Distribution of protons and Cd between bacterial surfaces and dissolved humic substances determined through chemical equilibrium modeling

Bacteria and dissolved humic substances are capable of binding significant concentrations of metals in natural environments. Recent advances in understanding bacteria-metal and humic-metal complexation have provided a framework for directly comparing the binding capacities of these components. In this study, we use chemical equilibrium modeling to construct an internally consistent set of thermodynamic equilibrium constants for proton and Cd binding onto dissolved humic substances, using a variety of published data sets. Our modeling approach allows for the direct comparison of humic substance binding constants and site densities to those previously published for proton and Cd binding onto natural consortia of bacteria. We then combine these constants into a unified model that accounts for the competition between bacterial surfaces and humic and fulvic acids in order to determine the relative importance of each component on the total Cd budget. The combined model is used to examine the relative contributions of bacteria and dissolved humic substances to Cd complexation in natural settings. Calculations are performed for three representative systems: (1) one with a maximum realistic concentration of bacteria and a minimum realistic concentration of humic substance, (2) one with a maximum realistic concentration of humic substance and a minimum concentration of bacteria, and (3) one with an intermediate concentration of both components.Our modeling results indicate that dissolved humic substances have 2 orders of magnitude more available binding sites than bacterial surfaces (per gram). Humic substances also have a greater affinity than bacterial surfaces for binding Cd over circumneutral pH ranges. The combined model results demonstrate that, depending upon their relative concentrations, both Cd-humic and Cd-bacteria complexes are capable of dominating Cd-speciation in specific natural environments. This modeling approach is useful in that it can easily be extended to include other metals and binding ligands; however, thermodynamic data must be gathered on additional components to facilitate the modeling of more realistic systems.     

Uranium(VI) sorption to hematite in the presence of humic acid

A long-standing problem in aquatic geochemistry has been the incorporation of natural organic matter (NOM) into speciation models. The general effect of NOM on metal ion sorption by particles has been understood for some time, and significant progress has been made in elucidating some of the details of the role of NOM through the use of surrogate organic acids such as citric acid. However, a gap exists between the general observations that have been made of NOM behavior and the inclusion of NOM in surface chemical models for metal ion sorption. In this paper, we report on the results of a study on the sorption of U(VI) by hematite in the absence and presence of Suwannee river humic acid (HA) and over a range of other system conditions (e.g., pH, I). Essential HA characteristics (e.g., its acid/base, metal binding, and surface chemical properties) were “captured” by representing the HA as an assembly of monoprotic acids with assumed pK values and without explicit correction for electrostatic effects. The ternary system (hematite/HA/U(VI)) was simulated through the combination of the binary submodels (i.e., CO₃²⁻/hematite, U(VI)/HA, U(VI)/hematite, and HA/hematite) with model constants fixed at the values determined from simulations of the respective experimental systems. However, the “summed-binary” approach undersimulated experimental results, and the ternary system model required the postulation of two ternary surface (Type A) complexes composed of the uranyl ion, hematite surface sites, and the model ligands comprising the HA. Consideration of the HA in this manner permitted the simulation of HA effects on U(VI) sorption by hematite over a range of solution conditions using a general speciation model.     

An overview of dissolved organic carbon in groundwater and implications for drinking water safety

Dissolved organic carbon (DOC) is composed of a diverse array of compounds, predominantly humic substances, and is a near ubiquitous component of natural groundwater, notwithstanding climatic extremes such as arid and hyper-arid settings. Despite being a frequently measured parameter of groundwater quality, the complexity of DOC composition and reaction behaviour means that links between concentration and human health risk are difficult to quantify and few examples are reported in the literature. Measured concentrations from natural/unpolluted groundwater are typically below 4 mg C/l, whilst concentrations above these levels generally indicate anthropogenic influences and/or contamination issues and can potentially compromise water safety. Treatment processes are effective at reducing DOC concentrations, but refractory humic substance reaction with chlorine during the disinfection process produces suspected carcinogenic disinfectant by-products (DBPs). However, despite engineered artificial recharge systems being commonly used to remove DOC from recycled treated wastewaters, little research has been conducted on the presence of DBPs in potable groundwater systems. In recent years, the capacity to measure the influence of organic matter on colloidal contaminants and its influence on the mobility of pathogenic microorganisms has aided understanding of transport processes in aquifers. Additionally, advances in polymerase chain reaction techniques used for the detection, identification, and quantification of waterborne pathogens, provide a method to confidently investigate the behaviour of DOC and its effect on contaminant transfer in aquifers. This paper provides a summary of DOC occurrence in groundwater bodies and associated issues capable of indirectly affecting human health.     

The use of natural analogues to assess radionuclide transport

Predicting the long-term safety and performance of a repository for intermediate- to high-level radioactive wastes requires the evaluation of various scenarios which may influence the integrity of the repository system. One such scenario, radionuclide transport, is described, and some of the geochemical processes which serve to enhance or retard transport are illustrated with examples selected from natural analogue or natural system studies. These studies, as distinct from laboratory simulations, help considerably in understanding how near- and far-field radionuclide transport mechanisms work over geological timescales (thousands to hundreds of thousands of years), more in line with the anticipated lifespan of a repository.

Processes addressed include: stability of the spent fuel UO₂ matrix; bentonite backfill as a barrier to radionuclide diffusion; retention of radionuclides by absorption on fracture minerals; transport and diffusion of radionuclides controlled by interconnected bedrock porosity; geochemical influence and behaviour of repository construction materials on radionuclide transport.     

Using data from natural environments to improve models of uranium speciation in groundwaters

It is essential that computer-based models used in the safety assessment of radioactive waste repositories accurately represent the processes occurring in real field systems. Confidence in long-term predictions of radionuclide migration will then depend upon the completeness of data available, particularly those obtained from the disposal site, and correct implementation of the model. The study of natural geochemical systems provides information on the adequacy of the underlying “generic” database and enhances our understanding of the transport mechanisms which form the basis of performance assessment. This paper concentrates on speciation-solubility modelling and describes four natural occurrences of uranium, each of which displays a different facet of uranium migration behaviour. The attributes of each site and the means by which uranium is immobilised are described. Retardation is highly species specific and this is illustrated through the use of site data in equilibrium speciation and coupled chemical transport calculations. Oxidation of U(IV) to U(VI) species promotes leaching of uranium ore at all the locations studied, emphasising the need to ensure that reducing conditions persist in a repository dominated by its actinide inventory.     

Computational methods for fitting statistical distribution models of multi-site binding equilibria

Statistical distribution models of multi-site binding equilibria have potential applicability in the study of acid-base and metal complexation chemistry of humic substances in soils, sediments, and natural waters. A mathematical derivation is presented for the general continuous model for the case of proton binding; computational methods are described for fitting numerically the parameters in such models. Among models considered are those based on nontruncated, truncated, and bimodal (mixed) distributions. Specific emphasis is placed on Gaussian distribution models.     

Metal ion binding to colloids from database to field systems

Nowadays, environmental problems related to soil pollution with heavy metals are numerous, therefore, it is important to understand metals behaviour in aquatic sediments and soils and to estimate their transfer. The fate of metals in the environment is closely related to their interactions with the major reactive compartments (organic matter, iron and manganese oxides, clays). The objective of this work is to develop an approach based on the combination of several models to study metal ion speciation in different environmental systems. Models used to describe the interactions of metals with the main reactive phases in the soil are CD-MUSIC (amorphous and crystallized iron oxides), NICA-Donnan (organic matter and manganese oxides) and cationic ion exchange model (clays). First, this work implies the definition of generic parameters to describe the interactions of the studied metals with iron and manganese oxides and part of this information is missing in the literature. Then, after a validation of the approach by comparison with analytical results, this multi-surface model is applied to test sites corresponding to one soil and two riverine environments.These new models give good predictions of the behaviour of major and trace metal ions even in heterogeneous systems characteristic of natural environment. The measured free metal concentrations in the solution are in agreement with those obtained from model calculations. In the case of the soil test site, the soil solution composition and speciation are predicted using the soil major constituents characteristics.     

Effect of humic acid on the pH-dependent adsorption of terbium (III) onto geological materials

Mobilization of actinides by interaction with humic colloids in aquifers is essentially determined by the geochemical conditions. In this study, the pH dependence of the influence of humic acid on metal adsorption on a variety of geological solids (kaolinite, phyllite, diabase, granite, sand) was investigated for Tb(III) as an analogue of trivalent actinides, using ¹⁶⁰Tb as a radiotracer. Humic material was radiolabelled with ¹³¹I to allow experiments at low DOC concentrations, as encountered in subsurface systems in the far-field of a nuclear waste repository. For all solids, a changeover from mobilization to demobilization is observed on acidification. Except for phyllite, the reversal occurs at slightly acidic pH values, and is thus relevant in respect of risk assessments. A composite distribution model was employed to reproduce the changeover on the basis of the underlying constituent processes. For this purpose, humate complexation of Tb(III) and adsorption of humic acid as a function of pH were investigated as well. Although the ternary systems cannot be constructed quantitatively by combining the binary subsystems, the relevant interdependences are adequately described by the composite approach. For a more general discussion in view of the diversity of natural organic colloids, adsorption isotherms of various humic and fulvic acids on sand were compared.     

Trace metal-humate interactions. II. The “conservative roof” model and its application

The modelling of metal-humate interactions has been a field of active research for more than 3 decades but despite all efforts there is still far from a consensus concerning humic binding models. The authors demonstrate that a synopsis of large sets of reliable experimental data for Ca, Co, Ni, Eu, Am, Cm, Np(V) and U(VI) reveals a consistent picture of the influence of metal concentration, pH and ionic strength on metal-humate interactions. However, this consistent behaviour cannot be interpreted with high numerical accuracy by simple binding models, the need for more adjustable parameters increases proportional to the width of the experimental parameter range to be fitted. This experience triggered the proposal of a pragmatic approach for performance assessment purposes. The “conservative roof” approach does not aim to accurately model all experimental data but rather allows estimates to be made of the maximum effects on metal complexation to be expected from humic substances. A specific “conservative roof” model is applied to situations generally to be expected in deep groundwater and selected cases of interest for planned Swiss repositories of radioactive waste are discussed in detail.     

Metal binding capacity of selected maine surface waters

Concentrations of Ca, Cd, Cu, Fe, and Pb and binding capacities for Cd, Cu, and Pb were determined for water samples collected from 12 lakes in southwestern Maine using atomic absorption and ion-selective electrodes, respectively. Surface waters in this area are soft and characterized by low pH. Some lakes were highly colored with refractory organics, whereas others had very low organic carbon concentrations. Both Cu and Pb concentrations were positively correlated with organic carbon content. Copper and Pb binding capacities were significantly correlated with organic carbon content, whereas Cd binding capacity was positively correlated with pH, but not with organic carbon. Surface water binding capacity for Pb was greater than that for Cu or Cd. More than 99% of the Ca from all waters studied was removed onto cationic exchange resins. Less than 1% of the total Cu existed as cationic species in highly humic waters, whereas as much as 65% existed as cationic species in less huic waters. Conversely, more than 99% of the Cd present in humic waters existed as cationic species, whereas as little as 50% existed as cationic species in less humic, more alkaline waters. These correlative studies indicate that binding by organic carbon is important for both Cu and Pb in this area and must be considered in models of trace metal speciation. However, Cd binding in the same waters is not correlated with organic carbon, which does not need to be considered in speciation models for Cd.     

Competitive adsorption of metal ions onto goethite–humic acid-modified kaolinite clay

A binary mixture of humic acid and geothite was prepared and used to modify kaolinite to produce geothite–humic acid (GHA)-modified kaolinite adsorbent useful for the adsorption of Pb²⁺, Cd²⁺, Zn²⁺, Ni²⁺ and Cu²⁺ from Single and Quinary (5) metal ion systems. The cation exchange capacity (CEC) and specific surface area of GHA-modified kaolinite clay adsorbent were found to be 40 meq/100 g and 13 m²/g, respectively, with the CEC being five times that of raw kaolinite clay (7.81 meq/100 g). The Langmuir–Freundlich equilibrium isotherm model gave better fit to experimental data as compared with other isotherm models. In Quinary metal ion system, the presence of Zn²⁺ and Cu²⁺ appears to have an antagonistic effect on the adsorption of Pb²⁺, Cd²⁺ and Ni²⁺, while the presence of Pb²⁺, Cd²⁺ and Ni²⁺ shows a synergistic effect on the adsorption of Zn²⁺ and Cu²⁺. The GHA-modified kaolinite showed strong preference for the adsorption of Pb²⁺ in both metal ion systems. Brouers–Weron–Sotolongo (BWS) kinetic model gave better fit to kinetic data compared with other kinetic models used. Data from BWS kinetic model indicate that adsorption of metal ions onto GHA-modified adsorbent in both metal ion systems followed strictly, diffusion-controlled mechanism with adsorption reaction proceeding to 50 % equilibrium in <2 min in the Single metal ion system and <1 min in the Quinary metal ion system. Adsorption of metal ions onto GHA-modified kaolinite is fairly spontaneous and endothermic in nature in both metal ion systems although the rate of metal ion uptake and spontaneity of reaction are reduced in the Quinary metal ion system.     

The relationship between molecular composition and fluorescence properties of humic substances

The quantity and quality of dissolved organic matters have been widely characterized by fluorescence spectroscopy, yet the relationship between the fluorescence properties of dissolved organic matters and its molecular composition remains poorly described in the literature. Here, we measured the fluorescence excitation–emission matrix of 17 well-characterized humic substance standards to determine a range of fluorescence parameters, including classical fluorescence indices (e.g., fluorescence index, biological index and humification index) and parameters derived from parallel factor analysis (e.g., component contribution). Relationships between humic substance’s fluorescence and compositional parameters were then statistically examined using canonical correspondence and simple correlation analyses. The canonical correspondence analysis generally suggested that most fluorescence parameters determined here are highly associated with the amount of aliphatic and aromatic compounds in humic substances. However, the correlation analysis between single molecular and fluorescence parameters indicated that the fluorescence properties of humic substances including the parallel factor analysis component contribution also significantly correlate well with several aspects of the molecular composition of humic substances, such as elemental composition, carbon species, acidic functional group and iron complexation. Overall, our results suggest that measurement of humic substance’s fluorescence is beneficial in understanding the molecular composition and environmental functions of dissolved organic matters in natural and engineered waters.     

Complexation and reduction as factors in the link between metal ion concentrations and organic matter in the Indian River

Complexation of metal ions by organic matter is frequently considered to play a part in metal ion dissolution in natural waters. A field study of a relatively unperturbed stream, high in organics, associates this with the fraction related to soil organic acids (humic acids). The association might have two origins. The first is complexation. However, well known sequences of complexing tendency do not predict the behaviour. A better theory uses the additional factor of the reducing capacity of dissolved organic matter toward Fe(III) and Mn(IV).     

重金属迁移转化模型研究

大量重金属污染物迁移转化的现象和研究成果都表明重金属以泥沙颗粒为载体迁移转化,描述重金属在天然水体中的迁移转化必须紧紧抓住泥沙颗粒运动及重金属与泥沙之间的转化关系进行.为此在对现有的重金属迁移转化数学模型进行概括分类的基础上,根据水沙运动与污染物相互作用关系,分析了泥沙颗粒运动及重金属吸附解吸不平衡过程,并结合水沙数学模型,建立了重金属迁移转化的耦合模型.同时在模型合理性分析的基础上,对模型进行了计算分析,分析表明模型能够合理地反映重金属污染物在水体中的迁移转化过程.     

Interactions of copper, organic acids, and sulfate in goethite suspensions

Sorption of copper and sulfate onto goethite (-FeOOH) in aqueous solution is examined in Cu---SO₄ binary-sorbate systems and in Cu-SO₄-organic acid (either phthalic acid or chelidamic acid) ternary-sorbate systems. Compared to single-sorbate systems, sorption of Cu onto goethite was enhanced at low pH values in the presence of sulfate. Sorption data for Cu and SO₄ in Cu---SO₄ binary-sorbate systems were described with the Generalized Two Layer Model by proposing formation of a Cu---SO₄ ternary surface complex. Addition of sulfate to a Cu-phthalic acid binary sorbate system had little effect on Cu sorption. However, addition of sulfate to Cu-chelidamic acid binary-sorbate systems resulted in significant reduction of Cu sorption at low pH values, primarily due to competition for surface sites between sulfate and Cu-chelidamic acid ternary surface complexes. While organic acids such as humic substances can potentially influence sorption of metal ions, results from this study suggest that the extent of such influence may be strongly dependent on the presence of other sorbing anions, such as sulfate. Sorption of Cu and SO₄ in Cu---SO₄-organic acid ternary-sorbate systems was predicted reasonably well, based on surface reactions and equilibrium constants derived from fitting of sorption data from single- and binary-sorbate systems. These modeling results provide a validation of the extrapolation of sorption from simple systems to multicomponent systems through surface complexation modeling.     

Contribution of organic complexation to Ni,Co and Cu speciation in surface waters: Implications for hydrogeochemicalsurveys

Organic materials dissolved in surface waters have long been implicated in metal binding and transport. In particular, fulvic and humic acids are considered to have a significant impact on speciation, total metal levels in solution and on the persistence of those metals. This work emphasizes the role played by dissolved organic matter (DOM) on the complexation of nickel, copper and cobalt and on its application to interpretation of surface water hydrogeochemical survey data. Waters from a number of well-known mining districts in Canada have been studied; in particular from Cobalt (Ontario), Sackville (New Brunswick) and Thetford Mines (Quebec). The diafiltration binding technique was used and shows that nickel, copper and cobalt are complexed significantly by DOM in natural waters. The tendency towards complexation was found to be Cu > Ni > Co. The binding functions determined were observed to be highly sensitive to pH and ligand:metal ratios; a gradation of binding site strength is evident.Data from some hydrogeochemical surveys conducted in the Kenora, Algoma and Ottawa districts of Ontario have been reinterpreted in the light of available data on the complexation behaviour of nickel, copper and cobalt. Occurrence of large water-borne anomalies unsupported by lake sediment loadings is most likely for cobalt and nickel and least likely for copper according to both field observations and experimental data. These studies provide good evidence for the formation of strong solution stable metal-organic species; the principal differences in persistence and migration behaviour are probably due to rates of coagulation and adsorption-precipitation processes which preferentially remove copper from solution. It is fair to conclude that these metals can be of use in mineral exploxation surveys using surface waters provided caution is exercised in interpretation of anomalies, especially in the absence of supporting sediment anomalies. Dissolved organic matter concentrations should always be determined when nickel, copper and cobalt are to be employed.     

Effect of fulvic acids on sorption of U(VI), Zn,Yb, I and Se(IV) onto oxides of aluminum,iron and silicon

The sorption of Yb³⁺, UO²⁺₂, Zn²⁺, I⁻ and SeO²⁻₃ onto Al₂O₃, Fe₂O₃ and SiO₂ were determined by a batch technique in the presence and absence of fulvic acids. The effects of fulvic acid on sorption were compared. The existing general consensus, that humic substances tend to enhance metal cation sorption at low pH, reduce metal cation sorption at high pH and reduce inorganic anion sorption between pH values 3 to 10, was generally shown to be true. However, in this work many exceptions to the general consensus were found. The study indicated that the effect of humic substances on sorption of inorganic cations or anions depends not only on pH, but also on the nature of the oxide, the nature of humic substance, fractionation of the humic substance by sorption, the relative strength of complexes of both soluble and sorbed humic substances, the extent of surface coverage by humic substance, the initial concentration of humic substance and the inorganic electrolyte composition.     

Electrochemical properties of solids at the aqueous–solid interface and heterogeneity of surfacePropriétés électrochimiques des solides à l'interface solide–eau et hétérogénéité de surface

In aqueous medium, solid surfaces are in general electrically charged. The induced electrical and chemical properties govern numerous phenomena, such as colloidal stability or transport of pollutants. Numerous industrial processes make use of these properties. The understanding of the underlying mechanisms at molecular level is of high importance in order to predict and master the behaviour of dispersed matter in the environment and in industrial processes. The present paper shows the evolution of theories and experimental methods, their recent developments and applications. To cite this article: F. Thomas et al., C. R. Geoscience 334 (2002) 633–648.     

The Development of Laser Ablation ICP-MS and Calibration Strategies: Examples from the Analysis of Trace Elements in Volcanic Glass Shards and Sulfide Minerals

This contribution presents a review of the recent developments in laser ablation inductively coupled plasma-mass spectrometry. We describe the important developments which have occurred in the laser systems used, leading to a spatial resolution of around 20 (im, and give an overview of the major instrument developments which have affected the geological applications of laser ablation ICP-MS. We describe the calibration of laser ablation for the analysis of trace elements in two different matrices: volcanic glass shards and sulfide minerals. We show how single glass shards can be analysed using the National Institute of Standards and Technology (NIST) glass certified reference materials for calibration and demonstrate the effect of using single spot analyses compared to rastering of the calibration sample. We show the importance of inter-shard variation and demonstrate that averaged single shard analyses produce data which compare well with bulk analyses. The calibration of the laser system for sulfide mineral analysis is discussed and two different strategies are proposed, one using spiked pressed powder pellets of sulfides and the other metal reference materials. We present conclusions and recommendations for the calibration of laser ablation ICP-MS instruments.