Direct Photocatalytic Synthesis of Acetic Acid from Methane and CO at Ambient Temperature Using Water as Oxidant.

Direct functionalization of methane selectively to value-added chemicals is still one of the main challenges in modern science. Acetic acid is an important industrial chemical produced nowadays by expensive and environmentally unfriendly carbonylation of methanol using homogeneous catalysts. Here, we report a new photocatalytic reaction route to synthesize acetic acid from CH4 and CO at room temperature using water as the sole external oxygen source. The optimized photocatalyst consists of a TiO2 support and ammonium phosphotungstic polyoxometalate (NPW) clusters anchored with isolated Pt single atoms (Pt1). It enables a stable synthesis of 5.7 mmol·L-1 acetic acid solution in 60 h with the selectivity over 90% and 66% to acetic acid on liquid-phase and carbon basis, respectively, with the production of 99 mol of acetic acid per mol of Pt. Combined isotopic and in situ spectroscopy investigation suggests that synthesis of acetic acid proceeds via a photocatalytic oxidative carbonylation of methane over the Pt1 sites, with the methane activation facilitated by water-derived hydroxyl radicals.

Graphene Nanoflake- and Carbon Nanotube-Supported Iron-Potassium 3D-Catalysts for Hydrocarbon Synthesis from Syngas.

Transformation of carbon oxides into valuable feedstocks is an important challenge nowadays. Carbon oxide hydrogenation to hydrocarbons over iron-based catalysts is one of the possible ways for this transformation to occur. Carbon supports effectively increase the dispersion of such catalysts but possess a very low bulk density, and their powders can be toxic. In this study, spark plasma sintering was used to synthesize new bulk and dense potassium promoted iron-based catalysts, supported on N-doped carbon nanomaterials, for hydrocarbon synthesis from syngas. The sintered catalysts showed high activity of up to 223 µmolCO/gFe/s at 300-340 °C and a selectivity to C5+ fraction of ~70% with a high portion of olefins. The promising catalyst performance was ascribed to the high dispersity of iron carbide particles, potassium promotion of iron carbide formation and stabilization of the active sites with nitrogen-based functionalities. As a result, a bulk N-doped carbon-supported iron catalyst with 3D structure was prepared, for the first time, by a fast method, and demonstrated high activity and selectivity in hydrocarbon synthesis. The proposed technique can be used to produce well-shaped carbon-supported catalysts for syngas conversion.

Light olefin synthesis from a diversity of renewable and fossil feedstocks: state-of the-art and outlook.

Light olefins are important feedstocks and platform molecules for the chemical industry. Their synthesis has been a research priority in both academia and industry. There are many different approaches to the synthesis of these compounds, which differ by the choice of raw materials, catalysts and reaction conditions. The goals of this review are to highlight the most recent trends in light olefin synthesis and to perform a comparative analysis of different synthetic routes using several quantitative characteristics: selectivity, productivity, severity of operating conditions, stability, technological maturity and sustainability. Traditionally, on an industrial scale, the cracking of oil fractions has been used to produce light olefins. Methanol-to-olefins, alkane direct or oxidative dehydrogenation technologies have great potential in the short term and have already reached scientific and technological maturities. Major progress should be made in the field of methanol-mediated CO and CO2 direct hydrogenation to light olefins. The electrocatalytic reduction of CO2 to light olefins is a very attractive process in the long run due to the low reaction temperature and possible use of sustainable electricity. The application of modern concepts such as electricity-driven process intensification, looping, CO2 management and nanoscale catalyst design should lead in the near future to more environmentally friendly, energy efficient and selective large-scale technologies for light olefin synthesis.

Formation of Polymer-Carbon Nanotube Composites by Two-Step Supercritical Fluid Treatment.

An approach for polymer-carbon nanotube (CNT) composite preparation is proposed based on a two-step supercritical fluid treatment. The first step, rapid expansion of a suspension (RESS) of CNTs in supercritical carbon dioxide, is used to de-bundle CNTs in order to simplify their mixing with polymer in solution. The ability of RESS pre-treatment to de-bundle CNTs and to cause significant bulk volume expansion is demonstrated. The second step is the formation of polymer-CNT composite from solution via supercritical antisolvent (SAS) precipitation. SAS treatment allows avoiding CNT agglomeration during transition from a solution into solid state due to the high speed of phase transition. The combination of these two supercritical fluid methods allowed obtaining a polycarbonate-multiwalled carbon nanotube composite with tensile strength two times higher compared to the initial polymer and enhanced elasticity.

Lactational exposure to polychlorinated biphenyls is higher in overweight /obese women and associated with altered infant growth trajectory: A pilot study.

BACKGROUND: Infant exposure to environmental chemicals, such as polychlorinated biphenyls (PCBs), may contribute to developmental programming of long-term metabolic disease risk. PCBs persist given their lipophilicity and long half-lives, allowing them to bio-accumulate in adipose tissue. These compounds can then be excreted into maternal milk resulting in infant exposure. OBJECTIVE: To determine the level of PCBs in milk from mothers with pre-pregnancy overweight and obese (OW/OB) versus normal weight status (NW) and evaluate the association of milk PCB levels with infant growth over the first 6 months of life. METHODS: A pilot study of a subset of milk samples from mothers with NW (pre-pregnancy body mass index (BMI) < 25 kg/m2, n = 11) and OW/OB (pre-pregnancy BMI ≥ 25 kg/m2, n = 8) were examined approximately 2-weeks postpartum. PCB congeners 138 + 163, 132 + 153, 180, and the sum were measured using gas chromatography/mass spectrometry and adjusted for milk fat content. Infant growth was monitored from birth to 6 months for weight-for-age (WFA), length-for-age (LFA), weight-for-length (WFL), head circumference-for-age (HCA), and associations with milk PCB content determined using linear mixed modeling. RESULTS: Total milk fat content did not differ by maternal weight status (p = 0.88). Milk from mothers with OW/OB had significantly higher PCB sum (p = 0.02) and PCB 138 + 163 (p = 0.03). PCB 132 + 153 (ß -0.0008, p = 0.0218), PCB 180 (ß -0.0010, p = 0.0279), and PCB sum (ß -0.0006, p = 0.0138) were negatively associated with HCA Z-score growth to 6 months. PCB 180 was negatively associated with infant WFA (ß -0.0015, p = 0.0058) and WFL Z-score (ß -0.0016, p = 0.0263) to 6 months. There were no associations of PCB sum content with WFL, LFA, WFL Z-score over the first 6 months of life. CONCLUSIONS: Maternal overweight and obesity are associated with higher levels of total PCB congeners (132, 138, 153, 163, 180) in human milk. PCB congeners have negative associations with infant head circumference and weight trajectory over the first 6 months of life.

Adsorption of water and n-hexane on pristine and oxidized carbon nanotube supports of cobalt-based Fischer-Tropsch catalysts.

Adsorption of model polar (water) and non-polar (n-hexane) compounds on the surface of oxidized and non-oxidized carbon nanotube (CNT) supports at different stages of Co/CNT catalyst preparation has been studied to reveal the influence of the surface functionalization of the CNT support on the catalyst selectivity in Fischer-Tropsch synthesis (FTS). Dynamic vapor sorption experiments showed that defunctionalization of the surface of the CNT support during catalyst annealing and reduction led to its hydrophobization and, as a result, no noticeable difference was observed between the adsorption properties of the oxidized and non-oxidized supports towards water and hydrocarbons. Therefore, oxidation of the CNT support does not significantly affect the adsorption properties of the supported catalyst and it is not a crucial factor for the catalyst selectivity in FTS.

Absence of PCB Hot Spot Effect in Walleye Sander vitreus from Lower Green Bay of Lake Michigan.

Under certain conditions, polychlorinated biphenyl (PCB) concentration in individuals of one sex of an adult fish population may exceed that of the other sex by more than a factor of two. This phenomenon, known as the PCB hot spot effect, has been postulated to be contingent upon the following two conditions: (1) presence of a PCB hot spot in the bottom sediments of the aquatic ecosystem, such that prey PCB concentrations in the hot spot region are substantially higher than prey PCB concentrations in locations distant from the hot spot, and (2) habitat use varying between the sexes, such that individuals of one sex inhabit the hot spot region to a considerably greater degree than individuals of the other sex. To test whether PCB concentrations in walleye Sander vitreus from lower Green Bay of Lake Michigan displayed a PCB hot spot effect, whole-fish PCB concentrations were determined in ten female and ten male adult walleye from the population spawning in the Fox River, the main tributary to lower Green Bay. In addition, mark-recapture data for the Fox River walleye population were analyzed to determine differences in spatial distributions between the sexes. Results revealed that the ratio of mean PCB concentration in males to mean PCB concentration in females was only 1.13, indicating the absence of a PCB hot spot effect. This result was corroborated by the mark-recapture data analysis, which showed no significant difference in habitat use between the sexes. Thus, although condition 1 was met, condition 2 was not met. Consequently, the PCB hot spot effect was not observed in the Fox River walleye population. Lack of a significant difference in PCB congener distributions between the sexes further corroborated our conclusions.

Kinetics of the defunctionalization of oxidized few-layer graphene nanoflakes.

Thermal defunctionalization of oxidized jellyfish-like few-layer graphene nanoflakes was studied under non-isothermal conditions by simultaneous thermal analysis. Activation energies for thermal decomposition of different oxygen functional groups were calculated by the Kissinger method and compared with those for oxidized carbon nanotubes. Oxygen content in graphene nanoflakes was found to significantly affect the decomposition activation energies of carboxylic and keto/hydroxy acids because of their acceptor properties and strong distortion of the graphene layers at the edges of the nanoflakes. The structure of the carbon material and the oxygen chemical state significantly influence the decomposition kinetics of thermally stable oxygen-containing groups. The activation energy for thermal decomposition of phenol groups (110-150 kJ mol-1) is close to that for graphene oxide reduction.

3D Frameworks with Variable Magnetic and Electrical Features from Sintered Cobalt-Modified Carbon Nanotubes.

3D frameworks of carbon nanotubes (CNTs) uniformly decorated by cobalt oxide or carbon-encapsulated cobalt nanoparticles were obtained by spark plasma sintering for the first time. The influence of the sintering temperature ( TS) and Co content on the morphology, structure, and electrical and magnetic properties of the obtained materials was investigated by Raman spectroscopy, electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and in situ magnetometry. It was shown that application of the SPS technique allowed simultaneous compaction of the material, formation of CNT framework, and Co oxide reduction. The appearance of the carbon shell around 4-10 nm Co particles was observed at TS > 600 °C. At higher TS, the Co particle size increased (up to 300 nm at 1400 °C), whereas the carbon shell ordered and thickened. The formation of large-size few-layers graphene sheets was observed at TS = 1400 °C. Electrical conductivity of the composites was found to be higher than that of sintered pristine CNTs and varied in the range of 500-12 500 Sm/m. Magnetic experiments demonstrated soft magnetization of the samples and the coercivity of 200-300 Oe. Thus, the obtained CNT-based material is simultaneously compact, formable, electroconductive, and ferromagnetic. Its properties can be tuned by variation of the sintering parameters. Synthesized cobalt-modified carbon 3D structures are promising for the application in magnetic separation, catalysis, fuel cells, and electromagnetic shielding.

Distributions of PCB Congeners and Homologues in White Sucker and Coho Salmon from Lake Michigan.

We tested the hypothesis of the proportion of higher chlorinated biphenyl (PCB) congeners increasing with increasing trophic level by comparing the respective PCB homologue distributions in an omnivore, white sucker ( Catostomus commersoni), and a top predator, coho salmon ( Oncorhynchus kisutch), from Lake Michigan. Adult females had the same congener and homologue proportions of total PCB concentration (ΣPCB) as adult males in both species. Hexachlorinated congeners comprised the largest proportion (32%) found in white sucker, followed by heptachlorinated (21%) and octochlorinated (18%) congeners. In contrast, pentachlorinated congeners comprised the largest proportion (33%) of ΣPCB found in coho salmon, followed by hexachlorinated (26%) and tetrachlorinated (24%) congeners. Coho salmon contained significantly higher proportions of tri-, tetra-, and pentachlorinated congeners, whereas white sucker contained significantly higher proportions of hexa- through decachlorinated congeners. Our results were opposite of the hypothesis of greater degree of PCB chlorination with increasing trophic level, and supported the contention that the PCB congener proportions in fish depends mainly on diet, and does not necessarily reflect the trophic level of the fish. Our results also supported the contention that diets do not vary between the sexes in most fish populations.

Oxidation, defunctionalization and catalyst life cycle of carbon nanotubes: a Raman spectroscopy view.

Pristine, oxidized and defunctionalized carbon nanotubes (CNTs) were studied by Raman spectroscopy, X-ray diffraction, transmission electron microscopy and low temperature nitrogen adsorption. The Raman spectra of the studied samples in the range of 900-1800 cm-1 were deconvoluted into five components to reveal the CNT oxidation mechanism. It was found that the oxidation resulted in the reduction of graphite components and ordering of both the structured and defect part of CNTs. Acid treatment also led to different types of disorders in the surface layers of CNTs. Polyene-type, polyphenylene-type and turbostratic fragments were detected as a result of partial exfoliation. Investigation of defunctionalized CNTs showed the ordering of edge carbon atoms as well as the invariability of the total amount of defects. The study of CNTs as supports for Co-based catalysts revealed a simultaneous decrease in the number of defect fragments and increase in the number of edge carbon atoms during catalyst preparation and reduction.

Sex differences in contaminant concentrations of fish: a synthesis.

A comparison of whole-fish polychlorinated biphenyl (PCB) and total mercury (Hg) concentrations in mature males with those in mature females may provide insights into sex differences in behavior, metabolism, and other physiological processes. In eight species of fish, we observed that males exceeded females in whole-fish PCB concentration by 17 to 43 %. Based on results from hypothesis testing, we concluded that these sex differences were most likely primarily driven by a higher rate of energy expenditure, stemming from higher resting metabolic rate (or standard metabolic rate (SMR)) and higher swimming activity, in males compared with females. A higher rate of energy expenditure led to a higher rate of food consumption, which, in turn, resulted in a higher rate of PCB accumulation. For two fish species, the growth dilution effect also made a substantial contribution to the sex difference in PCB concentrations, although the higher energy expenditure rate for males was still the primary driver. Hg concentration data were available for five of the eight species. For four of these five species, the ratio of PCB concentration in males to PCB concentration in females was substantially greater than the ratio of Hg concentration in males to Hg concentration in females. In sea lamprey (Petromyzon marinus), a very primitive fish, the two ratios were nearly identical. The most plausible explanation for this pattern was that certain androgens, such as testosterone and 11-ketotestosterone, enhanced Hg-elimination rate in males. In contrast, long-term elimination of PCBs is negligible for both sexes. According to this explanation, males not only ingest Hg at a higher rate than females but also eliminate Hg at a higher rate than females, in fish species other than sea lamprey. Male sea lamprey do not possess either of the above-specified androgens. These apparent sex differences in SMRs, activities, and Hg-elimination rates in teleost fishes may also apply, to some degree, to higher vertebrates including humans. Our synthesis findings will be useful in (1) developing sex-specific bioenergetics models for fish, (2) developing sex-specific risk assessment models for exposure of humans and wildlife to contaminants, and (3) refining Hg mass balance models for fish and higher vertebrates.

Hepatic polybrominated diphenyl ether (PBDE) levels in Wisconsin river otters (Lontra canadensis) and Michigan bald eagles (Haliaeetus leucocephalus).

Polybrominated diphenyl ethers (PBDEs) are persistent and toxic flame-retardant chemicals widespread in the Great Lakes ecosystem. These chemicals are now being regulated and phased-out of the region; therefore it remains important to understand the extent of contamination in order to track the efficacy of recent actions. Here, Σ4PBDE congeners (PBDE-47, 99, 100, 153;wetweight basis unless indicated)were determined in liver tissues from Wisconsin river otters (Lontra canadensis; n = 35; 2009-2010) and Michigan bald eagles (Haliaeetus leucocephalus; n = 33; 2009-2011). In otters, Σ4PBDE ranged from0.5 to 72.9 ng/g, with a mean (±SD) and median (25th-75th percentile inter-quartile range) of 16.3 ± 16.4 ng/g and 11.3 (5.6-18.9) ng/g, respectively. The mean lipid-adjusted Σ4PBDE was 1377 ± 1485 ng/g. In eagles, Σ4PBDE ranged from 0 to 1,538.8 ng/g, with a mean and median of 74.3 ± 266.7 ng/g and 21.2 (5.7-28.9) ng/g, respectively. The mean lipid-adjusted Σ4PBDE was 5274.5 ± 19,896.1 ng/g. In both species, PBDE-47 accounted for >50% of the Σ4PBDE, followed by PBDE-99 and PBDE-100 (each ~17-19% of the total). The PBDE levels reported here in otters are similar to mammalian wildlife elsewhere, though the levels in eagles are among the highest worldwide across studied birds. The findings indicate that apex Great Lakes wildlife remain exposed to appreciable levels of PBDEs and more work is needed to understand whether such exposures are associated with adverse health outcomes.

Effects of fuels, engine load and exhaust after-treatment on diesel engine SVOC emissions and development of SVOC profiles for receptor modeling.

Diesel exhaust emissions contain numerous semivolatile organic compounds (SVOCs) for which emission information is limited, especially for idling conditions, new fuels and the new after-treatment systems. This study investigates exhaust emissions of particulate matter (PM), polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), and sterane and hopane petroleum biomarkers from a heavy-duty (6.4 L) diesel engine at various loads (idle, 600 and 900 kPa BMEP), with three types of fuel (ultra-low sulfur diesel or ULSD, Swedish low aromatic diesel, and neat soybean biodiesel), and with and without a diesel oxidation catalyst (DOC) and diesel particulate filter (DPF). Swedish diesel and biodiesel reduced emissions of PM2.5, Σ15PAHs, Σ11NPAHs, Σ5Hopanes and Σ6Steranes, and biodiesel resulted in the larger reductions. However, idling emissions increased for benzo[k]fluoranthene (Swedish diesel), 5-nitroacenaphthene (biodiesel) and PM2.5 (biodiesel), a significant result given the attention to exposures from idling vehicles and the toxicity of high-molecular-weight PAHs and NPAHs. The DOC + DPF combination reduced PM2.5 and SVOC emissions during DPF loading (>99% reduction) and DPF regeneration (83-99%). The toxicity of diesel exhaust, in terms of the estimated carcinogenic risk, was greatly reduced using Swedish diesel, biodiesel fuels and the DOC + DPF. PAH profiles showed high abundances of three and four ring compounds as well as naphthalene; NPAH profiles were dominated by nitro-naphthalenes, 1-nitropyrene and 9-nitroanthracene. Both the emission rate and the composition of diesel exhaust depended strongly on fuel type, engine load and after-treatment system. The emissions data and chemical profiles presented are relevant to the development of emission inventories and exposure and risk assessments.

Performance and storage integrity of dried blood spots for PCB, BFR and pesticide measurements.

Dried blood spots (DBSs) can provide accurate and valuable estimates of exposure to environmental toxicants, and the use of information derived from archived newborn DBSs has enormous potential to open up new research on the impacts of early chemical exposure on disease. Broad application of DBS for the purpose of quantitative exposure estimation requires robust and validated methods. This study investigates the suitability of DBS analyses for population studies of exposure to three chemical groups: polychlorinated biphenyls (PCBs), brominated flame retardants (BFRs), and chlorinated pesticides. It examines background (matrix) contamination, recovery and extraction variability, sensitivity, and storage stability. DBS samples prepared using 50 µL of adult blood were analyzed by GC/MS, and method performance was confirmed by using certified materials and paired DBS-blood samples from six volunteers. Several of the target compounds and their degradation products have not been previously measured in DBSs. All target compounds were detected in DBS samples collected from the volunteers. Sample DBS cards showed background contamination of several compounds. When stored at room temperature, target compounds, excluding PBDEs, were stable for up to one month. When refrigerated or frozen, stability was acceptable for all compounds up to one year, and multiyear storage appears acceptable at colder (e.g., -80°C) temperatures. Multicompartment models may be used to estimate or correct for storage losses. Considering concentrations of contaminants for adults and children reported in the literature, and experimental values of detection limits and background contamination, DBS samples are suitable for quantifying exposures to many PCBs, BFRs and persistent pesticides.

Males exceed females in PCB concentrations of cisco (Coregonus artedi) from Lake Superior.

We determined whole-fish polychlorinated biphenyl (PCB) concentrations of 25 male and 25 female age-7 ciscoes (Coregonus artedi) captured from a spawning aggregation in Thunder Bay, Lake Superior, during November 2010. We also determined PCB concentrations in the ovaries and somatic tissue of five additional female ciscoes (ages 5-22). All 55 of these ciscoes were in ripe or nearly ripe condition. Bioenergetics modeling was used to determine the contribution of the growth dilution effect toward a difference in PCB concentrations between the sexes, as females grew substantially faster than males. Results showed that the PCB concentration of males (mean = 141 ng/g) was 43% greater than that of females (mean = 98 ng/g), and this difference was highly significant (P<0.0001). Mean PCB concentrations in the ovaries and the somatic tissue of the five females were 135 and 100 ng/g, respectively. Based on these PCB determinations for the ovaries and somatic tissue, we concluded that release of eggs by females at previous spawnings was not a contributing factor to the observed difference in PCB concentrations between the sexes. Bioenergetics modeling results indicated that the growth dilution effect could explain males being higher than females in PCB concentration by only 3-7%. We concluded that the higher PCB concentration in males was most likely due to higher rate of energy expenditure, originating from greater activity and a higher resting metabolic rate. Mean PCB concentration in the cisco eggs was well below the U. S. Food and Drug Administration and Ontario Ministry of Environment guidelines of 2000 and 844 ng/g, respectively, and this finding may have implications for the cisco roe fishery currently operating in Lake Superior.

PAHs (polycyclic aromatic hydrocarbons), nitro-PAHs, and hopane and sterane biomarkers in sediments of southern Lake Michigan, USA.

PAHs in the Great Lakes basin are of concern due to their toxicity and persistence in bottom sediments. Their nitro derivatives, nitro-PAHs (NPAHs), which can have stronger carcinogenic and mutagenic activity than parent PAHs, may follow similar transport routes and also are accumulated in sediments. Limited information exists regarding the current distribution, trends and loadings of these compounds, especially NPAHs, in Lake Michigan sediments. This study characterizes PAHs, NPAHs, and biomarkers steranes and hopanes in surface sediments collected at 24 offshore sites in southern Lake Michigan. The ΣPAH14 (sum of 14 compounds) ranged from 213 to 1,291 ng/g dry weight (dw) across the sites, levels that are 2 to 10 times lower than those reported 20 to 30 years earlier. Compared to consensus-based sediment quality guidelines, PAH concentrations suggest very low risk to benthic organisms. The ΣNPAH5 concentration ranged from 2.9 to 18.6 ng/g dw, and included carcinogenic compounds 1-nitropyrene and 6-nitrochrysene. ΣSterane6 and ΣHopane5 concentrations ranged from 6.2 to 36 and 98 to 355 ng/g dw, respectively. Based on these concentrations, Lake Michigan is approximately receiving 11, 0.16, 0.25 and 3.6 metrictons per year (t/yr) of ΣPAH14, ΣNPAH5, ΣSterane6 and ΣHopane5, respectively. Maps of OC-adjusted concentrations display that concentrations decline with increasing off-shore distance. The major sources of PAHs and NPAHs are pyrogenic in nature, based on diagnostic ratios. Using chemical mass balance models, sources were apportioned to emissions from diesel engines (56 ± 18%), coal power plants (27 ± 14%), coal-tar pavement sealants (16 ± 11%), and coke ovens (7 ± 12%). The biomarkers identify a combination of petrogenic and biogenic sources, with the southern end of the lake more impacted by petroleum. This first report of NPAH levels in sediments of Lake Michigan reveals several carcinogenic compounds at modest concentrations, and a need for further work to assess potential risks to aquatic organisms.

PAHs, nitro-PAHs, hopanes, and steranes in lake trout from Lake Michigan.

The present study examines concentrations and risks of polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), steranes, and hopanes in lake trout collected in Lake Michigan. A total of 74 fish were collected in 2 seasons at 3 offshore sites. The total PAH concentration (Σ9 PAH) in whole fish ranged from 223 pg/g to 1704 pg/g wet weight, and PAH concentrations and profiles were similar across season, site, and sex. The total NPAH (Σ9 NPAH) concentrations ranged from 0.2 pg/g to 31 pg/g wet weight, and carcinogenic compounds, including 1-nitropyrene and 6-nitrochrysene, were detected. In the fall, NPAH concentrations were low at the Illinois site (0.2-0.5 pg/g wet wt), and site profiles differed considerably; in the spring, concentrations and profiles were similar across sites, possibly reflecting changes in fish behavior. In the fall, the total sterane (Σ5 Sterane) and total hopane (Σ2 Hopane) levels reached 808 pg/g and 141 pg/g wet weight, respectively, but concentrations in the spring were 10 times lower. Concentrations in eggs (fall only) were on the same order of magnitude as those in whole fish. These results demonstrate the presence of target semivolatile organic compounds in a top predator fish, and are consistent with PAH biodilution observed previously. Using the available toxicity information for PAHs and NPAHs, the expected cancer risk from consumption of lake trout sampled are low. However, NPAHs contributed a significant portion of the toxic equivalencies in some samples. The present study provides the first measurements of NPAHs in freshwater fish, and results suggest that additional assessment is warranted.

Composition and Integrity of PAHs, Nitro-PAHs, Hopanes and Steranes In Diesel Exhaust Particulate Matter.

Diesel exhaust particulate matter contains many semivolatile organic compounds (SVOCs) of environmental and health significance. This study investigates the composition, emission rates, and integrity of 25 SVOCs, including polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), and diesel biomarkers hopanes and steranes. Diesel engine particulate matter (PM), generated using an engine test bench, three engine conditions, and ultra-low sulfur diesel (ULSD), was collected on borosilicate glass fiber filters. Under high engine load, the PM emission rate was 0.102 g/kWh, and emission rate of ΣPAHs (10 compounds), ΣNPAHs (6 compounds), Σhopanes (2 compounds), and Σsteranes (2 compounds) were 2.52, 0.351, 0.02 ~ 2 and 1µg/kWh, respectively. Storage losses were evaluated for three cases: conditioning filters in clean air at 25 °C and 33% relative humidity (RH) for 24 h; storing filter samples (without extraction) wrapped in aluminum foil at 4 °C for up to one month; and storing filter extracts in glass vials capped with Teflon crimp seals at 4 °C for up to six months. After conditioning filters for 24 h, 30% of the more volatile PAHs were lost, but lower volatility NPAHs, hopanes and steranes showed negligible changes. Storing wrapped filters and extracts at 4 °C for up to one month did not lead to significant losses, but storing extracts for five months led to significant losses of PAHs and NPAHs; hopanes and steranes demonstrated greater integrity. These results suggest that even relatively brief filter conditioning periods, needed for gravimetric measurements of PM mass, and extended storage of filter extracts can lead to underestimates of SVOC concentrations. Thus, SVOC sampling and analysis protocols should utilize stringent criteria and performance checks to identify and limit possible biases occurring during filter and extract processing.

Concentrations and speciation of polybrominated diphenyl ethers in human amniotic fluid.

Polybrominated diphenyl ethers (PBDEs) are persistent organic chemicals used as flame retardants in textiles, plastics, and consumer products. Although PBDE accumulation in humans has been noted since the 1970s, few studies have investigated PBDEs within the gestational compartment, and none to date has identified levels in amniotic fluid. The present study reports congener-specific brominated diphenyl ether (BDE) concentrations in second-trimester clinical amniotic fluid samples collected in 2009 from fifteen women in southeast Michigan, USA. Twenty-one BDE congeners were measured by GC/MS/NCI. The average total PBDE concentration was 3795 pg/ml amniotic fluid (range: 337-21,842 pg/ml). BDE-47 and BDE-99 were identified in all samples. Based on median concentrations, the dominant congeners were BDE-208, 209, 203, 206, 207, and 47 representing 23, 16, 12, 10, 9 and 6%, respectively, of the total detected PBDEs. PBDE concentrations were identified in all amniotic fluid samples from southeast Michigan, supporting a need for further investigations of fetal exposure pathways and potential impacts on perinatal health.