Sampling silica and ferrihydrite colloids with fiberglass wicks under unsaturated conditions

The suitability of passive capillary samplers (PCAPS) for collection of representative colloid samples under partially saturated conditions was evaluated by investigating the transport of negatively and positively charged colloids in fiberglass wicks. A synthetic pore water solution was used to suspend silica microspheres (330 nm in diameter) and ferrihydrite (172 nm in diameter) for transport experiments on fiberglass wicks. Breakthrough curves were collected for three unsaturated flow rates with silica microspheres and one unsaturated flow rate with ferrihydrite colloids. A moisture characteristic curve, relating tensiometer measurements of matric potential to moisture content, was developed for the fiberglass wick. Results indicate that retention of the silica and the ferrihydrite on the wick occurred; that is, the wicks did not facilitate quantitative sampling of the colloids. For silica microspheres, 90% of the colloids were transmitted through the wicks. For ferrihydrite, 80 to 90% of the colloids were transmitted. The mechanisms responsible for the retention of the colloids on the fiberglass wicks appeared to be physicochemical attachment and not thin-film, triple-phase entrapment, or mechanical straining. Visualization of pathways by iron staining indicates that flow is preferential at the center of twisted bundles of filaments. Although axial preferential flow in PCAPS may enhance their hydraulic suitability for sampling mobile colloids, we conclude that without specific preparation to reduce attachment or retention, fiberglass wicks should only be used for qualitative sampling of pore water colloids.     

Biosolid colloid-mediated transport of copper, zinc, and lead in waste-amended soils

Increasing land applications of biosolid wastes as soil amendments have raised concerns about potential toxic effects of associated metals on the environment. This study investigated the ability of biosolid colloids to transport metals associated with organic waste amendments through subsurface soil environments with leaching experiments involving undisturbed soil monoliths. Biosolid colloids were fractionated from a lime-stabilized, an aerobically digested, and a poultry manure organic waste and applied onto the monoliths at a rate of 0.7 cm/h. Eluents were monitored for Cu, Zn, Pb, and colloid concentrations over 16 to 24 pore volumes of leaching. Mass-balance calculations indicated significantly higher (up to 77 times) metal elutions in association with the biosolid colloids in both total and soluble fractions over the control treatments. Eluted metal loads varied with metal, colloid, and soil type, following the sequences Zn = Cu > Pb, and ADB > PMB > LSB colloids. Colloid and metal elution was enhanced by decreasing pH and colloid size, and increasing soil macroporosity and organic matter content. Breakthrough curves were mostly irregular, showing several maxima and minima as a result of preferential macropore flow and multiple clogging and flushing cycles. Soil- and colloid-metal sorption affinities were not reliable predictors of metal attenuation/elution loads, underscoring the dynamic nature of transport processes. The findings demonstrate the important role of biosolid colloids as contaminant carriers and the significant risk they pose, if unaccounted, for soil and ground water contamination in areas receiving heavy applications of biosolid waste amendments.     

Distance and flow effects on microsphere transport in a large gravel column

Consumption of microbially contaminated ground water can cause adverse health effects and the processes involved in pathogen transport in aquifers need to be understood. The influences of distance, flow velocity, and colloid size on colloid transport were examined in homogenous pea-gravel media using an 8-m column and three sizes (1, 5, and 10 microm) of microspheres. Experiments were conducted at three flow rates by simultaneously injecting microspheres with a conservative tracer, bromide. Observed concentrations were simulated with CXTFIT and analyzed with filtration theory. The results demonstrate that colloid concentration is strongly log-linearly related to transport distance (as suggested by filtration theory) in coarse gravels, similar to our previous field studies. In contrast, the log-linear relationship is often reported to be invalid in fine porous media. The observed log-linear relationship is possibly because straining is negligible in the coarse gravels investigated. This has implications in predicting setback distances for land disposal of effluent, and suggests that setback distances in gravel aquifers can be estimated using constant spatial removal rates (f). There was an inverse relationship between transport distance and colloidal concentration, but not with temporal attachment rate (katt) and collision coefficient (alpha). Increases in flow velocity result in increasing colloidal recovery, katt and alpha but decreasing f. Increases in sphere size result in decreasing colloidal recovery with increasing katt, f, alpha, and velocity enhancement. Diffusion is the dominant collision mechanism for 1-microm spheres (81-88%), while settling dominates for 5- and 10-microm spheres (> 87%), and interception is very small for all spheres investigated.     

对水敏感性的机理与影响因素的研究

通过对咸淡水界面水敏感性机理与影响因素的研究，表明在非反应性微粒的释放迁移、反应性微粒的膨胀和絮凝作用与胶体吸附架桥作用下多孔介质中微粒物质的释放、膨胀、迁移、重沉积等引起的孔喉阻塞是导致水敏感性的机理所在；临界盐浓度、临界盐浓度变化率、临界离子强度、一临界流速和pH值是水敏感性的主要影响因素；指出水敏感性的研究对防止海水入侵具有重要的理论意义和实用价值。     

DEVELOPMENT OF A BACTERIAL TRANSPORT MODEL FOR COARSE SOILS1

ABSTRACT: A bacterial transport model, developed to analyze bacterial translocation in coarse-grained soils, is presented. The complex governing equation is presented first, followed by analyses of each of the major processes influencing bacterial transport. These analyses suggest simplification of the governing equation is feasible when input data on specific processes are limited or unavailable. Model parameters, including bacterial die-off, bacterial distribution, input bacterial concentration, and saturated hydraulic conductivity, were randomly generated using a procedure known to produce either a normal or log-normal distribution of random numbers. Monte Carlo simulations were completed, and the resulting output was used to generate cumulative frequency distributions showing the probability of bacterial transport beyond various soil depths. Results from these simulations indicate that bacteria have a high probability of traveling through coarse-grained soils when low clay content and soil water temperatures limit bacterial retention and die-off.     

Adsorption and transport of arsenic(V) in experimental subsurface systems

The adsorption and transport of As(V) in a heterogeneous, iron oxide-containing soil was investigated in batch and column laboratory experiments. The As(V) adsorbed rapidly to the soil over the first 48 h, but continued to adsorb slowly over the next several weeks, clearly indicating the potential for rate-limited transport. The equilibrium As(V) adsorption isotherm was markedly nonlinear, further indicating the potential for nonideal transport. A model developed for the adsorption of As(V) to hydrous ferric oxide (HFO) was able to predict the pH-dependent adsorption of As(V) to the soil in batch experiments within 0.116 to 0.726 root mean square error (RMSE). Arsenic(V) was significantly retarded in column transport experiments. The column transport experiments were modeled using the one-dimensional advection-dispersion equation, considering both linear and nonlinear adsorption equilibrium. Although the nonlinear local equilibrium model (NLLE, RMSE = 0.273) predicted the data better than the linear local equilibrium model (LLE, RMSE = 0.317), As(V) breakthrough occurred more rapidly than predicted by either model due to adsorption nonequilibrium. However, due to the presence of an irreversible or slowly desorbing fraction, the peak aqueous As(V) concentration (0.624 mg L(-1)) and the total amount of As(V) recovered (44%) was lower than predicted based on the two equilibrium models (NLLE and LLE). For the conditions used in this study [1 mg L(-1) As(V), pH 4.5 and 9,0-0.25 mM PO4, 0.53-1.6 cm min(-1) pore water velocity], the effect on As(V) mobility and recovery increased in the order pH < pore water velocity < PO4.     

Modeling manure-borne bromide and fecal coliform transport with runoff and infiltration at a hillslope

Hillslope vegetated buffers are recommended to prevent water pollution from agricultural runoff. However, models to predict the efficacy of different grass buffer designs are lacking. The objective of this work was to develop and test a mechanistic model of coupled surface and subsurface flow and transport of bacteria and a conservative tracer on hillslopes. The testing should indicate what level of complexity and observation density might be needed to capture essential processes in the model. We combined the three-dimensional FEMWATER model of saturated-unsaturated subsurface flow with the Saint-Venant model for runoff. The model was tested with data on rainfall-induced fecal coliforms (FC) and bromide (Br) transport from manure applied at vegetated and bare 6-m long plots. The calibration of water retention parameters was unnecessary, and the same manure release parameters could be used both for simulations of Br and FC. Surface straining rates were similar for Br and bacteria. Simulations of Br and FC concentrations were least successful for the funnels closest to the source. This could be related to the finger-like flow of the manure from the strip along the bare slopes, to the transport of Br and FC with manure colloids that became strained at the grass slope, and to the presence of micro-ponds at the grassed slope. The two-dimensional model abstraction of the actual 3D transport worked well for flux-averaged concentrations. The model developed in this work is suitable to simulate surface and subsurface transport of agricultural contaminants on hillslopes and to evaluate efficiency of grass strip buffers, especially when lateral subsurface flow is important.     

Hydrophobicity of soil colloids and heavy metal mobilization: effects of drying

Drying of soil may increase the hydrophobicity of soil and affect the mobilization of colloids after re-wetting. Results of previous research suggest that colloid hydrophobicity is an important parameter in controlling the retention of colloids and colloid-associated substances in soils. We tested the hypothesis that air-drying of soil samples increases the hydrophobicity of water-dispersible colloids and whether air-drying affects the mobilization of colloid-associated heavy metals. We performed batch experiments with field-moist and air-dried (25 degrees C) soils from a former sewage farm (sandy loam), a municipal park (loamy sand), and a shooting range site (loamy sand with 25% C(org)). The filtered suspensions (<1.2 microm) were analyzed for concentrations of dissolved and colloidal organic C and heavy metals (Cu, Cd, Pb, Zn), average colloid size, zeta potential, and turbidity. The hydrophobicity of colloids was determined by their partitioning between a hydrophobic solid and a hydrophilic aqueous phase. Drying increased hydrophobicity of the solid phase but did not affect the hydrophobicity of the dispersed colloids. Drying decreased the amount of mobilized mineral and (organo-)mineral colloids in the sewage farm soils but increased the mobilization of organic colloids in the C-rich shooting range soil. Dried samples released less colloid-bound Cd and Zn than field-moist samples. Drying-induced mobilization of dissolved organic C caused a redistribution of Cu from the colloidal to the dissolved phase. We conclude that drying-induced colloid mobilization is not caused by a change in the physicochemical properties of the colloids. Therefore, it is likely that the mobilization of colloids in the field is caused by increasing shear forces or the disintegration of aggregates.     

A VERIFICATION OF THE QUAL-1 WATER QUALITY MODEL FOR THE LOWER MISSISSIPPI RIVER1

ABSTRACT: This paper describes the verification of the QUAL-1 mass transport model for the lower Mississippi River between St. Francisville and Point a la Hache using dye studies conducted by the U. S. Geological Survey. QUAL-1 is a one-dimensional steady-state model for rivers and is capable of predicting longitudinal profiles of soluble materials entering rivers from point sources. Both conservative and nonconservative parameters of water quality can be considered. The major problems surmounted were the determination of a diffusion coefficient and the use of transient data to verify a steady state model.     

Discussion of the paper "Cost effective policies for alternative distributions of stochastic water pollution" by Gren, Destouni and Tempone

This discussion addresses some aspects of a recent paper appearing in this journal which investigates cost effective coastal water management based on different assumptions of the probability distributions (normal and log-normal) of pollutant transport. We also suggest an alternative approach to overcome the technical problems of using the theoretical correct distribution for characterising environmental data (log-normal) within a probabilistic programming framework.     

Discussion of the paper “Cost effective policies for alternative distributions of stochastic water pollution” by Gren, Destouni and Tempone

This discussion addresses some aspects of a recent paper appearing in this journal which investigates cost effective coastal water management based on different assumptions of the probability distributions (normal and log-normal) of pollutant transport. We also suggest an alternative approach to overcome the technical problems of using the theoretical correct distribution for characterising environmental data (log-normal) within a probabilistic programming framework.     

Transport and retention of fullerene nanoparticles in natural soils

Commercial production and use of fullerene (C60) nanomaterials will inevitably lead to their release into the environment, where knowledge of C60 fate and transport is limited. In this study, a series of one-dimensional column experiments was conducted to assess the transport and retention of nanoscale fullerene aggregates (nC60) in water-saturated soils. Under the experimental conditions, complete retention of nC60 was observed in columns (2.5 cm inside diameter x 11 cm length) packed with Appling or Webster soil, which contain 0.75 and 3.33% organic carbon by weight, respectively. When the volume of aqueous nC60 suspension (approximately 4.5 mg L(-1)) applied to Appling soil was increased from 5 to 65 pore volumes, the travel distance increased from 3 to 8 cm, and the retention capacity approached a limiting value of 130 microg g(-1), although nC60 was not detected in the column effluent. The addition of 20 mg C L(-1) Suwannee River humic acid to the influent suspension increased the nC60 transport in Appling soil but did not resul in breakthrough. Attempts to simulate the experimental data using clean-bed filtration theory were not satisfactory, yielding retention profiles that failed to match observed data. Subsequent incorporation of a limiting retention capacity expression into the mathematical model resulted in accurate predictions of the measured nC60 retention profiles and transport behavior. The sizable retention capacities observed in this study suggest that transport of nC60 is limited in relatively fine-textured soils containing appreciable amounts of clay minerals and organic matter, with substantial accumulation of nC60 aggregates near the point of release.     

Do lab-derived distribution coefficient values of pesticides match distribution coefficient values determined from column and field-scale experiments? A critical analysis of relevant literature

In this study, we analyzed sorption parameters for pesticides that were derived from batch and column or batch and field experiments. The batch experiments analyzed in this study were run with the same pesticide and soil as in the column and field experiments. We analyzed the relationship between the pore water velocity of the column and field experiments, solute residence times, and sorption parameters, such as the organic carbon normalized distribution coefficient ( ) and the mass exchange coefficient in kinetic models, as well as the predictability of sorption parameters from basic soil properties. The batch/column analysis included 38 studies with a total of 139 observations. The batch/field analysis included five studies, resulting in a dataset of 24 observations. For the batch/column data, power law relationships between pore water velocity, residence time, and sorption constants were derived. The unexplained variability in these equations was reduced, taking into account the saturation status and the packing status (disturbed-undisturbed) of the soil sample. A new regression equation was derived that allows estimating the values derived from column experiments using organic matter and bulk density with an value of 0.56. Regression analysis of the batch/column data showed that the relationship between batch- and column-derived values depends on the saturation status and packing of the soil column. Analysis of the batch/field data showed that as the batch-derived value becomes larger, field-derived values tend to be lower than the corresponding batch-derived values, and vice versa. The present dataset also showed that the variability in the ratio of batch- to column-derived value increases with increasing pore water velocity, with a maximum value approaching 3.5.     

Assessment of the use of industrial by-products to remediate a copper- and arsenic-contaminated soil

Two water treatment sludges (WTS-A, WTS-B), two red muds (RM), and red gypsum (RG), all rich in iron oxy-hydroxides, were added to a soil highly polluted with As and Cu at 2% (w/w) to reduce metal bioavailability. Because the amendments increased soil pH to approximately 6, a lime treatment to the same pH and an unamended treatment were included for comparison. All the amendments had significant positive effects on the soil microbial biomass and growth of ryegrass (Lolium multiflorum Lam. cv. Avance), but only WTS-A improved lettuce (Lactuca sativa L. cv. Tom Thumb) growth. The mineralization of added ammonium nitrogen was not significantly affected by the treatments, while a physiologically based extraction test (PBET) showed that bioaccessibility of As was low (< 5%) and decreased only in the WTS-A treatment. Concentrations of As in soil pore water and extractable As only decreased in the WTS and RG treatments. In contrast, Cu concentrations in soil pore water and extractable Cu decreased in all treatments, by more than 84% in the WTS, RM, and RG treatments. Non-isotopically exchangeable As and Cu were present in colloids in the soil pore water. Untreated soil had < 4% isotopically exchangeable As and this decreased by approximately 50%, with WTS, RM, and RG. The labile Cu pool represented a large proportion (34%) of the total Cu pool, and the isotopically exchangeable and soluble Cu were strongly correlated with soil pH. Acidification of the treated soils showed that the labile As and Cu both increased in the treated soils compared with untreated soils. The significance of the treatment effects on soil fertility and potential off-site transport of As and Cu to ground water are discussed.     

Disturbance of water-extractable phosphorus determination by colloidal particles in a heavy clay soil from the Netherlands

Water extraction methods are widely used to extract phosphorus (P) from soils for both agronomic and environmental purposes. Both the presence of soil colloids in soil water filtrates, and the contribution of colloidal P to the molybdate-reactive phosphorus (MRP) concentration measured in these filtrates, are well documented. However, relatively little attention has been given to the direct disturbance by colloids of MRP measurement. The objective of this paper is to show this influence found for water extracts with a soil to solution ratio of 1:60 (v/v) (P(w)), obtained from a heavy clay soil in the Netherlands. Colloidal particles, which passed a 0.45-mum filter, caused a large overestimation of MRP. The low ionic strength of the P(w) filtrates (on average 0.64 mmol(c) L(-1)) probably caused soil dispersion and increased detachment of colloids from soil during extraction. After NaCl addition, followed by 0.45-mum filtration, MRP was on average 93% lower. This can be ascribed to flocculation of colloids and removal by filtration. A low ionic strength can thus lead to the direct disturbance by colloidal particles of MRP measurement in waters from soils sensitive to release of colloids.     

Uncertainty assessment of the model RICEWQ in northern Italy

Model predictions are often seriously affected by uncertainties arising from many sources. Ignoring the uncertainty associated with model predictions may result in misleading interpretations when the model is used by a decision-maker for risk assessment. In this paper, an analysis of uncertainty was performed to estimate the uncertainty of model predictions and to screen out crucial variables using a Monte Carlo stochastic approach and a number of statistical methods, including ANOVA and stepwise multiple regression. The model studied was RICEWQ (Version 1.6.1), which was used to forecast pesticide fate in paddy fields. The results demonstrated that the paddy runoff concentration predicted by RICEWQ was in agreement with field measurements and the model can be applied to simulate pesticide fate at field scale. Model uncertainty was acceptable, runoff predictions conformed to a log-normal distribution with a short right tail, and predictions were reliable at field scale due to the narrow spread of uncertainty distribution. The main contribution of input variables to model uncertainty resulted from spatial (sediment-water partition coefficient and mixing depth to allow direct partitioning to bed) and management (time and rate of application) parameters, and weather conditions. Therefore, these crucial parameters should be carefully parameterized or precisely determined in each site-specific paddy field before the application of the model, since small errors of these parameters may induce large uncertainty of model outputs.     

Modeling the Highly Dynamic Loading of Mercury Species in the Carson River and Lahontan Reservoir System,Nevada

The semiarid Carson River — Lahontan Reservoir system in Nevada, United States is highly contaminated with mercury (Hg) from historic mining with contamination dispersed throughout channel and floodplain deposits. Work builds on previous research using a fully dynamic numerical model to outline a complete conceptualization of the system that includes transport and fate of both sorbed and dissolved constituents. Flow regimes are defined to capture significant mechanisms of Hg loading that include diffusion, channel pore water advective flux, bank erosion, and overbank deposition. Advective flux of pore water is required to reduce dilution and likely represents colloidal‐mediated transport. Fluvial concentrations span several orders of magnitude with spatial and temporal trends simulated within 10‐24% error for all modeled species. Over the simulation period, 1991‐2008, simulated loads are 582 kg/yr (THg²⁺), 4.72 kg/yr (DHg²⁺), 0.54 kg/yr (TMeHg), and 0.07 kg/yr (DMeHg) with bank erosion processes the principal mechanism of loading for both total and dissolved species. Prediction error in the reservoir is within one‐order of magnitude and considered qualitative; however, simulated results indicate internal cycling within the receiving reservoir accounts for only 1% of the reservoir's water column contamination, with river channel sediment sources more influential in the upper reservoir and bank erosion processes having greater influence in the lower reservoir.     

Colloidal and dissolved phosphorus in sandy soils as affected by phosphorus saturation

Fertilization exceeding crop requirements causes an accumulation of phosphorus (P) in soils, which might increase concentrations of dissolved and colloidal P in drainage. We sampled soils classified as Typic Haplorthods from four fertilization experiments to test (i) whether increasing degrees of phosphorus saturation (DPS) increase concentrations of dissolved and colloidal P, and (ii) if critical DPS levels can be defined for P release from these soils. Oxalate-extractable concentrations of P, iron (Fe), and aluminum (Al) were quantified to characterize DPS. Turbidity, zeta potential, dissolved P, and colloidal P, Fe, Al, and carbon (C) concentrations were determined in water and KCl extracts. While concentrations of dissolved P decreased with increasing depth, concentrations of water-extractable colloidal P remained constant. In topsoils 28 +/- 17% and in subsoils 94 +/- 8% of water-extractable P was bound to colloids. Concentrations of dissolved P increased sharply for DPS > 0.1. Colloidal P concentrations increased with increasing DPS because of an additional mobilization of colloids and due to an increase of the colloids P contents. In addition to DPS, ionic strength and Ca(2+) affected the release of colloidal P. Hence, using KCl for extraction improved the relationship between DPS and colloidal P compared with water extraction. Accumulation of P in soils increases not only concentrations of dissolved P but also the risk of colloidal P mobilization. Leaching of colloidal P is potentially important for inputs of P into water bodies because colloidal P as the dominant water-extractable P fraction in subsoils was released from soils with relatively low DPS.