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Information on variability is important in the assessment of the releases and potential risks of brominated flame retardants (BRFs) in the environment, but related data are limited. In this study, two release-characterizing parameters, release fraction to final effluent and influent-biosolids transfer coefficient, were used to quantify releases of five BFRs from eight secondary wastewater treatment plants (WWTPs). The five BFRs are recalcitrant, hydrophobic, and low in volatility. The two parameters for these BFRs were found to vary from day to day and season to season within individual WWTPs as well as from one WWTP to another. These temporal and spatial variations were, however, comparable to each other and both within a factor of 3 above or below the parameter averages. Averages for release fraction were in the range of 0.02-0.29 and those for influent-biosolids transfer coefficient in the range of 3-26 L/g, depending upon a given BFR at a given WWTP. These ranges and the observed factor-3 variability are not only useful for estimating releases of the five BFRs, but more importantly provide read-across data for the assessment of substances with similar physical-chemical properties.

Concentrations and isomer compositions of hexabromocyclododecane (HBCD) were measured in six matrices in the Czech Republic (HBCD technical mixture; consumer products; indoor and outdoor air at industrial, urban and background locations; soils; and sediments) to provide insight into changes in concentrations and isomer profiles between environmental sources and environmental sinks. A distinct gradient of air concentrations was observed, from 1600 ng/m 3 in the industrial area to < 10 pg/m 3 in urban and background air. Isomer profiles also showed a distinct gradient in air, from 95% γ-HBCD in industrial air to 40% γ-HBCD in background air, suggesting the influence of differential atmospheric transport and phototransformation of γ- to α-HBCD. Concentrations and isomer compositions in consumer products were highly variable and indicated differences between products with intentional addition of HBCD as a flame retardant versus those with HBCD as an impurity, e.g., from recycled plastic. Understanding the isomer-specific environmental distributions and processes remains important for risk assessment and toxicology, considering the continued use of HBCD and the isomer-specific differences in uptake, metabolism, and toxicity, and further, demonstrates the utility of isomer profiles to better understand environmental processes of HBCDs.

Hexabromocyclododecanes (HBCDs) are a class of widely used brominated flame retardants (BFRs) that exhibit strong hydrophobicity. The ubiquity and persistence of HBCDs in sediment have attracted significant attention because of public health concerns. The environmental fate and ecological risks of HBCDs closely depend on their phase distribution in sediments. However, little information is available regarding the freely dissolved concentrations (C free ) of HBCDs in sediment porewater. In this study, we developed a method to measure C free of HBCDs in sediment porewater using triolein-embedded cellulose acetate membranes (TECAM). The TECAM-to-water partitioning coefficient (log K TECAM ) was 4.69, 4.77, and 4.63 for α-HBCD, β-HBCD, and γ-HBCD, respectively. In sediments, HBCDs sorbed to the sediment solid phase accounted for more than 99% of the total chemical mass. The dissolved organic carbon (DOC)-water partition coefficient (K DOC ) values were derived from TECAM measurements, and the log K DOC values ranged from 5.77 to 6.23 for the three HBCD diastereomers, suggesting a strong tendency for HBCDs to sorb to DOC. The high sorption of HBDCs for DOC implies a potential for DOC-facilitated transport which may enhance the environmental mobility of HBCDs.

Forty surface sediment samples from the Hunhe River in Northeast China were evaluated for contamination by polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD). The results showed that decabromodiphenyl ether (BDE-209) was the predominant congener, accounting for >98 % of PBDEs in all sediment. The concentrations of BDE-209 and HBCD ranged from 3.96 to 327 ng/g dry weight and 0.05 to 25.8 ng/g dry weight, respectively, suggesting that BDE-209 was more widely applied in the study area. The mean concentrations of BDE-209 and HBCD in the downstream portion of the Hunhe River (BDE-209 148 ng/g dry weight and HBCD 3.74 ng/g dry weight) were found to be relatively higher than those in the upstream portion of the Hunhe River and the Dahuofang Reservoir, revealing an association with municipal sewage and industrial effluent received from the cities of Fushun and Shenyang. γ-HBCD was the most abundant diastereoisomer of all three analyzed HBCD isomers; however, marked elevations of α-HBCD were also found in most sediment samples. Surprisingly, the relative abundance (mean 38%) of α-HBCD in sediment from the upstream portion of the Hunhe River was significantly higher (p < 0.006, t test) than those in Dahuofang Reservoir (mean 24%). Moreover, the severe heavy metal contamination associated with the frequent mining activities in this region was tentatively suggested as being responsible for the increased levels of α-HBCD.

Concentrations of hexabromocyclododecanes (HBCDs) were determined in surface sediments of Shanghai, China. The concentrations of total HBCD diastereoisomers (ΣHBCD) ranged from 0.01 to 13.70 ng g(-1) dry weight (dw) with a mean value of 3.41 ng g(-1) dw, which was up to several orders of magnitude lower than those reported for sediments from European countries. The ΣHBCD concentrations in sediments from chemical/textile industrial or densely populated areas were generally higher than those from rural or less chemical/textile industrialized areas in Shanghai. A high proportion of α-HBCD was observed in sediment samples and was significantly higher than that of commercial HBCD products. This might be due to thermal isomerization from γ-HBCD to α-HBCD and slower degradation rate of α-HBCD compared to γ-HBCD in anaerobic conditions. The mass inventory of ΣHBCD in surface sediments of Shanghai was estimated at 164.4 kg, representing a significant source of HBCDs to the Shanghai environment. This indicates that further study on potential transfer of HBCDs from sediments to aquatic organisms and ecological risk assessments is required.

In this work we used density functional theory (DFT) B3LYP/6-31G*(d) to study the stoichiometric reaction between the product (1S,3R,8S)-2,2-dichloro-3,7,7,10-tetramethyltricyclo[6,4,0,0(1.3)]dodec-9-ene (referred to here as P1) and dibromocarbene. We have shown that P1 behaves as a nucleophile, while dibromocarbene behaves as an electrophile; that the chemical potential of dibromocarbene is superior to that of P1 in absolute terms; and that P1 reacts with an equivalent quantity of dibromocarbene to produce two products: (1S,3R,8R,9S,11R)-10,10-dibromo-2,2-dichloro-3,7,7,11-tetramethyltetracyclo[6,5,0,0(1.3),0(9.11)] tridecane (referred to here as P2) and (1S,3R,8R,9R,11S)-10,10-dibromo-2,2-dichloro-3,7,7,11-tetramethyltetracyclo[6,5,0,0(1.3),0(9.11)] tridecane (referred to here as P3). P2 and P3 are formed at the α and β sides, respectively, of the C2 = C3 double bond of P1. This reaction is exothermic, stereoselective and chemospecific, and is controlled by charge transfer. Regioselectivity of the reaction was interpreted using the Lee-Yang-Parr functional.

This work aimed to evaluate the effectiveness of nutrients, H2O2, and tourmaline on the bioremediation of fields where the soil was contaminated with polybrominated diethyl ethers (PBDEs). The results showed that 39.2, 38.3, and 48.1 % of total PBDE removal was observed in microcosms with the addition of nutrients, such as NaNO3, NH4Cl, and NH4NO3, respectively, compared to only 15.2 and 5.8 % of PBDE removal from soil with added Aspergillus niger and control soil, respectively, after 50 days of incubation. In addition, 50.8 and 56.5 % of total PBDE removal were observed in microcosms with 0.5 and 1 μL H2O2. The addition of tourmaline increased total PBDE removal to 32.4 %. Significant increases in soil enzymatic activity with PBDE degraders and bacterial communities were observed using polymerase chain reaction (PCR)--denaturing gradient gel electrophoresis (DGGE). These observations suggested that the combination of inorganic nutrients with chemical, mineral, and biological treatment could improve the PBDE removal efficiency. However, the combination of H2O2 and biological treatment processes is the most efficient technology. This combination of technologies would not cause adverse effects on the subsequent bioremediation process. Therefore, this work offers a potential alternative for the remediation of soil contaminated with PBDE pollutants.

Hexabromocyclododecane (HBCD) is a globally produced brominated flame retardant used primarily as an additive flame retardant in polystyrene and textile products. Photodegradation of HBCD in the presence of Fe(III)-carboxylate complexes/H2O2 was investigated under simulated sunlight. The degradation of HBCD decreased with increasing pH in the Fe(III)-oxalate solutions. In contrast, the optimum pH was 5.0 for the Fe(III)-citrate-catalyzed photodegradation within the range of 3.0 to 7.0. For both Fe(III)-oxalate and Fe(III)-citrate complexes, the increase of carboxylate concentrations facilitated the photodegradation. The photochemical removal of HBCD was related to the photoreactivity and speciation distribution of Fe(III) complexes. The addition of H2O2 markedly accelerated the degradation of HBCD in the presence of Fe(III)-citrate complexes. The quenching experiments showed that ·OH was responsible for the photodegradation of HBCD in the Fe(III)-carboxylate complexes/H2O2 solutions. The results suggest that Fe(III) complexes/H2O2 catalysis is a potential method for the removal of HBCD in the aqueous solutions.

Ab initio calculations at the G2 level were used in a theoretical description of the kinetics and mechanism of the hydrogen abstraction reactions from fluoro-, chloro- and bromomethane by chlorine atoms. The profiles of the potential energy surfaces show that mechanism of the reactions under investigation is complex and consists of two - in the case of CH3F+Cl - and of three elementary steps for CH3Cl+Cl and CH3Br+Cl. The heights of the energy barrier related to the H-abstraction are of 8-10 kJ mol(-1), the lowest value corresponds to CH3Cl+Cl and the highest one to CH3F+Cl. The rate constants were calculated using the theoretical method based on the RRKM theory and the simplified version of the statistical adiabatic channel model. The kinetic equations derived in this study[Formula: see text]and[Formula: see text]allow a description of the kinetics of the reactions under investigation in the temperature range of 200-3000 K. The kinetics of reactions of the entirely deuterated reactants were also included in the kinetic analysis. Results of ab initio calculations show that D-abstraction process is related with the energy barrier of 5 kJ mol(-1) higher than the H-abstraction from the corresponding non-deuterated reactant molecule. The derived analytical equations for the reactions, CD3X+Cl, CH2X+HCl and CD2X+DCl (X = F, Cl and Br) are a substantial supplement of the kinetic data necessary for the description and modeling of the processes of importance in the atmospheric chemistry.

A novel approach for the simulation of host-guest systems by systematically scanning the host molecule's orientations within the guest cavity is presented along with a thermodynamic strategy for determining preferential binding modes and corresponding optimal interaction energies between host and guest molecules. By way of example, the elution order of hexabromocyclododecane stereoisomers from high performance liquid chromatography separation on a permethylated β-cyclcodextrin stationary phase has been computed using classical molecular dynamics simulations with the explicit solvents water and acetonitrile. Comparison of estimated with experimental separation data reveals remarkable squared coefficients of correlation with R(2) = 0.87 and a very high correlation R(LOO2) = 0.72 using the leave-one-out cross-validation method and water as solvent. In particular, the approach presented shapes up as very robust in terms of the evaluated time range under consideration, reflecting well thermodynamic equilibria. These and further observations correlating with experimental results suggest the suitability of the underlying force fields and our multi-mode approach for the estimation of relative binding affinities for host-guest systems with unknown binding modes.

Background and Aims: Hexabromocyclododecane (HBCD) is a brominated flame retardant used mainly in polystyrene foam as well as in textile applications. In recent years, measures were taken to reduce HBCD emissions during its production and use. To evaluate the efficacy of these measures, a monitoring project was initiated with fish as bioaccumulation indicators., Methods: Since 2007 bream was sampled annually at several European freshwater sites applying standardized methods. Muscle samples were analyzed by a validated liquid chromatography-tandem mass spectrometry (LC-MS/MS) method which allows the quantification of α-, β-, and γ-diastereomers of HBCD., Discussion: In most samples, α-HBCD was predominant. The lowest HBCD levels (11 μg/kg lipid weight (lw), sum of three HBCD diastereomers) were detected in bream sampled in 2009 from Lake Belau which is situated in a rural area of Northern Germany. During the 4-year study period, statistical significant decreases of HBCD concentrations were detected in bream from the rivers Rhone (France; -85%, level 2010, 205 μg/kg lw) and Western Scheldt (the Netherlands; -60%, level 2010, 36 μg/kg lw). High HBCD concentrations (9,480-14,500 μg/kg lw) without a clear time trend were observed in bream from the river Tees (UK). These high levels are in line with published data for fish from contaminated regions., Conclusions: Overall, the results indicate that environmental burdens of HBCD are decreasing at those locations where point sources and more diffuse emissions are expected.

Reactions of lithium halide (LiX, X = F, Cl, Br and I) and methyl halide (CH₃X, X = F, Cl, Br and I) have been investigated at the B3LYP/6-31G(d) level of theory using the microhydration model. Beginning with hydrated lithium ion, four or two water molecules have been conveniently introduced to these aqueous-phase halogen-exchange S(N)2 reactions. These water molecules coordinated with the center metal lithium ion, and also interacted with entering and leaving halogen anion via hydrogen bond in complexes and transition state, which to some extent compensated hydration of halogen anion. At 298 K the reaction profiles all involve central barriers ΔE ( cent ) which are found to decrease in the order F > Cl > Br > I. The same trend is also found for the overall barriers (ΔE(ovr)) of the title reaction. In the S(N)2 reaction of sodium iodide and methyl iodide, the activation energy agrees well with the aqueous conductometric investigation.

The geometry and the electronic structure of tricyclo[4.2.2.2(2,5)]dodeca-1,5-diene (TCDD) molecule were investigated by DFT/B3LYP and /B3PW91 methods using the 6-311G(d,p) and 6-311++G(d,p) basis sets. The double bonds of TCDD molecule are syn-pyramidalized. The structure of pi-orbitals and their mutual interactions for TCDD molecule were investigated. Potential energy surface (PES) of the TCDD-Br(2) system was studied by B3LYP/6-311++G(d,p) method and the configurations [molecular charge-transfer (CT) complex, transition states (TS1 and TS2), intermediate (INT) and product (P)] corresponding to the stationary points (minima or saddle points) were determined. Initially, a molecular CT-complex forms between Br(2) and TCDD. With a barrier of 22.336 kcal mol(-1) the CT-complex can be activated to an intermediate (INT) with energy 15.154 kcal mol(-1) higher than that of the CT-complex. The intermediate (INT) then transforms easily (barrier 5.442 kcal mol(-1)) into the final, N-type product. The total bromination is slightly exothermic. Accompanying the breaking of Br-Br bond, C1-Br, C5-Br and C2-C6 bonds are formed, and C1 = C2 and C5 = C6 double bonds transform into single bonds. The direction of the reaction is determined by the direction of intramolecular skeletal rearrangement that is realized by the formation of C2-C6 bond.

To protect against exotic forest pest, solid wood packing has to be treated before shipping. According to the international standard ISPM 15 containers are usually fumigated with bromomethane. During this quarantine treatment a chemical reaction of bromomethane with the transported goods can not principally be excluded. This study takes a look at the impact of bromomethane on selected potential sensitive active pharmaceutical ingredients during simulated container fumigation. Following a 24-hour exposure to 67-80 g bromomethane per cubic meter, up to 0.02% bromide has been confirmed in phenacetine. The bromide concentrations in other active pharmaceutical ingredients were below 0.002%. New reaction products have not been identified at a detection limit of 0.01-0.04%. The bromide residue detected in one active pharmaceutical ingredient does not represent a relevant impairment of quality according to the European Pharmacopoeia, nor does it lead to a relevant excess exposure compared to both the acceptable daily intake of bromide and to the actual daily uptake of bromide from other exposure paths, dominantly from food consumption.

The location of the most abundant peak of the molecular-ion pattern often differs from the molecular mass published in scientific databases. The location is also distinct from the value expected from average atomic masses. The cause of this phenomenon is a large number of atoms of carbon, sulfur, chlorine, bromine, silicon and boron. This due to the natural isotope abundances of some elements forming organic compounds. A parameter called location of the most abundant peak of an isotopometric cluster (LAPIC) denotes the location of the most abundant (the main) peak of an isotopomeric cluster, which is determined, e.g., by mass spectrometry and can be important for medium- and high-molecular mass compounds. The equations for LAPIC calculation are presented for elements usually observed in organic compounds. The LAPIC with elemental formula helps effectively, e.g., in mass spectra interpretation since the prediction of LAPIC allows the correct connection of the main peak of the investigated ion with the expected ion formula and the mass of the ion considered. This solution can be a substitute for the much more complex method of isotopometric analysis applied in mass spectra interpretation. [Figure: see text]. Differences of the most abundant peak location (Delta LAPIC(C)=f(n)) for carbon aggregates C(n).

Purpose: To develop and characterize a radiolabelled Substance-P antagonist useful for quantitation of neurokinin-1 receptors in the brain via PET imaging., Procedure: [18F]SPA-RQ (Substance-P antagonist - receptor quantifier) was synthesized in good yield and high specific activity by alkylation of a BOC protected phenolate anion using [18F]bromofluoromethane. Removal of the BOC protecting group with trifluoroacetic acid gave [18F]SPA-RQ., Results: SPA-RQ has high affinity for human, rhesus monkey and guinea pig NK1 receptors (h-IC50=67 pM) and has a log P value of 1.8. Biodistribution studies in guinea pig showed that this tracer penetrates the blood-brain barrier and selectively labels NK1 receptors in the striatum and cortex., Conclusion: [18F]SPA-RQ is a potent, high affinity Substance-P antagonist that can be conveniently labeled with high specific activity using [18F]fluoromethylbromide. This tracer is a useful tool for noninvasive imaging of central NK1 receptors.