An analytical procedure involving sequential chemicai extractions has been developed for the partitioning of particulate trace metals (Cd, Co, Cu, Ni, Pb, Zn, Fe, and Mn) into five fractions: exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter, and residual. Experimental results obtained on replicate samples of fluvial bottom sediments demonstrate that the relative standard deviation of the sequential extraction procedure Is generally better than =10%. The accuracy, evaluated by comparing total trace metal concentrations with the sum of the five Individual fractions, proved to be satisfactory. Complementary measurements were performed on the Individual leachates, and on the residual sediments following each extraction, to evaluate the selectivity of the various reagents toward specific geochemical phases. An application of the proposed method to river sediments is described, and the resulting trace metal speciation is discussed.

Sequential extraction procedure for the speciation of particulate trace metals

Aquatic chemistry is becoming both a rewarding and substantial area of inquiry and is drawing many prominent scientists to its fold. Its literature has changed from a compilation of compositional tables to studies of the chemical reactions occurring within the aquatic environments. But more than this is the recognition that human society in part is determining the nature of aquatic systems. Since rivers deliver to the world ocean most of its dissolved and particulate components, the interactions of these two sets of waters determine the vitality of our coastal waters. This significant vol ume provides not only an introduction to the dynamics of aquatic chem istries but also identifies those materials that jeopardize the resources of both the marine and fluvial domains. Its very title provides its emphasis but clearly not its breadth in considering natural processes. The book will be of great value to those environmental scientists who are dedicated to keeping the resources of the hydrosphere renewable. As the size of the world population becomes larger in the near future and as the uses of materials and energy show parallel increases, the rivers and oceans must be considered as a resource to accept some of the wastes of society. The ability of these waters and the sediments below them to accommodate wastes must be assessed continually. The key questions relate to the capacities of aqueous systems to carry one or more pollutants."

Metal pollution in the aquatic environment

Arsenic adsorption on amorphous Al and Fe oxides and the clay minerals, kaolinite, montmorillonite, and illite was investigated as a function of solution pH and As redox state, i.e., arsenite [As(III)] and arsenate [As(V)]. Arsenic adsorption experiments were carried out in batch systems to determine adsorption envelopes, amount of As(III), As(V), or both adsorbed as a function of solution pH per fixed total As concentration of 20 μM As. Arsenate adsorption on oxides and clays was maximal at low pH and decreased with increasing pH above pH 9 for Al oxide, pH 7 for Fe oxide and pH 5 for clays. Arsenite adsorption exhibited parabolic behavior with an adsorption maximum around pH 8.5 for all materials. There was no competitive effect of the presence of equimolar arsenite on arsenate adsorption. The competitive effect of equimolar arsenate on arsenite adsorption was small and apparent only on kaolinite and illite in the pH range 6.5 to 9. The constant capacitance model was able to fit the arsenate and arsenite adsorption envelopes to obtain values of the intrinsic As surface complexation constants. These intrinsic surface complexation constants were then used in the model to predict competitive arsenate and arsenite adsorption from solutions containing equimolar As(III) and As(V) concentrations. The constant capacitance model was able to predict As adsorption from mixed As(III)-As(V) solutions in systems where there was no competitive effect.

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Competitive Adsorption of Arsenate and Arsenite on Oxides and Clay Minerals

Geochemical speciation and risk assessment of heavy metals in the river estuarine sediments--a case study: Mahanadi basin, India.

A comprehensive review of the single and sequential extraction schemes for metal fractionation in environmental samples such as soil and industrially contaminated soils, sewage sludge and sludge amended soils, road dust and run off, waste and miscellaneous materials along with other approaches of sequential extraction methods are being presented. A discussion on the application of chemometric methods in sequential extraction analysis is also being given. The study of single and sequential extraction methods for various reference materials are also being looked into. The review covers several aspects of the single and sequential extraction methodologies. The use of each reagents involved in these schemes are also discussed briefly. Finally the present upto date information by different workers in various fields of environmental geochemistry along with the possible future developments are also being outlined.

A Review of the Different Methods Applied in Environmental Geochemistry For Single and Sequential Extraction of Trace Elements in Soils and Related Materials

Hydrous manganese and iron oxides of soils and sediments are strong scavenging agents for heavy metal ions. Information on heavy metals extracted along with manganese and iron oxides has been used in mineral exploration. But currently used methods do not differentiate metal ions associated with manganese oxides and those associated with iron oxides. Manganese oxides differ from iron oxides in solubility in response to oxidation-reduction conditions, charge characteristics, and the quantity and kind of metal ions scavenged. This paper reports the development of an extraction method for the selective dissolution of manganese oxides from soils and sediments with minimal attack on the coexisting iron oxides, based on the difference in behavior of manganese oxides and iron oxides toward reduction under various conditions. By dissolving manganese oxides and iron oxides separately and determining respective metal ions which are released in the process, the geochemical significance of interelement relationships may be established. Manganese oxides in soils and sediments are found to be readily dissolved by a hydroxylamine hydrochloride (NH₂OH · HCl) solution, leaving the major part of iron oxides in the residue. Although dissolution of manganese oxides is relatively independent of pH (pH 1, 2, and 3) and concentration of the NH₂OH · HCl solution (0.025 to 0.25M), and time of equilibration (15 to 60 min), progressively greater amounts of iron oxides are released with lower pH and higher concentration of NH₂OH · HCl solution, and with longer time of equilibration. A 0.1M NH₂OH · HCl solution prepared in 0.01M HNO₃ (pH 2) dissolves, on the average, 85% of manganese oxides and about 5% of iron oxides from various sediments after equilibrating for 30 min. Dissolution of manganese oxides and of iron oxides from four highly weathered soils by this solution amounts, respectively, to 50% and less than 1%. At pH 2, most heavy metal ions released during the dissolution of manganese oxides will be prevented from forming insoluble hydroxides or basic salts through hydrolysis, and then they can be determined in solution by appropriate analytical methods.

T. T. Chao

Papers

Selective Dissolution of Manganese Oxides from Soils and Sediments with Acidified Hydroxylamine Hydrochloride