Speciation study of trace elements in surface sediment of Winam Gulf,Lake Victoria,by sequential extraction,aqua-regia acid digestion,and ICP-OES

The speciation of trace metals in surface sediment in Kisumu Carwash area of Winam Gulf, was studied and results compared with those found at Usoma beach which was found to be several orders of magnitude less polluted. High proportions of the metals were bioavailable (fractions 1–6) with BA% ranging from 21.7% (Al) to 94.5% (Pb) at Carwash and 19.6% (Al) to ～100% (for Cd and Pb) at Usoma beach. The readily mobilizable fraction (fractions 1–4) decreased in the order: Pb > Mn > Sn > Cu > Co > Zn > Mg > Cd > Mo > Ni > Cr > Fe > Al at Carwash and Mn > Mo > Sn > Pb > Cd > Mg > Cu > Zn > Co > Ni > Fe > Cr > Al at Usoma beach. The total Zn, Cd, Cr, and Cu sediment concentrations at Carwash were higher than the threshold effect concentrations (TECs), although their bioavailable concentrations were lower than these limits. Both the total and bioavailable concentrations of Pb in surface sediment at Kisumu Carwash area were higher than the TEC threshold limit indicating significant contamination from this heavy metal. Although there was a general good agreement on data obtained by sequential extraction as compared with those obtained by direct aqua-regia digestion, there were large discrepancies for some specific metal analytes which could be accounted for in terms of analytical variations and lack of uniformity in physical and chemical composition of the sediment samples analyzed.     

Metal transport phases in rivers around Jameshedpur†

Transport phases of four metals of geochemical and water quality importance were investigated in rivers around Jamshedpur. The metals iron, manganese, zinc and copper were partitioned into dissolved, adsorbed and or ion exchangeable, solid organic, oxide coating and crystalline phases applying filtration for the dissolved phase and a chemical fractionation scheme for the particulates. Iron and copper were transported mainly in the particulate phases at all sites, while manganese and zinc were found in the dissolved phase up to a hundred percent depending on the pH of water sample and pollution at the site concerned. Except copper more than 75 percent of all other three metals occurred in transport modes thought to be available to aqueous and biotic interactions. Copper was in available phases from 50 to 70 percent. The significance of metal partitioning as a factor in controlling metal availability and toxicity to biota is discussed.     

Fluorescence studies of dye displacement from DNA by chromium(III) complexes: Evidence for cation induced DNA condensations

The interactions of 10 different chromium(III) complexes with isolated calf thymus DNA have been analysed by studying the electronic and fluoresence spectra of intercalated ethidiumbromide. Triply charged cationic complexes including: [Cr(urea)₆]Cl₃.3H₂O, [Cr(1,10‐phenanthroline)₃](ClO₄)₃.2H₂O, [Cr(2,2'‐bipyridyl)₃] (ClO₄)₃.2H₂O, [Cr(ethylendiamine)₃]Cl₃.3.5H₂O and [Cr(NH₃)₆](NO₃)₃ displaced the dye from DNA. Similar effects were observed in experiments using the non‐intercalating dye bisbenzimidazole ("Hoechst 33258"). However, singly charged cationic, anionic and uncharged chromium(III) complexes such as: cis‐[Cr(1,10‐phenanthroline)₂Cl₂]Cl.2H₂O, cis‐[Cr(2,2'‐bipyridyl)₂Cl₂]Cl.2H₂O, [Cr(glutathione)₂]Na₂, [Cr(cysteine)₂]Na.2H₂O and [Cr(glycine)₃] were unable to displace both ethidiumbromide and bisbenzimidazole from DNA. There was no evidence for the formation of co‐ordinate bonds between chromium(III) and DNA for any of the above complexes. The charge and type of ligand are important in controlling the interaction of chromium(III) with isolated DNA in vitro. Our findings indicate that the outer sphere interaction of a chromium(III) complex with DNA is weak and unlikely to be the mechanism by which chromate causes DNA impairments in vivo and in vitro.     

板蓝根水煎液中13种金属元素形态分析

利用电感耦合等离子体-质谱仪（ICP-MS）测定板蓝根原药材和水煎液中13种元素的含量。形态研究采用高速离心和滤膜分离水煎液中的溶解态和颗粒态,元素的溶解态再用树脂XAD-4、树脂D001、树脂D301和树脂D751分别区分非极性吸附态、阳离子交换态、阴离子交换态和螯合吸附态。结果表明,板蓝根药材含有微量Cu、Pb和Cd等重金属,同时含有丰富的Mg、Ca、Fe、Al等大量元素,其中Ca含量最高,为2739 mg·kg-1;Zn、Mg、Ca、Mn、Al和Fe的浸出率较高,在42.9%到81.9%之间;Pb和Cu的浸出率最低,只有10%左右。Zn、Mg、Ca、Mn和Pb元素颗粒态比例在0%到9.3%之间,其他元素颗粒态比例在14.3%到85.7%之间。在溶解态当中,所有元素都具有阴离子交换态;Cu、Sn、Cr和Al没有或者很少有阳离子交换态,其余元素的阳离子交换态在32.4%到98.3之间;Al、Fe、Cu、Cr和Sn没有或者很少螯合吸附态,其余元素在54.9%到98.4%之间;Zn、Cu、Sn、Cd和Pb有非极性吸附态,其余元素没有。     

密云水库上游某铁矿区土壤重金属含量及形态研究

应用富集因子法(EF)和风险评估编码方法(RAC)对北京市密云水库上游某铁矿矿区及其周边土壤中重金属的分布状况和潜在生态风险进行了研究.结果表明,各重金属元素含量除As外,其余均明显高于北京市土壤重金属背景值,矿区的选冶活动已经对下游的水体和土壤环境造成一定的影响.富集因子法评价表明Cd、Pb、Cr富集较为严重,达到显著污染水平.形态分析表明,残渣态是重金属元素的主要存在形态, Cd元素可交换态所占比例(2.88%~21.15%)最高,RAC评价结果显示Cd基本处于中等风险水平,Pb为无风险,风险等级由强至弱的顺序为:Cd>Mn>Zn>Cu>Co>Cr>Pb.     

东北污灌区草甸棕壤吸附重金属铅的形态分布及解吸行为

以沈阳市沈抚污灌区的草甸棕壤为模型土,采用Tessier顺序提取法分析了吸附重金属Pb(Ⅱ)在土壤中的化学形态分布特点,研究了吸附Pb(Ⅱ)的解吸行为,特别考察了冷冻对吸附Pb(Ⅱ)化学形态分布及解吸行为的影响.研究表明,吸附Pb(Ⅱ)在东北草甸棕壤上的化学形态分布规律为:可交换态碳酸盐结合态铁锰氧化物结合态有机结合态残渣态;吸附Pb(Ⅱ)的解吸动力学过程可分为快速和慢速两个阶段,符合准二级动力学方程;冷冻对吸附Pb(Ⅱ)的形态分布基本无影响,而对平衡解吸率有明显影响,随冷冻时间延长,平衡解吸率逐渐降低;随pH值减小,平衡解吸率增大;pH值在5—10范围内,平衡解吸率变化幅度相对很小,而pH值低于5后,平衡解吸率急剧增大.随离子强度增大,平衡解吸率先急剧上升,后趋于平缓.提出Pb(Ⅱ)在东北草甸棕壤上的吸附机理:化学吸附和静电吸附,后者又可分为静电键合吸附和离子交换吸附.在实验条件下,静电吸附约占75%,化学吸附约占25%.     

Accuracy and traceability concepts applied to environmental speciation analysis

Traceability issues are of increasing concern in all fields where chemical measurements form the basis for decisions. The concepts of accuracy and traceability as applied to environmental analysis are, however, still prone to misunderstandings, which has been recently illustrated by controversial discussions among the analytical community with respect to accuracy and traceability issues in the area of speciation analysis. Analytical techniques used for the determination of chemical species (speciation analysis) are generally based on a succession of steps (e.g. extraction derivatisation, separation, detection) which are all prone to various sources of systematic errors. Many speciation measurement techniques have been studied within the last decade through interlaboratory studies and certification of reference materials. These collaborative efforts have been understood as being directed towards strive for accuracy (trueness and precision). It has been recognised recently that the achievements actually enabled mostly to establish reference points (e.g. certified values in reference materials) which does not necessarily correspond to 'true values' but rather offer a mean for laboratories to compare their data internationally and, hence, achieve traceability. This ambiguity still generates confusion and misunderstandings among the scientific community. This communication discusses this issue, focusing on analytical measurements only. Extending discussions on general traceability issues would imply an examination of steps prior to laboratory work (sampling, storage, etc.) which is beyond the scope of this contribution.     

Environmental toxicity monitoring using electrochemical biosensing systems

Environmental monitoring faces the challenge of measuring an increasing number of analytes at ever decreasing concentrations. Since not all species of a given analyte have the same detrimental impact on the environment, new analytical devices and techniques are required to distinguish between the different species of a pollutant or different groups of pollutants. This paper describes analytical techniques based on biomaterials that are toxically sensitive to pollutants. This approach permits the biomonitoring of certain compounds by looking at their toxic properties. Although these techniques are based on a sound analytical strategy, their applications are limited because most of the interactions between the biological material and the analyte are irreversible. Additionally, the immobilised biological material has a limited stability. Several biomonitoring strategies based on electrochemical biosensing are discussed here and how to recover the bioactivity of biosensing system, both in discrete and automated procedures, is also reviewed.     

Formation of Reactive Gaseous Mercury in the Arctic: Evidence of Oxidation of Hg° to Gas-Phase Hg-II Compounds after Arctic Sunrise

We have measured total gaseous mercury concentrations(Hg°) at Point Barrow, Alaska since September 1998 in aneffort to determine the geographic extent and reaction mechanismof the so-called mercury depletion events (MDE) previouslyreported in the high Arctic at Alert, Canada. Hg° has beensampled now for nearly 2 years at Barrow. In September, 1999, webegan making the first automated measurements of reactive gaseousmercury (RGM) attempted in the Arctic, along with measurements ofHg accumulation in snowpack to determine the fate of the depleted Hg°. During the fall and early winter, Hg°and RGM exhibit only minor variation, Hg° remaining within10% of global background, near 1.6–1.8 ng m^-3. The MDEperiods are quite different, however; within days of Arcticsunrise in January, Hg° exhibits major variations from themean, rapidly dropping as low as 0.05 ng m^-3 and then cyclingback to typical levels, sometimes exceeding global background. These events continue throughout Arctic spring, then end abruptlyfollowing snowmelt, in early June. Prior to Arctic sunrise, RGMremains near detection (<2 pg m^-3), but after sunriseincreases dramatically (to levels as high as 900 pg/m³) insynchrony with the depletion of Hg°. Both phenomenaexhibit a strong diel cycle, in parallel with UV-B. We concludethat MDE's involve rapid in-air oxidation of Hg° to aspecies of RGM by photochemically-driven reactions, probablyinvolving the same reactive bromine and chlorine compoundsinvolved in ozone destruction. Sharp increases in Hg in thesurface snowpack after sunrise coincident with periods of peakRGM suggest surface accumulation of the RGM by dry deposition.     

污泥焚烧过程中氯化物对Cd迁移行为的影响

采用固定层燃炉及向污泥中添加Cd方式,分别研究了污泥焚烧过程中有机氯(PVC)与无机氯(NaCl)对Cd迁移转化行为的影响,同时考察了不同焚烧条件下Cd的迁移及分布规律.结果表明,污泥焚烧过程中不同氯化物的加入均增强了Cd向飞灰或者烟气中迁移,但随着氯化物加入量的增加,Cd挥发增加的趋势并不明显.随温度的升高,有机氯(PVC)与无机氯(NaCl)均使得Cd在底渣中的分布减少,而焚烧时间及初始浓度对Cd迁移分布没有显著影响.底渣和飞灰的SEM-EDS和XRD分析表明,污泥焚烧过程中NaCl的加入导致Cd易与氯化物形成CdCl2、Na2CdCl4、K2CdCl6、K2CdSiO4和NaCdO2,而PVC的加入,除了与Cd形成Na2CdCl4和CdCl2外,还生成了K4CdCl6和K6CdO4氯化物,可见有机氯(PVC)与无机氯(NaCl)对Cd迁移转化影响主要与Cd的生成物种类及形态有关.