Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques

Molecular-level understanding of soil Cu speciation and distribution assists in management of Cu contamination in mining sites. In this study, one soil sample, collected from a mining site contaminated since 1950s, was characterized complementarily by multiple synchrotron-based bulk and spatially resolved techniques for the speciation and distribution of Cu as well as other related elements (Fe, Ca, Mn, K, Al, and Si). Bulk X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that soil Cu was predominantly associated with Fe oxides instead of soil organic matter. This agreed with the closest association of Cu to Fe by microscopic X-ray fluorescence (U-XRF) and scanning transmission X-ray microscopy (STXM) nanoanalysis, along with the non-occurrence of photoreduction of soil Cu(II) by quick Cu L_3,2-edge XANES spectroscopy (Q-XANES) which often occurs when Cu organic complexes are present. Furthermore, bulk-EXAFS and STXM-coupled Fe L_3,2-edge nano-XANES analysis revealed soil Cu adsorbed primarily to Fe(III) oxides by inner-sphere complexation. Additionally, Cu K-edge μ-XANES, L_3,2-edge bulk-XANES, and successive Q-XANES results identified the presence of Cu₂S rather than radiation-damage artifacts dominant in certain microsites of the mining soil. This study demonstrates the great benefits in use of multiple combined synchrotron-based techniques for comprehensive understanding of Cu speciation in heterogeneous soil matrix, which facilitates our prediction of Cu reactivity and environmental fate in the mining site.     

Junge relationships in measurement data for cyclic siloxanes in air

In 1974, Junge postulated a relationship between variability of concentrations of gases in air at remote locations and their atmospheric residence time, and this Junge relationship has subsequently been observed empirically for a range of trace gases. Here, we analyze two previously-published datasets of concentrations of cyclic volatile methyl siloxanes (cVMS) in air and find Junge relationships in both. The first dataset is a time series of concentrations of decamethylcyclopentasiloxane (D₅) measured between January and June, 2009 at a rural site in southern Sweden that shows a Junge relationship in the temporal variability of the measurements. The second dataset consists of measurements of hexamethylcyclotrisiloxane (D₃), octamethylcyclotetrasiloxane (D₄) and D₅ made simultaneously at 12 sites in the Global Atmospheric Passive Sampling (GAPS) network that shows a Junge relationship in the spatial variability of the three cVMS congeners. We use the Junge relationship for the GAPS dataset to estimate atmospheric lifetimes of dodecamethylcyclohexasiloxane (D₆), 8:2–fluorotelomer alcohol and trichlorinated biphenyls that are within a factor of 3 of estimates based on degradation rate constants for reaction with hydroxyl radical determined in laboratory studies.     

Biodegradation of PCBs by ligninolytic fungi and characterization of the degradation products

The aim of the present study was to compare the degrading capabilities of eight ligninolytic fungal representatives towards a technical mixture of polychlorinated biphenyls (Delor 103). Axenic cultures of the fungi, either in complex or N-limited liquid media, were spiked with the technical mixture of Delor 103. All of the fungal strains were able to degrade the pollutant significantly after 6weeks of incubation in both media. Outstanding results were achieved by the treatment with Pleurotus ostreatus, which removed 98.4% and 99.6% of the PCB mixture in complex and mineral media, respectively. This fungus was the only one capable of breaking down penta- and hexachlorinated biphenyls in the complex medium. Ecotoxicological assays performed with the luminescent bacterium Vibrio fischeri demonstrated that all of the fungal strains employed in this study were able to remove the toxicity only temporarily (e.g., after 28d of incubation), while P. ostreatus was capable of suppressing the toxicity associated to PCBs along the whole incubation period in both media. We also performed an extensive set of qualitative GC/MS analyses and chlorinated derivatives of hydroxy- and methoxy-biphenyls were detected along with monoaromatic structures, i.e. chlorobenzoic acids, chlorobenzaldehydes and chlorobenzyl alcohols. This results indicate that both intracellular (cytochrome P-450 monooxigenase, aryl-alcohol dehydrogenase and aryl-aldehyde dehydrogenase) and extracellular (ligninolytic enzymes) enzymatic systems could be involved in the biotransformation of PCB by ligninolytic fungi. The data from this work also document that the fungi are able to degrade further the main metabolites on the PCB pathway (i.e. chlorobenzoic acids) simultaneously with PCBs.     

The Great Recession or progressive energy policies? Explaining the decline in US greenhouse gas emissions forecasts

This paper evaluates the causes of the 23% decline in 2030 US greenhouse gas emissions forecasts between 2007 and 2011. Dynamic regression modeling predicts that the Great Recession contributed to about 67% of the 2008–2009 emissions decline, but then fell to about an 18% share for the 2030 emissions forecast. An analysis of electricity generation forecasts show that switching from coal to gas contributed only 6% to the total 2030 decline. In contrast, regulatory impact assessments and policy analysis showed that state and federal policies were responsible for 46% of the 2030 decline in emissions.     

Low-heat alkaline pretreatment of biomass for dairy anaerobic codigestion

In this research, low-heat alkaline pretreatment was evaluated to determine the extent to which urban landscape waste (yard waste), corn stover, and switchgrass could be codigested under conditions typical of US farm-based anaerobic digestion (AD). Waste heat from combined heat and power (CHP) units associated with AD could make such pretreatment economical. Short-term batch digestion studies and 8-week continuous-feed studies were used to screen and evaluate various pretreatment conditions. Results indicate that maple and oak leaves did not digest well, even with pretreatment. Pretreatment did improve digestion of corn leaves and stalks as well as switchgrass. However, these materials also digested reasonably well even without pretreatment. No digester operational problems were observed during continuous-feed studies of intermittently stirred bench top digesters, but optimal levels of alkali, temperature, and pretreatment time may be specific to the feedstock, particle size, and digester loading rate. Results suggest that some common lignocellulosic biomass materials, such as corn stover and switchgrass, could be successfully codigested in many existing farm-based digesters. Interestingly, without pretreatment, switchgrass digestion improved over 20-fold when digested with seed culture from a dairy digester compared to seed culture from a municipal digester, suggesting that culture acclimation could be as important as pretreatment in improving digestion of specific lignocellulosic feedstocks.     

Climate Change and the Adaptability of Agriculture: A Review

ABSTRACT

The assessment of climate change impacts on agriculture has emerged as a recognizable field of research over the past 15 years or so. In a relatively short period, this area of work has undergone a number of important conceptual and methodological developments. Among many questions that have been debated are the adaptability of agriculture to climate change and the importance of land management adjustments in reducing the adverse effects of climate change. In turn, this latter focus has spawned a discussion regarding the nature of adaptation and the ability of agriculture to respond to sudden and rapid climatic changes. In this paper we present an overview of this debate.

It is argued that the first generation of climate change impact studies generally ignored the possibility that agriculturalists may adjust their farming practices in order to cope with climate change or to take advantage of new production opportunities. This conceptual oversight has been largely eliminated over the past five years or so. However, questions remain surrounding the likelihood that various adaptive strategies will actually be deployed in particular places. In this paper, we stress the importance of studying adaptation in the context of decision-making at the individual farm level and beyond.     

Valorisation of forestry waste by pyrolysis in an auger reactor

Pyrolysis of forestry waste has been carried out in an auger reactor to study the influence of operational variables on the reactor performance and the properties of the related products. Pine woodchips were used for the first time as raw material and fed continuously into the reactor. Ten experiments were carried out under inert atmosphere at: (i) different reaction temperature (1073, 973, 873, 823 and 773 K); (ii) different solid residence time (5, 3, 2 and 1.5 min); and (iii) different biomass flow rate (3.9, 4.8 and 6.9 kg/h). Results show that the greatest yields for liquid production (59%) and optimum product characterisation were obtained at the lowest temperature studied (773 K) and applying solid residence times longer than 2 min. Regarding bio-oil properties, GC/MS qualitative identification show that the most abundant compounds are volatile polar compounds, phenols and benzenediols; and very few differences can be observed among the samples regardless of the pyrolysis operating conditions. On the whole, experimental results demonstrate that complete reaction of forest woodchips can be achieved in an auger reactor in most of the experimental conditions tested. Moreover, this study presents the initial steps for the future scaling up of the auger reactor with the aim of converting it into a mobile plant which will be able to remotely process biomass such as energy crops, forestry and agricultural wastes to obtain bio-oil that, in turn, can be used as energy vector to avoid high transport costs.     

Assessment of the environmental fate and effects of the PPARgamma receptor agonist, pioglitazone

The environmental fate and effects of pioglitazone prescribed for the treatment of type 2 diabetes were evaluated in an environmental risk assessment following the European Medicines Agency (EMA) "Guideline on the Environmental Risk Assessment of Medicinal Products for Human Use"; EMEA/CHMP/SWP/4447/00. A predicted environment concentration (PEC) for surface water was estimated at 0.023μgL(-1), (action limit of 0.01μgL(-1)) triggering a comprehensive battery of laboratory evaluations. Pioglitazone and its major metabolites were determined not to significantly adsorb to sewage solids, were not persistent in the aquatic environment, did not bioaccumulate and were non-toxic to aquatic organisms. Pioglitazone does not pose an unacceptable risk to groundwater supplies, with concentrations not anticipated to be a risk to aquatic organisms or human drinking water supplies. Pioglitazone does not pose a risk of secondary poisoning.     

A rapidly equilibrating, thin film, passive water sampler for organic contaminants; characterization and field testing

Improving methods for assessing the spatial and temporal resolution of organic compound concentrations in marine environments is important to the sustainable management of our coastal systems. Here we evaluate the use of ethylene vinyl acetate (EVA) as a candidate polymer for thin-film passive sampling in waters of marine environments. Log K_EVA−W partition coefficients correlate well (r² = 0.87) with Log K_OW values for selected pesticides and polychlorinated biphenyls (PCBs) where Log K_EVA−W = 1.04 Log K_OW + 0.22. EVA is a suitable polymer for passive sampling due to both its high affinity for organic compounds and its ease of coating at sub-micron film thicknesses on various substrates. Twelve-day field deployments were effective in detecting target compounds with good precision making EVA a potential multi-media fugacity meter.