Recycled Iron Phosphates: A New Phosphorus Fertilizer for Paddy Rice.

The potential of recycled iron phosphates (FePs), e.g., vivianites (Fe3(PO4)2·8H2O) and Fe(III)-rich phosphorus (P) adsorbent materials, as phosphorus fertilizer is limited by the strong interaction between Fe and P. In this study, the efficiency of FePs as P fertilizer was explored by applying them as granules or powder in flooded strongly P-fixing soils (acid and calcareous), thereby taking advantage of increased P release induced by reductive dissolution of P-bearing Fe(III) minerals. First, no P diffusion from granular FeP fertilizers into flooded soils was detectable by the diffusive gradient in thin films (DGT) technique and microfocused X-ray fluorescence (µ-XRF) analysis of thin soil sections, in contrast to detectable P diffusion away from granules of soluble triple superphosphate (TSP) fertilizer. On the contrary, powdered FePs demonstrated an excellent increase in extractable P (1 mM CaCl2) in a 120-day incubation experiment in flooded soils. Second, a pot experiment was performed with rice (Oryza sativa) grown in flooded acid and calcareous soils. The fertilizer value of FePs was remarkable when dosed as powder, as it was even up to 3-fold higher than TSP in the acid soil and similar to TSP in the calcareous soil. The beneficial effect of FeP over TSP in the acid soil is attributed to the slow release of P from FePs, which allows to partly overcome P fixation. The promising results of FePs as P fertilizer applied as powders in flooded soils debunk the generally accepted idea that FePs are poor sources of P while demonstrating the importance of the timing of FeP fertilizer application.

Cottage industry as a source of high exposure to lead: A biomonitoring study among people involved in manufacturing cookware from scrap metal.

In low-income countries, a widespread but poorly studied type of cottage industry consists of melting scrap metal for making cookware. We assessed the exposure to lead (Pb) among artisanal workers, and their families, involved in manufacturing cookware from scrap metal. In a cross-sectional survey, we compared artisanal cookware manufacturing foundries with carpentry workshops (negative controls) and car battery repair workshops (positive controls), all located in residential areas, in Lubumbashi (DR Congo). We collected surface dust in the workspaces, and blood and urine samples among workers, as well as residents living in the cookware workshops. Trace elements were quantified in the samples by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). In surface dust, median Pb concentrations were higher in cookware foundries (347 mg/kg) than in carpentries (234 mg/kg) but lower than in battery repair workshops (22,000 mg/kg). In workers making the cookware (n = 24), geometric mean (GM) Pb blood cencentration was 118 µg/L [interquartile range (IQR) 78.4-204], i.e. nearly twice as high as among carpenters [60.2 µg/L (44.4-84.7), n = 33], and half the concentration of battery repair workers [255 µg/L (197-362), n = 23]. Resident children from the cookware foundries, had higher urinary Pb [6.2 µg/g creatinine (2.3-19.3), n = 6] than adults [2.3 (2.2-2.5), n = 3]. Our investigation confirms the high Pb hazard linked to car battery repair and reveals a high exposure to Pb among artisanal cookware manufacturers and their families, especially children, in residential areas of a city in a low-income country.

Effect of external and internal loading on source-sink phosphorus dynamics of river sediment amended with iron-rich glauconite sand.

Glauconite sands (GS) are abundantly available iron (Fe)-rich minerals that are efficient in lowering the release of phosphorus (P) from sediments to the overlying water. Many river sediments are, however, net sinks for P rather than sources and it is unclear if these GS minerals also enhance the P uptake from water. This is because the concentration of Fe(III) minerals at the sediment-water interface (SWI) depends on the redox potential that is affected by physicochemical processes. This study was set-up to investigate if a sediment amendment with GS can both lower P release from the sediment and enhance P uptake from the overlying water. The P fluxes across the SWI were compared between GS-amended (added at 10% weight fraction) and non-amended river sediment in static (incubation) and dynamic (flume) systems. The net P uptake was measured in response to a pulse external P loading (0.5-5 mg P L-1). Sodium glutamate was added to all treatments to simulate water with a high oxygen demand. Before the P pulse, the GS-amended sediments released significantly less P to the overlying water than the non-amended sediments in both static as dynamic systems. Spiking the water reverted the net P flux over the SWI only in the dynamic system, and the net P uptake in the sediment was factor two larger in GS-amended sediment compared to the non-amended sediment. This study showed that GS addition not only reduced internal P release, but also enhanced P uptake from the overlying water. However, the long-term efficiency in streams likely decreases over time due to saturation processes.

Screening redox stability of iron rich by-products for effective phosphate immobilisation in freshwater sediments.

Iron (Fe) rich by-products can be added to lake or river sediments to immobilise phosphate (PO4) and lower eutrophication risks. These Fe materials differ in mineralogy and specific surface area, hence differing in PO4 sorption capacity and stability under reducing conditions. This study was set up to identify key properties of these amendments in their capacity to immobilise PO4 in sediments. Eleven Fe rich by-products, collected from drinking water treatment plants and acid mine drainage, were characterised. The PO4 adsorption to these by-products was first determined under aerobic conditions and the solid-liquid distribution coefficient KD for PO4 correlated strongly to oxalate extractable Fe content. A static sediment-water incubation test was subsequently used to evaluate the redox stability of these by-products. The reductive processes gradually released Fe to solution and more Fe was release from the amended than from the control sediments. The total Fe release to solution was positively related to ascorbate reducible Fe fractions in the by-products, suggesting that such fractions indicate potential loss of P retention capacity on the long term. The final PO4 concentration in the overlying water was 5.6 mg P L-1 in the control and was successfully lowered by factor 30-420 depending on the by-product. The factor by which solution PO4 was reduced in Fe treatments increased with increasing KD determined under aerobic conditions. This study suggests that efficient by-products to trap P in sediments are characterised by a high oxalate Fe content and a low reducible Fe fraction.

Millimetre-resolution mapping of citrate exuded from soil-grown roots using a novel, low-invasive sampling technique.

The reliable sampling of root exudates in soil-grown plants is experimentally challenging. This study aimed at developing a citrate sampling and mapping technique with millimetre-resolution using DGT (diffusive gradients in thin films) ZrOH-binding gels. Citrate adsorption kinetics, DGT capacity, and stability of ZrOH gels were evaluated. ZrOH gels were applied to generate 2D maps of citrate exuded by white lupin roots grown in a rhizotron in a phosphorus-deficient soil. Citrate was adsorbed quantitatively and rapidly by the ZrOH gels; these gels can be stored after sampling for several weeks prior to analysis. The DGT capacity of the ZrOH gel for citrate depends on the ionic strength and the pH of the soil solution, but was suitable for citrate sampling. We generated for the first time 2D citrate maps of rhizotron-grown plants at a millimetre resolution to measure an illustrated plant response to phosphorus fertilization, demonstrating that DGT-based citrate sampling is suitable for studying root exudation in soil environments, at high spatial resolution. The change of binding material would also allow sampling of other exudate classes and exudation profiles of entire root systems. These aspects are crucial in cultivar breeding and selection.

A functional-structural model of upland rice root systems reveals the importance of laterals and growing root tips for phosphate uptake from wet and dry soils.

BACKGROUND AND AIMS: Upland rice is often grown where water and phosphorus (P) are limited. To better understand the interaction between water and P availability, functional-structural models that mechanistically represent small-scale nutrient gradients and water dynamics in the rhizosphere are needed. METHODS: Rice was grown in large columns using a P-deficient soil at three P supplies in the topsoil (deficient, sub-optimal and non-limiting) in combination with two water regimes (field capacity vs. drying periods). Root system characteristics, such as nodal root number, lateral types, interbranch distance, root diameters and the distribution of biomass with depth, as well as water and P uptake, were measured. Based on the observed root data, 3-D root systems were reconstructed by calibrating the structural architecure model CRootBox for each scenario. Water flow and P transport in the soil to each of the individual root segments of the generated 3-D root architectures were simulated using a multiscale flow and transport model. Total water and P uptake were then computed by adding up the uptake by all the root segments. KEY RESULTS: Measurements showed that root architecture was significantly affected by the treatments. The moist, high P scenario had 2.8 times the root mass, double the number of nodal roots and more S-type laterals than the dry, low P scenario. Likewise, measured plant P uptake increased >3-fold by increasing P and water supply. However, drying periods reduced P uptake at high but not at low P supply. Simulation results adequately predicted P uptake in all scenarios when the Michaelis-Menten constant (Km) was corrected for diffusion limitation. They showed that the key drivers for P uptake are the different types of laterals (i.e. S- and L-type) and growing root tips. The L-type laterals become more important for overall water and P uptake than the S-type laterals in the dry scenarios. This is true across all the P treatments, but the effect is more pronounced as the P availability decreases. CONCLUSIONS: This functional-structural model can predict the function of specific rice roots in terms of P and water uptake under different P and water supplies, when the structure of the root system is known. A future challenge is to predict how the structure root systems responds to nutrient and water availability.

Anaerobic Respiration in the Unsaturated Zone of Agricultural Soil Mobilizes Phosphorus and Manganese.

Anaerobic conditions mobilize phosphorus (P) in soils and sediments. The role of anaerobic microsites in well-drained soil on P migration is unknown. This study aimed to identify mechanisms that control field-scale vertical P mobility as affected by organic fertilizers that may trigger variable redox conditions. Soils were sampled at different depths in a well-drained Luvisol after 19 years of application of organic fertilizers. The concentrations of P and manganese (Mn) in 0.45-µm-filtered extracts (10-3 M CaCl2) of field-moist soil samples were strongly correlated (r = + 0.95), and both peaked in and below the compacted plough pan, suggesting that reductive processes mobilize P. Waterlogged soil incubations confirmed that anaerobic respiration comobilizes Mn and P and that this leads to the release of colloidal P and iron (Fe). The long-term applications of farmyard manure and immature compost enhanced the concentrations of Mn, Fe, and aluminum (Al) in the soil solution of subsurface samples, whereas less such effect was found under the application of more stable organic fertilizers. Farmyard manure application significantly enhanced soil P stocks below the plough layer despite a small P input. Overall, multiple lines of evidence confirm that anaerobic respiration, sparked by labile organic matter, mobilizes P in this seemingly well-drained soil.

Unprecedentedly High Dust Ingestion Estimates for the General Population in a Mining District of DR Congo.

The mining of metals in low income countries is often associated with high exposure to dust that contributes to metal exposure. Here, dust ingestion estimates were made from fecal excretion of inert tracers with corrections for dietary contribution. The study took place in the cobalt mining area of Lubumbashi (DR Congo) and involved 120 nonoccupationally exposed participants in the dry season, with 51 of these being repeated in the rainy season. For each participant, duplicate meals (0-96 h), feces (24-120 h), and indoor/outdoor dust (<250 µm) were collected. The dust ingestion estimates (g day-1) were derived from Nb, Ti, and V as best tracers and were 0.28 (geometric mean), 3.3 (mean), and 13 (P95); these values are almost a factor 10 above currently accepted estimates for the general population in high income countries. Mean dust ingestion in the dry season was twice that of the rainy season, and the P95s were significantly higher in children (3-15 years) than in male adults and toddlers; geophagy (>40 g day-1) was suspected in three individuals. These data explain the previously reported extreme cobalt exposures in children and support the need to manage dust in the metal mining operations.

Limited Dissolved Phosphorus Runoff Losses from Layered Double Hydroxide and Struvite Fertilizers in a Rainfall Simulation Study.

The enrichment of P in surface waters has been linked to P runoff from agricultural fields amended with fertilizers. Novel slow-release mineral fertilizers, such as struvite and P-exchanged layered double hydroxides (LDHs), have received increasing attention for P recycling from waste streams, and these fertilizers may potentially reduce the risk of runoff losses. Here, a rainfall simulation experiment was performed to evaluate P runoff associated with the application of recycled slow-release fertilizers relative to that of a soluble fertilizer. Monoammonium phosphate (MAP), struvite, and LDH granular fertilizers were broadcasted at equal total P doses on soil packed in trays (5% slope) and covered with perennial ryegrass ( L.). Four rainfall simulation events of 30 min were performed at 1, 5, 15, and 30 d after the fertilizer application. Runoff water from the trays was collected, filtered, and analyzed for dissolved P. For the MAP treatment, P runoff losses were high in the first two rain events and leveled off in later rain events. In total, 42% of the applied P in the MAP treatment was lost due to runoff. In the slow-release fertilizer treatments, P runoff losses were limited to 1.9 (struvite) and 2.4% (LDH) of the applied doses and were more similar over the different rain events. The use of these novel P fertilizer forms could be beneficial in areas with a high risk of surface water eutrophication and a history of intensive fertilization.

Foliar uptake of radiocaesium from irrigation water by paddy rice (Oryza sativa): an overlooked pathway in contaminated environments.

Flooded (paddy) rice (Oryza sativa) can take up ions from the irrigation water by foliar uptake via the exposed stem base. We hypothesised that the stem base uptake of radiocaesium (RCs) is a pathway for rice grown in RCs-contaminated environments. We developed a bi-compartmental device which discriminates the stem base from root RCs uptake from solutions, thereby using RCs isotopes (137 Cs and 134 Cs) with < 2% solution leak between the compartments. Radiocaesium uptake was linear over time (0-24 h). Radiocaesium uptake to the entire plant, expressed per dry weight of the exposed parts, was sixfold higher for the roots than for the exposed stem base. At equal RCs concentrations in both compartments, the exposed stem base and root uptake contributed almost equally to the total shoot RCs concentrations. Reducing potassium supply to the roots not only increased the root RCs uptake but also increased RCs uptake by the stem base. This study was the first to experimentally demonstrate active and internally regulated RCs uptake by the stem base of rice. Scenario calculations for the Fukushima-affected area predict that RCs in irrigation water could be an important source of RCs in rice as indirectly suggested from field data.

Nanospecific Phytotoxicity of CuO Nanoparticles in Soils Disappeared When Bioavailability Factors Were Considered.

Bioavailability-modifying factors such as soil type and aging have only rarely been considered in assessing toxicity of metal-containing nanoparticles in soil. Here, we examined the toxicity to barley (Hordeum vulgare) of CuO nanoparticles (CuO-NPs) relative to CuO bulk particles (CuO-BPs) and Cu acetate (Cu(OAc)2) in six different soils with or without aging. The set up allows identifying whether or not NPs-derived colloidal Cu in soil porewater contributes to toxicity. Ultrafiltration (50 kDa) was performed together with geochemical modeling to determine {Cu2+} (free Cu2+ activity in soil porewater). Based on total soil Cu concentration, toxicity measured with seedling root elongation ranked Cu(OAc)2 > CuO-NPs > CuO-BPs in freshly spiked soils. The differences in toxicity among the three toxicants became smaller in soils aged for 90 days. When expressing toxicity as {Cu2+}, there was no indication that nanoparticulate or colloidal Cu enhanced toxicity. A calibrated bioavailability-based model based on {Cu2+} and pH successfully explained (R2 = 0.78, n = 215) toxicity of all Cu forms in different soils with and without aging. Our results suggest that toxicity predictions and risk assessment of CuO-NPs can be carried out properly using the bioavailability-based approaches that are used already for their non-nano counterparts in soil.

Internal Loading and Redox Cycling of Sediment Iron Explain Reactive Phosphorus Concentrations in Lowland Rivers.

The phosphate quality standards in the lowland rivers of Flanders (northern Belgium) are exceeded in over 80% of the sampling sites. The factors affecting the molybdate reactive P (MRP) in these waters were analyzed using the data of the past decade (>200 000 observations). The average MRP concentration in summer exceeds that winter by factor 3. This seasonal trend is opposite to that of the dissolved oxygen (DO) and nitrate concentrations. The negative correlations between MRP and DO is marked (r = -0.89). The MRP concentrations are geographically unrelated to erosion sensitive areas, to point-source P-emissions or to riverbed sediment P concentration. Instead, MRP concentrations significantly increase with increasing sediment P/Fe concentration ratio (p < 0.01). Laboratory static sediment-water incubations with different DO and temperature treatments confirmed suspected mechanisms: at low DO in water (<4 mg L-1), reductive dissolution of ferric Fe oxides was associated with mobilization of P to the water column from sediments with a molar P/Fe ratio >0.4. In contrast, no such release was found from sediments with lower P/Fe irrespective of temperature and DO treatments. This study suggests that internal loading of the legacy P in the sediments explains the MRP concentrations which are most pronounced at low DO concentrations and in regions where the P/Fe ratio in sediment is large.

Systematic Evaluation of Chronic Metal-Mixture Toxicity to Three Species and Implications for Risk Assessment.

Metal contamination generally occurs as mixtures. However, it is yet unresolved how to address metal mixtures in risk assessment. Therefore, using consistent methodologies, we have set up experiments to identify which mixture model applies best at low-level effects, i.e., the independent action (IA) or concentration addition (CA) reference model. The toxicity of metal mixtures (Ni, Zn, Cu, Cd, and Pb) to Daphnia magna, Ceriodaphnia dubia, and Hordeum vulgare was investigated in different waters or soils, totaling 30 different experiments. Some mixtures of different metals, each individually causing <10% inhibition, yielded much larger inhibition (up to 66%) when dosed in combination. In general, IA was most accurate in predicting mixture toxicity, while CA was the most conservative. At low-effect levels important in risk assessments, CA overestimated mixture toxicity to daphnids and H. vulgare, on average, with a factor 1.4 to 3.6. Observed mixture interactions could be related to bioavailability or by competition interactions, either for binding sites of dissolved organic carbon or for biotic ligand sites. Our study suggests that the current metal-by-metal approach in risk evaluations may not be conservative enough for metal mixtures.

Element distribution and iron speciation in mature wheat grains (Triticum aestivum L.) using synchrotron X-ray fluorescence microscopy mapping and X-ray absorption near-edge structure (XANES) imaging.

Several studies have suggested that the majority of iron (Fe) and zinc (Zn) in wheat grains are associated with phytate, but a nuanced approach to unravel important tissue-level variation in element speciation within the grain is lacking. Here, we present spatially resolved Fe-speciation data obtained directly from different grain tissues using the newly developed synchrotron-based technique of X-ray absorption near-edge spectroscopy imaging, coupling this with high-definition µ-X-ray fluorescence microscopy to map the co-localization of essential elements. In the aleurone, phosphorus (P) is co-localized with Fe and Zn, and X-ray absorption near-edge structure imaging confirmed that Fe is chelated by phytate in this tissue layer. In the crease tissues, Zn is also positively related to P distribution, albeit less so than in the aleurone. Speciation analysis suggests that Fe is bound to nicotianamine rather than phytate in the nucellar projection, and that more complex Fe structures may also be present. In the embryo, high Zn concentrations are present in the root and shoot primordium, co-occurring with sulfur and presumably bound to thiol groups. Overall, Fe is mainly concentrated in the scutellum and co-localized with P. This high resolution imaging and speciation analysis reveals the complexity of the physiological processes responsible for element accumulation and bioaccessibility.

Interactions and Toxicity of Cu-Zn mixtures to Hordeum vulgare in Different Soils Can Be Rationalized with Bioavailability-Based Prediction Models.

Soil contamination with copper (Cu) is often associated with zinc (Zn), and the biological response to such mixed contamination is complex. Here, we investigated Cu and Zn mixture toxicity to Hordeum vulgare in three different soils, the premise being that the observed interactions are mainly due to effects on bioavailability. The toxic effect of Cu and Zn mixtures on seedling root elongation was more than additive (i.e., synergism) in soils with high and medium cation-exchange capacity (CEC) but less than additive (antagonism) in a low-CEC soil. This was found when we expressed the dose as the conventional total soil concentration. In contrast, antagonism was found in all soils when we expressed the dose as free-ion activities in soil solution, indicating that there is metal-ion competition for binding to the plant roots. Neither a concentration addition nor an independent action model explained mixture effects, irrespective of the dose expressions. In contrast, a multimetal BLM model and a WHAM-Ftox model successfully explained the mixture effects across all soils and showed that bioavailability factors mainly explain the interactions in soils. The WHAM-Ftox model is a promising tool for the risk assessment of mixed-metal contamination in soils.

Derivation of ecological criteria for copper in land-applied biosolids and biosolid-amended agricultural soils.

The difference in availability between soil metals added via biosolids and soluble salts was not taken into account in deriving the current land-applied biosolids standards. In the present study, a biosolids availability factor (BAF) approach was adopted to investigate the ecological thresholds for copper (Cu) in land-applied biosolids and biosolid-amended agricultural soils. First, the soil property-specific values of HC5add (the added hazardous concentration for 5% of species) for Cu2+ salt amended were collected with due attention to data for organisms and soils relevant to China. Second, a BAF representing the difference in availability between soil Cu added via biosolids and soluble salts was estimated based on long-term biosolid-amended soils, including soils from China. Third, biosolids Cu HC5input values (the input hazardous concentration for 5% of species of Cu from biosolids to soil) as a function of soil properties were derived using the BAF approach. The average potential availability of Cu in agricultural soils amended with biosolids accounted for 53% of that for the same soils spiked with same amount of soluble Cu salts and with a similar aging time. The cation exchange capacity was the main factor affecting the biosolids Cu HC5input values, while soil pH and organic carbon only explained 24.2 and 1.5% of the variation, respectively. The biosolids Cu HC5input values can be accurately predicted by regression models developed based on 2-3 soil properties with coefficients of determination (R2) of 0.889 and 0.945. Compared with model predicted biosolids Cu HC5input values, current standards (GB4284-84) are most likely to be less protective in acidic and neutral soil, but conservative in alkaline non-calcareous soil. Recommendations on ecological criteria for Cu in land-applied biosolids and biosolid-amended agriculture soils may be helpful to fill the gaps existing between science and regulations, and can be useful for Cu risk assessments in soils amended with biosolids.

Oxidation of iron causes removal of phosphorus and arsenic from streamwater in groundwater-fed lowland catchments.

The fate of iron (Fe) may affect that of phosphorus (P) and arsenic (As) in natural waters. This study addresses the removal of Fe, P, and As from streams in lowland catchments fed by reduced, Fe-rich groundwater (average: 20 mg Fe L(-1)). The concentrations of dissolved Fe (<0.45 µm) in streams gradually decrease with increasing hydraulic residence time (travel time) of the water in the catchment. The removal of Fe from streamwater is governed by chemical reactions and hydrological processes: the oxidation of ferrous iron (Fe(II)) and the subsequent formation of particulate Fe oxyhydroxides proceeds as the water flows through the catchment into increasingly larger streams. The Fe removal exhibits first-order kinetics with a mean half-life of 12 h, a value in line with predictions by a kinetic model for Fe(II) oxidation. The Fe concentrations in streams vary seasonally: they are higher in winter than in summer, due to shorter hydraulic residence time and lower temperature in winter. The removal of P and As is much faster than that of Fe. The average concentrations of P and As in streams (42 µg P L(-1) and 1.4 µg As L(-1)) are 1 order of magnitude below those in groundwater (393 µg P L(-1) and 17 µg As L(-1)). This removal is attributed to fast sequestration by oxidizing Fe when the water enters oxic environments, possibly by adsorption on Fe oxyhydroxides or by formation of ferric phosphates. The average P and As concentrations in groundwater largely exceed local environmental limits for freshwater (140 µg P L(-1) and 3 µg As L(-1)), but in streams, they are below these limits. Naturally occurring Fe in groundwater may alleviate the environmental risk associated with P and As in the receiving streams.

Biodegradation: Updating the concepts of control for microbial cleanup in contaminated aquifers.

Biodegradation is one of the most favored and sustainable means of removing organic pollutants from contaminated aquifers but the major steering factors are still surprisingly poorly understood. Growing evidence questions some of the established concepts for control of biodegradation. Here, we critically discuss classical concepts such as the thermodynamic redox zonation, or the use of steady state transport scenarios for assessing biodegradation rates. Furthermore, we discuss if the absence of specific degrader populations can explain poor biodegradation. We propose updated perspectives on the controls of biodegradation in contaminant plumes. These include the plume fringe concept, transport limitations, and transient conditions as currently underestimated processes affecting biodegradation.

The quantity and quality of dissolved organic matter as supplementary carbon source impacts the pesticide-degrading activity of a triple-species bacterial biofilm.

Effects of environmental dissolved organic matter (eDOM) that consists of various low concentration carbonic compounds on pollutant biodegradation by bacteria are poorly understood, especially when it concerns synergistic xenobiotic-degrading consortia where degradation depends on interspecies metabolic interactions. This study examines the impact of the quality and quantity of eDOM, supplied as secondary C-source, on the structure, composition and pesticide-degrading activity of a triple-species bacterial consortium in which the members synergistically degrade the phenylurea herbicide linuron, when grown as biofilms. Biofilms developing on 10 mg L⁻¹ linuron showed a steady-state linuron degradation efficiency of approximately 85 %. The three bacterial strains co-localized in the biofilms indicating syntrophic interactions. Subsequent feeding with eDOM or citrate in addition to linuron resulted into changes in linuron-degrading activity. A decrease in linuron-degrading activity was especially recorded in case of co-feeding with citrate and eDOM of high quality and was always associated with accumulation of the primary metabolite 3,4-dichloroaniline. Improvement of linuron degradation was especially observed with more recalcitrant eDOM. Addition of eDOM/citrate formulations altered biofilm architecture and species composition but without loss of any of the strains and of co-localization. Compositional shifts correlated with linuron degradation efficiencies. When the feed was restored to only linuron, the linuron-degrading activity rapidly changed to the level before the mixed-substrate feed. Meanwhile only minor changes in biofilm composition and structure were recorded, indicating that observed eDOM/citrate effects had been primarily due to repression/stimulation of linuron catabolic activity rather than to biofilm characteristics.

Cadmium concentrations in pore waters can largely increase during soil incubation: Artefacts with consequences for Cd limits in fertilisers.

A sound evaluation of the cadmium (Cd) mass balance in agricultural soils needs accurate data of Cd leaching. Reported Cd concentrations from in situ studies are often one order of magnitude lower than predicted by empirical models, which were calibrated to pore water data from stored soils. It is hypothesized that this discrepancy is related to the preferential flow of water (non-equilibrium) and/or artefacts caused by drying and rewetting soils prior to pore water analysis. These hypotheses were tested on multiple soils (n = 27) with contrasting properties. Pore waters were collected by soil centrifugation from field fresh soil samples and also after incubating the same soils (28 days, 20 °C), following two drying-rewetting cycles, the idea being that chemical equilibrium in the soil is reached after incubation. Incubation increased pore water Cd by a factor 4, on average, and up to a factor 16. That increase was statistically related to the decrease of pore water pH and the increase of nitrate, both mainly related to incubation-induced nitrification. After correcting for both factors, the Cd rise was also highest at higher pore water Ca. This suggests that higher Ca in soil enlarges Cd concentration gradients among pore classes in field fresh soils because high Ca promotes soil aggregation and separation of mobile from immobile water. Several empirical models were used to predict pore water Cd. Predictions exceeded observations up to a factor 30 for the fresh pore waters but matched well with those of incubated soils; again, deviations from the 1:1 line in field fresh soils were largest in high Ca (>0.8 mM) soils, suggesting that local equilibrium conditions in field fresh soils are not found at higher Ca. Our results demonstrate that empirical models need recalibration with field fresh pore water data to make accurate soil Cd mass balances in risk assessments.