连续浸提技术测定土壤和沉积物中硒的形态

本文建立了土壤和沉积物中硒的形态分析方法，应用连续化学浸提技术将土壤和沉积物进行连续五次抽提，根据不同形态硒的溶解度，将土壤和沉积中的硒分为可溶态（水溶态）、可交换态及碳酸盐结合态、铁－锰氧化物结合态、有机物－硫化物结合态及元素态、残渣态五种结合形态。种形态硒分级浸提的相对标准偏差均小于４．０％，总回收率（即：五种形态和与总硒的比值）为９３．２－９４．４％。     

福建丰产荔枝园土壤微量元素含量的研究

与我国红壤平均水平相比，福建丰产荔枝园土壤有效态锌、钼及水溶态硼含量较高，而活性锰及有效铜含量较低；土壤全锌、锰、钢量亦较低。在土壤ｐＨ４．５４—８．７６时，ｐＨ值与有效态钼含量呈较显著正相关，而与代换态锰、水溶态硼、有效态铁含量呈显著或极显著负相关。本文初步提出福建荔枝园土壤微量元素含量的适宜指标，可供土壤营养诊断及平衡施肥之参考。     

土壤pH对锰赋存形态的影响

以热带亚热带土壤为研究对象，用连续分级浸提法探讨了土壤中锰赋存形态与ｐＨ值的关系。结果表明：土壤中的锰处于一种动态平衡状态，各形态锰的含量及其占全锰的比例随ｐＨ的变化而变化，其中代换态锰和有机态锰随ｐＨ值升高而减少，氧化态锰、无定形铁结合态锰和晶形铁结合态锰则随ｐＨ值升高而增加，土壤中锰的生物有效性则随ｐＨ值升高而降低。     

有机肥料和无机肥料对土壤微量元素含量的影响

五年定位监测的田间试验结果表明，施用有机肥料对土壤铁、锰、铜、锌的消耗具有明显的补充作用，但对有效用的补充仍显不足．因此，土壤硼营养有可能成为作物产量的限制因子．长期单施正要素化肥的土壤有效态铁、锰、铜、锌、硼的含量均明显下降，下降量达3mg／kg以上，其中土壤有效态硼则有潜在缺乏的可能．     

不同耕作制度对土壤中锰赋存形态及其有效性的影响

以花岗岩母质发育的旱地红壤和水稻土为研究对象，探讨了不同耕作制度下土壤中锰的赋存形态及其生物有效性。结果表明：在水旱轮作条件下，土壤中的锰更多地以代换态和晶形铁结合态存在；旱作土壤中的锰则较多地以有机态和无定形铁结合态存在．然而，单位有机质络合的锰量却是水稻土大于红壤。水旱轮作措施具有活化锰的作用，使得土壤中锰有效性更大并且主要以代换态存在。旱作土壤则不同，土壤活性锰除来自代换衣外，尚有大约４５％以有机态或无定形铁结合态存在。     

水稻根表胶膜的浸提及其元素测定方法

选择柠檬酸钠作为络合剂,比较了碳酸氢钠、乙酸钠二种缓冲体系下,盐酸羟胺、抗坏血酸和1/2盐酸羟胺 1/2抗坏血酸组合对水稻根表铁、锰的浸提能力.结果表明,水稻根表铁、锰浸提量与还原剂种类和缓冲体系的pH值有关.在六种浸提剂中,抗坏血酸-柠檬酸钠-乙酸钠(ACA)浸提水稻根表铁、锰的浸提量最大,为57307mg·kg-1和1689mg·kg-1,相当于DCB浸提水稻根表铁、锰浸提量的99%和109%.ICP测定浸提液中铁、锰、磷、硫等的变异系数也低于DCB浸提的同类元素.因此,推荐ACA-ICP作为水稻根胶膜浸提与元素测定方法.     

用黑麦幼苗法测定土壤中污染元素的生物有效性

本文对全国污灌区１２个土样中Ｃｄ形态与生物有效性的试验表明，Ｃｄ的交换态，吸附态，有机结合态均有效，且有机结合态最为有效，对紫阳县富硒土壤的试验表明：黑麦幼苗中的总Ｓｅ量与０．１ｍｏｌ／１ＫＨ２ＰＯ４的浸提量最为相关，从而推荐该法为酸性土壤有效Ｓｅ的浸提方法，对西安污水厂污水污泥在娄土上不同施用量的试验表明：幼苗中Ｎ，Ｐ随施用量增加而增加，Ｎ，Ｐ的有效率分别为５０－７０％及１５－２８％；黑麦幼苗中     

小麦根际土壤汞的分布和形态变化

采用根际箱试验和连续化学萃取法,结合氢化物原子吸收光谱法,研究了非根际和根际土壤汞形态分布特征及小麦(Triticum aestivum)生长期土壤汞形态变化.结果表明.非根际汞形态分布顺序为:残渣态>强有机质结合态>碳酸盐铁锰氧化物结合态>腐殖酸络合态>水溶态>交换态,根际汞形态分布为:残渣态>碳酸盐铁锰氧化态>强有机质结合态>交换态>腐殖酸络合态>水溶态.当外源汞进入土壤后,在小麦生长60 d内,植物吸收使残渣态汞和水溶态汞含量明显降低,交换态汞和碳酸盐铁锰氧化态汞含量增加.土壤汞污染程度越大,在小麦中积累的汞就越多.其生物毒性增强,环境危害加大.     

硫磺对土壤中Pb和Zn形态的影响

研究了添加硫磺对Pb和Zn污染土壤的pH值、土壤中SO4^2-含量、土壤中Pb和Zn的NH4OAc浸提态含量及土壤中Pb和Zn的BCR(欧共体标准物资局)三步分级提取态含量的影响．结果表明：Pb和Zn污染土壤中添加硫磺后,土壤pH值降低,土壤中SO4^2-含量增加,土壤中Pb和Zn的NH4OAc浸提态含量随施硫水平的增加而增加;在对Pb和Zn的BCR三步分级提取态含量分析中,添加硫磺后,二者的B1态都有增加,Zn的B1态增加的比例要高于Pb,二者的B2和B3态都有不同程度的变化．     

二乙烯三胺五乙酸(DTPA)提取ICP-AES法测定土壤中有效态元素

本文参考《土壤有效态元素的测定二乙烯三胺五乙酸提取/电感耦合等离子体原子发射光谱法》最新环境验证标准和《ISO 14870—2001》方法标准,采用二乙烯三胺五乙酸(DTPA)作为提取剂,提取土壤中有效态铜、铁、锰、锌、镉、铬、镍和铅等元素并使用ICP-AES法进行了测定.该前处理方法不同于传统的元素全量消解方法,无需添加高腐蚀性、高氧化性的强酸.实验结果表明,方法线性相关系数良好,r0.9999,精密度RSD0.7%,测定结果与土壤标准物质GBW07414a中的有效态元素标准值吻合.     

几种萃取剂对土壤中重金属生物有效部分的萃取效果

采用6种萃取剂:pH=7的0.01mol/L CaCl_2、pH=7.3的0.005mol/L DTPA+0.1mol/L TEA(三乙醇胺)+0.01mol/L CaCl_2O.1mol/L NaNO_3、0.43mol/L HOAc、pH=7的0.05mol/L EDTA和pH=4.65的0.5mol/L NH_4OAc+0.02mol/L EDTA浸取液.对污染土壤中的重金属Cu、Zn、Cd、Pb、的进行了萃取,并比较了萃取剂的萃取能力。实验结果表明,HOAc、EDTA以及NH_4OAc-EDTA萃取各种重金属的能力远远大于其它几种萃取剂的萃取能力,是比较理想的萃取剂。     

Influence of soil-extractable aluminium and pH on the uptake of aluminium from soil into the soybean plant (Glycine max)

The effects of soil pH and other soil properties on the uptake of AI by soybean plants have been investigated in a greenhouse experiment. Six soils were compared that were developed over six contrasting bedrock types ranging widely in their AI content and other chemical and physical characteristics, namely Oxford Clay, Chalk, Lower Lias Clay, Devonian Shale, Granite and Lower Greensand. Soil pH varied naturally between soil types and each soil was also amended to give two other pH levels using elemental sulphur and/or calcium carbonate. AI concentrations in various parts of the soybean plants were determined by ICP-AES after acid digestion. The AI solubility in the soils and hence its availability to the plants was estimated using a number of different reagents designed to extract different forms of AI. The AI concentration measured in the soybean leaves was found to be predicted most accurately by the ‘available’ AI extracted from soils by 0.02 M CaCl₂. The relationship appears to the linear, with a correlation coefficient of 0.97 (p <0.01). The AI content of the leaves increases with decreasing soil pH. The relationship is non-linear with a marked increase in leaf AI for soils with pH <4.4. The amounts of ‘plant-available’ AI in the soils extracted with 0.02 M CaCl₂ was much less than that extracted with 0.05 M EDTA, although both increased markedly with decreasing soil pH. The amount of AI measured in the soybean plants was directly related to both the ‘available’ forms of AI in the soils, and also to the pH of the soils. Soil pH was identified as a major factor that controls the uptake of Al from soil into the soybean plant.     

柠檬酸对土壤养分的活化及对作物吸收Fe、P的影响

土壤pH值是影响石灰性土壤Fe、Zn、Mn等微量元素有效性的重要因素，利用土壤培养法，研究了不同浓度柠檬酸溶液对石灰性土壤的pH值以及对P、Fe、Mn、Zn等元素的活化效应。结果表明，浓度高于0．001mol／L的柠檬酸溶液培养土壤，可降低土壤pH值，增加土壤有效P、Fe、Mn、Zn等元素的质量分数。培养24h后，P、Fe、Mn、Zn等有效养分质量分数最高，随着培养时间的延长，有效养分的质量分数下降，活化效果减弱，土壤表现出一定的钝化效应。利用盆栽模拟滴灌施肥条件，柠檬酸溶液处理可显著促进花生、菜豆植株的生长，叶片SPAD读数增加，并提高植株对P、Fe元素的吸收量，因此滴灌施肥条件下，可考虑使用柠檬酸增加石灰性土壤根区微量元素的有效性。     

Chromium accumulation,transport and toxicity in plants∗

The predominant pathway for human exposure to chromium in non‐occupationally exposed individuals is via food with a daily intake of around 30–100 μgd^–1, with vegetables providing a major contribution. Unlike reports of chromium essentiality to man and animals, plants appear not to require chromium in spite of some early reports of a stimulatory growth effect.

Most reports on chromium in plants have been concerned with their growth on soils amended with sewage sludge, pF‐ash, tannery waste, or on ultra basic soils, which contain extreme concentrations of the element. Experimental studies with plants grown in hydroponic solution have often been undertaken at unrealistically high concentrations to examine the uptake of chromium in various forms, either as CrIII or CrVI at different pHs. In most cases, reports on chromium in plants deal with element concentrations and plant/soil relationships rather than detailed biochemical and physiological processes.

In general, chromium is largely retained in the roots of plants, although the oxidation state of chromium, pH, presence of humates and fulvates and plant species, affect plant uptake and transport. Leaves usually contain higher concentrations than grains. The uptake of CrIII is largely a passive process, whereas CrVI uptake is a metabolically mediated process via the sulphate pathway and is thus readily transported around the plant. The presence of a compound similar to trioxalate CrIII has been recorded while little chromium has been reported to be associated with cell organelles or soluble proteins.     

Four-decade responses of soil trace elements to an aggrading old-field forest: B, Mn, Zn, Cu, and Fe

In the ancient and acidic Ultisol soils of the Southern Piedmont, USA, we studied changes in trace element biogeochemistry over four decades, a period during which formerly cultivated cotton fields were planted with pine seedlings that grew into mature forest stands. In 16 permanent plots, we estimated 40-year accumulations of trace elements in forest biomass and O horizons (between 1957 and 1997), and changes in bioavailable soil fractions indexed by extractions of 0.05 mol/L HCl and 0.2 mol/L acid ammonium oxalate (AAO). Element accumulations in 40-year tree biomass plus O horizons totaled 0.9, 2.9, 4.8, 49.6, and 501.3 kg/ha for Cu, B, Zn, Mn, and Fe, respectively. In response to this forest development, samples of the upper 0.6-m of mineral soil archived in 1962 and 1997 followed one of three patterns. (1) Extractable B and Mn were significantly depleted, by -4.1 and -57.7 kg/ha with AAO, depletions comparable to accumulations in biomass plus O horizons, 2.9 and 49.6 kg/ha, respectively. Tree uptake of B and Mn from mineral soil greatly outpaced resupplies from atmospheric deposition, mineral weathering, and deep-root uptake. (2) Extractable Zn and Cu changed little during forest growth, indicating that nutrient resupplies kept pace with accumulations by the aggrading forest. (3) Oxalate-extractable Fe increased substantially during forest growth, by 275.8 kg/ha, about 10-fold more than accumulations in tree biomass (28.7 kg/ha). The large increases in AAO-extractable Fe in surficial 0.35-m mineral soils were accompanied by substantial accretions of Fe in the forest's O horizon, by 473 kg/ha, amounts that dwarfed inputs via litterfall and canopy throughfall, indicating that forest Fe cycling is qualitatively different from that of other macro- and micronutrients. Bioturbation of surficial forest soil layers cannot account for these fractions and transformations of Fe, and we hypothesize that the secondary forest's large inputs of organic additions over four decades has fundamentally altered soil Fe oxides, potentially altering the bioavailability and retention of macro- and micronutrients, contaminants, and organic matter itself. The wide range of responses among the ecosystem's trace elements illustrates the great dynamics of the soil system over time scales of decades.     

Soil organic matter and salinity affect copper bioavailability in root zone and uptake by Vicia faba L. plants

Processes that control the mobility, transformation and toxicity of metals in soil are of special importance in the root-developing zone. For this reason, there is a considerable interest in understanding trace elements (TEs) behavior in soil, emphasising the processes by which plants take them up. Increased root-zone salinity can affect plant TEs uptake and accumulation in plant tissue. Furthermore, copper (Cu) complexation by soil organic matter (SOM) is an effective mechanism of Cu retention in soils, controlling thus its bioavailability. Therefore, a greenhouse pot experiment was conducted to study the effects of soil Cu contamination in a saline environment on faba bean (Vicia faba L.) element uptake. Treatment with NaCl salinity was applied (control, 50 mM NaCl and 100 mM NaCl) on faba bean plants grown in a control and in a soil spiked with Cu (250 and 500 mg kg^?1). Low and high SOM content trial variants were studied. Cu accumulation occurred in faba bean leaf, pod and seed. Cu contamination affected plant element concentrations in leaves (Na, Ca, Mg, Mn), pod (Zn, Mn) and seed (Mn, Mo, Zn). Root-zone salinity also affected faba bean element concentrations. Furthermore, Cu contamination—salinity and salinity—SOM interactions were significant for pod Cu concentration, suggesting that Cu phytoavailability could be affected by these interactions. Future research will be focused on the mechanisms of Cu translocation in plant and adaptation aspects of abiotic stress.     

Lead availability in soils from Portugal’s Centre Region with special reference to bioaccessibility

Previous environmental biomonitoring studies indicated higher environmental lead (Pb) pollution levels at the districts of Aveiro and Leiria (Portugal). In evaluating the risk for human health, which is associated with contaminated soils after oral uptake, total soil concentrations have generally been held against criteria established from toxicological studies based upon the assumption that the uptake of the contaminant is similar in the toxicological studies and from the soils assessed. This assumption is not always valid, as most toxicological studies are carried out with soluble forms of the contaminants, whereas many soil contaminants are or become embedded in the soil matrix and thus exhibit limited availability. This study intends to estimate the soluble fraction of Pb in the soils from central Portugal, and to assess the bioaccessibility of Pb and, hence, infer exposure and risk for human health. Yet, as the physical–chemical properties of the soil exert some control over the solubility of Pb in the surface environment, the relation between such soil properties and the estimated soluble and/or bioaccessible fractions of Pb is also investigated. Other objective, with a more practical nature, was to give some contribution to find a suitable in vitro mimetic of the gastrointestinal tract environment. The results indicate relatively low total metal concentrations in the soils, even if differences between regions were observed. The Aveiro district has the higher total Pb concentration and the metal is in more soluble forms, that is, geoavailable. Soils with higher concentrations of soluble Pb show higher estimates of bioaccessible Pb. Soil pH seems to influence human bioaccessibility of Pb.     

Annual production and molecular weight as an influential factor for environmental distribution of chemicals — a case study in Japan

The changes promoted by treatment of a highly polluted soil with sulphuric acid or calcium hydroxide for changing its pH value are studied by controlling physical properties (particle size, TGA and DTA curves), evolution of metal species (exchangeable, as carbonates, related to Fe‐Mn oxides, linked to organic matter and residual) and metal uptake by plant cultures. Metal contents were determined, after wet digestion with HF—HNO₃—HC1O₄ when necessary, by AAS (Ca, Mg, Cu, Pb, Mn, Fe, Zn) or emission (Na, K). The treatment of soil with successive amounts of sulphuric leads to changes in particle size, hydration properties and exothermic peak for organic matter combustion. Very small changes were, however, detected in the alkaline treatment of soil. Soil treatments do not have practical influence on speciation of some metals (Na, K, Mg, Pb, Mn, Fe), but the intensity of the acid treatment leads to both an increase in the Cu extraction and a decrease in the Ca solubilization, probably through gypsum formation. In the case of zinc a maximum solubility in the middle of the range of acid treatment was observed. The comparison among extractants shows solubilities high for two pollutants (Pb, Cu), associated mainly to Fe—Mn oxides and organic matter, and low for two macrocomponents (Fe, K). The rest of metals, basically present in soil as carbonates or oxides, have intermediate extractions. Pot cultures weights depended mainly on both the treatment of soil (poor development in the more acid sample and drainage difficulties in the rest of acid treatments) and the situation (very low weights in laboratory runs as compared with outside), but the irrigation with water or a diluted sulphuric acid solution (at pH = 4.0) did not produce significant weight changes. Tendencies to increase plant pollution were observed for smaller soil pH, acid irrigation and probably for outside cultures, due to uptake by leaves.     

添加植物物料对2种酸性土壤可溶性铝的影响

在室内培养试验条件下,研究了添加非豆科的油菜秸秆、小麦秸秆、稻草、玉米秸秆和豆科的大豆秸秆、花生秸秆、蚕豆秸秆、紫云英、豌豆秸秆对酸性茶园黄棕壤和红壤可溶性铝总量及其形态的影响.结果表明,黄棕壤除添加油菜秸秆、小麦秸秆和稻草处理外,其余添加植物物料处理土壤可溶性铝总量、总单核铝和3种无机单核铝的含量有不同程度的降低,因为加入这些植物物料均使土壤pH值增大.5种豆科植物物料对黄棕壤pH值的影响大于非豆科植物物料,前者对土壤中3种无机单核铝含量的影响也大于后者.9种植物物料也使红壤pH值有不同程度升高,土壤可溶性铝含量降低,其中4种非豆科植物物料、花生秸秆和蚕豆秸秆处理效果较好.因此,施用植物秸秆能够有效改良土壤酸度,缓解土壤中铝对植物的毒害.总体而言,9种植物物料中花生秸秆增加酸性土壤pH值和降低土壤有毒形态铝含量效果最好.     

基于变化阶段特点的亚热带红壤硝化模式及其影响因素分析

在土壤最大持水量60%和温度30℃的实验室培养条件下,对采自江西的15个第三纪红砂岩母质发育的自然土壤（灌丛和林地）和农业利用土壤（茶园、旱地和水稻）进行了56 d实验室培养,研究了土壤NO3--N含量随时间的变化过程及阶段特点。结果显示,发生净硝化作用的14个土样NO3--N质量分数随时间的变化表现＂J＂型增长和＂S＂型增长2种模式。＂J＂型增长模式的6个土样,67%为自然土壤,其NO3--N质量分数增长具有15~35 d的延滞期,符合指数方程N=N0e kt（P〈0.001）,N0值与有效磷质量分数呈显著的指数关系（P〈0.05）。＂S＂型增长模式的8个土样,88%为农业利用土壤,NO3--N累积无明显延滞期,符合Logistic修正模型N=Np/（1＋e2.e-rt）（延滞期td=0,P〈0.001）,由模型获得的土样最大硝化速率vm与土壤全氮质量分数和全碳质量分数具有极显著的正相关关系（P〈0.001）,达到最大硝化速率所需的时间tm与风干土的NO3--N质量分数呈显著正相关（P〈0.05）。上述结果表明,农业利用措施,特别旱作种植可消除亚热带土壤硝化作用的延滞期,从而使铵态氮肥施入土壤后快速转化成为硝态氮,增大硝态氮淋失的风险。