Hydrothermal synthesis of [C6H16N2][In2Se3(Se2)]: a new one-dimensional indium selenide

A new organically templated indium selenide, [C6H16N2][In2Se3(Se2)], has been prepared hydrothermally from the reaction of indium, selenium and trans-1,4-diaminocyclohexane in water at 170 °C. This material was characterised by single-crystal and powder X-ray diffraction, thermogravimetric analysis, UV–vis diffuse reflectance spectroscopy, FT-IR and elemental analysis. The compound crystallises in the monoclinic space group C2/c (a=12.0221(16) Å, b=11.2498(15) Å, c=12.8470(17) Å, β=110.514(6)°). The crystal structure of [C6H16N2][In2Se3(Se2)] contains anionic chains of stoichiometry [In2Se3(Se2)]2−, which are aligned parallel to the [1 0 1] direction, and separated by diprotonated trans-1,4-diaminocyclohexane cations. The [In2Se3(Se2)]2− chains, which consist of alternating four-membered [In2Se2] and five-membered [In2Se3] rings, contain perselenide (Se2)2− units. UV–vis diffuse reflectance spectroscopy indicates that [C6H16N2][In2Se3(Se2)] has a band gap of 2.23(1) eV

Towards a unified approach for the determination of the bioaccessibility of organic pollutants

Bioaccessibility studies have been widely used as a research tool to determine the potential human exposure to ingested contaminants. More recently they have been practically applied for soil borne toxic elements. This paper reviews the application of bioaccessibility tests across a range of organic pollutants and contaminated matrices. Important factors are reported to be: the physiological relevance of the test, the components in the gut media, the size fraction chosen for the test and whether it contains a sorptive sink. The bioaccessibility is also a function of the composition of the matrix (e.g. organic carbon content of soils) and the physico-chemical characteristics of the pollutant under test. Despite the widespread use of these tests, there are a large number of formats used and very few validation studies with animal models. We propose a unified format for a bioaccessibility test for organic pollutants. The robustness of this test should first be confirmed through inter laboratory comparison, then tested in-vivo.

The role of root exuded low molecular weight organic anions in facilitating petroleum hydrocarbon degradation: current knowledge and future directions

Rhizoremediation is a bioremediation technique whereby enhanced microbial degradation of organic contaminants occurs within the plant root zone (rhizosphere). It is considered an effective and affordable ‘green technology’ for remediating soils contaminated with petroleum hydrocarbons (PHCs). This paper critically reviews the potential role of root exuded compounds in rhizoremediation, with emphasis on commonly exuded low molecular weight aliphatic organic acid anions (carboxylates). The extent to which remediation is achieved shows wide disparity among plant species. Therefore, plant selection is crucial for the advancement and widespread adoption of this technology. Root exudation is speculated to be one of the predominant factors leading to microbial changes in the rhizosphere and thus the potential driver behind enhanced petroleum biodegradation. Carboxylates can form a significant component of the root exudate mixture and are hypothesised to enhance petroleum biodegradation by: i) providing an easily degradable energy source; ii) increasing phosphorus supply; and/or iii) enhancing the contaminant bioavailability. These differing hypotheses, which are not mutually exclusive, require further investigation to progress our understanding of plant–microbe interactions with the aim to improve plant species selection and the efficacy of rhizoremediation.

Hydrocarbon biodegradation and soil microbial community response to repeated oil exposure

Bioremediation strategies continue to be developed to mitigate the environmental impact of petroleum hydrocarbon contamination. This study investigated the ability of soil microbiota, adapted by prior exposure, to biodegrade petroleum. Soils from Barrow Is. (W. Australia), a class A nature reserve and home to Australia’s largest onshore oil field, were exposed to Barrow production oil (50 ml/kg soil) and incubated (25 °C) for successive phases of 61 and 100 days. Controls in which oil was not added at Phase I or II were concurrently studied and all treatments were amended with the same levels of additional nutrient and water to promote microbial activity. Prior exposure resulted in accelerated biodegradation of most, but not all, hydrocarbon constituents in the production oil. Molecular biodegradation parameters measured using gas chromatography–mass spectrometry (GC–MS) showed that several aromatic constituents were degraded more slowly with increased oil history. The unique structural response of the soil microbial community was reflected by the response of different phospholipid fatty acid (PLFA) sub-classes (e.g. branched saturated fatty acids of odd or even carbon number) measured using a ratio termed Barrow PLFA ratio (B-PLFAr). The corresponding values of a previously proposed hydrocarbon degrading alteration index showed a negative correlation with hydrocarbon exposure, highlighting the site specificity of PLFA-based ratios and microbial community dynamics. B-PLFAr values increased with each Phase I and II addition of production oil. The different hydrocarbon biodegradation rates and responses of PLFA subclasses to the Barrow production oil probably relate to the relative bioavailability of production oil hydrocarbons. These different effects suggest preferred structural and functional microbial responses to anticipated contaminants may potentially be engineered by controlled pre-exposure to the same or closely related substrates. The bioremediation of soils freshly contaminated with petroleum could benefit from the addition of exhaustively bioremediated soils rich in biota primed for the impacting hydrocarbons.

Surface chemistry of alanine on Ni{111}

The adsorption of L-alanine on Ni{111} has been studied as a 10 model of enantioselective heterogeneous catalysts. Synchrotron-based X-ray 11 photoelectron spectroscopy and near-edge X-ray absorption fine structure 12 (NEXAFS) spectroscopy were used to determine the chemical state, bond 13 coordination, and out-of-plane orientation of the molecule on the surface. 14 Alanine adsorbs in anionic and zwitterionic forms between 250 and ≈320 K. 15 NEXAFS spectra exhibit a strong angular dependence of the π* resonance 16 associated with the carboxylate group, which is compatible with two distinct 17 orientations with respect to the surface corresponding to the bidentate and 18 tridentate binding modes. Desorption and decomposition begin together at 19 ≈300 K, with decomposition occurring in a multistep process up to ≈450 K. Comparison with previous studies of amino acid 20 adsorption on metal surfaces shows that this is among the lowest decomposition temperatures found so far and lower than typical 21 temperatures used for hydrogenation reactions where modified Ni catalysts are used.

Organic contaminant content and physico-chemical characteristics of waste materials recycled in agriculture

A range of wastes representative of materials currently applied, or with future potential to be applied, to agricultural land in the UK as fertilisers and soil improvers or used as animal bedding in livestock production, were investigated. In addition to full physico-chemical characterization, the materials were analysed for a suite of priority organic contaminants. In general, contaminants were present at relatively low concentrations. For example, polychlorinated dibenzo-p-dioxins/dibenzofurans and polychlorinated biphenyls in biosolids and compost-like-outputs (CLOs) were, in most cases, between 5-50 times lower than proposed and implemented European limit values for biosolids or composts applied to agricultural land. However, the technical basis for these limits may need to be re-evaluated. Polybrominated, and mixed halogenated, dibenzo-p-dioxins/dibenzofurans are not currently considered in risk assessments of dioxins and dioxin-like chemicals, but were detected in the biosolids and compost-like-outputs and their potential contribution to the overall toxic equivalency will be assessed. Other, ‘emerging’ contaminants such as perfluoralkyl compounds (PFCs) and organophosphate flame retardants were detected in several of the waste materials, and their potential significance is discussed. The study is part of a wider research programme that will provide evidence to improve confidence in the use of waste-derived materials in agriculture and establish guidelines to protect the food chain where necessary.

Application of biochar for soil remediation

Research into the use of biochar for the remediation of contaminated soils has expanded rapidly over the past 5 yr. We review recent developments in the field and present the findings emanating from small-scale batch sorption experiments, through soil incubations and bioassays, to large-scale field experiments. We discuss the evidence that these experiments have contributed toward a mechanistic understanding of how biochar is capable of remediating soils contaminated with both organic and inorganic contaminants. The effects of biochar pyrolysis temperature, biochar source material, soil type, and contaminant type on the performance of biochars for remediation are identified. The risks associated with applying biochar to uncontaminated agricultural soils are discussed. Knowledge gaps and questions are identified which, if addressed, will considerably advance the application of biochar as a soil remediation tool in the future.

Evaluation of the realism of climate reconstruction using the Coexistence Approach with modern pollen samples from the Tibetan Plateau

We apply the Coexistence Approach (CoA) to reconstruct mean annual precipitation (MAP), mean annual temperature (MAT), mean temperature of thewarmestmonth (MTWA) and mean temperature of the coldest month (MTCO) at 44 pollen sites on the Qinghai–Tibetan Plateau. The modern climate ranges of the taxa are obtained (1) from county-level presence/absence data and (2) from data on the optimum and range of each taxon from Lu et al. (2011). The CoA based on the optimumand range data yields better predictions of observed climate parameters at the pollen sites than that based on the county-level data. The presence of arboreal pollen, most of which is derived fromoutside the region, distorts the reconstructions. More reliable reconstructions are obtained using only the non-arboreal component of the pollen assemblages. The root mean-squared error (RMSE) of the MAP reconstructions are smaller than the RMSE of MAT, MTWA and MTCO, suggesting that precipitation gradients are the most important control of vegetation distribution on the Qinghai–Tibetan Plateau. Our results show that CoA could be used to reconstruct past climates in this region, although in areas characterized by open vegetation the most reliable estimates will be obtained by excluding possible arboreal contaminants.

Effect of impurities in biodiesel-derived waste glycerol on the performance and feasibility of biotechnological processes

The rapid development of biodiesel production technology has led to the generation of tremendous quantities of glycerol wastes, as the main by-product of the process. Stoichiometrically, it has been calculated that for every 100 kg of biodiesel, 10 kg of glycerol are produced. Based on the technology imposed by various biodiesel plants, glycerol wastes may contain numerous kinds of impurities such as methanol, salts, soaps, heavy metals and residual fatty acids. This fact often renders biodiesel-derived glycerol unprofitable for further purification. Therefore, the utilization of crude glycerol though biotechnological means represents a promising alternative for the effective management of this industrial waste. This review summarizes the effect of various impurities-contaminants that are found in biodiesel-derived crude glycerol upon its conversion by microbial strains in biotechnological processes. Insights are given concerning the technologies that are currently applied in biodiesel production, with emphasis to the impurities that are added in the composition of crude glycerol, through each step of the production process. Moreover, extensive discussion is made in relation with the impact of the nature of impurities upon the performances of prokaryotic and eukaryotic microorganisms, during crude glycerol bioconversions into a variety of high added-value metabolic products. Finally, aspects concerning ways of crude glycerol treatment for the removal of inhibitory contaminants as reported in the literature are given and comprehensively discussed

Separation of natural colorants from the fermented broth of filamentous fungi using colloidal gas aphrons

There is a worldwide interest in the development of processes for producing colorants from natural sources. Microorganisms provide an alternative source of natural colorants produced by cultivation technology and extracted from the fermented broth. The aim of the present work was to study the recovery of red colorants from the fermented broth of Talaromyces amestolkiae using the technique of colloidal gas aphrons (CGA) comprising surfactant-stabilized microbubbles. Preliminary experiments were performed to evaluate the red colorants’ solubility in different organic solvents, octanol/water partitioning, and their stability in surfactant solutions, namely hexadecyl trimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), and polyoxyethylenesorbitan monolaurate (Tween 20), which are cationic, anionic and nonionic surfactants, respectively. The first recovery experiments were carried out using CGA generated by these surfactants at different volumetric ratios (VR, 3–18). Subsequently, two different approaches to generate CGA were investigated at VR values of 6 and 12: the first involved the use of CTAB at pH 6.9–10.0, and the second involved the use of Tween 20 using red colorants partially dissolved in ethanol and Tween 20. The characterization results showed that red colorants have a hydrophilic nature. The highest recoveries were obtained with Tween 20 (78%) and CTAB (70%). These results demonstrated that the recovery of the colorants was driven by both electrostatic and hydrophobic interactions. The VR was found to be an important operating parameter and at VR 12 with CTAB (at pH 9) maximum recovery, partitioning coefficient (K = 5.39) and selectivity in relation to protein and sugar (SP = 3.75 and SS = 7.20 respectively) were achieved. Furthermore, with Tween 20, the separation was driven mainly by hydrophobic interactions. Overall CGA show promise for the recovery of red colorants from a fermented broth. Although better results were obtained with CTAB than with Tween 20 the latter may be more suitable for some application due to its lower toxicity.

The gut microbiota: a major player in the toxicity of environmental pollutants?

Exposure to environmental chemicals has been linked to various health disorders, including obesity, type 2 diabetes, cancer and dysregulation of the immune and reproductive systems, whereas the gastrointestinal microbiota critically contributes to a variety of host metabolic and immune functions. We aimed to evaluate the bidirectional relationship between gut bacteria and environmental pollutants and to assess the toxicological relevance of the bacteria–xenobiotic interplay for the host. We examined studies using isolated bacteria, faecal or caecal suspensions—germ-free or antibiotic-treated animals—as well as animals reassociated with a microbiota exposed to environmental chemicals. The literature indicates that gut microbes have an extensive capacity to metabolise environmental chemicals that can be classified in five core enzymatic families (azoreductases, nitroreductases, β-glucuronidases, sulfatases and β-lyases) unequivocally involved in the metabolism of >30 environmental contaminants. There is clear evidence that bacteria-dependent metabolism of pollutants modulates the toxicity for the host. Conversely, environmental contaminants from various chemical families have been shown to alter the composition and/or the metabolic activity of the gastrointestinal bacteria, which may be an important factor contributing to shape an individual’s microbiotype. The physiological consequences of these alterations have not been studied in details but pollutant-induced alterations of the gut bacteria are likely to contribute to their toxicity. In conclusion, there is a body of evidence suggesting that gut microbiota are a major, yet underestimated element that must be considered to fully evaluate the toxicity of environmental contaminants.

Survey of aflatoxin M1 in cheese from the North-east region of Sao Paulo, Brazil

In the present study, 24 samples of Minas Frescal cheese and 24 samples of Minas Padrao cheese produced in the North-east region of the state of Sao Paulo, Brazil, were analysed for aflatoxin M1 (AFM1) by high-performance liquid chromatography (HPLC) between March and August 2008. AFM1 was detected in 13 (27.1%) samples at concentrations ranging from 0.037 to 0.313 ng g-1. The mean concentrations of AFM1 in positive samples of Minas Frescal and Minas Padrao cheese were 0.142 +/- 0.118 and 0.118 +/- 0.054 ng g-1, respectively. It is concluded that the incidence of AFM1 in Minas cheese may contribute to an increase in the overall ingestion of aflatoxins in the diet, hence indicating the need for the adoption of a tolerance limit for AFM1 in cheese in Brazil.

Determination of volatile organic compounds in recycled polyethylene terephthalate and high-density polyethylene by headspace solid phase microextraction gas chromatography mass spectrometry to evaluate the efficiency of recycling processes

A method for the determination of volatile organic compounds (VOCs) in recycled polyethylene terephthalate and high-density polyethylene using headspace sampling by solid-phase microextraction and gas chromatography coupled to mass spectrometry detection is presented. This method was used to evaluate the efficiency of cleaning processes for VOC removal from recycled PET. In addition, the method was also employed to evaluate the level of VOC contamination in multilayer packaging material containing recycled HDPE material. The optimisation of the extraction procedure for volatile compounds was performed and the best extraction conditions were found using a 75 mu m carboxen-polydimethylsiloxane (CAR-PDMS) fibre for 20 min at 60 degrees C. The validation parameters for the established method were linear range, linearity, sensitivity, precision (repeatability), accuracy (recovery) and detection and quantification limits. The results indicated that the method could easily be used in quality control for the production of recycled PET and HDPE. (C) 2011 Elsevier B.V. All rights reserved.

Aflatoxins and cyclopiazonic acid in feed and milk from dairy farms in Sao Paulo, Brazil

The occurrence of aflatoxins (AF) B(1), B(2), G(1), G(2) and cyclopiazonic acid (CPA) in feeds, and AFM(1) and CPA in milk was determined in dairy farms located in the northeastern region of Sao Paulo state, Brazil, between October 2005 and February 2006. AF and CPA determinations were performed by HPLC. AFB(1) was found in 42% of feed at levels or 1.0-26.4 mu g kg(-1) (mean: 7.1 +/- 7.2 mu g kg(-1)). The concentrations of AFM(1) in raw milk varied between 0.010 and 0.645 mu g l(-1) (mean: 0.104 +/- 0.138 mu g l(-1)). Only one sample was above the tolerance limit adopted in Brazil (0.50 mu g l(-1)) for AFM(1) in milk. Regarding CPA in feed, six (12%) samples showed concentrations of 12.5-1533 mu g kg(-1) (mean: 57.6 +/- 48.7 mu g kg(-1)). CPA was detected in only three milk samples (6%) at levels of 6.4, 8.8 and 9.1 mu g l(-1). Concentrations of aflatoxins and CPA in feed and milk were relatively low, although the high frequency of both mycotoxins indicates the necessity to continuously monitor dairy farms to prevent contamination of feed ingredients.

Evaluating microfossil content of dental calculus from Brazilian sambaquis

To date, limited numbers of dental calculus samples have been analyzed by researchers in diverse parts of the world. The combined analyses of these have provided some general guidelines for the analysis of calculus that is non-destructive to archaeological teeth. There is still a need for a quantitative study of large numbers of calculus samples to establish protocols, assess the level of contamination, evaluate the quantity of microfossils in dental calculus, and to compare analysis results with the literature concerning the biology of calculus formation. We analyzed dental calculus from 53 teeth from four Brazilian sambaquis. Sambaquis are the shell-mounds that were established prehistorically along the Brazilian coast. The analysis of sambaqui dental calculi shows that there are relatively high concentrations of microfossils (phytoliths and starch), mineral fragments, and charcoal in dental calculus. Mineral fragments and charcoal are possibly contaminants. The largest dental calculi have the lowest concentrations of microfossils. Biologically, this is explained by individual variation in calculus formation between people. Importantly, starch is ubiquitous in dental calculus. The starch and phytoliths show that certainly Dioscorea (yam) and Araucaria angustifolia (Parana pine) were eaten by sambaqui people. Araceae (arum family), Ipomoea batatas (sweet potato) and Zea mays (maize) were probably in their diet. (C) 2009 Elsevier Ltd. All rights reserved.