Organic matter is an important component of soil with regard to the binding of contaminants. Hence, the partitioning of organic matter influences the partitioning of soil contaminants. The partitioning of organic matter is, among other factors, influenced by the ionic composition and ionic strength of the soil solution. This study focuses on the behavior of organic matter after a change in the ionic composition of the soil solution, particularly in Ca concentration and pH. Different amounts of Ca(NO3)2 and NaOH were added to soil suspensions. The dissolved organic carbon (DOC) concentration increased with increasing pH (addition of NaOH), whereas an increase in Ca (addition of Ca(NO3)2) had the opposite effect. A stronger increase in DOC was observed if a single dose of NaOH was added, compared to a gradual addition of the same amount of NaOH. Cation binding by organic matter in the supernatant was calculated using the NICA-Donnan model. The log DOC concentration appeared to be correlated to the Donnan potential, calculated under the assumption that all DOC equals humic acid. This correlation was found for all eight neutral to acidic soils used in this study, although the slopes and elevations of the regression lines varied. The slope varied by a factor of 2 and the elevation appeared to be strongly influenced by the DOC concentration in the untreated soils, which is related to the total organic matter in the soil. Finally, we predicted the Donnan potential on the basis of an extraction of untreated soil with 0.03 M NaNO3, and the total additions of Ca(NO3)2 and NaOH. Comparison of these predictions with speciation calculations in solution showed a good correlation, indicating that a combination of one batch experiment and the presented calculation procedure can provide good estimations of DOC concentrations after addition of chemicals.

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.

Abstract. Many agriculture-dominated lowland water systems worldwide suffer from eutrophication caused by high nutrient loads. Insight in the hydrochemical functioning of embanked polder catchments is highly relevant for improving the water quality in such areas or for reducing export loads to downstream water bodies. This paper introduces new insights in nutrient sources and transport processes in a polder in the Netherlands situated below sea level using high-frequency monitoring technology at the outlet, where the water is pumped into a higher situated lake, combined with a low-frequency water quality monitoring programme at six locations within the drainage area. Seasonal trends and short-scale temporal dynamics in concentrations indicated that the NO3 concentration at the pumping station originated from N loss from agricultural lands. The NO3 loads appear as losses via tube drains after intensive rainfall events during the winter months due to preferential flow through the cracked clay soil. Transfer function-noise modelling of hourly NO3 concentrations reveals that a large part of the dynamics in NO3 concentrations during the winter months can be related to rainfall. The total phosphorus (TP) concentration and turbidity almost doubled during operation of the pumping station, which points to resuspension of particulate P from channel bed sediments induced by changes in water flow due to pumping. Rainfall events that caused peaks in NO3 concentrations did not results in TP concentration peaks. The rainfall induced and NO3 enriched quick interflow, may also be enriched in TP but retention of TP due to sedimentation of particulate P then results in the absence of rainfall induced TP concentration peaks. Increased TP concentrations associated with run-off events is only observed during a rainfall event at the end of a freeze–thaw cycle. All these observations suggest that the P retention potential of polder water systems is primarily due to the artificial pumping regime that buffers high flows. As the TP concentration is affected by operation of the pumping station, timing of sampling relative to the operating hours of the pumping station should be accounted for when calculating P export loads, determining trends in water quality, or when judging water quality status of polder water systems.

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).

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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.

Metal-contaminated soils are potentially harmful to plants, animals, and humans. Harmful effects are often related to the free-metal concentration in the soil solution. Immobilization is a potentially useful method to improve the quality of metal-contaminated soils by transforming free-metal ions into species that are less mobile and less toxic. The effect of many immobilizing products can be attributed to sorption on the surface of the material. Alkaline materials also enhance adsorption to soil particles by decreasing proton competition. Immobilization should preferably be evaluated independently of soil pH to discriminate between these processes. In this study, the immobilizing effect of beringite, an alkaline alumino silicate, was compared with that of lime. Plants (Swiss chard [Beta vulgaris L. var. cicla]) were grown on a soil contaminated with cadmium and zinc and treated with graded amounts of beringite or lime. Metal availability, as determined by a 0.01 M CaCl2 extraction, and metal uptake by plants strongly decreased in all treated soils. Beringite did not reduce metal availability more than liming when the obtained pH levels were similar. The effect of beringite can, therefore, be explained as a liming effect, at least for the duration of our experiment (10 weeks). The effect of beringite and lime on metal accumulation by earthworms (Eisenia veneta and Lumbricus rubellus) was small or not significant, although the CaCl2-extractable metal concentration in treated soils decreased by more than 90%. We conclude that immobilizing agents based on a liming effect can decrease metal uptake by plants, but they will hardly affect metal uptake by earthworms. Hence, these materials can reduce negative ecological effects of metal contamination on plants and herbivores, but not on earthworm predators.

The free metal concentration in the soil solution is often considered a key parameter for metal uptake by and toxicity to soft-bodied soil organisms. The equilibrium partitioning theory, which assumes a relationship between the contaminant concentration in pore water and the contaminant concentration in the body tissue, can be used to describe uptake by earthworms. This theory has proved useful for organic chemicals, but its applicability is less clear for metals. In this study, the Cd concentration in soil pore water (pw) was varied by increasing the soil pH by the addition of lime (Ca(OH)2) and by adding manganese oxide (MnO2), which has a high metal binding capacity. Both lime (0.135% w/w) and MnO2 (1% w/w) decreased [Cd2+]pw by a factor of 25, while Cdworm was reduced only by a factor of 1.3 in lime-treated soils and 2.5 in MnO2-treated soils. Cadmium uptake was weakly related to the free metal concentration (R2adj = 0.66). Adding pH as an explanatory variable increased R2adj to 0.89, indicating that Cd uptake from pore water is pH dependent, which might be attributed to competition of protons and Cd at the surface of the earthwororm body. However, previous earthworm experiments in reconstituted groundwater showed a conspicuously smaller pH dependency of Cd uptake. The differences in metal uptake between earthworms in lime- and MnO2-treated soils are therefore more likely to reflect the predominance of pH-independent intestinal uptake of Cd. Equilibrating the soil with a solution of 0.01 M CaCl2 and 0.1 M triethanolamine (buffered at pH 7.2), simulating the conditions prevailing in the worm intestine, yielded free Cd concentrations that were closely (R2adj = 0.83) and linearly related to the Cd concentration in the earthworm tissue.