烟煤和无烟煤中碘的赋存形态及其环境效应分析

采用逐级化学提取和电感耦合等离子体质谱(ICP-MS)研究烟煤和无烟煤中碘的赋存形态。结果表明,烟煤和无烟煤中各种形态的碘含量由高到低依次都是有机态、铁锰氧化物结合态、水溶态、残留态、离子交换态和碳酸盐结合态。烟煤和无烟煤中有机结合态碘平均含量分别为47.4%±3.28%和43.3%±2.42%,Fe-Mn氧化物结合态碘分别为36.8%±3.70%和34.6%±4.77%,水溶态和离子交换态碘平均含量之和分别为10.3%±3.00%和14.3%±3.37%,碘的平均潜在淋失率分别10.9%和16.0%,平均潜在可淋失浓度分别为0.9μg/g和1.2μg/g。这说明无烟煤中生物有效态碘含量高于烟煤,在表生条件下烟煤和无烟煤中淋出的碘都能导致地表水中碘的浓度升高;无烟煤中碘的有利环境效应大于烟煤,而不良环境效应小于烟煤。     

延安市污水处理厂污泥中6种重金属元素的形态分析

采用Tessier连续提取法对延安市污水处理厂污泥中的Zn、Cu、Cr、Cd、Pb和Mn六种重金属元素进行形态提取,并用电感耦合等离子体发射光谱(ICP-AES)法对其中各元素的总量及其形态进行测定。结果表明： Pb、Cd多以可交换态、碳酸盐结合态存在,分别占总量的76.84%和78.59%, 对生物具有潜在有效性。Zn、Cu、Cr多以稳定的硫化物及有机结合态和残渣态存在,不易迁移到环境中去。     

污水厂污泥堆肥后重金属形态变化分析

采用高温好氧静态强制通风堆肥工艺,研究了污水厂污泥与稻草、锯末、粉煤灰、磷矿粉、石灰按不同比例混合堆肥前后重金属在交换态、碳酸盐结合态、铁锰氧化物结合态3种不稳定态和包括有机结合态、残渣态的稳定态含量的变化。结果表明,该试验可以显著降低污泥中交换态Cu、Pb、Zn、Cd和As的含量,提高其它形态的含量。由此可见,堆肥处理可以在一定程度上降低重金属活性并保持养分,从而达到农业利用的目的。     

可溶性有机质对污染土壤中铊迁移行为的影响

目的 为了查明可溶性有机质（DOM）对土壤中污染元素铊赋存形态的影响,方法 采用形态分级提取方法,将土壤中的铊重金属分成酸可交换态、铁锰氧化物结合态、有机质结合态和残留态4组分,并采用Elan 6100型ICP-MS质谱仪测定各组分中铊的质量浓度.结果 DOM可降低酸可交换态的Tl,增加铁锰氧化物结合态和有机质结合态Tl的百分含量,但对残留态Tl的百分含量没有明显影响.因此,DOM可降低铊在土壤中的活动性,从而改变了铊在土壤中的迁移行为.结论 可溶性有机质（DOM）自身的络合（螯合）能力及其吸附特性是改变重金属铊形态分布的主要因素.     

稀土矿开采过程中重金属铅活化过程分析

采用Tessier连续提取法确定矿样中Pb的存在形态和组成。通过土柱实验对稀土矿的开采过程进行模拟,研究稀土矿开采过程中NH_4~+活化重金属Pb的过程。结果表明:Fe-Mn氧化物结合态和可交换态是矿样中Pb最主要的存在形态,约占Pb总量68.75%和23.13%。土柱实验中可交换态的Pb减少0.7358 mg,占浸矿前含量的84.98%。浸出液中的Pb占浸矿前可交换态Pb的5.67%。土柱中碳酸盐结合态Pb和Fe-Mn氧化物结合态Pb含量增加,分别增加0.3224和0.091 mg,占未浸矿前可交换态Pb的37.24%和10.5%。因此,离子型稀土矿开采过程中优先活化可交换态Pb,被活化的可交换态Pb一部分随稀土母液流出矿体,另一部分在形态上转化为其他态。     

无烟煤中碘燃烧释放和转化行为研究

采用逐级化学提取法研究无烟煤及其不同温度燃烧产物中碘的各种赋存状态;以小型管式炉模拟煤燃烧装置,考察了加热温度、加热时间、O_2流量以及通入水蒸气对无烟煤中不同形态碘燃烧释放影响及其机理。结果表明,无烟煤中碘主要以有机结合态、铁锰氧化物结合态和水溶态形式存在。加热温度对碘释放和转化有明显影响,碘释放率随温度升高而增加,500-900℃是碘释放的主要阶段。其中,700℃以前,水溶态、离子交换态和有机结合态碘大部分释放,小部分转化为碳酸盐结合态、铁锰氧化物结合态和残留态碘;铁锰氧化物结合态碘主要在700-900℃释放,部分残留态碘在1 100℃前也可释放。无烟煤中碘释放率随燃烧时间延长和O_2流量增大而增大,水蒸气的参与能明显促进碘的释放。在1 100℃、通入水蒸气、O_2流量120 m L/min、燃烧20 min时,93.8%-95.9%碘主要以HI和I_2释放。     

中草药及其生长土壤中6种重金属元素含量相关性初探

采用电感耦合等离子体原子发射光谱法测定了中草药中重金属元素(铁、锰、铜、锌、镉、铅)的含量,并对中草药的生长环境土壤中重金属元素的化学形态及其分布进行了研究。文中提出了中草药样品用硝酸-过氧化氢-水(5+2+1)混合溶液消解,并叙述了土壤样品中元素的各种形态(水溶态、可溶态、碳酸盐结合态、铁锰氧化物态、有机质结合态)的提取方法和试液。结果表明:所测中草药中重金属元素含量明显低于土壤中元素的含量;土壤中铁、锌、铜主要以有机质结合态存在,锰以铁锰氧化物态为主。几种药材中均含有较高量的铁、锰、锌,土壤中也含有较高量的有效态铁、锰、锌,说明中草药与土壤中重金属之间存在有生物迁移作用。     

土壤样品中砷的形态分析方法研究

对生态地球化学土壤样品,在Tessier修正顺序提取方法(即七步法)的基础上对提取方法、提取时间、提取溶液的处理方法进行优化选择,用超声法提取水溶态、离子交换态、碳酸盐结合态、腐殖酸结合态、铁锰氧化物结合态、强有机质结合态和残渣态七种形态的砷元素,用原子荧光光谱法测定各个形态砷的含量。优化后的方法测得As元素各形态的检出限均小于1.0μg/g,相对标准偏差(RSD)小于10%,准确度高,质量参数均满足生态地球化学土壤样品评价形态分析的需要。     

西北旱田黄土中铅的赋存形态与转化规律研究

采用Tessier连续提取法分析不同条件下旱田黄土中Pb的形态分布与转化规律,通过正交试验确定影响Pb形态转化的主要因素,借助Mul1er地积累指数法初步评价污染状况。结果发现:所用黄土样品中Pb总量为68.85mg·kg-1,低于国家标准《土壤环境质量标准》二级标准。不同形态Pb含量分布为残渣态Fe-Mn氧化态有机结合态碳酸盐结合态可交换态,其中残渣态Pb占Pb总量的64.04%。土壤pH值、含水率、秸秆加入量、老化时间等环境因素能改变Pb的形态分布,但残渣态Pb含量始终最高。pH值是影响土壤Pb赋存形态的最主要因素,Pb的地积累指数Igeo为0.3314,说明采样区土壤人为污染比较严重。     

煤中碘的淋滤行为研究

用不同pH值溶液对煤进行动态淋滤实验,用电感耦合等离子体质谱(ICP-MS)测定不同pH值淋滤液在不同时间段获取的淋出液中碘的浓度,以及煤和淋滤后残留煤的高温热水解溶液中碘的含量。结果表明,淋滤液pH值、淋滤时间、煤中碘的赋存形态及在煤中的赋存部位对碘的淋出有重要影响。淋滤液的酸性越强,煤中碘的淋出越多,pH值为2.0和pH值为4.0溶液对煤中碘的淋出率(η)分别为7.22%和6.20%;但pH值为2.0溶液的淋出液中碘的量小于pH值为4.0溶液的淋出液中碘的量,其百分率(w_x)分别为1.920 0%和5.420 0%。pH 2.0淋滤液,在前30 h内淋出液中碘的平均浓度为10.9 μg/L;而pH值为4.0淋滤液,在前110 h内淋出液中碘的平均浓度为10.6 μg/L;pH值为6.0和pH值为7.5溶液能淋出煤中碘很少。在酸性溶液作用下,首先被淋出的碘是存在煤颗粒表面少量的水溶态和离子交换态碘及大部分碳酸盐态和铁锰氧化物结合态碘,然后煤基质内部的部分水溶态和离子交换态碘及少量的碳酸盐结合态及铁锰氧化物结合态碘等才被淋出。     

The fractionation and determination procedures for the speciation of Pb and Po in soil samples

A method for speciation and determination of ²¹⁰Pb and ²¹⁰Po in soil samples was developed. The speciation was carried out by fractionating the soil samples into five fractions which are water soluble or exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and bound to residue. After mineralisation, 10% solution of each fraction was used to spontaneously deposit polonium on a silver disk at 85-90 °C and pH 1.5, and ²¹⁰Po was measured by α-spectrometry; the remain solution was used to separate lead by anion-exchange resin and purified by precipitation as PbS and PbSO₄, and ²¹⁰Pb was determined by a low background β-counter. The IAEA-327 reference material (soil) was studied for ²¹⁰Pb and ²¹⁰Po speciation. The results show that: (1) the average yields are 88.7 ± 6.4% for ²¹⁰Pb and 93.8 ± 8.2% for ²¹⁰Po; (2) if compared to the total ²¹⁰Pb activity in the sample, ²¹⁰Pb fractions are 0.95% in exchangeable form, 10.6% bound to carbonates, 14.3% bound to Fe-Mn oxides, 7.0% bound to organic matter and 67.2% bound to residue or acid soluble, and the corresponding values for ²¹⁰Po are 0.17%, 0.97%, 21.0%, 0.47% and 77.4%, respectively; and (3) the obtained ²¹⁰Pb concentration is in good agreement with the recommended value given by the IAEA.     

中国不同类型土壤中稀土元素的形态分布特征

采用中子活化分析地中国不同地带土壤中的稀土元素含量分布模型及其赋存形态进行了系统的研究。结果表明，黄棕壤，褐土，淋溶黑钙土及白浆土中稀土元素的分布均为轻稀土富集，Ｅｕ亏损型，砖红壤，红壤为轻稀土富集，Ｃｅ亏损型。     

Determination of Trace Metal Species in the Suspended Matter of Riverine and Estuarine Waters

A sequential extraction technique was used to determine the chemical species of six metals (Fe, Mn, Cu, Zn, Pb, Cd) in suspended matter of the Kaoping and Tsengwen river basins. The samples were taken to cover the fresh and marine characteristics. The precision of the species determination was estimated by the relative difference between the concentration of total metal and the sum concentation of the five species. The accuracy for the measurement of total metal was examined from the recovery of metal spiking. The accuracy of the total determination is better than 94% and the precision of speciation is greater than 90%. Most of the studied metals were found in the Fe-Mn oxides and residual fractions except that Cd, Zn and Cu have significant amounts in the exchangeable, carbonate, and organic matter phases, respectively. Species other than residual fraction are generally considered as potentially available for biota in aquatic systems, and in most cases, metal pollution could be reflected from the variation of fraction distributions.     

Validation of the Tessier scheme for speciation of metals in soil using the Bland and Altman test

The Tessier extraction method was used for speciation of Cu, Pb, Zn, As, Fe and Mn in a large concentration range in contaminated soil with various mineralogical compositions. The results were compared by X-ray fluorescence spectrometry (XRF) as a reference method using the Bland and Altman test. A sum of five fractions (exchangeable, bound to carbonates, Fe-Mn oxides, organic matter and residual forms) was compared with the total content determined on solid matrix by the reference method. A good agreement between the methods in the whole concentration range was found for Cu, Zn, As, and Fe. For Mn and Pb, XRF was found suitable to verify the sequential extraction only for concentrations above 250 mg kg⁻¹. This was a consequence of a poorer reproducibility of Pb extraction using the Tessier scheme due to a great difference in the mineralogical composition and the diversity of the Pb species identified in soil. The poorer result of Mn was attributed to the spectral interference of Fe in XRF. Presented at the 34th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 21–25 May 2007.     

Speciation of vanadium in soil

A method for speciation of vanadium in soil is presented in this work. The sequential extraction analysis procedure of Tessier et al. for heavy metals was used for the vanadium separation. The method consists of sequential leaching of the soil samples to separate five fractions of metals: (1) exchangeable, (2) bound to carbonates, (3) bound to Fe-Mn oxides, (4) bound to organic matter and (5) residual. The leaching solutions of Tessier were used for the vanadium extraction, only for the residual fraction the HClO₄ was replaced with H₂SO₄. The optimum conditions for leaching of vanadium from soil (weight of sample, concentration and volume of extractants, time of extraction) were chosen for each fraction. A sensitive, spectrophotometric method based on the ternary complex V(IV) with Chrome Azurol S and benzyldodecyldimethylammonium bromide (ε=7.1×10⁴ l mol⁻¹ cm⁻¹) was applied for the vanadium determination after separation of V(V) by solvent extraction using mesityl oxide and reduction of V(V) using ascorbic acid. This method was applied for vanadium speciation in soil from two different regions of Poland: Upper Silesia (industrial region) and Podlasie (agricultural region). The content of vanadium in the fractions of Upper Silesia soil was respectively (in 10⁻³%): I, 3.39; III, 4.53; IV, 10.70; V, 8.70 and it was the highest in the organic fraction, indicating input by anthropogenic activities. The content of vanadium in Podlasie soil was clearly lower and it was (in 10⁻³%): I, 2.07; III, 0.92; IV, 0.69; V, 1.23. The concentration of vanadium in fraction 2 of both soils was less than detection limit of applied method. The total content of vanadium in the five soil fractions was in good correlation with the total content of this element in both soils found after HF-H₂SO₄ digestion. Analysis using the ICP-AES method gave comparable results.     

Geochemical variability of copper and iron in Oman Margin sediments

An analysis of the geochemical distribution of selected trace metals among various geochemical phases of the sediments in the Oman Margin was carried out using a sequential extraction technique. The present study showed that most Cu in abyssal sediment is associated with only oxidisable mainly organic and sulphide bound metals with insignificant bound to exchangeable, carbonates, easily/moderately reducible fraction. The preservation of Cu in the sediments indicates the importance of primary production and upwelling in the overlying waters and an organic flux in the sedimentary deposition of open-ocean environments. The early diagenetically formed oxidisable mainly organic and sulphide fraction are not degraded and results in a pronounced association of Cu with organic fraction in the sediments of the Oman continental margin. The strong correlation between Cu, TOC and Fe oxides associated with the oxidisable fraction in one of the core indicates that it is likely to be the presence of sulphides.     

The fate of As, Pb, Cd, Cr and Mn in a coal during pyrolysis

Transformation of As, Pb, Cd, Cr, and Mn in Chinese Datong coal during pyrolysis was studied. Experiments were carried out in a fixed-bed quartz reactor with a heating rate of 20 °C min⁻¹. Effects of the final temperature (300–1000 °C) and atmosphere (N₂ and H₂ at 0.1 MPa) were examined. Chemical form distribution of the elements in the coal and coal-derived chars (obtained at 1000 °C under N₂ and H₂) was investigated. As, Pb, Cr, Cd, and Mn in the coal and the chars were classified into five chemical forms (ion exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter, and in the residue) by a sequential dissolution method. Results show that As, Pb, and Cd are more volatile and tend to enrich in the volatile phase in the pyrolysis. Cr and Mn are relative non-volatile and tend to enrich in the solid phase. H₂ atmosphere promotes the release of the elements. The elements in all the five chemical forms undergo transformation in pyrolysis, and As, Pb, Cr and Cd show similar behavior.     

连续萃取法研究海湾养殖区沉积物中重金属形态

以连续萃取法研究海湾养殖区沉积物中重金属(Cd, Cu, Pb, Zn)的形态,将重金属分离为酸溶态、还原态、有机质结合态、硫化物结合态和残渣态.分别采用基体匹配法和内标法消除高盐基体对电感耦合等离子体光谱法(ICP-OES)和质谱法(ICP-MS)分析结果的影响.对海洋沉积物标准物质分析结果表明,样品稀释后测定值与标准值一致.比较了本连续萃取法和BCR法对沉积物样品中重金属形态的提取结果,并考察了萃取剂的选择性.实验表明,本方法可用于有机质污染和富营养化环境沉积物中重金属形态分析,特别是有机质结合态和硫化物结合态的分析.     

Speciation of heavy metals in sediments of the lagoon of Venice collected in the industrial area

In this study a procedure of sequential extraction of metals from sediments was applied to samples from the lagoon of Venice. Compared to the measurement of total concentrations, the knowledge of metal partitioning among sediment phases can help in estimating the risk posed by metal polluted sediments and give information on contamination sources and on the factors that influence metal enrichment in sediments. The results permitted to estimate for each metal the percentage of the total content that could be potentially remobilized from sediments, owing to changes in environmental conditions. The immediately available fraction represented in general a low proportion of the total content. An important proportion of most metals (except for Zn, Cd and Cu) was associated to residual phases and therefore was not expected to be released under the normal environmental conditions. The large amounts of metals bound to Fe-Mn oxides/hydroxides confirmed the strong scavenging efficiency of this phase. The carbonate phase was the preferential associative form for Pb, Cd and Zn, whereas Cu was bound in prevalence to the organic matter/sulphide phase.