Simplification of a Sequential Extraction Scheme To Determine the Mobilisable Heavy Metal Pool in Soils

This investigation had the purpose of evaluating the reliability of a sequential extraction procedure according to Zeien and Brümmer (1989) which is performed routinely to analyse the distribution of heavy metals to different soil phases. Reliability was tested by two hypotheses. According to the first hypothesis an error propagation increased during a morefold extraction of heavy metals from a single soil sample to such an extend that it does not allow a statistical comparison of different analyses. This assumption was confirmed in an interlaboratory study of five participants applying the sequential extraction scheme on two different soils. The heavy metal amounts extracted by the different partners were of the same magnitude, but from the results no statistical correspondence at the 95% confidence level could be observed. The second hypothesis stated that also weak extraction agents were able to release metals from the more immobile soil fractions, especially if the amount of easily soluble metals was comparatively small. To answer this question the sequential extraction was modified by carrying out selected weak extraction steps several times. As expected the intensified extraction conditions caused a decrease of the element content within the more resistant phases. However, the additional release in the first four extraction steps of Pb, Mn, Fe, and Zn was only in the range of 5 to 10%. Furthermore, it was observed that a single EDTA extraction (step four within the sequential extraction scheme) was capable to extract the same amount of metals as the first four extraction steps of the original scheme at a variation of about 15%. From these results it was concluded that the EDTA step alone already represents a reliable pool of mobilisable metals. Thus it can be maintained that such a simple single EDTA extraction can be used to assess the environmental risk from heavy metal contaminated soils or to predict the potential heavy metal release of soil remediation processes.     

洞庭湖沉积物腐殖酸的配位性与酸碱性研究

通过电位滴定研究了从洞庭湖沉积物中分离得到的腐殖酸（HA）的酸碱性和配位性,采用修正格兰函数进行了数据拟合。表征了六类可滴官能团含量和分布,pKa数值在2．35～10．50之间,羧基占可电离中心总数的62％,利用铜离子选择电极和汞齐电极（Pb、Cd和Zn）研究了腐殖酸与Cu^2＋、Pb^2＋、Cd^2＋和Zn^2＋配位性质,借助Scatchard方法对数据进行了处理,显示铜和铅为二配体,镉和锌为单配体。平均稳定常数顺序为：logKHA-Pb〉logKHA-Cd〉logKHAtZn,配位能力顺序为：Pb〉Cu〉Cd≈Zn。     

高钙低镁体系中钙镁测定方法的改进研究

EDTA络合滴定法是应用范围比较广的传统方法,但该方法对样品中钙镁摩尔比的适用范围约为1：10-10：1,时于超过该范围的钙镁比样品测定的准确度会有所下降;传统EDTA络合指示剂滴定法测定高钙低镁体系中钙镁含量时,终点不易判断,测定结果平行性差,甚至出现钙镁总量小于钙量的情况。通过往样品中加入一定量Mg’标准溶液的方法,改善了滴定反应效果。结果表明,Mg^2＋的加入能明显提高滴定终点变色灵敏度。加标回收试验表明,镁的回收率达到99．96％,钙的回收率达到99．40％。该方法准确度高,操作简单,适用性强。     

阳极泥及碲回收物料中高含量碲的测定

采用重铬酸钾容量法,测定铜铅阳极泥及碲回收物料中高含量碲。针对阳极泥样品成分复杂的特征,确定了最佳溶样介质;探讨了Cu^2 ,Cd^2 ,Bi^3 ,Ag^ ,Sb(Ⅲ）,As（Ⅲ）,Pb^2 ,Se（Ⅳ）,Sn（Ⅳ）,Au(Ⅲ）等共存元素的影响及其消除方法;改善了滴定条件。方法适用于w(Te)＞1％碲的测定,样品分析结果与原子吸收法测定结果一致,RSD（n＝5）为0.4％－4.1％。     

石墨炉原子吸收法测定生物样品中微量钒

生物样品用灼烧法,除去有机物,在浓度为5％的盐酸介质中,加入EDTA和铵盐作为基本改进剂,清除石墨炉原子吸收法测定钒时铜、铁离子的干扰,可直接测定钒．采用标准加入法回收率为96．4-106．8％,相对标准偏差3．95％。     

A comparison of iron limitation of phytoplankton in natural oceanic waters and laboratory media conditioned with EDTA

The solubility of iron in oxic waters is so low that iron can be a limiting nutrient for phytoplankton growth in the open ocean. In order to mimic low iron concentrations in algal cultures, Ethylenediaminetetraacetate (EDTA) is commonly used. The presence of EDTA enables culture experiments to be performed at a low free metal concentration, while the total metal concentrations are high. Using EDTA provides for a more reproducible medium. In this study Fe speciation, as defined by EDTA in culture media, is compared with complexation by natural organic complexes in ocean water where Fe is thought to be limited. To grow oceanic species into iron limitation, a concentration of at least 10⁻⁴ M EDTA is necessary. Only then does the calculated [Fe³⁺] concentrations resemble those found in natural sea water, where the speciation is governed by natural dissolved organic ligands at nanomolar concentrations. Moreover, EDTA influences the redox speciation of iron, and thus frustrates research on the preferred source of Fe-uptake, Fe(III) or Fe(II), by algae. Nowadays, one can measure the extent of natural organic complexation in sea water, as well as the dissolved Fe(II) state, and can use ultra clean techniques in order to prevent contamination. Therefore, it is advisable to work with more natural conditions and not use EDTA to create iron limitation. This is especially important when the biological availability of the different chemical fractions of iron are the subject of research. Typically, many oceanic algae in the smallest size classes can still grow at very low ambient Fe and are not easily cultivated into limitation under ambient sea water conditions. However, the important class of large oceanic algae responsible for the major blooms and the large scale cycling of carbon, silicon and other elements, commonly has a high Fe requirement and can be grown into Fe limitation in ambient seawater.     

Refining P nuclear magnetic resonance spectroscopy for marine particulate samples: Storage conditions and extraction recovery

Solution ³¹P nuclear magnetic resonance (NMR) spectroscopy has recently been used to characterize phosphorus species within marine particles. However, the effects of sample collection, storage and preparation have not been thoroughly examined. In this study, samples of settling particulates collected from a 1200-m sediment trap located in Monterey Bay, California, were subjected to various storage options (i.e., no storage, refrigeration, freezing, and oven-drying and grinding) prior to extraction for solution ³¹P-NMR spectroscopy. Freezing, refrigerating and drying samples for periods of up to 6 months prior to extraction with 0.25 M NaOH + 0.05 M Na₂EDTA increased the concentration of extracted P by an average of 16% relative to samples extracted without storage. Pre-extraction storage also introduced some minor changes in P speciation, by increasing the percentage of orthophosphate by up to 15% and decreasing the percentage of pyrophosphate by up to 5%, relative to the abundances of these P species in samples extracted without storage. Drying caused the biggest changes in speciation, specifically decreasing more extensively the relative percentage of pyrophosphate compared to other treatments. Nevertheless, observed changes in speciation due to sample storage within a specific sample were small relative to differences observed among samples collected sequentially in the same area, or reported differences among samples collected at different locations. Samples were also analyzed by solid-state ³¹P-NMR spectroscopy before and after extraction, to examine extraction-related changes in P speciation. Comparison of solution with solid-state ³¹P NMR indicates that extraction with NaOH–EDTA removes the majority of organic esters, but only a variable portion of phosphonates (39–67%). In addition, there was preferential extraction of Ca-associated phosphate over Mg-, Fe- and Al-associated phosphate. Solution ³¹P NMR enables much higher resolution of P species within samples, particularly when it is important to speciate orthophosphate monoesters and diesters, or if polyphosphates are present. However, combining solid-state ³¹P NMR with solution ³¹P NMR spectroscopy for marine particles should be conducted when examining inorganic P speciation and the abundance of phosphonates.     

水中硫酸盐测定方法研究

对EDTA容量法测定水中硫酸根时，对加入沉淀剂后样品静置时间对测定结果的影响进行了研究。结果表明，在本法规定的浓度范围内，样品静置时间对测定结果无影响。     

六氟磷酸锂的水分测定

六氟磷酸锂是锂离子电池电解液材料中应用最为广泛的一种 ,水含量的多少对其品质好坏有着决定性作用 ,在此介绍了用卡尔·费休法来测定电解质材料六氟磷酸锂中的水分 ,方法简便、准确 ,结果满意     

石膏岩中粘土矿物提取的一种新方法及在古气候重建中的应用

目前通用的前处理方法难以从石膏岩中有效提取足量粘土矿物进行测试分析,针对这一技术问题,本研究改进了原有的粘土矿物分析前处理方法,采用新的试剂乙二胺四乙酸二钠（以下简称EDTA）溶解石膏岩,释放其中所含的粘土矿物,有效提高石膏岩中粘土矿物的提取能力。本文以位于青藏高原东北缘西宁盆地塔山剖面（36.5°N,101.8°E） 始新世祁家川组、洪沟组和马哈拉沟组的9个石膏岩样品为研究对象,通过详细对比试验确定了EDTA的溶解条件,明确了采用EDTA提取石膏岩中粘土矿物的实验流程和方法,并探讨了溶解过程对粘土矿物的影响。实验结果表明,EDTA对石膏岩的最佳溶解条件为：温度=100℃、pH=10~12、浓度=0.32mol/L,改进后的前处理方法提取粘土矿物质量是原来的1~25倍,且不破坏粘土矿物的晶型结构。使用EDTA溶解法提取9个样品中的粘土矿物经X射线衍射分析结果表明,西宁盆地始新世石膏岩样品中粘土矿物含量以伊利石为主（62%~90%）,含少量绿泥石（3%~17%）,蒙脱石（含伊蒙混层矿物）含量变化较大（0~35 %）。粘土矿物组合特征反应该区域始新世以干旱气候为主,盆地内石膏岩地层形成时期的气候环境可能存在一定程度的干湿波动现象。