Crystal structure of δ-isobutoxypentabromo-cyclododecanes, kinetics and selectivity of their isomerization during thermal treatment of flame-proofed polystyrenes

Hexabromocyclododecanes (HBCDs) are persistent organic pollutants now ubiquitous in the environment. Technical HBCD mixtures and with it flame-proofed polystyrenes (FP-PS) also contain isobutoxypentabromocyclododecanes (iBPBCDs) as minor constituents, which are possibly released together with HBCDs. So far, eight diastereomeric pairs of enantiomers named as α-, β-, γ-, δ-, ?-, ξ-, η-, and θ-iBPBCDs with proportions of 10%, 5%, 2%, 21%, 11%, 11%, 12% and 28% were found in technical HBCD. Herein the crystal structure of racemic δ-iBPBCD, the second most prominent diastereomer, is presented and assigned to (1S)-1-isobutoxy-(2R,5R,6S,9S,10S)-2,5,6,9,10-pentabromocyclododecane and its enantiomer. During thermal treatment of FP-PS, e.g. the production of extruded polystyrenes (XPS), proportions of δ-iBPBCDs decrease and those of other stereoisomers increase. Evidence was found that δ-iBPBCDs isomerize stereo- and regioselectively to β-iBPBCDs. Based on structural and kinetic data, a transformation mechanism was proposed. Apparent first-order rate constants (k_iso) of 0.0019, 0.0050, and 0.012 min⁻¹ are found for the δ- to β-iBPBCD isomerization at 120, 130, and 140 °C, respectively, corresponding to half-lives of 360, 140, and 56 min. These transformations also occur during the production of XPS, which predominantly contain β-iBPBCDs, whereas δ-iBPBCDs dominate in materials experiencing lower thermal stress, e.g. expanded polystyrenes (EPS). The relative configurations of δ- and θ-iBPBCDs are TtCtCt, like the one of γ-HBCDs. γ-HBCDs are the kinetically and α-HBCDs with a TcCtCc configuration the thermodynamically favored products. In analogy, β-iBPBCDs are assumed to have a TcCtCc configuration like α-HBCDs because they are formed from δ-iBPBCDs under thermodynamic control. In conclusion, HBCD- and iBPBCD-patterns in flame-proofed polystyrenes vary substantially, reflecting the thermal stress these materials have experienced. When released to the environment, these patterns might further change, as observed for HBCDs.     

Is PCBs concentration variability between and within freshwater fish species explained by their contamination pathways?

Many chemical, physiological, and trophic factors are known to affect bioaccumulation of polychlorinated biphenyls (PCBs) in biota. Understanding the primary factors affecting fish contamination is critical for predicting and assessing risks to upper-trophic level consumers, including humans. Here we identify PCB contamination pathways that could explain within- and between-species variability in fish concentration levels. Three freshwater river fish species (barbel, chub and bream) were sampled at three sites along the Rhone River (France) where fish consumption is partially prohibited because of PCB levels exceeding the European health-based benchmark. The trophic position was assessed using an innovative approach based on stable isotope analyses and Bayesian inference, which takes into account both isotope data variability and parameter uncertainty. The effect of foraging habitat on fish contamination was addressed using stable isotope mixing models. The fish trophic position and PCB concentrations were found to be unrelated while the exploitation of sediment detrital carbon as a food source appeared to be a critical factor affecting fish contamination. Fish length, PCB concentration of the sediment, and individual fish foraging habitat (exploitation of detrital versus planktonic carbon sources) explained 80% of within- and between-species variability observed in PCB concentrations. These results, obtained for species that have overlapping TPs and exploit different carbon sources, reveal that the important factor in fish PCB contamination is not only what fish consume, but also and essentially the feeding location.     

Do laboratory salinity tolerances of freshwater animals correspond with their field salinity?

The degree to which laboratory derived measures of salinity tolerance reflect the field distributions of freshwater biota is uncertain. In this paper we compare laboratory-derived acute salinity tolerance (LC(50) values) of freshwater macroinvertebrates (range 5.5-76 mS/cm) and fish (range 2.7-82 mS/cm) from southeastern Australia with the salinity from which they have been collected in the field. Only 4% of the macroinvertebrates were collected at salinity levels substantially higher than their 72-h LC(50) obtained from directly transferring animals from low salinity water to the water they were tested (direct transfer LC(50)). This LC(50) value was correlated with the maximum salinity at which a species had been collected. For common macroinvertebrates, the maximum field salinity was approximated by the direct transfer 72-h LC(50). For adult freshwater fish, 21% of species were collected at salinities substantially greater than their acute direct transfer LC(50) and there was a weak relationship between these two variables. Although there was a weak correlation between the direct transfer LC(50) of early life stages of freshwater fish and the maximum field salinity, 58% of the field distribution were in higher than their LC(50) values. In contrast, LC(50) determined from experiments that acclimated adult fish to higher salinity (slow acclimation) provided a better indication of the field distribution: with only one fish species (7%) being in conflict with their maximum field salinity and a strong positive relationship between these variables. This study shows that laboratory measures of acute salinity tolerance can reflect the maximum salinity that macroinvertebrate and fish species inhabit and are consistent with some anecdotal observations from other studies.     

Identification and assessment of ship emissions and their effects in the harbour of Göteborg,Sweden

The effect of ship emissions in the urban environment of Göteborg has been studied by multivariate analysis. The simultaneous measurements of relevant gases and sub-micron particles make identification of ship plumes possible. Increased concentrations of these species due to ship emissions are quantified for ships entering the inner part of the harbour. Annual depositions of SO₂ and NO₂ are estimated to be 220 and 115 kg km⁻² yr⁻¹, respectively. Exposure of transient particles (less than 0.1 μm in diameter) to this part of the harbour increased by a factor of 3 in number concentration when a ship plume was recorded. Ni, Pb, V and Zn are shown to have positive correlation with NO emissions from ships.     

Measurements of JNO3− in snow by nitrate-based actinometry

Chemical actinometry was used to measure nitrate photolysis rate coefficients, J_NO3⁻, on and in snowpack at Summit, Greenland. Sealed glass tubes containing nitrate and a hydroxyl radical trapping system were buried in snow and exposed for between 2 and 24 h. Average J_NO3⁻ values for 2-h midday exposures in early June on surface snow were 10–14×10⁻⁷ s⁻¹. Averages over 24 h were 3.5–4.5×10⁻⁷ s⁻¹. These values reflect the integrated photon flux and also any variation of the nitrate photolysis rate with temperature. Attenuation of J_NO3⁻ within the firn was 0.03–0.04 cm⁻¹ for 24-h exposures and 0.08 cm⁻¹ for a 2-h exposure. Different attenuation coefficients may relate to differential light penetration due to changes in sun angle over the course of 24 h.     

Abiotic oxidation of 17β-estradiol by soil manganese oxides

The degradation of 17β-estradiol (E2) in sterile soil and Mn-free soil slurries was determined. In 0.075 g ml⁻¹ soil slurry, E2 with an initial concentration of 0.0267 μmol g⁻¹ was rapidly degraded and near equimolar estrone (E1) accumulated. A mass balance involving E2 and E1 existed throughout the reaction. The E2 degradation was thus an oxidation process and E1 was the only product. The concurrent release of Mn(II) during E2 oxidation and a lack of E2 oxidation in Mn-free soil slurry together demonstrated that soil manganese oxides were responsible for E2 oxidation. The degree of E2 oxidation was higher at high pH than at low pH, consistent with the fact that the reaction released protons. This study suggests that manganese oxides may be used as soil amendments to effectively oxidize E2 to less potent E1 in soil.     

Effects of biodegradation and sorption by humic acid on the estrogenicity of 17β-estradiol

The removal of 17β-estradiol (E2) by biodegradation and sorption onto humic acid (HA) was examined at various HA concentrations. Subsequently, estrogenicity associated with E2 removal was estimated using E-screen bioassay. Results showed that E2 biodegradation and its subsequent transformation to estrone (E1) were significantly reduced with increasing HA concentration. In addition, the presence of nutrients enhanced the biodegradation of E2. Overall, E2 biodegradation was the dominating contributor to its removal, which demonstrated a significantly negative correlation with E2 sorption at various HA concentrations. The sorption of E2 by HA was significantly enhanced with increasing HA concentration. Estrogenicity associated with residual E2 showed that there existed a significant difference among various HA concentrations, with the lowest value in the absence of HA. The findings suggest that the presence of HA and nutrients in natural waters should be considered in assessing estrogenicity of environmental samples due to complex sorption and biodegradation processes.     

Determination of picogram quantities of chlortoluron in soil samples by luminol–chitosan chemiluminescence system

Based on the enhancing effect of chitosan (CS) on luminol-dissolved oxygen chemiluminescence (CL) reaction, a flow injection (FI) luminol–CS CL system was established. It was found that the increase of CL intensity was proportional to the concentrations of CS ranging from 0.7 to 10.0 μmol l^?1. In the presence of chlortoluron (CTU), the CL intensity of luminol–CS system could be obviously inhibited and the decrements of CL intensity were linearly proportional to the logarithm of CTU concentrations ranging from 0.01 to 70.0 ng ml^?1, giving the limit of detection 3.0 pg ml^?1 (3σ). At a flow rate of 2.0 ml min^?1, the whole process including sampling and washing could be accomplished within 36 s, offering a sample throughput of 100 h^?1. The proposed FI–CL method was successfully applied to the determination of CTU in soil samples with recoveries ranging from 95.0 % to 105.3 % and the relative standard deviations (RSDs) of less than 4.0 %.     

Release of soil bound (nonextractable) residues by various physiological groups of microorganisms∗

Abstract

Soil bound ¹⁴C‐labeled residues were released by four different physiological groups of microorganisms from an organic soil treated with ¹⁴C‐ring‐labeled prometryn [2‐(methylthio) ‐4,6‐bis(isopropylamino)‐s‐triazine]. The extent to which the different microbial populations released bound ¹⁴C residues (25–30% of the total bound ¹⁴C) from the Y‐irradiated soil after 28 days incubation did not differ considerably. Analysis of the extractable material from the incubated soil showed the presence of small amounts of the parent compound, and its hydroxy and mono‐N‐dealkylated analogues. Low level of ¹⁴CO₂ (1.5–3.0% of the total bound ¹⁴C) was evolved from the microbial systems indicating ring cleavage of the released material as being a very minor reaction.     

Physico-chemical characteristics of pulverized coals and their interrelations—a spontaneous combustion and explosion perspective

Environmental Science and Pollution Research - Characteristics of pulverized coals have significant influence on the spontaneous combustion and explosion processes. This paper presents an...     

Sustainable mechanochemical synthesis of β-cyclodextrin polymers by twin screw extrusion

Environmental Science and Pollution Research - Cyclodextrin nanosponges (CD-NS) are cross-linked cyclodextrin polymers characterized by a nanostructured three-dimensional network. CD-NSs in the...     

Decomposition of NO in automobile exhaust by plasma–photocatalysis synergy

The combination of plasma discharge and TiO₂ photocatalysis exhibits high performances in the removal of nitrogen monoxide (NO). This article is aimed at elucidating the relationships between NO decomposition efficiency and various experimental parameters, including voltages, humidity and temperature. The experimental results indicate that the efficiency of NO removal by synergic plasma-catalyst coupling is significantly higher than plasma only or photocatalyst only systems. Moreover, the NO removal efficiency improves with the increase of applied voltage. Meanwhile, a higher humidity results in a reduced number of electron–hole pairs at the surface of TiO₂ photocatalyst, leading to lower synergic purification efficiencies. Finally, the efficiency of NO removal is raised with the increase of temperature due to the fact that the adsorption of NO and water by nano-TiO₂ is affected by environmental temperature.     

High uptake of 2,4,6-trinitrotoluene by vetiver grass--potential for phytoremediation?

2,4,6-Trinitrotoluene (TNT) is a potent mutagen, and a Group C human carcinogen that has been widely used to produce munitions and explosives. Vast areas that have been previously used as ranges, munition burning, and open detonation sites are heavily contaminated with TNT. Conventional remediation activities in such sites are expensive and damaging to the ecosystem. Phytoremediation offers a cost-effective, environment-friendly solution, utilizing plants to extract TNT from contaminated soil. We investigated the potential use of vetiver grass (Vetiveria zizanioides) to effectively remove TNT from contaminated solutions. Vetiver grass plants were grown in hydroponic systems containing 40 mg TNTL(-1) for 8d. Aqueous concentrations of TNT reached the method detection limit ( approximately 1 microg L(-1)) within the 8-d period, demonstrating high affinity of vetiver for TNT, without any visible toxic effects. Results from this preliminary hydroponic study are encouraging, but in need of verification using TNT-contaminated soils.     

Organic micropollutants’ distribution within sludge organic matter fractions explains their dynamic during sewage sludge anaerobic digestion followed by composting

The simultaneous fate of organic matter and 4 endocrine disruptors (3 polycyclic aromatic hydrocarbons (PAHs) (fluoranthene, benzo(b)fluoranthene, and benzo(a)pyrene) and nonylphenols (NP)) was studied during the anaerobic digestion followed by composting of sludge at lab-scale. Sludge organic matter was characterized, thanks to chemical fractionation and 3D fluorescence deciphering its accessibility and biodegradability. Total chemical oxygen demand (COD) removal was 41% and 56% during anaerobic digestion and composting, respectively. 3D fluorescence highlighted the quality changes of organic matter. During continuous anaerobic digestion, organic micropollutants’ removal was 22?±?14%, 6?±?5%, 18?±?9%, and 0% for fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, and nonylphenols, respectively. Discontinuous composting allowed to go further on the organic micropollutants’ removal as 34?±?8%, 31?±?20%, 38?±?10%, and 52?±?6% of fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, and nonylphenols were dissipated, respectively. Moreover, the accessibility of PAH and NP expressed by their presence in the various sludge organic matter fractions and its evolution during both treatments was linked to both the quality evolution of the organic matter and the physicochemical properties of the PAH and NP; the presence in most accessible fractions explained the amount of PAH and NP dissipated.

     

Biodegradation of α and β Endosulfan in Soil as Influenced by Application of Different Organic Materials

Abstract

A laboratory pot experiment was conducted to study the effect of amending soil with four different sources of organic matter on the degradation rate of α and β endosulfan isomers. Poultry by-product meal, poultry manure, dairy manure, and municipal solid waste compost were cured, dried, ground (<1 mm) and thoroughly mixed with a calcareous soil at a rate of 2% and placed in plastic pots. Endosulfan was added at the rate of 20 mg kg^?1. The moisture level was kept near field capacity and the pots were kept at room temperature. Soil sub-samples, 100 g each, were collected from every pot at days 1, 8, 15, 22, 29, 43, and 57 for the measurement of endosulfan isomers. Endosulfan residues were extracted from the soil samples with acetone. The supernatant was filtered through anhydrous sodium sulphate, 5 mL aliquot was diluted to 25 mL with hexane, mixed well, and then two sub-samples from the filtrates were analyzed for α and β endosulfan isomers by gas chromatography. The results indicated that the half-life (T _½) of α-endosulfan in the poultry by-product meal treatment was 15 days compared to about 22 days in the other treatments. The T _½ of β-endosulfan was 22 days in the poultry by-product meal treatment and followed a bi-phasic pattern, 57 days in the municipal solid waste compost treatment and the extrapolated T _½ was about 115 days for the other three treatments.     

Detection of indoor PCB contamination by thermal desorption of dust. A rapid screening method?

Although PCB in caulking materials has been forbidden for many years in most of Europe, including Denmark, there has been continued interest to measure PCB levels in the air of contaminated buildings and blood of the occupants (Mengon and Schlatter 1993, Fromme et al. 1996, Ewers et al. 1998, Currado and Harrad 1998, Gabrio et al. 2000). The relatively low priority for investigations of this contamination is probably due to the small quantities inhaled compared to exposure via food, and the rapid metabolism of the most volatile congeners demonstrated by low concentrations of all congeners in the blood of exposed persons (Ewers et al. 1998, Gabrio et al. 2000). There is, however, evidence that PCB containing caulking materials have been used even during the '90s (Fromme et al. 1996). In Denmark, it is estimated that 75 t PCB is still in buildings (Organization of Sealant Branch's Manufacturers and Distributors 2000). During an investigation of dust from buildings with excessive microbial growth (including 35 rooms from 9 buildings), the analysis of semivolatile compounds by thermal desorption-GC/MS of samples from a single building surprisingly revealed large amounts of PCBs containing 3, 4 and 5 chlorine atoms, 10-20 times the amounts found in samples from other buildings. Extraction of the dust by SFE followed by GC/ECD analysis for 12 PCB congeners showed that there was approximately 20 times the total PCB concentrations in dust from the polluted building compared to the levels in the other buildings. Subsequent headspace analysis of caulking material from the polluted building revealed this to be the source. Shelf dust functions as a passive sampling medium and, thus, can be used as a screening method to detect PCB and other semivolatile pollution indoors.     

Long-term measurements of iron-containing aerosols by Mössbauer spectroscopy in Poland

Mössbauer spectroscopy was applied to analyze the iron compounds present in atmospheric aerosol. As a significant part of air pollution, especially in winter months, iron appeared in the form of iron sulfides (FeS₂, FeS and Fe_1−xS), which were products of coal combustion. Also, iron oxyhydroxides and iron oxides, mostly α-Fe₂O₃ (bulk) and in the form of ultra fine particles in superparamagnetic state were observed. The concentration of iron in atmospheric air was calculated from the experimental spectra. Seasonal variations of iron concentration in atmospheric air measured over twenty years in the mountain region of Poland are discussed.     

Modeling redistribution of α-HCH in Chinese soil induced by environment factors

This study explores long-term environmental fate of α-HCH in China from 1952 to 2007 using ChnGPERM (Chinese Gridded Pesticide Emission and Residue Model). The model captures well the temporal and spatial variations of α-HCH concentration in Chinese soils by comparing with a number of measured data across China in different periods. The results demonstrate α-HCH grasshopping effect in Eastern China and reveal several important features of the chemical in Northeast and Southeast China. It is found that Northeast China is a prominent sink region of α-HCH emitted from Chinese sources and α-HCH contamination in Southwest China is largely attributed to foreign sources. Southeast China is shown to be a major source contributing to α-HCH contamination in Northeast China, incurred by several environmental factors including temperature, soil organic carbon content, wind field and precipitation.