Minerals and organic matter (OM) may form intricate associations via myriad interactions. In soils, the associations of OM with mineral surfaces are mainly investigated because of their role in determining the long-term retention of OM. OM “must decay in order to release the energy and nutrients that drive live processes all over the planet” ( Janzen, 2006 ). Thus, the processes and mechanisms that retain OM in soil are a central concern to very different branches of environmental research. An agronomist may want to synchronize periods of high nutrient and energy release with the growth stages of a crop. An environmental chemist may wish to either immobilize an organic soil contaminant or enhance its decomposition into less harmful metabolites, while climate scientists need to understand the processes that mediate the production of potent greenhouse gases from decomposing OM. Associations of OM with pedogenic minerals (henceforth termed mineral–organic associations (MOAs)) are known to be key controls in these and many other processes. Here we strive to present an overview of the current knowledge on MOAs and identify key questions and future research needs.

Chapter One – Mineral–Organic Associations: Formation, Properties, and Relevance in Soil Environments

Role of organic amendments on enhanced bioremediation of heavy metal(loid) contaminated soils

A general description of the mathematical and numerical formulations used in modern numerical reactive transport codes relevant for subsurface environmental simulations is presented. The formulations are followed by short descriptions of commonly used and available subsurface simulators that consider continuum representations of flow, transport, and reactions in porous media. These formulations are applicable to most of the subsurface environmental benchmark problems included in this special issue. The list of codes described briefly here includes PHREEQC, HPx, PHT3D, OpenGeoSys (OGS), HYTEC, ORCHESTRA, TOUGHREACT, eSTOMP, HYDROGEOCHEM, CrunchFlow, MIN3P, and PFLOTRAN. The descriptions include a high-level list of capabilities for each of the codes, along with a selective list of applications that highlight their capabilities and historical development.

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Reactive transport codes for subsurface environmental simulation

The complexation of heavy metals with dissolved organic matter (DOM) in the environment influences the solubility and mobility of these metals. In this paper, we measured the complexation of Cu, Cd, Zn, Ni, and Pb with DOM in the soil solution at pH 3.7-6.1 using a Donnan membrane technique. The results show that the DOM-complexed species is generally more significant for Cu and Pb than for Cd, Zn, and Ni. The ability of two advanced models for ion binding to humic substances, e.g., model VI and NICA-Donnan, in the simulation of metal binding to natural DOM was assessed by comparing the model predictions with the measurements. Using the default parameters of fulvic and humic acid, the predicted concentrations of free metal ions from the solution speciation calculation using the two models are mostly within 1 order of magnitude difference from the measured concentrations, except for Ni and Pb in a few samples. Furthermore, the solid-solution partitioning of the metals was simulated using a multisurface model, in which metal binding to soil organic matter, dissolved organic matter, clay, and iron hydroxides was accounted for using adsorption and cation exchange models (NICA-Donnan, Donnan, DDL, CD-MUSIC). The model estimation of the dissolved concentration of the metals is mostly within 1 order of magnitude difference from those measured except for Ni in some samples and Pb. The solubility of the metals depends mainly on the metal loading over soil sorbents, pH, and the concentration of inorganic ligands and DOM in the soil solution.

Complexation with dissolved organic matter and solubility control of heavy metals in a sandy soil.

Al(III) and Fe(III) binding by humic substances in freshwaters, and implications for trace metal speciation.

A multisurface model is used to evaluate the contribution of various sorption surfaces to the control of heavy metal activity in sandy soil samples at pH 3.7−6.1 with different sorbent contents. This multisurface model considers soil as a set of independent sorption surfaces, i.e. organic matter (NICA-Donnan), clay silicate (Donnan), and iron hydroxides (DDL, CD-MUSIC). The activities of Cu2+, Cd2+, Zn2+, Ni2+, and Pb2+ in equilibrium with the soil have been measured using a Donnan membrane technique. The metal activities predicted by the model agree with those measured reasonably well over a wide concentration range for all the metals of interest except for Pb. The modeling results suggest that soil organic matter is the most important sorbent that controls the activity of Cu2+, Cd2+, Zn2+, and Ni2+ in these sandy soils. When metal loading is high in comparison with soil organic matter content, the contribution of clay silicates to metal binding becomes more important. Adsorption to iron hydroxides is fo...

Contribution of Individual Sorbents to the Control of Heavy Metal Activity in Sandy Soil

Interactions of calcium and fulvic acid at the goethite-water interface

Acidity (pH) has been realized to be the most important soil characteristic that modulates bioavailability of heavy metals by affecting both the chemical speciation of metals in soil and the metal binding to the active sites on biota. In this work, we show that besides soil pH, metal bioavailability also depends to a certain extent on the type of soil. A better understanding of the role of soil type in regulating metal availability can be achieved with the analysis of soil composition and with calculations using chemical speciation models. Results of pot experiments, in which three different soils were spiked with nickel, show that the EC50 of total nickel in decreasing the biomass production of oats varies widely (0.7−22.5 mmol kg-1 soil, more than 30 times). pH (4.7−7.0) is the most important factor, explaining up to a factor of 14 difference of nickel bioavailability in the soils. The remaining variation is caused by other differences in soil composition (soil type). The bioavailability and toxicity of...

Understanding the effects of soil characteristics on phytotoxicity and bioavailability of nickel using speciation models.

Accurate measurement of the free metal ion is difficult, especially for trace metals present in very small concentrations (less than micromolar) in natural systems. The recently developed Donnan membrane technique can measure the concentrations in solution in the presence of inorganic and organic complexing agents. We have developed this method further to make it applicable for analysing soil samples. The major development is the linkage of a soil column with the Donnan cell. The operational aspects of the method, including equilibrium time, buffering capacity and correction for differences in ionic strength, were investigated and optimized. The method was applied to determine concentrations of free Cu2 , Cd2 , Pb2 and Zn2 in the soil solution of 15 soil samples (pH 2.97.1, organic C < 2.9137.4 g kg1, clay 0.251.6Ž Compared with other speciation methods, the Donnan membrane technique has the advantage of allowing the measurement of several elements simultaneously and it minimizes the disturbance of substrate. The detection limit of the technique is about 109 m. This method can be applied to study the biogeochemical behaviour of metals in soils, sediments and other solid materials.

L.P. Weng

Papers

Contribution of Individual Sorbents to the Control of Heavy Metal Activity in Sandy Soil

Interactions of calcium and fulvic acid at the goethite-water interface

Understanding the effects of soil characteristics on phytotoxicity and bioavailability of nickel using speciation models.

Determination of the free ion concentration of trace metals in soil solution using a soil column Donnan membrane technique

Humic acid protein complexation