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1.
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
2.
An evaluation of metal bioaccessibility in estuarine sediments using the commercially available protein, bovine serum albumin 总被引：2，自引：0，他引：2
The bioaccessibility of metals (Al, Ca, Fe, Mn, Ag, Cd, Co, Cu, Ni, Pb, Sn, Zn) in oxic estuarine sediments has been evaluated using solutions of a commercially available protein (bovine serum albumin; BSA) that mimic the chemical conditions encountered in the gut environment of many deposit-feeding organisms. Over a 20 h incubation period with 5 g L− 1 BSA, metal mobilisation was generally biphasic in that a relatively short period of rapid release was succeeded by more gradual release or approach to equilibrium, although in some cases metal readsorption was evident during the time-courses. Availability to BSA, defined as metal released after 20 h relative to metal extracted by boiling aqua regia, was greatest for Cd, Ni, Ca and Zn and lowest for Fe and Mn, and correlated well with, but was an order of magnitude lower than, metal digested by acidified hydrogen peroxide. Time-courses conducted in the absence of the protein revealed that significant quantities of Ca and Mn were water-soluble, reflecting the partial dissolution of carbonates and hydrous Mn oxides, respectively. Additional experiments indicated a net increase in metal release with increasing BSA concentration and, with the exception of Ca and Mn, a substantial increase in metal mobilisation after sediment organic matter had been digested by peroxidation. These observations suggest that, apart from Ca and Mn, metal release proceeds via complexation with component amino acids of the protein, denudation of organic host phases, and exposure of inorganic, metal-bearing minerals. Accordingly, the bioaccessibility of a metal is predicted to be dependent on its (i) affinity for proteinaceous ligands, (ii) association with components of digestible sediment organic matter, and (iii) degree of binding at relatively weak sites on sediment phases that are exposed or modified by the action of proteins and other chemical constituents of the gut environment. 相似文献
3.
The Effect of Organic Carbon-Iron Oxide Association on the Preservation of Sedimentary Organic Carbon in Marine Environments 总被引：1，自引：0，他引：1
Understanding the mechanisms responsible for long-term storage of organic carbon (OC) in marine environment is important for studying the marine carbon cycling and predicting how the global carbon cycle will respond to climate change. It is estimated that more than 20% of the OC in marine sediments is associated with iron oxides and thus these complexes are one of the most important factors in the long-term storage of OC. The OC-iron oxide (OC-Fe) association can be formed through either adsorption or co-precipitation, but the dominant mechanism of OC-Fe association in marine environments is co-precipitation. The combination of OC from different sources with iron oxides is selective. Iron oxides preferentially combine with marine OC in most marine environments, but in estuarine delta regions they prefer terrestrial OC. Due to large inputs of terrestrial materials, high primary production and frequent re-suspension, estuarine and marginal seas are suitable sites for OC-Fe association studies, which should be emphasized in the future. 相似文献
4.
Valfredo A. Lemos Emanuel V. dos Santos Vieira Eldevan dos Santos Silva Liz O. dos Santos 《洁净——土壤、空气、水》2012,40(3):268-271
A method for the determination of nickel in water was developed. The procedure involves preconcentration of nickel by using dispersive liquid–liquid microextraction. The Ni(II) ions were extracted in chloroform in the form of complex with the reagent 2‐(2′‐benzothiazolylazo)‐p‐cresol. Ethanol was used as the disperser solvent. After injection of the extracting mixture in a solution of nickel, a cloudy mixture was observed. A quick centrifugation induces phase separation and thus the settling of rich phase. The nickel content in the rich phase is measured by flame atomic absorption spectrometry. Under optimal conditions, the limit of detection and quantification obtained were 1.4 and 4.7 µg L?1, respectively. Some parameters used to characterize preconcentration systems, such as enrichment factor and consumption index were calculated and resulted in 29 and 0.34 mL, respectively. After optimization of variables and determination of analytical characteristics, the method was used for the analysis of certified reference materials (BCR‐713: wastewater, effluent and BCR‐414: plankton) and real water samples. 相似文献
5.
This research is aimed at investigating possible neutralization of cyanide in tailing dam of Muteh gold processing plant in
Isfahan, Iran at various conditions such as pH and temperature using USEPA Visual MINTEQ geochemical model simulation. The
model is based on geochemical equilibrium which uses the simultaneous solution of the non-linear mass action expressions and
linear mass balance relationships to formulate and solve the multiple-component chemical equilibrium problems. In this study
the concentration of aqueous species in tailing dam as an aqueous, solid and gaseous were used as input in the model. Temperature
and pH variation were simulated. The results of the model indicated that cyanide may be complexes in 10 < pH < 5. In other
pH values complexation is not important. The results also indicated that cyanide reduction mechanism in acidic pH and temperature
above 30°C is due to cyanide acid formation which is vaporized. 相似文献
6.
Kevin G. Knauss Sally A. Copenhaver Robert L. Braun Alan K. Burnham 《Organic Geochemistry》1997,27(7-8)
Hydrous pyrolysis in flexible gold-bag autoclaves was used to study the production of carboxylic acids and light hydrocarbons from two marine type IIb source rocks (New Albany and Phosphoria Shales). Kerogen pyrolysis produced significant amounts of the monocarboxylic acids (acetic > propionic > butyric). The gases were dominated by CO2 and methane, in that order, and progressively smaller amounts of the alkanes (ethane > propane > butane > pentane). Kinetic analyses of production rates for the New Albany Shale suggest mean activation energies (E) of 51-54 kcal/mol for both the light hydrocarbons and acids. Pressure had little effect on measured production rates for either shale over the pressure range investigated. Chemical thermodynamic speciation modeling suggests that in these experiments metal-organic acid anion complexation had little impact on aluminum speciation/solubility, but was important with respect to the alkaline earths. 相似文献
7.
Pore waters of natural clays, which are investigated as potential host rock formations for high-level nuclear waste, are known to contain large amounts of low-molecular weight organic compounds. These small organic ligands might impact the aqueous geochemistry of the stored radionuclides and, thus, their migration behavior. In the present work, the complexation of Cm(III) with formate in aqueous NaCl solution is investigated by time-resolved laser fluorescence spectroscopy (TRLFS) as a function of the ionic strength (0.5–3.0 mol/kg), the ligand concentration (0–0.2 mol/kg) and the temperature (20–90 °C). The Cm(III) speciation is determined by deconvolution of the emission spectra. The obtained distribution of Cm(III) species is used to calculate the conditional stability constants (log K′(T)) at a given temperature and ionic strength which are extrapolated to zero ionic strength by using the specific ion interaction theory (SIT). Thus, the thermodynamic log K0n(T) values for the formation of [Cm(Form)n](3−n)+ (n = 1, 2) and the ion interaction coefficients (ε(i,k)) for [Cm(Form)n](3−n)+ (n = 1, 2) with Cl− are obtained. The log K01(T) (2.11 (20 °C)–2.49 (90 °C)) and log K02(T) values (1.17 (30 °C–2.01 (90 °C)) increase continuously with increasing temperature. The log K0n(T) values are used to derive the standard reaction enthalpies and entropies (ΔrH0m, ΔrS0m) of the respective complexation reactions according to the Van’t Hoff equation. In all cases, positive ΔrH0m and ΔrS0m values are obtained. Thus, both complexation steps are endothermic and entropy-driven. 相似文献
8.
In this paper, size‐exclusion chromatography (SEC) was used to determine the metal concentration in different size fractions of a bog lake water. Two methods were applied: (a) preparative SEC with off‐line metal concentration analysis and (b) direct coupling of an analytical SEC system on‐line with an inductively‐coupled plasma mass spectrometer (ICP‐MS). In the preparative SEC measurements, maximum concentrations were found for different metal ions in different size fractions of the natural organic matter (NOM). Normalization of metal concentrations to dissolved organic carbon concentration (DOC) yielded two maxima in the high and in the very low molecular‐weight fractions. Whereas good recoveries were found for Al, Fe, and Ni, only 40% were obtained for Pb. This indicates that Pb formed labile complexes with NOM, and hence could strongly interact with the column material. In the experiments with the analytical SEC‐ICP‐MS system, the same trends were observed, but with even lower recoveries than in the preparative system. Sample preconcentration and storage were also investigated with respect to decrease in metal concentration. During the ultrafiltration preconcentration step Al and Fe were removed only to a small extent, whereas about half of the initial Pb was lost. This indicates that Al and Fe were mainly bound to high molecular‐weight fractions of NOM. In contrast to that, Al and in particular Fe were removed from solution more than proportionally with respect to DOC because of aggregation of the NOM during storage, whereas Pb and Ni were concentrated relative to the DOC. 相似文献
9.
The sorption of reactive (textile) dyes onto cucurbituril, a cyclic polymer with hydrophobic cavity, was studied. Dye sorption is strongly enhanced by Ca2+ or Sr2+ concentrations up to 100 mmol/L for all studied dyes. Mg2+ and alkaline ions had similar effects for only one dye (Reactive Red 120), and only at higher concentrations. Concentrations above 100 mmol/L – depending on cation and dye – dissolve cucurbituril and prevent dye removal. As shown in previous studies by our group loadings obtained under suitable conditions (calcium concentration between 2 and 100 mmol/L, total salt concentration not exceeding 100 mmol/L) are 1 to 1.7 mol/mol or 0.9 to 1.8 g/g. The chemical mechanism responsible for the ionic influences is still under investigation. Generally, cucurbituril is a potent sorbent for reactive dyes. However, the technical application is still limited by the lack of a support material that would allow use in fixed bed filters. 相似文献
10.
于1990年10月 - 1992年7月在室内条件下测定黄河中游乌拉特前旗、包头黄河大桥及清水河地段水体中天然配体与铜、铅、锌、镉反应的络会容量（C?C），计算总条件稳定常数（K）和络合容量指数（I）。实验证明：乌拉特前旗水体中络合客量最大，包头和清水河相近。络合容量顺序为：Cu＞Zn＞Cd＞Pb，和可溶性有机碳及碳酸盐分析结果一致。总条件稳定常数为：KPbL最大，KCuL，KZnL，KCdL相近。和长江水做了比较。络合容量指数在IgK相近情况下，随络合容量增大而增大。 相似文献