Abstract-Four copper (0, 250, 500, and 750 kg Cu·ha Ϫ1 ) and pH (4.0, 4.7, 5.4, and 6.1 in 1 M KCl) treatments were applied to an arable agroecosystem. Effects on the nematode community were assessed after 10 years of exposure under field conditions. Both copper and pH had major influences on nematodes. The effect of copper was generally enhanced with decreasing soil pH. The lowest copper application rate which had a significant negative effect on the total number of nematodes was 250 kg·ha Ϫ1 at pH 4.0, which is equivalent to a copper concentration of 0.32 mg·L Ϫ1 in 0.01 M calcium chloride (Cu-CaCl 2 ). Species composition and the abundance of trophic groups were more sensitive than the total number of nematodes. Combinations of high copper and low pH significantly reduced the number of bacterial-feeding nematodes, whereas the number of hyphal-feeding nematodes increased. Omnivorous and predacious nematodes showed the most sensitive response, becoming extinct when Cu-CaCl 2 was 0.8 to 1.4 mg·L Ϫ1

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 EC 50 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 nickel in the organic matter-rich soil studied is less than half of that in the sandy and clay soil studied at a similar pH. The chemical calculations using a multi-surface speciation model show that soil organic matter binds Ni much stronger than clay silicates and iron (hydr)-oxides within the acidic pH range, which supports the experimental findings. In all three soils, the EC 50 of Ni expressed in terms of Ni in 0.01 M CaCl 2 soil extraction is rather stable (24-58 µM), suggesting the possibility to use this extraction as an estimation of metal availability in soil.

The effect of pH on the bioaccumulation of nickel (Ni) by plants is opposite when using a nutrient solution or a soil as a growing medium. This paradox can be understood if the pH effect on the bioaccumulation, on the chemical speciation in the soil solution, and on the binding to the soil of Ni are all taken into account. Using simple equations to describe the individual relationships, it is possible to quantify these effects once the relationships have been established. Increased Ni uptake leads to reduced plant dry weight production for a certain growing period. The median effective concentration (EC50) decreased from 23 to 1.7 microM Ni in the nutrient solution for pH 4.0 to 7.0, whereas the EC50 of added Ni in a sandy soil increased from 0.72 to 9.95 mmol Ni/kg soil for pH 4.7 to 6.8. Bioaccumulation, binding to the soil solid phase, and binding to the dissolved organic matter all increase with increasing pH. However, the magnitude of the effect is the least for bioaccumulation as a function of pH, causing the apparent paradox.

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In situ immobilization of heavy metals in contaminated soils is a technique to improve soil quality. Synthetic zeolites are potentially useful additives to bind heavy metals. This study selected the most effective zeolite in cadmium and zinc binding out of six synthetic zeolites (mordenite-type, faujasite-type, zeolite X, zeolite P, and two zeolites A) and one natural zeolite (clinoptilolite). Zeolite A appeared to have the highest binding capacity between pH 5 and 6.5 and was stable above pH 5.5. The second objective of this study was to investigate the effects of zeolite addition on the dissolved organic matter (DOM) concentration. Since zeolites increase soil pH and bind Ca, their application might lead to dispersion of organic matter. In a batch experiment, the DOM concentration increased by a factor of 5 when the pH increased from 6 to 8 as a result of zeolite A addition. A strong increase in DOM was also found in the leachate of soil columns, particularly in the beginning of the experiment. This resulted in higher metal leaching caused by metal-DOM complexes. In contrast, the free ionic concentration of Cd and Zn strongly decreased after the addition of zeolites, which might explain the reduction in metal uptake observed in plant growth experiments. Pretreatment of zeolites with acid (to prevent a pH increase) or Ca (to coagulate organic matter) suppressed the dispersion of organic matter, but also decreased the metal binding capacity of the zeolites due to competition of protons or Ca.

Free metal ions in aqueous and terrestrial systems strongly influence bioavailability and toxicity. Most analytical techniques determine the total metal concentration, including the metal ions bound by dissolved organic matter. Ion activity can be measured with ion-specific electrodes (ISEs) for some metals, but an electrode for Zn is not commercially available. As a result, very few data are available on Zn binding by natural dissolved organic matter. The aim of this study is to determine free Zn concentrations in purified humic acid solutions using the recently developed Donnan membrane technique. However, several analytical aspects of the Donnan membrane technique had to be clarified before reliable data could be composed. Cd was chosen for validation. This study shows that free Cd concentrations as measured by the Donnan membrane technique agreed well with Cd ISE measurements. It is also shown that the Donnan membrane technique could be used at high pH. The Donnan membrane technique provided consistent results in a range of p[Cd2+] = 3-9 and p[Zn2+] = 3-8 at pH 4, 6, and 8. Metal speciation in humic acid solutions was also calculated with the consistent NICA-Donnan model using generic parameters. The model could excellently describe the experimental data without adjusting any of the parameters (R2Cd = 0.971, R2Zn = 0.988).

In situ immobilization of heavy metals in contaminated soils is a technique to improve soil quality. Synthetic zeolites are potentially useful additives to bind heavy metals. This study selected the most effective zeolite in cadmium and zinc binding out of six synthetic zeolites (mordenite-type, faujasite-type, zeolite X, zeolite P, and two zeolites A) and one natural zeolite (clinoptilolite). Zeolite A appeared to have the highest binding capacity between pH 5 and 6.5 and was stable above pH 5.5. The second objective of this study was to investigate the effects of zeolite addition on the dissolved organic matter (DOM) concentration. Since zeolites increase soil pH and bind Ca, their application might lead to dispersion of organic matter. In a batch experiment, the DOM concentration increased by a factor of 5 when the pH increased from 6 to 8 as a result of zeolite A addition. A strong increase in DOM was also found in the leachate of soil columns, particularly in the beginning of the experiment. This resulted in higher metal leaching caused by metal-DOM complexes. In contrast, the free ionic concentration of Cd and Zn strongly decreased after the addition of zeolites, which might explain the reduction in metal uptake observed in plant growth experiments. Pretreatment of zeolites with acid (to prevent a pH increase) or Ca (to coagulate organic matter) suppressed the dispersion of organic matter, but also decreased the metal binding capacity of the zeolites due to competition of protons or Ca.

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