Effect of clays, metal oxides, and organic matter on rhamnolipid biosurfactant sorption by soil

Rhamnolipids produced by Pseudomonas aeruginosa have been proposed as soil washing agents for enhanced removal of metal and organic contaminants from soil. A potential limitation for the application of rhamnolipids is sorption by soil matrix components. The objective of this study is to empirically determine the contribution of representative soil constituents (clays, metal oxides, and organic matter) to sorption of the rhamnolipid form most efficient at metal complexation (monorhamnolipid). Sorption studies show that monorhamnolipid (R1) sorption is concentration dependent. At low R1 concentrations that are relevant for enhancing organic contaminant biodegradation, R1 sorption followed the order: hematite (Fe(2)O(3))>kaolinite>MnO(2) approximately illite approximately Ca-montmorillonite>gibbsite (Al(OH)(3))>humic acid-coated silica. At high R1 concentrations, relevant for use in complexation/removal of metals or organics, R1 sorption followed the order: illite>humic acid-coated silica>Ca-montmorillonite>hematite>MnO(2)>gibbsite approximately kaolinite. These results allowed prediction of R1 sorption by a series of six soils. Finally, a comparison of R1 and R2 (dirhamnolipid) shows that the R1 form sorbs more strongly alone than when in a mixture of both the R1 and R2 forms. The information presented can be used to estimate, on an individual soil basis, the extent of rhamnolipid sorption. This is important for determining: (1) whether rhamnolipid addition is a feasible remediation option and (2) the amount of rhamnolipid required to efficiently remove the contaminant.     

A review of the PGM industry,deposit models and exploration practices: Implications for Australia's PGM potential

Australia is prospective for platinum group metal (PGM) mineralisation (in particular primary magmatic reef, primary magmatic by-product, late magmatic and hydrothermal, and alluvial placer type) but its known PGM endowment is negligible compared to that of South Africa, Russia, the USA and Canada. Most Australian PGM projects are operated by mid-cap or junior companies and form part of larger, more diverse project portfolios held by these explorers. Most projects were ‘hot’ while market conditions were favourable. However, as other metals became ‘fashionable’ and market conditions for PGM changed, so did the focus of these companies. Pure PGM companies are rare in Australia. The search for and development of PGM-only deposits in Australia are high risk business activities. No new primary PGM deposits have been discovered since the mid to late 1980s and none of the significant deposits that were discovered or evaluated in the 1980s have been mined. This review suggests that at least several A$10 million but more likely several A$100 million were sunk into PGM exploration and development projects but none advanced to the mining stage. The viability of Australian PGM projects is very sensitive to (1) metal prices, (2) the US$/A$ exchange rate, and (3) large capital expenditure requirements relative to the small size of Australian PGM-only deposits. Most PGM-only projects were initiated at times of high PGM prices. However, advanced exploration, feasibility studies and project development always lagged behind the price booms. South Africa, Russia and Canada contain approximately 98% of the known global PGM reserves. This situation has a very negative effect on the Australian PGM industry as the well-endowed nations continue to receive the lion's share of exploration spend and new projects.     

Formation of oxidation by-products of the iodinated X-ray contrast medium iomeprol during ozonation

The present work describes the investigation of the formation of oxidation by-products of the iodinated X-ray contrast medium (ICM) iomeprol during ozonation in water treatment. Bench-scale investigations revealed that ICM can be partly oxidized during ozonation processes, whereas the ionic diatrizoic acid showed the lowest reactivity. Iomeprol, as a representative of ICM, was not fully mineralized during ozonation. Thus, unknown oxidation by-products were formed. Aqueous solutions of iomeprol were treated by ozonation in order to assess the formation of oxidation by-products. The by-products were characterized by different liquid chromatography methods including detection of single-stage mass spectra, product ion mass spectra, and induced in-source fragmentation for analysis of iodine containing oxidation by-products. Aldehyde and carbonyl containing compounds were proposed to be among the stable by-products. A derivatization step confirms that the aldehyde and carbonyl moieties are major functional groups in oxidation by-products of iomeprol. Furthermore, oxidation by-products of iomeprol were detected at the outlet of an ozone reactor at a full-scale waterworks. However, the toxicological relevance of the by-products is a major future research tasks.     

Phytostabilization potential of quailbush for mine tailings: growth, metal accumulation, and microbial community changes

Abandoned mine tailings sites in semiarid regions remain unvegetated for extended periods of time and are subject to eolian dispersion and water erosion. This study examines the potential phytostabilization of a lead-zinc mine tailings site using a native, drought-tolerant halophyte, quailbush [Atriplex lentiformis (Torr.) S. Wats.]. In a greenhouse study germination, growth, and metal uptake was evaluated in two compost-amended mine tailings samples, K4 (pH 3) and K6 (pH 6) at 75, 85, 90, 95, and 100% mine tailings, and two controls, off-site and compost. Microbial community changes were monitored by performing MPN analysis of iron- and sulfur-oxidizing bacteria as well as heterotrophic plate counts. Results demonstrate that germination is not a good indicator for phytostabilization since it was only inhibited in the unamended K4 treatment. Plant growth was significantly reduced in 95 and 100% mine tailings, while growth in 75, 85, and 90% treatments was similar to the off-site control. Quailbush accumulated elevated levels of the nutrient metals Na, K, Mn, and Zn in the shoot tissues; however, metal accumulation was generally below the domestic animal toxicity limit. Initially, autotrophic population estimates were four to six logs higher than heterotrophic counts, indicating extremely stressed conditions. However, post-harvest, heterotrophic bacterial counts increased to normal levels (approximately 10(6) CFU g-1 dry tailings) and dominated the rhizosphere. Therefore, with compost amendment, quailbush has good potential as a native species candidate for phytostabilization of mine tailings in semiarid environments.     

Assisted Migration in Normative and Scientific Context

Assisted migration (AM), an ecosystem engineering technology, is receiving increasing attention and significant support as a means to save biodiversity in a changing climate. Few substantive, or not obviously deficient, reasons have been offered for why pursuing this conservation goal via these means might be good. Some proponents of AM, including those who identify themselves as “pragmatists,” even suggest there is little need for such argument. We survey the principal reasons offered for AM, as well as reasons offered for not offering reasons. As exemplified by the case for translocating whitebark pine, which may at first seem especially strong, we note the incongruence of framing the goal of AM in terms of “saving biodiversity,” neglect of some crucial moral questions, marginalization of normative and scientific context when AM is cast as the lesser of two evils in a “crisis,” doubtful validity and, in any case, marginal importance of arguments that AM projects ought to be undertaken, inconsistent use of scientific facts, and omission of science that counters sanguine assessments. All told—even in cases such as whitebark pine for which AM may seem most defensible—there is little reason to think that AM projects are good as means to “save biodiversity,” or good as means to other goals that have accreted into arguments for these projects.     

Oxy-fuel coal combustion—A review of the current state-of-the-art

Carbon dioxide emissions will continue being a major environmental concern due to the fact that coal will remain a major fossil-fuel energy resource for the next few decades. To meet future targets for the reduction of greenhouse gas (GHG) emissions, capture and storage of CO₂ is required. Carbon capture and storage technologies that are currently the focus of research centres and industry include: pre-combustion capture, post-combustion capture, and oxy-fuel combustion. This review deals with the oxy-fuel coal combustion process, primarily focusing on pulverised coal (PC) combustion, and its related research and development topics. In addition, research results related to oxy-fuel combustion in a circulating fluidised bed (CFB) will be briefly dealt with.During oxy-fuel combustion, a combination of oxygen, with a purity of more than 95 vol.%, and recycled flue gas (RFG) referred to as oxidant is used for combusting the fuel producing a gas consisting of mainly CO₂ and water vapour, which after purification and compression, is ready for storage. The high oxygen demand is supplied by a cryogenic air separation process, which is the only commercially available mature technology. The separation of oxygen from air as well as the purification and liquefaction of the CO₂-enriched flue gas consumes significant auxiliary power. Therefore, the overall net efficiency is expected to be decreased by 8–12% points, corresponding to a 21–35% increase in fuel consumption. Alternatively, ion transport membranes (ITMs) are proposed for oxygen separation, which might be more energy efficient. However, since ITMs are far away from becoming a mature technology, it is widely expected that cryogenic air separation will be the selected technology in the near future. Oxygen combustion is associated with higher temperatures compared with conventional air combustion. Both fuel properties as well as limitations of steam and metal temperatures of the various heat exchanger sections of the boiler require a moderation of the temperatures in the combustion zone and in the heat-transfer sections. This moderation in temperature is accomplished by means of recycled flue gas. The interdependencies between the fuel properties, the amount and temperature of the recycled flue gas, and the resulting oxygen concentration in the combustion atmosphere are reviewed.The different gas atmosphere resulting from oxy-fuel combustion gives rise to various questions related to firing, in particular, with respect to the combustion mechanism, pollutant reduction, the risk of corrosion, and the properties of the fly ash or its resulting deposits. In this review, detailed nitrogen and sulphur chemistry was investigated in a laboratory-scale facility under oxy-fuel combustion conditions. Oxidant staging succeeded in reducing NO formation with effectiveness comparable to that typically observed in conventional air combustion. With regard to sulphur, a considerable increase in the SO₂ concentration was measured, as expected. However, the H₂S concentration in the combustion atmosphere in the near-flame zone increased as well. Further results were obtained in a pilot-scale test facility, whereby acid dew points were measured and deposition probes were exposed to the combustion environment. Slagging, fouling and corrosion issues have so far been addressed via short-term exposure and require further investigation.Modelling of PC combustion processes by computational fluid dynamics (CFD) has become state-of-the-art for conventional air combustion. Nevertheless, the application of these models for oxy-fuel combustion conditions needs adaptation since the combustion chemistry and radiative heat transfer is altered due to the different combustion gas atmosphere.CFB technology can be considered mature for conventional air combustion. In addition to its inherent advantages like good environmental performance and fuel flexibility, it offers the possibility of additional heat exchanger arrangements in the solid recirculation system, i.e. the ability to control combustion temperatures despite relatively low flue gas recycle ratios even when combusting in the presence of high oxygen concentrations.     

Stability constants for the complexation of various metals with a rhamnolipid biosurfactant

The presence of toxic metals in natural environments presents a potential health hazard for humans. Metal contaminants in these environments are usually tightly bound to colloidal particles and organic matter. This represents a major constraint to their removal using currently available in situ remediation technologies. One technique that has shown potential for facilitated metal removal from soil is treatment with an anionic microbial surfactant, rhamnolipid. Successful application of rhamnolipid in metal removal requires knowledge of the rhamnolipid-metal complexation reaction. Therefore, our objective was to evaluate the biosurfactant complexation affinity for the most common natural soil and water cations and for various metal contaminants. The conditional stability constant (log K) for each of these metals was determined using an ion-exchange resin technique. Results show the measured stability constants follow the order (from strongest to weakest): Al3+ > Cu2+ > Pb2+ > Cd2+ > Zn2+ > Fe3+ > Hg2+ > Ca2+ > Co2+ > Ni2+ > Mn2+ > Mg2+ > K+. These data indicate that rhamnolipid will preferentially complex metal contaminants such as lead, cadmium, and mercury in the presence of common soil or water cations. The measured rhamnolipid-metal stability constants were found in most cases to be similar or higher than conditional stability constants reported in the literature for metal complexation with acetic acid, oxalic acid, citric acid, and fulvic acids. These results help delineate the conditions under which rhamnolipid may be successfully applied as a remediation agent in the removal of metal contaminants from soil, as well as surface waters, ground water, and wastestreams.     

Environmental cadmium levels increase phytochelatin and glutathione in lettuce grown in a chelator-buffered nutrient solution

Phytochelatins are enzymatically synthesized peptides involved in metal detoxification and have been measured in plants grown at very high Cd concentrations, but few studies have examined the response of plants at lower environmentally relevant Cd concentrations. Using an ethylenediaminetetraacetic acid (EDTA)-buffered nutrient medium, we have varied Cd exposure and measured phytochelatin and glutathione concentrations in romaine lettuce (Lactuca sativa L. var. longifolia Lam. var. Parris Island) grown in a flow-through hydroponic (FTH) system. Very low free ionic Cd (10(-9.6) M) increased average phytochelatin concentrations above those of controls, and increasing Cd resulted in increased phytochelatin production, though increases were tissue dependent. Glutathione concentrations also increased with increasing Cd. In other standard hydroponic experiments, the media were manipulated to vary total Cd concentration while the ionic Cd was fixed. We found that the total amount of Cd (primarily EDTA bound) in the medium altered thiol production in roots, whereas thiols in leaves remained constant. The Cd uptake into roots and translocation to old leaves was also influenced by the total concentration in the medium. Cadmium in all tissues was lower and in some tissues thiol concentrations were higher than in FTH-grown plants grown in identical medium, suggesting that nutrient delivery technique is also an important variable. Though phytochelatin and glutathione production can be sensitive to changes in bioavailable Cd, thiol concentrations will not necessarily reflect the Cd content of the plant tissues.     

Characterization of lead removal from contaminated soils by nontoxic soil-washing agents

Few effective strategies exist for remediating and restoring metal-contaminated soils. We have evaluated the potential of two environmentally compatible, nondestructive, biological soil-washing agents for remediating aged, lead-contaminated soils. Two contaminated soils were washed with 10 mM rhamnolipid biosurfactant and 5.3% carboxymethyl-beta-cyclodextrin (CMCD). The metal removal efficiency of these agents was compared with 10 mM diethylenetriamine pentaacetic acid (DTPA) and 10 mM KNO3. Lead removal rates by both soil-washing agents exceeded the removal by KNO3, but were an order of magnitude less than removal by the synthetic chelator, DTPA. Analysis of soil extractions revealed that the Pb in the first soil (3780 mg kg(-1)) was primarily associated with the soluble, exchangeable, oxide, and residual fractions while the Pb in the second soil (23 900 mg kg(-1)) was found in the soluble, exchangeable, carbonate, and residual fractions. After 10 consecutive washes, rhamnolipid had removed 14.2 and 15.3% of the Pb from the first and second soils, respectively, and CMCD had removed 5 and 13.4% from the same two soils. The Pb removal rate by both agents either increased or was consistent throughout the 10 extractions, indicating a potential for continued removal with extended washing. Significant levels of Cu and Zn in both soils did not prevent Pb removal by either agent. Interestingly, the effectiveness of each agent varied as a function of Pb speciation in the soil. Rhamnolipid was more effective than CMCD in removing Pb bound to amorphous iron oxides, while both agents demonstrated similar potential for removing soluble, exchangeable, and carbonate-bound Pb. Neither agent demonstrated potential for the complete remediation of metal-contaminated soils.