Diffusive exchange of PAHs across the air-water interface of the Kaohsiung Harbor lagoon, Taiwan.

Instantaneous air-water polycyclic aromatic hydrocarbons (PAHs) exchange fluxes were calculated in 22 pairs of ambient air and water samples from Kaohsiung Harbor lagoon, from December 2003 to January 2005. The highest net volatilization (3135 ng m(-2) day(-1)) and absorptive (-1150 ng m(-2) day(-1)) fluxes in the present study were obtained for the three-ring PAH phenanthrene on 7 April and 27 January 2004, respectively. All PAH diffusive fluxes for three-ring PAHs except phenanthrene were mainly volatilization exchange across the air-water interface. Phenanthrene and the four-ring PAHs were absorbed primarily from the atmosphere and deposited to the surface water, although some minor volatilization fluxes were also observed. Differences in flux magnitude and direction between the dry and wet seasons were also evident for PAHs. Strong absorptive/weaker volatilization PAH fluxes occurred in the dry season, but the opposite was found in the wet season. The mean daily PAH diffusive fluxes were an in flux of -635 ng m(-2) day(-1) in the dry season and an efflux of 686 ng m(-2) day(-1) in the wet season. The integrated absorbed and emitted fluxes of PAHs for harbor lagoon surface waters in the dry and wet seasons were 3.1 kg and 3.4 kg, respectively. Different from water bodies located in temperate zone, phenanthrene diffusive fluxes in Kaohsiung Harbor lagoon was favored in volatilization from surface waters during the wet season (April to September) because of scavenging by precipitation and dilution by prevailing southwesterly winds. In addition, this study used both of salinity and temperature to improve estimation of Henry's law constants (H) of PAHs in a tropical coastal area and show that correction for salinity produced 13-15% of differences in H values.

A Case of a Thoracic Arteriovenous Fistula Between an Intercostal Artery and a Pulmonary Vein.

Arteriovenous (AV) fistulas are irregular connections between arteries and veins, and thoracic AV fistulas are rarely identified in clinical practice. We report a case of a 56-year-old female with a history of esophageal adenocarcinoma treated with radiation and resection who presented to the hospital due to hemoptysis. She underwent bronchoscopy revealing a tracheobronchial fistula, and esophagogastroduodenoscopy revealing active arterial bleed. Subsequent angiography uncovered an AV fistula between her right T8 intercostal artery and pulmonary vein with a pseudoaneurysm. She underwent coiling of her T8 and T9 intercostal arteries with resolution of her symptoms.

Early planetesimal melting from an age of 4.5662 Gyr for differentiated meteorites.

Long- and short-lived radioactive isotopes and their daughter products in meteorites are chronometers that can test models for Solar System formation. Differentiated meteorites come from parent bodies that were once molten and separated into metal cores and silicate mantles. Mineral ages for these meteorites, however, are typically younger than age constraints for planetesimal differentiation. Such young ages indicate that the energy required to melt their parent bodies could not have come from the most likely heat source-radioactive decay of short-lived nuclides ((26)Al and (60)Fe) injected from a nearby supernova-because these would have largely decayed by the time of melting. Here we report an age of 4.5662 +/- 0.0001 billion years (based on Pb-Pb dating) for basaltic angrites, which is only 1 Myr younger than the currently accepted minimum age of the Solar System and corresponds to a time when (26)Al and (60)Fe decay could have triggered planetesimal melting. Small (26)Mg excesses in bulk angrite samples confirm that (26)Al decay contributed to the melting of their parent body. These results indicate that the accretion of differentiated planetesimals pre-dated that of undifferentiated planetesimals, and reveals the minimum Solar System age to be 4.5695 +/- 0.0002 billion years.

Air toxics exposure from vehicle emissions at a U.S. border crossing: Buffalo Peace Bridge Study.

The Peace Bridge in Buffalo, New York, which spans the Niagara River at the east end of Lake Erie, is one of the busiest U.S. border crossings. The Peace Bridge plaza on the U.S. side is a complex of roads, customs inspection areas, passport control areas, and duty-free shops. On average 5000 heavy-duty diesel trucks and 20,000 passenger cars traverse the border daily, making the plaza area a potential "hot spot" for emissions from mobile sources. In a series of winter and summer field campaigns, we measured air pollutants, including many compounds considered by the U.S. Environmental Protection Agency (EPA*) as mobile-source air toxics (MSATs), at three fixed sampling sites: on the shore of Lake Erie, approximately 500 m upwind (under predominant wind conditions) of the Peace Bridge plaza; immediately downwind of (adjacent to) the plaza; and 500 m farther downwind, into the community of west Buffalo. Pollutants sampled were particulate matter (PM) < or = 10 microm (PM10) and < or = 2.5 microm (PM2.5) in aerodynamic diameter, elemental carbon (EC), 28 elements, 25 volatile organic compounds (VOCs) including 3 carbonyls, 52 polycyclic aromatic hydrocarbons (PAHs), and 29 nitrogenated polycyclic aromatic hydrocarbons (NPAHs). Spatial patterns of counts of ultrafine particles (UFPs, particles < 0.1 microm in aerodynamic diameter) and of particle-bound PAH (pPAH) concentrations were assessed by mobile monitoring in the neighborhood adjacent to the Peace Bridge plaza using portable instruments and Global Positioning System (GPS) tracking. The study was designed to assess differences in upwind and downwind concentrations of MSATs, in areas near the Peace Bridge plaza on the U.S. side of the border. The Buffalo Peace Bridge Study featured good access to monitoring locations proximate to the plaza and in the community, which are downwind with the dominant winds from the direction of Lake Erie and southern Ontario. Samples from the lakeside Great Lakes Center (GLC), which is upwind of the plaza with dominant winds, were used to characterize contaminants in regional air masses. On-site meteorologic measurements and hourly truck and car counts were used to assess the role of traffic on UFP counts and pPAH concentrations. The array of parallel and perpendicular residential streets adjacent to the plaza provided a grid on which to plot the spatial patterns of UFP counts and pPAH concentrations to determine the extent to which traffic emissions from the Peace Bridge plaza might extend into the neighboring community. For lake-wind conditions (southwest to northwest) 12-hour integrated daytime samples showed clear evidence that vehicle-related emissions at the Peace Bridge plaza were responsible for elevated downwind concentrations of PM2.5, EC, and benzene, toluene, ethylbenzene, and xylenes (BTEX), as well as 1,3-butadiene and styrene. The chlorinated VOCs and aldehydes were not differentially higher at the downwind site. Several metals (aluminum, calcium, iron, copper, and antimony) were two times higher at the site adjacent to the plaza as they were at the upwind GLC site on lake-wind sampling days. Other metals (beryllium, sodium, magnesium, potassium, titanium, manganese, cobalt, strontium, tin, cesium, and lanthanum) showed significant increases downwind as well. Sulfur, arsenic, selenium, and a few other elements appeared to be markers for regional transport as their upwind and downwind concentrations were correlated, with ratios near unity. Using positive matrix factorization (PMF), we identified the sources for PAHs at the three fixed sampling sites as regional, diesel, general vehicle, and asphalt volatilization. Diesel exhaust at the Peace Bridge plaza accounted for approximately 30% of the PAHs. The NPAH sources were identified as nitrate (NO3) radical reactions, diesel, and mixed sources. Diesel exhaust at the Peace Bridge plaza accounted for 18% of the NPAHs. Further evidence for the impact of the Peace Bridge plaza on local air quality was found when the differences in 10-minute average UFP counts and pPAH concentrations were calculated between pairs of sites and displayed by wind direction. With winds from approximately 160 degrees through 220 degrees, UFP counts adjacent to the plaza were 10,000 to 20,000 particles/cm3 higher than those upwind of the plaza. A similar pattern was displayed for pPAH concentrations adjacent to the plaza, which were between 10 and 20 ng/m3 higher than those at the upwind GLC site. Regression models showed better correlation with traffic variables for pPAHs than for UFPs. For pPAHs, truck counts and car counts had significant positive correlations, with similar magnitudes for the effects of trucks and cars, despite lower truck counts. Examining all traffic variables, including traffic counts and counts divided by wind speed, the multivariate regression analysis had an adjusted coefficient of determination (R2) of 0.34 for pPAHs, with all terms significant at P < 0.002. Study staff members traversed established routes in the neighborhood while carrying instruments to record continuous UFP and pPAH values. They also carried a GPS, which was used to provide location-specific time-stamped data. Analyses using a geographic information system (GIS) demonstrated that emissions at the Peace Bridge plaza, at times, affected ambient air quality over several blocks (a few hundred meters). Under lake-wind conditions, overall spatial patterns in UFP and pPAH levels were similar for summer and winter and for morning and afternoon sampling sessions. The Buffalo Peace Bridge Study demonstrated that a concentration of motor vehicles resulted in elevated levels of mobile-source-related emissions downwind, to distances of 300 m to 600 m. The study provides a unique data set to assess interrelationships among MSATs and to ascertain the impact of heavy-duty diesel vehicles on air quality.

Newly Diagnosed Idiopathic Thrombocytopenia Post COVID-19 Vaccine Administration.

A few individuals are believed to have developed immune thrombocytopenia (ITP) following the administration of the coronavirus disease 2019 (COVID-19) vaccine. This phenomenon has been reported in a few case reports and also in some recent news articles. In this report, we discuss a case of a 54-year-old Caucasian female who presented to the emergency room with life-threatening thrombocytopenia in the setting of de novo ITP following COVID-19 vaccine administration. Due to the relapsing nature of ITP, it is unclear if the patient has achieved complete remission of the disease.

Mg isotope evidence for contemporaneous formation of chondrules and refractory inclusions.

Primitive or undifferentiated meteorites (chondrites) date back to the origin of the Solar System, and thus preserve a record of the physical and chemical processes that occurred during the earliest evolution of the accretion disk surrounding the young Sun. The oldest Solar System materials present within these meteorites are millimetre- to centimetre-sized calcium-aluminium-rich inclusions (CAIs) and ferromagnesian silicate spherules (chondrules), which probably originated by thermal processing of pre-existing nebula solids. Chondrules are currently believed to have formed approximately 2-3 million years (Myr) after CAIs (refs 5-10)--a timescale inconsistent with the dynamical lifespan of small particles in the early Solar System. Here, we report the presence of excess (26)Mg resulting from in situ decay of the short-lived (26)Al nuclide in CAIs and chondrules from the Allende meteorite. Six CAIs define an isochron corresponding to an initial (26)Al/(27)Al ratio of (5.25 +/- 0.10) x 10(-5), and individual model ages with uncertainties as low as +/- 30,000 years, suggesting that these objects possibly formed over a period as short as 50,000 years. In contrast, the chondrules record a range of initial (26)Al/(27)Al ratios from (5.66 +/- 0.80) to (1.36 +/- 0.52) x 10(-5), indicating that Allende chondrule formation began contemporaneously with the formation of CAIs, and continued for at least 1.4 Myr. Chondrule formation processes recorded by Allende and other chondrites may have persisted for at least 2-3 Myr in the young Solar System.

Bioavailability of decabromodiphenyl ether to the marine polychaete Nereis virens.

The flame retardant decabromodiphenyl ether (BDE 209) accumulates in humans and terrestrial food webs, but few studies have reported the accumulation of BDE 209 in aquatic biota. To investigate the mechanisms controlling the bioavailability of BDE 209, a 28-d bioaccumulation experiment was conducted in which the marine polychaete worm Nereis virens was exposed to a decabromodiphenyl ether (deca-BDE) commercial mixture (>85% BDE 209) in spiked sediments, in spiked food, or in field sediments. Bioaccumulation from spiked substrate with maximum bioavailability demonstrated that BDE 209 accumulates in this species. Bioavailability depends on the exposure conditions, however, because BDE 209 in field sediments did not accumulate (<0.3 ng/g wet weight; 28-d biota-sediment accumulation factors [BSAFs] <0.001). When exposed to deca-BDE in spiked sediments also containing lower brominated congeners (a penta-BDE mixture), bioaccumulation of BDE 209 was 30 times lower than when exposed to deca-BDE alone. Selective accumulation of the lower brominated congeners supports their prevalence in higher trophic level species. The mechanisms responsible for limited accumulation of BDE 209 may involve characteristics of the sediment matrix and low transfer efficiency in the digestive fluid.

Assessment of PCB contamination, the potential for in situ microbial dechlorination and natural attenuation in an urban watershed at the East Coast of the United States.

Sediment contamination is a major environmental issue in many urban watersheds and coastal areas due to the potential toxic effects of contaminants on biota and human health. Characterizing and delineating areas of sediment contamination and toxicity are important goals of coastal resource management in terms of ecological and economical perspectives. Core and surficial sediment samples were collected from an industrialized urban watershed at the East Coast of the United Stated and analyzed to evaluate the PCB contamination profile and toxicity resulting from dioxin-like PCBs as well as reductive dechlorination potential of indigenous PCB halorespiring bacteria through dechlorination activity assays. To support the experimental results an anaerobic dechlorination model was applied to identify microbial dechlorination pathways. The total PCB concentration in core samples ranged from 3.9 to 225.6 ng/g·dry weight (dw) decreasing with depth compared to 353.2 to 1213.7 ng/g·dw in surficial samples. The results of this study indicated an increase in PCB contamination over the last century as the industrial activity intensified. The toxicity resulting from dioxin-like PCBs was reduced up to 94% in core samples via 21 pathways resulting from the dechlorination model. Dechlorination rates in surficial sediment were between 1.8 and 13.2 ·â€¯10-3 mol% PCB116/day, while lower rates occurred in the core sediment samples. Dechlorination was achieved mainly through meta followed by para dechlorination. However, the rarer ortho dechlorination was also observed. Detection of indigenous PCB dechlorinating bacteria in the sediments and reduction of toxicity indicated potential for natural attenuation when point and nonpoint source PCBs in the urban watershed are controlled and PCB loading reduced.

Seasonality of diffusive exchange of polychlorinated biphenyls and hexachlorobenzene across the air-sea interface of Kaohsiung Harbor, Taiwan.

Gaseous and dissolved concentrations of polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) were measured in the ambient air and water of Kaohsiung Harbor lagoon, Taiwan, from December 2003 to January 2005. During the rainy season (April to September), gaseous PCB and HCB concentrations were low due to both scavenging by precipitation and dilution by prevailing southwesterly winds blown from the atmosphere of the South China Sea. In contrast, trace precipitation and prevailing northeasterly winds during the dry season (October to March) resulted in higher gaseous PCB and HCB concentrations. Instantaneous air-water exchange fluxes of PCB homologues and HCB were calculated from 22 pairs of air and water samples from Kaohsiung Harbor lagoon. All net fluxes of PCB homologues and HCB in this study are from water to air (net volatilization). The highest net volatile flux observed was +172 ng m(-)(2) day(-1) (dichlorobiphenyls) in December, 2003 due to the high wind speed and high dissolved concentration. The PCB homologues and HCB fluxes were significantly governed by dissolved concentrations in Kaohsiung Harbor lagoon. For low molecular weight PCBs (LMW PCBs), their fluxes were also significantly correlated with wind speed. The net PCB and HCB fluxes suggest that the annual sums of 69 PCBs and HCB measured in this study were mainly volatile (57.4 x 10(3) and 28.3 x 10(3) ng m(-2) yr(-1), respectively) and estimated yearly, 1.5 kg and 0.76 kg of PCBs and HCB were emitted from the harbor lagoon surface waters to the ambient atmosphere. The average tPCB flux in this study was about one-tenth of tPCB fluxes seen in New York Harbor and in the Delaware River, which are reported to be greatly impacted by PCBs.

Accumulation and maternal transfer of polychlorinated biphenyls in snapping turtles of the upper Hudson River, New York, USA.

We conducted field studies over three years to assess body burdens and maternal transfer of polychlorinated biphenyls (PCBs) as well as indices of sexual dimorphism in snapping turtles (Chelydra serpentina) of the upper Hudson River (NY, USA.) We collected adult turtles in areas known to be contaminated with PCBs and in nearby reference areas for measurement of body size, precloacal length, and penis size. We analyzed PCB concentrations in eggs collected over three years and in whole blood from adults in one year. Total PCB concentrations (mean +/- standard error) in eggs were 2,800 +/- 520 and 59 +/- 5 ng/g wet weight in the contaminated area and the reference area, respectively. Eggs from the contaminated area were significantly enriched in tri-, penta-, and hepta-PCBs relative to the reference area. Blood from adults in the contaminated area averaged 475 +/- 200 and 125 +/- 34 ng/g wet weight for males and females, respectively. In the reference area, blood PCB concentrations were 7 +/- 3 and 4 +/- 1 ng/g wet weight for males and females, respectively. Significant positive relationships were found between carapace length and blood PCB concentration for both sexes in the contaminated area; however, only a marginal relationship was found between female carapace length and concentration of PCBs in their eggs. Our results suggest that PCB contamination of the upper Hudson River presents risks of establishing high body burdens and of maternal transfer of PCBs to eggs, although our measures of gross morphology revealed no discernable expression of abnormal sexual development or reproduction.

Composition and distribution of polycyclic aromatic hydrocarbons in the surface sediments from the Susquehanna River.

Polycyclic aromatic hydrocarbon (PAH) concentrations in 34 surface sediments along the Susquehanna River were investigated in 2000. The total concentrations of PAHs in the surface sediments of Lake Clarke, Lake Aldred, the upper Conowingo Reservoir, and the lower Conowingo Reservoir were 3.3+/-1.5 microg g-1 (n=9), 1.6+/-1.3 microg g-1 (n=4), 9.8+/-5.5 microg g-1 (n=7), and 4.0+/-1.2 microg g-1 (n=14), respectively. These represent the first comprehensive measurement of PAHs in Susquehanna River surface sediments. Overall, total PAH concentrations were relatively lower in Lake Aldred, which is more shallow and sloped, and significantly higher in the upper Conowingo Reservoir. The sediment PAH levels were related to river flow rates, which are indirectly correlated with the particle size of the surface sediments. Total PAH levels in all the studied sites were below the effects range median (ERM) of 44.8 microg g-1 with 38% (13 of the 34 sampling sites) exceeding the effects range low (ERL) of 4.02 microg g-1. Principal component analysis indicated that variations in the PAH compound patterns of each reservoir decreased from upstream to downstream, indicating that the surface sediments were mixed along the Susquehanna River. The PAH patterns in the lower Conowingo Reservoir sediments were a combination of those upstream sources. Source analysis using isomer ratios as indicators suggested that PAHs in the Susquehanna River surface sediment are derived from the combustion of fossil fuels such as coal and gasoline with coal as the major source of contaminants.

Sources and distribution of polycyclic aromatic hydrocarbons in the sediments of Kaoping River and submarine canyon system, Taiwan.

In this study, we measured and analyzed polycyclic aromatic hydrocarbons (PAHs) in surface sediment samples collected from the Kaoping river and submarine canyon (KPSC) system to determine the compositional patterns and characteristic distributions of PAH and to elucidate the transport and fate of these land-derived particles. Concentrations of total PAH (sum of 28 PAH compounds) ranged from 22.6 to 45,100 ngg(-1) dry weight (dw) and the highest concentrations were found in the sediments of Donggang Harbor. The ratio of perylene to sum of penta-aromatic PAH isomers (47-55%) was higher in off-shore stations, suggesting a diagenetic PAH source. Various isomeric ratios also indicated that combustion was a significant source of PAH to the sediment at stations located along the Kaoping river and the north-western shelf of the Kaoping estuary. However, in the south-eastern shelf and some canyon sites, petroleum-derived PAHs were a more significant source of these compounds. Principal component analysis and hierarchical cluster analysis suggest PAHs in the sediments from the north-western shelf, and river and canyon sediments might be a pyrogenic product of coal and diesel-burning vehicles, while those of the south-eastern shelf may be petrogenic. PAH concentrations and compositional patterns are effective tracers of particulate transport in KPSC system. The seaward transport of riverine particulates was found to be mostly directed to NW-shelf and/or canyon.

Development of suspect and non-target screening methods for detection of organic contaminants in highway runoff and fish tissue with high-resolution time-of-flight mass spectrometry.

Untreated urban stormwater runoff contributes to poor water quality in receiving waters. The ability to identify toxicants and other bioactive molecules responsible for observed adverse effects in a complex mixture of contaminants is critical to effective protection of ecosystem and human health, yet this is a challenging analytical task. The objective of this study was to develop analytical methods using liquid chromatography coupled to high-resolution quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) to detect organic contaminants in highway runoff and in runoff-exposed fish (adult coho salmon, Oncorhynchus kisutch). Processing of paired water and tissue samples facilitated contaminant prioritization and aided investigation of chemical bioavailability and uptake processes. Simple, minimal processing effort solid phase extraction (SPE) and elution procedures were optimized for water samples, and selective pressurized liquid extraction (SPLE) procedures were optimized for fish tissues. Extraction methods were compared by detection of non-target features and target compounds (e.g., quantity and peak area), while minimizing matrix interferences. Suspect screening techniques utilized in-house and commercial databases to prioritize high-risk detections for subsequent MS/MS characterization and identification efforts. Presumptive annotations were also screened with an in-house linear regression (log Kowvs. retention time) to exclude isobaric compounds. Examples of confirmed identifications (via reference standard comparison) in highway runoff include ethoprophos, prometon, DEET, caffeine, cotinine, 4(or 5)-methyl-1H-methylbenzotriazole, and acetanilide. Acetanilide was also detected in runoff-exposed fish gill and liver samples. Further characterization of highway runoff and fish tissues (14 and 19 compounds, respectively with tentative identification by MS/MS data) suggests that many novel or poorly characterized organic contaminants exist in urban stormwater runoff and exposed biota.

Toxicological effects of polychlorinated biphenyls (PCBs) on freshwater turtles in the United States.

Prediction of vertebrate health effects originating from persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) has remained a challenge for decades thus making the identification of bioindicators difficult. POPs are predominantly present in soil and sediment, where they adhere to particles due to their hydrophobic characteristics. Animals inhabiting soil and sediment can be exposed to PCBs via dermal exposure while others may obtain PCBs through contaminated trophic interaction. Freshwater turtles can serve as bioindicators due to their strong site fidelity, longevity and varied diet. Previous research observed the health effects of PCBs on turtles such as decreased bone mass, changed sexual development and decreased immune responses through studying both contaminated sites along with laboratory experimentation. Higher deformity rates in juveniles, increased mortality and slower growth have also been observed. Toxicological effects of PCBs vary between species of freshwater turtles and depend on the concertation and configuration of PCB congeners. Evaluation of ecotoxicological effects of PCBs in non-endangered turtles could provide important knowledge about the health effects of endangered turtle species thus inform the design of remediation strategies. In this review, the PCB presence in freshwater turtle habitats and the ecotoxicological effects were investigated with the aim of utilizing the health status to identify areas of focus for freshwater turtle conservation.

Evaluating Contaminants of Emerging Concern as tracers of wastewater from septic systems.

Bacterial and nutrient contamination from anthropogenic sources impacts fresh and marine waters, reducing water quality and restricting recreational and commercial activities. In many cases the source of this contamination is ambiguous, and a tracer or set of tracers linking contamination to source would be valuable. In this work, the effectiveness of utilizing a suite of Contaminants of Emerging Concern (CECs) as tracers of bacteria from human septic system effluent is investigated. Field sampling was performed at more than 20 locations over approximately 18 months and analyzed for a suite of CECs and fecal coliform bacteria. The sampling locations included seeps and small freshwater discharges to the shoreline. Sites were selected and grouped according to level of impact by septic systems as determined by previous field sampling programs. A subset of selected locations had been positively identified as being impacted by effluent from failing septic systems through dye testing. The CECs were selected based on their predominant use, their frequency of use, and putative fate and transport properties. In addition, two rounds of focused sampling were performed at selected sites to characterize short-term variations in CEC and fecal coliform concentrations, and to evaluate environmental persistence following source correction activities. The results indicate that a suite of common use compounds are suitable as generalized tracers of bacterial contamination from septic systems and that fate and transport properties are important in tracer selection. Highly recalcitrant or highly labile compounds likely follow different loss profiles in the subsurface compared to fecal bacteria and are not suitable tracers. The use of more than one tracer compound is recommended due to source variability of septic systems and to account for variations in the subsurface condition. In addition, concentrations of some CECs were measured in receiving waters at levels which suggested the potential for environmental harm, indicating that the possible risk presented from these sources warrants further investigation.

Determination and comparison of nitrated-polycyclic aromatic hydrocarbons measured in air and diesel particulate reference materials.

The National Institute of Standards and Technology has issued numerous environmental matrix standard reference materials (SRMs) for the measurement of polycyclic aromatic hydrocarbons; however, only one SRM (diesel particulate material) was issued with certified and reference values for four nitrated-polycyclic aromatic hydrocarbons (nitro-PAH). The objective of this study was to develop an improved analytical procedure to quantify 28 mononitro- and dinitro-PAHs, including numerous isomers, in air and diesel particulate SRMs. Two air particulate matrix SRMs, SRM 1649a Urban Dust and SRM 1648 Urban Particulate Matter, and fine particulate matter, collected from Baltimore MD for use as an "interim reference material" for the determination of organic contaminants, have been characterized for nitro-PAHs. Concentrations of nitro-PAHs in all three air particulate materials were at the ng/g level with the highest nitro-PAH concentration being 2-nitrofluoranthene (range between 246 and 340 ng/g). For the three diesel particulate-related SRMs, SRM 1650a Diesel Particulate Matter, SRM 1975 Diesel Particulate Extract, and SRM 2975 Diesel Particulate Matter (Industrial Fortlift), concentrations of nitro-PAHs were in the microg/g range, with 1-nitropyrene as the dominant nitro-PAH (range between 18 and 40 microg/g). Distinct nitro-PAH isomer patterns were present between the air and diesel particulate materials. These results will provide isomer identification and reference concentrations for a large number of nitro-PAHs in the existing diesel and air particulate SRMs. Published by Elsevier Science Ltd.

Dietary accumulation and metabolism of polybrominated diphenyl ethers by juvenile carp (Cyprinus carpio).

Polybrominated diphenyl ethers (PBDEs) are hydrophobic organic contaminants with properties and nomenclature similar to polychlorinated biphenyls (PCBs). While much information is available on the bioaccumulation and pharamcokinetics of PCBs, little information is available on PBDEs. In this study, juvenile carp were exposed to a diet spiked with a cocktail of four BDE congeners (2,4,4'-tribromoDE [BDE 28], 2,2',4,4'-tetrabromoDE [BDE 47], 2,2',4,4',5-pentabromoDE [BDE 99], and 2,2',4,4',5,5'hexabromoDE [BDE 153]) for 60 d followed by a 40-d depuration period. As a positive control, three PCB congeners with similar log K(ow), values (2,2',5,5'-tetrachlorobiphenyl [PCB 52], 2,2',4,4', 5,5'-hexachlorobiphenyl [PCB 153], and 2,2',3,4,4',5,5'-heptachlorobiphenyl [PCB 180]) were included in the cocktail to compare their assimilation and fate with the model BDE congeners. Concentrations of BDEs and PCBs were monitored in whole-fish tissues and liver tissues over the duration of the experiment. In addition, blood serum samples were taken and pooled among replicates to determine if any phenolic metabolites of BDE and PCBs were formed. Rapid assimilation of BDE 47 was observed relative to all other BDE and PCB congeners, whereas apparently no accumulation of BDE 99 occurred over the course of the experiment. Assimilation efficiencies for BDE 47 suggest that approximately 100% of the BDE 47 exposure was absorbed by carp tissues after 60 d. However, based on the time course of BDE 47 assimilation, it is improbable that all BDE 47 was assimilated; more likely, production of BDE 47 in carp tissues occurred as a result of debromination of higher-brominated compounds, possibly BDE 99. The net assimilation efficiencies of BDE 28 and BDE 153 were also apparently low (20 and 4%, respectively) relative to the three PCBs (40% assimilated) examined in this study. The low assimilation efficiency and high depuration rates for BDEs suggest a higher potential for biotransformation. While all three PCB compounds displayed very similar assimilation and depuration rates, three of the four BDE compounds displayed significantly different assimilation rates among BDE congeners and relative to the PCBs. This study suggests that BDEs have significantly different fate dynamics relative to PCBs in wild carp and likely other species of fish.

Seasonal and annual loads of hydrophobic organic contaminants from the Susquehanna River basin to the Chesapeake Bay.

Water from the Susquehanna River was collected and analyzed for polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyl (PCB) congeners to estimate seasonal and annual riverine loads to the Chesapeake Bay. Temporal variations in the chemical loads resulted from the large changes in the water flow rates and in the particle-associated contaminant concentrations. Concentrations of PCBs and PAHs in river particles (ng/g) were twice as great as those in the northern Chesapeake Bay, indicating that the Susquehanna River is an important source of these contaminants to the bay. The river carries a majority of its hydrophobic organic contaminants (HOCs) in the particulate phase. During periods of high flow, large amounts of suspended particles in the river result in elevated HOC levels and increased loadings of these contaminants to the bay. From 1997 to 1998, 60% of the total annual HOC loading occurred in the early spring coincident with high river flows. The total PCB and PAH annual loadings from the Susquehanna River to the Chesapeake Bay were 76 and 3160 kg/year, respectively and 75% of the loaded organic contaminants were in the particulate phase. Principal component analysis of PAH and PCB congener patterns in the particles reveals that the river suspended particles were dominated by autochthonous production in the summer and by resuspended sediment and watershed erosion during the winter and early spring.

Perfluorinated compounds in the surface waters of Puget Sound, Washington and Clayoquot and Barkley Sounds, British Columbia.

Perfluorinated compounds (PFCs) are persistent organic contaminants detected in various environmental matrices including sediment, air, biota, and water. The objectives of this study was to evaluate the occurrence of these contaminants within the surface waters of the Pacific Northwest region and through relative concentrations and ratios, to assess their possible sources. Surface waters were extracted and analyzed by liquid chromatography tandem mass spectrometry (LCMSMS). Perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were the most commonly detected PFCs. Total PFC concentrations detected ranged from 1.5 to 41 ng L-1. Surprisingly, levels of PFCs in the more urbanized Puget Sound waters were comparable to those measured from the more rural region of Clayoquot and Barkley Sounds in British Columbia. The ratio of PFHpA/PFOA were also similar between the two regions, suggesting that the burden of PFCs throughout the region results from direct input from regional sources.

Enhanced photovoltaic performance of perovskite CH3NH3PbI3 solar cells with freestanding TiO2 nanotube array films.

Freestanding TiO2 nanotube array films are fabricated and first applied as electrodes in perovskite CH3NH3PbI3 sensitized solar cells. The device demonstrates improved light absorption with more than 90% of light absorbed in the whole visible range and a reduced charge recombination rate, leading to a significant improvement of the photocurrent and efficiency. This study suggests a promising way of improving the conversion efficiency of perovskite solar cells through novel electrodes.