Heavy metal accumulation in soils at three field sites subject to effluent irrigation

Three field sites were chosen to study the environmental assimilative capacity of heavy metals in soil. These sites were the Werribee Farm and the Myome Farm in Australia and Shenyang Zhangshi Irrigation Area in China. The Werribee Farm and the Shenyang Zhangshi Irrigation Area received sewage treatment and application on land for a long time. The Myome farm is an experimental site in which investigations on land application of municipal wastewater on water repellent soils is currently being trailed. Heavy metal contamination, in particular Cr, Cu and Zn, in the Land Filtration soil of Werribee Farm was widespread. More than a century of sewage irrigation has occurred in the Werribee Farm. The temporal distribution pattern of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) in the soil at this site follow an exponential trend with time and the spatial distribution pattern of accumulation of heavy metals in different paddocks correlates with the number of years of sewage irrigation at that site in the Farm. Extensive sewage irrigation at Shenyang Zhangshi Irrigation Area resulted in significant Cd pollution in soil-plant (rice) system and poses a significant threat to the health of local people. Even after eight years since cessation of sewage irrigation, the bioavailable fractions of Cd in the soil as analyzed by sequential extraction techniques were very high thus illustrating long-term persistence. The simultaneous competitive adsorption of metals in water repellent soils (at Myome Farm in South Australia) was studied. In the competitive situation, Cr, Pb and Cu are the heavy metal cations more strongly adsorbed by the soil, whereas Cd, Ni and Zn are the least adsorbed. The increase in Freundlich adsorption capacity by clay amendment suggested that clayed soils are capable sorption of higher heavy metal loadings compared to the non-clayed water repellent soil, which is more vulnerable to heavy metal inputs. A simple model of environmental assimilative capacity is proposed. The results of comparison of the three field sites shows that the Werribee Farm has a higher environmental assimilative capacity of heavy metals in soil than the soils at Shenyang Zhangshi Irrigation Area and Myome Farm, however heavy metal contamination at Werribee Farm is still a concern. The model of environmental assimilative capacity of heavy metals in soil is an effective tool to assist management of effluent applied land irrigation systems and can be used to better design environmental engineering systems.

Nonadditivity of faradaic currents and modification of double layer capacitance in the voltammetry of mixtures of ferrocene and ferrocenium salts in ionic liquids

Electrochemical studies on the Fc + e− Fc+ (Fc = ferrocene) process have been undertaken via the oxidation of Fc and reduction of Fc+ as the hexafluorophosphate (PF6−) or tetrafluoroborate (BF4−) salts and their mixtures in three ionic liquids (ILs) (1-butyl-1-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide, 1-butyl-3-methylimidazolium tetrafluoroborate, and 1-butyl-3-methylimidazolium hexafluorophosphate). Data obtained at macro- and microdisk electrodes using conventional dc and Fourier-transformed large-amplitude ac (FT-ac) voltammetry reveal that diffusion coefficients for Fc and Fc+ differ significantly and are a function of the Fc and Fc+ concentration, in contrast to findings in molecular solvents with 0.1 M added supporting electrolyte media. Thus, the Faradaic currents associated with the oxidation of Fc (Fc0/+) and reduction of FcPF6 or FcBF4 (Fc+/0) when both Fc and Fc+ are simultaneously present in the ILs differ from values obtained when individual Fc and Fc+ solutions are used. The voltammetry for both the Fc0/+ and Fc+/0 processes exhibited near-Nernstian behavior at a glassy carbon macrodisk electrode and a platinum microdisk electrode, when each process was studied individually in the ILs. As expected, the reversible formal potentials (E°′) and diffusion coefficients (D) at 23 ± 1 °C were independent of the electrode material and concentration. However, when Fc and FcPF6 or FcBF4 were both present, alterations to the mass transport process occurred and apparent D values calculated for Fc and Fc+ were found to be about 25−39% and 32−42% larger, respectively, than those determined from individual solutions. The apparent value of the double layer capacitance determined by FT-ac voltammetry from individual and mixed Fc and Fc+ conditions at the GC electrode was also a function of concentration. Double layer capacitance values increased significantly with the concentration of Fc and FcPF6 or FcBF4 when species were studied individually or simultaneously, but had a larger magnitude under conditions where both species were present. Variation in the structure of the ILs and hence mobilities of the ionic species, when Fc and FcPF6 or FcBF4 are simultaneously present, is considered to be the origin of the nonadditivity of the Faradaic currents and variation in capacitance.

Competitive sorbtion of metals in water repellent soils: implications for irrigation recycled water

Australia is a water-stressed nation and demand on potable water supply is increasing. Consequently water conservation and reuse are increasingly becoming important. Irrigation of recycled wastewater on water repellent soils is a technology that is being trialled as a means of improving crop production and conserving potable supply. However, recycled water contains potentially harmful heavy metals. This paper reports the competitive sorption and desorption of several common heavy metals found in soils collected from a farm located in the south-east of South Australia. The soil from this location is severely water repellent, but some sites were amended with kaolinite clay (Si₄Al₄O₁₀(OH)₈) about 7 and 15 years ago. The metals studied were Cu, Pb, Cd, Cr, Ni, and Zn. Competitive sorption of the metals was distinctly observed. For all heavy metals, the quantity of metal sorbed was higher in amended soil, and there was a strong correlation between the specific sorption to total sorption ratio and the amount of clay in the soil. The sorption intensities varied with metal, Cr, Pb, and Cu having a high sorption tendencies and Zn, Cd, and Ni having comparatively low sorption tendencies. The total sorption capacity for all metals increased in clay-treated soils compared with non-treated soils. On average, clay-amended water repellent soils had a 20–40% increased capacity to adsorb total metals; however, this increase was largely caused by the increased capacities to adsorb Zn, Cd, and Ni. The effect of clay treatment largely enhanced the sorption capacity of relatively weakly adsorbing heavy metals. The implications for using recycled wastewater on the long-term sustainable agro-environmental management of these soils are discussed.

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.

Quantifying effects of soil heterogeneity on groundwater pollution at four sites in the USA

Four sites located in the north-eastern region of the United States of America have been chosen to investigate the impacts of soil heterogeneity in the transport of solutes (bromide and chloride) through the vadose zone (the zone in the soil that lies below the root zone and above the permanent saturated groundwater). A recently proposed mathematical model based on the cumulative beta distribution has been deployed to compare and contrast the regions' heterogeneity from multiple sample percolation experiments. Significant differences in patterns of solute leaching were observed even over a small spatial scale, indicating that traditional sampling methods for solute transport, for example the gravity pan or suction Iysimeters, or more recent inventions such as the multiple sample percolation systems may not be effective in estimating solute fluxes in soils when a significant degree of soil heterogeneity is present. Consequently, ignoring soil heterogeneity in solute transport studies will likely result in under- or overprediction of leached fluxes and potentially lead to serious pollution of soils and/or groundwater. The cumulative beta distribution technique is found to be a versatile and simple technique of gaining valuable information regarding soil heterogeneity effects on solute transport. It is also an excellent tool for guiding future decisions of experimental designs particularly in regard to the number of samples within one site and the number of sampling locations between sites required to obtain a representative estimate of field solute or drainage flux.

Genotoxicity assessment of soils from wastewater irrigation areas and bioremediation sites using the Vicia faba root tip micronucleus assay

Genotoxicity potential of soils taken from wastewater irrigation areas and bioremediation sites was assessed using the Vicia faba root tip micronucleus assay. Twenty five soils were tested, of which 8 were uncontaminated soils and taken as the control to examine the influence of soil properties; 6 soils were obtained from paddy rice fields with a history of long-term wastewater irrigation; 6 soils were obtained from bioremediation sites to examine effects of bioremediation; and 5 PAH-contaminated soils were used to examine methodological effects between direct soil exposure and exposure to aqueous soil extracts on micronuclei (MN) frequency () in the V. faba root tips. Results indicate that soil properties had no significant influences on MN frequencies (p > 0.05) when soil pH varied between 3.4 to 7.6 and organic carbon between 0.4% and 18.6%. The MN frequency measured in these control soils ranged from 1.6‰ to 5.8‰. MN frequencies in soils from wastewater irrigation areas showed 2- to 48-fold increase as compared with the control. Soils from bioremediation sites showed a mixed picture: MN frequencies in some soils decreased after bioremediation, possibly due to detoxification; whereas in other cases remediated soils induced higher MN frequencies, suggesting that genotoxic substances might be produced during bioremediation. Exposure to aqueous soil extracts gave a higher MN frequency than direct exposure in 3 soils. However, the opposite was observed in the other two soils, suggesting that both exposure routes should be tested in case of negative results from one route. Data obtained from this study indicate that the MN assay is a sensitive assay suitable for evaluating genotoxicity of soils.

Concepts and dimensionality in modeling unsaturated water flow and solute transport

Many environmental studies require accurate simulation of water and solute fluxes in the unsaturated zone. This paper evaluates one- and multi-dimensional approaches for soil water flow as well as different spreading mechanisms to model solute behavior at different scales. For quantification of soil water fluxes,Richards equation has become the standard. Although current numerical codes show perfect water balances, the calculated soil water fluxes in case of head boundary conditions may depend largely on the method used for spatial averaging of the hydraulic conductivity. Atmospheric boundary conditions, especially in the case of phreatic groundwater levels fluctuating above and below a soil surface, require sophisticated solutions to ensure convergence. Concepts for flow in soils with macro pores and unstable wetting fronts are still in development. One-dimensional flow models are formulated to work with lumped parameters in order to account for the soil heterogeneity and preferential flow. They can be used at temporal and spatial scales that are of interest to water managers and policymakers. Multi-dimensional flow models are hampered by data and computation requirements.Their main strength is detailed analysis of typical multi-dimensional flow problems, including soil heterogeneity and preferential flow. Three physically based solute-transport concepts have been proposed to describe solute spreading during unsaturated flow: The stochastic-convective model (SCM), the convection-dispersion equation (CDE), and the fraction aladvection-dispersion equation (FADE). A less physical concept is the continuous-time random-walk process (CTRW). Of these, the SCM and the CDE are well established, and their strengths and weaknesses are identified. The FADE and the CTRW are more recent,and only a tentative strength weakness opportunity threat (SWOT)analysis can be presented at this time. We discuss the effect of the number of dimensions in a numerical model and the spacing between model nodes on solute spreading and the values of the solute-spreading parameters. In order to meet the increasing complexity of environmental problems, two approaches of model combination are used: Model integration and model coupling. Amain drawback of model integration is the complexity of there sulting code. Model coupling requires a systematic physical domain and model communication analysis. The setup and maintenance of a hydrologic framework for model coupling requires substantial resources, but on the other hand, contributions can be made by many research groups.

Degradation of phenanthrene and pyrene in soil slurry reactors with immobilized bacteria Zoogloea sp.

The environmental fate of polycyclic aromatic hydrocarbons (PAHs) in soils is motivated by their wide distribution, high persistence, and potentially deleterious effect on human health. Polycyclic aromatic hydrocarbons constitute the largest group of environmental contaminants released in the environment. Therefore, the potential biodegradation of these compounds is of vital importance. A biocarrier suitable for the colonization by micro-organisms for the purpose of purifying soil contaminated by polycyclic aromatic hydrocarbons was developed. The optimized composition of the biocarrier was polyvinyl alcohol (PVA) 10%, sodium alginate (SA) 0.5%, and powdered activated carbon (PAC) 5%. There was no observable cytotoxicity of biocarriers on immobilized cells and a viable cell population of 1.86 × 10¹⁰ g^–1 was maintained for immobilized bacterium. Biocarriers made from chemical methods had a higher biodegradation but lower mechanical strengths. Immobilized bacterium Zoogloea sp. had an ideal capability of biodegradation for phenanthrene and pyrene over a relative wide concentration range. The study results showed that the biodegradation of phenanthrene and pyrene reached 87.0 and 75.4%, respectively, by using the optimal immobilized method of Zoogloea sp. cultivated in a sterilized soil. Immobilized Zoogloea sp. was found to be effective for biodegrading the soil contaminated with phenanthrene and pyrene. Even in "natural" (unsterilized) soil, the biodegradation of phenanthrene and pyrene using immobilized Zoogloea sp. reached 85.0 and 67.1%, respectively, after 168 h of cultivation, more than twice that achieved if the cells were not immobilized on the biocarrier. Therefore, the immobilization technology enhanced the competitive ability of introduced micro-organisms and represents an effective method for the biotreatment of soil contaminated with phenanthrene and pyrene.

Annetocin and TCTP expressions in the earthworm Eisenia fetida exposed to PAHs in artificial soil

The toxicity of sublethal polycyclic aromatic hydrocarbons (PAHs) levels in soils was assessed by testing their impact on expression of annetocin, a reproduction regulating gene, and translationally controlled tumor protein (TCTP), a tumorigenic response gene, in the earthworm Eisenia fetida cultured in artificial soil spiked with, phenanthrene (Phe), pyrene (Pyr), fluoranthene (Flu), or benzo(a)pyrene (Bap). Annetocin and TCTP were both up-regulated by 0.1 and 1.0 mg kg−1 benzo(a)pyrene and TCTP was down-regulated by 10.0 mg kg−1 phenanthrene. Weight loss and cocoon production of the worms were also analyzed. Only 10.0 mg kg−1 phenanthrene impacted earthworm weight loss significantly and no significant differences on cocoon production were observed. Our study indicated that the potential ecotoxicity of sublethal PAHs in soil should not be neglected and mRNA transcription level in earthworms was a more sensitive indicator of PAHs exposure than traditional indexes using cocoon production as endpoints and/or using the whole-organism as the test materials.

High conductivity molten salts based on the imide ion

The bis(trifluoromethanesulfonyl)imide ion has recently been used in its lithium salt as a useful ion in solid polymer electrolytes because of the reduced degree of ion interaction its diffuse charge generates. In this work we have synthesised a number of novel salts based on the ammonium and pyrrolidinium cations of this anion. The salts all show reduced melting points compared with analogous halide salts. In some cases they are molten at room temperature. This latter group of salts have been characterized with respect to their properties as ionic liquids; the highest room temperature conductivity 2 mS cm^−1 being exhibited by methyl butyl pyrrolidinium imide. Many of the salts are glass forming, exhibiting glass transition temperatures in the region of −90°C.

Combination of calcium and magnesium ions prevents substrate inhibition and promotes biomass and lipid production in thraustochytrids under higher glycerol concentration

Effect of calcium and magnesium ions was studied in detail in batch mode in shake flask cultures of two fast growing strains of thraustochytrids (Aurantiochytrium sp. DBTIOC-18 and Schizochytrium sp. DBTIOC-1) for biomass and lipid production. These strains were previously isolated from Indian marine biodiversity. Screening of these two strains on different carbon and nitrogen sources revealed the suitability of glycerol over glucose and sodium nitrate over yeast extract for the cultivation of these strains. The presence of higher concentration of glycerol in the medium inhibited the glycerol utilization by the cell thus resulting in lower biomass and lipid production in both the strains. Supplementing media with calcium and magnesium ions promoted glycerol utilization thus resulted in a substantial rise in volumetric production of biomass (55.12 g L-1, 48.12 g L-1), fatty acid for biodiesel (27.14 g L-1, 22.15 g L-1) and docosahexaenoic acid (14.57 g L-1, 10.12 g L-1) with both strains Aurantiochytrium sp. DBTIOC-18 and Schizochytrium sp. DBTIOC-1, respectively. Growth profile study of these two strains showed further improvement in production of biomass, fatty acid for biodiesel and docosahexaenoic acid when cultures were extended up to 7 days. Finding of this work underlines the importance of calcium and magnesium salts in designing new fermentation strategies to prevent substrate inhibition and achieve high cell density culture under high nutrient concentration especially carbon sources.

Pastures to woodlands: changes in soil microbial communities and carbon following reforestation

Reforestation of agricultural lands has the potential to sequester C, while providing other environmental benefits. It is well established that reforestation can have a profound impact on soil physicochemical properties but the associated changes to soil microbial communities are poorly understood. Therefore, the objective of this study was to quantify changes in soil physicochemical properties and microbial communities in soils collected from reforested pastures and compare then to remnant vegetation and un-reforested pastures. To address this aim, we collected soil from two locations (pasture and its adjacent reforested zone, or pasture and its adjacent remnant vegetation) on each of ten separate farms that covered the range of planting ages (0-30 years and remnant vegetation) in a temperate region of southeastern Australia. Soils were analysed for a range of physicochemical properties (including C and nutrients), and microbial biomass and community composition (PLFA profiles). Soil C:N ratios increased with age of tree planting, and soil C concentration was highest in the remnant woodlands. Reforestation had no clear impact on soil microbial biomass or fungal:bacterial ratios (based on PLFA's). Reforestation was associated with significant changes in the molecular composition of the soil microbial community at many farms but similar changes were found within a pasture. These results indicate that reforestation of pastures can result in changes in soil properties within a few decades, but that soil microbial community composition can vary as much spatially within pastures as it does after reforestation.