Temporal trends, congener patterns, and sources of octa-, nona-, and decabromodiphenyl ethers (PBDE) and hexabromocyclododecanes (HBCD) in Swiss lake sediments

With the recent ban of pentabromodiphenyl ether (technical PentaBDE) and octabromodiphenyl ether (technical OctaBDE) mixtures in the European Union (EU) and in parts of the United States, decabromodiphenyl ether (technical DecaBDE) remains as the only polybrominated diphenyl ether (PBDE) based flame retardant available, today. The EU risk assessment report for DecaBDE identified a high level of uncertainty associated with the suitability of the current risk assessment approach for secondary poisoning by debromination of DecaBDE to toxic lower brominated diphenylethers. Addressing this still open question, we investigated concentrations and temporal trends of DecaBDE, NonaBDE, and OctaBDE congeners in the sediments of Greifensee, a small lake located in an urban area close to Zürich, Switzerland. PBDE appeared first in sediment layers corresponding to the mid 1970s. While total Tri-HeptaBDE (BDE-28, -47, -99, -100, -153, -154 and -183) concentrations leveled off in the mid 1990s to about 1.6 ng/g dw (dry weight), DecaBDE levels increased steadily to 7.4 ng/g dw in 2001 with a doubling time of 9 years. Hexabromocyclododecanes (HBCD) appeared in Greifensee sediments in the mid 1980s. They are an important class of flame retardants that are being used in increasing amounts, today. As was observed for DecaBDE, HBCD concentrations were continuously increasing to reach 2.5 ng/g dw in 2001. Next to DecaBDE, all 3 NonaBDE congeners (BDE-208, BDE-207, and BDE-206) and at least 7 out of the 12 possible OctaBDE congeners (BDE-202, BDE-201, BDE-197/204, BDE-198/203, BDE-196/200, BDE-205, and BDE-194) were detected in the sediments of Greifensee. Highest concentrations were found in the surface sediments with 7.2, 0.26, 0.14, and 1.6 ng/g dw for Deca-, Nona-, Octa-, and the sum of Tri-HeptaBDE, respectively. While DecaBDE and NonaBDE were found to increase rapidly, the increase of OctaBDE was slower. Congener patterns of Octa- and NonaBDE present in sediments of Greifensee did not change with time. Consequently, there was no evidence for sediment mediated long-term transformation of PBDE within the observed time span of almost 30 years. Despite the high persistence of DecaBDE, environmental debromination occurs, as shown by the detection of a shift in congener patterns of Octa- and NonaBDE in sediments, compared to the respective congener patterns in technical PBDE products. The OctaBDE congener BDE-202 was detected in sediments, representing a transformation product that is not reported in any of the technical PBDE products. Comparison of OctaBDE congener patterns in sediments with OctaBDE congener patterns from known sources reveals that (i) they were distinctively different from the congener patterns in technical PBDE products and (ii) that they were similar to the OctaBDE patterns in house dust and photodegradation products of DecaBDE, suggesting contributions from these sources.     

Predicted secondary organic aerosol concentrations from the oxidation of isoprene in the eastern United States

Isoprene, the most abundant non-methane hydrocarbon emitted into the troposphere, has generally not been considered a major source of SOA due to the relatively high volatility of its oxidation products. In this study, the SOA formed from the oxidation of isoprene is predicted using a three-dimensional chemical transport model, PMCAMx, across the eastern U.S. for July, October, January, and April 2001-2002. The variability of the measured SOA yields in the available smog chamber studies is captured by combining the base case scenario with upper and lower bound estimates of the measurements. For the base case simulation, the predicted annual average isoprene SOA concentration in the southeast is 0.09 microg m(-3) (bounds 0.04-0.23 microg m(-3)). Isoprene is predicted to produce 70% less SOA across the entire domain for spring and fall than during the summer and negligible amounts of SOA during the winter. During the summer, the average concentrations in the northeast are predicted to be 0.11 microg m(-3) (bounds 0.04-0.31 microg m(-3)) and in the southeast 0.19 microg m(-3) (bounds 0.11 -0.58 microg m(-3)). PMCAMx predictions are compared to available measurements of some isoprene SOA components in North Carolina and New York State. These modeling results suggest that on an annual basis isoprene oxidation is a small but non-negligible organic aerosol source in the eastern U.S. Its contribution is relatively more important during the summer and in the southeast U.S.     

Concentrations and spatial variations of polybrominated diphenyl ethers and several organochlorine compounds in fishes from the northeastern United States

Fish from four lakes, two small lakes in the northeastern United States and two of the Great Lakes, were analyzed to determine the concentrations and spatial variations of polybrominated diphenyl ethers (PBDE) in this region. Three of the lakes were considered to have background levels of PBDEs; one lake was close to a suspected source. The PBDE concentrations were compared to organochlorine pesticide and PCB concentrations. Age and trophic position did not influence the organohalogen concentrations in the fish collected from the four locations. At the three background locations, the sum of PBDE concentrations ranged from 6.9 +/- 1.4 to 18 +/- 1 ng/g wet weight, or 150 +/- 9 to 300 +/- 80 ng/g lipid, and these values were similar to those of some of the organochlorine pesticides, such as total chlordane, but lower than sum of PCB concentrations. At the lake near the suspected source, the sum of PBDE concentration was 65 +/- 8 ng/g wet weight, or 2,400 +/- 600 ng/g lipid, and it exceeded the sum of PCB concentration. The hexabrominated congeners made up 43% of the total mass of PBDEs at this lake, and 7% at the background locations. Fish to sediment concentration ratios indicated that the tetra- through hexa-substituted congeners have a similar bioavailability, while the deca-substituted congener does not seem to be bioavailable at all.     

Hexabromocyclododecanes in indoor dust from Canada, the United Kingdom, and the United States

alpha-, beta-, and gamma-hexabromocyclododecane diastereomers (HBCDs) were measured in house dust from Birmingham, U.K. (n=31, median concentration=730 ng sigmaHBCDs g(-1)); Amarillo/Austin, TX (n=13, 390 ng g(-1)); and Toronto, Canada (n=8, 640 ng g(-1)). Concentrations in dust (n=6, 650 ng g(-1)) from U.K. offices were within the range for UK homes. Concentrations from each country were statistically indistinguishable. In one UK house dust sample, 110,000 ng g(-1) was recorded-the highest recorded in indoor dust to date. While upper bound average U.K. dietary exposures for adults and toddlers, respectively, are 413 and 240 ng sigmaHBCDs day(-1), U.K. adults and toddlers daily ingesting, respectively, 50 and 200 mg of dust contaminated at the 95th percentile concentration are exposed, respectively, to 1100 and 4400 ng sigmaHBCDs day(-1). Normalized to body weight, this high-end exposure scenario estimate for toddlers is within the range reported elsewhere for occupationally exposed adults. While in commercial formulations gamma-HBCD predominates (>80%), alpha-HBCD in dust constitutes 14-67% of sigmaHBCDs (average 32%). Hence the predominance of the alpha-diastereomer in humans may arise partly from dust ingestion, and not solely to in vivo metabolism (when alpha-HBCD is formed from bioisomerization of other diastereomers), or dietary exposure (where alpha-HBCD predominates in most foodstuffs).     

Atmospheric transport of toxaphene from the southern United States to the Great Lakes Region

Toxaphene was used extensively as an insecticide on cotton in the southern United States until its use was restricted in 1982. Toxaphene has been found in the water and fishes from the Great Lakes, and several authors have qualitatively linked this observation to atmospheric transport from the southern United States, although no detailed field study has been done to confirm this suggestion. We implemented a sampling network to measure the gas-phase concentrations of toxaphene near Lake Michigan at Sleeping Bear Dunes, MI; Bloomington, IN; Lubbock, TX; and Rohwer, AR. The toxaphene concentrations referenced to 288 K were 11 +/- 1, 25 +/- 1, 160 +/- 3, and 950 +/- 30 pg/ m3, respectively. We combined these concentration data with a nonparametric, backward trajectory, multiple regression model of the following form: ln(P) = a0 + a1/T + a2theta where P is the partial pressure of toxaphene (in atm) in a given sample, T is the atmospheric temperature at the sampling site during sampling (in degrees Kelvin), and theta is 0 if the backward trajectory comes from the north and 1 if the trajectory comes from the south. The parameters of this model were generally significant, giving a temperature coefficient (a1) corresponding to 45 +/- 8 kJ/mol and a positive directional coefficient (a2) of 0.6 +/- 0.2 (except for Texas, which was not significant). The positive sign and magnitude of the directional coefficient indicates that the sources of toxaphene are located south of the sampling sites. We also compared the chemical behavior of toxaphene in the atmosphere and found that the congener ratios were similar at the different sampling sites but slightly different from various toxaphene standards.     

Estimating ground-level PM2.5 in the eastern United States using satellite remote sensing

An empirical model based on the regression between daily PM2.5 (particles with aerodynamic diameters of less than 2.5 microm) concentrations and aerosol optical thickness (AOT) measurements from the multiangle imaging spectroradiometer (MISR) was developed and tested using data from the eastern United States during the period of 2001. Overall, the empirical model explained 48% of the variability in PM2.5 concentrations. The root-mean-square error of the model was 6.2 microg/m3 with a corresponding average PM2.5 concentration of 13.8 microg/m3. When PM2.5 concentrations greater than 40 microg/m3 were removed, model results were shown to be unbiased estimators of observations. Several factors, such as planetary boundary layer height, relative humidity, season, and other geographical attributes of monitoring sites, were found to influence the association between PM2.5 and AOT. The findings of this study illustrate the strong potential of satellite remote sensing in regional ambient air quality monitoring as an extension to ground networks. With the continual advancement of remote sensing technology and global data assimilation systems, AOT measurements derived from satellite remote sensors may provide a cost-effective approach as a supplemental source of information for determining ground-level particle concentrations.     

Trends in hydrophobic organic contaminants in urban and reference lake sediments across the United States, 1970-2001

A shift in national policy toward stronger environmental protection began in the United States in about 1970. Conversely, urban land use, population, energy consumption, and vehicle use have increased greatly since then. To assess the effects of these changes on water quality, the U.S. Geological Survey used sediment cores to reconstruct water-quality histories for 38 urban and reference lakes across the United States. Cores were age-dated, and concentration profiles of polycyclic aromatic hydrocarbons (PAHs) and chlorinated hydrocarbons were tested statistically. Significant trends in total DDT, p,p'-DDE, and total PCBs were all downward. Trends in chlordane were split evenly between upward and downward, and trends in PAHs were mostly upward. Significant trends did not occur in about one-half of cases tested. Concentrations of p,p'-DDE, p,p'-DDD, and PCBs were about one-half as likely to exceed the probable effect concentration (PEC), a sediment quality guideline, in sediments deposited in the 1990s as in 1965-1975, whereas PAHs were twice as likely to exceed the PEC in the more recently deposited sediments. Concentrations of all contaminants evaluated correlated strongly with urban land use. Upward trends in PAH concentrations, the strong association of PAH with urban settings, and rapid urbanization occurring in the United States suggest that PAHs could surpass chlorinated hydrocarbons in the threat they pose to aquatic biota in urban streams and lakes.     

Spatial and seasonal variability of dissolved methylmercury in two stream basins in the eastern United States

We assessed methylmercury (MeHg) concentrations across multiple ecological scales in the Edisto (South Carolina) and Upper Hudson (New York) River basins. Out-of-channel wetland/floodplain environments were primary sources of filtered MeHg (F-MeHg) to the stream habitat in both systems. Shallow, open-water areas in both basins exhibited low F-MeHg concentrations and decreasing F-MeHg mass flux. Downstream increases in out-of-channel wetlands/floodplains and the absence of impoundments result in high MeHg throughout the Edisto. Despite substantial wetlands coverage and elevated F-MeHg concentrations at the headwater margins, numerous impoundments on primary stream channels favor spatial variability and lower F-MeHg concentrations in the Upper Hudson. The results indicated that, even in geographically, climatically, and ecologically diverse streams, production in wetland/floodplain areas, hydrologic transport to the stream aquatic environment, and conservative/nonconservative attenuation processes in open water areas are fundamental controls on dissolved MeHg concentrations and, by extension, MeHg availability for potential biotic uptake.     

Advanced factor analysis of spatial distributions of PM2.5 in the eastern United States

This work analyzes PM2.5 24-h average concentrations measured every third day at over 300 locations in the eastern United States during 2000. The non-negative factor analytic model, Positive Matrix Factorization, has been enhanced by modeling the dependence of PM2.5 concentrations on temperature, humidity, pressure, ozone concentrations, and wind velocity vectors. The model comprises 12 general factors, augmented by 5 urban-only factors intended to represent excess concentration present in urban locations only. The computed factor components or concentration fields are displayed as concentration maps, one for each factor, showing how much each factor contributes to the average concentration at each location. The factors are also displayed as flux maps that illustrate the spatial movement of PM2.5 aerosol, thus enabling one to pinpoint potential source areas of PM2.5. The quality of the results was investigated by examining how well the model reproduces especially high concentrations of PM2.5 on specific days at specific locations. Delimiting the spatial extent of all such factors that exhibit a clear regional maximum surrounded by an almost-zero outer domain lowered the uncertainty in the computed results.     

Levels and distribution of polybrominated diphenyl ethers in water, surface sediments, and bivalves from the San Francisco Estuary

Polybrominated diphenyl ethers (PBDEs) were found in water, surface sediments, and bivalve samples that were collected from the San Francisco Estuary in 2002. sigmaPBDE concentrations in water samples ranged from 3 to 513 pg/ L, with the highest concentrations found in the Lower South Bay (range 103-513 pg/L) region, which receives approximately 26% of the Estuary's wastewater treatment plant effluents. The sigmaPBDEs in sediments ranged from below detection limits to 212 ng/g dry wt, with the highest concentration found at a South Bay station (212 ng/g dry wt), which was up to 3 orders of magnitude higher than other stations. The sigmaPBDE concentrations ranged from 9 to 64 ng/g dry wt in oysters (Crassostrea gigas), from 13 to 47 ng/g dry wt in mussels (Mytilus californianus), and from 85 to 106 ng/g dry wt in clams (Corbicula fluminea). Only three PBDE congeners were detected in bivalves, BDE-47, BDE-99, and BOE-100; these are the most bioaccumulative congeners from the commercial Penta-BDE mixture.     

Filter ventilation and nicotine content of tobacco in cigarettes from Canada, the United Kingdom, and the United States

OBJECTIVES: The purpose was to determine filter ventilation and the nicotine content of tobacco and their contribution to machine-smoked yields of cigarettes from the United States, Canada, and the United Kingdom. METHODS: Ninety-two brands of cigarettes (32 American, 23 Canadian, and 37 British brands) were purchased at retail outlets in State College, Pennsylvania, United States, Toronto, Canada, and London, United Kingdom. A FIDUS FDT filter ventilation tester measured the percentage air-dilution from filter vents. High-pressure, liquid chromatography was used to measure the nicotine content of tobacco. Regression techniques were used to examine the contributions of tobacco nicotine content and filter ventilation to machine-smoked yields of tar, nicotine, and carbon monoxide (CO). RESULTS: Ninety-four per cent of the American brands, 91% of the Canadian brands, and 79% of British brands were ventilated. The total nicotine content of tobacco and percent nicotine (by weight of tobacco) averaged 10.2 mg (standard error of the mean (SEM) 0.25, range: 7.2 to 13.4) and 1.5% (SEM 0.03, range 1.2 to 2) in the United States, 13.5 mg (SEM 0.49, range: 8.0 to 18.3) and 1.8% (SEM 0.06, range: 1.0 to 2.4) in Canada, 12.5 mg (SEM 0.33, range: 9 to 17.5) and 1.7% (SEM 0.04, range: 1.3 to 2.4) in the United Kingdom. Multiple regression analyses showed that ventilation was by far the largest factor influencing machine-smoked yields of tar, nicotine, and CO. CONCLUSION: Filter ventilation appears to be the predominant method for reducing machine-smoked yields of tar, nicotine, and CO in three countries. However, some brands contain about twice as much nicotine (total content or percent nicotine) as do others, indicating that tobacco types or blends and tobacco castings can be used to manipulate nicotine content and nicotine delivery of cigarettes.     

Emissions from ships in the northwestern United States

Recent inventory efforts have focused on developing nonroad inventories for emissions modeling and policy insights. Characterizing these inventories geographically and explicitly treating the uncertaintiesthat result from limited emissions testing, incomplete activity and usage data, and other important input parameters currently pose the largest methodological challenges. This paper presents a commercial marine vessel (CMV) emissions inventory for Washington and Oregon using detailed statistics regarding fuel consumption, vessel movements, and cargo volumes for the Columbia and Snake River systems. The inventory estimates emissions for oxides of nitrogen (NOx), particulate matter (PM), and oxides of sulfur (SOx). This analysis estimates that annual NOx emissions from marine transportation in the Columbia and Snake River systems in Washington and Oregon equal 6900 t of NOx (as NO2) per year, 2.6 times greater than previous NO, inventories for this region. Statewide CMV NO, emissions are estimated to be 9,800 t of NOx per year. By relying on a "bottom-up" fuel consumption model that includes vessel characteristics and transit information, the river system inventory may be more accurate than previous estimates. This inventory provides modelers with bounded parametric inputs for sensitivity analysis in pollution modeling. The ability to parametrically model the uncertainty in commercial marine vessel inventories also will help policy-makers determine whether better policy decisions can be enabled through further vessel testing and improved inventory resolution.     

Photolysis studies of technical decabromodiphenyl ether (DecaBDE) and ethane (DeBDethane) in plastics under natural sunlight

Photodebromination of technical decabromodiphenyl ether (DecaBDE) incorporated into high-impact polystyrene (HIPS) and TV casings was compared under natural sunlight conditions with that of technical decabromodiphenyl ethane (DeBDethane). BDE 209 in pulverized HIPS+DecaBDE samples degraded with a half-life of 51 days. In contrast, no marked loss of DeBDethane occurred throughout the experimental period of 224 days. During BDE 209 photolysis in HIPS+DecaBDE samples, partly debromination to nona- and octa-BDE was observed, however, environmentally relevant polybrominated diphenyl ether (PBDE) congeners such as BDE 47, 99, and 100 were not formed. Formation of polybrominated dibenzofurans (PBDFs) was clearly apparent in the flame-retarded plastics that we investigated. In the HIPS+DecaBDE samples, the PBDF concentration increased by about 40 times after 1 week of exposure, with a concomitant decrease in BDE 209. In the TV casing, tetra- to octa-BDF congener concentrations increased continuously during the experiment Although the concentrations of PBDFs found in the plastic matrices tested were 1 to 4 orders of magnitude lower than those of PBDEs, more attention should be paid to the fact that PBDFs are formed by sunlight exposure during normal use as well as disposal/recycling processes of flame-retarded consumer products.     

Contribution of biogenic emissions to the formation of ozone and particulate matter in the eastern United States

As anthropogenic emissions of ozone (O3) precursors, fine particulate matter (PM2.5), and PM2.5 precursors continue to decrease in the United States, the fraction of O3 and PM2.5 attributable to natural sources may become significant in some locations, reducing the efficacy that can be expected from future controls of anthropogenic sources. Modeling studies were conducted to estimate the contribution of biogenic emissions to the formation of O3 and PM2.5 in Nashville/TN and the northeastern United States. Two approaches were used to bound the estimates. In an anthropogenic simulation, biogenic emissions and their influence at the domain boundaries were eliminated. Contributions of biogenic compounds to the simulated concentrations of O3 and PM2.5 were determined by the deviation of the concentrations in the anthropogenic case from those in the base case. A biogenic simulation was used to assess the amounts of O3 and PM2.5 produced in an environment free from anthropogenic influences in emissions and boundary conditions. In both locations, the contribution of biogenic emissions to O3 was small (<23%) on a domain-wide basis, despite significant biogenic volatile organic compounds (VOC) emissions (65-89% of total VOC emissions). However, the production of O3 was much more sensitive to biogenic emissions in urban areas (22-34%). Therefore, the effects of biogenic emissions on O3 manifested mostly via their interaction with anthropogenic emissions of NOx. In the anthropogenic simulations, the average contribution of biogenic and natural sources to PM2.5 was estimated at 9% in Nashville/TN and 12% in the northeast domain. Because of the long atmospheric lifetimes of PM2.5, the contribution of biogenic/natural PM2.5 from the boundary conditions was higher than the contribution of biogenic aerosols produced within the domain. The elimination of biogenic emissions also affected the chemistry of other secondary PM2.5 components. Very little PM2.5 was formed in the biogenic simulations.     

Prevalence and population analysis of Vibrio parahaemolyticus in retail aquatic products from the southern Fujian coast,China

Vibrio parahaemolyticus is one of the most hazardous pathogens causing seafood-borne diseases in the southern Fujian coast, China. From June to October 2016, a total of 250 samples were collected from retail markets in the Xiamen, Quanzhou, and Zhangzhou regions. Seventy-seven V. parahaemolyticus isolates were identified using polymerase chain reaction (PCR). Then, molecular typing was performed using repetitive extragenic palindromic-PCR (REP-PCR). The distribution of seven virulence genes was detected by PCR. In aquatic products, the prevalence of V. parahaemolyticus was 30.8%, and the prevalence of tdh⁺ and trh⁺ was 2.6 and 1.3%, respectively. The prevalence of type III secretion system-2 (T3SS2) and the ureC gene was 5.2 and 3.9%, respectively. All 77 strains and the reference strain V. parahaemolyticus ATCC 17802 were classified into seven molecular types using REP-PCR. Thus, our findings demonstrated that the prevalence of V. parahaemolyticus was severe in the southern Fujian coast and that the regulations for aquatic food safety should be strengthened.     

Serum levels of polybrominated diphenyl ethers (PBDEs) in foam recyclers and carpet installers working in the United States

Increased exposure to the flame retardants known as polybrominated diphenyl ethers (PBDEs) may be expected to occur during the recycling of polyurethane foam containing these chemicals. To date, no studies in the United States have investigated occupational exposure to these flame retardants during recycling processes. The objective of the present study was to determine if individuals working in foam recycling facilities, and/or carpet installers who may install carpet padding manufactured from recycled foam, possess significantly higher PBDE serum levels relative to that of the general U.S. population. As a control group, serum was collected from four spouses and one clerical worker. In addition, levels in workers were also compared to the recently published national health and nutrition examination survey (NHANES) data set on PBDEs in the general U.S. population. Serum samples were collected in duplicate and analyzed by two different laboratories as quality control. Total PBDE levels were found to be significantly higher (p < 0.05) in the individuals recycling foam and installing carpet (n = 15) relative to the control group (n = 5). Median sigmaPBDE levels in the foam recyclers, carpet layers, and control group were 160, 178, and 19 ng/g lipid, respectively. In contrast, concentrations of a polybrominated biphenyl (BB-153) and a polychlorinated biphenyl (CB-153) were equivalent among all groups tested. The PBDE congeners BDE-47, 99, 100, and 153 contributed 90% of the sigmaPBDE concentration in serum and no differences in congener patterns were apparent among the different groups. Relative to concentrations measured in the NHANES, foam recyclers and carpet layers have body burdens that are an order of magnitude higher. These data suggest individuals recycling foam-containing products, and/ or using products manufactured from recycled foam (i.e., carpet padding), have higher body burdens of PBDEs, and thus may be at higher risk from adverse health effects associated with brominated flame retardant exposure.     

Declining mortality from smoking in the United States.

The proportion of Americans who smoke cigarettes has declined 50% since 1965. The effect on mortality of this considerable reduction has received little attention and is described in this study. U.S. national data were used to enumerate current, former, and never-smokers aged 35 years or older in 1987 and 2002. Mortality rate ratios were used to estimate smoking-attributable deaths among these groups, and corresponding age-adjusted smoking-attributable mortality rates (SAMRs) were calculated. There were 402,000 deaths attributable to smoking in 1987 and 322,000 in 2002. The SAMR for men aged 35 years or more was 556 deaths per 100,000 person-years in 1987, accounting for 24% of all male deaths. By 2002 the SAMR declined 41% to 329 and accounted for only 17% of deaths. The SAMR for women in 1987 was 175, accounting for 12% of deaths. By 2002 the SAMR among women had declined 30% to 122, representing 9% of deaths. The U.S. mortality rate attributable to smoking declined about 35% between 1987 and 2002. The impact of smoking on American society will diminish even further in the foreseeable future as smoking prevalence continues its decline among men and women.