G.F. Koopmans

Prediction of cadmium uptake by brown rice and derivation of soil-plant transfer models to improve soil protection guidelines.

Cadmium (Cd) levels in paddy fields across Taiwan have increased due to emission from industry. To ensure the production of rice that meets food quality standards, predictive models or suitable soil tests are needed to evaluate the quality of soils to be used for rice cropping. Levels of Cd in soil and rice grains were measured in 19 paddy fields across the western plains in Taiwan. Cadmium levels in soil range from less than 0.1 mg kg(-1) to 30 mg kg(-1). Measured Cd levels in brown rice were predicted very well (R(2) > 0.8) based on Cd and Zinc in a 0.01 M CaCl(2) extract or a soil-plant transfer model using the reactive soil Cd content, pH, and cation exchange capacity. In contrast to current soil quality standards used in Taiwan, such models are effective in identifying soils where Cd in rice will exceed food quality standards.

Feasibility of phytoextraction to remediate cadmium and zinc contaminated soils

A Cd and Zn contaminated soil was mixed and equilibrated with an uncontaminated, but otherwise similar soil to establish a gradient in soil contamination levels. Growth of Thlaspi caerulescens (Ganges ecotype) significantly decreased the metal concentrations in soil solution. Plant uptake of Cd and Zn exceeded the decrease of the soluble metal concentrations by several orders of magnitude. Hence, desorption of metals must have occurred to maintain the soil solution concentrations. A coupled regression model was developed to describe the transfer of metals from soil to solution and plant shoots. This model was applied to estimate the phytoextraction duration required to decrease the soil Cd concentration from 10 to 0.5 mg kg(-1). A biomass production of 1 and 5 t dm ha(-1) yr(-1) yields a duration of 42 and 11 yr, respectively. Successful phytoextraction operations based on T. caerulescens require an increased biomass production.

Soil phosphorus quantity–intensity relationships to predict increased soil phosphorus loss to overland and subsurface flow

Soil phosphorus (P) quantity-intensity (q-i) relationships, based on common extraction methods, may potentially be used to estimate the risk of P loss in overland flow and subsurface drainage water. Some workers have used nonlinear q-i relationships to derive thresholds in soil test P (STP; a quantity factor) above which the risk of P loss increases, while others find linear relationships and no threshold. We present here a simple modelling exercise (based on Langmuir adsorption theory) along with data from literature to explain the behaviour of q-i relationships, and to give an explanation for this apparent discrepancy. The data indicate that q-i relationships are dependent upon the soil to solution ratio of the P intensity parameter, adsorption capacity (Qmax) and strength (K) of the soil, and the total range in STP. In turn, this affects the calculation of a threshold in STP. The q-i relationship tends towards linearity under conditions of a narrow total range of STP and/or when using a wide soil to solution ratio for estimating the P intensity parameter. Under such conditions, a threshold is difficult to detect, and uncertain. We conclude that the sensitivity of thresholds to experimental conditions and soils needs to be considered if thresholds are to be successful in environmental management to decrease P loss to surface waters.

Uncertainty Analysis of the Nonideal Competitive Adsorption−Donnan Model: Effects of Dissolved Organic Matter Variability on Predicted Metal Speciation in Soil Solution

Ion binding models such as the nonideal competitive adsorption-Donnan model (NICA-Donnan) and model VI successfully describe laboratory data of proton and metal binding to purified humic substances (HS). In this study model performance was tested in more complex natural systems. The speciation predicted with the NICA-Donnan model and the associated uncertainty were compared with independent measurements in soil solution extracts, including the free metal ion activity and fulvic (FA) and humic acid (HA) fractions of dissolved organic matter (DOM). Potentially important sources of uncertainty are the DOM composition and the variation in binding properties of HS. HS fractions of DOM in soil solution extracts varied between 14 and 63% and consisted mainly of FA. Moreover, binding parameters optimized for individual FA samples show substantial variation. Monte Carlo simulations show that uncertainties in predicted metal speciation, for metals with a high affinity for FA (Cu, Pb), are largely due to the natural variation in binding properties (i.e., the affinity) of FA. Predictions for metals with a lower affinity (Cd) are more prone to uncertainties in the fraction FA in DOM and the maximum site density (i.e., the capacity) of the FA. Based on these findings, suggestions are provided to reduce uncertainties in model predictions.

Emerging technologies for removing nonpoint phosphorus from surface water and groundwater: introduction.

Coastal and freshwater eutrophication continues to accelerate at sites around the world despite intense efforts to control agricultural P loss using traditional conservation and nutrient management strategies. To achieve required reductions in nonpoint P over the next decade, new tools will be needed to address P transfers from soils and applied P sources. Innovative remediation practices are being developed to remove nonpoint P sources from surface water and groundwater using P sorbing materials (PSMs) derived from natural, synthetic, and industrial sources. A wide array of technologies has been conceived, ranging from amendments that immobilize P in soils and manures to filters that remove P from agricultural drainage waters. This collection of papers summarizes theoretical modeling, laboratory, field, and economic assessments of P removal technologies. Modeling and laboratory studies demonstrate the importance of evaluating P removal technologies under controlled conditions before field deployment, and field studies highlight several challenges to P removal that may be unanticipated in the laboratory, including limited P retention by filters during storms, as well as clogging of filters due to sedimentation. Despite the potential of P removal technologies to improve water quality, gaps in our knowledge remain, and additional studies are needed to characterize the long-term performance of these technologies, as well as to more fully understand their costs and benefits in the context of whole-farm- and watershed-scale P management.

Use of reactive materials to bind phosphorus

Phosphorus (P) losses from agricultural soils have caused surface water quality impairment in many regions of the world, including The Netherlands. Due to the large amounts of P accumulated in Dutch soils, the generic fertilizer and manure policy will not be sufficient to reach in time the surface water quality standards of the European Water Framework Directive. Additional measures must be considered to further reduce P enrichment of surface waters. One option is to immobilize P in soils or manure or to trap P when it moves through the landscape by using reactive materials with a large capacity to retain P. We characterized and tested two byproducts of the process of purification of deep groundwater for drinking water that could be used as reactive materials: iron sludge and iron-coated sand. Both materials contain low amounts of inorganic contaminants, which also have a low (bio)availability, and bound a large amount of P. We could describe sorption of P to the iron sludge in batch experiments well with the kinetic Freundlich equation (Q = × t (m) × C(n)). Kinetics had a large influence on P sorption in batch and column experiments and should be taken into account when iron-containing materials are tested for their capability to immobilize or trap P. A negative aspect of the iron sludge is its low hydraulic conductivity; even when mixed with pure sand to a mixture containing 20% sludge, the conductivity was very low, and only 10% sludge may be needed before application is possible in filters or barriers for removing P from groundwater. Due to its much higher hydraulic conductivity, iron-coated sand has greater potential for use under field conditions. Immobilizing P could be an option for using iron sludge as a reactive material.

Phytoextraction of phosphorus-enriched grassland soils.

High soil P contents in agricultural soils in the Netherlands cause excessive losses of P to surface waters. The reductions in P application rates in the present manure policy are not sufficient to reach surface water quality standards resulting from the European Water Framework Directive in 2015. Accordingly, additional measures are necessary to reduce P loading to surface water. Greenhouse experiments showed that a rapid reduction in soluble P and readily available soil P can be obtained by zero P application. However, field data confirming these findings are scarce. In 2002 a phytoextraction experiment started on four grasslands sites on sand, peat, and clay soils. The phytoextraction (mining) plots receive no P and 300 kg N ha(-1) yr(-1) and the grass is removed by mowing. The experiment showed that zero P application, over a period of 5 yr, led to a strong (30-90%) reduction in P concentrations in soil solution in the upper soil layer (0-0.05 m). The reduction in concentrations declined with depth. Mining also resulted in a decline in P pools in the soil solid phase. The largest decline (10-60%) was found in weakly bound P pools (water extractable P; P(w), and ammonium lactate extractable P; P-AL), whereas reductions in more strongly bound P forms were relatively small. It may be concluded that phytoextraction appears an effective method of reducing soil P concentrations in the uppermost soil layers in a couple of years and prolonged mining may thus be effective in reducing leaching and runoff of P.

Predictions of spatially averaged cadmium contents in rice grains in the Fuyang valley, P.R. China.

Soils in the Fuyang valley (Zhejiang province, southeast China) have been contaminated by heavy metals. Since rice (Oryza sativa L.) is the dominant crop in the valley and because of its tendency to accumulate Cd in its grains, assessment of the human health risk resulting from consumption of locally produced rice is needed. In this study, we used a regression model to predict the average Cd content in rice grains for paddy fields. The multiple linear model for log(Cd) content in rice grains with log(HNO(3)-Cd), pH, log(clay), and log(soil organic matter, SOM) as predictors performed much better (R(2)(adj) = 66.1%) than the model with log(CaCl(2)-Cd) as a single predictor (R(2)(adj) = 28.1%). This can be explained by the sensitivity of CaCl(2)-extracted Cd for changes in redox potential and as a result of the drying of the soil samples in the laboratory. Consequently, the multiple linear model was used to predict the average Cd contents in rice grains for paddy fields, and to estimate the probability that the FAO/WHO standard of 0.2 mg kg(-1) will be exceeded. Eleven blocks had a probability smaller than 10% of exceeding this standard (safe blocks). If a lognormal distribution is assumed, 35 blocks had a probability larger than 90% (blocks at risk). Hence, risk reduction measures should be undertaken for the blocks at risk. For 27 blocks the probability was between 10 and 90%. For these blocks the uncertainty should be reduced via improvement of the regression model and/or increasing the number of sample locations within blocks.

A feasibility test to estimate the duration of phytoextraction of heavy metals from polluted soils.

The practical applicability of heavy metal (HM) phytoextraction depends heavily on its duration. Phytoextraction duration is the main cost factor for phytoextraction, both referring to recurring economic costs during phytoextraction and to the cost of the soil having no economic value during phytoextraction. An experiment is described here, which is meant as a preliminary feasibility test before starting a phytoextraction scheme in practice, to obtain a more realistic estimate of the phytoextraction duration of a specific HM-polluted soil. In the experiment, HM-polluted soil is mixed at different ratios with unpolluted soil of comparable composition to mimic the gradual decrease of the HM content in the target HM-polluted soil during phytoextraction. After equilibrating the soil mixtures, one cropping cycle is carried out with the plant species of interest. At harvest, the adsorbed HM contents in the soil and the HM contents in the plant shoots are determined. The adsorbed HM contents in the soil are then related to the HM contents in the plant shoots by a log–log linear relationship that can then be used to estimate the phytoextraction duration of a specific HM-polluted soil. This article describes and evaluates the merits of such a feasibility experiment. Potential drawbacks regarding the accuracy of the described approach are discussed and a greenhouse–field extrapolation procedure is proposed.

Characterization of colloidal phosphorus species in drainage waters from a clay soil using asymmetric flow field-flow fractionation.

Phosphorus transport from agricultural land contributes to eutrophication of surface waters. Pipe drain and trench waters from a grassland field on a heavy clay soil in the Netherlands were sampled before and after manure application. Phosphorus speciation was analyzed by physicochemical P fractionation, and the colloidal P fraction in the dissolved fraction (<0.45 μm) was analyzed by asymmetric flow field-flow fractionation (AF4) coupled to high-resolution inductively coupled plasma-mass spectrometry and ultraviolet diode array detector. When no manure was applied for almost 7 mo, total P (TP) concentrations were low (<21 μmol L), and TP was almost evenly distributed among dissolved reactive P (DRP), dissolved unreactive P (DUP), and particulate P (PP). Total P concentrations increased by a factor of 60 and 4 when rainfall followed shortly after application of cattle slurry or its solid fraction, respectively. Under these conditions, DRP contributed 50% or more to TP. The P speciation within the DUP and PP fractions varied among the different sampling times. Phosphorus associated with dissolved organic matter, probably via cation bridging, comprised a small fraction of DUP at all sampling times. Colloidal P coeluted with clay particles when P application was withheld for almost 7 mo and after application of the solid cattle slurry fraction. At these sampling times, PP correlated well with particulate Fe, Al, and Si, indicating that P is associated with colloidal clay particles. After cattle slurry application, part of DUP was probably present as phospholipids. Physicochemical fractionation combined with AF4 analysis is a promising tool to unravel the speciation of colloidal P in environmental water samples.