涨渡湖沉积物中色素的测定和环境意义研究

对涨渡湖沉积物柱样中叶绿素、胡萝卜素、颤藻黄素和蓝藻叶黄素等几种色素进行了提取并用紫外可见分光光度法进行测定;根据各色素所代表的环境意义, 揭示了涨渡湖近百多年来的环境、历史气候变化等特征. 结果表明, 近几十年来, 涨渡湖一直处于富营养化状态, 其富营养化态势与该地区上世纪50年代后的一系列人类活动密切相关.     

电感耦合等离子体质谱法测定土壤中有效态镉

建立电感耦合等离子体质谱(ICP–MS)仪测量土壤样品中有效态镉的方法。为了提高ICP–MS法测量的稳定性和准确度,优化样品粒度、称样量、振荡时间等条件,以二乙三胺五乙酸–三乙醇胺–氯化钙混合溶液(DTPA)为提取剂(固液比为1∶12.5),元素铑为内标,ICP–MS仪测定有效态镉的含量。有效态镉的线性范围为0～0.200 mg/L,线性相关系数为0.999 8,检出限为0.000 9mg/kg。测定结果的相对标准偏差为1.56%～3.16%(n=6)。用该法测定国家标准物质土壤中的有效态镉,测定值与标准值基本一致,相对误差为–2.92%～3.13%。该方法减少了样品的浪费,提高了工作效率,增加了测量稳定性,测定结果准确可靠,在检测大批量土壤有效态镉时更具有优越性。     

同位素稀释电感耦合等离子体质谱测定环境和生物样品中的镉

应用同位素稀释电感耦合等离子体质谱（ID—ICP—MS）对环境和生物样品茶叶、湖沉积物和人发标准物质中的镉进行测定研究。对电感耦合等离子体质谱（ICP—MS）的工作条件和参数进行了最优化。讨论了多原子离子和同量异位素对镉同位素比值的影响,通过天然镉标准溶液对质量歧视进行了校正,并优化同位素稀释剂的加入量。将该方法应用于茶叶、人发和沉积物标准物质的测定。     

成都经济生态区大气降尘中镉赋存形态的研究

采用Tessier连续提取法对成都经济生态区不同区域的24个大气降尘样中镉的赋存形态进行了研究。研究结果表明,大气降尘中的镉主要以残留态形态存在;各形态镉在总镉中所占百分比含量由大到小排列顺序依次是:残留态,碳酸盐结合态,交换态,铁锰结合态,有机结合态;交换态镉、碳酸盐结合态镉这两种具有较高生物有效性的形态镉在总镉中所占的平均百分比含量分别是6.420%和8.917%;铁锰氧化物结合态、有机结合态、残留态镉这三种形态镉生物有效性很低,分别在总镉中所占的平均百分比含量分别是3.419%、2.365%和78.907%。通过分析可得出,汽油和煤的燃烧以及工厂排放镉能加大城市大气降尘的镉污染。     

连续萃取法研究海湾养殖区沉积物中重金属形态

以连续萃取法研究海湾养殖区沉积物中重金属(Cd, Cu, Pb, Zn)的形态,将重金属分离为酸溶态、还原态、有机质结合态、硫化物结合态和残渣态.分别采用基体匹配法和内标法消除高盐基体对电感耦合等离子体光谱法(ICP-OES)和质谱法(ICP-MS)分析结果的影响.对海洋沉积物标准物质分析结果表明,样品稀释后测定值与标准值一致.比较了本连续萃取法和BCR法对沉积物样品中重金属形态的提取结果,并考察了萃取剂的选择性.实验表明,本方法可用于有机质污染和富营养化环境沉积物中重金属形态分析,特别是有机质结合态和硫化物结合态的分析.     

石墨炉原子吸收光谱法测定痕量镉的基体改进效应研究及其应用

研究了磷酸氢二钾对石墨炉原子吸收光谱法测定痕量镉的基体改进效应,试验表明,在磷酸盐存在下,镉的灰化温度能显著提高,钾对镉有一定的增感效应。以此建立了用磷酸氢二钾作基体改进剂,直接测定岩石、土壤和水系沉积物中痕量镉的方法。     

蒸气发生-原子荧光光谱法测定痕量镉(Ⅱ)的研究

研究了在硼氢化钠-1,10-二氮杂菲-钴(Ⅱ)体系中镉的荧光信号,发现1,10-二氮杂菲-钴(Ⅱ)能显著提高镉的荧光强度。据此,建立了一种蒸气发生-原子荧光光谱法测定痕量镉的新方法。优化了测定镉的实验参数,在优化的实验条件下。方法的检出限为0.014μg/L,线性范围为0~50μg/L,相关系数r=0.9971,相对标准偏差不超过3.2%。用该法测定了水系沉积物标准样品中镉的含量,取得了满意结果。     

伏安极谱仪测定海水中活性态痕量金属

阳极溶出伏安法是一种可以直接用于海水中痕量金属元素检测分析的有效方法,不仅能够实现多元素同时检测,而且不需要样品预浓缩处理.通过伏安极谱仪,研究了富集电位和富集时间等关键参数对阳极溶出伏安法测定痕量金属铜、铅、镉、锌的影响,对过滤后的海水样品直接进行检测,实现了烟台四十里湾不同站位海水中活性态痕量金属铜、铅、镉、锌的测定,为海水中痕量金属元素的形态分析及生物可利用性研究提供了有效技术手段.     

原子吸收光谱法测定茶叶中铅和镉时消解方法的优化

采用多种方法对同一种茶叶进行消解,用原子吸收光谱法测定不同方法消解的茶叶中有害微量元素铅和镉的含量并进行对比,探索了茶叶中微量元素铅和镉低损耗的最佳消解条件.实验结果表明,不同的消解方式对茶叶中微量元素的测定结果影响很大.测定茶叶中铅和镉元素时,采用硝酸-高氯酸加盖浸泡过夜方法较为理想.     

高频燃烧-红外分析仪测定海洋沉积物的总碳含量

应用高频红外分析仪测定海洋沉积物的总碳含量。于坩埚中预置纯铁屑0.2g,准确称取沉积物样品50.0 mg置于坩埚中,再加入纯铁屑0.2g,使其与样品充分混匀,再加入钨粒1.6g,使其均匀覆盖在样品上面。加入的铁屑与钨粒起了助熔剂的作用。以下按仪器工作条件进行通氧燃烧和测定。按所提出的分析条件测定了两种标准物质(GBW 07364和GBW 07366)中的总碳量,测定结果与认定值相符,测定值的相对标准偏差(n=10)分别为2.3%,1.8%。该方法的检出限(3s)为0.000 4%。应用此方法测定了18种海洋沉积物样品中的总碳量,并用元素分析仪对这些样品进行了校对试验,结果表明两方法的测定结果基本相符。     

Reduction des interferences sur la determination des metaux lourds dans les sediments de cours d'eau et les boues de stations d'epuration par spectrometrie d'absorption atomique en four graphite

(Reduction of interferences in the determination of trace heavy metals in river sediments and sewage sludges by electrothermal atomic absorption spectrometry.)The interferences of synthetic matrices of river sediments and sewage sludges in the determination of lead, copper, cadmium, chromium and nickel by electrothermal atomic absorption spectrometry were studied; Pb, Cd and Ni were the most sensitive to interferences. The effects of hydrochloric, nitric, perchloric and hydrofluoric acids were tested; perchloric acid was found to interfere most during the determinations. Hydrofluoric acid must be eliminated by evaporation. Techniques for reducing chemical interferences were evaluated. The best method was found to be matrix modification with ammonium dihydrogenphosphate and ascorbic acid for the determination of lead and nickel, and rapid heating (Max Power) for the determination of cadmium. Determinants of copper and chromium were less prone to interference.     

微波消解-GFAAS测定浅水湖泊底泥中重金属元素

探讨了采用微波消解作为底泥样品的前处理方法,运用石墨炉原子吸收法测定浅水湖泊底泥中Cu,Pb,Zn,Cd,Cr含量的实验条件.方法的RSD为2.0％～4.1％,平均回收率为97.4％～101.5％,Cu,Pb,Zn,Cd,Cr的检出限分别为0.4,5,2.8,0.25,2.5ng.该法适合于浅水湖泊底泥中重金属含量的测定.     

The use of dithizone extraction and atomic absorption spectrometry for the determination of cadmium,zinc, copper,nickel and cobalt in rocks and sediments

A method is presented for the determination of cadmium, zinc, copper, nickel and cobalt in sediments. The sediments are digested with hydrofluoric, sulphuric and perchloric acids. The metals are extracted into dithizone. Cadmium and zinc are back-extracted into dilute hydrochloric acid, but the other metals are determined in a solution prepared after the destruction of the organic extract. The method has been applied to USGS rock reference samples and to estuarine sediments.     

Voltammetric method for the determination of Zn,Cd, Pb,Cu and Ni in interstitial water

To determine heavy metals in interstitial water from Baltic sea sediments a sampling method with subsequent voltammetric determination is described. Copper, lead, zinc and cadmium are determined in the UV-digested samples of interstitial water by differential pulse anodic stripping voltammetry while nickel is determined by adsorption voltammetry. The determination of five metals in one sample in a wide concentrations range is possible using a low cost apparatus. The profiles of the metal concentrations in interstitial water of subsequent layers of sediments, sampled from Puck Bay, Gdańsk Bay, the Bornholm area and the S?upsk area are presented.     

Study of parameters associated with the determination of cadmium in lake sediments by slurry sampling electrothermal atomic absorption spectrometry

Cadmium concentration in lake sediments is determined by suspending the solid samples in a solution containing 5% (v/v) concentrated nitric acid and 0.1% (v/v) Triton X-100. Three modifiers were tested for the direct determination. The furnace temperature programmes and appropriate amount for each modifier were optimised to get the highest signal and the best separation between the atomic and background signals. The drying stage is performed by programming a 400 °C temperature, a ramp time of 25 s and hold time of 10 s on the power supply of the atomiser. No ashing step is used and platform atomisation is carried out at 2200 °C. W–Rh permanent modifier combined with conventional modifier by delivering 10 μl of 0.50% (w/v) NH₄H₂PO₄ solution was the best chemical modifier for cadmium determination. This modifier also acts as a liquid medium for the slurry, thus simplifying the procedure. Calibration is performed using aqueous standards in the 1–5 μg l⁻¹ range. The optimised method gave a limit of detection of 0.56 ng ml⁻¹, characteristic mass of 10.1±0.8 pg for aqueous standard, 9.6±0.7 pg for slurry samples containing different Cd concentrations and good precision (7.6–5.2%). The method was validated by analysing four certified reference lake sediment materials: LKSD-1, LKSD-2, LKSD-3 and LKSD-4; satisfactory recoveries were obtained (90.0–96.3%) and no statistical differences were observed between the experimental and the certified cadmium concentration. The developed methodology was used to determine cadmium in three ‘real’ sediment samples from lakes in the area of Wielkopolski National Park, Poland.     

Instrumental neutron activation analysis of tree rings for dendrochemical studies

Instrumental neutron activation analysis (INAA) was employed to determine zinc, cadmium and potassium concentrations in the growth rings of ponderosa pine (Pinus ponderosa Dougl.) trees growing along the shores of Lake Roosevelt in Washington State, U.S.A. where mineral processing activities have resulted in high burdens of zinc and cadmium in the lake sediments. The tree growing along the contaminated waterway display elevated concentrations of zinc in its growth rings relative to a tree growing along an uncontaminated tributary of Lake Roosevelt. Cadmium concentrations in the growth rings from both sites are similar from 1988 to 1993. Water quality data indicate an increased concentration of cadmium in the lake from 1984 to 1988. The increased concentrations of cadmium in the lake water were reflected in apparent increases in concentrations of cadmium in individual rings of the tree sampled at the contaminated site. This suggests that translocation of cadmium in the sapwood of heartwood-forming species does not occur in the short term, and thus may not be a limiting factor in using trees as environmental monitors for cadmium. In addition, five-year tree ring segments were analyzed and subsequently reanalyzed as individual single-year ring segments. The analytical data obtained for the pooled individual rings are essentially the same as for the five-year segments, demonstrating the utility of NAA for dendrochemical studies.     

Mercury speciation in environmental solid samples using thermal release technique with atomic absorption detection

A sensitive and very simple method for determination of mercury species in solid samples has been developed involving thermal release analysis in combination with atomic absorption (AAS) detection. The method allows determination of mercury(II) chloride, methylmercury and mercury sulfide at the level of 0.70, 0.35 and 0.20 ng with a reproducibility of the results of 14, 25 and 18%, respectively. The accuracy of the developed assay has been estimated using certified reference materials and by comparison of the results with those of an independent method. The method has been applied for Hg species determination in original samples of lake sediments and plankton.     

离子色谱法测定盐湖沉积物中可溶性阴离子

盐湖沉积物中可溶性阴离子提取和测试方法对其实验结果至关重要,但不同的前处理提取和测试条件缺乏系统的对比和优化。本文对比了水浴加热、超声提取、涡旋震荡三种前处理条件的提取效率,发现涡旋震荡离心的前处理方法回收率最佳,并进一步优化了水土比例、涡旋震荡离心方法的浸提时间和浸提次数。在离子色谱测试方法方面,发现以30 mmol/L KOH溶液作为淋洗液,流速1 mL/min,柱温30 oC,电导检测器进行离子色谱分析效果最好。最终建立了以涡旋震荡离心为前处理提取,离子色谱法测定盐湖沉积物中四种无机可溶性阴离子（F-、Cl-、SO42-和NO3-）的检测方法。该方法中,四种阴离子检出限≤0.026 mg/L,线性相关性良好R2≥0.998,加标回收率为80%~114%,精密度RSD为0.64%~1.31%,具有快速准确、灵敏度高、简单可靠等优点,可适用于高盐度盐湖沉积物样品中无机阴离子的测定,并利用该方法对六份西藏地区盐湖表层沉积物样品进行分析。     

Comparison of action of mixed permanent chemical modifiers for cadmium and lead determination in sediments and soils by slurry sampling graphite furnace atomic absorption spectrometry

Slurry sampling atomic absorption spectrometry with electrothermal atomization was used to the determination of cadmium (Cd) and lead (Pb) in soils and sediments using permanent modifiers. Comparison of action of mixed permanent modifiers niobium (Nb)/iridium (Ir) and tungsten (W)/iridium (Ir) were studied in detail. The effect of amount of Ir, W and Nb on analytical signals of Cd and Pb was examined. The optimal amounts of modifiers for Cd and Pb determination were stated. Niobium carbide formation on graphite surface was studied for different pyrolysis temperatures. Finally for Cd determination in sediments and soils 200 μg of Nb mixed with 5 μg of Ir was used as permanent modifiers and 15 μg of Nb mixed with 200 μg of Ir for Pb determination. Suspensions were prepared in 5% HNO₃. The analytical procedure was optimized carefully basing on data from pyrolysis and atomization curves studies. Ammonium dihydrogen phosphate was used additionally as matrix modifier during Cd determination in samples in order to prevent interferences coming from matrix components. The analysis of CRMs confirmed the reliability of the proposed approach. The precision and accuracy of Cd and Pb determination by the described method for soils and sediments were acceptable.     

Determination of plutonium in environmental samples with quadrupole ICP-MS

A method for rapid determination of plutonium isotopes in environmental samples with ultrasonic nebulisation and quadrupole ICP-MS detection was established. Techniques for sample dissolution, pre-concentration and chemical separation were evaluated and the optimal scheme outlined. Comparisons with α-spectrometry and high resolution ICP-MS confirmed the suitability of the method when applied to different environmental matrices within the global fallout concentration range in the northern hemisphere as well as more contaminated sites. Operational detection limits were 0.5–1.5 fg/l for fresh waters and 0.03–0.1 ng/kg for lake sediments and saline marsh sediments.