Physical and oxidative stability of pre-emulsified oil bodies extracted from soybeans

Soybeans contain oil bodies that are coated by a layer of oleosin proteins. In nature, this protein coating protects the oil bodies from environmental stresses and might be utilised by food manufacturers for the same purpose. In this study, an aqueous extraction method was developed to increase the yield of oil bodies extracted from soybean. This method involved a two-step procedure: (i) blending, dispersion, and filtration of soybeans; (ii) homogenisation, suspension, and centrifugation of the filter cake. Using this extraction method about 65% of the oil bodies could be obtained. The mean particle diameter (d₄₃) and sedimentation of the resulting oil bodies increased during storage, suggesting they were prone to aggregation. Heat treatment (90 °C, 30 min) of the oil body suspensions immediately after extraction improved their storage stability, which was attributed to deactivation of endogenous enzymes such as lipase and lipoxygenase. Heat treatment did not adversely affect the oxidative stability of the oil body suspensions at pH 3 or 7 during storage at 37 °C. These results suggest that this aqueous extraction method can be used to prepare oil body suspensions with improved long-term stability.     

Microstructure and elastic modulus of mixed gels of gelatin + oxidized starch: Effect of pH

The microstructure and elastic shear modulus of cold-set gels formed from high-sugar aqueous mixtures of gelatin (7 wt%) + oxidized starch (0-6 wt%) were investigated as a function of pH. Samples prepared at 90 °C, with citric acid added to adjust the pH, were rapidly quenched to ∼1 °C, subjected to a standard thermal treatment (40 °C for 10 min), and then investigated by confocal microscopy and small-deformation rheology at 24 °C. Under ‘natural’ conditions of pH ≈ 5.2 (no citric acid addition), the samples exhibited phase separation with a characteristic spinodal-type morphology. The spatial extent of the structural heterogeneity, expressed by a single length-scale parameter, was found to increase with starch concentration. Gradual acidification led to a reduction in this length-scale parameter, leading to complete inhibition of phase separation below a certain characteristic pH value in the range 4.5-4.9 (depending on starch content). Over the investigated pH range, the effect of starch addition was to reduce the storage modulus of the resulting gel. This reduction was more pronounced for the phase-separated samples. The pH of maximum rigidity was found to decrease from pH_max ≈ 4.6 for 0 wt% starch to pH_max ≈ 4.2 for 6 wt% starch. Taken all together, these observations can be understood in terms of the effects of pH on the cross-linking behaviour of the gelatin and the nature of the gelatin-starch electrostatic interactions. The microscopy results are consistent with a transition in behaviour from thermodynamic incompatibility (segregative interactions) at high pH to soluble complexation (associative interactions) at low pH.     

Measurements of isoprene-derived organosulfates in ambient aerosols by aerosol time-of-flight mass spectrometry - part 1: single particle atmospheric observations in Atlanta

Organosulfate species have recently been identified as a potentially significant class of secondary organic aerosol (SOA) species, yet little is known about their behavior in the atmosphere. In this work, organosulfates were observed in individual ambient aerosols using single particle mass spectrometry in Atlanta, GA during the 2002 Aerosol Nucleation and Characterization Experiment (ANARChE) and the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS). Organosulfates derived from biogenically produced isoprene were detected as deprotonated molecular ions in negative-ion spectra measured by aerosol time-of-flight mass spectrometry; comparison to high-resolution mass spectrometry data obtained from filter samples corroborated the peak assignments. The size-resolved chemical composition measurements revealed that organosulfate species were mostly detected in submicrometer aerosols and across a range of aerosols from different sources, consistent with secondary reaction products. Detection of organosulfates in a large fraction of negative-ion ambient spectra - ca. 90-95% during ANARChE and ~65% of submicrometer particles in AMIGAS - highlights the ubiquity of organosulfate species in the ambient aerosols of biogenically influenced urban environments.     

Stability, bioavailability, and bacterial toxicity of ZnO and iron-doped ZnO nanoparticles in aquatic media

The stability and bioavailability of nanoparticles is governed by the interfacial properties that nanoparticles acquire when immersed in a particular aquatic media as well as the type of organism or cell under consideration. Herein, high-throughput screening (HTS) was used to elucidate ZnO nanoparticle stability, bioavailability, and antibacterial mechanisms as a function of iron doping level (in the ZnO nanoparticles), aquatic chemistry, and bacterial cell type. ζ-Potential and aggregation state of dispersed ZnO nanoparticles was strongly influenced by iron doping in addition to electrolyte composition and dissolved organic matter; however, bacterial inactivation by ZnO nanoparticles was most significantly influenced by Zn(2+) ions dissolution, cell type, and organic matter. Nanoparticle IC(50) values determined for Bacillus subtilis and Escherichia coli were on the order of 0.3-0.5 and 15-43 mg/L (as Zn(2+)), while the IC(50) for Zn(2+) tolerant Pseudomonas putida was always >500 mg/L. Tannic acid decreased toxicity of ZnO nanoparticles more than humic, fulvic, and alginic acid, because it complexed the most free Zn(2+) ions, thereby reducing their bioavailability. These results underscore the complexities and challenges regulators face in assessing potential environmental impacts of nanotechnology; however, the high-throughput and combinatorial methods employed promise to rapidly expand the knowledge base needed to develop an appropriate risk assessment framework.     

Evaluation of passive samplers for assessment of community exposure to toxic air contaminants and related pollutants

The precision, accuracy, and sampling rates of Radiello and Ogawa passive samplers were evaluated in the laboratory using a flow-through chamber and under field conditions prior to their use in the 2007 Harbor Community Monitoring Study (HCMS), a saturation monitoring campaign in the communities adjacent to the Ports of Los Angeles and Long Beach. Passive methods included Radiello samplers for volatile organic compounds (benzene, toluene, ethylbenzene, xylenes, 1,3-butadiene), aldehydes (formaldehyde, acetaldehyde, acrolein) and hydrogen sulfide, and Ogawa samplers for nitrogen oxides and sulfur dioxide. Additional experiments were conducted to study the robustness of the passive sampling methods under variable ambient wind speed, sampling duration, and storage time before analysis. Our experimentally determined sampling rates were in agreement with the rates published by Radiello and Ogawa with the following exceptions: we observed a diffusion rate of 22.4 ± 0.1 mL/min for benzene and 37.4 ± 1.5 mL/min for ethylbenzene compared to the Radiello published values of 27.8 and 25.7 mL/min, respectively. With few exceptions, the passive monitoring methods measured one-week average ambient concentrations of selected pollutants with sensitivity and precision comparable to conventional monitoring methods averaged over the same period. Radiello Carbograph 4 VOC sampler is not suitable for the collection of 1,3-butadiene due to backdiffusion. Results for the Radiello aldehyde sampler were inconclusive due to lack of reliable reference methods for all carbonyl compounds of interest.     

Kinetic analysis of cooking losses from beef and other animal muscles heated in a water bath--effect of sample dimensions and prior freezing and ageing

Cooking loss kinetics were measured on cubes and parallelepipeds of beef Semimembranosus muscle ranging from 1 cm × 1 cm × 1 cm to 7 cm × 7 cm × 28 cm in size. The samples were water bath-heated at three different temperatures, i.e. 50°C, 70°C and 90°C, and for five different times. Temperatures were simulated to help interpret the results. Pre-freezing the sample, difference in ageing time, and in muscle fiber orientation had little influence on cooking losses. At longer treatment times, the effects of sample size disappeared and cooking losses depended only on the temperature. A selection of the tests was repeated on four other beef muscles and on veal, horse and lamb Semimembranosus muscle. Kinetics followed similar curves in all cases but resulted in different final water contents. The shape of the kinetics curves suggests first-order kinetics.     

Combined speciation analysis by X-ray absorption near-edge structure spectroscopy, ion chromatography, and solid-phase microextraction gas chromatography-mass spectrometry to evaluate biotreatment of concentrated selenium wastewaters

In this study we evaluate the potential of anaerobic granular sludge as an inoculum for the bioremediation of selenium-contaminated waters using species-specific analytical methods. Solid species formed by microbial reduction were investigated using X-ray absorption near-edge structure (XANES) spectroscopy at the selenium K-edge. Furthermore, dissolved selenium species were specifically determined by ion chromatography (IC) and solid-phase microextraction gas chromatography-mass spectrometry (SPME-GC-MS). Least-squares linear combination of the XANES spectra for samples incubated with the highest selenate/selenite concentrations (10(-3) M) show the predominance of elemental selenium and a Se(-I) selenide, such as ferroselite, the thermodynamically most stable iron selenide. In contrast, elemental selenium and Se(-II) selenides are the main species detected at the lower selenate/selenite concentrations. In each repeated fed batch incubation, most aqueous selenite anions were converted into solid selenium species, regardless of the type of electron donor used (acetate or H(2)/CO(2)) and the selenium concentration applied. On the other hand, at higher concentrations of selenate (10(-4) and 10(-3) M), significant amounts of the oxyanion remained unconverted after consecutive incubations. SPME-GC-MS demonstrated selenium alkylation with both electron donors investigated, as dimethyl selenide (DMSe) and dimethyl diselenide (DMDSe). Selenite was even more alkylated in the presence of H(2)/CO(2) (maximum 2156 μg of Se/L of DMSe + DMDSe) as compared to acetate (maximum 50 μg of Se/L). In contrast, selenate was less alkylated using both electron donors (maximum 166 and 3 μg of Se/L, respectively). The high alkylation potential for selenite limits its bioremediation in selenium laden waters involving H(2)/CO(2) as the electron donor despite the fact that nontoxic elemental selenium and thermodynamically stable metal selenide species are formed.     

Bioaccumulation, biotransformation, and biochemical effects of brominated diphenyl ethers in juvenile lake trout (Salvelinus namaycush)

Juvenile lake trout (Salvelinus namaycush) were exposed to three dietary concentrations (0, approximately 2.5, and approximately 25 ng/g per BDE congener) of 13 BDE congeners (3-10 Br atoms) in the laboratory for 56 days, followed by 112 days of clean food, to examine bioaccumulation parameters and potential biochemical effects. The bioaccumulation of BDEs by the trout was highly influenced by biotransformation, via debromination, which resulted in bioaccumulation parameters that were much different than would be expected based on studies of chlorinated organic compounds (e.g., PCBs). Half-lives (t1/2's) for some BDE congeners (e.g., BDE-85 and -190) were much lower than expected based on their Kow, which was likely due to biotransformation, whereas t1/2's of other BDE congeners (e.g., BDE-66, -77, -153, and -154) were much longer than anticipated based on Kow. This was likely because the metabolites of BDE formed via debromination had the same chemical structure of these BDE congeners, which supplemented measured concentrations. The detection of three BDE congeners (an unknown penta, BDE-140, and an unknown hexa) in the fish that were not present in the food or in the control fish provide further evidence forthe debromination of BDEs. Half-lives of BDEs ranged from 38 +/- 9 to 346 +/- 173 days and biomagnification factors ranged from 1.6 (BDE-190) to 45.9 (BDE-100), but these bioaccumulation parameters need to be viewed with caution because they were highly influenced by debromination and relative abundance of individual BDEs that the fish were exposed to. CYP1A enzyme activity, measured as EROD, and free tri-iodothyronine (T3) concentrations in the plasma of lake trout varied significantly throughout the experiment but were not related to BDE exposure. In contrast, plasma levels of thyroxine levels (T4) were lower in both groups of PBDE-exposed fish compared with control fish after 56 days of exposure, and after 168 days in the high dose, suggesting that PBDEs may influence thyroid homeostasis at levels that are higher than what is normally found in the environment.     

Indoor and outdoor polycyclic aromatic hydrocarbons in residences surrounding a Söderberg aluminum smelter in Canada

Ambient air in 18 residences surrounding an aluminum smelter were sampled to study the relationship between indoor and outdoor polycyclic aromatic hydrocarbons (PAHs). Objectives of the study were to quantify the indoor distribution of PAHs, indoor/outdoor (I/O) concentration ratios, and the relationship among PAH compounds. Correlation coefficients inside residences suggested an indoor source of 2-3 ring PAHs and an external source of 4-6 ring PAHs. The I/O ratios of 4-6 ring PAHs for homes without any substantial indoor sources were below unity, indicating that the presence of these PAHs was attributable to the aluminum smelter. Least squares linear regression of the coupled measurements without indoor sources of 5-6 ring PAHs resulted in average infiltration efficiencies (P(PAH)) of 0.49, 0.20, and 0.47 for benzo[a]pyrene, benzo[k]fluoranthene, and benzo[g,h,i]perylene, respectively. These P(PAH) values suggest that simultaneous measurements of indoor and outdoor concentrations of PAHs > 4 rings predominantly associated with the fine fraction of particulate matter could provide useful estimates of particle infiltration efficiency. Overall, study results indicate that when an industrial facility is the main source of outdoor 4-6 ring PAHs, the contribution of facility emissions may greatly exceed indoor sources in nonsmoking residences.     

Effects of phosphate on uranium(VI) adsorption to goethite-coated sand

U(VI)-phosphate interactions are important in governing the subsurface mobility of U(VI) in both natural and contaminated environments. We studied U(VI) adsorption on goethite-coated sand (to mimic natural Fe-coated subsurface materials) as a function of pH in systems closed to the atmosphere, in both the presence and the absence of phosphate. Our results indicate that phosphate strongly affects U(VI) adsorption. The effect of phosphate on U(VI) adsorption was dependent on solution pH. At low pH, the adsorption of U(VI) increased in the presence of phosphate, and higher phosphate concentration caused a larger extent of increase in U(VI) adsorption. Phosphate was strongly bound by the goethite surface in the low pH range, and the increased adsorption of U(VI) at low pH was attributed to the formation of ternary surface complexes involving both U(VI) and phosphate. In the high pH range, the adsorption of U(VI) decreased in the presence of phosphate at low total Fe concentration, and higher phosphate concentration caused a larger extent of decrease in U(VI) adsorption. This decrease in U(VI) adsorption was attributed to the formation of soluble uranium-phosphate complexes. A surface complexation model (SCM) was proposed to describe the effect of phosphate on U(VI) adsorption to goethite. This proposed model was based on previous models that predict U(VI) adsorption to iron oxides in the absence of phosphate and previous models developed to predict phosphate adsorption on goethite. A postulated ternary surface complex of the form of (>FePO4UO2) was included in our model to account for the interactions between U(VI) and phosphate. The model we established can successfully predict U(VI) adsorption in the presence of phosphate under a range of conditions (i.e., pH, total phosphate concentration, and total Fe concentration).