三种土壤中土霉素浸提方法的比较研究

以棕壤、褐土和红壤为研究对象,比较了不同浸提方法,不同浸提剂对土壤中土霉素的浸提效率.结果表明,在所用的3种方法中,采用振荡浸提方法,以及Na2EDTA-McIlvaine缓冲液对土霉素具有稳定、高效的浸提回收率.土霉素形态初步分析连续浸提步骤为:以H2O、0.1mol/L CaCl2、和Na2EDTA-McIlvaine缓冲液为浸提剂依次浸提可分别得到水溶态、可交换态、吸附态和固定态土霉素.3种土壤中土霉素形态呈现吸附态>可交换态>水溶态的规律.     

超声辐射协同草酸-HEDTA浸提污泥中重金属

利用超声波辐射协同草酸-羟乙基替乙二胺三乙酸(HEDTA)浸提城市污泥中重金属Cu、Zn、Cr、Ni,研究了超声辐射时间、功率密度、搅拌作用对Cu、Zn、Cr、Ni浸出的影响,并利用Tessier连续浸提法分析了超声波协同草酸-HEDTA浸提对污泥中重金属形态的影响.结果表明,随着超声时间、功率密度的增加和污泥搅动,污泥中Cu、Cr和Ni的浸提率呈上升趋势, Zn的浸提率无明显提高.污泥在超声辐射浸提处理后,Cu、Cr、Ni的有机物结合态和残渣态含量下降,金属离子可交换态和碳酸盐结合态含量有所增加,Zn的形态无明显变化.     

Application of chemometrics methods for the estimation of heavy metals contamination in river sediments

The concentration and speciation of six heavy metals in sediments of eight sampling sites of Haihe River were investigated. The metals, namely Cd, Cu, Co, Ni, Mn and Pb were considered. By using sequential extraction(SE), the total metals were divided into five fractions: exchangeable, carbonate bound, iron/manganese oxide bound, sulfides and organic matter fraction and residual fraction. A multivariate statistical approach( principal component analysis, PCA) was used to evaluate the contamination of heavy metals by the total levels and chemical forms, respectively. The results showed that the total metals concentration(TMC) could not provide sufficient and accurate information because the mobility, bioavailabllity and toxicity of metals depend not only on their total concentration but also on the physicochemical form in which they occur.     

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%.     

Spatial and temporal distribution of atmospheric mercury species over the Adriatic Sea

Field measurements of atmospheric mercury and related species were carried out during an intensive cruise campaign performed over the Adriatic sea from October 26th to November 12th, 2004 on board the R/V Urania. Hg⁰ ranged between 0.8 and 3.3 ng/m³ with an average of 1.6 ± 0.4 ng/m³ over the entire period. Hg(II) concentrations ranged from 0.1 to 62.8 pg/m³ with an average of 6.7 ± 11.7 pg/m³ whereas Hg-p levels were in a range of 0.04 and 51 pg/m³ with an average of 4.5 ± 8 pg/m³. Higher Hg⁰ and Hg-p concentrations were observed in the Gulf of Venice and Gulf of Trieste due primarily to air masses transported from the mainland reflecting the contribution from anthropogenic sources. In contrast, higher Hg(II) concentrations observed during the first period of the cruise campaign were likely due to the occurrence of photo-oxidants production which are the main players of the gas phase oxidation of to Hg(II)_(g). These findings have been confirmed by the backward trajectories analysis of air masses crossing the studied area during selected days.     

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.     

鸡粪堆肥处理对重金属形态的影响

选用鸡粪和玉米秸秆作为堆肥原料,进行高温好氧堆肥试验,研究了堆肥处理对鸡粪中重金属形态的影响.结果表明,堆肥过程中,堆料的总质量下降,重金属含量相对增加,但绝对量变化不明显,因此堆肥处理并不能减少堆肥体系中重金属的绝对量.但对重金属形态有一定的影响,Ni、Cd的铁锰氧化物结合态比例提高了5.0%～8.7%;Cu的有机结合态比例增加达到14.1%～19.1%,Cr的有机结合态比例增加达到22.0%～28.7%;Hg、Pb、As、Zn的残渣态比例均有不同程度提高.Hg、Pb、Cr、As、Cu和Zn等6种元素的稳定形态比例均有所上升,其中Cu的上升幅度最大,最高达到10.9%,说明堆肥处理能够降低重金属的生物活性和毒性.所添加的复合菌剂对鸡粪中重金属形态未有显著影响.     

不同价态外源硒在石灰性土壤中的形态转化及其生物有效性

通过盆栽试验和连续浸提的方法,研究了外源硒酸盐(六价硒)和亚硒酸盐(四价硒)施入石灰性土壤后的形态转化及其对小白菜生物有效性的影响.结果表明,不同价态外源硒施入土壤后,土壤各形态硒含量均随外源硒添加量的增加而显著增大(p0.01).但两种外源硒在土壤中的形态变化明显不同,施入土壤的硒酸盐主要以可溶态形式存在,在土壤中的移动性相对较大;而亚硒酸盐主要以可交换态及碳酸盐结合态形式存在,并可由可溶态转化为其他土壤形态,从而降低了其生物有效性.Monod方程拟合结果表明,小白菜根系对六价硒的亲和能力显著大于四价硒,从而使得硒酸盐处理小白菜地上和地下部最大硒含量分别为亚硒酸盐处理的5倍和2倍,说明在石灰性土壤上硒酸盐比亚硒酸盐的生物有效性更高.另外,亚硒酸盐处理小白菜地下部最大硒含量是地上部的2.3倍,而硒酸盐处理小白菜地下部和地上部最大硒含量相近,说明小白菜根系吸收在硒累积和转运过程中起着至关重要的作用.