Oxidation mechanisms and chemical bioavailability of chromium in agricultural soil – pH as the master variable     

《Applied Geochemistry》2016

Chromium (Cr) is a heavy metal that exists in soils in two stable oxidation states, +III and +VI. The trivalent species is an essential nutrient, whereas the hexavalent species is highly toxic. This study investigated the environmental impact of Cr^III potentially released into soil from wastes and various materials by determining the risk of oxidation of initially soluble inorganic Cr^III into hazardous Cr^VI. The principal aim was to describe the pH-dependent mechanisms that regulate 1) the formation of Cr^VI from the easily soluble Cr^III and 2) the potential bioavailability of Cr^III and that of Cr^VI species produced in the oxidation of Cr^III in agricultural soil (fine sand, organic carbon 3.2%). The amount of Cr^VI formed in oxic soil conditions was regulated by two counteracting reactions: 1) oxidation of Cr^III into Cr^VI by manganese oxide (Mn^IVO₂) and 2) the subsequent reduction of Cr^VI by organic matter back to Cr^III. The effect of pH on this net-oxidation of Cr^III and on the chemical availability of both Cr^III and Cr^VI species was investigated in soil samples incubated with or without excessive amounts of synthetic MnO₂, over the chemically adjusted pH range of 3.9–6.3 (+22 °C, 47 d). In soil subsamples without added MnO₂, the net-oxidation of Cr^III into Cr^VI (1 mM CrCl₃ in soil suspensions, 1:10 w/V) was negligible. As for the MnO₂-treated soils, at maximum only 4.7% of added Cr^III was oxidized – regardless of the high oxidation potential of these subsamples. The lowest production of Cr^VI was observed under acidic soil conditions at pH ∼4. At low pH, the net-oxidation diminished as result of enhanced reduction of Cr^VI back to Cr^III. At higher pHs, the oxidation was limited by enhanced precipitation (or adsorption) of Cr^III, which lowered the overall amount of Cr^III susceptible for oxidation. Moreover, the oxidation reactions by MnO₂ were inhibited by formation of Cr(OH)₃ coverage on its surface. The pH-dependent chemical bioavailability of added Cr^III differed from that of the Cr^VI formed. At elevated pHs the chemical availability of Cr^III decreased, whereas that of Cr^VI produced increased. However, the risk of Cr^VI formation through oxidation of the easily soluble inorganic Cr^III was considered to be low in agricultural soils high in organic matter and low in innate MnO₂.  相似文献   

Combination of single and sequential chemical extractions to study the mobility and host phases of potentially toxic elements in airborne particulate matter     

《Chemie der Erde / Geochemistry》2016,76(4):481-489

Risk assessment of metals associated to airborne particulate matter (PM) has usually been based on the analysis of their total concentrations, which is a poor indicator of metal mobility. Chemical fractionation processes may provide an additional level of information, however, chemical complexity and small sample sizes do not allow to combine several extraction methods. Additionally, analysing the metal concentrations during the extractions exceptionally provides restricted information about metals’ speciation. To overcome these limitations we collected total suspended particulate matter (TSP) samples from the air filters placed in the air supply channel of methane-heated turbines of thermal power stations which allows collecting large amounts of TSP materials. Additionally, we combined single and sequential chemical extractions in which not only the concentrations of potentially toxic elements (PTE) (Cd, Cr, Cu, Ni, Pb, Zn) but also that of the major chemical components (Al, Ca, Fe, K, Mg, Mn, Na, P, S, Ti) were analysed. Our aims were to study these metals’ mobility and speciation through the study of their association to major chemical components.Accumulation of the studied PTEs in the TSP material suggests moderate contamination for Ni, Cd and Cr whereas a heavy one for Cu, Zn and Pb. Three groups of these PTEs could be distinguished based on their mobility. The highly mobile Zn and Cd (large ratios of water and weak acid soluble fractions) can be considered as especially harmful elements to environment. The moderately mobile Pb and Cu (large ratios of reducible and oxidizable fractions, respectively) may potentially have a negative effect on the environment, whereas the immobile Cr and Ni cannot be expected to pose a serious risk. Based on the statistical evaluation of extraction data, the potential phases for Zn and Cu are presented by metal-sulphates, -nitrates, -chlorides, -carbonates and -hydroxides, as well as sorbed forms. Lead primarily hosted by metal-carbonates and sorbed forms, as well as by -hydroxides, whereas Cu by organic matter. Finally, Cr and Ni are mostly incorporated into very resistant phases, most probably by magnetite or other resistant metal-oxides.Combination of single and sequential extractions, as well as that of the analysis of not only the target elements but also the major chemical components were found to be a very effective tool to study the host phases of PTEs in the TSP material. The necessity for relatively large sample amounts for such analyses could be fulfilled using special sampling methodology; however, obvious disadvantages of this kind of sampling must be taken into account when resulted data are evaluated.  相似文献   

地热水中竞争巯基化影响下的砷、锑形态分布：以西藏阿里典型水热区为例          下载免费PDF全文

詹海鹏  郭清海 《沉积与特提斯地质》2023,43(2):442-451

砷、锑是地热水中的典型有害组分,受地热水独特水化学条件影响,常呈现与其他类型天然水体相异的形态分布特征。本文以西藏阿里的朗久、曲色涌巴、门士、莫落江等地热区为研究区,分析了含硫化物地热水中砷、锑在竞争巯基化过程影响下的形态分布特征。受富砷、锑岩浆流体输入或高温条件下热储围岩加强淋滤的影响,上述地热区排泄的地热水中砷、锑浓度范围分别可达5 833～20 750μg/L和579～2 129μg/L。地热水中砷以亚砷酸盐和砷酸盐为主要存在形态,但同时存在占总砷百分比在0.1%～55.1%之间的硫代砷酸盐;与砷的情况不同,地热水中锑检测出的形态均为亚锑酸盐和/或锑酸盐,所有样品中均未检出硫代锑酸盐。考虑到相当一部分地热水样品的S/Sb摩尔比在理论上满足硫代锑酸盐的形成条件,且所有样品中砷的富集程度均不同程度高于锑,我们认为地热水中锑的含氧络阴离子的巯基化过程受到了共存砷的强烈抑制。在硫化物相对于砷、锑总量并不充分盈余的情况下,砷的竞争巯基化是控制地热水中硫代锑酸盐形成的最重要因素。本工作及其研究结果有助于深入理解西藏地热水环境中砷、锑的环境地球化学行为。  相似文献   

Fluxes of iron and manganese across the sediment–water interface under various redox conditions     

Svetlana V. Pakhomova  Per O.J. Hall  Mikhail Yu. Kononets  Alexander G. Rozanov  Anders Tengberg  Andrei V. Vershinin 《Marine Chemistry》2007

Fluxes of dissolved forms of iron and manganese across the sediment–water interface were studied in situ in the Gulf of Finland and the Vistula Lagoon (Baltic Sea), and in the Golubaya Bay (Black Sea) from 2001 to 2005. Fluxes were measured using chamber incubations, and sediment cores were collected and sliced to assess the porewater and solid phase metal distribution at different depths. Measured and calculated benthic fluxes of manganese and iron were directed out of sediment for all sites and were found to vary between 70–4450 and 5–1000 µmole m^− 2 day^− 1 for manganese and iron, respectively. The behavior of the studied metals at various redox conditions in the near-bottom water and in the sediment was the main focus in this study. Our results show the importance of bottom water redox conditions for iron fluxes. We measured no fluxes at oxic conditions, intermediate fluxes at anoxic conditions (up to 200 μmole m^− 2 day^− 1) and high fluxes at suboxic conditions (up to 1000 μmole m^− 2 day^− 1). Total dissolved iron fluxes were generally dominated by iron(II). Contribution of iron(III) to the total iron flux did not exceed 20%. Obtained fluxes of manganese at all studied regions showed a linear correlation (r² = 0.97) to its concentration in the porewater of the top sediment layer (0–5 mm) and did not depend on dissolved oxygen concentrations of bottom water. Organically complexed iron and manganese were in most cases not involved in the benthic exchange processes.  相似文献   

东海—图们江水中Zn,Cd,Pb,Cu的形式分析          下载免费PDF全文

张首临  李泽林 《海洋与湖沼》1993,24(6):609-615

用防吸附物理涂汞电极反向极谱进行了东海至图们江水中Ｚｎ，Ｃｄ，Ｐｂ，Ｃｕ（１９９１年５－６月）的形式分析研究。结果表明，该４种元素不稳定态的平均浓度分别为５．７，０．０６０，０．０３５，０．６２μｇ／Ｌ，分布较为均匀。该结果证实了痕量金属离子（自由离子及不稳定络离子）的均匀分布规律。有机结合态Ｚｎ，Ｐｂ，Ｃｕ和颗粒态的Ｚｎ，Ｃｕ的较高含量，位于长江口及东海水中。  相似文献   

Uptake of platinum group elements by the marine macroalga, Ulva lactuca     

Andrew Turner  Marie S. Lewis  Leyla Shams  Murray T. Brown 《Marine Chemistry》2007,105(3-4):271-280

Uptake of environmentally relevant platinum group elements (PGE) by the marine macroalga, Ulva lactuca, has been studied. Removal of nM concentrations of Rh(III), Pd(II) and Pt(IV) added to filtered sea water appeared to proceed via pseudo-first-order kinetics, with respective forward rate constants of either 0.0039 or 0.0042 h^− 1, 0.0058 or 0.0096 h^− 1 and 0.0017 or 0.0032 h^− 1, depending on whether an irreversible or reversible reaction was invoked. The (quasi-) equilibrium distribution coefficients, derived from linear fits to uptake (sorption) isotherms, were about 1400, 900 and 350 mL g^− 1 on a dry mass basis for Rh, Pd and Pt, respectively. With increasing sea water pH, over the range 7.9 to 8.4, uptake of Rh by Ulva increased considerably, whereas a small increase in Pt removal was observed; in contrast, uptake of Pd exhibited no clear dependence on pH. The percentage of metal taken up that was internalised within cells, evaluated by washing selected algal samples in 3 mM EDTA, was about 40% for Rh, 80% for Pd and 95% for Pt. Results of this study were interpreted in terms of what is known about the aqueous speciation of PGE in sea water. Thus, Rh exists as cationic hydrated chloride complexes which are readily adsorbed at the algal surface. Palladium has an exceptional affinity for organic ligands, and uptake (and internalisation) appears to be governed by competition for Pd²⁺ from aqueous and algal binding sites. Platinum (IV) exists predominantly as a series of (mainly) negatively charged chloride and mixed hydroxychloride complexes that have little propensity to interact with the algal surface; however, its high degree of internalisation requires at least some interaction with specific and perhaps physiologically active sites.  相似文献   

干旱区绿洲土壤共存重金属元素形态变化及生物有效性实验分析     

赵转军  南忠仁  王胜利  刘晓文  陶燕 《地球科学进展》2008,23(11):1193-1200

采用盆栽试验,初步研究了干旱区绿洲土壤—胡萝卜系统中镉、锌、镍3种重金属的形态变化特征及其生物有效性问题。结果表明：供试绿洲土壤原状土中,Cd、Zn、Ni均以稳定的残渣态形式存在,而处理土壤中重金属被钝化的量有限,Cd的存在形式主要以碳酸盐态为主,Zn、Ni则主要以铁锰氧化态为主;3种元素的活性大小依次为Cd＞Ni＞Zn。根据回归分析,元素Zn对胡萝卜块茎和茎叶吸收Zn量贡献最大的分别是Zn的碳酸盐结合态和铁锰氧化态;元素Ni对胡萝卜各部位吸收贡献最大的均为Ni的铁锰氧化态。  相似文献   

Accumulation discrepancy of heavy metal and organic pollutants in three near-shore depositional environments, southeastern China     

Huan-Xin Weng  Yang-Ming Zhu  Ya-Chao Qin  Jian-Yu Chen  Xun-Hong Chen   《Journal of Asian Earth Sciences》2008,31(4-6):522-532

Heavy metal and organic pollutants in sediments along the coastal zone of southeastern China have been investigated. Sediment samples are retrieved from three depositional environments: coast, estuary, and tide-affected river mouth. The relative abundance of heavy metal and organic pollutants is related to their geochemical properties as well as depositional environments and anthropogenic discharge. Based on a sequential extraction method, it is revealed that anthropogenic Pb, Cr, Cu, and Cd are mainly bound to Fe–Mn oxides, suggesting that adsorption and co-precipitation of Fe–Mn oxides are in the control of their transfer processes from water column to sediment. Heavy metal bound to carbonates is also an important pool especially for Cd, Mn, and Pb. The main organic pollutants found in the study area include petroleum-related alkanes, phthalic acid ester, organic silicon, chlorophenol, phenyl ether, and amine. The accumulation of heavy metals and organics in surficial sediments has a decrease tendency from estuarine environment to coastal environment and to tide-affected river mouth.  相似文献   

Competitive adsorption,release and speciation of heavy metals in the Yellow River sediments,China   总被引：2，自引：0，他引：2  

Qingyun Fan  Jiang He  Hongxi Xue  Changwei LÜ  Ying Liang  Saruli  Ying Sun  Lili Shen 《Environmental Geology》2007,53(2):239-251

The competitive adsorption and the release of selected heavy metals and their speciation distribution before and after adsorption in the Yellow River sediments are discussed. The adsorption of metals onto sediments increases with increasing pH value and decreases with increasing ionic strength. The competitive coefficient K _c and the distribution coefficient K _d are obtained to analyze the competitive abilities of selected heavy metals, which are ranked as Pb > Cu >> Zn > Cd. The competition among selected heavy metals becomes more impetuous with increasing ion concentration in water. Speciation analysis was done by an improved analytical procedure involving five steps of sequential extraction. Cu, Pb and Zn were mainly transformed into the carbonate-bound form (50.8–87.7%) in adsorption. Most of (60.7–77.3%) Cd was transformed into the exchangeable form, and the percentage of carbonate-bound Cd was 19.7–30.4%. The release reaction was so quick that the release capacity of selected heavy metals from sediments to aqueous solution reached half of the maximum value only in 30 s. As opposed to adsorption, the release capacities of selected heavy metals were ranked as Cd > Zn >> Cu > Pb. In this study, Cd produces the most severe environmental hazards, because its concentration in the release solution is 85.8 times more than the human health criteria of US EPA.  相似文献   

Speciation of Arsenic Using Chelation Solvent Extraction and High Performance Liquid Chromatography     

Shamil J. Cathum  Carl E. Brown  Alison Obenauf  Monique Punt 《洁净——土壤、空气、水》2007,35(1):71-80

Research interest in speciation of arsenic stems from its species dependent behavior in the environment and in living organisms. The complexity of the matrix to be analyzed and low concentrations of target arsenic species that may be labile or difficult to chromatogram, indicate that a suitable pre‐treatment methodology is required. This study investigated the usefulness of chelation solvent extraction – high performance liquid chromatography (CSE‐HPLC) for the speciation of arsenic in water. It involved reacting arsenic with the chelant known for its affinity towards arsenic, followed by extraction, separation, and identification of the arsenic‐chelant‐arsenic complex. Arsenic species having different physicochemical properties were investigated. Species, such as, As₂O₃, As₃O₅, KH₂AsO₄, Na₂HAsO₄, and NaAsO₂ were detected as a group of closely eluted peaks with different retention times and spectral properties, whereas, the organic arsenic species CH₃Na₂AsO₃, o‐arsanilic acid, roxarson and triphenyl arsine separated quite well on the EnviroseP‐CM HPLC column. Key method parameters, such as, type of HPLC column, composition of mobile phase and organic solvents affecting peak resolution and sensitivity were optimized. Real environmental matrices contaminated with arsenic were analyzed under varying wavelengths (λ_max = 190, 210, 220, 234, 244, and 282 nm), with good precision. Different arsenic species were detected in these samples with excellent background and signal‐to‐noise ratios demonstrating the robustness of the method. The detection limit, reproducibility, selectivity, accuracy, and dynamic range of the calibration curves were evaluated.  相似文献