全国土壤污染状况详查重金属元素可提取态提取试剂的选择

土壤重金属元素可提取态是衡量其生物有效性的重要指标,但其含量随着土壤酸碱性等环境条件的变化而改变,在提取土壤重金属元素可提取态时,不可避免地面临着提取剂与提取方法的选择。中国有关土壤重金属元素可提取态的标准分析方法或技术规范涉及的提取剂多达7种(pH=5.8盐酸溶液、0.1mol/L盐酸溶液、0.43±0.02mol/L硝酸溶液、0.11mol/L乙酸溶液、1mol/L硝酸铵溶液、0.005mol/L DTPA浸提剂、0.01mol/L氯化钙溶液),不同学者对不同提取剂有不同的研究结论,对于通用提取剂的系统研究未见报道。本文选择代表性农耕土壤样品,采用以上7种提取剂提取其中8种重金属元素(镉镍铜锌铬铅砷汞),电感耦合等离子体质谱法(ICP-MS)测定镉铬铜铅锌镍含量,原子荧光光谱法(AFS)测定砷和汞含量,对比了7种提取剂对各重金属元素的提取率,并研究了土壤酸碱性质对重金属元素提取率的影响。结果表明：(1)稀酸溶液对土壤重金属元素的提取率较高,且与土壤的酸碱性无关;(2) 1mol/L硝酸铵溶液虽然对镉的提取能力表征了镉在酸性土壤中的活性远大于碱性土壤的特点,但其对碱性土壤中铅的提取率...     

AB-DTPA通用提取剂法测定土壤地球化学样品元素有效性的可行性研究

在多目标地球化学调查基础上进行的生态地球化学评价工作已陆续在各省展开,这项工作需要首先解决的问题是大批量土壤样品、多元素指标有效态的分析测试。常规的元素有效态分析方法针对性强,但操作繁琐,并且目前仅有个别重金属元素有国家标准的有效态分析方法,因此需要选择一种可以对不同类型土壤、不同元素指标通用的有效态提取剂。在已有研究工作基础上,为了进一步探讨用AB-DTPA提取量替代常规分析方法测定结果的可行性,对不同酸碱性土壤进行了试验研究,结果证明以AB-DTPA提取的元素有效量结果重现性好,且与标准方法分析结果之间以及与农作物籽实含量之间都有很好的相关性(除As),初步说明用AB-DTPA作为不同类型土壤的多元素有效态通用提取剂,可以满足多目标地球化学调查和生态地球化学评价研究的需要。     

AB-DTPA提取法在重金属污染土壤修复模拟试验中的应用可行性

将碳酸氢铵-二乙三胺五乙酸(AB-DTPA)提取重金属生物有效态的方法应用于重金属污染土壤修复的模拟试验中,该土壤的污染元素主要是铜、锌和镉,试验所用修复材料是钠化膨润土。研究表明,AB-DTPA提取法具有很好的稳定性,而且能准确指示铜、锌、镉元素在土壤中的有效态含量,同时AB-DTPA对土壤中铜、锌、镉元素的提取率也适用于模拟试验中修复效果的平行对比。AB-DTPA提取法在重金属污染土壤修复模拟试验中的应用是可行的。     

盐酸提取条件下土壤重金属元素的释放特征

采用河南省黄淮海平原典型农田土壤样品,开展了不同浓度盐酸(1,0.1,0.001,0.000 01 mol/L)和振荡时间(2,24,48,96 h)的土壤重金属元素提取实验,分析了盐酸浓度和振荡时间等对土壤重金属元素释放的影响,探讨了不同提取条件下土壤重金属元素的释放效果及其影响因素。研究表明:土壤Cr、Cu、Ni、Zn和Pb采用1 mol/L盐酸振荡48 h时萃取率显著高于其他处理,其中Pb的萃取率最高,土壤As采用1 mol/L盐酸振荡2 h时萃取率最高,碱性土壤Cd采用0.1 mol/L盐酸振荡2 h时萃取率最高。在此基础上,根据1 mol/L盐酸振荡2 h的提取结果,采用统计分析方法分析了土壤重金属元素全量、理化性质以及土壤类型对土壤重金属元素释放的影响,结果表明:土壤Cr全量越高,Cr萃取率越高;土壤干密度越大,Pb萃取率越高;土壤pH值越低,土壤Ni萃取率越高,而土壤Pb正好相反;土壤有机质对重金属元素萃取率无统计上的显著影响;Cu、As、Pb在碱性土壤(黄河流域)萃取率相对较高,而Cr、Ni、Zn在酸性土壤(淮河流域)萃取率相对较高;土壤类型对重金属元素释放的影响表现为砂姜黑土Cr,水稻土Cu、Ni、Zn,潮土As、Pb的萃取率相对较高。     

中性盐溶液提取土壤中金属活动态及其对隐伏矿的指示: 以甲基卡稀有金属矿区为例

以甲基卡稀有金属矿区X03 号超大型稀有金属矿体以及804 号脉等两个典型隐伏矿体作为研究对象,采用硫酸钾 （K2SO4） 中性盐溶液作为金属活动态提取剂,进行了土壤中Li 元素活动态的提取试验。结果表明,Li 元素活动态的地球化 学异常很好地对应了隐伏矿体的位置,能够有效地指示隐伏矿体的存在。在甲基卡土壤中目标元素内生组分/外生组分比值 很高的稀有金属矿区,采用中性盐溶液这类弱提取剂,才能最大程度地排除土壤内生组分的干扰,有效识别隐伏矿体。通 过提取条件优化实验,在甲基卡地区采用硫酸钾（K2SO4） 溶液提取土壤中Li 元素活动态的最佳技术参数为：提取剂浓度 0.2 mol/L,粒级200 目,pH为6.82,固液比为1:5,提取时间为48 h。     

土壤重金属生物有效性研究进展

土壤重金属污染具有巨大环境风险。笔者围绕土壤重金属元素生物有效性(可给性)概念、元素形态与有效性影响因素、有效态(可给态)实验技术,综述了国内外研究现状。土壤金属元素形态和生物有效性取决于其地球化学行为、元素成因来源、土壤理化条件(p H值、有机质、粘土矿物与化学活性矿物、土壤粒级组成等)以及植物根际效应等。选择性单步提取和连续提取是检测土壤元素形态、有效态的有效和可行方法。针对手—口是土壤铅等污染物在儿童群体暴露的重要途径,发展了生物可给态体外试验方法。土壤污染物生物有效性和可给性已成为土壤污染风险评价的重要指标参数,实验成果也为土壤污染修复提供了重要依据。     

万山汞矿区稻田土壤生物有效性汞的提取方法

土壤中汞的生物有效性是决定土壤汞污染和农作物汞富集的重要指标。然而,采用不同提取方法所得到的有效态汞含量存在差异。为探索适用于汞矿区稻田土壤生物有效性汞的提取方法,研究对比了4种提取剂(超纯水、0.005 mol/L DTPA混合液、0.1 mol/L CaCl2和0.1 mol/L HCl)对万山汞矿区内两条典型河流沿岸稻田土壤生物有效态汞的测定结果。结果表明,万山汞矿区稻田土壤总汞含量均值为(12.7±0.42)mg/kg,超标率为93%。土壤生物有效态汞含量较低,4种试剂提取的有效态汞占总汞比例依次为0.005%、0.018%、0.003%和0.036%;超纯水提取的土壤生物有效态汞与稻田土壤、水稻根和茎的总汞浓度显著相关,表明超纯水提取方法最适用于测定万山汞矿区稻田土壤的生物有效态汞。本研究可为评估土壤汞污染风险提供技术和数据参考。     

浊点萃取-火焰原子吸收光谱法测定土壤中的有效态钴

重金属的毒性和迁移性不仅取决于总量,而且取决于特殊的化学形态,其中有效态容易被植物吸收,对人体的危害更严重,因此准确测定土壤中的重金属有效态含量非常重要。但土壤中有效态金属的含量通常很低,而且干扰组分多,直接进行仪器分析测定比较困难。本文以0.1 mol/L盐酸为浸提剂,甲基红为螯合剂,Triton X-114为表面活性剂,建立了一种浊点萃取-火焰原子吸收光谱测定土壤中有效态钴的新方法,提高了测定的选择性和灵敏度。在最佳实验条件下,钴的线性范围为0.10~2.00 μg/mL,方法检出限为0.03 μg/mL,方法回收率为94.0%~104.0%,应用于分析0.5 μg/mL钴标准溶液,9次平行测定的相对标准偏差为3.3%。通过测定发现不同地区土壤中有效态钴占钴总量的比例差别很大,土壤中重金属有效态含量更能直观地传递出重金属在土壤中的迁移能力、存在状态以及危害程度等信息。     

重铬酸钾保护氯化钙提取-原子荧光光谱法测定土壤中可提取态汞

为了更好地对土壤中可提取态汞进行测定,针对目前常用的氯化钙提取-原子荧光光谱法测定土壤中可提取态汞的方法存在测定结果偏低和重现性差的问题,对该方法进行优化。研究采用在氯化钙提取液提取可提取态汞的滤清液中加入适量的重铬酸钾作为保护剂,以保护提取液中的汞不被器壁、溶液胶体吸附,从而解决溶液放置一段时间后测定结果偏低和重现性差的问题,同时考察了测定酸度、硼氢化钾浓度、提取温度、提取液浓度、土液比、提取时间和重铬酸钾的加入量对测定结果的影响,并优选出最佳条件：测定酸度为10%(V/V)的盐酸、硼氢化钾的浓度为10 g/L、提取温度为20℃±2℃、提取液浓度为0.01 mol/L、土液比为1∶10、提取时间为60 min、重铬酸钾的加入体积为2.0 mL。试验结果表明,以本试验推荐的最佳条件测定土壤中的可提取态汞,精密度(RSD,n=7)小于5%,相对误差(RE)小于5%,适用于土壤中可提取态汞的测定。     

四种浸提剂对果园与菜地土壤有效硒浸提效果的对比研究

有效硒是评价土壤中硒对植物供给能力的重要指标,我国目前尚无测试有效硒的国家标准方法。浸提剂的选择对于准确测定有效硒的含量至关重要,本文根据浸提的有效硒与硒形态的关联性来确定最优浸提剂种类。实验中选取了碳酸氢钠、磷酸二氢钾、硝酸和盐酸四种浸提剂,对天津果园和菜地的土壤进行有效硒浸提,采用原子荧光光谱法测定各形态硒的含量,并分别对浸提的有效硒与水溶态+离子交换态+碳酸盐结合态硒的最小值、25%处数据值、中位数、75%处数据值和最大值进行比较分析和差异性检验。结果表明:采用碳酸氢钠和磷酸二氢钾提取菜地土壤有效硒的平均含量均约为0.039mg/kg,高于硝酸和盐酸的提取量;采用碳酸氢钠、磷酸二氢钾、硝酸和盐酸提取果园土壤有效硒的含量依次降低。两种土壤中,磷酸二氢钾浸提有效硒的最小值、25%处数据值、中位数、75%处数据值和最大值与水溶态+离子交换态+碳酸盐结合态硒的含量最为接近,而且无显著差异性。研究认为,0.1mol/L磷酸二氢钾适合作为天津果园和菜地土壤有效硒的浸提剂。     

Zinc desorption kinetics in bean (Phaseolus vulgaris L.) rhizosphere in sewage sludge-amended calcareous soils

Desorption of Zinc (Zn) in the rhizosphere soil is the primary factor that affects bioavailability of Zn. To improve predictions of Zn availability in amended soil, it is important that time-dependent desorption behavior of Zn in the rhizosphere soil should be understood. The greenhouse experiment was performed to determine Zn desorption characteristics in the bulk and the bean rhizosphere soils amended with municipal sewage sludge (1 % w/w) using rhizobox. The kinetics of Zn desorption was determined by successive extraction with 10-mM citric acid in a period of 1–504 h at 25 ± 1 °C in the bulk and the rhizosphere soils. Moreover, Zn was extracted using three extractants (DTPA-TEA, AB-DTPA, and Mehlich 3) in the bulk and the rhizosphere soils. The results showed that Zn extracted and Zn desorption rate in the bean rhizosphere soils were significantly (P < 0.01) lower than in the bulk soils. The mean of Zn desorption in the bulk and the rhizosphere soils were 16.47 and 15.50 mg kg^?1, respectively. Desorption kinetics of Zn conformed fairly well to first-order, parabolic diffusion, and power function equations. The results of kinetics study indicated that desorption rate coefficients decreased in the rhizosphere soils compared to the bulk soils. The correlation studies showed that the rate constants in the power function equation were significantly correlated (P < 0.05) with Zn extracted using DTPA-TEA, AB-DTPA and Mehlich 3 in the bean rhizosphere and the bulk soils. The results of this research showed that Zn desorption in citric acid in the bean rhizosphere of amended soils were lower than the bulk of amended soils.     

Copper desorption kinetics in wheat (Triticum aestivum L.) rhizosphere in some sewage sludge amended soils

Rhizosphere has different chemical and biological properties from bulk soils. Information about copper (Cu) desorption characteristics in the rhizosphere soils is limited. The objectives of this study were to determine Cu desorption characteristics and the correlation of its parameters with Cu extracted by DTPA-TEA, AB-DTPA and Mehlich 3 in bulk and rhizosphere amended soils with sewage sludge (10 g of sewage sludge was added to 1 kg soil) under greenhouse conditions in a rhizobox. The kinetics of Cu desorption in the rhizosphere and bulk was determined by successive extraction with DTPA-TEA in a period of 1 to 504 h at 25 ± 1 °C. The results showed that Cu extracted using several chemical extractants in the rhizosphere were significantly (P < 0.05) lower than in the bulk amended soils. In addition, Cu extracted using successive extraction in the rhizosphere were significantly (P < 0.01) lower than in the bulk soils. The best model for describing extraction data for the bulk and rhizosphere soils was the parabolic diffusion equation. Desorption kinetics of Cu conformed fairly well to first order and power function models. The results indicated that Cu diffusion rate in the wheat rhizosphere soils lower than in the bulk soils. Cu desorption rate in parabolic diffusion ranged from 0.326 to 0.580 mg kg^?1 h^?1/2 in the bulk soils, while it ranged from 0.282 to 0.490 mg kg^?1 h^?1/2 in the rhizosphere soils. Significant correlation (P < 0.05) between determine R values of parabolic diffusion and Cu desorption during 504 h with extracted Cu using DTPA-TEA, AB-DTPA and Mehlich 3 were found in the bulk and the rhizosphere soils. The results of this research revealed that Cu desorption characteristics in the wheat rhizosphere soils are quite different from bulk soils amended with sewage sludge.     

土壤腐殖质提取和分组综述

土壤腐殖质的定量提取、分离与纯化是深入研究土壤腐殖质的重要前提。本文详细综述了国内外腐殖质提取和分组的实验手段和研究进展;以国际腐殖质协会提供的标准方法为参考,对比论述了提取剂种类,提取次数、提取剂用量等的选择;对比讨论了两种主要的土壤腐殖质的分组方法。超滤分离和体积排阻色谱是腐殖质物理化学表征研究中的两种新兴技术,笔者认为组合使用两种实验手段对土壤腐殖质进行细致的分离与分组研究有助于深化理解土壤腐殖质的化学性质和分子结构。     

Extraction and distribution of soil organic and inorganic selenium in coal mine environments of Wyoming, USA

 Selenium (Se), an animal toxicant and aquifer contaminant, occurs in coal mine environments of Wyoming. There is a paucity of information on solution-phase Se speciation in mine soils. The objectives of this study were to compare Se extraction efficiencies of various reagents and to characterize SeO^2– ₃ (selenite), SeO^2– ₄ (selenate) and organic Se components in these extracts. Forty coal mine soils were extracted using DI (deionized) water, hot water (0.1% CaCl₂), AB-DTPA, NaOH, and KH₂PO₄. Each solution was analyzed for total dissolved Se, and inorganic and organic Se fractions. Both inorganic and organic Se fractions were detected in the soil extracts. The order of Se (total, inorganic, and organic) extraction efficiency for different reagents was DI water < hot water < AB-DTPA < NaOH < KH₂PO₄. The inorganic–organic Se ratios in DI water, hot water, AB-DTPA, NaOH, and KH₂PO₄ extracts were 60 : 40, 26 : 74, 61 : 39, 87 : 13, and 52 : 48, respectively, indicating predominance of inorganic Se in all but the hot water extract. Selenite was the dominant inorganic species in AB-DTPA and KH₂PO₄ extracts, while SeO^2– ₄ was the major Se species in the DI water, hot water, and NaOH extracts. Significant correlations (P<0.01) were observed among extractable inorganic Se [NaOH and KH₂PO₄ (r=0.95); hot water and AB-DTPA (r=0.89)], total soluble Se [DI water with hot water (r=0.98) and AB-DTPA (r=0.95)], and Se species [SeO^2– ₃ in AB-DTPA with SeO^2– ₄ in NaOH (r=0.94) and SeO^2– ₃ in KH₂PO₄ (r=0.88)]. These correlations are indicative of Se extraction efficiency, thermodynamically predicted chemical transformations (such as oxidation of SeO^2– ₃ to SeO^2– ₄), and probable interconversions between the organic and inorganic Se fractions (r=0.70 in KH₂PO₄ extracts); as a whole the correlations can be used as statistical validations of possible geochemical processes. Received: 21 August 1995 · Accepted: 16 October 1995     

Comparison of extractants and applicability of MALDI–TOF-MS in the analysis of soil proteinaceous material from different types of soil

In order to understand better the chemistry of soil proteinaceous material, there is a need for an effective extraction and purification method for different types of soil. The aim of this study was to test the effectiveness of different extractants and of phenol extraction for the extraction and purification of native soil proteinaceous material and the added protein (bovine serum albumin, BSA) from different types of soil, and to test the applicability of matrix-assisted laser desorption/ionization–time-of-flight-mass spectrometry (MALDI–TOF-MS) for the analysis of soil proteinaceous material. Extraction of three types of boreal soil was carried out with water or different buffers. Purification of the extracted proteinaceous material was carried out with phenol extraction, the concentration being measured using Bradford’s method, and the analysis performed with MALDI–TOF-MS. The concentration of extracted proteinaceous material was dependent on the soil and the extractant, and the amount of N in the extracted material was ca. 3–90% of soil total N, being highest for sandy soil and lowest for highly organic forest floor and fine-textured clay soil. Non-purified extracts contained high amounts of non-proteinaceous (e.g. humic) material, especially the highly organic soil; this material may cause artifacts with Bradford’s method. The recovery of BSA was dependent on soil and extractant, suggesting a different sorption mechanism for different types of soil. MALDI–TOF-MS spectra suggested that the molecular weight of the extracted compounds was mainly <10 kDa, but compounds in the range ca. 15–50 kDa were also detected. However, individual compounds could not be identified.     

Buffering from secondary minerals as a migration limiting factor in lead polluted soils at historical smelting sites

Examination of calcareous slags from several historical smelting sites has indicated that the specific soil environment, in particular the soil pH, may have a very significant effect on the rate of weathering and metal release. A series of acid titration experiments were used to investigate whether the weathering of the calcareous slags could be increasing the buffering effect of the soils through accumulating CaCO₃ in the slag-rich horizons. Such a buffering mechanism would maintain high pH levels and so limit the migration of Pb through the soil profile. Three sites were chosen; one with high levels of Ca in the soil, one with relatively low Ca levels and one with intermediate Ca levels. Analysis of metal concentrations was determined using ICP-AES. The results support the hypothesis that, while the soil pH remains between 8 and 5, the CaCO₃ provides an effective buffer against the mobilisation of Pb. Between soil pH 5 and 4 it is suggested that both CaCO₃ and PbCO₃ participate in the buffering reaction, which slows down with a further drop in pH. However, this reaction ultimately releases Pb into the soil solution, although at a much slower rate than would be the case in an unbuffered soil. An important implication of these findings is that migration rates of metals in soils cannot be assumed to be constant over time, if such buffering mechanisms are operational.     

Element fractionation by sequential extraction in a soil with high carbonate content

The influence of carbonate and other buffering substances in soils on the results of a 3-step sequential extraction procedure (BCR) used for metal fractionation was investigated. Deviating from the original extraction scheme, where the extracts are analysed only for a limited number of metals, almost all elements in the soils were quantified by X-ray fluorescence spectroscopy, in the initial samples as well as in the residues of all extraction steps. Additionally, the mineral contents were determined by X-ray diffractometry. Using this methodology, it was possible to correlate changes in soil composition caused by the extraction procedure with the release of elements. Furthermore, the pH values of all extracts were monitored, and certain extraction steps were repeated until no significant pH-rise occurred. A soil with high dolomite content (27%) and a carbonate free soil were extracted. Applying the original BCR-sequence to the calcareous soil, carbonate was found in the residues of the first two steps and extract pH-values rose by around two units in the first and second step, caused mainly by carbonate dissolution. This led to wrong assignment of the carbonate elements Ca, Mg, Sr, Ba, and also to decreased desorption and increased re-adsorption of ions in those steps. After repetition of the acetic acid step until extract pH remained low, the carbonate was completely destroyed and the distributions of the elements Ca, Mg, Sr, Ba as well as those of Co, Ni, Cu, Zn and Pb were found to be quite different to those determined in the original extraction. Furthermore, it could be shown that the effectiveness of the reduction process in step two was reduced by increasing pH: Fe oxides were not significantly attacked by the repeated acetic acid treatments, but a 10-fold amount of Fe was mobilized by hydroxylamine hydrochloride after complete carbonate destruction. On the other hand, only small amounts of Fe were released anyway. Even repeated reduction steps did not destroy the amorphous Fe oxides completely, showing that 0.1 mol L⁻¹ hydroxylamine hydrochloride was not strong enough to attack these oxides effectively.The extraction sequences were carried out not only on the soil samples, but also on their coarse and fine fractions (> or <2 μm). The fine fraction of the calcareous soil contained only 10% dolomite, but was enriched in organic matter and clay minerals, which also resulted in increased extract pH-values during the sequential extraction. Hence, the effects on ion release in the fine fraction were similar to those of the whole soil. Since the destruction of the organic matter was incomplete after regular oxidation, the H₂O₂-treatment of the fine fraction had to be repeated. The addition of the extractable amounts of the two fractions showed good agreement to the results obtained for extraction of the whole soils. Likewise the pH-values of the carbonate-free soil extracts did not increase significantly, therefore it was concluded that repetitions of extraction steps for this soil were not necessary.Extract-pHs should always be controlled so that extraction conditions are comparable; to be able to use the BCR extraction scheme or similar ones for carbonate- and organic-rich samples this is mandatory. Single extraction steps should be repeated if pH rises too much; additionally the oxidizing step should be performed more than twice for samples rich in organic substances, depending upon the violence of the reaction with H₂O₂. If these precautions are neglected the validity of the extraction data is likely to be questionable.