Towards development of a rapid and effective non-destructive testing strategy to identify brominated flame retardants in the plastics of consumer products

Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants (BFRs) once extensively used in the plastics of a wide range of consumer products. The listing of certain congeners that are constituents of commercial PBDE mixtures (including c-octaBDE) in the Stockholm Convention and tightening regulation of many other BFRs in recent years have created the need for a rapid and effective method of identifying BFR-containing plastics. A three-tiered testing strategy comparing results from non-destructive testing (X-ray fluorescence (XRF)) (n = 1714), a surface wipe test (n = 137) and destructive chemical analysis (n = 48) was undertaken to systematically identify BFRs in a wide range of consumer products. XRF rapidly identified bromine in 92% of products later confirmed to contain BFRs. Surface wipes of products identified tetrabromobisphenol A (TBBPA), c-octaBDE congeners and BDE-209 with relatively high accuracy (> 75%) when confirmed by destructive chemical analysis. A relationship between the amounts of BFRs detected in surface wipes and subsequent destructive testing shows promise in predicting not only the types of BFRs present but also estimating the concentrations present. Information about the types of products that may contain persistent BFRs will assist regulators in implementing policies to further reduce the occurrence of these chemicals in consumer products.

Open and closed-loop recycling of textile and apparel products

Textile waste is a significant contributor to landfill yet the majority of textiles can be recycled, allowing for the energy and fibre to be reclaimed. This chapter examines the open-loop and closed loop recycling of textile products with particular reference to the fashion and apparel context. It describes the fibres used within apparel, the current mechanical and chemical methods for textile recycling, LCA findings for each method, and applications within apparel for each. Barriers for more effective recycling include ease of integration into existing textile and apparel design methods as well as coordinated collection of post-consumer waste. The chapter concludes with a discussion of innovations that point to future trends in both open-loop and closed-loop recycling within the apparel industry.

Reducing Browning of Fresh-cut ‘Maha’ Carambola with Chemical Additives and Low-oxygen Atmospheres

The greatest attraction to using carambola (Averrhoa carambola L.) in the fresh-cut market is the star shape that the fruit presents after a transverse cut. Carambola is well-suited for minimal processing, but cut surface browning is a main cause of deterioration. This problem is exacerbated as a result of mechanical injuries occurring during processing and is mainly induced by the leakage of phenolic compounds from the vacuole and subsequent oxidation by polyphenol oxidase (PPO) (Augustin et al., 1985). The use of browning inhibitors in processed fruits is restricted to compounds that are non-toxic, ‘wholesome’, and that do not adversely affect taste and flavour (Gil et al., 1998). In the past, browning was mainly controlled by the action of sulphites, but the use of this compound has declined due to allergic reactions in asthmatics (Weller et al., 1995). The shelf life of fresh-cut products may be extended by a combination of oxygen exclusion and the use of enzymatic browning inhibitors. The objectives of this work were to determine the effects of: (1) post-cutting chemical treatments of ascorbic, citric, oxalic acids, and EDTA-Ca; (2) atmospheric modification; and (3) combinations of the above, on the shelf life of carambola slices based on appearance, colour and polyphenol oxidase activity

Chemical synthesis and structure elucidation of bovine K-casein (1-44)

The caseins (αs1, αs2, β, and κ) are phosphoproteins present in bovine milk that have been studied for over a century and whose structures remain obscure. Here we describe the chemical synthesis and structure elucidation of the N-terminal segment (1–44) of bovine κ-casein, the protein which maintains the micellar structure of the caseins. κ-Casein (1–44) was synthesised by highly optimised Boc solid-phase peptide chemistry and characterised by mass spectrometry. Structure elucidation was carried out by circular dichroism and nuclear magnetic resonance spectroscopy. CD analysis demonstrated that the segment was ill defined in aqueous medium but in 30% trifluoroethanol it exhibited considerable helical structure. Further, NMR analysis showed the presence of a helical segment containing 26 residues which extends from Pro8 to Arg34. This is the first report which demonstrates extensive secondary structure within the casein class of proteins.

Chemical aspects of the hypergolic preignition reactions of some hybrid hypergols

A new class of solid compounds, viz., bisthiocarbonohydrazones and thiosemicarbazones, have been found to be hypergolic with fuming nitric acid. The observed ignition delays of these hypergols have been compared with those of the monothiocarbonohydrazones-nitric acid systems and explained in terms of the chemical reactions-neutralization, oxidation, and nitration-occurring in the preignition stage. p-Nitrobenzoic acid, benzoic acid, benzaldehyde, sulfur trioxide, nitrogen dioxide, and nitrogen have been isolated as preignition reaction intermediates in the mono- and bisbenzaldehydethiocarbonohydrazone-nitric acid systems. A scheme of reactions occurring in the preignition stage is proposed based on the formation of these products.

Biorefineries – creating economic opportunities from biofuels and bio-products

Biorefineries, producing fuels, green chemicals and bio-products, offer great potential for improving the profitability and sustainability of tropical agricultural industries. Biomass from tropical crops like sugarcane, sweet sorghum, palm and cassava offer great potential because of the high biomass growth potential under favourable climatic conditions. Biorefineries aim to convert waste residues through biochemical and enzymatic processes to low cost fermentable sugars which are a platform for value-adding. Through subsequent fermentation utilising microbial biotechnologies or chemical synthesis, the sugars can be converted to fuels including ethanol and butanol, oils, organic acids such as lactic and levulinic acid and polymer precursors. Other biorefinery products can include food and animal feeds, plastics, fibre products and resins. Pretreatment technologies are a key to unlocking this potential and new technologies are emerging. This paper will address the opportunities available for tropical biorefineries to contribute to the future profitability of tropical agricultural industries. The importance of pretreatment technologies will be discussed.

Chemical phytotoxicity testing facility for warm-season turfgrasses

The registration of new agricultural chemicals (particularly herbicides) for turf use requires supporting data on their possible phytotoxic effects across a representative range of turfgrass species and cultivars. This process has been streamlined by the establishment of dedicated phytotoxicity testing site. This facility has enabled phytotoxicity screening of new chemicals to be conducted more quickly, thoroughly and economically than the previous piecemeal ad hoc approach. During the three years of this project, 39 products were screened on the site.

Physio-chemical assessment of beauty leaf (Calophyllum inophyllum) as second-generation biodiesel feedstock

Recently, second-generation (non-vegetable oil) feedstocks for biodiesel production are receiving significant attention due to the cost and social effects connected with utilising food products for the production of energy products. The Beauty leaf tree (Calophyllum inophyllum) is a potential source of non-edible oil for producing second-generation biodiesel because of its suitability for production in an extensive variety of atmospheric condition, easy cultivation, high fruit production rate, and the high oil content in the seed. In this study, oil was extracted from Beauty leaf tree seeds through three different oil extraction methods. The important physical and chemical properties of these extracted Beauty leaf oils were experimentally analysed and compared with other commercially available vegetable oils. Biodiesel was produced using a two-stage esterification process combining of an acid catalysed pre-esterification process and an alkali catalysed transesterification process. Fatty acid methyl ester (FAME) profiles and important physicochemical properties were experimentally measured and estimated using equations based on the FAME analysis. The quality of Beauty leaf biodiesels was assessed and compared with commercially available biodiesels through multivariate data analysis using PROMETHEE-GAIA software. The results show that mechanical extraction using a screw press produces oil at a low cost, however, results in low oil yields compared with chemical oil extraction. High pressure and temperature in the extraction process increase oil extraction performance. On the contrary, this process increases the free fatty acid content in the oil. A clear difference was found in the physical properties of Beauty leaf oils, which eventually affected the oil to biodiesel conversion process. However, Beauty leaf oils methyl esters (biodiesel) were very consistent physicochemical properties and able to meet almost all indicators of biodiesel standards. Overall this study found that Beauty leaf is a suitable feedstock for producing second-generation biodiesel in commercial scale. Therefore, the findings of this study are expected to serve as the basis for further development of Beauty leaf as a feedstock for industrial scale second-generation biodiesel production.

Commercial products from bio-active extractives in cypress milling residues.

Extractive components obtained from milling residues of white cypress were studied for chemical identity and bioactivity with a view to developing a commercial use for these components, thus increasing the value of the residues and improving the economics of cypress sawn wood production. Extracts obtained by solvent or steam extraction techniques from cypress sawdust were each fractionated by a range of techniques into groups of similar compounds. Crude extracts and fractions were screened against a range of agricultural pests and diseases, including two fungi, subterranean termites, fruit spotting bugs, two-spotted mites, thrips, heliothis, banana scab moths, silverleaf whiteflies, cattle tick adults and larvae, and ruminant gastrointestinal nematodes. Additional screening was undertaken where encouraging results were achieved, for two-spotted mites, thrips, silverleaf whiteflies, cattle tick adults and ruminant gastrointestinal nematodes. After considering degrees of efficacy against, and economic importance of, the agricultural pests, and likely production costs of extracts and fractions, the crude extract (oil) produced by steam distillation was chosen for further study against silverleaf whitefly. A useful degree of control was achievable when this oil was applied to tomato or eggplant at 0.1%, with much less harmful effects on a beneficial insect. Activity of the oil against silverleaf whitefly was undiminished 3.5 years after it was generated. There was little benefit from supplementing the extract with co-formulated paraffinic oil. From the steam distilled oil, fifty-five compounds were characterised, thirty-five compounds representing 92.478 % of the oil, with guaiol (20.8%) and citronellic acid (15.9%) most abundant. These two compounds, and a group of oxygenated compounds containing bulnesol and a range of eudesmols, were found to account for most of the activity against silverleaf whitefly. This application was recommended for first progression to commercialisation.

Weed age affects chemical control of Conyza bonariensis in fallows

In the last decade, Conyza bonariensis has become a widespread and difficult-to-control weed in Australian broad-acre cropping, particularly in glyphosate-based zero-tilled fallows of the subtropical grain region. The first Australian populations of C. bonariensis, where it is known as flaxleaf fleabane, were confirmed resistant to glyphosate in 2010. Control with alternative herbicides in fallows has been inconsistent, with earlier research indicating that weed age could be a potential contributing factor. In two field experiments, the impact of weed age (one, two and three months) was measured on the efficacy of six non-selective herbicide mixtures and sequential applications for control in fallows. In another two experiments we evaluated 11 non-selective herbicides, mixtures and sequential applications applied to one and three month old weeds using higher rates on older weeds. When herbicide rates were consistent for different weed ages, efficacy was reduced only by an average of 1% when two month old weeds were treated compared to one month old weeds. However when applied to three month old weeds, efficacy of treatments was significantly (P < 0.001) reduced by 3-30%. When herbicide rates were increased, weed age had no adverse effect on efficacy, which ranged from 90 to 100%, for amitrole, glyphosate mixed with 2,4-D amine plus picloram, and three sequential application treatments of glyphosate mixtures followed with bipyridyl products. Thus, this problem weed can be controlled effectively and consistently at the rosette stage of one to two months old, or three month old weeds with several different treatments at robust rates. These effective glyphosate alternatives and sequential-application tactics will minimise replenishment of the soil seed-bank and further reduce the risk for further evolution of glyphosate resistance. (C) 2012 Elsevier Ltd. All rights reserved.

Tracking and identifying wastewater toxicants and assessing their biodegradation products

Screening of wastewater effluents from municipal and industrial wastewater treatment plants with biotests showed that the treated wastewater effluents possess only minor acute toxic properties towards whole organisms (e.g. bacteria, algae, daphnia), if any. In vitro tests (sub-mitochondrial membranes and fish hepatocytes) were generally more susceptible to the effluents. Most of the effluents indicated the presence of hormonally active compounds, as the production of vitellogenin, an egg yolk precursor protein, was induced in fish hepatocytes exposed to wastewater. In addition, indications of slight genotoxic potential was found in one effluent concentrate with a recombinant bacteria test. Reverse electron transport (RET) of mitochondrial membranes was used as a model test to conduct effluent assessment followed by toxicant characterisations and identifications. Using a modified U.S. EPA Toxicity Identification Evaluation Phase I scheme and additional case-specific methods, the main compound in a pulp and paper mill effluent causing RET inhibition was characterised to be an organic, relatively hydrophilic high molecular weight (HMW) compound. The toxicant could be verified as HMW lignin by structural analyses using nuclear magnetic resonance. In the confirmation step commercial and in-house extracted lignin products were used. The possible toxicity related structures were characterised by statistical analysis of the chemical breakdown structures of laboratory-scale pulping and bleaching effluents and the toxicities of these effluents. Finally, the biological degradation of the identified toxicant and other wastewater constituents was evaluated using bioassays in combination with chemical analyses. Biological methods have not been used routinely in establishing effluent discharge limits in Finland. However, the biological effects observed in this study could not have been predicted using only routine physical and chemical effluent monitoring parameters. Therefore chemical parameters cannot be considered to be sufficient in controlling effluent discharges especially in case of unknown, possibly bioaccumulative, compounds that may be present in small concentrations and may cause chronic effects.

Novel Oxidation of Pyridoxal in Ternary Metal Complexes. An X-Ray Study of the Products

Attempts to prepare ternary metal complexes of pyridoxylidene-amino acid Schiff bases culminated in the oxidation of pyridoxal to pyridoxic acid or to its lactone and their complex formation, as evidenced from an X-ray study.

Biology and Management of Psocids Infesting Stored Products

Previously regarded as minor nuisance pests, psocids belonging to the genus Liposcelis now pose a major problem for the effective protection of stored products worldwide. Here we examine the apparent biological and operational reasons behind this phenomenon and why conventional pest management seems to be failing. We investigate what is known about the biology, behavior, and population dynamics of major pest species to ascertain their strengths, and perhaps find weaknesses, as a basis for a rational pest management strategy. We outline the contribution of molecular techniques to clarifying species identification and understanding genetic diversity. We discuss progress in sampling and trapping and our comprehension of spatial distribution of these pests as a foundation for developing management strategies. The effectiveness of various chemical treatments and the availability and potential of nonchemical control methods are critically examined. Finally, we identify research gaps and suggest future directions for research.

Syntheses of the trans,meso- and racemic C11 acids, degradation products of diterpene acids

Syntheses of the isomers of the C11 acid, 1(a),3(a)- dimethylcyclohexane-1 (e),2(e),3(e)-tricarboxylic acid (A) and 1(a),3(e)-dimethylcyclohexane-1(e),2(e),3(a)-tricarboxylic acid (B), the latter by two different routes, are reported. Two of the four possible isomers of the precursor triester, trimethyl 1-methylcyclohexane-1,2,3-tricarboxylate, on individual methylation followed by hydrolysis, gave the trans,meso-acid (A), identified by comparison with an authentic sample, and the cis,trans-form (B) whose structure and configuration were proved by comparison with a specimen obtained by the unambiguous and highly stereoselective second synthesis. This demonstrated that methylation of the triester isomers occurs stereospecifically and exclusively at C-3. In the second sequence, it has been possible to assign definite conformations to four key intermediates and the final product, directly from n.m.r. spectra, from changes in these spectra accompanying specific steps, and from chemical evidence. Comparison of the n.m.r. spectra of the isomeric triesters (A) and (B) has provided unequivocal proof of the accepted trans,meso configuration for the abietic acid degradation product (A).