Mercury mobility and bioavailability in soil from contaminated area

The mobility and bioavailability of mercury in the soil from the area near a plant using elemental mercury for manufacturing thermometers, areometers, glass energy switches and other articles made of technical glass has been evaluated. Mercury has been determined by sequential extraction method and with additional thermo desorption stage to determine elemental mercury. The procedure of sequential extraction involves five subsequent stages performed with the solutions of chloroform, deionized water, 0.5 M HCl, 0.2 M NaOH and aqua regia. The mean concentration of total mercury in soil was 147 ± 107 μg g⁻¹ dry mass (range 62–393), and the fractionation revealed that mercury was mainly bound to sulfides 56 ± 8% (range 45–66), one of the most biounavailable and immobile species of mercury in the environment. The fractions that brought lower contribution to the total mercury content were semi-mobile humic matter 22 ± 9% (range 11–34) and elemental mercury 17 ± 5% (range 8–23). The contributions brought by the highly mobile and toxic organomercury compounds were still lower 2.3 ± 2.7% (range 0.01–6.5). The lowest contributions brought the acid-soluble mercury 1.5 ± 1.3% (range 0.1–3.5) and water-soluble mercury 1.0 ± 0.3% (range 0.6–1.7). The surface layer of soil (0–20 cm) was characterized by higher mercury concentrations than that of the subsurface soil (60–80 cm), but the fractional contributions were comparable. The comparison of mercury fractionation results obtained in this study for highly polluted soils with results of fractionation of uncontaminated or moderately contaminated samples of soil and sediments had not shown significant statistical differences; however, in the last samples elemental mercury is usually present at very low concentrations. On the basis of obtained correlation coefficients it seems that elemental mercury soils from “Areometer” plant are contaminated; the main transformation is its vaporization to atmosphere and oxidation to divalent mercury, probably mainly mediated by organic matter, and next bound to humic matter and sulfides.     

Speciation Study of Cr in a Geochemical Reference Material Sediment Series Using Sequential Extraction and XANES Spectroscopy

Speciation of Cr in geochemical reference materials was characterised by sequential extraction and X‐ray absorption near‐edge structure (XANES) spectroscopy to identify Cr(III) resulting from the reduction of pollutant Cr(VI). Sequential extraction suggested that the amount of Cr associated with an acetic acid soluble fraction was low; Cr associated with a reducible phase and an oxidisable phase was extracted at 5–10% of the total Cr concentration, and the residual phase was found to be the dominant Cr‐containing fraction. Cr speciation in soil artificially doped with Cr(VI) and sediment samples collected from highly populated and industrialised areas was different from that in naturally occurring materials. Substantial Cr was extracted as a reducible phase (15–30%) and an oxidisable phase (30–60%) for these samples. Through subsequent XANES spectroscopy analysis, the reducible phase was explained by Cr bound to Fe hydroxide, while the oxidisable phase was a mixture of Cr bound to humic substances and Cr hydroxides. That is, Cr(VI) present as a contaminant in sediments and soils was reduced to Cr(III), which then bound to Fe hydroxide and humic substances, precipitating as a hydroxide. Thus, a combination of sequential extraction and XANES spectroscopy allows for effective identification and quantification of the chemical forms of Cr in sediments and soils.     

土壤中汞存在形式的研究

本文运用部分连续萃取不同地球化学相的化学分析方法，对高汞区，人为汞污染区和背景参考区五个采样点土壤样品的七种汞形态进行了分析，研究表明，人为汞污染和地质作用都会造成土壤中汞的富集，但这两类土壤中汞的相态分布有明显的差别。     

Assessment of mercury mobility and bioavailability by fractionation method in sediments from coastal zone inundated by the 26 December 2004 tsunami in Thailand

The 26 December 2004 tsunami covered significant portion of a coastal zone with a blanket of potentially contaminated sediments. In this report are presented results on mercury concentrations in sediments deposited by the tsunami in a coastal zone of Thailand. Since the total mercury concentrations are insufficient to assess mercury mobility and bioavailability in sediment, its fractionation was applied. Sediments were sampled within 50 days after the event and analyzed by sequential extraction method. The procedure of sequential extraction involved five subsequent stages performed with solutions of chloroform, deionized water, 0.5 M HCl, 0.2 M NaOH, and aqua regia. The mean concentration of total mercury in sediments was 119 ± 50 ng g⁻¹ dry mass (range 66–230). The fractionation revealed that mercury is mainly bound to the least bioavailable sulphides 75 ± 6% (range 62–86), organomercury compounds 14 ± 7% (range 4–26), and humic matter 9 ± 7% (range 1–27). The lowest contributions bring fractions of water-soluble mercury 0.8 ± 1.0% (range 0.1–3.6) and acid soluble mercury 0.9 ± 0.5% (range 0.2–2.1). Although, the total mercury content is similar in a reference sample and in the tsunami sediments, the highly toxic organomercury fraction contribution is higher in the latter. The results were compared with chemical and sedimentological properties of the sediments but no significant correlations were obtained between them.     

广州市黄埔港区土壤中汞的形态分析及分布特征

采用化学浸提技术对广州市黄埔港区土壤中的汞进行形态分析,通过实验确定了可交换态汞(包括水溶性汞)、盐酸溶汞、元素汞、腐殖酸结合态汞、有机质结合态汞、硫化汞、残渣态汞的浸提条件,探讨了各种形态汞在表层及总量在垂直方向上的分布特征。分析结果表明,广州市黄埔港区土壤中汞以比较稳定的形态存在,活动态约占6%。总汞含量随深度增加而降低,总汞在垂直方向中的含量差异在一定程度上反映出汞受人为污染的影响情况。     

渭北石炭二叠系煤中汞的含量及分布特征

采用原子荧光和化学分析方法,研究了渭北部分矿区石炭二叠系煤中汞的含量及汞在煤中的分布特征。结果表明,渭北石炭二叠系煤中汞含量较高,高于地壳中汞的平均含量(0.08×10-6)及已经报导的煤和石油中汞的含量(0.001×10-6~0.03×10-6)。煤中汞主要以HgS的形式存在,与煤中无机硫成正比关系。同时论述了煤中汞含量与灰分等的关系。      

Effects of long-term irrigation with treated wastewater. Part II: Role of organic carbon on Cu,Pb and Cr behaviour

The long-term impact of irrigation on a Mediterranean sandy soil irrigated with treated wastewater (TWW) since 1980 was evaluated. The main soil properties (CEC, pH, size distribution, exchangeable cations and chloride, hydraulic conductivity) as well as the organic matter and Cu, Cr and Pb speciation in an irrigated soil and a non-irrigated control soil at various soil depths were monitored and compared during a 2 year experiment. In this second part, we focused on Cu, Cr and Pb behaviour in relation with soil organic carbon (SOC). Soil samples were collected every 3 months during 2 years at the depths 0–20, 20–40 and 40–60 cm and were analysed for exchangeable and total metals, organic carbon content, metal sequential extraction and humic substances – Humic Acids (HA), Fulvic Acids (FA) and Non-Humified Fraction (NHF). Long-term irrigation with a domestic treated wastewater (TWW) may be considered safe with regard to trace metal accumulation in soil. Irrigation lowered the HA and NHF fractions of SOC and made the FA fraction more mobile. Cu bound preferentially to the SOC fraction, Cr was found mainly in the reducible fraction and Pb was bound to all fractions indiscriminately. Cu exhibited a high affinity for the HA fraction, while Pb and Cr had a high affinity for the FA fraction, which indicates a greater mobility of the organically-bound Pb and Cr than of the organically-bound Cu. Evaluation of the potential metal mobility has to take into account not only the usual speciation between labile, reducible and oxidisable fractions, but also the nature of the SOC responsible for the oxidisable fraction.     

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。     

The Distrbution of Various Mercury Species in Soil

According to the mercury species with different solubilities,the analytical procedure involving sequential chemical extraction has been applied to partitioning the mercury species in soils into seven fractions.Soil samples collected from five localities in different areas (the high-mercury ares.the man-made mercury-polluted area and the reference area)were an alyzed for the seven mercury species.It is found that high mercury contents of soils can be attributed to both man-made pollution and geological processes,but the two kinds of solis show obvious differences in the distribution of their mercury species.     

卧龙湖煤矿岩浆蚀变煤层中汞的分布与赋存特征

系统采集淮北卧龙湖煤矿岩浆蚀变煤层中岩浆岩、煤及顶底板岩石样品,测试分析了样品中汞、灰分、挥发分、水 分以及各形态硫的含量,探讨了岩浆蚀变煤层中汞的分布与赋存特征。结果表明：（1） 岩浆侵入导致煤中灰分升高,挥发 分降低,煤中硫主要以黄铁矿硫和有机硫存在;（2） 岩浆侵入导致煤中汞的富集,卧龙湖煤矿岩浆蚀变煤层中汞的平均含 量高达0.23×10-6,是华北石炭-二叠纪煤、中国煤以及美国煤中汞的平均含量的1.4 倍,1.2 倍和1.3 倍;（3） 煤中汞的含量 随离岩浆侵入体距离增大有逐渐降低的趋势,但在煤岩接触带附近,汞在岩浆侵入体上方和下方的煤中呈现不同的分布特 征;（4） 煤中的汞主要以无机结合态的形式存在,且大部分赋存在煤中的黄铁矿中,同时亦存在与有机硫结合的汞。岩浆 热液对煤层的侵入,导致煤质以及煤中汞的含量和赋存方式发生了显著变化。     

煤中汞的赋存状态研究

对采自贵州省二叠系龙潭组煤层的 32个煤样进行了连续化学浸取实验研究 ,并利用重液分离方法 ,将另外 8个采自同一地区的煤样按密度从 1.4至 2 .8× 10 3kg m3分成 10个密度段。通过测定化学浸取过程主要矿物组成的变化及汞的浸取量 ,对比研究各密度段分样中矿物组成和有机质含量与汞含量间关系 ,得出煤中汞主要赋存于黄铁矿中 ,煤样黄铁矿中汞的分布是不均匀的。研究表明 ,当煤炭被开采堆放到地表后 ,煤中大部分汞可以被酸性矿井水带入环境中 ,这一环境污染问题应予以重视。在洗煤过程中 ,平均 5 1%的汞可以被脱除。因此 ,提高原煤入洗率可以有效地降低煤中汞的含量     

福州市土壤硒形态分析及其迁移富集规律

通过对福州市土壤和岩石中Se形态的分析研究结果表明,表层土壤中强有机态Se、腐殖酸结合态Se约占全量的57.44%,残渣态Se占28.77%,残渣态Se是土壤Se的重要储备库源,三者均与表层土壤Se全量呈极显著的线性正相关关系。表层土壤Se含量随土壤酸性的加强而增加,随有机质含量加大而增加的幅度较小;深层土壤Se受pH值的影响不明显,但受有机质含量的影响很大,两者线性回归关系达到极显著水平;不同岩石类型对土壤含Se量没有明显的影响规律,各介质中Se含量表层土壤>深层土壤>岩石,并且差幅巨大。这些研究结果揭示了在岩石风化、土壤发育(熟化)过程中有机质和黏土矿物吸附Se,致使Se较其他元素流失比例少,从而造成从深部到表层土壤Se相对富集的结果。同时,提出了利用全量来推导Se形态值的方法,建立了土壤Se全量与形态间的关系模型以及决定土壤有效态Se的公式,建议在评价土壤Se时只要考虑有机结合态Se、残渣态Se、离子交换态Se和全量Se。     

Evaluation of uranium and arsenic retention by soil from a low level radioactive waste management site using sequential extraction

The European Communities Bureau of Reference (BCR) and Chunguo sequential extraction procedures were employed to evaluate the retention of U and As by a soil contaminated with low level radioactive waste. Modifications were made to both procedures to optimize the measurement of soil and extractant samples using epithermal neutron activation analysis. Based on the BCR procedure, approximately 20% of the U appeared to be bound to the carbonate fraction, 10% to the mineral oxide fraction and 20% to the organic fraction. In the case of As, the majority was strongly bound in the residue fraction. The results obtained with the Chunguo procedure supported these conclusions to some extent, in that the majority of the U and As was found to be strongly bound to the soil in a manner consistent with its presence in the residue fraction.     

Mercury and mercury compounds in surface air, soil gas, soils and rocks

Secondary mercury dispersion haloes were detected and defined above sulphide mineralization by in-situ mercury in soil gas measurements. The meteorological factors controlling the concentration of mercury in soil gas were investigated by long-term experiments. Different mercury compounds in soils and rocks have been determined by a thermal destruction technique. In areas with sulphide mineralization, adsorbed mercury, HgCl₂, HgS, HgSO₄ and organically fixed mercury are the most important mercury compounds. The concentrations, transport and secondary formation of mercury and its compounds is controlled by: (1) the content of organic matter, Fe-oxides/hydroxides and clay minerals of the soils; and (2) the composition of the underlying rocks.The occurrence of mercury-sulphur compounds indicates the topographic influence on down-slope dispersion and the direction of inclination of the ore body. HgS and HgSO₄ are the dominant mercury compounds in the ore; in the bedrock, mercury occurs mainly as adsorbed mercury.     

Characterisation of brown coal humic acids and modified humic acids using pyrolysis gcms and other techniques

It has been proposed that Victorian brown coal can be considered as a two-component structure — a lignocellulosic “host”, containing various amounts of weakly bound or entrapped “guest” material together with very small amounts of inorganic and/or mineral matter. The latter predominantly consists of wax esters and/or terpenoid material. In this paper we describe attempts to gain structural information regarding the more complex, “host” component of the coal. Our initial model compound has been humic acid that can be readily obtained from the coal by alkaline extraction. It has been found that “pure” humic acid, free from material associated with the “guest” components of the coal, can be obtained by a highly selective, low-yielding alkaline extraction. This humic acid has been studied by nmr spectroscopy and pyrolysis gas chromatography-mass spectroscopy (py-gc/ms). The products arising from py-gc/ms have been compared with those obtained from similar pyrolysis of whole coals. Alkylation of humic acids using alkyl halides in the presence of base has been successfully carried out and reactivity of the resulting materials compared with those of the parent coal and humic acid.     

北京市土壤Hg污染的区域生态地球化学评价

城市土壤Hg异常/污染是中国普遍存在的重大生态环境问题。文章对北京市近1000km2范围内的地表土壤、壤中气、大气干湿沉降、大气颗粒物、大气中的Hg含量水平和空间分布模式进行了系统研究,查明北京地表土壤Hg平均含量为0.41mg/kg,大气干湿沉降物中的Hg平均含量为0.194mg/kg,壤中气Hg的平均含量为559.65ng/m3,大气颗粒物PM10和PM2.5中的Hg含量分别为0.59和0.67ng/m3,大气中的Hg平均含量为3.13ng/m3。北京市自2000年起实现了由燃煤转变为燃气的减排措施,导致干湿沉降物中的Hg沉降通量显著减少,2006年大气干湿沉降物中Hg的沉降通量1.837mg·m-2·a-1,北京市城区(近1000km2)Hg全年沉降为1837kg,空气中总Hg浓度由1998年的8.3~24.7ng/m3下降到2006年的3.13ng/m3,大气颗粒物中Hg含量由2003年的1.18ng/m3下降到2006年的0.59ng/m3(PM10)和0.67ng/m3(PM2.5),表明北京市煤改气减排措施的实施显著改善了大气环境质量。通过对土壤中Hg的存在形式研究,发现土壤中有硫化物(辰砂)及各种Hg盐(HgCl2)的含Hg矿物,Hg也可以各种吸附方式或壤中气方式存在。研究证实北京壤中气Hg与大气Hg存在显著的相关性(n=131,R=0.267,p<0.01),表明壤中气Hg是大气Hg的重要来源之一。利用2005年地表土壤总Hg与Hg释放速率的线性方程估算,土壤Hg平均释放速率为102.42ng·m-2·h-1,2005年土壤释放进大气的Hg通量为936.70kg。在查明土壤中存在大量辰砂矿物的同时,还分布有大量具有高温熔融特征的金属微球粒和玻璃质微球粒,证明燃煤和冶金烟尘是地表土壤Hg的主要来源。土壤中Hg、S、pH和辰砂颗粒浓度在空间上的高度耦合性表明,碱性条件下,土壤中高含量的S和Hg是辰砂形成的重要原因。按国家土壤环境质量标准,北京市I级土壤Hg环境质量的面积为176km2,Ⅱ级为808km2,Ⅲ级为24km2,超Ⅲ为36km2。Ⅲ级、超Ⅲ级主要分布在二环路以内的中心城区。城南(长安街为界)大气Hg环境质量明显优于城北,在北四、北五环之间的部分地区,大气颗粒Hg的环境质量为Ⅲ级或超Ⅲ级。在地表土壤Hg含量较高的中心城区,居民每天因呼吸摄入的Hg高达364ng,对人体健康构成潜在风险。根据我国"十一五"规划中每年实现10%节能减排的目标,对北京市未来50年土壤Hg含量的时空演变趋势预测,预测2050年北京因干湿沉降带来的Hg输入量为16.03kg,地表土壤释放Hg的输出量为37.36kg,明显大于Hg的输入通量,土壤Hg的环境质量将得到根本改善。预测到2040年Ⅲ级土壤Hg环境质量的区域将完全消失,到2060年以Ⅰ级土壤为主。     

电感耦合等离子体质谱法测定砂岩型铀矿样品中分步提取的铀

本文研究地质样品中铀形态的分析方法及应用技术,以进一步说明铀形态分析在地球化学找矿中的重要作用。该方法参考Tessier流程,将样品中的铀分为可交换离子态、碳酸盐结合态、铁锰氧化物结合态、硫化物及有机物结合态和结晶态,分别提取,提取溶液用高分辨率电感耦合等离子体质谱仪进行测量。设计的形态提取配方具有良好的可选择性和可重复性,经过国家标准物质、国际形态标准物质和人工模拟样品验证,证明形态提取试剂配方适合所定义的形态分析。通过对实际样品(总量铀为635μg/g)验证表明,碳酸盐结合态铀提取结果的可重复性最好(RSD为2.6%),其次为硫化物及有机物结合态铀(RSD为4.0%)、结晶态铀(RSD为6.0%)和铁锰氧化物结合态铀(RSD为6.1%),可交换离子态铀提取结果的可重复性最差(RSD为26%)。碳酸盐结合态铀与结晶态铀之比,可以用于反映地下铀矿的存在概率。     

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.     

Further Information of the Associated Li Deposits in the No.6 Coal Seam at Jungar Coalfield,Inner Mongolia,Northern China

Total 138 coal samples and 14 parting samples were taken from the No. 6 Seam of the Jungar Coalfield, Inner Mongolia. These samples were analysed by optical microscopy, sequential chemical extraction procedure (SCEP), inductively coupled plasma mass spectrometry (ICP-MS), X-ray powder diffraction (XRD), and scanning electron microscope in conjunction with an energy-dispersive X-ray spectrometer (SEM-EDX) analysis. The results indicate that the Li contents have reached the industrial grade of the coal associated Li deposit, and the total Li reserves have reached 2406600 tons, that is, 5157000 tons Li2O in the No. 6 seam in the Jungar Coalfield. The sequential chemical extraction procedure results suggest that the Li concentration is mainly related to inorganic matter. The minerals in the coals consist of kaolinite, boehmite, chlorite-group mineral, quartz, calcite, pyrite, siderite and amorphous clay material. Some Li could be absorbed by clay minerals in the Li-bearing coal seam. The chlorite phase?could be?most likely the host for a part of Li. The Yinshan Oldland should be the most possible source of Li of the coal.     

淮南采煤沉陷区土壤中汞的时空分布特征

以淮南采煤沉陷区土壤为研究对象,测试分析了样品中汞的含量,结合土壤pH值、有机质含量特征,探讨了采煤沉陷区土壤中汞的时空分布特征。结果表明:与未沉陷区土壤相比,沉陷区土壤有机质破坏严重,最高下降了46%;采煤沉陷区土壤中汞的含量为0.013~0.050 mg/kg,平均值为0.027 mg/kg,69.7%的采样点超过了淮南市土壤背景值;沉陷8 a后土壤汞含量最高,为0.033 mg/kg,是未沉陷土壤汞含量的1.74倍,且随着沉陷时间的增加,土壤中汞存在富集趋势;水稻土壤汞富集能力最高,高于玉米和大豆土壤;在垂直剖面上,汞含量由表层向下依次降低;且汞与pH值表现出显著负相关,有机质与汞显著正相关。