Speciation of trace metals in sediments of a tropical estuary     

C. K. Nair  A. N. Balchand 《Environmental Geology》1993,21(1-2):96-102

Axial surveys were performed in the two river tributaries of the Cochin estuary, SW India during November 1988. Surficial sediments were subjected to sequential chemical extractions to delineate five metal fractions, namely, exchangeable, carbonate bound, easily reducible, organic/sulfide bound, and residual. The results indicated selective accumulation of Mn and Ni in carbonate bound and organic/sulfide forms, along with marginal amounts of Co in the exchangeable fraction. Large portions of Fe and Cr occurred in the residual fraction, whereas composite fractionation of Zn species was noticed. The exchangeable fractions of Fe and Cr as well as of easily reducible cobalt were below detection limits. The levels of Cr and Zn indicate anthropogenic inputs in this estuary, whereas Co and Ni show regional contamination exceeding natural levels. The analytical speciation procedure helps to deduce the sedimental diagenetic processes in the estuarine environment.  相似文献   

Mercury speciation in surface and deep waters of the Mediterranean Sea     

Jože Kotnik  Milena Horvat  Emmanuel Tessier  Nives Ogrinc  Mathilde Monperrus  David Amouroux  Vesna Fajon  Darija Gibičar  Suzana Žižek  Francesca Sprovieri  Nicola Pirrone 《Marine Chemistry》2007

Mercury speciation and its distribution in surface and deep waters of the Mediterranean Sea were studied during two oceanographic cruises on board the Italian research vessel URANIA in summer 2003 and spring 2004 as part of the Med Oceaneor and MERCYMS projects. The study included deep water profiles of dissolved gaseous Hg (DGM), reactive Hg (RHg), total Hg (THg), monomethyl Hg (MeHg) and dimethyl Hg (DMeHg) in open ocean waters. Average concentrations of measured Hg species were characterized by seasonal and spatial variations. Overall average THg concentrations ranged between 0.41 and 2.65 pM (1.32 ± 0.48 pM) and were comparable to those obtained in previous studies of the Mediterranean Sea. A significant fraction of Hg was present as “reactive” Hg (average 0.33 ± 0.32 pM). Dissolved gaseous Hg (DGM), which consists mainly of Hg⁰, represents a considerable proportion of THg (average 20%, 0.23 ± 0.11 pM). The portion of DGM typically increased towards the bottom, especially in areas with strong tectonic activity (Alboran Sea, Strait of Sicily, Tyrrhenian Sea), indicating its geotectonic origin. No dimethyl Hg was found in surface waters down to the depth of 40 m. Below this depth, its average concentration was 2.67 ± 2.9 fM. Dissolved fractions of total Hg and MeHg were measured in filtered water samples and were 0.68 ± 0.43 pM and 0.29 ± 0.17 pM for THg and MeHg respectively. The fraction of Hg as MeHg was in average 43%, which is relatively high compared to other ocean environments. The concentrations reported in this study are among the lowest found in marine environments and the quality of analytical methods are of key importance. Speciation of Hg in sea water is of crucial importance as THg concentrations alone do not give adequate data for understanding Hg sources and cycling in marine environments. For example, photoinduced transformations are important for the presence of reactive and elemental mercury in the surface layers, biologically mediated reactions are important for the production/degradation of MeHg and DGM in the photic zones of the water column, and the data for DGM in deep sea indicate the natural sources of Hg in geotectonicaly active areas of the Mediterranean Sea.  相似文献   

Modelling the equilibrium speciation of nickel in the Tweed Estuary, UK: Voltammetric determinations and simulations using WHAM     

Andrew Turner  Manuela Martino   《Marine Chemistry》2006,102(3-4):198-207

The complexation of dissolved Ni has been evaluated in a rapidly-flushed, rural estuary (Tweed, UK) by ligand exchange-adsorptive cathodic stripping voltammetry. Results suggest the presence of strongly binding ligands, L, throughout, with average stability constants of about 10¹⁹ and which are saturated by ambient Ni concentrations. Equilibrium speciation calculations incorporating these constants in WHAM, version 6, predict an increase in Ni complexation (as NiL) from about 50% of total dissolved Ni in fresh water to over 90% in sea water. Equivalent calculations using the default-mode fulvic and humic substances (FS and HS, respectively) encoded in the WHAM database predict a reduction in complexation (as NiFS + NiHS) from about 20% in fresh water to less than 1% in sea water. Discrepancies arising from the two approaches are largely attributed to the different analytical detection windows employed. Thus, a better representation of Ni complexation is derived from including both types of complexant in the speciation calculations, resulting in estimates of net complexation in excess of 60% of total dissolved Ni throughout the estuary. The uncertainties and assumptions inherent in all computations illustrate the difficulty in measuring or predicting metal complexation in estuaries.  相似文献   

Thermodynamic characterization of the partitioning of iron between soluble and colloidal species in the Atlantic Ocean   总被引：2，自引：1，他引：2  

Jay T. Cullen  Bridget A. Bergquist  James W. Moffett 《Marine Chemistry》2006,98(2-4):295-303

Recent electrochemical measurements have shown that iron (Fe) speciation in seawater is dominated by complexation with strong organic ligands throughout the water column and have provided important thermodynamic information about these compounds. Independent work has shown that iron exists in both soluble and colloidal fractions in the Atlantic Ocean. Here we have combined these approaches in samples collected from a variety of regimes within the Atlantic Ocean. We measured the partitioning of Fe between soluble (< 0.02 μm) and colloidal (0.02 to 0.4 μm) size classes and characterized the concentrations and conditional stability constants of Fe ligands within these size classes. Results suggest that equilibrium partitioning of Fe between soluble and colloidal ligands is partially responsible for the distribution of Fe between soluble and colloidal size classes. However, a significant fraction of the colloidal Fe was inert to ligand exchange as soluble Fe concentrations were generally lower than values predicted by a simple equilibrium partitioning model.In surface waters, strong ligands with conditional stability constants of 10¹³ relative to total inorganic Fe appeared to dominate speciation in both the soluble and colloidal fractions. In deep waters these ligands were absent, and instead we found ligands with stability constants 12–15 fold smaller that were predominantly in the soluble pool. Nevertheless, significant levels of colloidal Fe were found in these samples, which we inferred must be inert to coordination exchange.  相似文献   

Determination of cadmium(II), copper(II), manganese(II) and nickel(II) species in Antarctic seawater with complexing resins   总被引：1，自引：0，他引：1  

Raffaela Biesuz  Giancarla Alberti  Girolamo D'Agostino  Emanuele Magi  Maria Pesavento 《Marine Chemistry》2006,101(3-4):180-189

The strong species of cadmium(II), copper(II), manganese(II) and nickel(II) in an Antarctic seawater sample are investigated by a method based on the sorption of metal ions on complexing resins. The resins compete with the ligands present in the sample to combine with the metal ions. Two resins with different adsorbing strengths were used. Very stable metal complexes were investigated with the strong sorbent Chelex 100 and weaker species with the less strong resin, Amberlite CG-50. Strong species were detected for three of the considered metal ions, but not for Mn(II). Cu(II) is completely linked to species with a side reaction coefficient as high as log α_M(I) = 11.6 at pH = 7.3. The ligand concentration was found to be similar to that of the metal ion, and the conditional stability constant was around 10²⁰ M^− 1. In the considered sample, only a fraction of the metal ions Cd(II) and Ni(II) is bound to the strong ligands, with side reaction coefficients equal to log α_M(I) = 5.5 and 6.5 at pH = 7.3 for Cd(II) and Ni(II), respectively. These findings were confirmed by the test with the weaker sorbent Amberlite CG-50. It can be calculated from the sorption equilibria that neither Mn(II) nor Ni(II) is adsorbed on Amberlite CG-50 under the considered conditions and, in fact, only a negligible fraction of Mn(II) and Ni(II) was adsorbed. A noticeable fraction of Cd(II) was adsorbed on Amberlite CG-50, meaning that cadmium(II) is partially linked to weak ligands, possibly chloride, while no copper(II) was adsorbed on this resin, confirming that copper(II) is only combined in strong species. These results are similar, but not identical, to those obtained for other seawater samples examined in previous investigations.  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——以Cd、Zn、Ni元素为例   总被引：3，自引：0，他引：3  

赵转军  南忠仁  王胜利  刘晓文  陶燕 《地球科学进展》2008,23(11):1194-1200

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   

Geochemical fractionation of Ni,Cu and Pb in the deep sea sediments from the Central Indian Ocean Basin: An insight into the mechanism of metal enrichment in sediment     

《Chemie der Erde / Geochemistry》2016,76(1):39-48

Metal speciation study in combination with major element chemistry of deep sea sediments provided possible metal enrichment pathways in sediments collected from environmentally different locations of Central Indian Ocean Basin (CIB). Metal speciation study suggests that Fe–Mn oxyhydroxide phase was the major binding phase for Ni, Cu and Pb in the sediments. The second highest concentrations of all these metals were present within the structure of the sediments. Easily reducible oxide phase (within the Fe–Mn oxyhydroxide binding phases) was the major host for all the three metals in the studied sediments. Major element chemistry of these sediments revealed that there was an increased tendency of Cu and Ni to get incorporated into the deep sea sediment via the non-terrigenous Mn-oxyhydroxide fraction, whereas, Pb gets incorporated mostly via amorphous Fe-hydroxides into the sediment from the CIB. This is the first attempt to provide an insight into the mechanism of metal enrichment in sediment that host vast manganese nodule.  相似文献   

Arsenic in mine waters: an international study   总被引：4，自引：4，他引：4  

M. Williams 《Environmental Geology》2001,40(3):267-278

 Hydrochemical data are presented for arsenic (As) in the mine waters of 34 gold and base-metal mining localities in seven countries of south-east Asia, Africa and Latin America, encompassing contrasting climatic settings and at least eight discrete styles of primary mineralization. Peak dissolved As concentrations at these sites range from 0.005–72 mg/l, with the United States Environmental Protection Agency (US-EPA) potable water threshold of 50 μg/l exceeded in 25 cases. Arsenate (As⁵⁺) constitutes the dominant species at over 80% of sites. Very high dissolved As concentrations (>1 mg/l) show no systematic between-site relationship with mine water pH/Eh regime. Important determinants of mine water As fluxes include iron hydrochemistry, the presence of cyanic ore processing effluents, site geology, the paragenetic sequence that follows sulphide oxidation, climate and mine management. Human toxicological impacts of As contamination have been recognized at only one case-study site, with a further four considered to warrant more detailed risk assessment. Received: 2 November 1999 · Accepted: 21 March 2000  相似文献   

Two Experimental Methods to Determine the Speciation of Cadmium in Sediment from the River Neckar     

N. Martin  I. Schuster  St. Peiffer 《洁净——土壤、空气、水》1996,24(2):68-76

The binding forms of Cd to an anaerobic sediment of low sulfide content from Lauffen reservoir (River Neckar, Germany) were studied using two different approaches, i. e. sequential extraction (modified from published protocols) and titrimetric study of the pH-dependent Cd release. Thermodynamic equilibrium calculations were applied to calculate both the release pattern of Cd during the titrations and the speciation of Cd within the single fractions of the extraction protocol. The calculations were based on measured sediment parameters such as hydrous ferric oxide (HFO), acid volatile sulfide, carbonate content and total Cd content, and the extractants (oxalate, acid etc.) used. The results of the two independent approaches coincided well in that they both assigned more than two thirds of the total Cd content to be adsorbed to organic matter. Cd bound as CdS is of little importance. Sequential extraction after a 3-month oxidation period at pH 7 revealed a shift of Cd from being mainly bound in stronger surface complexes with organic matter to being mainly bound in weaker surface complexes with organic matter and HFO, and thus becoming more bioavailable. This study suggests that the use of sequential extraction although being frequently criticized due to its operational character can be used to determine binding forms of metal ions if they are accompanied by 1) careful supporting experiments, 2) analysis of important sediment parameters, and 3) the use of thermodynamic equlibrium models which can help to understand Cd speciation within the extraction fractions.  相似文献   

The speciation of dissolved copper,cadmium and zinc in Manila Bay,Philippines     

Velasquez IB  Jacinto GS  Valera FS 《Marine pollution bulletin》2002,45(1-12):210-217

At present, there is a very limited information on the levels and distribution of dissolved metals in Manila Bay. In this study, the horizontal and vertical distribution of operationally defined species (labile, bound and total) of dissolved copper (Cu), cadmium (Cd) and zinc (Zn) were determined using differential pulse anodic and cathodic stripping voltammetry in water samples obtained from 18 stations in November 1998. In addition, the 24-h variability in the concentrations of these species at different depths in the water column was determined. These measurements were complemented by the determination of temperature, salinity, dissolved oxygen, chlorophyll a, particulate organic carbon and nutrients. Results showed that more than 50% of total dissolved copper and cadmium were labile while 50% of total dissolved zinc was organically bound. Vertical profiles showed that Cu, Cd and Zn concentrations were generally high at the surface. Zinc and cadmium were characterised by the presence of a mid-depth minimum while copper did not show any clear vertical trend.

Dissolved Cu concentrations during the spatial and diurnal samplings ranged from 0.32 to 6.95 nM and 1.52 to 45.65 nM, respectively. For Cd, the concentrations in 18 stations ranged from 0.05 to 2.92 nM, and from 0.03 to 2.42 nM over a 24-h period. Zn concentrations ranged from 2.48 to 147.43 nM and 2.87 to 88.27 nM during the spatial and diurnal samplings, respectively. The large variation in the concentration of Cu, Cd and Zn in the bay was observed to be associated with the presence of a large vertical density gradient in the water column, which appeared to limit the exchange of materials between the surface and bottom waters. Elevated levels of these metals near point sources suggest anthropogenic inputs in the bay.  相似文献