Polybrominated diphenyl ethers (flame retardants) in mother-infant pairs in the Southeastern U.S.

Polybrominated diphenyl ethers (PBDEs) are commonly used flame retardants in foams, building material, electronics, and textiles. These chemicals leach into the environment, where they persist, and are found today in virtually every population worldwide. Several studies in recent years have detected the presence of PBDEs in maternal and infant samples. However, few of these studies were conducted in the U.S., and few examined paired or matched mother blood-cord blood samples. We analyzed serum from 10 mother-infant pairs for the presence of PBDEs in a patient population in the Southeastern U.S. Out of 35 measured PBDE congeners, five (BDE-28, -47, -99, -100, and -153) were present, with detection frequencies of 65-100 %. The total PBDE concentrations in maternal and infant sera were highly correlated (r2 = 0.710, p = 0.0043). The levels of BDE-47, -99, and -100 and of total PBDEs were higher in the infant cord sera when compared with those in maternal sera (p < 0.017), suggesting that fetuses and neonates might have higher circulating concentrations of these potentially neurotoxic and endocrine disrupting chemicals compared with their mothers. The primary focus henceforward should be whether there are any deleterious effects from exposure to these chemicals on human health.

Spatial and Temporal Trends of Particle Phase Organophosphate Ester Concentrations in the Atmosphere of the Great Lakes.

The concentrations of six organophosphate esters (OPEs) in atmospheric particle phase samples collected once every 12 days at five sites in the North American Great Lakes basin over the period of March 2012 to December 2014, inclusive, are reported. These OPEs include tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), and tris(1,3-dichloroisopropyl) phosphate (TDCIPP), tri-n-butyl phosphate (TNBP), triphenyl phosphate (TPHP), and 2-ethylhexyl diphenyl phosphate (EHDP). Median total OPE concentrations (∑OPE) ranged from 93 pg/m3 at Sleeping Bear Dunes to 1046 pg/m3 at Chicago. The ∑OPE levels were significantly (P < 0.05) higher at Chicago and Cleveland, our urban sites, than at our rural and remote sites. The composition profiles were dominated by chlorinated OPEs at the urban and rural sites and by nonchlorinated OPEs at the remote sites. The concentrations of all OPEs were significantly (P < 0.001) correlated to one another, suggesting that these compounds share similar sources. Most atmospheric ∑OPE concentrations were significantly (P < 0.05) decreasing over time, with halving times of about 3.5 years at the urban sites and about 1.5 years at the rural and remote sites. Interestingly, TCEP and EHDP concentrations were increasing over time at the rural and remote sites with doubling times of 2.2 and 3.7 years, respectively.

Locating POPs Sources with Tree Bark.

Locating sources of persistent organic pollutants (POPs) to the atmosphere can sometimes be difficult. We suggest that tree bark makes an excellent passive atmospheric sampler and that spatial analysis of tree bark POPs concentrations can often pinpoint their sources. This is an effective strategy because tree bark is lipophilic and readily adsorbs and collects POPs from the atmosphere. As such, tree bark is an ideal sampler to find POPs sources globally, regionally, or locally. This article summarizes some work on this subject with an emphasis on kriged maps and a simple power-law model, both of which have been used to locate sources. Three of the four examples led directly to the pollutant's manufacturing plant.

Variations of Flame Retardant, Polycyclic Aromatic Hydrocarbon, and Pesticide Concentrations in Chicago's Atmosphere Measured using Passive Sampling.

Atmospheric concentrations of flame retardants, polycyclic aromatic hydrocarbons, and pesticides were measured using passive air samplers equipped with polyurethane foam disks to find spatial information in and around Chicago, Illinois. Samplers were deployed around the greater Chicago area for intervals of 6 weeks from 2012 to 2013 (inclusive). Volumes were calculated using passive sampling theory and were based on meteorology and the compounds' octanol-air partition coefficients. Geometric mean concentrations of total polybrominated diphenyl ethers ranged from 11 to 150 pg/m3, and tributyl phosphate, tris(2-chloroethyl)phosphate, tris(1-chloro-2-propyl)phosphate, and triphenyl phosphate concentrations were in the ranges of 54-290, 32-340, 130-580, and 170-580 pg/m3, respectively. The summed concentrations of 16 PAHs ranged from 8700 to 52,000 pg/m3 over the sampling area, and DDT, chlordane, and endosulfan concentrations were in the ranges of 2.7-9.9, 8.2-66, and 16-85 pg/m3, respectively. Sampling sites were split into two groups depending on their distances from the Illinois Institute of Technology campus in Chicago. With a few exceptions, the concentrations of most compound groups in the city's center were the same or slightly higher than those measured >45 km away. The data also showed that the concentrations measured with a passive atmospheric sampling system are in good agreement with those measured with an active, high-volume, sampling system. Given that the sampling times are different (passive, 43 days; active, 1 day), and that both of these measured concentrations cover about 5 orders of magnitude, the agreement between these passive and active sampling methods is excellent.

Air is still contaminated 40 years after the Michigan Chemical plant disaster in St. Louis, Michigan.

The Michigan Chemical (also known as Velsicol Chemical) plant located in St. Louis, Michigan operated from 1936-1978. During this time, the plant manufactured polybrominated biphenyls (PBBs), hexabromobenzene (HBB), 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane (DDT), and tris(2,3-dibromopropyl) phosphate (TDBPP), among other products. Due to widespread PBB contamination of Michigan, the plant eventually became a Superfund site, and despite years of cleanup activities, many of the compounds can still be found in the local ecosystem. To investigate the current atmospheric levels and to determine their spatial distributions, we collected tree bark samples from around Michigan and measured the concentrations of these pollutants. For comparison, other organic pollutants, such as polybrominated diphenyl ethers (PBDEs) and organophosphate esters (OPEs), which were not manufactured at the Michigan Chemical plant, were also measured in the same tree bark samples. Our results show levels of PBBs, DDT, and HBB in tree bark collected within 10 km of the Velsicol Superfund site (43, 477, and 108 ng/g lipid wgt., respectively) are 1-2 orders of magnitude higher than at sites located more than 10 km from the site (0.36, 28, and 0.36 ng/g lipid wgt., respectively). Levels of PBDEs and OPEs did not depend on distance from St. Louis. This is the first study on the atmospheric distribution of these chemicals around the Superfund site.

Electrochemical determination of trihalomethanes in water by means of stripping analysis.

A protocol has been developed and evaluated for the determination of trihalomethanes (THMs) at the submicromolar concentration level in water. This method is based on a three-step stripping analysis that utilizes a single electrochemical cell and that entails (a) direct electrochemical reduction of a trihalomethane at a silver cathode to form halide ions in an aqueous sample containing tetraethylammonium benzoate, (b) capture of the released halide ions as a silver halide film on the surface of a silver gauze anode, and (c) cathodic reduction and quantitation of the silver halide film by means of differential pulse voltammetry. Using this procedure, we have determined THMs individually; bromoform and chloroform have been successfully quantitated in 30 min and with a detection limit of 3.0 µg L(-1) (12 nM) and 6.0 µg L(-1) (50 nM), respectively. In addition, we have employed our methodology to determine the total trihalomethane (TTHM) content in a prepared water sample at a level commensurate with the maximum allowable annual average of 80 µg L(-1) mandated by the United States Environmental Protection Agency. We have compared our TTHM results to those obtained by an independent testing laboratory.

Octopods versus concave nanocrystals: control of morphology by manipulating the kinetics of seeded growth via co-reduction.

Au/Pd octopods and concave core@shell Au@Pd nanocrystals have been prepared by coupling for the first time a seed-mediated synthetic method with co-reduction. The integration of these two methods is central to the formation of these binary Au/Pd nanocrystals wherein the kinetics of seeded growth are manipulated via the co-reduction technique to control the final morphology of the nanocrystals. Significantly, the synthesis of these structures under similar reaction conditions illustrates that they are structurally related kinetic products. Detailed characterization by STEM-EDX analysis highlights the unique structural features of these nanocrystals and indicates that Pd localizes on the higher-energy features of the nanocrystals. Optical and electrocatalytic characterization also demonstrates their promise as a new class of multifunctional nanostructures.

Chicago's Sanitary and Ship Canal sediment: Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, brominated flame retardants, and organophosphate esters.

The Chicago Sanitary and Ship Canal (CSSC) links the Great Lakes to the Mississippi River starting in downtown Chicago. In addition to storm water, the CSSC receives water from Chicago's wastewater treatment plants (WWTP). Such effluents are known to be sources of organic pollutants to water and sediment. Therefore in 2013, we collected 10 sediment samples from the CSSC and measured the concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), brominated flame retardants, and organophosphate esters (OPEs). Geometric mean concentrations of the summed concentrations of 16 PAHs ranged from 11,000 to 420,000 ng/g dw, with the highest concentrations located at each end of the canal. Total PCB concentrations had a geometric mean of 1,400 ± 500 ng/g dw. Brominated flame retardants were separated into two groups: polybrominated diphenyl ethers (PBDEs) and non-PBDEs. Concentrations of PBDEs and those of the non-PBDE flame retardants had a geometric average of 83 ± 19 and 7.0 ± 5.8 ng/g dw, respectively. The summed concentrations of 8 OPEs ranged from 470 to 2,800 ng/g dw, with the highest concentration detected at a site located downstream of the Stickney water reclamation plant. Using ANOVA results, some hypotheses on sources to the CSSC could be formulated: downtown Chicago is probably a source of PAHs, the Cal-Sag Channel may be a source of PCBs, and neither the WWTP nor the Cal-Sag Channel seem to be significant sources of brominated flame retardants or OPEs.