The “Zero-order Model” revisited: Paul Schindler's influence on the development of trace metal scavenging models     

Santschi  Peter H.  Honeyman  Bruce D.  Quigley  Matthew S. 《Aquatic Sciences - Research Across Boundaries》1993,55(4):230-239

In 1975 Paul Schindler produced the first oceanic trace metal scavenging model to explicitly include the role of surface chemistry as a control on trace metal water column residence times. The eighteen years that have elapsed since the publication of Schindler's seminal paper have seen the development of a variety of oceanic scavenging models; yet, the fundamental insight of his Zero-order Model remains the benchmark. This paper describes the role of Paul Schindler's work on surface chemistry in providing a framework for the current generation of trace element scavenging models.  相似文献   

A surface complexation model for cadmium and lead adsorption onto diatom surface     

A. Glabert  O.S. Pokrovsky  C. Reguant  J. Schott  A. Boudou 《Journal of Geochemical Exploration》2006,88(1-3):110

This work is devoted to the physico-chemical study of cadmium and lead interaction with diatom–water interfaces for two marine planktonic (Thalassiosira weissflogii = TW, Skeletonema costatum = SC) and two freshwater periphytic species (Achnanthidium minutissimum = AMIN, Navicula minima = NMIN) by combining adsorption measurements with surface complexation modeling. Reversible adsorption experiments were performed at 20 °C after 3 h of exposure as a function of pH, metal concentration in solution, and ionic strength. While the shape of pH-dependent adsorption edge is similar among all four diatom species, the constant-pH adsorption isotherm and maximal binding capacities differ. These observations allowed us to construct a surface complexation model for cadmium and lead binding by diatom surfaces that postulates the constant capacitance of the electric double layer and considers Cd and Pb complexation with mainly carboxylic and, partially, silanol groups. Parameters of this model are in agreement with previous acid–base titration results and allow quantitative reproduction of all adsorption experiments.  相似文献   

Adsorption of Copper, Nickel, and Cadmium on Goethite in the Presence of Organic Ligands   总被引：2，自引：0，他引：2  

Diane Buerge-Weirich  Philippe Behra  Laura Sigg 《Aquatic Geochemistry》2003,9(2):65-85

Adsorption of copper, cadmium and nickel at low concentrations on goethite was studied in the presence of the simple organic ligands oxalate, salicylate, and pyromellitate. The experimental metal adsorption behavior was compared to calculations with a surface complexation model to evaluate the most important interactions. Oxalate mostly decreased Cu and Ni adsorption at high pH-values by competition between solution and surface complexation but had no effect on Cd adsorption. Cu adsorption in the presence of oxalate below pH 6 could best be described by defining a ternary complex of type A (surface-metal-ligand). Salicylate had only minor effects on metal adsorption. The adsorption of Cu in the presence of salicylate above pH 5 could be explained by a ternary complex of type A. Pyromellitate increased the adsorption of Cu and Cd in the acidic pH-range, likely by formation of ternary surface complexes of type B (surface-ligand-metal).  相似文献   

热液中二氧化硅与成矿元素锡络合作用的实验标定   总被引：2，自引：0，他引：2  

樊文苓  陈紫新  王声远  田弋夫 《矿物岩石地球化学通报》1997,(3)

热液中二氧化硅与成矿元素锡络合作用的实验标定＊樊文苓陈紫新王声远田弋夫（中国科学院矿床地球化学开放研究实验室，贵阳５５０００２）关键词锡石溶解度二氧化硅的络合作用迁移形式前人对锡在流体中迁移形式的实验研究和热力学计算表明，锡（Ⅱ）的多种氯络合物是高温...  相似文献   

Free cupric ion concentrations and Cu complexation in selected Swiss lakes and rivers   总被引：1，自引：0，他引：1  

Hanbin Xue  Andrea Oestreich  David Kistler  Laura Sigg 《Aquatic Sciences - Research Across Boundaries》1996,58(1):69-87

[Cu²⁺] and Cu complexation parameters in some selected freshwater systems in Switzerland were determined by the technique of ligand-exchange and DPCSV. Results from the water columns of some eutrophic and oligotrophic lakes are presented and compared to small acid lakes. Cu is strongly complexed by organic ligands which with very high stability constants at low concentrations are probably biologically produced, as indicated by the seasonal variations in the eutrophic lakes and by the relationship between Cu complexation and algal activity in the eutrophic (pCu=15–16), oligotrophic (pCu=13–14) and acidic (pCu=9–10) lakes. The extent of Cu complexation in river waters was generally lower than in the eutrophic lakes, at similar DOC levels. No obvious correlation between Cu complexation and DOC was observed, indicating that Cu complexing ligands are specific organic compounds.  相似文献   

Surface complexation at hydrous fluorapatite     

Willis Forsling  Liuming Wu 《Aquatic Sciences - Research Across Boundaries》1993,55(4):336-346

The adsorption of H⁺, OH^– and ARS (Alizarin Red S) onto hydrous fluorapatite surfaces and Ca²⁺—ARS complexation in solution were studied by means of combined potentiometric and spectrophotometric titrations, as well as zeta potential and FT-IR measurements. Corresponding equilibrium constants of surface and solution reactions are determined. The application in flotation processes is discussed.  相似文献   

Photochemical degradation of organic iron complexing ligands in seawater     

Rodney?T.?PowellEmail author  Amy?Wilson-Finelli 《Aquatic Sciences - Research Across Boundaries》2003,65(4):367-374

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Size Fractionation (Dissolved, Colloidal and Particulate) of Trace Metals in the Thur River, Switzerland     

Laura Sigg  Hanbin Xue  David Kistler  René Sshönenberger 《Aquatic Geochemistry》2000,6(4):413-434

The distribution of some trace metals (Cu, Zn, Ni, Co,Fe, Mn) and of DOC over a particulate (> 1 m),a colloidal (size < 0.45 m and molecular weight > 10 kD) and an ultrafiltered fraction (< 10 kD)was determined at several sites on the Thur River,Switzerland, at various times of the year. Thecomplexation of Cu by strong ligands in theultrafiltrate and in the conventional filtrate (<0.45 m) was compared using a ligand-exchange/CSV method.The <0.45 m concentrations of Cu (from anaverage of 7 nM to 24 nM), Zn (<5–23 nM), Ni (5–13 nM),Co (1.5–3 nM) and Mn (7–92 nM)increased downstream. The major part of Cu, Zn, Niand Co usually occurred in the ultrafiltratefraction at all sites, whereas Fe and Mn were mostlyin the particulate fraction, under conditions of lowsuspended matter content (< 10 mg L^-1) in theriver. The percentage of metal in the colloidalfraction, with respect to the 0.45-m filtrate,decreased in the order: Cu (median 11%) > Zn Ni(median 5–6%) > Mn Co (median < 5%). DOCalso consisted mostly of molecules in the < 10 kDrange.Cu was strongly complexed by natural organic ligandsin all filtrate and ultrafiltrate samples. A largepart of the strong Cu binding ligands consisted ofcompounds in the < 10 kD range, but colloidalligands with similar properties also occurred. Cu wasdistributed among the dissolved and the colloidalligands, roughly in proportion to organic carbon.The colloidal fraction (as defined here) did notincrease in its proportional amount downstream and wasonly of limited significance in transporting traceelements in the Thur River under low discharge conditions.  相似文献   

Physico-chemical Speciation of Lead in South San Francisco Bay     

P.B. Kozelka  S. Sañudo-Wilhelmy  A.R. Flegal  K.W. Bruland 《Estuarine, Coastal and Shelf Science》1997,44(6):649-658

The speciation of lead at a site in the South San Francisco Bay was determined using a combination of physical size fractionation and electrochemical analyses. The ‘ total dissolvable ’ Pb was 8·1 nM from analysis of an acidified unfiltered sample. The ‘ dissolved ’ Pb was equal to 0·20 nM (41 ng l⁻¹), only 2·5% of the ‘ total dissolvable ’ Pb. The difference yielded the ‘ particulate ’ Pb equal to 7·9 nM (1·6 μg l⁻¹). Results from crossflow ultrafiltration indicated that almost all (0·19 nM) of the dissolved Pb was ‘ in solution ’ [<10K nominal molecular weight (MW)] and that colloidal Pb (10K MW to 0·2 μm)accounted for onlyc. 1% of the dissolved Pb at this station. This small concentration (0·01 nM) of colloidal Pb may be attributed to the low amount of organic carbon associated with colloid size fraction as determined by dissolved organic carbon analyses.The chemical speciation of lead was determined in the dissolved sample and ultrafiltered sub-sample. Differential pulse anodic stripping voltammetry (DPASV) on a thin mercury film (TMF) rotating glassy carbon disk electrode (RGCDE) was used to distinguish the kinetically labile inorganic species (Pb′) from the Pb-chelated by organic ligands (PbL_i). Lead titration results were similar for both samples revealing that Pb′, PbL_iand excess unbound ligands were present primarily in the ultrafiltrate, rather than in the colloidal phase. The titration data can be interpreted as dissolved Pb being influenced by two classes of Pb-binding ligands. In the dissolved sample, the concentration of the stronger class of ligands was [L₁]=0·89±0·35 nM, with a conditional stability constant ofK^cond_L1,Pb′=3±1×10¹⁰M⁻¹. The weaker class was [L₂]=12·8±1·9 nM, withK^cond_L1,Pb′=4±1×10⁸ M⁻¹. The presence of these ligands, in excess of the dissolved Pb, resulted in [Pb′]=7±2 pM and [Pb²⁺]=0·3 pM (62 pg l⁻¹). While less than 2·4% of the ambient Pb was ‘ in solution ’, it existed chiefly in the form of organic complexes with [PbL₁]=0·15 nM and [PbL₂]=0·03 nM. More significantly, there were large concentrations of unchelated Pb-binding ligands, (L_i′), available to buffer the free Pb²⁺concentration in the event of perturbations in dissolved Pb.  相似文献   

Reactive transport in unsaturated soil: Comprehensive modelling of the dynamic spatial and temporal mass balance of water and chemical components     

L. Wissmeier  D.A. Barry 《Advances in water resources》2008

By implementing the moisture-based form of Richards’ equation into the geochemical modelling framework PHREEQC, a generic tool for the simulation of one-dimensional flow and solute transport in the vadose zone undergoing complex geochemical reactions was developed. A second-order, cell-centred, explicit finite difference scheme was employed for the numerical solution of the partial differential equations of flow and transport. In this scheme, the charge-balanced soil solution is treated as an assembly of elements, where changes in water and solute contents result from fluxes of elements across cell boundaries. Therefore, water flow is considered in terms of oxygen and hydrogen transport.  相似文献