Reductive debromination of nonabrominated diphenyl ethers by sodium borohydride and identification of octabrominated diphenyl ether products

A method was developed to study reductive transformation of highly brominated diphenyl ethers (BDEs). The method development is a part of a broader project where it will be used to determine the susceptibility of environmental pollutants to reductive conditions, in an attempt to create a scheme for determination of chemical’s persistence. This paper focuses on identification of octabrominated diphenyl ether transformation products from reductive debromination of the three nonabrominated diphenyl congeners (nonaBDE), BDE-206, -207 and -208. Sodium borohydride was used to explore the reductive debromination of the nonaBDEs. The transformation products were collected at two time-points and identified products were quantified by GC-MS. The reduction of the nonaBDEs lead primarily to debrominated products, mainly octaBDEs. The three nonabrominated DEs gave isomer-related transformation product patterns. BDE-207 and BDE-208 showed a propensity for ortho-debromination in the initial reaction step, while no discrimination between initial debromination positions was seen for BDE-206. All three nonabrominated DEs displayed a preferred initial debromination on the fully brominated DE ring.     

Soot reduction by addition of dimethyl carbonate in normal and inverse ethylene diffusion flames: Nanostructural evidence

Oxygenated fuel represents an attractive alternative as an additive for reducing soot emissions.Dimethyl carbonate(DMC) is an oxygenated compound which is a good option to reduce soot,but the detailed characteristics of soot produced from combustion of hydrocarbon fuels blended with DMC are still lacking. The present research studied the nanostructure and reactivity of soot particles in ethylene/DMC normal and inverse diffusion flames. High resolution transmission electron microscopy(HRTEM), X-ray diffraction(XRD), and thermogravimetric analysis(TGA)were used to analyze the nanostructure and reactivity of soot. It was found that DMC addition was effective in decreasing the average weights of soot formed in flames. The results of HRTEM images showed that soot particles obtained with DMC addition showed liquid-like material and tight bonding, and exhibited more highly disorganized layers, which give it higher reactivity than soot obtained without DMC addition. Furthermore, HRTEM was used to analyze soot fringe characteristics consisting of fringe tortuosity, fringe length, and fringe separation. XRD was used to crosscheck the results for fringe separation, and was consistent with HRTEM results. In addition, the mass loss curve of TGA experiments showed that DMC addition could enhance the reactivity of soot particles.     

炼焦过程排放挥发性有机物的排放特征和组成分布研究

为控制炼焦排放以及为预防城市大气污染提供可靠的污染源数据支持,利用不锈钢采样罐和全自动预浓缩/GC/MS系统,研究了58-Ⅱ型和JN43-80型焦炉在装煤时刻和炼焦过程(包括装煤时刻)中挥发有机物(VOCs)的排放特征及其组成分布,分析了焦化行业排放VOCs的反应活性。研究发现,在装煤时刻和炼焦过程中,58-Ⅱ型焦炉产生的总挥发性有机物(TVOCs)浓度分别为7022μg/m~3和6266μg/m~3;JN43-80型焦炉产生的TVOCs浓度分别为4185μg/m~3和3298μg/m~3。装煤时刻产生的TVOCs浓度明显高于炼焦过程产生的。炼焦过程无组织排放的VOCs包含烯烃、烷烃、芳香烃、卤代烃以及少量的醛和酮,其中乙烯、乙烷、丙烯、苯、甲苯等为主要成分。这些产生的VOCs反应活性各不相同,活性最大的是烯烃类物质,其活性占TVOCs反应活性比重为(86.2±2.1)%;其次是芳香烃类物质,其活性比重为(9.2±3.1)%;反应活性最大的5个物种分别是丙烯、乙烯、1,3-丁二烯、1-丁烯以及苯乙烯。     

Do microbial processes regulate the stability of a coral atoll's enclosed pelagic ecosystem?

Complex marine ecosystems contain multiple feedback cycles that can cause unexpected responses to perturbations. To better predict these responses, complicated models are increasingly being developed to enable the study of feedback cycles. However, the sparseness of ecological data often limits the direct empirical parameterization of all model parameters. Here we use a Bayesian inverse analysis approach to synthesize empirical data and ecological theory derived from published studies of a coral atoll's enclosed pelagic ecosystem (Takapoto Atoll, French Polynesia). We then use the estimates of flux magnitudes to parameterize probabilistic compartment models with two forms of heterotrophic consumption: (1) “bottom-up” donor-controlled heterotrophic consumption and (2) “top-down” mass-action heterotrophic consumption. We explore how the flux magnitudes affect the ecosystem's stability properties of resilience, reactivity, and resistance under both assumptions for heterotrophic consumption. The models suggest that the microbial uptake of dissolved organic carbon (DOC) regulates the long term rate of return to steady state following a temporary or pulse perturbation (resilience), and the cycling of carbon between abiotic pools and heterotrophic compartments regulates the short-term response (reactivity). In the bottom-up process model, the sensitivity of steady state masses following a sustained or press perturbation (resistance) is highest for the DOC pool following a sustained change to the microbial uptake rate of DOC. Further, a change in the microbial uptake of DOC propagates through the ecosystem and affects the steady state values of zooplankton. The analysis suggests that the food web is highly dependent on the recycling between the abiotic and biotic carbon pools, particularly as mediated by the microbial consumption of DOC, and this recycling determines how the ecosystem responds to perturbations.     

Annual nonmethane hydrocarbon trends in Beijing from 2000 to 2019

High loads of ground-level ozone have occurred with the implementation of the Air Pollution Prevention and Control Action Plan. However, the long temporal variation in precursor nonmethane hydrocarbons(NMHCs) has rarely been studied. In this study, we examined the evolution of NMHCs in Beijing based on ambient measurements from 2000 to 2019. The results indicated that the annual variation of ambient NMHCs during 2000 and 2019 could be divided into two stages. The mixing ratios of NMHCs rapidly r...     

Oxidant denuder sampling for analysis of polycyclic aromatic hydrocarbons and their oxygenated derivates in ambient aerosol: evaluation of sampling artefact

The concentrations of some polycyclic aromatic hydrocarbons (PAH) and oxygenated PAH (O-PAH) can be changed by oxidation reactions during sampling. This can lead to an over- or underestimation of the corresponding adverse health effects. The aim of this study was the evaluation of these sampling artefacts. The potential of using an oxidant denuder was shown by parallel low-volume sampling with and without MnO₂ ozone denuder. Twenty-three PAH and 11 O-PAH in ambient air were analysed, both in the vapour and particulate phase. The denuder was proven to be highly efficient for stripping ozone from air while causing no significant particle losses. In general, the concentrations of 5- to 7-ring PAH, which are predominantly associated with particles, were underestimated in non-denuded samples. The highest losses due to reaction with ozone and other atmospheric oxidants were observed for benzo[a]pyrene and perylene. Concurrently, the concentrations of most of the mainly particle-associated 4- to 5-ring O-PAH were higher in the non-denuded samples. The denuder did not only remove ozone, moreover other gaseous species such as more volatile PAH and O-PAH were partially oxidized on the catalytic surface, too. Degradation of PAH and concurrent degradation/formation reactions of O-PAH occurred. The corresponding reactivities of selected PAH and O-PAH are discussed.     

Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms

Background, aim, and scope  The adverse environmental impacts of chlorinated hydrocarbons on the Earth’s ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C–F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF₃CF₂CF₂OCH₃) (1) and its isomer CF₃CF₂CF₂CH₂OH (2). Materials and methods  Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube–mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266–333 and 298–353 K for reactions of HFE-7000 and CF₃CF₂CF₂CH₂OH, respectively. Results  The measured room temperature rate constants were k(Cl+CF₃CF₂CF₂OCH₃) = (1.24 ± 0.28) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹and k(Cl+CF₃CF₂CF₂CH₂OH) = (8.35 ± 1.63) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ (errors are 2σ + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k ₁(266–333 K) = (6.1 ± 3.8) × 10⁻¹³exp[−(445 ± 186)/T] cm³ molecule⁻¹ s⁻¹ and k ₂(298–353 K) = (1.9 ± 0.7) × 10⁻¹²exp[−(244 ± 125)/T] cm³ molecule⁻¹ s⁻¹ (errors are 2σ). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 ± 0.38 and 0.97 ± 0.16 (errors are 2σ) were obtained for CF₃CF₂CF₂OCH₃ and CF₃CF₂CF₂CH₂OH, respectively. Discussion  The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k ₁ and k ₂, HFE-7000 is significantly less reactive than its isomer C₃F₇CH₂OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of –CF₂– in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of –CF₂– without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C₃H₇CH₂OH, respectively. Conclusions  The studied CFCs’ substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, τ _Cl values as low as 2.5 and 0.4 years for HFE-7000 and C₃H₇CH₂OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF₃CF₂CF₂OCH₃, significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. Recommendations and perspectives  The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure–reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.     

Introduction of cob(I)alamin as an analytical tool: application to reaction-kinetic studies of oxiranes

The strongly nucleophilic cob(I)alamin, i.e. Vitamin B₁₂ with Co(III) reduced to Co(I), is introduced as a trapping agent in the determination of concentrations of electrophilic reagents. This compound was applied, in comparison with the previously used moderately reactive nicotinamide (H.J.C.F. Nelis and J.E. Sinsheimer (1981). Anal. Biochem., 115, 151.). Oxiranes, metabolites of 1-alkenes, were chosen as model electrophiles. The reagents (nicotinamide and cob(I)alamin) were evaluated in the determination of the rates of reaction toward valine methylamide, a model of N-terminal valines in hemoglobin often used for monitoring of doses in vivo of genotoxic carcinogens. The rate constants for reaction at 37°C with valine methylamide (k _VMA) determined by the cob(I)alamin and nicotinamide procedure, respectively, were for ethylene oxide (1.6, 1.7), propylene oxide (0.9, 1.1), 1,2-epoxybutane (0.7, 0.8) and 1,2-epoxyoctane (0.5, 0.6) M^?1?h^?1, decreasing with increasing number of carbons of the oxirane. Concentrations of oxiranes trapped with nicotinamide are underrated in reaction mixtures containing valine methylamide due to consumption by reaction with the competing nucleophile, a disturbance that is not observed in trapping with cob(I)alamin which reacts about 10⁵ times faster than nicotinamide. Cob(I)alamin which was demonstrated to be an efficient nucleophile for trapping of electrophiles, also in the presence of competing nucleophiles, is promising as an analytical tool in toxicological studies of reactive compounds. Furthermore, cob(I)alamin can be used to detect, measure and compare electrophilic reactivity of chemical substances, a property that is associated with genotoxic potency.     

Sodium borohydride reduction of individual polybrominated diphenyl ethers

Many chemicals in use today lack appropriate documentation on their environmental properties, fate, and effects. To counteract this lack of documentation it is vital to thoroughly investigate a compound’s fate in the environment before it comes into use. The present study is describing a novel method for assessing the reduction potential of polybrominated diphenyl ethers (PBDEs), as a part of a project aimed to create an experimental model for determination of chemical persistence. The reductive transformation of 15 PBDE congeners using sodium borohydride was determined. Pseudo-first-order reaction rate constants of the transformations were determined by monitoring the disappearance of the investigated congeners. The reductions lead primarily to formation of lower brominated PBDEs. Each PBDE congener was tested in a total of ten replicates which showed a relative standard deviation of 31% or less. The decaBDE, BDE-209 was approximately 3 times as prone to reductive transformation as BDE-207. The three nonaBDEs, BDE-206, BDE-207, and BDE-208, showed similar reductive potential. The reactivity of the tested octaBDEs was quite variable, from 5% to 24% of the reactivity of BDE-209 for BDE-196 and BDE-198, respectively. The heptaBDEs studied were in the range of the less reactive octaBDEs, except for BDE-181 which was as high as 13% of the reactivity of BDE-209. The results presented give a method for measuring the propensity of PBDEs, and possibly similar compounds, to undergo reductions. They indicate a potential route to a vital piece of information in the assessment of environmental persistence of chemicals.