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Calcium (Ca) and magnesium (Mg) are the most abundant alkaline-earth metal ions in nature, and their interaction with ferrihydrite (Fh) affects the geochemical cycling of relevant ions, including phosphate (PO4). The interfacial interactions of Ca and Mg (M2+) with PO4 have not been analyzed yet for freshly precipitated Fh. Here, we studied experimentally this interaction in binary M2+-PO4 systems over a wide range of pH, M2+/PO4 ratios, and ion loadings. The primary adsorption data were scaled to the surface area of Fh using a recent ion-probing methodology that accounts for the size-dependent chemical composition of this nanomaterial (FeO1.4(OH)0.2·nH2O). The results have been interpreted with the charge distribution (CD) model, combined with a state-of-the-art structural surface model for Fh. The CD coefficients have been derived independently using MO/DFT/B3LYP/6-31+G** optimized geometries. M2+ and PO4 mutually enhance their adsorption to Fh. This synergy results from the combined effect of ternary surface complex formation and increased electrostatic interactions. The type of ternary complex formed (anion- vs cation-bridged) depends on the relative binding affinities of the co-adsorbing ions. For our Ca-PO4 systems, modeling suggests the formation of two anion-bridged ternary complexes, i.e., ≡(FeO)2PO2Ca and ≡FeOPO3Ca. The latter is most prominently present, leading to a relative increase in the fraction of monodentate PO4 complexes. In Mg-PO4 systems, only the formation of the ternary ≡FeOPO3Mg complex has been resolved. In the absence of Ca, the pH dependency of PO4 adsorption is stronger for Fh than for goethite, but this difference is largely, although not entirely, compensated in the presence of Ca. This study enables the use of Fh as a proxy for the natural oxide fraction, which will contribute to improved understanding of the mutual interactions of PO4 and M2+ in natural systems. Universidad de Costa Rica/[]/UCR/Costa Rica UCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Agroalimentarias::Centro de Investigaciones Agronómicas (CIA)

The production and degradation of plastic remains can result in nanoplastics (NPs) formation. However, insufficient information regarding the environmental behaviors of NPs impedes comprehensive assessment of their significant threats. In this study, the transport behavior of unmodified NPs (PSNPs), carboxyl-modified NPs (PSNPs−COOH), and amino-modified NPs (PSNPs−NH2) was investigated using column experiments in the presence and absence of goethite (GT) and diethylhexyl phthalate (DEHP). Quantum chemical computation was performed to reveal the transport mechanisms. The results showed that GT decreased the transport of NPs and the presence of DEHP decreased it further. Van der Waals forces and small electrostatic interactions coexisted between the PSNPs and GT and caused deposition. Ligand exchange caused greater deposition of PSNPs−COOH on GT-coated sand than that of PSNPs. Although hydrogen bonding existed between the DEHP and NPs with functional groups, an increase in the positive charge and chemical heterogeneity of the collector was the main reason for DEHP promoting the deposition of NPs. Because of low absolute negative zeta potential values, PSNPs−NH2 was sensitive to chemical heterogeneity, and thus fully deposited (over 96.9%) in GT and GT-DEHP-coated columns. Generally, the deposition of NPs due to chemical heterogeneity was more significant than that due to the formation of chemical bonds and van der Waals, electrostatic, and hydrogen interactions. Our results highlight that the surface charge and functional groups significantly influence the transport behaviors of NPs and elucidate the fate of NPs in the terrestrial environment.

Multi-element soil extractions such as Mehlich 3 (M3) have gained popularity in recent years, but comparing outcomes to other soil testing methods is not always straightforward. In this study, extraction mechanisms of M3, Olsen and neutral 1 M ammonium acetate (AA) soil tests were explored and transfer functions were derived between P-Olsen and P-M3 as well as between K-AA and K-M3. Soils from tropical and temperate areas were used to derive these P and K transfer functions and were evaluated separately. The application of these transfer functions for tropical soils was evaluated by using them as input for the Quantitative Evaluation of the Fertility of Tropical Soils (QUEFTS). AA and M3 generally extracted similar amounts of K, but relations between K-AA and K-M3 were different for tropical and temperate soils. For tropical soils, the transfer function did not require additional parameters besides K-M3 to predict K-AA, but for temperate soils inclusion of clay content and pH was needed. This difference between tropical and temperate soils was explained by clay mineralogy. The relation between P-Olsen and P-M3 in tropical soils was found to be dependent on pH, Al-M3, Fe-M3 and Ca-M3. P-Olsen and K-AA values, calculated with their respective transfer functions, were used as input for QUEFTS. The yields predicted with measured P-Olsen and Exch. K were used as benchmark. For 63 out of 81 soil samples, predicted maize yields with transfer functions deviated less than 10% from the benchmark. The largest deviations from the benchmark were found for low P-Olsen and K-AA values, which corresponds to QUEFTS maize yield predictions up to 3000 kg ha−1. We conclude that a M3 extraction results and soil pH can reliably be transferred to, and thus replace P-Olsen and K-AA determinations with the functions developed for tropical soils. The transfer functions can be used to generate input for the QUEFTS model with minor effects on yield predictions, thus expanding its applicability in cases where only M3 extraction results are available.

Purpose Large parts of the Amazon rainforest grow on weathered soils depleted in phosphorus and rock-derived cations. We tested the hypothesis that in this ecosystem, fine roots stimulate decomposition and nutrient release from leaf litter biochemically by releasing enzymes, and by exuding labile carbon stimulating microbial decomposers. Methods We monitored leaf litter decomposition in a Central Amazon tropical rainforest, where fine roots were either present or excluded, over 188 days and added labile carbon substrates (glucose and citric acid) in a fully factorial design. We tracked litter mass loss, remaining carbon, nitrogen, phosphorus and cation concentrations, extracellular enzyme activity and microbial carbon and nutrient concentrations. Results Fine root presence did not affect litter mass loss but significantly increased the loss of phosphorus and cations from leaf litter. In the presence of fine roots, acid phosphatase activity was 43.2% higher, while neither microbial stoichiometry, nor extracellular enzyme activities targeting carbon- and nitrogen-containing compounds changed. Glucose additions increased phosphorus loss from litter when fine roots were present, and enhanced phosphatase activity in root exclusions. Citric acid additions reduced litter mass loss, microbial biomass nitrogen and phosphorus, regardless of fine root presence or exclusion. Conclusions We conclude that plant roots release significant amounts of acid phosphatases into the litter layer and mobilize phosphorus without affecting litter mass loss. Our results further indicate that added labile carbon inputs (i.e. glucose) can stimulate acid phosphatase production by microbial decomposers, highlighting the potential importance of plant-microbial feedbacks in tropical forest ecosystems.

Knowledge on organic matter (OM) concentration and composition is of major importance for predicting Zn speciation and bioavailability in soils, especially for low-Zn soils. However, comprehensive knowledge on the effect of soil-like organic amendments such as compost on metal speciation is limited. For the first time, multisurface modeling is applied on compost to study the effect of solid and dissolved OM composition on the speciation of reactive Zn as influenced by conditions applied in frequently used extractions to estimate Zn bioavailability. First, compost OM composition was determined by fractionation in operationally defined humic, fulvic, and hydrophilic acid pools under various extraction conditions, and subsequently, Zn speciation was modeled using the generic non-ideal competitive adsorption-Donnan (NICA-Donnan) model in addition to adsorption to hydrous ferric oxide (HFO) and clay. The results show a strong effect of extraction conditions on OM concentration and composition and related dissolved Zn speciation. Model predictions show that Zn in solution is mainly bound to dissolved humic acids. Analysis of deviations between measured and modeled Zn concentrations reveal specific limitations of the current generic model parameters, particularly with regard to Zn binding to OM at low concentrations and Ca-Zn competition, that is, typical conditions that occur in low-Zn soils.

Among natural organic matter (NOM), oxyanions and metal (hydr)oxides, a complicated interaction exists in natural aquatic and terrestrial systems and in waste waters. Effects of seven types of NOM (four humic acids (HA), three fulvic acids (FA)) that vary in properties on the adsorption of oxyanions, including phosphate, arsenate and arsenite, at goethite-water interface were quantitatively studied. Results show that the adsorption of oxyanions to goethite is decreased by the presence of NOM, especially for phosphate and arsenate at low pH. In general, the effects of the three FA are similar, which are more effective than HA in reducing oxyanion adsorption at low pH (

Arsenic (As) and cadmium (Cd) are unnecessary metal(loids) toxic at high concentration to plants and humans, hence lessening their rice grain accumulation is crucial for food security and human healthiness. Charred eggshell (EB), corncob biochar (CB), and eggshell-corncob biochar (ECB) were produced and amended to As and Cd co-polluted paddy soil at 1% and 2% application rates to alleviate the metal(loids) contents in rice grains using pot experiments. All the amendments increased paddy yields at 1%, while EB at 2% significantly reduced the yields compared to untreated control. The resulting yield loss in 2%EB was from the combined effects of its high CaCO3 supplementation, and the increment of rhizosphere soil pH which could insolubilize plant nutrients. The amendments were inefficient in decreasing rice grain As (AsGrain), but all the treatments significantly reduced the rice grain Cd (CdGrain) at both 1% (44.4–77.1%) and 2% (79.8–91.5%) application rates compared to that of control. Regression analysis for contribution weights of control factors revealed that rhizosphere soil Eh and pH were vital influential factors regulating the AsGrain, whereas porewater Cd was main factor controlling CdGrain accumulation. These investigations indicated that the Ca-enriched eggshell-corncob biochar even at high application rate (i.e., 2%ECB) could be a potential tactic for grain accumulation remediation of the cationic pollutant (i.e., Cd) from the paddy soil to rice grain scheme with concurrent increase in rice yields.

Humic substances are increasingly used as biostimulants in agriculture because of their supposed effects on nutrient uptake and crop yield. The objective of this study was to assess the effect of fulvic acid (FA) and humic acid (HA) addition with and without fertilization (N, P, K, S, and Ca) on (i) grass yield (Poa trivialis) and nutrient uptake and (ii) composition of soil porewater and 0.01 M CaCl2 soil extracts. Therefore, a pot experiment was performed using a loamy soil and a non-calcareous sandy soil. Fertilization increased N and P uptake and grass yield but there was no effect of FA or HA application (200 mg C kg���1 soil) regardless of whether N or P was the growth limiting nutrient. Nutrient availability was assessed in soil pore water samples extracted by centrifugating moist soil and by 0.01 M CaCl2 extracts of oven-dried soil. HA and FA had no effect on the availability of NO3 or ortho-P, neither in soil porewater nor in 0.01 M CaCl2 soil extracts. Fertilization led to an increase in 0.01 M CaCl2-extractable ortho-P but, remarkably, to a decrease in ortho-P and Dissolved Organic Carbon (DOC) concentrations in soil pore water samples. This discrepancy was explained by the higher ionic strength of pore water in the fertilized soils, which caused the pH to drop by 0.2 to 0.4 units and thereby stimulated adsorption of ortho-P and DOC to reactive soil minerals. Such salt-induced effects do not occur in 0.01 M CaCl2 soil extracts where the ionic strength is nearly constant.

The aim of this study was to develop an analytical method to determine free concentrations of Europium (Eu(III)) in natural waters. Europium(III) in solution was detected using cathodic stripping voltammetry after complexation with N-nitroso-N-phenylhydroxylamine (cupferron). Optimization of analytical parameters allowed us to detect nanomolar levels of Eu(III) in solution. Free Eu(III) in solution was measured using the Donnan membrane technique in which a natural solution (the “donor”, containing various ligands) is separated from a ligand-free solution (the “acceptor”) by a cation-exchange membrane. This membrane allows only non-colloidal cationic species to pass through it, and after an adequate time equilibrium is reached between both compartments. Total Eu(III) concentration can then be quantified in the acceptor solution and related to free Eu(III) in the natural sample. Due to its high valency, free Eu(III) tends to adsorb strongly to the cation-exchange membrane. In order to determine the physicochemical conditions minimizing this adsorption, we analyzed solutions of different Eu(III) and Ca(II) (as background ion) concentrations. Results showed that 100 mM of Ca(II) were necessary to make adsorption of Eu(III) onto the membrane negligible. The optimized setup was then used to quantify Eu(III) complexation in a Eu(III)-dissolved organic matter solution.

Arsenic (As) and cadmium (Cd) are nonessential toxic metal(loids) that are carcinogenic to humans. Hence, reducing the bioavailability of these metal(loids) in soils and decreasing their accumulation in rice grains is essential for agroecology, food safety, and human health. Iron (Fe)-enriched corncob biochar (FCB), Fe-enriched charred eggshell (FEB), and Fe-enriched corncob-eggshell biochar (FCEB) were prepared for soil amelioration. The amendment materials were applied at 1% and 2% application rates to observe their alleviation effects on As and Cd loads in rice paddy tissues and yield improvements using pot trials. The FCEB treatment increased paddy yields compared to those of FCB (9-12%) and FEB (3-36%); this could be because it contains more plant essential nutrients than FCB and a lower calcite content than that of FEB. In addition, FCEB significantly reduced brown rice As (AsBR, 29-60%) and Cd (CdBR, 57-81%) contents compared to those of the untreated control (CON). At a 2% application rate, FCEB reduced the average mobility of As (56%) and Cd (62%) in rhizosphere porewater and enhanced root Fe-plaque formation (76%) compared to those of CON. Moreover, the enhanced Fe-plaque sequestered a substantial amount of As (171.4%) and Cd (90.8%) in the 2% FCEB amendment compared to that of CON. Pearson correlation coefficients and regression analysis indicated that two key mechanisms likely control AsBR and CdBR accumulations. First, rhizosphere soil pH and Eh controlled As and Cd availabilities in porewaters and their speciation in the soil. Second, greater Fe-plaque formation in paddy roots grown in the amended soils provided a barrier for plant uptake of the metal(loids). These observations demonstrate that soil amendment with Fe-enriched corncob-eggshell biochar (e.g., 2% FCEB) is a prospective approach for the remediation of metal accumulation from the soil to grain system while simultaneously increasing paddy yield.

Cadmium is an extremely toxic substance known to cause serious health problems. The uptake of Cd in plants is critically affected by dissolved Cd in soil porewater, controlled by soil physicochemical properties. Rhizo-availability of Cd is assumed, as the Cd fraction is found on the plasma membrane of surface root cells. Based on the theory of Cd transformation in soil–crop systems, we established a novel combined mechanistic model related to soil, soil solutions, and crops. The combined model comprises a multisurface model (MSMs; solid adsorbent and porewater) and the Gouy–Chapman–Stern model (GCS; porewater and root surface). The results suggested that in mildly contaminated soil samples, optimum prediction was achieved when DTPA-extractable Cd was used as input variable (R2 = 0.723). Our approach was superior to single-step model calculation (MSMs: R2 = 0.613; GCS: R2 = 0.629) and prediction based on extractable soil Cd (R2 = 0.281). Introducing DTPA extraction expanded the range of model applications at different soil pHs. Our proposed mechanism model was based on soil physicochemical properties for Cd migration from soil to cabbage. Our model showed promise in predicting Cd bioavailability in soil with a wide pH range and evaluating soil risk near the standard Cd safety level.

Iron (Fe) minerals, organic matter (OM), and pH can effectively regulate phosphorus (P) transport in the soil. However, their respective contributions in this regard are still unclear. In this study, P transport in soil columns was investigated by monitoring breakthrough curves and transport model fitting, and the contributions of Fe and total organic carbon (TOC) concentrations, as well as pH to P retention, were determined using multiple linear regression (MLR). The results showed that the rate of P transport in Fe-rich laterite soil was significantly lower (retardation factor R = 458.5) than that in the other soil types (R = 108.4–247.6). Additionally, it was observed that OM formed rate-limited adsorption sites, causing the rapid release of labile P, and owing to P release and readsorption. Even though more significant P releases were observed, chernozem soil had an obvious inhibiting effect on P transport owing to its relatively high Fe content, and the high P-Fe increment (48.9–90.4%) indicated the essential role of Fe minerals in P immobilization. Further, P was readily transported in natural or artificially modified fluvo-aquic soils with high calcium concentrations, and it was also observed that the convection–dispersion equation (CDE) and Thomas models were suitable for describing P retardation and adsorption, respectively. Furthermore, the contribution weights of Fe and TOC concentrations as well as pH to P retardation, based on MLR calculations, were approximately 1.0, −0.3, and −0.2, respectively. Our findings can support the control of eutrophication pollution caused by P leaching.

In the environment, simultaneous presence of arsenic (As) of different oxidation states is common, which hampers our understanding of As behavior. In the current study, the pH dependency of arsenite (As(III)) and arsenate (As(V)) adsorption to goethite under the influence of calcium (Ca2+) (as a major cation) and phosphate (PO43−) (as a major anion) was studied, and the reliability of the CD-MUSIC model prediction was tested. The results show that the presence of the major ions led in general to a weaker and more complicated pH dependency of As adsorption. Calcium promoted As(V) adsorption especially at high pH, which can reverse the direction of the pH dependency. The presence of Ca2+ can even decrease As(III) adsorption when As(V) and/or PO43− are present. Phosphate competed strongly with both As(III) and As(V) in their adsorption, especially at intermediate and low pH. In the multi-component system, As(III) adsorbs weaker than As(V) over the environmental relevant pH range, therefore it is often the dominant As species in solution and soluble As(III) concentration generally decreases with increasing pH. In the same pH range, As(V) adsorption shows a complicated pH dependency. Soluble As(V) reaches a minimum around pH 6 at high concentration of major bivalent cations (e.g. Ca2+), whereas soluble As(V) will decrease with pH at low bivalent cation concentrations. The experimental results can be reliably predicted and explained with the CD-MUSIC model. The outcome of this study can provide understanding needed in the risk assessment and remediation of As contaminated soils and water.

Abstract Elevated CO2 (eCO2) can stimulate plant productivity and increase carbon (C) input to soils, but nutrient limitation restricts productivity. Despite phosphorus (P)-limited ecosystems increasing globally, it is unknown how nutrient cycling, particularly soil microbial extra cellular enzyme activity (EEA), will respond to eCO2 in such ecosystems. Long-term nutrient manipulation plots from adjacent P-limited acidic and limestone grasslands were exposed to eCO2 (600 ppm) provided by a mini-Free Air CO2 Enrichment system. P-limitation was alleviated (35 kg-P ha−1 y−1 (P35)), exacerbated (35 kg-N ha−1 y−1 (N35), 140 kg-N ha−1 y−1 (N140)), or maintained (control (P0N0)) for > 20 years. We measured EEAs of C-, N- and P-cycling enzymes (1,4-β-glucosidase, cellobiohydrolase, N-acetyl β-D-glucosaminidase, leucine aminopeptidase, and acid phosphatase) and compared C:N:P cycling enzyme ratios using a vector analysis. Potential acid phosphatase activity doubled under N additions relative to P0N0 and P35 treatments. Vector analysis revealed reduced C-cycling investment and increased P-cycling investment under eCO2. Vector angle significantly increased with P-limitation (P35 2 or nutrient treatment for all enzyme indicators signaled consistent responses to changing P-limitation and eCO2 in both grasslands. Our findings suggest that eCO2 reduces C limitation, allowing increased investment in P- and N-cycle enzymes with implications for rates of nutrient cycling, potentially alleviating nutrient limitation of ecosystem productivity under eCO2. Graphic abstract "Image missing"

The adsorption and desorption of boric acid onto reactive materials such as metal (hydr)oxides and natural organic matter are generally considered to be controlling processes for the leaching and bioavailability of boron (B). We studied the interaction of B with ferrihydrite (Fh), a nanosized iron (hydr)oxide omnipresent in soil systems, using batch adsorption experiments at different pH values and in the presence of phosphate as a competing anion. Surface speciation of B was described with a recently developed multisite ion complexation (MUSIC) and charge distribution (CD) approach. To gain insight into the B adsorption behavior in whole-soil systems, and in the relative contribution of Fh in particular, the pH-dependent B speciation was evaluated for soils with representative amounts of ferrihydrite, goethite, and organic matter. The pH-dependent B adsorption envelope of ferrihydrite is bell-shaped with a maximum around pH 8–9. In agreement with spectroscopy, modeling suggests formation of a trigonal bidentate complex and an additional outer-sphere complex at low to neutral pH values. At high pH, a tetrahedral bidentate surface species becomes important. In the presence of phosphate, B adsorption decreases strongly and only formation of the outer-sphere surface complex is relevant. The pH-dependent B adsorption to Fh is rather similar to that of goethite. Multisurface modeling predicts that ferrihydrite may dominate the B binding in soils at low to neutral pH and that the relative contribution of humic material increases significantly at neutral and alkaline pH conditions. This study identifies ferrihydrite and natural organic matter (i.e., humic substances) as the major constituents that control the B adsorption in topsoils. The Dutch Research Council/[Grant N°14688]/NWO/Países Bajos UCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Agroalimentarias::Centro de Investigaciones Agronómicas (CIA)

Phosphorus (P) immobilization has potential for reducing diffuse P losses from legacy P soils to surface waters and for regenerating low-nutrient ecosystems with a high plant species richness. Here, P immobilization with iron oxide sludge application was investigated in a field trial on a noncalcareous sandy soil. The sludge applied is a water treatment residual produced from raw groundwater by Fe(II) oxidation. Siliceous ferrihydrite (Fh) is the major Fe oxide type in the sludge. The reactive surface area assessed with an adapted probe ion method is 211–304 m2 g−1 for the Fe oxides in the sludge, equivalent to a spherical particle diameter of ~6–8 nm. This size is much larger than the primary Fh particle size (~2 nm) observed with transmission electron microscopy. This can be attributed to aggregation initiated by silicate adsorption. The surface area of the indigenous metal oxide particles in the field trial soils is much higher (~1100 m2 g−1), pointing to the presence of ultra-small oxide particles (2.3 ± 0.4 nm). The initial soil surface area was 5.4 m2 g−1 and increased linearly with sludge application up to a maximum of 12.9 m2 g−1 when 27 g Fe oxides per kg soil was added. In case of a lower addition (~10–15 g Fe oxides per kg soil), a 10-fold reduction in the phosphate (P-PO4) concentration in 0.01 M CaCl2 soil extracts to 0.3 µM was possible. The adapted probe ion method is a valuable tool for quantifying changes in the soil surface area when amending soil with Fe oxide-containing materials. This information is important for mechanistically predicting the reduction in the P-PO4 solubility when such materials are used for immobilizing P in legacy P soils with a low P-PO4 adsorption capacity but with a high surface loading.

The by-product of the traditional Fenton reaction, colloidal arsenic-‑iron oxide, is migratable and may cause secondary environmental pollution. This paper reported a new strategy involving oxidizing and immobilizing inorganic arsenic using the Fenton reaction, and avoiding the risk of secondary contamination. Lab synthesized ferrihydrite-loaded biochar (FhBC) was developed for oxidizing and binding As(III) and As(V) in aqueous solution. Batch experiments and a series of spectrum analysis (e.g., X-ray photoelectron spectroscopy [XPS], electron paramagnetic resonance [EPR], and Fourier transform infrared spectroscopy [FTIR]) were conducted to study the oxidizing or adsorption capacity and mechanism. The maximum adsorption capacity of FhBC for As(III) and As(V) is 1.315 and 1.325 mmol/g, respectively. In addition, FhBC has an efficient oxidizing capacity within a wide pH range, which is because biochar promotes the Fenton reaction by acting as an electron donator, electron shuttler, or by providing persistent free radicals. Moreover, the adsorption mechanism was studied by FTIR spectroscopy, XPS, and X-ray diffraction (XRD). The formation of internal spherical complexes and iron oxides with a higher degree of crystallization was observed, which indicate that the products of adsorption are stable and robust in a complex environment and can exist in a highly crystallized form after adsorbing arsenic ions. Therefore, the use of FhBC as an adsorbent for arsenic represents a new strategy of using the Fenton reaction while reducing secondary contamination. These results may contribute to further mechanistic studies or extensive practical applications of FhBC.

Because phosphorus (P) is one of the most limiting nutrients in agricultural systems, P fertilisation is essential to feed the world. However, declining P reserves demand far more effective use of this crucial resource. Here, we use meta-analysis to synthesize yield responses to P fertilisation in grasslands, the most common type of agricultural land, to identify under which conditions P fertilisation is most effective. Yield responses to P fertilisation were 40–100% higher in (a) tropical vs temperate regions; (b) grass/legume mixtures vs grass monocultures; and (c) soil pH of 5–6 vs other pHs. The agronomic efficiency of P fertilisation decreased for greater P application rates. Moreover, soils with low P availability reacted disproportionately strong to fertilisation. Hence, low fertiliser application rates to P-deficient soils result in stronger absolute yield benefits than high rates applied to soils with a higher P status. Overall, our results suggest that optimising P fertiliser use is key to sustainable intensification of agricultural systems.

Evaluating speciation of arsenic (As) is essential to assess its risk in paddy soils. In this study, effects of phosphate on speciation of As in six paddy soils differing in redox status were studied over a range of pH (pH 3-9) and different background calcium (Ca) levels by batch adsorption experiments and speciation modeling. Contrasting effects of phosphate on As speciation were observed in suboxic and anoxic soils. Under suboxic conditions, phosphate inhibited Fe and As reduction probably due to stabilization of Fe-(hydr)oxides, but increased soluble As(V) concentration as a result of competitive adsorption between As(V) and phosphate. In anoxic soils, phosphate stimulated Fe and As reduction and caused increases of As(III) in soil solution under both acidic and neutral/alkaline pH. The LCD (Ligand and Charge Distribution) and NOM-CD (Natural Organic Matter-Charge Distribution) model can describe effects of pH, calcium and phosphate on As speciation in these paddy soils. The results suggest that phosphate fertilization may decrease (at low pH) or increase (at neutral/alkaline pH) As mobility in paddy soils under (sub)oxic conditions, but under anoxic conditions and in phosphorus deficient soils phosphate fertilization may strongly mobilize As by promoting microbial activities.

Boron is an essential micronutrient for plants, but can also be toxic when present in excess in the soil solution. A multi-surface geochemical model was used to assess the important processes that affect the distribution of the geochemically reactive B in soils over the solution and solid phase. The multi-surface model was based on the adsorption of B on dissolved and solid humic acids, representing reactive organic matter, ferrihydrite, representing the Fe and Al (hydr)oxides, and clay mineral edges. In addition, the performance of previously proposed extraction methods for measuring reactive B was evaluated. Based on B measured in 0.01 M CaCl2 soil extracts (7–85 μmol kg−1 soil), we calculated the reactive boron concentration for 5 temperate and 5 tropical soils (8–106 μmol kg−1 soil). We found that extractions with 0.43 M HNO3 or with 0.2 M mannitol + 0.1 M triethanolamine buffer extract on average 240 and 177% of the reactive B predicted by the model, thus releasing additional B that is assumed to be not or only very slowly available for exchange with the soil solution. Reactive B calculated by the model corresponded best to the B measured in a 0.05 M KH2PO4 (pH 4.5) extraction. In general, the multi-surface modeling showed that 68% or more of reactive boron was present in the solution phase for the soils in this study and that the adsorption was dominated by oxides in the tropical soils, while solid organic matter was the main adsorbent in the temperate soils. When changing the soil pH(CaCl2), B concentration was found to decrease with increasing pH, and both experimental data and modelling suggests that this effect is mainly due to increased binding of B to organic matter.

Over the last few decades, a suite of inorganic proxies based on foraminiferal calcite have been developed, some of which are now widely used for palaeoenvironmental reconstructions. Studies of foraminiferal shell chemistry have largely focused on cations and oxyanions, while much less is known about the incorporation of anions. The halogens fluoride and chloride are conservative in the ocean, which makes them candidates for reconstructing palaeoceanographic parameters. However, their potential as a palaeoproxy has hardly been explored, and fundamental insight into their incorporation is required. Here we used nanoscale secondary ion mass spectrometry (NanoSIMS) to investigate, for the first time, the distribution of Cl and F within shell walls of four benthic species of foraminifera. In the rotaliid species Ammonia tepida and Amphistegina lessonii, Cl and F were distributed highly heterogeneously within the shell walls, forming bands that were co-located with the bands observed in the distribution of phosphorus (significant positive correlation of both Cl and F with P; p). In the miliolid species Sorites marginalis and Archaias angulatus, the distribution of Cl and F was much more homogeneous without discernible bands. In these species, Cl and P were spatially positively correlated (p), whereas no correlation was observed between Cl and F or between F and P. Additionally, their F content was about an order of magnitude higher than in the rotaliid species. The high variance in the Cl and F content in the studied foraminifera specimens could not be attributed to environmental parameters. Based on these findings, we suggest that Cl and F are predominately associated with organic linings in the rotaliid species. We further propose that Cl may be incorporated as a solid solution of chlorapatite or may be associated with organic molecules in the calcite in the miliolid species. The high F content and the lack of a correlation between Cl and F or P in the miliolid foraminifera suggest a fundamentally different incorporation mechanism. Overall, our data clearly show that the calcification pathway employed by the studied foraminifera governs the incorporation and distribution of Cl, F, P, and other elements in their calcite shells.

Elevated CO2 (eCO(2)) experiments provide critical information to quantify the effects of rising CO2 on vegetation 1-6 . Many eCO(2) experiments suggest that nutrient limitations modulate the local magnitude of the eCO(2) effect on plant biomass(1,3,5), but the global extent of these limitations has not been empirically quantified, complicating projections of the capacity of plants to take up CO27,9. Here, we present a data-driven global quantification of the eCO(2) effect on biomass based on 138 eCO(2) experiments. The strength of CO2 fertilization is primarily driven by nitrogen (N) in similar to 65% of global vegetation and by phosphorus (P) in similar to 25% of global vegetation, with N- or P-limitation modulated by mycorrhizal association. Our approach suggests that CO2 levels expected by 2100 can potentially enhance plant biomass by 12 +/- 3% above current values, equivalent to 59 +/- 13 PgC. The globalscale response to eCO(2) we derive from experiments is similar to past changes in greenness(9) and bio-mass(10) with rising CO2, suggesting that CO2 will continue to stimulate plant biomass in the future despite the constraining effect of soil nutrients. Our research reconciles conflicting evidence on CO2 fertilization across scales and provides an empirical estimate of the biomass sensitivity to eCO(2) that may help to constrain climate projections.

Aims: The study aimed to find soil parameters that are best related to Se plant uptake for low Se soils with predominantly organic Se, and to explore the mechanisms that control Se bioavailability in the soils under study. Methods: A pot experiment using nineteen soil samples taken from different fields of arable land (potato fields) in the Netherlands was conducted on summer wheat (Triticum aestivum L.). Selenium in wheat shoots and soil parameters, including basic soil properties, C:N ratio, inorganic selenite content, and Se and organic C in different soil extractions (0.01 M CaCl2, 0.43 M HNO3, hot water, ammonium oxalate, aqua regia) were analysed. Regression analysis was performed to identify soil parameters that determine Se content in wheat shoots. Results: The regression model shows that Se:DOC ratio in 0.01 M CaCl2 soil extraction explained about 88 % of the variability of Se uptake in wheat shoots. Selenium uptake increased with Se:DOC ratio in CaCl2 extraction, which can be interpreted as a measure of the content of soluble Se-rich organic molecules. Selenium:DOC ratio in CaCl2 extraction and Se uptake increased towards higher soil pH and lower soil C:N ratio. The soil C:N ratio is also negatively correlated to Se:organic C ratio in other extractions (0.43 M HNO3, hot water, ammonium oxalate, aqua regia), indicating that at low soil C:N ratio soil organic matter is richer in Se. Contrarily, the soil pH is positively and strongly correlated to Se:organic C ratio in CaCl2 and hot water extractions, but only weakly correlated to Se:organic C ratio in other extractions. Conclusions: Selenium-rich dissolved organic matter is the source of bioavailable Se in low Se soils with predominantly organic Se. The soil pH and quality of soil organic matter (i.e. soil C:N ratio) are the main soil properties determining Se bioavailability in these soil types.

Amazonian Dark Earths (ADE), highly fertile pre-Columbian anthropic soils found in the Amazon, have intrigued scientists for decades. Despite tropical conditions, these soils exhibit large contents of carbon (C) and nutrients (particularly Ca and P), contrasting with the poor adjacent soils (ADJ) from the Amazon. High carbon (C) content in ADE has been linked with the occurrence of black carbon (BC) in these soils. BC has been claimed to be highly resistant to decomposition due to its polycondensed aromatic structure. However, recent advancements indicate that intrinsic chemical characteristics do not fully explain long-term persistence of soil organic matter (SOM). Soil minerals are known to play an important role on the mechanisms of SOM stabilization mainly through adsorption of SOM onto the surface of reactive soil minerals (i.e. Fe and Al oxides). However, the relative contribution of mineral protection versus chemical recalcitrance in explaining long-term persistence of SOM in ADE is poorly understood. The overall objective of this PhD thesis was to investigate the interactive roles of BC, Ca and P in explaining long-term persistence of SOM in ADE. Overall, my results (Chapter 3-5) have major implications for a common SOM methodology proposed to isolate a 'stable' pool of SOM upon chemical oxidation with NaOCl and to subsequently differentiate and quantify the relative contribution of two mechanisms of SOM stabilization (i.e. mineral association and chemical recalcitrance) upon soil demineralization with HF. Combining data from Chapters 4 and 5, it seems like BC is removed upon chemical oxidation with NaOCl and therefore is part of the operationally defined 'labile' rather than the 'stable' SOM pool. Removal of BC with NaOCl raises questions about the contrast between low resistance of BC towards chemical oxidation and apparent high resistance of BC against biological oxidation, which certainly deserves more attention in future studies. Furthermore, my results shed light on the importance of high Ca and P inputs (Chapter 2 and 5) besides the occurrence of BC in ADE (Chapter 5) in explaining long-term persistence of SOM in ADE. In my thesis, I propose that it is the interaction between OM inputs (including BC inputs), Ca and P that are responsible for the long-term persistence of large SOM contents in ADE, which brings major implications for the sole use of charred OM (i.e. biochar) as a strategy to reproduce ADE desirable characteristics in other soils. Made available in DSpace on 2019-11-25T18:15:54Z (GMT). No. of bitstreams: 1 TeseCarlosFranciscoBrazaoVieiraAlho2019.pdf: 4036024 bytes, checksum: 13a31588c45cb68b359d8ba72bcd6402 (MD5) Previous issue date: 2019 Thesis (Doctor) - Wageningen University & Research, Wageningen. Promotors: T. W. M. Kuyper, Wageningen University & Research. Co-promotors: T. Hiemstra, Wageningen University & Research; Wenceslau Geraldes Teixeira, CNPS.

Boron (B) is highly mobile in the environment. This characteristic easily leads to plant deficiency upon leaching from soil or to toxicity upon accumulation. Boric acid may interact with mineral surfaces as well as natural organic matter. In this study, the boric acid interaction with humic acid (HA) was measured in 0.01 M NaCl and CaCl2 background solutions as a function of pH and the initial B concentration. In the Na-HA suspensions, the free boric acid concentration was determined using a novel approach, applying the Donnan Membrane Technique (DMT) in the dynamic mode. In the method, the experimental rate of diffusion is used as a measure for the free boric acid concentration. B adsorption in Na-HA and Ca-HA systems can be described with the NICA-Donnan model using a single set of boron binding parameters. In Na-HA systems, the adsorption of boric acid strongly increases with the background electrolyte concentration, due to a better screening of the HA charge. In this respect, the adsorption behavior of boric acid is opposite to that of heavy metal ions. Modeling shows that the boric acid adsorption is determined by the competition of H+, Ca2+, and B(OH)3 at binding to the sites of HA. The parameterized NICA-Donnan model is well able to predict the pH-dependent adsorption of boric acid in soil organic horizons. The model is a promising tool for future predictions of the fate of boric acid in a variety of natural multicomponent environments, including soil and seawater.

Phosphorus (P) is an important nutrient for plant growth. However, P is often poorly available for uptake by roots because it strongly adsorbs to the soil mineral phase. Recent research shows that earthworms can temporally and locally increase P availability to plants. However, the pathways through which they do so are not fully understood, and it remains unclear to what extent this capacity varies among earthworm species. Here we study the variation among earthworm species with respect to readily-available P in casts as well as other physico-chemical cast properties, in a greenhouse pot experiment using a soil with a low P status. The earthworms belong to eight commonly occurring earthworm species in the Netherlands: two epigeic species (a mixture of the compost earthworms Dendrobaena veneta/Eisenia fetida; Lumbricus rubellus); four endogeic species (Allolobophora chlorotica, Aporrectodea caliginosa, Aporrectodea rosea, Octolasion lacteum); and two anecic species (Aporrectodea longa; Lumbricus terrestris). For all species, the pH in water extracts of earthworm cast (pH = 7.4–8.2) was significantly higher (p < 0.001) than for the control bulk soil (pH = 6.6) and differed significantly (p = 0.003) among earthworm species. Similarly, the dissolved organic carbon (DOC) concentration in the same water extracts was an order of magnitude higher in earthworm cast compared to the control bulk soil and varied among species (p < 0.001). The size of the total pool of reversibly adsorbed P in earthworm cast was greater than in the control bulk soil, but no significant differences were found among earthworm species. Differences among species were present for the readily-available P pools extracted from casts, including P-Olsen and water-extractable ortho-P. Water-extractable ortho-P concentrations were much higher in the casts of all species as compared to the control bulk soil (0.9–6.8 vs 0.06 mg l−1 or to 9.0–68 vs 0.6 mg kg−1). Highest ortho-P levels were measured in L. rubellus casts and the lowest in casts of A. chlorotica. A positive correlation between the concentrations of DOC and ortho-P was observed (R2 = 0.72, p < 0.001). The observed variation in all measured physico-chemical cast properties could not be explained by conventional ecological earthworm classifications. Our results show that the nature and magnitude of earthworm-induced increased P availability differs dramatically among earthworm species. This strongly suggests that, apart from its size, species composition of the earthworm community is key to optimizing P availability to plants.

The pH-dependent availability and leaching of major and trace elements was investigated for a wide range of biomass ash from different fuels and conversion technologies. A technical and environmental assessment of selected biomass ash for application in soil or cement mortars was performed, using both the total content and leaching of elements. A large variation in biomass ash composition, yet consistent pH dependent leaching patterns were observed for most elements and conversion technologies. Chromium showed a distinct behaviour which was hypothesized to reflect redox conditions during conversion of the biomass. The leaching based approach was found to provide a more realistic assessment of the availability of desired (i.e. nutrients) and undesired elements (i.e. contaminants) in soil systems. When applied to a reference soil at a rate of 2% by weight, the selected biomass ash increased the concentration of particularly Cr, Mo and Zn in soil solution to a level of concern. For cement applications, the release of Ba, Cr and Mo can become of concern during the second life stage, but the release was not attributed to the included biomass ash. Both soil and cement matrixes were found to control the release of elements such as Cu, V and Ni (soil) and As, Cr and Mo (cement) when compared to the released from pure biomass ash, underlining the importance of evaluating the availability and leaching of desired and undesired elements in the application scenario. Given current regulatory criteria, beneficial utilization of biomass ash in cement may be more feasible than in soil, but regulatory criteria based on leaching rather than total content of elements may widen the application potential of biomass ash. A© 2019 Elsevier Ltd

Alternating flooding and drainage conditions have a strong influence on redox chemistry and the solubility of trace metals in paddy soils. However, current knowledge of how the effects of water management on trace metal solubility are linked to trace metal uptake by rice plants over time is still limited. Here, a field-contaminated paddy soil was subjected to two flooding and drainage cycles in a pot experiment with two rice plant cultivars, exhibiting either high or low Cd accumulation characteristics. Flooding led to a strong vertical gradient in the redox potential (Eh). The pH and Mn, Fe, and dissolved organic carbon concentrations increased with decreasing Eh and vice versa. During flooding, trace metal solubility decreased markedly, probably due to sulfide mineral precipitation. Despite its low solubility, the Cd content in rice grains exceeded the food quality standards for both cultivars. Trace metal contents in different rice plant tissues (roots, stem, and leaves) increased at a constant rate during the first flooding and drainage cycle but decreased after reaching a maximum during the second cycle. As such, the high temporal variability in trace metal solubility was not reflected in trace metal uptake by rice plants over time. This might be due to the presence of aerobic conditions and a consequent higher trace metal solubility near the root surface, even during flooding. Trace metal solubility in the rhizosphere should be considered when linking water management to trace metal uptake by rice over time.

SUMMARYSoil organic matter (SOM) is important for long-term crop productivity through maintenance of soil quality and is also now receiving attention due to its potential for climate change mitigation. The objectives of the present study were to investigate the effects of 9 years of fertilization on soil organic carbon (SOC) and total organic nitrogen (TON) and their fractions for the 0–50 cm profile in clayey (Luvisols) and sandy (Arenosols) soils in Murewa District, Zimbabwe. Three treatments were assessed: unfertilized (Control), nitrogen fertilizer (Nfert) and nitrogen fertilizer plus cattle manure (Nfert+manure). Density fractionation was used to assess the distribution of SOC and TON in three SOM fractions and their sensitivity to fertilization in fields 0–50 m away from homesteads (Homefields) and > 100 m away from homesteads (outfields). The relationship between light and heavy fraction organic carbon (C) were analysed to determine equilibrium levels that give an indication of carbon storage potential. In clayey soils total organic C under Nfert+manure was 4% higher than Nfert and 16% higher than the control. In sandy soils, SOC stocks were lowest in the control and highest in Nfert treatments at all depths. Nine years of fertilization significantly influenced SOC concentrations and storage up to 20 cm depth, below which stocks and concentrations of C and N were statistically insignificant. Distribution of C and N in density fractions showed greater stabilization under Nfert+manure in clayey soils, whereas it was greater under Nfert in sandy soils. Estimation of equilibrium levels suggested that homefields had potential to store more C, whereas outfields and control treatments had limited capacity due to attainment of lower equilibrium levels. Application of manure can be a low-cost alternative for enhancing soil quality and promoting soil C sequestration under conventionally tilled continuous maize cropping systems in Zimbabwe.

Sustained increased productivity of trees growing in elevated CO2 depends in part on their stoichiometric flexibility, i.e., increasing their nutrient use efficiency, or on increased nutrient uptake from the soil. Phosphorus (P) may be a nutrient as limiting as nitrogen (N) in terrestrial ecosystems and may play a key-process in global terrestrial C storage. For this study archived litter and soil samples of two free air CO2 enrichment (FACE) experiments were analyzed for C, N and P. Populus euramericana, nigra and alba and Betula pendula, Alnus glutinosa and Fagus sylvatica were grown in ambient and elevated CO2 at respectively the Euro- and BangorFACE experiments. At EuroFACE, aboveground litter accumulated in L, F and H layers, while at BangorFACE almost all aboveground litter was incorporated into the mineral soil due to bioturbation. At EuroFACE, more P was lost from the F and H litter layers due to trees growing in elevated CO2, while at BangorFACE more P was lost from the mineral soil. Results of this study imply that trees growing in elevated CO2 were P limited at both experiments. Therefore, with increasing atmospheric CO2, P may play a more pronounced role than previous thought in regulating secondary forest growth. Moreover, increased atmospheric CO2 and ample N may allow a larger pool of P to become available for uptake due to, for instance, increased phosphatase activity resulting in increased organic matter turnover and biogenic weathering. Therefore, it may be postulated that under non-N-limited conditions, e.g., during regrowth, under high N deposition or in systems with high N2-fixation, increased P availability and uptake may allow P-limited forests to sustain increased growth under increasing atmospheric CO2.

The toxicity of silver nanoparticles (AgNPs) has been related to the release of ionic silver. This process is influenced by a large variety of factors and is poorly understood. The key to understanding Ag(+) release by AgNPs is its subvalency. This is a fundamental property of Ag that can be elucidated by analyzing the crystal structures of a specific class of Ag materials as well as MO/DFT (molecular orbital/density functional theory)-optimized Ag13(OH)4 clusters, being precursors of AgNPs. Semimetallic silver at the (111) faces of AgNPs has a subvalency of +(1)/3 v.u., forming ≡Ag3OH(0) surface groups with a maximum site density of 4.7 sites/nm(2). Oxidative dissolution may remove these groups with the simultaneous formation of oxygen radicals that may further interact with the surface via different pathways. Reactive oxygen species (ROS) can create a circular process with the dissolution of ≡Ag3OH(0), exposure of new metallic sites at the underlying lattice, and subsequent oxidation to ≡Ag3OH(0). This regeneration process is interrupted by the penetration of O(•) radicals into the lattice, forming highly stable Ag6O octahedra with subvalent silver that protects the AgNP from further oxidation. A thermodynamic model has been developed that quantitatively describes the equilibrium condition between ≡Ag3OH(0) and ≡Ag6O(0) and explains a large variety of collectively observed phenomena.

Free concentrations of Zn2+, Fe3+, Ca2+ and Mg2+ in a red wine (Raimat, Catalonia, Spain) have been determined, with the Donnan Membrane Technique (DMT) for the first time. The required equilibration time benefits from the acceptor solution including major cations. K+ and Na+, mainly unbound to any ligand in the sample, have been identified as suitable reference ions. A free Zn concentration of 1.76 micromol L-1 determined with DMT was in excellent agreement with the free Zn concentration independently provided by the electroanalytical technique Absence of Gradients and Nernstian Equilibrium Stripping (AGNES), 1.7 micromol L-1, amounting to 14.4% of the total Zn. The free concentrations found in this wine were 1.79 micromol L-1 Fe3+, 1.11 mmol L 1 Ca2+ and 3.4 mmol L-1 Mg2+ (8.82%, 40% and 57% of their total concentrations). Prior to the application of the techniques to the red wine, they had been cross-validated in Zn-tartrate solutions. This work was financially supported by the Spanish Ministerio de Economía y Competitividad (projects CTM2013-48967 and CTM2016-78798), and from the “Comissionat per a Universitats i Recerca del Departament d’Innovació, Universitats i Empresa de la Generalitat de Catalunya”.

Studying the modes of selenium occurrence in high-Se soils and its behaviors can improve understanding and evaluating its cycling, flux, and balance in geo-ecosystems and its influence on health. In this paper, using a modified sequential chemical extraction technique, seven operationally defined selenium fractions and Se valence distribution were determined about five soils in which paddy was planted (W1, W2, W3, W4, W5) and five soils in which maize was planted (H1, H2, H3, H4, H5) around the selenium-rich core, Ziyang County, Shaanxi Province, China. The results show that selenium fractions in the soils mainly include sulfide/selenide and base-soluble Se, and ligand-exchangeable Se is also high for five soils in which paddy was planted. For water-soluble Se, Se (IV) is main Se valence and almost no Se (VI) was determined about five soils in which paddy was planted, while almost 1:1 of Se (IV) and Se (VI) coexist about five soils in which maize was planted. For exchangeable Se, similar results were found. For the first time, two typical high-Se soils (W1 soil and H1 soil) were chosen to measure the pH-dependent solid-solution distribution of selenite in the pH range 3–9, and the results were explained using LCD (ligand and charge distribution) adsorption modeling. The desorbed selenite concentrations from the two soils are in general underestimated by the model due to a comparable binding affinity of phosphate and selenite on goethite and much lower amount of total selenite than total reactively adsorbed phosphate. The pH dependency of adsorption of selenite added to the soil can be successfully described with the LCD model for W1 soil. Whereas considering the influence of Al-oxides, by lowering selenite adsorption affinity constant K of Se adsorption on goethite by 16 times, the LCD model can describe the adsorption much better. The results can help to understand selenium cycling, flux, and balance in typical high-Se soils.

Grasslands are a major form of agricultural land use worldwide. Current and future declines of phosphorus (P) inputs into production grasslands necessitate a shift towards selecting grass species based on high efficiency under suboptimal, rather than optimal P conditions. It is therefore imperative to identify key root traits that determine P acquisition of grasses in soils with a low P status. In a 9-month greenhouse experiment, we grew eight common grass species and cultivars on a soil with a low P status and related root morphological traits to their performance under P-limiting conditions. We applied (P1) or withheld (P0) P fertilization while providing adequate amounts of all other nutrients. Omitting P fertilization greatly reduced yield and nutrient acquisition for the various grass species. Biomass production differed significantly (P < 0.1%) among species and P fertilization treatments, varying from 17.1 to 72.1 g pot−1 in the P0 treatment and from 33.4 to 85.8 g pot−1 in the P1 treatment. Root traits were species-specific and unresponsive to P fertilization, but overall we observed a trade-off between root biomass and specific root length. Structural equation modeling identified total root length as key factor with respect to resistance to P deficiency, especially when roots explored the subsoil. Optimizing root length and subsoil exploration could be the key to maintaining high productivity of production grasslands with decreasing P availability. This is relevant for both plant breeding programs and for composing seed mixtures.

The surface complexation modeling of metal adsorption to birnessites is in its infancy compared to the charge-distribution multi-site ion complexation (CD-MUSIC) models for iron/aluminum (hydr)oxides. Therefore, using X-ray diffraction with Rietveld refinement to obtain the reactive sites and their densities, a CD-MUSIC model combined with a Stern-Gouy-Chapman electrical double layer (EDL) model for the external surface and a Donnan model for the interlayer surface is developed for birnessites with different Mn average oxidation state (MnAOS). Proton affinity constants and the charge distributions of Pb surface complexes were calculated a priory. By fitting Pb adsorption data to the model the obtained equilibrium constants (logKPb) of Pb complexes were 6.9-10.9 for the double-corner-sharing and double-edge-sharing Pb2+ complexes on the edge sites and 2.2-6.5 for the triple-corner-sharing Pb2+ complex on the vacancies. The larger logKPb value was obtained for higher MnAOS. Speciation calculations showed that with increasing MnAOS from 3.67 to 3.92 the interlayer surface contribution to the total Pb2+ adsorption increased from 43.2% to 48.6%, and the vacancy contribution increased from 43.9% to 54.7%. The vacancy contribution from interlayer surface was predominant. The present CD-MUSIC-EDL model contributes to understand better the difference in metal adsorption mechanism between birnessite and iron/aluminum (hydr)oxides.

Simulating the storage of aerobic soils under water, the chemical speciation of heavy metals and arsenic was studied over a long-term reduction period. Time-dynamic and redox-discrete measurements in reactors were used to study geochemical changes. Large kinetic differences in the net-complexation quantities of heavy metals with sulfides was observed, and elevated pore water concentrations remained for a prolonged period (>1 year) specifically for As, B, Ba, Co, Mo, and Ni. Arsenic is associated to the iron phases as a co-precipitate or sorbed fraction to Fe-(hydr)oxides, and it is being released into solution as a consequence of the reduction of iron. The composition of dissolved organic matter (DOM) in reducing pore water was monitored, and relative contributions of fulvic, humic and hydrophylic compounds were measured via analytical batch procedures. Quantitative and qualitative shifts in organic compounds occur during reduction; DOM increased up to a factor 10, while fulvic acids become dominant over humic acids which disappear altogether as reduction progresses. Both the hydrophobic and hydrophilic fractions increase and may even become the dominant fraction. Reactive amorphous and crystalline iron phases, as well as dissolved FeII/FeIII speciation, were measured and used as input for the geochemical model to improve predictions for risk assessment to suboxic and anaerobic environments. The release of arsenic is related to readily reducible iron fractions that may be identified by 1 mM CaCl2 extraction procedure. Including DOM concentration shifts and compositional changes during reduction significantly improved model simulations, enabling the prediction of peak concentrations and identification of soils with increased emission risk. Practical methods are suggested to facilitate the practice of environmentally acceptable soil storage under water.

As many soils are unable to supply sufficient amounts of phosphorus (P) to plants, P availability is often a growth-limiting factor. Literature shows that levels of readily available P can be considerably higher in earthworm casts than in the surrounding bulk soil, possibly resulting in increased plant P uptake. However, the underlying mechanisms through which this increase of readily available P occurs are unclear. In a greenhouse pot experiment with annual ryegrass (Lolium multiflorum) on a soil with low P availability, we tested whether the presence of the anecic earthworm Lumbricus terrestris resulted in increased grass growth and P uptake and explored the possible mechanisms behind such an effect. During the pot experiment, earthworm casts were collected and analysed for water-extractable P as well as for most other relevant ions. The earthworm's presence significantly increased grass yield from 9.80 to 10.80 g dry matter per pot (p = 0.044) and P uptake from 6.32 to 8.04 mg per pot (p = 0.002). Due to increased microbial activity, the solution chemistry in the water extracts of the casts was dramatically changed compared to the bulk soil samples. The concentrations of dissolved inorganic P in cast were enhanced by a factor ~ 30–1000 compared to the levels found in bulk soil. The pH in earthworm casts increased from 5.9 to values between 7.4 and 9.0 and the Ca concentrations decreased by about a factor ~ 2-3 compared to bulk soil samples. In addition, there was an increase in dissolved organic carbon (35 mg L− 1 in casts versus 3 mg L− 1 in soil). Surface complexation modelling, using the Charge Distribution model, suggests that, besides an increase in pH, particularly an enhanced interaction of dissolved organic matter with reactive surface of metal (hydr)oxides is likely to be a major driving force for the augmented release of orthophosphate (PO4) via competitive adsorption and desorption. This competition for adsorption sites is an alternative pathway, next to mineralisation of organic matter, through which earthworms can increase soil fertility.

Environmental contextStudying the mechanism of binding between metals and natural organic matter is fundamental to understanding the transport and availability of these contaminants in the environment. The influence of sample treatment on the purification of organic matter showed significant differences in the interaction with metals. The results will contribute to improved modelling of metal binding to organic matter in soils, thereby providing a basis for a more realistic risk assessment. AbstractWe studied the changes in metal binding characteristics of extracted humic acids induced by HF/HCl treatment followed by dialysis, i.e. the last step of the International Humic Substances Society (IHSS) extraction protocol. We performed metal binding experiments with both the alkaline-extracted material (AE) and the fully purified (FP) humic acid using the electrochemical stripping technique (AGNES) and modelled the results using the NICA-Donnan model. The results showed an increase of free Zn, Cd and Pb concentrations of similar to 1 order of magnitude for the AE compared with the FP. These differences may be mostly explained by the different carbon content (51.3% FP and 36.5% AE) associated with an AE/FP carboxyl ratio of 0.5. Simulations using the NICA-Donnan model showed that halving the amount of carboxylic groups (Q(max,1)) for the FP reduced this difference to 0.25 log units for Cd and Zn and to 0.15 log unit for Pb. There is a clear need for further research on the differences between purified v. less-disturbed natural organic material, which will contribute to improved modelling of metal binding to organic matter in soils, hence providing a basis for a more realistic risk assessment. Coordenadoria de Aperfeicoamento do Pessoal de Nivel Superior (CAPES CSF) [981313-6] Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq PVE) [400572/2013-3] French national research agency (ANR) [ANR-10-LABX-21-01/LABEX RESSOURCES 21] Portuguese national funding agency for science, research and technology [FCT-ANR/AAG-MAA/0065/2012] Region Lorraine

Distinct extractable organic matter (EOM) fractions have been used to assess the capacity of soils to supply nitrogen (N). However, substantial uncertainty exists on their role in the N cycle and their functional dependency on soil properties. We therefore examined the variation in mineralizable N and its relationship with EOM fractions, soil physical and chemical properties across 98 agricultural soils with contrasting inherent properties and management histories. Mineralizable N was determined by aerobic incubation at 20 °C and optimum moisture content for 20 weeks. We used multivariate statistical modelling to account for multi-collinearity, an issue generally overlooked in studies evaluating the predictive value of EOM fractions. Mineralization of N was primarily related to the size of OM pools and fractions present; they explained 78% of the variation in mineralizable N whereas other soil variables could explain maximally 8%. Both total and extractable OM expressed the same soil characteristic from a mineralization perspective; they were positively related to mineralizable N and explained a similar percentage of the variation in mineralizable N. Inclusion of mineralizable N in fertilizer recommendation systems should be based on at least one OM variable. The most appropriate EOM fraction can only be identified when the underlying mechanisms are known; regression techniques are not suitable for this purpose. Combination of single EOM fractions is not likely to improve the prediction of mineralizable N due to high multi-collinearity. Inclusion of texture-related soil variables or variables reflecting soil organic matter quality may be neglected due to their limited power to improve the prediction of mineralizable N.

The effect of in situ immobilization of lead (Pb) and arsenic (As) in soil with respectively phosphate and iron is well recognized. However, studies on combined Pb and As-contaminated soil are fewer, and assessment of the effectiveness of the immobilization on mobility and bioaccessibility is also necessary. In this study, a Pb and As-contaminated soil was collected from an abandoned lead/zinc mine in Shaoxing, Zhejiang province of China, which has been treated with three phosphates, i.e., calcium magnesium phosphate (CMP), phosphate rock, and single super-phosphate (SSP) for 6 months in a field study. The ferrous sulfate (FeSO4) at 20 g kg−1 was then amended to the soil samples and incubated for 8 weeks in a greenhouse. The solubility and bioaccessibility tests were used to assess the effectiveness of the in situ immobilization. The result showed that phosphates addition decreased the concentrations of CaCl2-extractable Pb; however, the concentrations of water-soluble As increased upon CMP and SSP addition. With the iron addition, the water-soluble As concentrations decreased significantly, but CaCl2-extractable Pb concentrations increased. The bioaccessibility of As and Pb measured in artificial gastric and small intestinal solutions decreased with phosphate and iron application except for the bioaccessibility of As in the gastric phase with SSP addition. Combined application of phosphates and iron can be an effective approach to lower bioaccessibility of As and Pb, but has opposing effects on mobility of As and Pb in contaminated soils.

Freshly prepared simulated milk ultrafiltrate (SMUF) is a solution that is supersaturated with respect to various calcium phosphate phases that precipitate in time. As a consequence, the ion composition of equilibrated SMUF was found to be significantly different from that of freshly prepared SMUF. This study proposes a thermodynamic ion-speciation model that is able to describe ion equilibria in SMUF. Moreover, it is also able to describe calcium phosphate precipitation in fresh SMUF on its way to equilibrium by using an apparent solubility product for CaHPO 4 ·2H 2 O as a function of time. The model was validated by experiments in which CaCl 2 and Na 2 HPO 4 were added to freshly prepared SMUF. The changes in calcium activity and pH were followed and the precipitates were characterised by X-ray diffraction. The model was able to predict the observed changes.

Information on the particle size and reactive surface area of natural samples is essential for the application of surface complexation models (SCM) to predict bioavailability, toxicity, and transport of elements in the natural environment. In addition, this information will be of great help to enlighten views on the formation, stability, and structure of nanoparticle associations of natural organic matter (NOM) and natural oxide particles. Phosphate is proposed as a natively present probe ion to derive the effective reactive surface area of natural samples. In the suggested method, natural samples are equilibrated (⩾10 days) with 0.5 M NaHCO3 (pH = 8.5) at various solid–solution ratios. This matrix fixes the pH and ionic strength, suppresses the influence of Ca2+ and Mg2+ ions by precipitation these in solid carbonates, and removes NOM due to the addition of activated carbon in excess, collectively leading to the dominance of the PO4–CO3 interaction in the system. The data have been interpreted with the charge distribution (CD) model, calibrated for goethite, and the analysis results in an effective reactive surface area (SA) and a reversibly bound phosphate loading Γ for a series of top soils. The oxidic SA varies between about 3–30 m2/g sample for a large series of representative agricultural top soils. Scaling of our data to the total iron and aluminum oxide content (dithionite–citrate–bicarbonate extractable), results in the specific surface area between about 200–1200 m2/g oxide for most soils, i.e. the oxide particles are nano-sized with an equivalent diameter in the order of ∼1–10 nm if considered as non-porous spheres. For the top soils, the effective surface area and the soil organic carbon fraction are strongly correlated. The oxide particles are embedded in a matrix of organic carbon (OC), equivalent to ∼1.4 ± 0.2 mg OC/m2 oxide for many soils of the collection, forming a NOM–mineral nanoparticle association with an average NOM volume fraction of ∼80%. The average mass density of such a NOM–mineral association is ∼1700 ± 100 kg/m3 (i.e. high-density NOM). The amount of reversibly bound phosphate is rather close to the amount of phosphate that is extractable with oxalate. The phosphate loading varies remarkably (Γ ≈ 1–3 μmol/m2 oxide) in the samples. As discussed in part II of this paper series ( Hiemstra et al., 2010 ), the phosphate loading (Γ) of field samples is suppressed by surface complexation of NOM, where hydrophilic, fulvic, and humic acids act as a competitor for (an)ions via site competition and electrostatic interaction.

The performance of a multisurface sorption model approach, composed of well-accepted surface complexation models in combination with published "generic" parameter sets, is evaluated for its possible use in risk assessment. For that purpose, the leaching of a broad range of potential soil contaminants (Ni, Cu, Zn, Cd, Pb, Ba, Cr, Co, Mo, V, Sn, Sb, S, As, Se) from eight diffusely and industrially contaminated soils is predicted simultaneously without any parameter optimization. The model approach includes aqueous speciation in combination with sorption to organic matter (NICA-Donnan model), Fe/Al(hydr)oxides (Generalized Two-Layer Model), and clay (Donnan model). Independent data generated by pH-static leaching experiments, performed with individual subsamples over a wide pH range (pH 0.4-12), provide a sensitive evaluation of the model performance. Root-mean-squared error values between predicted and measured log concentrations over the entire pH range, RMSE(log), are < 0.5 for Cu, Ni, Cd, Co, S, and Se, and RMSE(log) < 1 for Zn, Ba, Cr, Pb, Sn, Mo, Sn and As. The approach without parameter optimization has led to recommendations for further research with particular emphasis on identification of leaching mechanisms for Pb, Mo, Sb, and V and further expansion of the data sets to reduce the uncertainty of the available generic sorption parameters for Sn, Sb, Ba, Cr, and V.

Data for interactions between arsenate (AsO4(3-) and fulvic acids (FA) or humic acids (HA) at the surface of goethite are presented (pH 3-7, ionic strength 2 mM and 10 mM). Adsorption of FA and HA leads to desorption of arsenate and a correspondingly strong increase of arsenic concentration in solution. Adsorption of both FA and HA is mutually decreased by the competition with arsenate. The competition between FA and arsenate is much stronger than that between HA and arsenate. Using an advanced model, the LCD model (Ligand and Charge Distribution), arsenate adsorption to goethite in the presence of both adsorbed FA and HA can be predicted reasonably well. The stronger effects of FA on arsenate adsorption are caused, according to the model, by its spatial location which is closer to the oxide surface, and as a consequence, the electrostatic interactions between adsorbed FA particles and arsenate ions are much stronger than those for HA particles. The results show that site and electrostatic competition are the major mechanisms explaining the effects of natural organic matter on the arsenic speciation, whereas other possible mechanisms, such as a chemical reduction of arsenate to arsenite and formation of ternary organic arsenic complexes, are of minor significance.

The interaction between copper ions (Cu2+), Strichen fulvic acid (FA), and goethite has been studied with batch experiments in the pH range of 3–11. Similar systems with Ca2+ have been studied previously and are used here for comparison. Depending on the pH and Cu2+ loading, the binding of Cu ions to the solid phase is enhanced or reduced by the presence of FA. Cu2+ complexation in the ternary systems can be mostly described reasonably well with the assumption of linear additivity neglecting the interaction of FA and Cu2+ at the goethite surface, except for low Cu loading and high FA loading. A surface complexation model, the Ligand and Charge Distribution (LCD) model, is used to describe Cu binding to the mixture of goethite and FA. By considering both type A (goethite–Cu–FA) and type B (goethite–FA–Cu) ternary complexes, the LCD model descriptions of Cu adsorption are in general in good agreement with the data. Results show that the ternary complex with cation bridging (type A) is the dominating Cu species at low pH, low Cu loading and high FA loading, whereas Cu bound to goethite only is more important at high pH, high Cu loading and low FA loading. Complexation by only ligands of adsorbed FA (type B ternary complexes) is not important for Cu. In the interface, Ca2+ ions attribute more charge than Cu2+ to the 1-plane, where a large fraction of the negative charge of the FA resides, which explains the stronger enhancement of FA adsorption in the presence of Ca2+ compared to Cu2+.

Four soils were collected from different sites of China in Lechang (LC, Guangdong province), Changsha (CS, Hunan province), Jiaxing UX, Zhejiang province) and Hangzhou (HZ, Zhejiang province), and were spiked with Cu (50 mg kg(-1)) and Cd (5 mg kg(-1)). The effects of rice straw addition (6%) on the chemical distribution of both metal ions were studied by measuring the soluble metal ion concentrations and the free metal ion concentrations (using the Donnan membrane technique) after 1-, 3- and 6-month incubation. Results show that the addition of rice straw increased soil pH by about 0.4 pH unit on average, and increased DOC significantly in soil LC, CS and JX, but not in soil HZ. With the addition of rice straw, total soluble Cu concentration increased from 0.82 mu mol l(-1) (0.26-2.4 mu mol l(-1)) to 1.22 mu mol l(-1) (0.70-3.60 mu mol l(-1)), whereas total soluble Cd concentration decreased from 20 nmol l(-1) (2-70 nmol l(-1)) to 15 nmol l(-1) (2-56 nmol l(-1)). When rice straw was added, both free Cu 2 and Cd 21 concentrations decreased, for free Cu2+ concentration from 217 nmol l(-1) (31 to 369 nmol l(-1)) to 124 nmol l(-1) (22 to 263 nmol l(-1)) and for free Cd2+ concentration from 16 nmol l(-1) (1-55 nmol l(-1)) to 12 nmol l(-1) (1-43 nmol l(-1)). With the increase of incubation time, free Cu2+ concentration tended to increase but free Cd2+ concentration decreased. Speciation model calculations show that compared to the binding capacity of soil organic matter, the capacity of rice straw is much less important. The decrease of free metal ion concentration upon rice straw addition can be attributed mainly to the increased pH. The higher DOC content in the rice straw treatment could be the reason for higher soluble Cu concentration when rice straw was added. Adsorption to DOC is much less important for Cd than for Cu. Calculation also shows that adsorption to clay minerals plays a more important role for Cd than for Cu, which may explain the stronger ageing effects on Cd distribution. (c) 2008 Elsevier B.V. All rights reserved.

Colloidal phosphorus (P) may represent an important fraction of the P in natural waters, but these colloids remain poorly characterized. In this work, we demonstrate the applicability of asymmetric flow field-flow fractionation (AF4) coupled to high resolution ICP-MS for the characterization of low concentrations of P-bearing colloids. Colloids from five streams draining catchments with contrasting properties were characterized by AF4-ICP-MS and by membrane filtration. All streams contain free humic substances (2-3 nm) and Fe-bearing colloids (3-1200 nm). Two soft water streams contain primary Fe oxyhydroxide-humic nanoparticles (3-6 nm) and aggregates thereof (up to 150 nm). In contrast, three harder water streams contain larger aggregates (40-1200 nm) which consist of diverse associations between Fe oxyhydroxides, humic substances, clay minerals, and possibly ferric phosphate minerals. Despite the diversity of colloids encountered in these contrasting streams, P is in most of the samples predominantly associated with Fe-bearing colloids (mostly Fe oxyhydroxides) at molar P:Fe ratios between 0.02 and 1.5. The molar P:Fe ratio of the waters explains the partitioning of P between colloids and truly dissolved species. Waters with a high P:Fe ratio predominantly contain truly dissolved species because the Fe-rich colloids are saturated with P, whereas waters with a low P:Fe ratio mostly contain colloidal P species. Overall, AF4-ICP-MS is a suitable technique to characterize the diverse P-binding colloids in natural waters. Such colloids may increase the mobility or decrease the bioavailability of P, and they therefore need to be considered when addressing the transport and environmental effects of P in catchments.

The As(V) and As(III) interaction with HCO3 has been studied for goethite systems using a pH and As concentration range that is relevant for field situations. Our study shows that dissolved bicarbonate may act as a competitor for both As(V) and As(III). In our closed systems, the largest effect of bicarbonate occurs at the lowest experimental pH values (pH approximately 6.5), which is related to the pH dependency of the carbonate adsorption process. The experimental data have been modeled with the charge distribution (CD) model. The CD model was separately parametrized for goethite with "single ion" adsorption data of HCO3, As(III), and As(V). The competitive effect of HCO3 on the As(III) and As(V) release could be predicted well. Application of the model shows that the natural As loading of aquifer materials (approximately0.01-0.1 micromol/m2 or1-5 mg/kg) is at least about1-2 orders of magnitude smaller than the As loading based on the competition of As-HCO3 alone. It indicates that another, very prominent competitor, like phosphate and natural organic matter, will strongly contribute to the control of As in natural systems.

FeEDDHA products are applied to correct iron chlorosis in plants and consist of a mixture of EDDHA isomers chelated to iron. In this study such mixtures have been divided into four (groups of) isomers: racemic o,o-EDDHA, meso o,o-EDDHA, o,p-EDDHA and rest-EDDHA. The physical and chemical properties of these isomers differ and hence does their ability to deliver Fe to plants. To come to a soil-specific iron fertilization recommendation, the behaviour of the EDDHA isomers in the soil needs to be understood. This behaviour has been examined in a soil interaction experiment as a function of time, and it has been related to soil properties. The isomer fractions remaining in solution can be ranked racemic o,o-FeEDDHA > meso o,o-FeEDDHA > rest-FeEDDHA > o,p-FeEDDHA, regardless of soil properties. The o,o-EDDHA isomers largely determine the Fe concentration in solution. Although rest-EDDHA also consists of compounds that chelate Fe more strongly than meso o,o-EDDHA, the latter is on average better capable of keeping Fe in solution upon interaction with soil. The principal adsorption surface differs per EDDHA isomer. For racemic o,o-FeEDDHA it is organic matter, for meso o,o-FeEDDHA it is iron (hydr)oxide and for o,p-FeEDDHA clay minerals. Cu and Al are important competing cations. Cu forms soluble complexes with o,p-EDDHA, and Al with meso o,o-EDDHA not chelated to Fe. Al is likely to affect the effectiveness of a potential shuttle effect. The tendency of o,p-FeEDDHA and rest-FeEDDHA to be removed from solution, makes these isomers less effective as iron fertilizer in soil application, in particular on clay soils.