Particle Leaching Rates from a Loamy Soil Are Controlled by the Mineral Fines Content and the Degree of Preferential Flow.

The mobilization and transport of colloid particles in soils can have negative agronomic and environmental effects. This work investigates the controls of particle release and transport from undisturbed soil columns sampled from an agricultural, loamy field with clay and silt contents of 0.05 to 0.14 and 0.07 to 0.16 kg kg, respectively. Forty-five soil columns (20 × 20 cm) were collected from the field and exposed to a constant irrigation of 10 mm h for 8 h. The accumulated mass of particles in the outflow from each column was highly correlated ( = 0.88) with the volumetric mass of fines (MF). The MF is defined as the sum of clay and fine silt (<20 µm) multiplied by the soil bulk density and divided by the particle density of the mineral fines. Thereby, MF represents both the particle source available for mobilization and leaching and an indicator of soil structure. The particle release process showed two linear particle release rates. Although the two particle release rates were distinctly different, both were strongly correlated with MF. The difference between the two rates was related to the degree of preferential flow characterized by the 5% arrival time of an applied tracer pulse. Soil columns with a longer 5% arrival time (less preferential flow) showed a distinct difference between the two rates, whereas soil columns with a short 5% arrival time and fast water transport showed resemblance between the two particle release rates. Thus, the combined effects of particle source, type, and pathways (via soil structure and compaction) need consideration to understand and predict particle transport dynamics through intact topsoil.

Humic acids modify the pulse size distributions in the characterization of plastic microparticles by Tunable Resistive Pulse Sensing.

Tunable Resistive Pulse Sensing, TRPS, is an emerging technique used in quantification and measuring the size (particle-by-particle) of viruses, exosomes and engineered colloidal spheres in biological fluids. We study the features of TRPS to enhance size characterization and quantification of submicron-sized microplastics, also called plastic microparticles, MP, in freshwater environments. We report alterations on the detection of the resistive pulses in the TRPS caused by humic acids, HA, during the size measurement of polystyrene microspheres used as MP surrogate. We discuss the alteration of the electric field in the measuring channel of the TRPS apparatus induced by the passage of HA. TRPS is a fast and precise technique for counting and size determination of MP but needs the evaluation of the influence of the organic matter on the current blockades. We show that statistical clustering models of the magnitude distribution of the resistive pulses can help to detect and quantify changes in the pulse size distributions induced by flocculation of humic acids. Conclusions of this study indicate that TRPS can be a valuable tool to improve the knowledge of the MP fate in surface waters, in the vadose zone and groundwater.

Effects of Biochar on Dispersibility of Colloids in Agricultural Soils.

The mobility of water-dispersible colloids (WDCs) in soil may be influenced by soil management practices such as organic soil amendments. Biochar has recently been promoted as a useful soil amendment, and extensive research has been devoted to investigating its effects on soil macroscopic properties and functions. However, there is limited understanding of the effects of biochar application on micro-scale particle dynamics. We conducted a field study to investigate the effects of the application of birch ( spp.) wood biochar on colloid dispersibility with respect to application rate, history, and physicochemical soil properties. Undisturbed soil cores (100 cm) were collected from the topsoil of two agricultural sites in Denmark with soils of sandy loam texture. The two sites received biochar at different application rates (0-100 Mg ha) and were sampled 7 to 19 mo later. The WDC content was determined using an end-over-end shaking method on 100-cm intact soil cores, and the colloid solution was analyzed for electrical conductivity, pH, and zeta potential. The WDC content increased with biochar application rate because of biochar-induced changes in soil chemistry and was strongly and positively correlated with the concentration of exchangeable monovalent cations in the soils. Biochar application increased pH and decreased electrical conductivity and zeta potential in the colloid suspension more in the short term (7 mo) than in the long term (19 mo). Thus, there is potential for biochar to induce short-term changes in soil solution chemistry in agricultural soils, which may influence the mobility of soil colloids.

Water and solute transport in agricultural soils predicted by volumetric clay and silt contents.

Solute transport through the soil matrix is non-uniform and greatly affected by soil texture, soil structure, and macropore networks. Attempts have been made in previous studies to use infiltration experiments to identify the degree of preferential flow, but these attempts have often been based on small datasets or data collected from literature with differing initial and boundary conditions. This study examined the relationship between tracer breakthrough characteristics, soil hydraulic properties, and basic soil properties. From six agricultural fields in Denmark, 193 intact surface soil columns 20cm in height and 20cm in diameter were collected. The soils exhibited a wide range in texture, with clay and organic carbon (OC) contents ranging from 0.03 to 0.41 and 0.01 to 0.08kgkg(-1), respectively. All experiments were carried out under the same initial and boundary conditions using tritium as a conservative tracer. The breakthrough characteristics ranged from being near normally distributed to gradually skewed to the right along with an increase in the content of the mineral fines (particles ≤50µm). The results showed that the mineral fines content was strongly correlated to functional soil structure and the derived tracer breakthrough curves (BTCs), whereas the OC content appeared less important for the shape of the BTC. Organic carbon was believed to support the stability of the soil structure rather than the actual formation of macropores causing preferential flow. The arrival times of 5% and up to 50% of the tracer mass were found to be strongly correlated with volumetric fines content. Predicted tracer concentration breakthrough points as a function of time up to 50% of applied tracer mass could be well fitted to an analytical solution to the classical advection-dispersion equation. Both cumulative tracer mass and concentration as a function of time were well predicted from the simple inputs of bulk density, clay and silt contents, and applied tracer mass. The new concept seems promising as a platform towards more accurate proxy functions for dissolved contaminant transport in intact soil.

Predicting release and transport of pesticides from a granular formulation during unsaturated diffusion in porous media.

The release and transport of active ingredients (AIs) from controlled-release formulations (CRFs) have potential to reduce groundwater pesticide pollution. These formulations have a major effect on the release rate and subsequent transport to groundwater. Therefore the influence of CRFs should be included in modeling non-point source pollution by pesticides. We propose a simplified approach that uses a phase transition equation coupled to the diffusion equation that describes the release rate of AIs from commercial CRFs in porous media; the parameters are as follows: a release coefficient, the solubility of the AI, and diffusion transport with decay. The model gives acceptable predictions of the pesticides release from commercial CRFs in diffusion cells filled with quartz sand. This approach can be used to study the dynamics of the CRF-porous media interaction. It also could be implemented in fate of agricultural chemical models to include the effect of CRFs.

Effects of biochar on air and water permeability and colloid and phosphorus leaching in soils from a natural calcium carbonate gradient.

Application of biochar to agricultural fields to improve soil quality has increased in popularity in recent years, but limited attention is generally paid to existing field conditions before biochar application. This study examined the short-term physicochemical effects of biochar amendment in an agricultural field in Denmark with a calcium carbonate (CaCO) gradient. The field comprised four reference plots and four plots to which biochar (birch wood pyrolyzed at 500°C) was applied at a rate of 20 t ha. Five undisturbed soil columns (10 cm diam., 8 cm height) were sampled from each plot 7 mo after biochar application, and a series of leaching experiments was conducted. The leachate was analyzed for tritium (used as a tracer), colloids, and phosphorus concentration. The results revealed that the presence of CaCO has resulted in marked changes in soil structure (bulk density) and soil chemical properties (e.g., pH and ionic strength), which significantly affected air and water transport and colloid and phosphorous leaching. In denser soils (bulk density, 1.57-1.69 g cm) preferential flow dominated the transport and caused an enhanced movement of air and water, whereas in less dense soils (bulk density, 1.38-1.52 g cm) matrix flow predominated the transport. Compared with reference soils, biochar-amended soils showed slightly lower air permeability and a shorter travel time for 5% of the applied tracer (tritium) to leach through the soil columns. Colloid and phosphorus leaching was observed to be time dependent in soils with low CaCO. Biochar-amended soils showed higher colloid and P release than reference soils. Field-scale variations in total colloid and P leaching reflected clear effects of changes in pH and ionic strength due to the presence of CaCO. There was a linear relationship between colloid and P concentrations in the leachate, suggesting that colloid-facilitated P leaching was the dominant P transport mechanism.

Modeling the influence of raindrop size on the wash-off losses of copper-based fungicides sprayed on potato (Solanum tuberosum L.) leaves.

Modeling the pesticide wash-off by raindrops is important for predicting pesticide losses and the subsequent transport of pesticides to soil and in soil run-off. Three foliar-applied copper-based fungicide formulations, specifically the Bordeaux mixture (BM), copper oxychloride (CO), and a mixture of copper oxychloride and propylene glycol (CO-PG), were tested on potato (Solanum tuberosum L.) leaves using a laboratory raindrop simulator. The losses in the wash-off were quantified as both copper in-solution loss and copper as particles detached by the raindrops. The efficiency of the raindrop impact on the wash-off was modeled using a stochastic model based on the pesticide release by raindrops. In addition, the influence of the raindrop size, drop falling height, and fungicide dose was analyzed using a full factorial experimental design. The average losses per dose after 14 mm of dripped water for a crop with a leaf area index equal to 1 were 0.08 kg Cu ha(-1) (BM), 0.3 kg Cu ha(-1) (CO) and 0.47 kg Cu ha(-1) (CO-PG). The stochastic model was able to simulate the time course of the wash-off losses and to estimate the losses of both Cu in solution and as particles by the raindrop impacts. For the Cu-oxychloride fungicides, the majority of the Cu was lost as particles that detached from the potato leaves. The percentage of Cu lost increased with the decreasing raindrop size in the three fungicides for the same amount of dripped water. This result suggested that the impact energy is not a limiting factor in the particle detachment rate of high doses. The dosage of the fungicide was the most influential factor in the losses of Cu for the three formulations studied. The results allowed us to quantify the factors that should be considered when estimating the losses by the wash-off of copper-based fungicides and the inputs of copper to the soil by raindrop wash-off.

Effects of past copper contamination and soil structure on copper leaching from soil.

Copper contamination affects biological, chemical, and physical soil properties and associated ecological functions. Changes in soil pore organization as a result of Cu contamination can dramatically affect flow and contaminant transport in polluted soils. This study assessed the influence of soil structure on the movement of water and Cu in a long-term polluted soil. Undisturbed soil cores collected along a Cu gradient (from about 20 to about 3800 mg Cu kg soil) were scanned using X-ray computed tomography (CT). Leaching experiments were performed to analyze tracer transport, colloid leaching, and dissolved organic carbon (DOC) and Cu losses. The 5% arrival time () and apparent dispersivity (λ) for tracer breakthrough were calculated by fitting the experimental data to a nonparametric, double-lognormal probability density function. Soil bulk density, which did not follow the Cu gradient, was the main driver of preferential flow, while macroporosity determined by X-ray CT (for pores >180 µm) proved the best predictor of solute transport. Higher preferential flow due to the presence of well-aligned pores and small cracks controlled water movement in compacted soil. Transport of Cu was rapid during the first flush (≈1 pore volume) in association with the movement of colloid particles, followed by slower transport in association with the movement of DOC in the soil solution. The relative amount of Cu released was strongly correlated with macroporosity as determined by X-ray CT, indicating the promising potential of this visualization technique for predicting contaminant transport through soil.

Influence of pore water velocity on the release of carbofuran and fenamiphos from commercial granulates embedded in a porous matrix.

Pore water flow velocity can influence the processes involved in the contaminant transport between relative stagnant zones of porous media and their adjacent mobile zones. A particular case of special interest is the occurrence of high flow rates around the controlled release granules containing pesticides buried in soil. The release of the pesticides carbofuran and fenamiphos from commercial controlled release formulations (CRFs) was studied, comparing release tests in a finite volume of water with water flow release tests in saturated packed sand at different seepage velocities. For water release kinetics, the time taken for 50% of the pesticide to be released (T(50)) was 0.64 hours for carbofuran and 1.97 hours for fenamiphos. In general, the release rate was lower in the porous matrix than in the free water tests. The faster release rate for carbofuran was attributed to its higher water diffusivity. The seepage velocity has a strong influence on the pesticide release rate. The dominant release mechanism varies with the progress of release. The evolution of the mechanism is discussed on the basis of the successive steps that involve the moving boundary of the dissolution front of the pesticide inside the granule, the concentration gradient inside the granule and the flow boundary layer resistance to solute diffusion around the granule. The pore water velocity influences the overall release dynamics. Therefore, seepage velocity should be considered in pesticide release to evaluate the risk of pesticide leaching, especially in scenarios with fast infiltration.

Facilitated transport of Cu with hydroxyapatite nanoparticles in saturated sand: effects of solution ionic strength and composition.

Column experiments were conducted to investigate the facilitated transport of Cu in association with hydroxyapatite nanoparticles (nHAP) in water-saturated quartz sand at different solution concentrations of NaCl (0-100 mM) or CaCl(2) (0.1-1.0 mM). The experimental breakthrough curves and retention profiles of nHAP were well described using a mathematical model that accounted for two kinetic retention sites. The retention coefficients for both sites increased with the ionic strength (IS) of a particular salt. However, the amount of nHAP retention was more sensitive to increases in the concentration of divalent Ca(2+) than monovalent Na(+). The effluent concentration of Cu that was associated with nHAP decreased significantly from 2.62 to 0.17 mg L(-1) when NaCl increased from 0 to 100 mM, and from 1.58 to 0.16 mg L(-1) when CaCl(2) increased from 0.1 to 1.0 mM. These trends were due to enhanced retention of nHAP with changes in IS and ionic composition (IC) due to compression of the double layer thickness and reduction of the magnitude of the zeta potentials. Results indicate that the IS and IC had a strong influence on the co-transport behavior of contaminants with nHAP nanoparticles.

Influence of soluble copper on the electrokinetic properties and transport of copper oxychloride-based fungicide particles.

This article describes the influence of dissolved copper on the electrokinetic properties and transport of a copper oxychloride-based fungicide (COF) in porous media. The Zeta potential (ζ) of COF particles increases (viz. becomes less negative) with increasing concentration of Cu(2+) in the bulk solution. ζ decreases for COF when the electrolyte (NaNO(3)) concentration is raised from 1 to 10mM. This can be ascribed to ion correlation of Cu(2+) in the electrical double layer (EDL). COF transport tests in quartz sand columns showed the addition of Cu(2+) to the bulk solution to result in increased retention of the metal. Modelling particle deposition dynamics provided results consistent with kinetic attachment. Based on the effect of soluble Cu on colloid mobility, the transport of particulate and soluble forms of copper is coupled via the chemistry of pore water and colloid interactions. Mutual effects between cations and colloids should thus be considered when determining the environmental fate of particulate and soluble forms of copper in soil and groundwater (especially at copper-contaminated sites).

Transport behavior of humic acid-modified nano-hydroxyapatite in saturated packed column: effects of Cu, ionic strength, and ionic composition.

The surfaces of nano-hydroxyapatite (nHAP) used for contaminated soil and groundwater remediation may be modified to render nHAP highly mobile in the subsurface. Humic acid (HA) is widely used to modify and stabilize colloid suspensions. In this work, column experiments were conducted to determine the effects of contaminant (e.g., Cu) concentration, ionic strength (IS), and ion composition (IC) on the transport behavior of HA-modified nHAP in saturated packed columns. IS and nature of the cation had strong effects on the deposition of nHAP, and the effect was greater for divalent than for monovalent cations. Divalent cations have a greater capacity to screen the surface charge of nHAP, and Ca(2+) bridges the HA-modified nHAP colloidal particles, which causes greater deposition. Moreover, Cu(2+) had a greater effect on the transport behavior than Ca(2+) due to their strong exchange with Ca(2+) of nHAP and its surface complexation with nHAP. The relative travel distance L(T), of the injected HA-modified nHAP colloids, ranges from less than one to several meters at varying Cu concentrations, ISs, and ICs in saturated packed columns. The results are crucial to evaluate the efficacy of nHAP on the remediation of contaminated soil and groundwater environments.

Effect of particle size on copper oxychloride transport through saturated sand columns.

Understanding the mechanisms behind the transport of particulate contaminants in porous media is crucial with a view to evaluating their potential impact on the environment. Much of the copper used in agriculture is sprayed as colloidal copper oxychloride, and despite its potential environmentally adverse consequences, colloidal transport of particulate formulations of copper remains poorly understood. In this work, transport of copper colloids from a commercial copper oxychloride based fungicide formulation was studied by measuring its breakthrough in saturated quartz sand columns. The influence of ionic strength and flow rate on the test results suggests that retention of copper oxychloride based colloids is governed by weak forces. The particle deposition dynamics of the studied copper formulation was consistent with a two-site kinetic attachment model. The proposed colloid retention mechanisms are highly sensitive to the fungicide particle size. A comparison of our test results with reported data for other copper oxychloride wettable powder fungicide formulations revealed that transport of copper oxychloride is strongly influenced by its particle size. This is consistent with the theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO), but only if binding occurs at the secondary minimum in the potential, where attachment is less favorable with small particles. The influence of particle size is also consistent with the results of previous studies where deposition was ascribed to retention at a secondary minimum. The mobility of colloidal formulations of these copper-based fungicides in saturated porous media increases with increasing particle size.

Influence of soil characteristics on copper sorption from a copper oxychloride fungicide.

The objective of this work was to assess the sorption of copper (Cu) applied as a Cu-oxychloride metalaxyl formulation by soils characterized by anthropogenic accumulation of Cu due to agricultural activity. The methods involved batch incubation of soils with a Cu-oxychloride metalaxy-based fungicide suspended in 0.01 M CaCl(2), phase separation, and determination of the concentration of Cu (Cu) in solution. Results showed that specific soil properties influenced solubilization of the Cu from the fungicide. The amount of dissolved Cu depended on the soil pH, its potential acidity, and its cation exchange capacity. The amount of anthropogenic Cu in the soil had a minor influence on soluble Cu after the addition of the fungicide. Thus, Cu-based antifungal treatment can increase the local concentration of soluble Cu in acid soils but is not likely to affect the [Cu] in moderately acidic or neutral soils.