富硒土壤镉的赋存状态

采用7步提取法对某地富硒土壤样品进行镉的形态分析,发现镉质量分数较高,镉平均为0.374 mg/kg,最高为0.943 mg/kg。各形态含量差异较大,基本是残渣态离子交换态铁锰氧化物结合态腐殖酸结合态强有机结合态碳酸盐态水溶态,在7种形态中以残渣态、离子交换态、铁锰氧化物结合态3种形态占主导。     

呼和浩特市大气降尘中镉赋存形态分析

采用Tessier连续提取法对呼和浩特市不同区域的9个大气降尘样品中镉的赋存形态进行了研究。结果表明,各形态含量在总镉中所占比例由大到小排列顺序依次是:铁锰氧化物结合态>残渣态>碳酸盐结合态>强有机结合态>可交换态。大气降尘中镉的5种形态占总镉的平均质量分数由大到小为:铁锰氧化物结合态31.80%,残渣态24.42%,碳酸盐结合态19.04%,强有机结合态14.61%,可交换态10.13%;铁锰氧化物结合态是主要存在形态;铁锰氧化物结合态镉、有机结合态镉、残留态镉这三种形态镉生物有效性很低,但当环境改变时可能发生镉释放,应予以关注。汽油和煤的燃烧以及工厂排放镉能加大城市大气降尘中的镉含量。     

北京城区土壤中Hg、Pb、Cd、Cu及Zn化学形态及环境效应

为弄清北京城区土壤中Hg、Pb、Cd、Cu及Zn五种重金属元素的化学形态分布特征,系统采集了126件城区表层土壤样品,采用连续提取法对重金属元素各化学形态含量进行了测定。结果表明:土壤中土壤中Hg、Pb、Cd、Cu、Zn含量差异显著。Hg元素以残渣态和强有机结合态为主,Cd元素离子交换态、碳酸盐结合态、残渣态、铁锰氧化物结合态含量较高,Pb、Cu、Zn元素以残渣态、铁锰氧化物结合态为主。Hg元素的有效态含量最低(不足1%),现情况下不会对环境造成污染;Cd元素的有效态含量最高(40%),生物有效性和潜在生态危害性较大,运用植物修复技术对其治理为经济有效的方法;Pb、Cu、Zn有效态含量较低(约10%),生物有效性和潜在生态危害性均有限。各元素形态与全量之间相关程度虽有差别,但基本呈正相关关系。     

金沙江(攀枝花段)水系沉积物中重金属的形态特征

采用连续提取法,并用原子吸收光谱法进行分析研究了金沙江攀枝花段水系沉积物中重金属的形态及分布特征。研究发现:①各重金属的形态以残渣态为主,离子交换态含量很少;②各元素的形态有自己的特点。铜在有机硫化物结合态中的含量较高,钴在碳酸盐结合态中的含量较高,铅锌钴的铁锰氧化物结合态均较高;③有效态对水环境质量具有潜在的危害。     

干旱区绿洲土壤共存重金属元素形态变化及生物有效性实验分析——以Cd、Zn、Ni元素为例

采用盆栽试验,初步研究了干旱区绿洲土壤—胡萝卜系统中镉、锌、镍3种重金属的形态变化特征及其生物有效性问题。结果表明:供试绿洲土壤原状土中,Cd、Zn、Ni均以稳定的残渣态形式存在,而处理土壤中重金属被钝化的量有限,Cd的存在形式主要以碳酸盐态为主,Zn、Ni则主要以铁锰氧化态为主;3种元素的活性大小依次为Cd>Ni>Zn。根据回归分析,元素Zn对胡萝卜块茎和茎叶吸收Zn量贡献最大的分别是Zn的碳酸盐结合态和铁锰氧化态;元素Ni对胡萝卜各部位吸收贡献最大的均为Ni的铁锰氧化态。     

干旱区绿洲土壤共存重金属元素形态变化及生物有效性实验分析

采用盆栽试验,初步研究了干旱区绿洲土壤—胡萝卜系统中镉、锌、镍3种重金属的形态变化特征及其生物有效性问题。结果表明：供试绿洲土壤原状土中,Cd、Zn、Ni均以稳定的残渣态形式存在,而处理土壤中重金属被钝化的量有限,Cd的存在形式主要以碳酸盐态为主,Zn、Ni则主要以铁锰氧化态为主;3种元素的活性大小依次为Cd＞Ni＞Zn。根据回归分析,元素Zn对胡萝卜块茎和茎叶吸收Zn量贡献最大的分别是Zn的碳酸盐结合态和铁锰氧化态;元素Ni对胡萝卜各部位吸收贡献最大的均为Ni的铁锰氧化态。     

茶园土壤不同形态镍的含量及其影响因素

通过自然茶园土壤采样和室内实验分析,探讨浙江、江苏和安徽13个茶园土壤镍的污染状况、形态分布规律以及不同形态镍的含量与土壤镍总量和土壤理化性质的关系。结果表明：部分茶园土壤受到不同程度的镍污染;茶园土壤镍的形态分布有一定差异,按镍的含量多少排序,一般为残渣态＞交换态＞铁锰氧化物结合态＞有机结合态＞碳酸盐结合态;除了交换态以外的所有其他形态的镍含量均随土壤镍含量的增加而显著增加;碳酸盐结合态、铁锰氧化物结合态和残渣态镍含量随土壤pH的升高呈显著增加趋势,而交换态镍则呈减少趋势,但不显著;随土壤有机质含量的增加,铁锰氧化物结合态镍显著减少,而其他形态增加或减少的趋势均不显著;碳酸盐结合态、有机结合态和残渣态的镍含量均随阳离子交换量的增加显著增加;随粘粒含量的增加所有形态中的镍呈增加趋势,但除了残渣态外增加趋势均不显著。     

土壤样品中镉的形态分析研究

采用改进的Tessier连续提取法对武汉地区的土壤样品中镉的形态进行了分析,结果表明土壤中镉主要以离子交换态形式存在,总体看其顺序为离子交换态(包含水溶态)>碳酸盐结合态>铁锰氧化物结合态>腐殖酸结合态>残渣态>强有机结合态,说明土壤中镉较活泼,易于迁移转化,对植物的可给性大,是环境中的重要污染元素.     

辽河流域土壤镉有效性的地球化学研究

利用辽宁省辽河流域生态地球化学调查中取得的土壤镉深表层含量及形态分析等测试数据,对土壤镉的存在形态及其影响因素进行了系统对比研究,结果表明：辽河流域土壤镉主要以离子交换态、水溶态、铁锰氧化态、碳酸盐结合态、强有机结合态、腐殖酸结合态及残渣态等七种形态存在,其中离子交换态及水溶态是可被生物吸收利用的有效态,其含量主要受土壤镉全量、pH值、有机质、土壤粘度等因素制约。     

类芽孢杆菌对铜陵新桥矿区土壤中Cu化学形态的影响

采用Tessier五步连续提取法和红外光谱技术,研究类芽孢杆菌对铜陵新桥矿区重金属污染土壤中Cu化学形态的影响,初步探讨了Cu形态变化的机理。结果表明,不同投入量的类芽孢杆菌接种到土壤培养一周后,土壤溶液pH值降低,土壤中可交换态、有机结合态Cu含量增加,碳酸盐结合态、铁锰氧化物结合态和残渣态Cu的含量降低。土壤中可交换态、铁锰氧化物结合态和残渣态Cu含量的变化主要受土壤溶液的pH值控制;有机结合态升高主要与类芽孢杆菌菌数及其代谢产生的低分子量有机酸有关。类芽孢杆菌可以改变矿区土壤中Cu的化学形态,影响Cu的生物有效性。     

Relationship of chemical fractions of heavy metals with microbial and enzyme activities in sludge and ash-amended acid lateritic soil from India

The influence of metals, Cd, Cr, Cu, Ni, Pb and Zn, on the microbial biomass and enzyme activities of an amended acid lateritic soil were investigated under field conditions receiving a one-time application of 52 t ha^–1 of sludge, coal ash and their mixtures at 1:3, 1:1 and 3:1 proportions, and including control and chemical fertilizer treatment at crop-specific recommended doses. Paddies and peanuts were grown in the experimental plots and soil was sampled twice after 6 months and 1 year after amendment application. The heavy metals in the soil were fractionated using sequential extraction and the increments in their concentrations in amended soil with respect to the control were determined. Concentrations of Cd, Ni and Zn were determined to have increased in their mobile fractions and were more pronounced in soil collected during the second sampling, which was associated with a decrease in soil organic carbon. The size of the microbial biomass carbon and the soil enzyme activities increased with the addition of an amendment and was highest at equal proportions of coal ash and sludge. Further increase in the proportion of sludge resulted in a significant decrease in biomass carbon. Simple correlation revealed significant and strong negative relations of mobile fractions of Cd and Ni with the ratio between microbial biomass C and organic carbon in soil, while the organic carbon content and the pH were positively correlated. The microbial activities were determined to be sensitive to the concentrations of some heavy metals in mobile fractions and therefore indicated possibilities of being useful as indicators for evaluation of toxic effects of sludge-borne metals on soil organisms.     

Speciation of heavy metals in electroplating industry sludge and wastewater residue using inductively coupled plasma

The speciation of metals in environmental samples is a critical factor in assessing the potential environmental impacts, before their disposal. The distribution and speciation of toxic heavy metals in plating wastewater residues and sludge was investigated for four samples using sequential extraction method. Tessier method was used to fractionate the metal content into exchangeable, acid extractable, reducible and oxidizable fractions. Residual and total metal contents were determined in aqua regia digest. The extracts were analysed for metals using inductively coupled plasma -atomic emission spectrometry. The bioavailable fraction (exchangeable and acid extractable fractions) is comprised less than the other forms. The oxidisable and reducible forms are dominants for all the four samples studied. The major metal constitute in the samples is iron, the wastewater residue contains (12.3 and 7.4 g/Kg respectively on dry basis) and the sludge contains (31.5 and 41.6 g /Kg) respectively. Cr concentration is higher in wastewater residue of second electroplating industry. The descending order of the average total metal contents for these four samples were Fe > Cr > Sn > Zn >Cu > Ni > Mn > Pb > Cd > Ag. Based on the average of absolute values for the four samples the highest bioavailability order of metals is Cr (39 %) in wastewater residues and Zn (32 %) in sludge samples. Metal recovery was good, with < 10 % difference between the total metal recovered through the extractant steps and the total metal determined using aqua regia extract.     

Soil and groundwater pollution of an urban catchment by trace metals: case study of the Addis Ababa region, central Ethiopia

Analysis of the total heavy metal (Cr, Cd, Pb, As, Cu, Ni, Zn, Co) concentration was performed on 33 soil samples taken from different profiles and soil types in a highly urbanized and industrial sector of Addis Ababa, central Ethiopia. They were analyzed using aqua regia extraction coupled with a four-stage sequential extraction (SE) procedure. The objectives of the analysis were to investigate the degree of soil heavy metal contamination, its binding forms, mobility and the implications for the groundwater resource. The results show a relatively high content of the analyzed trace metals in the soil attributed to anthropogenic and geogenic sources. Although most of the trace metals are found in the upper few centimeters of the residual soils, because of churning processes within the black cotton soils, vertical distribution of the trace metals is complex. According to the heavy metal SE analysis, the major heavy metal contribution is from the residual followed by the hydroxide phases. Groundwater heavy metal contamination is present with more than 90 and 50% of the analyzed groundwater samples exceeding WHO guidelines for Cr and Cd, respectively. Since the degree of soil heavy metal contamination has apparently not surpassed the soil’s buffering capacity, it appears that the transport path of these toxic metals to the groundwater is through fractures, joints, and related preferential flow paths.     

Distribution and immobilization of heavy metals in Pliocene aquifer sediments in Wadi El Natrun depression, Western Desert

The Pliocene aquifer receives inflow of Miocene and Pleistocene aquifer waters in Wadi El Natrun depression. The aquifer also receives inflow from the agricultural activity and septic tanks. Nine sediment samples were collected from the Pliocene aquifer in Wadi E1 Natrun. Heavy metal (Cu, Sr, Zn, Mn, Fe, Al, Ba, Cr, Ni, V, Cd, Co, Mo, and Pb) concentrations of Pliocene aquifer sediments were investigated in bulk, sand, and mud fractions. The determination of extractable trace metals (Cu, Zn, Fe, Mn, and Pb) in Pliocene aquifer sediments using sequential extraction procedure (four steps) has been performed in order to study environmental pathways (e.g., mobility of metals, bounding states). These employ a series of successively stronger chemical leaching reagents which nominally target the different compositional fractions. By analyzing the liquid leachates and the residual solid components, it is possible to determine not only the type and concentration of metals retained in each phase but also their potential ecological significance. Cu, Sr, Zn, Mn, Fe, and Al concentrations are higher in finer sediments than in coarser sediments, while Ba, Cr, Ni, V, Cd, Co, Mo, and Pb are enriched in the coarser fraction. The differences in relative concentrations are attributed to intense anthropogenic inputs from different sources. Heavy metal concentrations are higher than global average concentrations in sandstone, USEPA guidelines, and other local and international aquifer sediments. The order of trace elements in the bulk Pliocene aquifer sediments, from high to low concentrations, is Fe?>?Al?>?Mn?>?Cr?>?Zn?>?Cu?>?Ni?>?V?>?Sr?>?Ba?>?Pb?>?Mo?>?Cd?>?Co. The Pliocene aquifer sediments are highly contaminated for most toxic metals, except Pb and Co which have moderate contamination. The active soluble (F0) and exchangeable (F1) phases are represented by high concentrations of Cu, Zn, Fe, and Mn and relatively higher concentrations of Pb and Cd. This may be due to the increase of silt and clay fractions (mud) in sediments, which act as an adsorbent, retaining metals through ion exchange and other processes. The order of mobility of heavy metals in this phase is found to be Pb?>?Cd?>?Zn?>?Cu?>?Fe?>?Mn. The values of the active phase of most heavy metals are relatively high, indicating that Pliocene sediments are potentially a major sink for heavy metals characterized by high mobility and bioavailability. Fe–Mn oxyhydroxide phase is the most important fraction among labile fractions and represents 22% for Cd, 20% for Fe, 11% for Zn, 8% for Cu, 5% for Pb, and 3% for Mn. The organic matter-bound fraction contains 80% of Mn, 72% of Cu, 68% of Zn, 60% of Fe, 35% of Pb, and 30% of Cd (as mean). Summarizing the sequential extraction, a very good immobilization of the heavy metals by the organic matter-bound fraction is followed by the carbonate-exchangeable-bound fraction. The mobility of the Cd metal in the active and Fe–Mn oxyhydroxide phases is the highest, while the Mn metal had the lowest mobility.     

大亚湾表层沉积物重金属元素形态特征、控制因素及风险评价分析

为了解大亚湾表层沉积物中重金属的污染状况,对大亚湾海域23个点位表层沉积物中7种重金属元素（Cr、Ni、Cu、Pb、Zn、Cd、As）的质量分数、形态特征、来源控制因素以及潜在生态风险进行了研究。采用优化BCR提取法分析重金属元素赋存形态,并依据各种重金属元素的形态特征与沉积物基质属性进行了相关因子分析,了解其分布的控制因素。结果表明：大亚湾沉积物重金属元素呈现环带状分布特征,从岸向湾内逐渐减小;重金属元素质量分数的高值区主要分布于大鹏澳、哑铃湾及范和港附近;重金属元素赋存形态中Cr、Ni、Cu、Zn、As主要以残渣态存在,Pb主要以可还原态存在,Cd主要以酸提取态存在;7种重金属元素各自非残渣态所占比率从大到小为Pb(78.83%)、Cd(78.65%)、Cu(48.54%)、Zn(48.10%)、Ni(38.31%)、Cr(28.43%)、As(27.76%),即Pb最高,As最低,表明Pb的迁移性最强;通过因子分析,大亚湾重金属主要为沿岸自然风化产物的输入,其次为工业废水及养殖污水。运用酸提取态风险评估法对重金属元素潜在生态风险进行评价,发现研究区所选重金属元素综合风险评价Cd为高风险,其余重金属为中-低风险等级。     

The influence of physicochemical parameters on bioavailability and bioaccessibility of heavy metals in sediments of the intertidal zone of Asaluyeh region,Persian Gulf,Iran

In this research, we have worked on the evaluation of heavy metal contamination in the sediments taken from the intertidal zone of Asaluyeh region using Modified Community Bureau of Reference sequential extraction method (mBCR), the simplified bioaccessibility extraction test (SBET), and calculated enrichment factor (EF). Also, potential influencing factors including sediment characteristics that may affect the heavy metals bioavailability and bioaccessibility were investigated. mBCR extraction analysis indicated that among the metals, Mn, Zn, V, Cu, and Cd exhibit relatively higher mobility, while Ti, Pb, Cr, and Ni occur mainly in the residual fractions. Based on the mean values, the bioaccessibility of metals decreased in the order: Mn (50.01%)>Cd (46.26%)>Zn (14.61%)>V (13.97%)>Pb (10.88%)>Ni (9.2%)>Ti (8.43%)>Cr (6.66%)>Cu (6.23%). The obtained results from the principal component analysis (PCA), EF and mBCR extraction showed that most anthropogenic-derived metals with higher solubility are more bioaccessible compared to those of natural origin. Multiple linear regression analysis demonstrated that the main physicochemical variables of the sediment influencing the bioaccessibility of metals include cation exchange capacity (CEC), pH, and particle size fraction.     

Speciation and mobility of heavy metals in mud in coastal reclamation areas in Shenzhen,China

Coastal reclamation has been carried out along the coastal areas near Shenzhen, China in a large scale since 1980s by dumping fill materials over the marine mud at the sea bottom. Usually the area to be reclaimed is drained first and some of the mud is air-dried for a few weeks before it is buried by fill. After reclamation, the terrestrial groundwater, which is relatively acidic and with high dissolved oxygen, gradually displaces the seawater, which is alkaline with high salinity. The changes in the burial conditions of mud and the properties of the pore water in the mud may induce the release of some heavy metals into the mud. Field survey confirms that the pH and salinity of the groundwater in the reclamation site are much lower than the seawater. Chemical analyses of mud and groundwater samples collected from the reclamation sites reclaimed in different years indicate that most of the heavy metals in the mud decrease gradually with time, but the heavy metals in the groundwater are increased. The release of heavy metals into pore water due to reactivation of heavy metals in the mud is of environmental concern. To understand why some of the heavy metals can be released from the mud more easily than others, a sequential extraction method was used to study the operationally determined chemical forms of five heavy metals (Cu, Ni, Pb, Zn, and Cd) in the mud samples. Heavy metals can be presented in five chemical forms: exchangeable, carbonate, Fe–Mn oxide, organic, and residual. Ni and Pb were mainly associated with the Fe–Mn oxide fraction and carbonate fraction; Zn was mainly associated with organic fraction and Fe–Mn oxide fraction, while Cu and Cd were associated with organic fraction and carbonate fraction, respectively. If the residual fraction can be considered as an inert phase of the metal that cannot be mobilized, it is the other four forms of heavy metal that cause the noticeable changes in the concentration of heavy metals in the mud. On the basis of the speciation of heavy metals, the mobility of metals have the following order: Pb (36.63%) > Cu (31.11%) > Zn (20.49%) > Ni (18.37%) > Cd (13.46%). The measured metal mobility fits reasonably well with the degree of concentration reduction of the metals with time of burial observed in the reclamation site.     

Accumulation and partitioning of heavy metals in mangrove rhizosphere sediments

A field study was conducted to clarify the effect of rhizosphere processes on the accumulation and partitioning of heavy metals (Pb, Zn, Cu, Cr, Cd and Ni) in mangrove sediments. Metals were fractionated by a sequential extraction procedure into three chemically distinct fractions: water soluble, exchangeable and carbonate bound (B1), Fe–Mn oxide bound (B2), and organic and sulfide bound (B3). Results indicate that rhizosphere processes tend to increase the metal concentrations in the rhizosphere sediments. However, plant uptake may result in the decrease of the metal concentrations in the rhizosphere sediments when the metal concentrations are relatively low in the bulk sediments. Compared with the bulk sediments, the rhizosphere sediments have low concentrations of heavy metals in the B1 and B2 fractions and high concentrations in the B3 fraction. Either an increase or decrease in the residual fraction of heavy metals in the rhizosphere sediments may appear, depending on whether the formation of the refractory metal-organic compounds or the activation of the residual fractions dominates. Results also indicate that mangrove plants absorb and store non-essential metals in the perennial tissues, thus reducing the export of non-essential metals via leaf litter transport. Mangrove plants are excellent candidates for phytostabilization of heavy metals in intertidal substrates.     

某城市规划新区表层土壤重金属潜在生态风险评价

为评价某城市规划新区表层土壤质量,利用网格法采集表层土样1000件,分析8种重金属(Cd、 Cu、 Zn、 Ni、Cr、Pb、Hg、As)元素的含量,并分别运用污染负荷指数(PLI)和潜在生态危害指数(RI)评价研究区表层土壤中重金属的污染程度和危害等级。利用克里金插值法研究土壤PLI和RI的空间分布特征。结果表明:研究区内表层土壤重金属平均值均大于中国土壤背景值,Cd、Cu、Ni较为富集。研究区Cd和Cu元素为重度污染,Cd的生态危害性较强,87.90%的土样为重金属轻微污染,60.83%的土样为中等生态危害。污染较为严重和风险较强的地区主要位于研究区西南部河流两岸,Cu和Cd可能受到了人类活动的影响而偏高。     

深港西部通道填海区淤泥重金属化学形态分析

以深港西部通道填海区淤泥为研究对象,研究了重金属的化学形态特征,分析了填海工程活动带来的填海区地下水物理化学条件变化对重金属各个形态的影响。结果表明:除残留态外,填海区重金属存在形态主要为铁锰结合态、碳酸盐结合态和硫化物及有机结合态,其中,Pb和Ni以铁锰氧化物结合态和碳酸盐结合态为主,Cu以碳酸盐结合态和有机结合态为主,Zn以有机结合态和铁锰氧化物结合态为主,而Cd则以碳酸盐结合态为主。各金属在深港西部通道填海区淤泥的潜在迁移能力序列如下:Pb(39.68%)>Cu(31.59%)>Zn(20.49%)>Cd(12.80%)>Ni(10.98%)。