气相色谱和薄层色谱法在形态分析中的应用

评述了气相色谱和薄层色谱法用于氯、溴、碘、硫、硒、碲、铬、氮、磷、砷、钒、碳、锡、铅、铁和汞１６种元素的不同形态分析的进展。这些形态包括不同价态、有机态、无机态、阳离子和阴离子态等。由于气相色谱和薄层色谱法都具有分离和检测两种功能结合的特点，因此它们是用于元素形态分析的有效和方便的方法。引用１９８０～１９９４年文献９２篇     

一种新的流动注射在线共沉淀技术的研究及应用

建立了应用流动注射在线共沉淀分离富集火焰原子吸收法测定天然水样中痕量铬的价态分析方法。利用铬（Ⅲ）在碱性条件下与氢氧化镧形成共沉淀而与共存离子分离并得到富集，沉淀不需过滤，直接用稀盐酸从编织反应器（ＫＲ）中溶解并洗脱下来，用原子吸收测定。本体系的浓集倍率２２，检出限（３σ）０．８μｇ／Ｌ，相对标准偏差（ｎ＝１１）２．７２％，用水标样考察，分析结果与推荐值相符。该方法成功地用于天然水中铬的快速测定。     

Distribution and Elimination of Lead Species in Soils Related to GAP of Chinese Medicinal Materials of Ligusticum Chuanxiong Hort

In this paper, the sequential extraction procedure was used for the selection of fractions of lead in seven stages corresponding to lead exchangeable, lead bounded to carbonates, to manganese oxides, to organic matters, to amorphous iron, and lead associated to crystallized iron, and to residuals. The vertical distributions of lead species were carried out in the soils related to good agriculture progress (GAP) of Chinese medical materials of Ligusticum chuanxiong Hort in Dujiangyan city and Wenchuan County, Sichuan Province. Based on those researches, it is found that the plant of Glycine Max (L.) Merr. has the character of lead enrichment and sorption, which is not reported in the literature. Using Glycine Max (L.) Merr. alternate planting with Ligusticum chuanxiong Hort is a valuable recommended in order to produce a high quality Chinese medical materials in order to eliminate the barrier on the beyond the lead limit for the import and export of Ligusticum chuanxiong Hort.     

L'archivage des activités humaines par les neiges et glaces polaires : le cas du plomb

The investigation of the occurrence of lead in dated snow and ice from Greenland and Antarctica has played a major role in our understanding of the history of the pollution of the atmosphere of our planet by this metal. Such studies have however proved to be very demanding, mainly because of the extreme purity of polar snow and ice. Reliable measurements can be obtained only if ultra-clean and highly sensitive procedures are used, as pioneered by Clair Patterson. The Greenland data show evidence of large-scale pollution of the atmosphere of the Northern Hemisphere for lead as early as two millennia ago during Greco–Roman times, especially because of mining and smelting activities in southern Spain. It peaked at the end of the 1960s, with lead concentrations in snow about 200 times higher than natural values, before declining during recent times because of the fall in the use of leaded gasoline. Lead pollution in Antarctica was already significant at the end of the 19th century as a consequence of whaling activities, the traffic of coal-powered ships crossing the Cape Horn, and mining activities in South America, South Africa and Australia. After declining because of the opening of the Panama Canal, the great economic depression and World War II, it reached a maximum during the 1980s, with lead concentrations 20 times higher than natural values. Other studies focus on past natural variations of lead in ancient ice dated from the last climatic cycles. To cite this article: C. Boutron et al., C. R. Geoscience 336 (2004).     

Copper Speciation in a Collection of Geochemical Reference Materials Using Sequential Extraction and Evaluation of the Validity Using XANES Spectroscopy

Copper speciation in a collection of Japanese geochemical reference materials (JSO‐1, JLk‐1, JSd‐1, ‐2, ‐3 and ‐4, JMs‐1 and JMs‐2) was achieved by sequential extraction and characterised using X‐ray absorption near‐edge structure spectroscopy. In the first step of the extraction, referred to as the acid fraction, between 1% and 20% total Cu within the reference materials was extracted. Such a result is typically accounted for by absorption of Cu onto clay minerals. However, the presence of Cu sulfate (an oxidation product of chalcopyrite) was observed in some of the stream sediments affected by mining activity (JSd‐2 and JSd‐3) instead. Copper was extracted in the reducible fraction (targeting Fe hydroxide and Mn oxide) (2–49% total Cu). Between 2% and 51% Cu was extracted in the oxidised fraction (targeting sulfides and organic matter). X‐ray absorption near‐edge structure spectroscopy clarified that the reducible fraction consisted of Cu bound to Fe hydroxide, whereas the oxidised fraction was a mixture of Cu bound to humic acid (HA) and Cu sulfide. In the oxidisable fraction, chalcopyrite was the predominant species identified in JSd‐2, and Cu bound to HA was the major species identified in JSO‐1 (a soil sample).     

长江口和浙江近岸海域表层沉积物中颗粒磷的形态分布和影响因素

研究长江口和浙江近岸海域的水团流向、缺氧程度、潮汐作用以及养殖活动对表层沉积物中颗粒磷赋存形式的影响,对东海生态环境的可持续发展有着重要的意义。长江口以北和浙江近岸泥质区各存在一个缺氧中心,杭州湾属于强潮区,而象山港遍布养殖场。2018年8—9月在上述4个海域分别采集表层沉积物,采用SEDEX方法进行了颗粒磷的形态划分和含量测定。研究结果表明：在长江口外北部缺氧区和浙江近岸泥质区的南部缺氧区,由于沉积物-水界面的还原环境可以活化铁结合态磷,使之转变为生物可以直接利用的弱吸附态无机磷,因此表现出沉积物中铁结合态磷的低值和弱吸附态无机磷的高值;前者的缺氧程度高于后者,因此其铁结合态磷的含量相应更低。杭州湾和象山港海域均受潮汐作用影响,两者沉积物中磷的分布比较均匀。象山港表层沉积物中铁结合态磷含量均较低,这可能是因为养殖活动造成的水体缺氧通过潮汐活动扩散到整个港底。象山港废弃养殖场沉积物中的碎屑磷和残余有机磷含量显著低于非养殖区,可能是由于养殖活动累积的生物沉积稀释了陆源输入的碎屑颗粒。     

Formation and stability of mixed Mg/Ca/phytate species in synthetic seawater media: Consequences on ligand speciation

The results of a potentiometric investigation (by ISE-H⁺, glass electrode) on the speciation of phytate ion (Phy¹²⁻) in an ionic medium simulating the major components (Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻ and SO₄²⁻) of natural seawater, at different salinities and t = 25 °C, are reported. The work was particularly aimed at determining the possible formation of mixed Ca²⁺–Mg²⁺–phytate ion pairs, and to establish how including the formation of these mixed species would affect the speciation modeling in seawater media. After testing various speciation models, that considering the formation of the MgCaH₃Phy⁵⁻, MgCaH₄Phy⁴⁻, Mg₂CaH₃Phy³⁻ and Mg₂CaH₄Phy²⁻ species was accepted, and corresponding stability constants were determined at two salinities (S = 5, 10). A discussion is reported both on the choice of the experimental conditions and on the possibility to extend these results to those typical of real seawater. A detailed procedure is also described to demonstrate that the stability of these species is higher than that statistically predicted. As reported in literature, a parameter, namely log X, has been determined in order to quantify this extra stability for the formation of each mixed species at various salinities. For example, at S = 10, log X₁₁₃ = 2.67 and log X₁₁₄ = 1.37 for MgCaH₃Phy⁵⁻ and MgCaH₄Phy⁴⁻ (statistical value is log X_stat = 0.60), and log X₂₁₃ = 6.11 and log X₂₁₄ = 2.15 for Mg₂CaH₃Phy³⁻ and Mg₂CaH₄Phy²⁻ (log X_stat = 1.43), respectively. Results obtained also showed that the formation of these species may occur even in conditions of low salinity (i.e. low concentration of alkaline earth cations) and low pH (i.e., more protonated ligand).     

Migration and speciation transformation mechanisms of mercury in undercurrent zones of the Tongguan gold mining area,Shaanxi Loess Plateau and impact on the environment

In order to study the migration and transformation mechanism of Hg content and occurrence form in subsurface flow zone of gold mining area in Loess Plateau and its influence on water environment, the field in-situ infiltration test and laboratory test were carried out in three typical sections of river-side loess, alluvial and proluvial strata in Tongguan gold mining area of Shaanxi Province, and the following results were obtained: (1) The source of Hg in subsurface flow zone is mainly caused by mineral processing activities; (2) the subsurface flow zone in the study area is in alkaline environment, and the residual state, iron and manganese oxidation state, strong organic state and humic acid state of mercury in loess are equally divided in dry and oxidizing environment; mercury in river alluvial or diluvial strata is mainly concentrated in silt, tailings and clayey silt soil layer, and mercury has certain stability, and the form of mercury in loess is easier to transform than the other two media; (3) under the flooding condition, most of mercury is trapped in the silt layer in the undercurrent zone where the sand and silt layers alternate with each other and the river water and groundwater are disjointed, and the migration capacity of mercury is far less than that of loess layer and alluvial layer with close hydraulic connection; (4) infiltration at the flood level accelerates the migration of pollutants to the ground; (5) the soil in the undercurrent zone is overloaded and has seriously exceeded the standard. Although the groundwater monitoring results are safe this time, relevant enterprises or departments should continue to pay attention to improving the gold extraction process, especially vigorously rectify the small workshops for illegal gold extraction and the substandard discharge of the three wastes, and intensify efforts to solve the geological environmental problems of mines left over from history. At present, the occurrence form of mercury in the undercurrent zone is relatively stable, but the water and soil layers have been polluted. The risk of disjointed groundwater pollution can not be ignored while giving priority to the treatment of loess and river alluvial landform areas with close hydraulic links. The research results will provide a scientific basis for water conservancy departments to groundwater prevention and control in water-deficient areas of the Loess Plateau.     

西北冰洋表层沉积物中重金属的赋存形态研究

用连续提取法对选自西北冰洋的32个表层沉积物进行分析,测定了Cr、Cu、Pb在全样中及其在P1-2、P3、P4、P5中的含量.结果表明随着离岸距离增加,水深加深,Cr、Cu、Pb含量呈增高的趋势.研究区陆架沉积物中Cr、Cu、Pb含量分别为60.66、14.77、16.65μg/g;深海沉积物中Cr、Cu、Pb的含量分别为80.40、41.70、25.62μg/g.元素赋存形态分析表明,Cr、Cu、Pb主要赋存在残渣态,残渣态中三元素的含量平均值分别为64.97、19.67、17.56μg/g,占元素总量的比例分别为93.58%、75.02%和83.76%.三元素在各赋存形态中的含量分布是:Cu为残渣态>有机质和硫化物态>铁锰氧化态>可交换及碳酸盐态;Pb和Cr则为残渣态>铁锰氧化物态>有机质硫化物态>可交换态及碳酸盐态.研究区重金属元素在不同赋存形态中的含量分布与北太平洋深海沉积物中类似.     

A new method for the quantification of different redox-species of molybdenum (V and VI) in seawater

A new method for the direct determination of reduced and oxidized Mo species (Mo (V) and Mo (VI)) in seawater was developed and used for the first time. The method includes the complexation of Mo (V) with tartrate, solid phase extraction of the Mo (V)–tartrate complex by a XAD 7HP resin, followed by elution with acidic acetone. In this study, the eluted Mo (V) was quantified by graphite furnace atomic absorption spectrometry. The detection limit of this protocol was on the order of 0.2 nM. The analytical precision was 10% of ~ 10 nM. This method was successfully applied to the determination of Mo (V) and Mo (VI) in surface and bottom waters at the head of Peconic River Estuary. Total Mo (Mo (V) + Mo (VI)) ranged from 100–120 nM in most bottom saline waters, and 2.5–15 nM for surface fresher waters. Concentrations of Mo (V) in these environments ranged from 0 nM to ~ 15 nM, accounting for 0%–15% of the total dissolved Mo pool. The time series experiments showed that the Mo speciation changed within 1 h after the water collection, and therefore it is strongly suggested that speciation analysis be carried out within the first 15 min. However, since these are the first Mo speciation data in concentration ranges typical of normal marine and coastal waters, additional research may be required to optimize the methodology and further explore Mo cycling mechanisms.