Films Made by Blending Poly(ε-Caprolactone) with Starch and Flour from Sagu Rhizome Grown at the Venezuelan Amazons

Starch-based composite films have been proposed as food packaging. In this context, the study of non-conventional starch sources (sagu, Canna edulis Kerr) has worldwide special attention, because these materials can impart different properties as carbohydrate polymers. A thorough study of the matrices used (sagu starch and flour) was carried out. In the same way, thermoplastic starch (TPS)/PCL blend and thermoplastic flour (TFS)/PCL blend were obtained by melt mixing followed by compression moulding containing glycerol as plasticizer. In this study, chemical composition of the matrices and their properties were related with the properties of the developed films. Moisture content, water solubility, X-ray diffraction, thermogravimetric analysis and mechanical and microstructural properties were evaluated in the films. Taking into account the results, the sagu flour has great potential as starchy source for food packaging applications. However, concretely the flour had lower compatibility with the PCL compared to the starch/PCL blend.     

Spatial trends of polyfluorinated compounds in guillemot (Uria aalge) eggs from North-Western Europe

Polyfluorinated alkyl compounds (PFCs) are a group of chemicals of growing concern that have been detected in biological and abiotic samples worldwide. This study reports the concentrations of a suite of PFCs: perfluorooctyl sulfonate (PFOS), perfluorooctyl sulfonamide (PFOSA) and perfluorinated carboxylic acids (PFCAs) in guillemot (Uria aalge) eggs, collected in North-Western Europe, from Iceland, the Faroe Islands, Sweden and two locations in Norway. The highest concentrations of PFOS were found in samples from Sweden (mean 400 ng g(-1) wet weight (w.w.)), which were almost five times higher than concentrations found in Norwegian samples (mean 85 ng g(-1)w.w. from both sample sites). The concentrations found in Icelandic and Faroe samples were lowest (mean 16 and 15 ng g(-1)w.w., respectively). Only Swedish samples differed significantly from the other locations. In general, PFCAs show a different spatial trend than PFOS. Perfluorooctanoic acid (PFOA) was not detected in any sample and perfluorononanoic acid (PFNA) was only detected in samples from Sweden. The most abundant PFCA was perfluoroundecanoic acid (PFUA) with highest concentrations in samples from Sweden (mean 82 ng g(-1)w.w.), samples from the Faroe Islands had the second highest concentration (mean 57 ng g(-1)w.w.) and samples from Iceland and Norway had concentrations ranging between 18 and 30 ng g(-1)w.w. The original hypothesis was based on the idea that PFC concentrations are the highest close to more densely populated and industrialized areas and lower levels in remote areas. However, the geographic pattern is more complicated than predicted and varies among different PFCs.     

Structure characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane

1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) is used primarily as an additive flame retardant. 1H NMR spectroscopy and an X-ray structure determination have revealed that a technical mixture consists largely of two (of the four possible) diastereomers, rac-(1R,2R)-1,2-dibromo-(4S)-4-((1S)-1,2-dibromoethyl)cyclohexane (alpha-TBECH) and rac-(1R,2R)-1,2-dibromo-(4S)-4-((1R)-1,2-dibromoethyl)cyclohexane (beta-TBECH), in a mole ratio of approximately 1:1. The two other possible isomers, gamma- and delta-TBECH, were not detected in a technical mixture. The TBECH isomers are thermally sensitive and can easily interconvert at temperatures of 125 degrees C. A thermal equilibrium mixture of alpha-, beta-, gamma- and delta-TBECH consists of approximately 33%, 33%, 17% and 17% of these isomers, respectively. Separation of all four TBECH diastereomers, with minimal thermal interconversion of the isomers, was achieved by careful selection of GC-capillary column length and injector temperature. Although technical TBECH does not contain the gamma- and delta-isomers, they may still be relevant environmental contaminants since manufacturing processes utilize thermal processes which may induce their formation.     

Synthesis, isolation and purification of C10-C13 polychloro-n-alkanes for use as standards in environmental analysis

Short chain (C10-C13) polychloro-n-alkanes (sPCAs) mixtures were synthesized by refluxing pure n-alkane (> 99%) with sulfuryl chloride (SO2Cl2) in the presence of UV-light (550 W). The free radical initiated reactions produced analogs containing approximately 4-9 chlorine atoms on each carbon chain. Purification of reaction products was achieved by adsorption chromatography on Florisil. The products were characterized by high-resolution gas chromatography/mass spectrometry (HRGC/MS) operated in the electron capture negative ionization (ECNI) and in electron ionization (EI) modes. Individual standards can now be combined to create standards whose profiles resemble that of environmental samples. Quantification of a known amount of the newly synthesized sPCAs mixture, using an industrial formulation as an external standard, resulted in an overestimation (approximately 28%) in its true value.     

Structural characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2,5,6-tetrabromocyclooctane (TBCO)

1,2,5,6-Tetrabromocyclooctane (TBCO) is a commercial brominated flame retardant that is employed mainly as an additive in textiles, paints and plastics. Very little is known about its presence or behavior in the environment or its analysis. TBCO can exist as two diastereomers, the stereochemistries of which have not been previously reported. We have named the first eluting isomer, under HPLC conditions, as alpha-TBCO (α-TBCO) and the later eluting isomer as beta-TBCO (β-TBCO) when using an Acquity UPLC BEH C₁₈ column with methanol/acetonitrile/water as the mobile phase. The structural elucidation of these two isomers was accomplished by ¹H NMR spectroscopy, GC/MS, LC/MS and X-ray structure determinations. α-TBCO is (1R,2R,5S,6S)-1,2,5,6-tetrabromocyclooctane and β-TBCO is rac-(1R,2R,5R,6R)-1,2,5,6-tetrabromocyclooctane. As with some other brominated cycloaliphatic compounds, TBCO is thermally labile and the isomers easily interconvert. A thermal equilibrium mixture of α- and β-TBCO consists of approximately 15% and 85% of these isomers, respectively. Separation of the two diastereomers, with minimal thermal interconversion between them, is achievable by careful selection of GC-capillary column length and injector temperature. LC/MS analyses of TBCO also presents an analytical challenge due to poor resolution of the isomers on chromatographic stationary phases, and weak intensity of molecular ions (or major fragment ions) when using LC-ESI/MS. Only bromide ions were seen in the mass spectra. APCI and APPI also failed to produce the molecular ion with sufficient intensity for identification.     

Synthesis of the two minor isomers, delta- and epsilon-1,2,5,6,9,10-hexabromocyclododecane, present in commercial hexabromocyclododecane

Hexabromocyclododecane (HBCD) is prepared commercially by bromination of cis,trans,trans-cyclododecatriene (ctt-CDT) and widely used as a flame retardant, particularly in polystyrene foams. Commercial HBCD consists largely of three diastereomers, alpha-, beta-, and gamma-HBCD, the structures of which have been known for many years. Recently, the presence in the mixture of small amounts of two minor diastereomers, delta- and epsilon-HBCD, has been reported. Bearing in mind the manner in which commercial HBCD is generated, it was anticipated that these components are probably formed by bromination of trans,trans,trans-cyclododecatriene (ttt-CDT), a common contaminant in commercial ctt-CDT. Indeed, when a sample of ttt-CDT was brominated it gave two products, the NMR spectra and LC/MS and GC/MS behaviour of which confirmed that they are identical to the minor components, delta- and epsilon-HBCD, present in commercial HBCD.     

Can biotransformation of BDE-209 in lake trout cause bioaccumulation of more toxic, lower-brominated PBDEs (BDE-47, -99) over the long term?

Much debate exists on the future direction of policy related to the deca-brominated diphenyl ethers (deca-BDE) mixture. This debate, in part, results from the fact that BDE-209 can debrominate to more toxic lower-polybrominated diphenyl ethers (PBDEs). However, such debromination is difficult to study using measured concentrations alone because of the short-term nature of laboratory experiments and the presence of lower-brominated congeners in the environment. Here, a rigorously calibrated, multichemical, dynamic fish model (Bhavsar et al. 2008, Environ. Sci. Technol., 42, 3724-3731) is used to predict the debromination of BDE-209 to more toxic lower-brominated PBDEs over a 15-year life period of piscivorous- and non-piscivorous lake trout (pLT, npLT; Salvelinus namaycush). A sensitivity analysis was performed by changing BDE-209 dietary dose, gut absorption efficiency and half-life for generally conservative scenarios. Estimated BDE-209, -99 and -47 concentrations were compared with human fish consumption guidelines developed using the draft U.S.EPA tolerable daily intakes. The model predicted that bioaccumulation of BDE-209 as well as BDE-47 and -99 due to dietary exposure to deca-BDE over the 15-year period would not be appreciable in pLT (generally unrestricted consumption advisory) and would be moderate in npLT (unrestricted to 2 meals/month advisory) even for worst-case scenarios.     

Active and Intelligent Films Made from Starchy Sources/Blackberry Pulp

Functional, active and intelligent films were prepared from biopolymeric matrices (plantain starch and pre-gelatinized plantain flour) with and without the addition of a natural filler (blackberry pulp) using the casting methodology. A thorough examination of the physicochemical, antioxidant and antimicrobial properties of the both the matrices used and the developed films was then carried out. The films developed from matrices incorporating the blackberry pulp were more amorphous, thicker, less sensitive to moisture, and with higher melting temperatures than the films made without this natural filler. The degree of substitution, average molecular weight and attenuated total reflectance Fourier transform infrared spectroscopy of the films made with blackberry pulp suggest that the starch chains were cross-linked. This is probably because the citric acid contained in the pulp functions as a cross-linking agent. Films with added blackberry pulp responded to changes in pH, i.e. were pH-sensitive, and also showed antimicrobial activity especially against Escherichia coli. In general, the addition of blackberry pulp improved the physicochemical and mechanical properties of the films developed due to cross-linking, as well as increasing their antioxidant activity.     

Distribution of hexabromocyclododecane in Detroit River suspended sediments

The distribution of hexabromocyclododecane (HBCD) isomers (alpha, beta and gamma) was determined in Detroit River suspended sediments using liquid chromatography tandem mass spectrometry (LC/MS/MS). Individual isomers of HBCD were measured at concentrations ranging from <0.025 to 1.9 ng/g (dry wt.) for the alpha-isomer, <0.025 to 0.28 ng/g for the beta-isomer, and <0.025 to 2.3 ng/g for the gamma-isomer. Concentrations of total HBCD ranged from <0.075 to 3.7 ng/g. Roughly two-thirds of HBCD profiles in suspended sediments were dominated by the gamma-isomer, and were similar to profiles of commercial technical mixtures. Profiles in the remaining samples were dominated by the alpha-isomer. The beta-isomer was consistently detected at substantially lower levels than the other isomers; this isomer is a minor constituent in the commercial technical mixtures. Seasonal sampling showed significant shifts in the relative ratios of the HBCD isomers. The spatial distribution of HBCD in the Detroit River was similar to other persistent organic pollutants (e.g., PCBs), and showed a strong association with urban/industrial activities in the watershed. However, the highest HBCD concentrations (2.6-3.7 ng/g) were associated with areas of contemporary industrial activity, and were much lower than maximum concentrations of PCBs (2.2 microg/g) found in areas of the Detroit River associated with historical industrial activity.     

Direct measurement of octanol-water partition coefficients of some environmentally relevant brominated diphenyl ether congeners

Octanol-water partition coefficients (K(OW)) of nine environmentally relevant brominated diphenyl ether (BDE) congeners present in two technical mixtures were directly measured using a slow-stir technique. LogK(OW) values of tri- to heptabrominated BDE congeners ranged from 5.74 to 8.27, and were related to bromine content by the equation logK(OW)=0.621(#Br)+4.12(R(2)=0.970). The directly determined K(OW) values were generally lower than those calculated using fragment constant methods, particularly at higher levels of bromine substitution. The quasi-experimental approach of using fragment constants to modify a "backbone" compound of known K(OW) was much more successful than using the fragment constants to "build" the entire molecule. The tri- and tetrabrominated congeners are in the range of optimum bioaccumulation potential.