Dane Lamb

Role of organic amendments on enhanced bioremediation of heavy metal(loid) contaminated soils.

As land application becomes one of the important waste utilization and disposal practices, soil is increasingly being seen as a major source of metal(loid)s reaching food chain, mainly through plant uptake and animal transfer. With greater public awareness of the implications of contaminated soils on human and animal health there has been increasing interest in developing technologies to remediate contaminated sites. Bioremediation is a natural process which relies on soil microorganisms and higher plants to alter metal(loid) bioavailability and can be enhanced by addition of organic amendments to soils. Large quantities of organic amendments, such as manure compost, biosolid and municipal solid wastes are used as a source of nutrients and also as a conditioner to improve the physical properties and fertility of soils. These organic amendments that are low in metal(loid)s can be used as a sink for reducing the bioavailability of metal(loid)s in contaminated soils and sediments through their effect on the adsorption, complexation, reduction and volatilization of metal(loid)s. This review examines the mechanisms for the enhanced bioremediation of metal(loid)s by organic amendments and discusses the practical implications in relation to sequestration and bioavailability of metal(loid)s in soils.

Heavy metal (Cu, Zn, Cd and Pb) partitioning and bioaccessibility in uncontaminated and long-term contaminated soils.

We investigated the pore-water content and speciation of copper (Cu), zinc (Zn), cadmium (Cd) and lead (Pb) in a range of uncontaminated and long-term contaminated soils in order to establish their potential bioaccessibility to soil biota, plants and humans. Among the samples, soil pH (0.01 M CaCl(2)) ranged from 4.9 to 8.2. The total metal content of the uncontaminated soils ranged from 3.8 to 93.8 mg Cu kg(-1), 10.3 to 95 mg kg(-1) Zn, 0.1 to 1.8 mg Cd kg(-1) and 5.2 to 183 mg kg(-1) Pb, while metal content in the contaminated soils ranged from 104 to 6841 mg Cu kg(-1), 312 to 39,000 mg kg(-1) Zn, 6 to 302 mg Cd kg(-1) and 609 to 12,000 mg kg(-1) Pb. Our analysis of pore-water found the Cu concentrations to be much higher in contaminated soils than in uncontaminated soils, with the distribution coefficients (K(d)) correlating significantly with the log of dissolved organic carbon concentrations. Despite the high total metal content of the contaminated soil, Zn, Cd and Pb were not generally found at elevated levels in the pore-water with the exception of a single contaminated soil. A long period of ageing and soil weathering may have led to a substantial reduction in heavy metal concentrations in the pore-water of contaminated soils. On the other hand, Pb bioaccessibility was found to be comparatively high in Pb contaminated soils, where it tended to exceed the total Pb values by more than 80%. We conclude that, despite the extensive ageing of some contaminated soils, the bioaccessibility of Pb remains relatively high.

Comparative Sorption and Mobility of Cr(III) and Cr(VI) Species in a Range of Soils: Implications to Bioavailability

The sorption of chromium (Cr) species to soil has become the focus of research as it dictates the bioavailability and also the magnitude of toxicity of Cr. The sorption of two environmentally important Cr species [Cr(III) and Cr(VI)] was examined using batch sorption, and the data were fitted to Langmuir and Freundlich adsorption isotherms. The effects of soil properties such as pH, CEC, organic matter (OM), clay, water-extractable SO42– and PO43–, surface charge, and different iron (Fe) fractions of 12 different Australian representative soils on the sorption, and mobility of Cr(III) and Cr(VI) were examined. The amount of sorption as shown by Kf was higher for Cr(III) than Cr(VI) in all tested soils. Further, the amount of Cr(III) sorbed increased with an increase in pH, CEC, clay, and OM of soils. Conversely, the chemical properties of soil such as positive charge and Fe (crystalline) had a noticeable influence on the sorption of Cr(VI). Desorption of Cr(VI) occurred rapidly and was greater than desorption of Cr(III) in soils. The mobility of Cr species as estimated by the retardation factor was higher for Cr(VI) than for Cr(III) in all tested soils. These results concurred with the results from leaching experiments which showed higher leaching of Cr(VI) than Cr(III) in both acidic and alkaline soils indicating the higher mobility of Cr(VI) in a wide range of soils. This study demonstrated that Cr(VI) is more mobile and will be bioavailable in soils regardless of soil properties and if not remediated may eventually pose a severe threat to biota.

Phytocapping: An Alternative Technology for the Sustainable Management of Landfill Sites

Landfill remains the predominant means of waste disposal throughout the globe. Numerous landfills exist in developed and underdeveloped countries, engineered with contrasting degrees of effectiveness. Modern landfill closure in developed countries involves the conventional capping of waste with materials such as compacted clay or geosynthetic clay liners, typically overlain with other soil materials. Conventional capping technologies are now accepted to be increasingly ineffective in reducing percolation into waste. Cost-effective alternative systems are of increasing interest, including the use of plants to control and limit water entry into waste, otherwise known as “Phytocapping”. Phytocapping reduces percolation through three main mechanisms: (a) canopy interception of rainfall, (b) storage of moisture in the soil layers, and (c) evapotranspiration (i.e., hydraulic lift) of stored water. Phytocapping has been shown to be at least as effective as clay capping in reducing percolation through landfill cover materials, provided site specific conditions are factored into design, and providing many additional benefits, including increased cap stability, reduced erosion of capping materials, reduction of wind-blown dust, enhanced biological diversity, increased opportunity to establish commercial plants, carbon sequestration, and enhanced methane oxidation from microbial communities. Phytocapping has been suggested as having potential in phytoremediation of landfill leachate. The most common phytocapping approach to date is the construction of vegetation assemblages for the purposes of creating natural vegetation nodes. Phytocapping technology can be enhanced by appropriate selection of soil amendments such as biosolids, biochar, compost, or other materials. Appropriate selection of plant species and soil amendment products can enhance methane oxidation in capping soils. There is considerable potential for the use of high biomass energy plants but further work is needed in choosing appropriate plant species that will serve both purposes of site water balance as well as commercial (e.g., timber, bioenergy) and biodiversity needs of the community.

Bioavailability of lead in contaminated soil depends on the nature of bioreceptor.

Long-term lead (Pb) contaminated soils from two lead-zinc smelters and a shooting range, along with freshly spiked control soil, were studied by means of chemical, biological or a physiological method to examine the effect of ageing on Pb bioavailability. The freshly Pb spiked control soil was subjected to an earthworm toxicity test to observe the avoidance and mortality response of the earthworms. Meanwhile, an extractable fraction of Pb on the spiked soil as a result of ageing was examined and further compared with physiologically based in vitro bioaccessibility extraction tests. Their differences in lethal concentration, LC(50), to the earthworm population from spiked soils varied substantially as a function of soil pH. The strong effect of ageing on toxicity was also reflected in the extractability of Pb which was far greater in acidic soil, labelled AC, compared to the alkaline soil, labelled BC. This demonstrates that the bioavailable fraction causing toxicity to earthworms was achieved at a much lower total Pb content for acidic soils relative to alkaline soils. Moreover, the effect of ageing also exhibits that a marked decline in bioavailable Pb results in lowering toxicity. Significant amounts of weight loss in earthworms during an acute toxicity test in long-term contaminated soils at a relatively low Pb concentration suggested that other metal or combined metal toxicity may also play a significant role. This study demonstrates that the soil characteristics and ageing period greatly influence the bioavailable fraction of Pb which is related to the bioreceptor.

Copper behaviour in a Podosol. 1. pH-dependent sorption-desorption, sorption isotherm analysis, and aqueous speciation modelling

The effects of pH and Cu loading on the solid/solution partitioning of Cu in a Podosol from south-east Queensland, Australia was examined. Sorption-desorption of Cu exhibited maximum linear distribution coefficients (KD) at approximately pH 5. Observed decrease in KD values at pH >5 was attributed to increased solubility of native dissolved organic carbon (DOC) at higher pH and subsequent formation of non-sorbing Cu-DOC complexes. Speciation modelling with the MINTEQA2 code indicated that >90% of aqueous Cu was present as Cu-DOC complexes at pH >5.5. The effect of Cu loading was examined with sorption isotherm analysis at pH 5 using solid : solution ratio approaches that were both constant (1 : 2 and 1 : 10) and variable. As the solid : solution ratio increased, the proportion of Cu sorbed decreased due to the formation of Cu-DOC complexes. However, this effect was negligible once these Cu-DOC complexes were accounted for via free Cu 2+ sorption isotherms. This indicated that Cu 2+ sorption at concentrations <0.08 mg/L was described by a KD value of approximately 3000 L/kg. Despite this relatively high KD value for Cu 2+ sorption, the results indicate that Cu-DOC complexes significantly enhance Cu solubility in soils high in DOC. Additional keywords: trace metals, partitioning, solubility, MINTEQA2.

Pyrogenic carbon and its role in contaminant immobilization in soils

ABSTRACT Pyrogenic carbon (PyC), including soil native PyC and engineered PyC (biochars), is increasingly being recognized for its potential role as a low-cost immobilizer of contaminants in soils. Published reviews on the role of soil native PyC as a sorbent in soils have so far focused mainly on organic contaminants and paid little or no attention to inorganic contaminants. Further, a comprehensive review on the production of both natural PyC and engineered PyC (biochars), mechanisms involved, and factors influencing their role as soil contaminant immobilizer is so far not available. The objective of this review is thus to systematically summarize the sources, formation, and properties of PyC, including its quantification in soils, followed by their roles in the immobilization of both organic and inorganic contaminants in soils. Effectiveness of PyC on bioavailability, leaching, and degradation of soil contaminants was summarized. Notably, the mechanisms and factors (for the first time) influencing the immobilization processes for soil contaminants were also extensively elucidated. This review helps better understand and design PyC for soil contaminant immobilization.

Bioaccessibility of arsenic and cadmium assessed for in vitro bioaccessibility in spiked soils and their interaction during the Unified BARGE Method (UBM) extraction.

Recent decades have seen a growing popularity of in vitro bioaccessibility being utilised as a screening tool in human health risk assessment. However the existing bioaccessibility studies only focus on single contaminant. Considering human are likely to ingest multi-contaminants, these contaminants could interact within human gastrointestinal tract which may lead to an increase or decrease in bioaccessibility. In this study, seven different types of soil were spiked with arsenic (As) or cadmium (Cd) and aged for one year. The effects of soil properties on the bioaccessibility were examined. Moreover, the interaction between As and Cd in simulated human digestive system was studied by mixing As-spiked soil with Cd-spiked soil of the same type during bioaccessibility test. Results shows the bioaccessibility of As ranged from 40 ± 2.8 to 95 ± 1.3% in the gastric phase and 16 ± 2.0 to 96 ± 0.8% in the intestinal phase whilst a significant difference was observed between Cd gastric bioaccessibility (72 ± 4.3 to 99 ± 0.8%) and intestinal bioaccessibility (6.2 ± 0.3 to 45 ± 2.7%). Organic carbon, iron oxide and aluminium oxide were key parameters influencing the bioaccessibility of As (gastric and intestinal phases) and Cd (intestinal phase). No interactions between As and Cd during bioaccessibility test were observed in any soils, which indicates As and Cd may age independently and did not interact while being solubilised during bioaccessibility test. Thus additive effect may be proposed when estimating the bioaccessibility of mixtures of independently-aged As and Cd in soils.

Pore-water chemistry explains zinc phytotoxicity in soil.

Zinc (Zn) is a widespread soil contaminant arising from a numerous anthropogenic sources. However, adequately predicting toxicity of Zn to ecological receptors remains difficult due to the complexity of soil characteristics. In this study, we examined solid-solution partitioning using pore-water data and toxicity of Zn to cucumber (Cucumis sativus L.) in spiked soils. Pore-water effective concentration (ECx, x=10%, 20% and 50% reduction) values were negatively related to pH, indicating lower Zn pore water concentration were needed to cause phytotoxicity at high pH soils. Total dissolved zinc (Znpw) and free zinc (Zn(2+)) in soil-pore water successfully described 78% and 80.3% of the variation in relative growth (%) in the full dataset. When the complete data set was used (10 soils), the estimated EC50pw was 450 and 79.2 µM for Znpw and Zn(2+), respectively. Total added Zn, soil pore water pH (pHpw) and dissolve organic carbon (DOC) were the best predictors of Znpw and Zn(2+) in pore-water. The EC10 (total loading) values ranged from 179 to 5214 mg/kg, depending on soil type. Only pH measurements in soil were related to ECx total Zn data. The strongest relationship to ECx overall was pHca, although pHw and pHpw were in general related to Zn ECx. Similarly, when a solution-only model was used to predict Zn in shoot, DOC was negatively related to Zn in shoot, indicating a reduction in uptake/ translocation of Zn from solution with increasing DOC.

Cadmium solubility and bioavailability in soils amended with acidic and neutral biochar

This study was designed to investigate the effects of acidic and neutral biochars on solubility and bioavailability of cadmium (Cd) in soils with contrasting properties. Four Cd contaminated (50mg/kg) soils (EN: Entisol, AL: Andisol, VE: Vertisol, IN: Inceptisol) were amended with 5% acidic wood shaving biochar (WS, pH=3.25) and neutral chicken litter biochar (CL, pH=7.00). Following a 140-day incubation, the solubility and bioavailability/bioaccessibility of cadmium (Cd) were assessed. Results showed that both biochars had no effect on reducing soluble (pore water) and bioavailable (CaCl2 extractable) Cd for higher sorption capacity soils (AL, IN) while CL biochar reduced those in lower sorption capacity soils (EN, VE) by around 50%. Bioaccessibility of Cd to the human gastric phase (physiologically based extraction test (PBET) extractable) was not altered by the acidic WS biochar but reduced by neutral CL biochar by 18.8%, 29.7%, 18.0% and 8.82% for soil AL, EN, IN and VE, respectively. Both biochars reduced soluble Cd under acidic conditions (toxicity characteristic leaching procedure (TCLP) extractable) significantly in all soils. Pore water pH was the governing factor of Cd solubility among soils. The reduction of Cd solubility and bioavailability/bioaccessibility by CL biochar may be due to surface complexation while the reduced mobility of Cd under acidic conditions (TCLP) by both biochars may result from the redistribution of Cd to less bioavailable soil solid fractions. Hence, if only leaching mitigation of Cd under acidic conditions is required, application of low pH biochars (e.g., WS biochar) may be valuable.