Coupling Size-Exclusion Chromatography and ICP-MS to Investigate the Speciation of Platinum-Group Elements in Environmental Samples     

Christoph M. Menzel  Zsolt Berner  Doris Stüben 《Geostandards and Geoanalytical Research》2001,25(2-3):239-251

The applicability of size-exclusion chromatography (SEC) coupled online with a high resolution ICP-MS (HR-ICP-MS) to investigate the speciation of the platinum-group elements (PGE), Rh, Pd and Pt, was evaluated. Experiments were carried out to determine the efficiency of different hydrophilic and hydrophobic size-exclusion gel materials to select the optimal eluent in respect of resolution, recovery, reproducibility and limit of detection. The suitability of HR-ICP-MS as a reliable detection instrument at low pg ml⁻¹ levels was investigated by examining possible mass interferences with Rh, Pd and Pt. Laboratory experiments demonstrated the interaction and capability of forming complexes of humic substances with PGE, demonstrating the potential role of these ubiquitous natural substances in the mobilisation of PGE in the environment.  相似文献   

S(IV) Autoxidation in Atmospheric Liquid Water: The Role of Fe(II) and the Effect of Oxalate     

Irena Grgićc  Marjeta Pozničc  Mirko Bizjak 《Journal of Atmospheric Chemistry》1999,33(1):89-102

The reactivity of dissolved iron compounds towards different pollutants and photooxidants in atmospheric liquid water depends upon the oxidation state and speciation of iron. Our measurements of the oxidation state of dissolved iron eluted from aerosol particles (Dae: 0.4–1.6 m) collected in the urban atmosphere of Ljubljana showed that a large fraction of the iron content is present as Fe(II). The concentration ratio [Fe(II)]/[Fe(III)] varied between 0.9 and 3.1. The kinetics of S(IV) autoxidation catalyzed by Fe(II) under the conditions representative for acidified atmospheric liquid water and the influence of oxalate on this reaction under dark conditions was investigated. The reaction rate is the same if Fe(II) or Fe(III) is used as a catalyst under the condition that Fe(II) can be oxidized in Fe(III), which is the catalytically active species. Oxalate has a strong inhibiting effect on the S(IV) autoxidation in the presence of Fe(II). The reaction is autocatalytic with an induction period, that increases with higher concentrations of oxalate. The inhibiting effect of oxalate differs according to whether iron is initially in the Fe(II) or Fe(III) state. However, in both cases the inhibition by oxalate is a result of the formation of complexes with the catalyst.  相似文献   

The Speciation of (CH3)2Sn2+ in Electrolyte Solution Containing the Major Components of Natural Waters     

Claudia Foti  Antonio Gianguzza  Frank J. Millero  Silvio Sammartano 《Aquatic Geochemistry》1999,5(4):381-398

Hydrolysis constants of dimethyltin(IV) cation, in different salt solutions (CaCl₂: 0.15 I 0.90; MgCl₂: 0.30 I 0.60; NaCl-–NaClO₄, NaCl-–NaNO₃ mixtures: I = 3; NaCl-–Na₂SO₄ mixtures: I = 1 mol dm^-3) were determined by potentiometric ([H⁺]-glass electrode) measurements. These data, together with previous data (De Stefano et al., 1996b) were interpreted in terms of DHT (Debye–Hückel type) and Pitzer equations. The mixed electrolyte solution results also allowed us to obtain and parameters for the Pitzer equation. Calorimetric measurements were made at different ionic strengths in order to find the temperature dependence of hydrolysis constants and of the relative interaction parameters. The body of results allows us to determine the speciation of natural waters in a wide range of ionic strengths and temperatures.  相似文献   

离子色谱-六极碰撞等离子质谱法同时测定水样的砷形态     

张国平  刘丛强  黄荣生 《矿物学报》2004,24(4):325-328

经阴离子色谱柱分离，3mmol／L KH2PO4-K2HPO4(3％CH3OH改进剂)的淋洗液等梯度淋洗，用六极碰撞等离子体质谱仪在线测定了三种砷形态。检出限分别为：As(V)0．49μg/L，As(Ⅲ)0．39μg/L，DMA 0．16μg/L。重复性优于6．0％，三日复现性优于6．1％。为了检验该方法的实际应用性，测定了贵阳市饮用水源阿哈湖的湖水及入湖河水中的砷形态，结果比较理想。  相似文献   

A new schedule for copper chemical speciation analysis in soil and water sediment     

Hui ZHANG 《中国地球化学学报》2006,25(B08):197-197

The speciation of heavy metals is very important to evaluate their environmental impact. This issue has become an interested topic many decades ago and many significative studies were carried out such as direct detecting, calculation with mathematical model represented in recent years as well as Tessier＇s work in 1979, BCR＇s work in 1993, etc. In all of them, the methods recommended by Tessier and BCR are most often used in practical study today. But it should be seen that experimental schedule and agents define these methods including BCR＇s method, which improved on Tessier＇s method, only. In many cases, there always are deviations between analytical results and real content of the speciation. Otherwise, steps of the extraction experiment are always strict and excessive in the experimental process. The method, which is fitting to extract the speciation of bioavailability and easy to assess the effect of metals in the environment, is very anticipant. In this paper, the sequential three steps schedule of speciation analysis of copper in soil and water sediment is discussed as an example based on the comparative results of experimental analysis with the schedules of BCR＇s （mended by Rauret et al. in 1999） and TDPA （diethylenetriamine pentacetic acid） extraction, respectively. The results from sequential three steps method and other methods recommended by prevenient work suggest that the analytical schedule of sequential three steps of separating speciation （the speciation of easy effect to life-form, the speciation available to life-form, and the speciation of no effect to life-form） is valuable for copper speciation analysis in soil and sediment. Because of easy process and saving time to evaluate its availability for life form,  相似文献   

Speciation of Chromium in Artificially Contaminated Soil Reference Material GSJ JSO-2 Using XANES and Chemical Extraction Methods     

Hiroshi Tsuno  Atsuyuki Ohta  Hiroyuki Kagi  Noboru Imai  Hiroaki Tao  Masaharu Nomura 《Geostandards and Geoanalytical Research》2006,30(1):55-62

The oxidation states of chromium in GSJ JSO-2 (artificially contaminated soil) and three other geochemical reference materials (GSJ JSO-1, JLS-1 and JMS-1) were observed using X-ray near edge structure (XANES). For comparison, other artificially contaminated soil materials (mimic-JSO-2) were prepared by adding Cr(VI) into JSO-1. Their oxidation states of chromium were determined using XANES. The chromium contents were 1118 μg g^-1 for JSO-2, 1352 μg g^-1 for mimic-JSO-2 and 69-113 μg g^-1 for the other reference materials. Most chromium was present as hexavalent in mimic-JSO-2. No hexavalent species were detected in other samples. These results for chromium oxidation state in JSO-2 and mimic-JSO-2 obtained with XANES resembled those obtained from a chemical extraction method. The present JSO-2 has no trace of Cr(VI), although Cr(VI) was added as a major species during preparation. On the other hand, the content of Cr(VI) obtained in mimic-JSO-2 agreed with the original Cr(VI) content. A time-elapse study showed that Cr(VI) contents in mimic-JSO-2 decreased gradually to 70% of the original abundance during 240-day preservation in dry conditions. Moreover, the abundance of Cr(VI) decreased markedly to 15% after 240 days in the wet mimic-JSO-2 containing 20% m/m of water. These experiments suggested that soil humidity enhanced the reduction of Cr(VI) and that Cr(VI) was reduced even in dry conditions. Consequently, it is reasonable to infer that Cr(VI) doped into JSO-2 was completely reduced to Cr(III) during the preservation period of 5 years. The certification of the long-term stability of the chemical form in reference materials will be much more important in future.  相似文献   

Trace Element Determination by ICP-AES and ICP-MS: Developments and Applications Reported During 2004 and 2005     

Kathryn L. Linge 《Geostandards and Geoanalytical Research》2006,30(3):157-174

This review describes significant developments in trace element determination using inductively coupled plasma-atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS) that were reported in 2004 and 2005. It focuses on the application of ICP techniques to geological and environmental samples; fundamental studies in ICP-MS and ICP-AES instrumentation are not included. The literature reviewed indicated that the majority of new publications concerned advances in ICP-MS analysis rather than ICP-AES. However, ICP-AES developments are still being published, particularly in the areas of sample preconcentration and sample introduction. The trend in increasing publication of developments in hyphenated speciation techniques looks set to persist as knowledge of elemental speciation becomes critical for many environmental studies. Collision or reactions cells were the most reported technique for spectral interference removal in ICP-MS, probably reflecting the growing adoption of cell instruments in laboratories during the last few years.  相似文献   

Effects of pH and Ca competition on complexation of cadmium by fulvic acids and by natural organic ligands from a river and a lake     

Jun Cao  Hanbin Xue  Laura Sigg 《Aquatic Geochemistry》2006,12(4):375-387

The technique of competitive ligand-exchange/anodic stripping voltammetry (CLE-SV) was used to investigate effects of pH and Ca concentration on cadmium complexation by fulvic acid (FA), as well as Cd speciation in two different freshwaters, a hardwater Lake Greifen and a softwater River Wyre. Binding of Cd to Suwannee river FA (10 mg/l) was determined at different pH (7–8.5) and in the presence of various concentration of Ca²⁺ (0–2 mmol/l). The results from one-ligand discrete models were compared to simulations by the WHAM VI model. In Lake Greifen, the determined dissolved [Cd²⁺] ranged from 10⁻¹³ to 10⁻¹² mol/l, and the conditional stability constant with natural ligands was log K _CdL about 9.5–10.5 (pH 8.6–8.8) with ligand concentrations of 1.2–7.8 × 10⁻⁶ mol/g C. In the softwater River Wyre, dissolved [Cd²⁺] ranged from 4 × 10⁻¹² to 1 × 10⁻¹¹ mol/l, and the ligands were weaker (log K _CdL 8.9–9.8, pH 8.0) with lower ligand concentrations (0.9–2.3 × 10⁻⁶ mol/g C). The titration curves of FA samples were close to the simulated curves by the WHAM VI model at pH 8.0–8.5, but deviated more from the model at lower pH, indicating that the results determined with CLE-SV for Cd-FA complexation are relevant to the data base in the model. Calculation of the Ca competition for Cd binding by FA showed a competition effect of similar strength as the measured one, but indicated a systematic difference between measured and modeled data at pH 7.5. Using the WHAM model for comparison with FA, the complexation of Cd by the River Wyre ligands was close to that of FA, whereas stronger complexation was observed in the Lake Greifen water. These differences may originate from different ligand composition in the lake and the river.  相似文献   

Geochemical characteristics of trace elements in sediments of Dongting Lake, central China     

Zhigang YAO Zhengyu BAO Pu GAO 《中国地球化学学报》2006,25(B08):137-137

Although eutrophication and trace element contamination are two key environmental problems in Dongting Lake, a systematic study of the distribution of trace elements in sediments of this lake has not previously been undertaken. In order to identify the current levels of trace metal contamination in Dongting Lake, the concentrations of trace elements （Cd, Cr Cu, Ni, Pb, Zn, As and Hg） in the sediments at 53 locations were investigated in this study. The lake, the second largest fresh-water lake in China, boasts three China wetlands of international importance. Dongting Lake which lies in the south of the middle Yangtze River is the most important reservoir lake in the Yangtze River drainage area, and is characterized by fast flow-through water, large runoff volume and short period of exchanging water （no more than 20 days）. The granulometric analysis result of sediments shows that a large proportion of the sediments measures at 2-63 μm in size; the result of mineralogical analysis shows that original mineral is the main composition of the sediments, followed by clay mineral and carbonate. The contents of copper, lead, zinc, cadmium, arsenic and mercury are higher than the background levels of soil （ Ⅰ Soil） in China, but lower than the threshold values for severely polluted soil （Ⅲ Soil） in China except Cd higher than that in Ⅲ Soil. The concentrations of trace elements analyzed are higher than the Threshold Effect Level of Interim Sediment Quality Guideline by Canada EPA and are lower than the Probable Effect Level. The assessment by geoaccumulation index shows that the contamination of Cd reached strong level in Dongting Lake. Study on speciation of metals by a BCR procedure indicates that the trace elements （Cu, Zn, Cr, and Ni） analyzed are mainly distributed in residual phases but Pb in Fe/Mn oxhydroxide phase and Cd in soluble and carbonate-bound fraction. The potential risk was the highest in East Dongting Lake based on the calculated contamination factors which are mostly probably caused by the deposition of the trace element pollutants via the Xiangjiang River and the discharge of the pollution sources in the vicinity of East Dongting Lake.  相似文献   

Speciation and role of iron in cloud droplets at the puy de Dôme station     

Marius Parazols  Angela Marinoni  Pierre Amato  Otman Abida  Paolo Laj  Gilles Mailhot 《Journal of Atmospheric Chemistry》2006,54(3):267-281

Iron is the most abundant transition metal in the atmosphere and can play a significant role in cloudwater chemistry where its reactivity is closely related to the partitioning between Fe(II) and Fe(III). The objective of this work is to determine the total iron content and the iron speciation in a free tropospheric site, and to understand which factors influence these parameters. We collected 147 samples of cloudwater during 34 cloud events over a period of four years at the puy de Dôme summit. Besides iron we measured other chemical compounds, solar radiation, physico-chemical and meteorological parameters potentially connected with iron reactivity. The total iron concentrations ranged from 0.1 to 9.1 μM with the major frequency occurring at low levels. The pH and presence of organic complexants seem to be the most significant factors connected with total dissolved iron; while the iron oxidation state seems to be an independent factor. Light intensity, presence of complexants or oxidants (H₂O₂) do not influence the Fe(II)/Fe(Total) ratio, that was quite constant at about 0.75. This could be due to the potential redox that forces the Fe(II)-Fe(III) couple to the reduced form or, more probably to the complexation by Natural Organic Matter, that can stabilize iron in its reduced form and prevent further oxidation. Our field measurements did not show the diurnal cycle observed in surface water and predicted by models of atmospheric chemistry. This result prompts a more careful review of the role of iron and, by analogy, all the transition metals in atmospheric liquid phase, often over-estimated in the literature.  相似文献