固定作用,降低土壤中Cd、Pb高活性态比例,进而减少植物对Cd、Pb的累积.     

鄱阳湖湿地重金属形态分布及植物富集研究

研究了鄱阳湖湿地土壤中Cu,Zn,Pb和Cd形态与植物富集的关系. 结果表明:鄱阳湖土壤中Cu,Pb和Zn主要以有机态和残渣态为主,水溶态和离子交换态等生物有效性态含量很少;而Cd则主要以水溶态和离子交换态等生物有效性态为主,因此Cd的生态危害较大. 相关分析和偏相关分析均显示:植物中重金属含量与其生存环境中重金属水溶态或离子交换态含量直接相关,这与理论上植物只能吸收重金属水溶态相符. 植物对重金属的富集能力表现出Zn＞Cu＞Cd＞Pb的趋势. 用重金属水溶态或离子交换态进行植物富集研究,更具有可比性和科学性.      

大型铜尾矿库区节节草(Hippochaete ramosissimum)根际土壤重金属形态分布与影响因素研究

通过野外调查和实验分析,对安徽省铜陵市铜官山铜尾矿库、狮子山铜尾矿库及狮子山铜尾矿库周边农田3处生长的节节草根际与非根际土壤中重金属(Cu、Cd、Pb、Zn)的形态、含量和分布进行了研究.结果表明,节节草根际与非根际土壤重金属的主要形态分布基本一致,均表现为矿物态含量占据了重金属全量的大部分,而交换态含量偏低.与非根际土壤相比较,根际土壤中交换态、有机态重金属所占比例显著增加,其中Cu的有机结合态所占比例增加了53 25%、Cd、Pb的有机结合态所占比例增加超过17%,Zn则增加了5.67%;与此同时,碳酸盐结合态和铁锰氧化物结合态含量有所下降.统计分析表明,Cu、Cd、Pb、Zn在根际土壤中的形态分布与土壤pH值、有机质含量、植物生长等因素密切相关.     

Changes of Cu, Zn, and Cd speciation in sewage sludge during composting

The potential toxicity risks from heavy metals depend on their chemical speciation. The four stages of the Tessier sequential extraction method were employed to investigate changes in heavy metal speciation （Cu, Zn, and Cd） of sewage sludge during forced aeration composting, and then to identify whether the composting process would reduce or enhance their toxicities. Throughout the composting process, the exchangeable, carbonate-bound, Fe-Mn oxide-bound, and organic matter-bound fractions of Cu were converted to the residual Cu fraction. The organic matter-bound Cu fraction greatly contributed to this transformation. Residual Zn fraction was transformed to the Fe-Mn oxide-bound and organic matter-bound fractions after composting. The residual Zn fraction was a major contributor to the organic matter-bound Zn fraction. The availability of Cu and Zn was reduced by composting such that the risk of heavy metal toxicity decreased with prolonged treatment times. Additionally, attention should be paid to the increased availability of Cd in sewage sludge after composting treatment.     

湖北省铜绿山矿区农业土壤重金属形态及生物有效性

以铜绿山矿区农业土壤为研究对象,采用BCR连续提取法提取并测定了土壤中Cu、Zn、Pb、Cd四种重金属的形态和含量,分析了重金属各形态、土壤p H和有机质之间的相关性;并对重金属分布特征和有效性进行了分析,探究土壤本身性质对矿区农业土壤重金属及其生物有效性的影响因子。结果表明:矿区农业土壤受到重金属不同程度的污染,重金属的污染程度大小为:CuZnPbCd;各重金属之间存在不同程度的相关性,Pb和Zn之间显著相关,二者可能属于同源污染物;四种重金属总量与土壤的p H和有机质不存在相关性;Pb与Cu、Zn和Cd有效态含量之间有显著相关性,表明矿区农业土壤中重金属Pb与Cu、Zn和Cd有效态含量之间相互促进、相互影响的作用较强;矿区农业土壤p H值与Pb_(可还原态)、Cd_(可还原态)、Cd_(弱酸提取态)、Cd_(可氧化态)之间均存在显著相关关系;有机质含量与Pb_(可还原态)、Pb_(残渣态)、Cu_(残渣态)、Cd_(弱酸提取态)、Cd_(可还原态)、Cd_(可氧化态)之间相关性显著,可见土壤的p H值、有机质都会对土壤中重金属的化学形态产生一定的影响;土壤中Pb、Cd的生物有效性主要受其全量、土壤p H和有机质的影响,而Zn和Cu受其全量、土壤p H和有机质的影响较小。     

改良剂对Cu、Cd污染土壤重金属形态转化的影响

采用室内培养的方法,比较石灰、钙镁磷肥、硅肥、紫云英、猪粪和泥炭等几种改良剂作用下Cu、Cd污染酸性水稻土中不同形态重金属的动态变化.结果表明,土壤添加石灰、钙镁磷肥、硅肥、紫云英和猪粪培养120d期间,土壤pH值呈现先增加至最大值而后缓慢降低的趋势,但均高于对照,而添加泥炭后土壤pH值略有下降.各改良剂的使用均显著降低了土壤水溶态和交换态Cu、Cd含量,且在培养期间呈现先逐渐降低至最小值而后再增加的趋势.相关分析结果表明,土壤水溶态和交换态Cu、Cd含量与土壤pH值之间均存在极显著的负相关关系.土壤添加改良剂后碳酸盐结合态、铁锰氧化物结合态、有机结合态和残渣态Cu、Cd含量均有不同幅度的增加,说明改良剂的应用能够使土壤重金属由有效态向某些潜在有效态或无效态转变,从而达到修复重金属污染土壤的目的.     

Speciation and fractionation of heavy metals in soil experimentally contaminated with Pb,Cd, Cu and Zn together and effects on soil negative surface charge

Speciation and fractionation of heavy metals in soil subsamples experimentally loaded with Pb, Cd, Cu and Zn in orthogonal design was investigated by sequential extraction, and operationally defined as water-soluble and exchangeable(SE), weakly specific adsorbed( WSA),Fe and Mn oxides-bound(OX) and organic-bound( ORG). The results showed that fractions of heavy metals in the soil subsamples depended on their speciation. About 90% of Cd and 75% of Zn existed in soil subsamples in the SE fraction. Lead and Cu existed in soil subsamples as SE, WSA and OX fractions simultaneously, although SE was still the major fraction. Organic-bound heavy metals were not clearly apparent in all the soil subsamples. The concentration of some heavy metal fractions in soil subsamples showed the good correlation with ionic impulsion of soil, especially for the SE fraction. Continuous saturation of soil subsamples with 0.20 mol/L NH4CI, which is the first step for determination of the negative surface charge of soil by the ion retention method, resulted in desorption of certain heavy metals from the soil. It was found that the percentage desorption of heavy metals from soil subsamples depended greatly on pH, the composition and original heavy metal content of the soil subsamples. However, most of the heavy metals in the soil subsamples were still be retained after multiple saturation. Compared with the parent soil, the negative surface charge of soil subsamples loaded with heavy metals did not show difference significantly from that of the parent one by statistical analysis. Heavy metals existed in the soil subsamples mainly as exchangeable and precipitated simultaneously.     

Chemical speciation and mobility of heavy metals in municipal solid waste incinerator fly ash

Chemical speciation is a significant factor that govems the toxicity and mobility of heavy metals in municipal solid waste incinerator fly ash. Sequential extraction procedure is applied to fractionate heavy metals( Pb, Zn, Cd, Cu, and Cr) into five defined groups: exchangeable, carbonate, Fe-Mn oxide, organic, and residual fractions. The mobility of heavy metals is also investigated with the aid of toxicity characteristic leaching procedure. In the fly ash sample, Pb is primarily presented in the carbonate (51%) and exchangeable(20% ) fractions; Cd and Zn mainly exist as the exchangeable(83% and 49% respectively) ; Cu is mostly contained in the last three fractions(totally 87% ) ; and Cr is mainly contained in the residual fraction(62% ). Pb, Zn and Cd showed the high mobility in the investigation, thus might be of risk to the natural environment when municipal solid waste incinerator fly ash is landfilled or reutilized.     

Effect of moisture regime on the redistribution of heavy metals in paddy soil

Sequential extraction procedure was applied to assess the dynamics of solid-phase transformation of added Cu, Pb, Cd, and Hg in a typical Chinese paddy soil incubated under three moisture regimes (75% field capacity, wetting-drying cycle, and flooding). The heavy metals spiked in the soil were time-dependently transferred from the easily extractable fraction (the exchangeable fraction) into less labile fractions (Fe-Mn oxide- and organic matter-bound fractions), and thus reduced lability of the metals. No significant changes were found for the carbonate-bound and residual fractions of the heavy metals in the soil during the whole incubation. Change rate of the mobility factor (MF), a proportion of weakly bound fractions (exchangeable and carbonate-bound) in the total metal of soil, reflected the transformation rate of metal speciation from the labile fractions toward stable fractions. It was found that soil moisture regime did not change the direction and pathways of transformation of metal speciation, but it significantly a ected the transformation rate. In general, the paddy soil under flooding regime had higher metal reactivity compared with 75% field capacity and wetting-drying cycle regimes, resulting in the more complete movement of metals toward stable fractions. This might be related to the increased pH, precipitation of the metals with sulfides and higher concentration of amorphous Fe oxides under submerged condition.     

沈阳张士污灌区土壤重金属元素形态分析

选取沈阳张士污灌区土攘样品,采用欧共体标准局的三步提取法研究土壤中5种重金属元素的形态分布.研究结果表明,在该污灌区土壤中,Cd和zn主要以B1(水溶态、可交换态与碳酸盐结合态)和B2(铁-锰氧化物结合态)为主,分别占总量的49.4%、26.4%和43.9%、44.3%.Cu、Pb主要以B2(铁-锰氧化物结合态)和B3(有机物与硫化物结合态)为主分别占总量的43.4%、66.6%和29.1%、25.3%.Cr以B3(有机物与硫化物结合态)和残渣态为主,分别占总量的40.4%和42.5%.元素总量和形态分析的结果表明该地区土壤污染为单一的镉污染土壤,且镉的可迁移性强,易被植物吸收.     

Risk assessment of heavy metal contaminated soil in the vicinity of a lead/zinc mine

Heavy metal contamination of soils through anthropogenic activities is a widespread and serious problem confronting scientists and regulators throughout the world. In this study we investigated the distribution, chemical species and availability of lead, zinc, cadmium and copper in nine surface（0 to 20 cm） soils from near an abandoned lead/zinc mine tailings located in Shaoxing, Zhejiang, China. Total heavy metal contents ranged from 5271 to 16369 mg/kg for Pb, 387 to 1221 mg/kg for Zn, 3.0 to 9.3 mg/kg for Cd and 65 to 206 mg/kg for Cu. In general, all heavy metals exceeded China National Standards for Soil Environmental Quality of Heavy Metals by a factor of 3-65 times. Comparison of the heavy metal concentrations（Pb, Zn, Cd and Cu） with clay content revealed a strongly significant relationship while significant relationship（ P 〈 0.001 ） was also obtained between Cd ＋ Zn and Pb ＋ Cu. Solid phase speciation of the soils using Tessier procedure showed that the heavy metals were distributed in the order： residual 〉〉 organically complexed-Fe-Mn oxides occluded 〉 carbonate bound 〉 exchangeable 〉 water soluble. In the organic matter fraction, the ratio of Pb（29.1% ） to its total concentration in the soils was higher than those of Zn（4.70% ）, Cd（3.16% ） and Cu（9.50% ）. The percentages of the water soluble and the exchangeable fractions of Pb（1.80% ） and Cd（2.74% ） were markedly greater than those of Zn（0.10% ） and Cu（0.15% ）, suggesting that Pb and Cd are relatively more mobile and hence more toxic in the contaminated soils. Strongly significant relationships between H20-Pb, H20-Zn and H20-Cu, strong positive correlations between H20-Pb, H20-Zn, H20-Cu and organic matter in soil were found. The content of H20-Pb, H20-Zn, H20-Cu was negatively correlated with pH values. The similar negative relationships between pH values and exchangeable heavy metals were also recorded. It is suggested that increasing soil pH or liming the soil could decrease bioavailability of heavy metals in the soil.