Modern and fossil contributions to polycyclic aromatic hydrocarbons in PM₂.₅ from North Birmingham, Alabama in the southeastern U.S

Analyzing the radiocarbon ((14)C) content of polycyclic aromatic hydrocarbons (PAHs) in atmospheric particulate matter can provide estimates on the source contributions from biomass burning versus fossil fuel. The relative importance of these two sources to ambient PAHs varies considerably across regions and even countries, and hence there is a pressing need to apportion these sources. In this study, we advanced the radiocarbon analysis from bulk carbon to compound class specific radiocarbon analysis (CCSRA) to determine Δ(14)C and δ(13)C values of PAHs in PM(2.5) samples for investigating biomass burning and fossil fuel source contributions to PAHs from one of the Southeastern Aerosol Research and Characterization (SEARCH) sites in North Birmingham (BHM), Alabama during winter (December 2004-February 2005) and summer (June-August 2005) by accelerator mass spectrometry. To compare our ambient samples to known sources, we collected and analyzed fenceline samples from the vicinity of a coke plant in BHM. As expected, PAHs from the coke plant fenceline samples had very low radiocarbon levels. Its Δ(14)C varied from -990 to -970‰, indicating that 97 to 99% were of fossil source. PAHs in the ambient PM(2.5) had Δ(14)C from -968 to -911 ‰, indicating that 92-97% of PAHs were from fossil fuel combustion. These levels indicated the dominance of fossil sources of ambient PAHs. The radiocarbon level of ambient PAHs was higher in winter than in summer. Winter samples exhibited depleted δ(13)C value and enriched Δ(14)C value because of the increased contribution of PAHs from biomass burning source. However, biomass burning contributed more to heavier PAHs (modern source accounting for 6-8%) than lighter ones with a modern contribution of 3%.     

Determination of polycyclic aromatic hydrocarbons in edible oils and barbecued food by HPLC/UV–Vis detection

Determination of nine polycyclic aromatic hydrocarbons in corn, sunflower, olive oils and barbecued meat and fish by HPLC/UV–Vis method is described. The extraction procedure included a saponification, liquid–liquid extraction and finally purification of PAHs through a house-made silica–alumina column. Chromatographic determination was based on separation of PAHs on ODS column and measurement at 254 nm. All polycyclic aromatic hydrocarbons were separated and analyzed in 12 min on reversed phase ODS column with acetonitrile/water mobile phase at 1.5 mL min⁻¹ flow rate. The detection limits of nine polycyclic aromatic hydrocarbons ranged from 0.26 to 1.15 μg L⁻¹ at a signal/noise ratio of 3. The linearity of the method was between 0.9951 and 0.9996. Oil samples contain different PAHs ranging from 0.44 to 98.92 μg L⁻¹. Barbecuing process increased the concentration (in the range of 2- to 8-fold) and caused the formation of PAHs in food samples.     

Lowering of concentration of polycyclic aromatic hydrocarbons in liquid media by sorption into polyethylene terephtalate—a model study

Rapeseed oil and water were spiked with polycyclic aromatic hydrocarbon (PAH) solutions at the total levels of 955.1 and 711.4 g kg^–1, respectively, filled into polyethylene terephtalate (PET) cylindrical receptacles and the PAH concentrations in both liquid media followed for more than 90 h by HPLC. During this time, the PAH concentrations decreased by 315.1 in oil and 212.7 g kg^–1 in water due to an interaction of PAHs with PET. Using a modified kinetic equation, the diffusion coefficients for PAHs in both liquid media were determined. Values of the diffusion coefficients obtained indicate that the polarity of medium did not affect the rate of PAH removal. Calculation of the area occupied by a PAH molecule on the PET surface suggests that either the multilayer adsorption or the diffusion of PAHs into PET bulk came into account as the decisive factor bringing about the decrease of PAH concentrations in both media.     

Carbon isotope signature of polycyclic aromatic hydrocarbons (PAHs): evidence for different sources in tropical and temperate environments?

In tropical soils, naphthalene and, partly also, perylene occur at elevated concentrations while pyrolytic higher molecular weight PAHs are almost absent. We hypothesize that there are recent biological PAH sources in the tropical environment related with woody plants and termites. We used the C isotope signature of individual PAHs in temperate and tropical soils and in tropical wood and termite nests to distinguish different PAH sources. The mean delta13C values of the benzo[b+j+k]fluoranthenes and of benzo[a+e]pyrenes in temperate soils ranged between -24.6/1000 and -25.3/1000, being similar to values reported in the literature for PAHs with pyrolitic origin. The mean delta13C values of perylene decreased in the order temperate soils (-27.0/1000) > termite nests (-31.4/1000) > tropical soil (-32.4/1000), while those of naphthalene (-24.6/1000 to -26.2/1000) were similar among the tropical and temperate soils, tropical wood, and termite nests. Our results support the assumption that perylene in the tropical environment is recently biologically produced, as indicated by the depletion in 13C. The C isotope composition of naphthalene, however, cannot be used to distinguish different sources.     

Comparison of donor–acceptor and alumina columns for the clean-up of polycyclic aromatic hydrocarbons from edible oils

Two methods for clean-up and sample enrichment for the analysis of polycyclic aromatic hydrocarbons (PAHs) in edible oils are compared; a clean-up based on a donor–acceptor complex chromatography (DACC) column and a standardized method widely used in the food industry consisting in a low pressure column chromatography with alumina as stationary phase. Both methods are followed by a reversed-phase high-performance liquid chromatography with fluorescence detection for the separation and quantitation of each PAH. Certified materials were used in order to validate the methods. The limits of detection were lower than 1 ng/g and good selectivity was achieved in both cases. The DACC column clean-up is faster and better accuracies were obtained. The advantages and disadvantages of both methods are discussed.     

Influence of collagen and natural casings on the polycyclic aromatic hydrocarbons in traditional dry fermented sausage (Petrovská klobása) from Serbia

The aim of this study was to determine the content of polycyclic aromatic hydrocarbons—PAHs (acenaphthylene, anthracene, fluorene, phenanthrene, pyrene, benz[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, chrysene, indeno[1,2,3-cd]pyrene, dibenz[a,h]anthracene, and benzo[ghi]perylene)—from Environmental Protection Agency list (United States Environmental Protection Agency) in traditional dry fermented sausage (Petrovská klobása) stuffed in collagen (C) and natural casings (N). Benzo[a]pyrene as well as PAH4 (benz[a]anthracene, benzo[b]fluoranthene, benzo[a]pyrene, and chrysene) were not detected in all examined samples. Results obtained in this study indicated that at the end of drying, as well as at the end of storage period, total content of 13 US-EPA PAH was significantly (P < 0.05) lower in sausages with collagen casing (56.2 and 73.6 μg/kg, respectively) than in sausages with natural casing (137.1 and 206.2 μg/kg, respectively).     

Occurrence of 15 + 1 EU priority polycyclic aromatic hydrocarbons (PAH) in various types of tea (Camellia sinensis) and herbal infusions

For the analysis of 15 + 1 EU priority PAH in tea and herbal infusions, an online-SPE-LVI-GC-MS method was developed. This method includes sample extraction of the tea and herbal infusions with saponification followed by an automated SPE clean-up step. For brews a liquid–liquid extraction with cyclohexane was performed before an automated SPE clean-up. Gas chromatographic separation was done using an Agilent J&W Select PAH (15 m × 0.15 mm × 0.10 µm) column, which allows the separation of the three benzofluoranthenes as well as triphenylene from chrysene. Method performance criteria such as method linearity, limit of quantitation (LOQ) and repeatability were determined and demonstrated that the method was fit for purpose. The method was used to analyse 15 + 1 EU priority PAH in 91 tea and herbal infusion samples. The levels of PAHs ranged from below 0.5 (LOQ) to 460 µg kg^?1, with a median of 4.7 µg kg^?1 and a mean of 39 µg kg^?1 for BaP, and from below 1.0 (LOQ) to 2700 µg kg^?1, with a median of 39 µg kg^?1 and a mean of 250 µg kg^?1 for total PAH, which were in good agreement with other studies reported in the literature. For the brews prepared under normal house preparation (20 g material in 2 L boiling tap water for 10 min), no total 15 + 1 PAH could be detected above the LOQ. With an extended brewing time of 30 min, a transfer rate between 0.25% and 0.52% could be determined, which results in no exceeding of the maximum limits given by the European Union directive for drinking water (EU Council Directive 98/83/EC).     

The analysis of saturated and aromatic mineral oil hydrocarbons in dry foods and from recycled paperboard packages by online HPLC–GC–FID

ABSTRACT

The purpose of this study was to determine the concentrations of mineral oil hydrocarbons in dry foodstuffs packed in recycled paperboard, which were imported from different foreign countries to Germany. After collection, mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) in dry foodstuffs and recycled paperboard were analysed using online coupled high-performance liquid chromatography–gas chromatography–flame ionisation detection (online HPLC–GC–FID) far before the end of the shelf life of the samples. Our results showed that recycled paperboard has MOAH content higher than that of dry foodstuffs. The proportion of MOAH within total mineral oil hydrocarbons was determined to be 7–45% in dry foodstuffs and 4–48% in paperboard. In addition, 29% of the products were found to contain over 1.00 mg/kg MOAH, with a maximum of 2.72 mg/kg in oatmeal. White colour recycled paperboard contained lower amounts of MOSH and MOAH than that of brown and grey colour recycled paperboard. The MOSH concentration in dry foodstuffs ranged from 0.11 to 21.92 mg/kg (?C25 hydrocarbons), which may be an indication of rapid migration. The lowest determined MOSH concentrations (?C25 hydrocarbons) were found in sea salt and soda samples, even when their paperboard contained high mineral oil hydrocarbons. Our three samples in packages containing internal bags (for complete barriers) were found to have low mineral oil concentration due to reduced migration through plastic (acrylate-coated polypropylene). However, one sample, a ‘crispy’ product with an internal bag, contained the extreme amount of 21.92 mg/kg. Differences in contaminants observed in both dry foodstuffs and recycled paperboard may have been due to the different packaging and production techniques of the different countries. In addition, 8 of 24 dry foodstuff samples contained MOSH concentrations frequently exceeding the 2.0 mg/kg limit for MOSH C₂₀–C₃₅.     

Sources, vertical fluxes, and equivalent toxicity of aromatic hydrocarbons in coastal sediments of the Río de la Plata Estuary, Argentina

Settling particles and bottom sediments collected at 1, 2.5, and 4 km off the metropolitan Buenos Aires coast in the Río de la Plata were analyzed to evaluate the sources and toxicity of resolved (PAHs) and unresolved (AROUCM) aromatic hydrocarbons. PAHs (0003-2.1 microg g(-1)) and AROUCM (0.01-78 microg g(-1)) presented the highest concentrations nearthe Buenos Aires port and sewer and decreasing values up- and downstream and along on- and offshore gradients. Sediment traps deployed in the Central area revealed large aromatic fluxes (1.3 +/- 1.5 and 31 +/- 47 mg m(-2) day(-1) for PAHs and AROUCM). The composition of sedimentary PAHs was dominated by uniformly distributed high molecular weight pyrogenic PAHs (53 +/- 11% fluoranthene, pyrene, and heavier PAHs), followed by diagenetically derived perylene more abundant in less polluted sites (29 +/- 15%) and lower molecular weight petrogenic PAHs (18 +/- 7.1% phenanthrene, anthracene, and methylated compounds), which covaried inversely with perylene. PAH diagnostic ratios indicated a stronger influence of petrogenic discharges close to the shore and the prevalence of combustion of fossil fuels and vehicle emissions over wood in offshore sediments. Sediment cores showed sustained hydrocarbon levels with decreasing proportion of petrogenic PAHs and relative enrichment of pyrogenic components and perylene down to 20-cm depth. PAH toxicity assessment by sediment quality guidelines (SQG) and dioxin-equivalent factors (PAH TEQ: 0.08-395 pg g(-1) dw) identified 1-2.5 km sediments close to the port and sewer as the most affected area. According to SQG, dibenz[a,h]anthracene and pyrene were the most critical PAHs, followed by benzo[a]pyrene, benz[a]anthracene, and chrysene. In contrast, PAH TEQs were dominated by indeno[1,2,3-cd]pyrene, benzo[k]fluoranthene, benzo[a]pyrene, perylene, and benz[a]anthracene which accounted for an average 86 +/- 5.7% of total TEQs.     

Does participating in physical activity in outdoor natural environments have a greater effect on physical and mental wellbeing than physical activity indoors? A systematic review

Our objective was to compare the effects on mental and physical wellbeing, health related quality of life and long-term adherence to physical activity, of participation in physical activity in natural environments compared with physical activity indoors. We conducted a systematic review using the following data sources: Medline, Embase, Psychinfo, GreenFILE, SportDISCUS, The Cochrane Library, Science Citation Index Expanded, Social Sciences Citation Index, Arts and Humanities Citation Index, Conference Proceedings Citation Index--Science and BIOSIS from inception to June 2010. Internet searches of relevant Web sites, hand searches of relevant journals, and the reference lists of included papers and other review papers identified in the search were also searched for relevant information. Controlled trials (randomized and nonrandomized) were included. To be eligible trials had to compare the effects of outdoor exercise initiatives with those conducted indoors and report on at least one physical or mental wellbeing outcome in adults or children. Screening of articles for inclusion, data extraction, and quality appraisal were performed by one reviewer and checked by a second with discrepancies resolved by discussion with a third if necessary. Due to the heterogeneity of identified studies a narrative synthesis was performed. Eleven trials (833 adults) were included. Most participants (6 trials; 523 adults) were young students. Study entry criteria and methods were sparsely reported. All interventions consisted of a single episode of walking or running indoors with the same activity at a similar level conducted outdoors on a separate occasion. A total of 13 different outcome measures were used to evaluate the effects of exercise on mental wellbeing, and 4 outcome measures were used to assess attitude to exercise. Most trials (n = 9) showed some improvement in mental wellbeing on one or other of the outcome measures. Compared with exercising indoors, exercising in natural environments was associated with greater feelings of revitalization and positive engagement, decreases in tension, confusion, anger, and depression, and increased energy. However, the results suggested that feelings of calmness may be decreased following outdoor exercise. Participants reported greater enjoyment and satisfaction with outdoor activity and declared a greater intent to repeat the activity at a later date. None of the identified studies measured the effects of physical activity on physical wellbeing or the effect of natural environments on exercise adherence. The hypothesis that there are added beneficial effects to be gained from performing physical activity outdoors in natural environments is very appealing and has generated considerable interest. This review has shown some promising effects on self-reported mental wellbeing immediately following exercise in nature which are not seen following the same exercise indoors. However, the interpretation and extrapolation of these findings is hampered by the poor methodological quality of the available evidence and the heterogeneity of outcome measures employed. The review demonstrates the paucity of high quality evidence on which to base recommendations and reveals an undoubted need for further research in this area. Large, well designed, longer term trials in populations who might benefit most from the potential advantages of outdoor exercise are needed to fully elucidate the effects on mental and physical wellbeing. The influence of these effects on the sustainability of physical activity initiatives also awaits investigation.     

β-Conglycinin (7S) and glycinin (11S) exert a hypocholesterolemic effect comparable to that of fenofibrate in rats fed a high-cholesterol diet

The hypocholesterolemic effect of isolated soybean proteins and fenofibrate in rats was compared. Forty-five rats were divided into five groups: standard (STD; casein), high cholesterol (HC; STD plus 1% cholesterol/0.5% cholic acid), HC + β-conglycinin, HC + glycinin and HC + fenofibrate. The proteins and the drug were administered by gavage for 28 days. The proteins decreased total cholesterol (TC) and triacylglycerol (TG) in the plasma of the rats fed HC diet, to values very close to those fed on fenofibrate. High density lipoprotein cholesterol (HDL-C) levels in the plasma were increased by the β-conglycinin, glycinin and fenofibrate groups. The largest TC reduction in the liver was observed in the fenofibrate group; in contrast, the β-conglycinin and glycinin groups exhibited reduced the levels of hepatic TG and TC. Based on these data, it could be suggested that the oral daily administration of isolated soybean proteins, in the range of 2.75% of the protein ingested daily, can promote a reduction in TC and TG in the plasma of rats fed hypercholesterolemic diets.     

Monitoring and identification of bacteria associated with safety concerns in the manufacture of São Jorge, a Portuguese traditional cheese from raw cow's milk

The aim of this study was to assess the hygienic quality of raw milk used in the manufacture of S?o Jorge, a Protected Denomination of Origin Portuguese semihard cheese, as well as to ascertain the sanitary conditions prevailing during its processing. Viable counts of Enterobacteriaceae and Micrococcaceae were accordingly obtained, pertaining to 21 independent batches (including samples of raw milk, curd, and cheeses after 1, 3, and 4 months of ripening), from 7 dairy farms. Standard plate counts (log CFU per milliliter or per gram) ranged from 6.1 to 8.6 in raw milk, whereas they ranged from 7.0 to 8.0 in 4-month-old cheeses. Viable counts of Enterobacteriaceae ranged between 5.9 and 7.0 in raw milk and between 0.0 and 1.3 in 4-month-old cheeses. Species identified within this family encompassed Klebsiella oxytoca, Klebsiella cloacae, Klebsiella pneumoniae, Enterobacter sakazakii, and Escherichia coli; Klebsiella ornithinolytica, Klebsiella terrigena, and Serratia odorifera were detected only in raw milk. No Salmonella whatsoever could be detected in any of the samples. Viable counts of Micrococcaceae ranged between 4.7 and 5.9 and between 1.3 and 3.3 in raw milk and 4-month-old cheeses, respectively. Species identified within this family encompassed Staphylococcus sciuri, Staphylococcus epidermidis, Staphylococcus saprophyticus (which was found mainly in ripened cheeses), and Staphylococcus aureus (which was not detected in 4-month-old cheeses). Accompanying physicochemical analyses included determination of moisture, salt, and pH. Statistical analyses revealed a negative correlation between salt content and viable numbers of Enterobacteriaceae in cheese, whereas in the case of Micrococcaceae, a more negative correlation was found between viable numbers and moisture content than between viable numbers and pH. The results of our study indicate, in general, poor milk handling conditions in all farms, given that the indicators total mesophile and Enterobacteriaceae counts were high, between 100- and 1,000-fold those enforced by international standards pertaining to the matrices in question. However, by the time of regular consumption (i.e., after 4 months of ripening), S?o Jorge cheeses exhibit low levels of contamination by Enterobacteriaceae and S. aureus, as well as absence of Salmonella.     

Role of general stress-response alternative sigma factors σ(S) (RpoS) and σ(B) (SigB) in bacterial heat resistance as a function of treatment medium pH

This investigation aimed to determine the role of general stress-response alternative sigma factors σ^S (RpoS) and σ^B (SigB) in heat resistance and the occurrence of sublethal injuries in cell envelopes of stationary-phase Escherichia coli BJ4 and Listeria monocytogenes EGD-e cells, respectively, as a function of treatment medium pH. Given that microbial death followed first-order inactivation kinetics (R² > 0.95) the traditional D_T and z values were used to describe the heat inactivation kinetics.Influence of rpoS deletion was constant at every treatment temperature and pH, making a ΔrpoS deletion mutant strain approximately 5.5 times more heat sensitive than its parental strain for every studied condition. Furthermore, the influence of the pH of the treatment medium on the reduction of the heat resistance of E. coli was also constant and independent of the treatment temperature (average z value = 4.9 °C) in both parental and mutant strains.L. monocytogenes EGD-e z values obtained at pH 7.0 and 5.5 were not significantly different (p > 0.05) in either parental or the ?sigB deletion mutant strains (average z value = 4.8 °C). Nevertheless, at pH 4.0 the z value was higher (z = 8.4 °C), indicating that heat resistance of both L. monocytogenes strains was less dependent on temperature at pH 4.0. At both pH 5.5 and 7.0 the influence of sigB deletion was constant and independent of the treatment temperature, decreasing L. monocytogenes heat resistance approximately 2.5 times. In contrast, the absence of sigB did not decrease the heat resistance of L. monocytogenes at pH 4.0.The role of RpoS in protecting cell envelopes was more important in E. coli (4 times) than SigB in L. monocytogenes (1.5 times). Moreover, the role of σ^S in increasing heat resistance seems more relevant in enhancing the intrinsic resilience of the cytoplasmic membrane, and to a lesser extent, outer membrane resilience.Knowledge of environmental conditions related to the activation of alternative sigma factors σ^S and σ^B and their effects on heat resistance would help us to avoid and/or identify situations that increase bacterial stress resistance. Therefore, more efficient food preservation processes might be designed.