酸化及施碳酸钙对土壤各形态锰的影响

以灰潮土为对照 ,研究了华中地区 3种已明显发生酸化的土壤在施用碳酸钙前后各形态锰的变化情况。结果表明 ,已酸化的红壤、棕红壤和黄褐土施用碳酸钙降低了土壤酸度 ,土壤交换态锰随 pH值上升而降低 ,其降幅分别为 42 % ,49%和 39% ;其它形态锰的增减随各土而异 ,残留态锰较稳定 ,变幅小。作为对照 ,灰潮土虽与前 3种已酸化土壤一样种植过多茬作物 ,但其交换态锰含量仍甚微。无论是否施用碳酸钙 ,在灰潮土的交换态锰、碳酸钙结合态锰和易还原态锰 3种形态锰中 ,易还原态锰占 80 %以上 ,说明易还原态锰是其活性锰的主要部分     

有机物料对土壤的外源铜和镉形态变化的不同影响

采用盆栽和连续提取法研究稻草和紫云英对土壤外源铜和镉形态分布的不同影响。研究结果表明，添加稻草和紫云英可促进潮土中外源铜逐步向生物有效性较低的紫有机质结合态铜和无定形铁结合态铜转化，降低铜的生物有效性，但添加有机物料对潮土中外源镉形态的影响完全不同，添加稻草和紫云英，在分蘖期可减少潮土交换态镉、提高紧有机质结合态和氧化锰结合态镉，但这种作用并不稳定。随着时间的推移，氧化锰和紧有机质吸附的镉将随着活性锰的还原和紧有机质的分解被释放出来，并向交换态镉转化，提高镉的生物有效性。铜和镉离子与土壤的固相不同的结合能力导致稳草和紫去英对潮土中外源铜、镉形态的再分配过程的影响不同。     

河北主要土壤中Cd和Pb的形态分布及其影响因素

采用网室盆栽试验和大田取样 ,运用连续提取方法 ,研究了河北平原潮土和潮褐土两种土壤中Cd、Pb的化学形态特征及与其影响因素的关系。结果表明 :随着Cd、Pb污染程度的增加 ,其交换态有增加趋势。当高浓度重金属污染土壤时 ,Cd(潮土 >1mgkg- 1、潮褐土 >5mgkg- 1)主要以交换态存在 ,并表现为 :交换态 >碳酸盐结合态 >铁锰氧化物结合态 >有机结合态 >残留态 ;Pb主要以碳酸盐结合态和铁锰氧化物结合态存在。在低浓度重金属污染的土壤中 ,Cd (潮土 <1mgkg- 1、潮褐土 <5mgkg- 1)的残留态、有机结合态成倍增加 ,甚至超过交换态 ,表现为 :残留态 >碳酸盐结合态 >有机结合态 >交换态 >铁锰氧化物结合态 ;Pb主要以铁锰氧化物结合态和残留态存在。Cd、Pb在土壤中的分布与土壤的pH值 ,有机质含量密切相关。     

有机物料对土壤中外源铜形态及土壤化学性质的影响

在室内培养条件下,运用连续提取法研究了稻草,紫云英,猪粪对红壤,潮土中外源铜的形态及土壤化学性质的影响。结果表明,经过１个月培养后,两种土壤中外源铜主要以有机结合态铜为主,交换态铜的消长主要取决于有机结合态铜。在潮土中添加稻草和紫云英经在红壤中添加稻草和紫云英更有效地降低交换态铜的含量。     

有机物料对土壤中外源镉形态与生物有效性的影响研究

盆栽试验研究稻草与紫云英对土壤中外源Cd形态及其生物有效性的影响结果表明 ,添加稻草与紫云英可降低水稻分蘖期潮土和红壤交换态镉含量 ,且二者在不同土壤的影响不同。 2种有机物料在水稻分蘖期固定作用并不稳定 ,随时间的推移 ,氧化锰结合态和紧有机质结合态吸附的镉将随紧有机质的分解和活性锰的还原被释放出来 ,并向交换态镉转化 ,提高Cd的生物有效性。水稻对外源Cd吸收与Cd在土壤中形态密切相关 ,水稻分蘖期稻草与紫云英均可抑制水稻根和茎叶对外源Cd的吸收 ,至成熟期水稻根、茎叶和糙米中Cd含量迅速增加 ,其根本原因是由于土壤中交换态镉含量提高和紧有机质结合态镉含量降低所致     

EDTA对Cu污染农田土壤的淋洗实验研究

为了解鄂西南地区土壤铜的赋存形态及其污染修复,采用Tessier连续提取法测定土壤铜的赋存形态,采用振荡淋洗法研究了乙二胺四乙酸二钠(EDTA)在提取时间、淋洗浓度、固液比、p H等四个因素作用下对重金属铜(Cu)去除效果的影响。结果表明:农田土壤中铜的赋存形态依次表现为残渣态(4.26 mg kg-1)铁锰氧化物结合态(3.29 mg kg-1)硫化物及有机结合态(2.29 mg kg-1)可交换态(2.10 mg kg-1)碳酸盐结合态(1.63 mg kg-1);在EDTA修复Cu高污染土壤时,单因素实验分析表明当提取时间、淋洗浓度、固液比、p H分别为18 h、0.01 mol L-1、1∶10和7时为最佳实验条件,最佳单因素组合后对Cu的去除率为20.14%,将之应用于农田土壤,重金属Cu的去除率略有降低,可达18.29%。EDTA对土壤Cu处理前后对其赋存形态分析表明,土壤中重金属Cu交换态、碳酸盐结合态和铁锰氧化物结合态去除效果明显,但不能有效去除土壤中有机及硫化物态和残渣态。     

施用有机物料对土壤镉形态的影响

采用室内培养试验,研究作物新鲜秸秆和腐熟猪粪对模拟镉（Cd）污染的土壤中Cd形态转化的动态影响。结果表明,各处理土壤交换态Cd含量随培养时间均逐渐降低。碳酸盐结合态和铁锰氧化物结合态Cd含量先增加后降低, 而有机质结合态和残渣态Cd含量则逐渐增加。添加秸秆可增加土壤交换态Cd含量,但随时间延长,增幅逐渐降低, 猪粪则可降低土壤交换态Cd含量。添加有机物后土壤交换态Cd含量的变化主要是由有机质结合态或残渣态Cd含量的变化而引起。秸秆和猪粪对土壤Cd形态的转化与土壤胡敏酸（HA）和富里酸（FA）的变化有关。秸秆对能活化土壤Cd的FA增加幅度大于对能钝化土壤Cd的HA增加幅度,降低HA/FA比,但降幅随时间逐渐减少; 猪粪在整个培养阶段对HA增加幅度均大于FA的增加幅度,增加HA/FA比。秸秆和猪粪均可降低潮土pH而提高红壤pH,但只有猪粪可通过提高红壤pH降低Cd向交换态转化。添加秸秆和猪粪后,Cd由低活性态向交换态转化与HA/FA呈显著负相关。     

稳定同位素~(202)Hg稀释技术测定土壤汞有效性——与化学提取方法比较

准确评价汞(Hg)在土壤中的有效性对预测污染土壤中Hg的潜在生态风险及其环境质量标准的修订具有十分重要的意义。本研究通过稳定同位素202Hg稀释技术及同位素交换动力学方法(IEK)分析红壤和潮土中同位素可交换Hg含量(E值)及同位素可利用态Hg含量(Ea),并与4种单一提取法和1种连续提取法(改进的BCR法)获得的土壤有效态Hg含量进行比较。结果表明,外源稳定同位素202Hg加入土壤后,红壤和潮土的悬浮液中同位素交换均在24 h后达到稳定状态。同位素交换动力学方程对悬浮液中同位素比值及土壤同位素交换态含量Et值的变化有比较理想的拟合效果,红壤三个间段的E值(E1 min、E1 min-24 h和E24 h)及所占全量的比例均高于潮土。两种土壤Ea(为E1 min与E1 min-24 h之和)所占全量的比例为38%~60%,显著高于单一提取法中提取率最高的0.03%TGA-1/15 mol L-1Na2HPO4(10%~15%)及连续提取的∑BCR(20%~27%,为酸可提取态、还原态和氧化态占全量之和),这表明与化学方法相比较,用土壤同位素可利用态Hg含量(Ea)作为土壤中有效态Hg含量的表征可能偏高,原因可能与外源同位素被土壤固持及土壤悬浮液的性质有关。     

苏南经济快速发展区土壤Cu、Ni、Pb、Zn形态及其有效性定量分析——以昆山市为例

研究了江苏省昆山市农田土壤有效态Cu、Ni、Pb、Zn各形态含量及其有效性。结果表明,土壤重金属Cu、Ni、Pb、Zn各形态含量以残渣态有机质结合态铁锰氧化物结合态碳酸盐结合态、可交换态,残渣态含量明显高于其他形态。Cu和Pb有机质结合态所占比例相对也较高,分别达36.09%和28.30%。土壤可交换态含量、碳酸盐结合态含量、Fe-Mn氧化物结合态含量及残渣态含量均以Zn最高;土壤有机质结合态含量以Cu最高;土壤可交换态含量变异系数、土壤碳酸盐结合态含量变异系数及土壤Fe-Mn氧化物结合态含量变异系数以Ni为最大;土壤有机质结合态含量变异系数以Zn最大;土壤残渣态含量变异系数以Pb最大。土壤铁锰氧化物结合态铜和可交换态铜对土壤有效态铜含量影响最大;土壤可交换态镍含量对土壤有效态镍含量最大;土壤铁锰氧化物结合态铅和有机质结合态铅对土壤有效态铅含量影响最大;土壤可交换态锌和碳酸盐结合态锌对土壤有效态锌含量影响最大。     

有机物料对稻作与非稻作土壤外源镉形态的影响研究

试验研究稻草、紫云英对稻作土壤和非稻作土壤中外源Cd形态及其变化的影响结果表明 ,稻草、紫云英显著降低培养 30d和培养 90d后非稻作土壤中交换态Cd含量。强烈还原条件下形成的硫化镉沉淀是稳定非稻作土壤交换态Cd含量的重要机制。稻草和紫云英对稻作土壤中外源Cd形态转化的影响不同 ,培养 30d后稻草和紫云英提高稻作土壤中氧化锰结合态和紧有机质结合态Cd含量 ,降低交换态Cd含量 ,其作用随时间的推移 ,氧化锰结合态Cd和紧有机质结合态Cd被释放出来并向交换态Cd转化 ,使交换态Cd含量提高。     

长三角和珠三角农业土壤中铅、铜、镉的化学形态与转化

研究了重金属Pb、Cu、Cd在长江三角洲和珠江三角洲土壤中的转化及不同Pb、Cu、Cd负荷水平对土壤重金属形态的影响。结果表明:未明显污染土壤中重金属主要以残余态为主,可提取态组分的比例Cd>Cu>Pb,但不同土壤之间有较大变化;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,对环境威胁增大;当重金属加入量较低时,重金属优先向氧化物结合态、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明显增加;pH和土壤组分对重金属在土壤中的转化有显著影响,土壤pH下降可使交换态Cd、Cu、Pb的比例递增。     

Distribution of Trace Elements in Soils from the Sudbury Smelting Area (Ontario,Canada)

The sequential extraction procedure proposed by the European Commission Measurement and Testing Programme, combined with Scanning Electron Microscopy and Energy Dispersive X-ray Analysis(SEM/EDS), was applied to identify and quantify the chemical andmineralogical forms of Cu, Ni, Fe, Mn, Zn, Pb, Cr and Cd presentin the topsoil from a mining and smelting area near Sudbury (Ontario, Canada). The possible mobility of the chemical forms was also assessed. The metal fractions: (1) soluble and exchangeable, (2) occluded in manganese oxides and in easily reducible iron oxides, (3) organically bound and in form of sulphides, (4) residual mainly present in the mineral lattice structures were separated. Cu and Ni were the major metallic contaminants, occurring in soils in broad ranges of concentrations: Cu 11–1890 and Ni 23–2150 mg kg^-1. Cu was uniformly distributed among allthe extracted fractions. Ni was found associated mainly withthe residual forms, accounting for 17–92%, with an averageof 64%, of the total Ni present in the soils. Fe, Mn, Zn,Pb, Cr and Cd, while occurring in most analysed samples innormal soil concentrations, were primarily held in theresidual mineral fraction (on average >50%). The solubleand exchangeable forms made a small contribution (≤8.1%)to the total content of metals extracted. At least 14% ofthe total Cd, Mn and Pb was mobilised from the reducibleforms. The oxidizable fraction assumed mean values higher than10% only for Pb and Zn. Statistical treatment of the experimental data showed significant correlations between totalmetal content of the soils, some soil properties such as pH value, clay and organic matter content, and metal concentrationsin the various fractions. SEM/EDS analysis showed Fe in form ofoxides and sulphides in soils and Cu, Ni, Mn, Zn and Cr in association with iron oxides. Numerous black carbonaceous particles and precipitates of aluminium fluoride salts, observedin the solid residue left after `total’ digestion, were found tocontain Fe, Ni and Cr.     

Long‐term transformations of cadmium,cobalt, copper,nickel, zinc,vanadium, manganese,and iron in arid‐zone soils under saturated condition

Abstract

The bioavailability and toxicity of metals in soils to plants, hence to animals and human beings through the food chain, and their mobility in the ecosystems highly depends upon their forms, pathways and kinetic rates of transformation in soil. Long‐term transformation pathways, kinetics and lability of cadmium (Cd), cobalt (Co), copper (Cu), nickel (Ni), zinc (Zn), manganese (Mn), and iron (Fe) in two arid‐zone soils were studied under saturated water regime (simulating the moisture regime in the soil during the raining season and shortly after irrigation) by using operationally selective sequential dissolution techniques. Iron, Mn, Co, vanadium (V), Ni, Zn, and Cu were transformed from the non‐available form (reducible oxide fraction) and potential available form (easily reducible oxide fraction) into the available and readily available form (exchangeable and carbonate fractions), thereby increasing their mobility, availability or toxicity. However, Cd was transformed from the readily available form into the potentially available form, thus decreasing its lability. The fast transformations of all metals occurred in the first month, followed by a much slower process.     

The forms of occurrence of manganese in some acidic soils

The forms of occurrence of Mn were examined in some acidic surface and sub-soils from areas of permanent grassland using chemical extractants. Despite high total contents of Mn in some of the soils and low pH, only minor proportions occurred as exchangeable Mn²⁺. Much larger proportions were present as reducible hydrous oxides, e.g. up to 38% and 54% of the total contents in surface and subsoils, respectively, were present as hydroquinone extractable, or easily reducible, Mn. Reducible forms of Mn were poorly correlated with other more mobile forms. Large proportions of the total Mn contents were accounted for when estimates of different fractions were calculated from differences in amounts extracted by different individual extractants, i.e. M NH₄OAc, 0.2% hydroquinone, 0.1 M pyrophosphate, and ammonium oxalate. The distribution of Mn amongst the different fractions as determined by a sequential fractionation scheme differed markedly from the distribution calculated by differences. In particular, there was a marked change in form after extraction with pyrophosphate.     

吉林省西部氟病区苏打盐碱土氟的赋存形态及分布特征

为了研究吉林省西部氟病流行区农田土壤的氟形态及其分布特征,采用连续浸提法,对该区域内45个表层土壤和6个剖面土壤的氟含量进行了测定,并与土壤理化性质进行相关分析。结果表明,表层土壤全氟含量变化范围为200~450 mg/kg,平均值为266.17 mg/kg,低于全国土壤氟背景值和对照黑土,但是其生物有效性强,水溶态氟和交换态氟平均含量分别为13.73、8.49 mg/kg,均高于对照黑土。土壤剖面中,残余态氟和全氟含量呈40~60 cm0~20 cm20~40 cm;铁锰结合态氟分布较均匀;其他形态氟则随着土层加深呈降低趋势。交换态氟与其他形态氟间呈显著或极显著的正相关关系,为各形态氟相互转换的过渡形式。pH与水溶态氟、有机束缚态氟、铁锰结合态氟呈极显著或显著正相关,与交换态氟呈极显著负相关;碳酸钙、CEC分别与水溶态氟和交换态氟呈极显著正相关;另外,有效磷与交换态氟呈显著正相关;有机质与水溶态氟、铁锰结合态氟和有机束缚态氟呈显著或极显著正相关;游离氧化铁和游离氧化铝分别与交换态氟和铁锰结合态氟呈显著或极显著正相关。降低苏打盐碱土pH是降低氟生物有效性的首选方法。通过对以上土壤参数进行分析,为今后降低该区域土壤中氟的生物有效性提供技术支持。     

对矿区和冶炼区土壤重金属污染进行化学和矿物学特征分析

The binding of metallic contaminants （Pb, Cd, and Zn） and As on soil constituents was studied on four highly contaxninated alluvial soil profiles from the mining/smelting district of Pribram （Czech Republic） using a combination of mineralogical and chemical methods. Sequential extraction analysis （SEA） was supplemented by mineralogical investigation of both bulk samples and heavy mineral fractions using X-ray diffraction analysis （XRD） and scanning electron microscopy with an energy dispersive X-ray spectrometer （SEM/EDS）. The mineralogy of Fe and Mn oxides was studied by voltammetry of microparticles （VMP） and diffuse reflectance spectrometry （DRS）. Zinc and Pb were predominantly bound in the reducible fraction attributed to Fe oxides and Mn oxides （mainly birnessite, Na4Mn14O27.9H2O）, which were detected in soils by XRD and SEM/EDS. In contrast, Cd was the most mobile contaminant and was predominantly present in the exchangeable fraction. Arsenic was bound to the residual and reducible fractions （corresponding to Fe oxides or to unidentified Fe-Pb arsenates）. SEM/EDS observations indicate the predominant affinity of Pb for Mn oxides, and to a lesser extent, for Fe oxides. Thus, a more suitable SEA procedure should be used for these mining-affected soils to distinguish between the contaminant fraction bound to Mn oxides and Fe oxides.     

四川省紫色土天然和添加的镍不同形态的分布及转化

The distribution and transformation of added and native Ni in purple soils were investigated with both sequential extraction procedure and isotopic tracer technique.The distribution of added and native Ni was greatly dependent on soil properties.Low soil pH was favorable for soluble plus exchangeable(EX) Fraction,while Fe/Mn oxides and clay for Fe/Mn oxide bound(OX) and residual(RES) fractions.The added Ni,however,has not yet reached the distribution equilibrium up to the 150th day after incubation.This was reflected in the fact that the proportion of EX fraction from added Ni was 150%-600% as much as that of native Ni,while that of RES fraction was only about 80%,Once entering soil,the applied soluble Ni was rapidly transformed into other fractions,but the organic complexe (OM) fraction of added Ni was relatively stable during incubation.The carbonate bound(CAB)fraction showed a progressive increase and attained a peak value after 0-14d of incubation and thereafter decreased gradually.The occurrence time of this peak advanced as initial soil pH increased.but the peak would disappear when initial soil pH was higher than 7.5(or containing free CaCO3).The transformation processes of the EX,OX and RES fractions could be described by Elovich and two-constant rate equations,and the rate were positively correlated with soil pH,CEC and clay.These finding could explain why there are differences in ecological and environmental effects of Ni in different soils and at various intervals.     

Chemical Fractions of Mn in Acidic Soils and Selection of Suitable Soil Extractants for Assessing Mn Availability to Maize (Zea Mays L.)

Twenty surface (0–15 cm) samples of acidic soils were analyzed for water soluble (WS), exchangeable (EX), lead displaceable (Pb-disp.), acid soluble (AS), manganese (Mn) oxide occluded (MnOX), organically bound (OB), amorphous Fe oxide occluded (AFeOX), crystalline iron (Fe) oxide occluded (CFeOX) and residual (RES) fractions of Mn, and also for extractable Mn in some common soil extractants: (diethylenetriaminepentaacetic acid (DTPA) (pH 7.3), DTPA (pH 5.3), AB-DTPA (pH 7.6), Mehlich-3 (pH 2.0), Modified Olsen, 0.005 M calcium chloride (CaCl₂), 1 M magnesium chloride (MgCl₂) and ion exchange resins. The WS-Mn fraction showed a significant and positive correlation with Mn extractable in DTPA (pH 5.3) and AB-DTPA (pH 7.6), while both WS-Mn and EX-Mn fractions correlated significantly and positively with Mn concentration and uptake by maize plants grown in these soils. The AB-DTPA (pH 7.6) and DTPA (pH 5.3) appeared suitable to assess the availability of Mn in acidic soils.     

Distribution of Aluminum Fractionation in the Acidic Rhizosphere Soils of Masson Pine (Pinus massoniana Lamb)

The modified Tessier’s sequential extraction procedure and rhizobox cultivation were employed to investigate the distribution of aluminum (Al) fractions in the acidic rhizosphere soil of Masson pine (Pinus massoniana lamb) seedlings. The results showed that the Al in soils was fractionated into five operationally defined fractions. Three sets of soil samples used in the rhizoboxes were collected from the three forest sites in the southeast of China: Sichuan, Zhejian, and Jiangsu. At the end of 100-day cultivation, the rhizosphere Al fractions for the original or bulk soils were in the order of residual > iron-manganese (Fe-Mn) oxides > organic > carbonate > exchangeable. However, in rhizosphere soil, the Al fraction follows the order of residual > organic > Fe-Mn oxides > carbonate > exchangeable. On average, the rhizosphere experienced significant increase in organically bound Al and slight decrease in exchangeable Al contents, but had decreases in contents for the other three Al fractions compared to the nonrhizosphere. The correlation analysis indicated that the Al contents accumulated in roots were significantly and positively correlated with exchangeable Al contents in the rhizosphere, and also characterized by the major portion of organically bound Al, which exhibited a bioavailable transformation of Al fractions. Results indicated that decreases in both redox potential and soil pH, as well as increase in dissolved organic carbon (DOC), were observed in the rhizosphere. Exchangeable Al and organic Al fractions were dependent mainly on soil pH (hydrogen ion concentration) and DOC, accordingly. Decreasing rhizosphere pH from 5.93 to 3.42 accelerated the secretion of organic carbon. These data are helpful for understanding the mobility and bioavailability of Al fractions in the acidic rhizosphere soils of Masson pine.