Modelling the fate of chromated copper arsenate in a sandy soil

A pulse of chromated copper arsenate (CCA, a timber preservative) was applied in irrigation water to an undisturbed field soil in a laboratory column. Concentrations of various elements in the leachate from the column were measured during the experiment. Also, the remnants within the soil were measured at the end of the experiment. The geochemical modelling package, PHREEQC-2, was used to simulate the experimental data. Processes included in the CCA transport modelling were advection, dispersion, non-specific adsorption (cation exchange) and specific adsorption by clay minerals and organic matter, as well as other possible chemical reactions such as precipitation/dissolution. The modelling effort highlighted the possible complexities in CCA transport and reaction experiments. For example, the uneven dosing of CCA as well as incomplete knowledge of the soil properties resulted in simulations that gave only partial, although reasonable, agreement with the experimental data. Both the experimental data and simulations show that As and Cu are strongly adsorbed and therefore, will mostly remain at the top of the soil profile, with a small proportion appearing in leachate. On the other hand, Cr is more mobile and thus it is present in the soil column leachate. Further simulations show that both the quantity of CCA added to the soil and the pH of the irrigation water will influence CCA transport. Simulations suggest that application of larger doses of CCA to the soil will result in higher leachate concentrations, especially for Cu and As. Irrigation water with a lower pH will dramatically increase leaching of Cu. These results indicate that acidic rainfall or significant accidental spillage of CCA will increase the risk of groundwater pollution.

Near-surface distributions of soil water and water repellency under three effluent irrigation schemes in a blue gum (Eucalyptus globulus) plantation

Water repellent soils are difficult to irrigate and susceptible to preferential flow, which enhances the potential for accelerated leaching to groundwater of hazardous substances. Over 5 Mha of Australian soil is water repellent, while treated municipal sewage is increasingly used for irrigation. Only if a critical water content is exceeded will repellent soils become wettable. To avoid excessive loss of water from the root zone via preferential flow paths, irrigation schemes should therefore aim to keep the soil wet enough to maintain soil wettability. Our objective was to monitor the near-surface water content and water repellency in a blue gum (Eucalyptus globulus) plantation irrigated with treated sewage. The plantation's sandy soil surface was strongly water repellent when dry. For 4 months, three rows of 15 blue gum trees each received no irrigation, three other rows received 50% of the estimated potential water use minus rainfall, and three more rows received 100%. During this period, 162 soil samples were obtained in three sampling rounds, and their water content (% dry mass) and degree of water repellency determined. Both high and low irrigation effectively wetted up the soil and eliminated water repellency after 2 (high) or 4 (low) months. A single-peaked distribution of water contents was observed in the soil samples, but the water repellency distribution was dichotomous, with 44% extremely water-repellent and 36% wettable. This is consistent with a threshold water content at which a soil sample changes from water repellent to wettable, with spatial variability of this threshold creating a much wider transition zone at the field scale. We characterized this transition zone by expressing the fraction of wettable samples as a function of water content, and demonstrated a way to estimate from this the wettable portion of a field from a number of water content measurements. To keep the plantation soil wettable, the water content must be maintained at a level at which a significant downward flux is likely, with the associated enhanced leaching. At water contents with negligible downward flux, the field is water repellent, and leaching through preferential flow paths is likely. Careful management is needed to resolve these conflicting requirements.

Effect of soil texture and wheat plants on N₂O fluxes: a lysimeter study

Agricultural soils are a major source of nitrous oxide (N2O) emissions and an understanding of factors regulating such emissions across contrasting soil types is critical for improved estimation through modelling and mitigation of N2O. In this study we investigated the role of soil texture and its interaction with plants in regulating the N2O fluxes in agricultural systems. A measurement system that combined weighing lysimeters with automated chambers was used to directly compare continuously measured surface N2O fluxes, leaching losses of water and nitrogen and evapotranspiration in three contrasting soils types of the Riverine Plain, NSW, Australia. The soils comprised a deep sand, a loam and a clay loam with and without the presence of wheat plants. All soils were under the same fertilizer management and irrigation was applied according to plant water requirements. In fallow soils, texture significantly affected N2O emissions in the order clay loam > loam > sand. However, when planted, the difference in N2O emissions among the three soils types became less pronounced. Nitrous oxide emissions were 6.2 and 2.4 times higher from fallow clay loam and loam cores, respectively, compared with cores planted with wheat. This is considered to be due to plant uptake of water and nitrogen which resulted in reduced amounts of soil water and available nitrogen, and therefore less favourable soil conditions for denitrification. The effect of plants on N2O emissions was not apparent in the coarse textured sandy soil probably because of aerobic soil conditions, likely caused by low water holding capacity and rapid drainage irrespective of plant presence resulting in reduced denitrification activity. More than 90% of N2O emissions were derived from denitrification in the fine-textured clay loam-determined for a two week period using K15NO3 fertilizer. The proportion of N2O that was not derived from K15NO3 was higher in the coarse-textured sand and loam, which may have been derived from soil N through nitrification or denitrification of mineralized N. Water filled pore space was a poorer predictor of N2O emissions compared with volumetric water content because of variable bulk density among soil types. The data may better inform the calibration of greenhouse gas prediction models as soil texture is one of the primary factors that explain spatial variation in N2O emissions by regulating soil oxygen. Defining the significance of N2O emissions between planted and fallow soils may enable improved yield scaled N2O emission assessment, water and nitrogen scheduling in the pre-watering phase during early crop establishment and within rotations of irrigated arable cropping systems.

Spatial and temporal distribution of solute leaching in heterogeneous soils: analysis and application to multisampler lysimeter data

Accurate assessment of the fate of salts, nutrients, and pollutants in natural, heterogeneous soils requires a proper quantification of both spatial and temporal solute spreading during solute movement. The number of experiments with multisampler devices that measure solute leaching as a function of space and time is increasing. The breakthrough curve (BTC) can characterize the temporal aspect of solute leaching, and recently the spatial solute distribution curve (SSDC) was introduced to describe the spatial solute distribution. We combined and extended both concepts to develop a tool for the comprehensive analysis of the full spatio-temporal behavior of solute leaching. The sampling locations are ranked in order of descending amount of total leaching (defined as the cumulative leaching from an individual compartment at the end of the experiment), thus collapsing both spatial axes of the sampling plane into one. The leaching process can then be described by a curved surface that is a function of the single spatial coordinate and time. This leaching surface is scaled to integrate to unity, and termed S can efficiently represent data from multisampler solute transport experiments or simulation results from multidimensional solute transport models. The mathematical relationships between the scaled leaching surface S, the BTC, and the SSDC are established. Any desired characteristic of the leaching process can be derived from S. The analysis was applied to a chloride leaching experiment on a lysimeter with 300 drainage compartments of 25 cm2 each. The sandy soil monolith in the lysimeter exhibited fingered flow in the water-repellent top layer. The observed S demonstrated the absence of a sharp separation between fingers and dry areas, owing to diverging flow in the wettable soil below the fingers. Times-to-peak, maximum solute fluxes, and total leaching varied more in high-leaching than in low-leaching compartments. This suggests a stochastic–convective transport process in the high-flow streamtubes, while convection–dispersion is predominant in the low-flow areas. S can be viewed as a bivariate probability density function. Its marginal distributions are the BTC of all sampling locations combined, and the SSDC of cumulative solute leaching at the end of the experiment. The observed S cannot be represented by assuming complete independence between its marginal distributions, indicating that S contains information about the leaching process that cannot be derived from the combination of the BTC and the SSDC.

Extraction of compounds associated with water repellency in sandy soils of different origin

After an initial evaluation of several solvents, the efficiency of Soxhlet extractions with isopropanol/ammonia (s.g. 0.88) (70 : 30 v : v; 24 h) in extracting compounds associated with water repellency in sandy soils was examined using a range of repellent and wettable control soils (n = 15 and 4) from Australia, Greece, Portugal, The Netherlands, and the UK. Extraction efficiency and the role of the extracts in causing soil water repellency was examined by determining extract mass, sample organic carbon content and water repellency (after drying at 20°C and 105°C) pre- and post-extraction, and amounts of aliphatic C–H removed using DRIFT, and by assessing the ability of extracts to cause repellency in acid-washed sand (AWS).

Key findings are: (i) none of organic carbon content, amount of aliphatic C–H, or amount of material extracted give any significant correlation with repellency for this diverse range of soils; (ii) sample drying at 105°C is not necessarily useful before extraction, but may provide additional information on extraction effectiveness when used after extraction; (iii) the extraction removed repellency completely from 13 of the 15 repellent samples; (iv) extracts from all repellent and wettable control soils were capable of inducing repellency in AWS. The findings suggest that compounds responsible for repellency represent only a fraction of the extract composition and that their presence does not necessarily always cause repellency.

Investigation of compounds causing water repellency in the rhizosphere of sandy soils from a wide range of locations.

Although soils are generally considered to wet readily, some are actually water repellent at the surface and in the rhizosphere. This phenomenon occurs at low to moderate moisture contents and has been reported from soils under a range of vegetation types and from many regions around the globe. Water repellency in soils can have serious environmental implications including reduced seed germination and plant growth as well as irrigation efficiency, accelerated soil erosion, and enhanced leaching of agrochemicals through preferential flow. it has been proposed that water repellency is caused by the accumulation of hydrophobic organic compounds released as root exudates, microbial byproducts or from decomposing organic matter, which are deposited on mineral or aggregate surfaces, or are present as interstitial matter, Few studies to date have attempted to isolate and characterize these compounds and their structure is therefore only poorly understood, These studies have generally focussed on only a single soil or a small range of samples, have not included non-repellent soils as a control and have not always been able to demonstrate that the substances isolated are indeed responsible for repellency formation.

This study reports on the first part (extraction procedures) of a research programme addressing these gaps in current knowledge by investigating a wide range of severely repellent and wettable ‘control’ samples from different countries, and by including assessments of extraction efficiency and ability of extracts to cause repellency. Analytical methods include DRIFT (Diffuse Reflectance Infrared Fourier Transform Spectroscopy) of soils and IR (Infrared) analysis of extracts.

Key findings are that (i) soil sample heating after extraction is valuable in assessing the effectiveness of the extraction procedure, (ii) Soxhlet extraction using isopropanol/ ammonia (70/30 v/v) was the most effective method in extracting hydrophobic compounds, while leaving the ability of extracted compounds to induce water repellency virtually unaffected, (iii) wettable control soils also contain hydrophobic substances capable of inducing water repellency, (iv) the amount of organic compounds extracted was poorly related to sample repellency, indicating that compounds responsible for repellency may only represent a small fraction of the extract, (v) differences in extraction efficiency between different samples indicate that the compounds responsible may differ generically and/or in terms of their bonding to minerals, and (vi) the combination of repellency assessments with DRIFT on soils and JR on extracts used with internal standards has considerable potential to allow quantification of CH bearing organic matter in the soil, the efficiency of extraction processes for its removal, and its significance in causing water repellency in soils.