Corelease of Genotoxic Polycyclic Aromatic Hydrocarbons and Nanoparticles from a Commercial Aircraft Jet Engine - Dependence on Fuel and Thrust.

Jet engines are important contributors to global CO2 emissions and release enormous numbers of ultrafine particles into different layers of the atmosphere. As a result, aviation emissions are affecting atmospheric chemistry and promote contrail and cloud formation with impacts on earth's radiative balance and climate. Furthermore, the corelease of nanoparticles together with carcinogenic polycyclic aromatic hydrocarbons (PAHs) affects air quality at airports. We studied exhausts of a widely used turbofan engine (CFM56-7B26) operated at five static thrust levels (idle, 7, 30, 65, and 85%) with conventional Jet A-1 fuel and a biofuel blend composed of hydro-processed esters and fatty acids (HEFA). The particles released, the chemical composition of condensable material, and the genotoxic potential of these exhausts were studied. At ground operation, particle number emissions of 3.5 and 0.5 × 1014 particles/kg fuel were observed with highest genotoxic potentials of 41300 and 8800 ng toxicity equivalents (TEQ)/kg fuel at idle and 7% thrust, respectively. Blending jet fuel with HEFA lowered PAH and particle emissions by 7-34% and 65-67% at idle and 7% thrust, respectively, indicating that the use of paraffin-rich biofuels is an effective measure to reduce the exposure of airport personnel to nanoparticles coated with genotoxic PAHs (Trojan horse effect).

Chemical synthesis and characterization of single-chain C18-chloroparaffin materials with defined degrees of chlorination.

Technical chlorinated paraffins (CPs) are produced via radical chlorination of n-alkane feedstocks with different carbon chain-lengths (∼C10-C30). Short-chain CPs (SCCPs, C10-C13) are classified as persistent organic pollutants (POPs) under the Stockholm Convention. This regulation has induced a shift to use longer-chain CPs as substitutes. Consequently, medium-chain (MCCPs, C14-C17) and long-chain (LCCPs, C>17) CPs have become dominant homologues in recent environmental samples. However, no suitable LCCP-standard materials are available. Herein, we report on the chemical synthesis of single-chain C18-CP-materials, starting with a pure n-alkane and sulfuryl chloride (SO2Cl2). Fractionation of the crude product by normal-phase liquid-chromatography and pooling of suitable fractions yielded in four C18-CP-materials with different chlorination degrees (mCl,EA = 39-52%). In addition, polar side-products, tentatively identified as sulfite-, sulfate- and bis-sulfate-diesters, were separated from CPs. The new single-chain materials were characterized by LC-MS, 1H-NMR and EA. LC-MS provided Relative retention times for different C18-CP homologues and side-products. Mathematical deconvolution of full-scan mass spectra revealed the presence of chloroparaffins (57-93%) and chloroolefins (COs, 7-26%) in the four single-chain C18-CP-materials. Homologue distributions and chlorination degrees were deduced for CPs and COs. 1H-NMR revealed chemical shift ranges of mono-chlorinated (δ = 3.2-5.3 ppm) and non-chlorinated (δ = 1.0-3.2 ppm) hydrocarbon moieties. The synthesized C18-single-chain standard materials and respective spectroscopic data are useful to identify and quantify LCCPs in various materials and environmental samples. CP- and CO-distributions resemble the ones of existing SCCP and MCCP reference materials and technical mixtures. Furthermore, these materials now allow specific studies on the environmental fate and the transformation of long-chain chloroparaffins and chloroolefins.

Effects of Four Prototype Gasoline Particle Filters (GPFs) on Nanoparticle and Genotoxic PAH Emissions of a Gasoline Direct Injection (GDI) Vehicle.

The fast replacement of traditional gasoline port-fuel injection technology with gasoline direct-injection (GDI) vehicles is expected to have a substantial impact on urban air quality. Herein we report on effects of four prototype gasoline particle filters (GPFs) on exhausts of a 1.6 L Euro-5 GDI vehicle. Two noncoated and two filters with catalytic coatings were investigated. These filters, on average, lowered PN emissions 4-7-fold to 4.0-6.8 × 1011 particles/km. Genotoxic PAHs were lowered 2-5-fold too with GPF-1-3, with GPF-1 having the highest efficiency, 79% and resulting in 45 ng toxic equivalent concentration (TEQ)/km. Thus, particle filtration efficiencies and reduction of the genotoxic potentials are correlated. GPF-4 showing the poorest particle filtration efficiency (66-78%) also released exhausts with highest genotoxic potential of 240-530 ng TEQ/km. We recently reported particle-number (PN) emissions of four generations of GDI vehicles (Euro-3 to Euro-6) which released, on average, 2.5 × 1012 ± 1.8 × 1012 particles/km exceeding the current European limit of 6.0 × 1011 particle/km. Thus, the implementation of filters to GDI vehicles requires best-available technology (BAT) with PN efficiencies >98% and catalytic activity, to avoid store-and-release of genotoxic PAHs. In-series applications of BAT-filters to GDI vehicles can lower genotoxic PAHs and soot nanoparticles.

Bioethanol Blending Reduces Nanoparticle, PAH, and Alkyl- and Nitro-PAH Emissions and the Genotoxic Potential of Exhaust from a Gasoline Direct Injection Flex-Fuel Vehicle.

Bioethanol as an alternative fuel is widely used as a substitute for gasoline and also in gasoline direct injection (GDI) vehicles, which are quickly replacing traditional port-fuel injection (PFI) vehicles. Better fuel efficiency and increased engine power are reported advantages of GDI vehicles. However, increased emissions of soot-like nanoparticles are also associated with GDI technology with yet unknown health impacts. In this study, we compare emissions of a flex-fuel Euro-5 GDI vehicle operated with gasoline (E0) and two ethanol/gasoline blends (E10 and E85) under transient and steady driving conditions and report effects on particle, polycyclic aromatic hydrocarbon (PAH), and alkyl- and nitro-PAH emissions and assess their genotoxic potential. Particle number emissions when operating the vehicle in the hWLTC (hot started worldwide harmonized light-duty vehicle test cycle) with E10 and E85 were lowered by 97 and 96% compared with that of E0. CO emissions dropped by 81 and 87%, while CO2 emissions were reduced by 13 and 17%. Emissions of selected PAHs were lowered by 67-96% with E10 and by 82-96% with E85, and the genotoxic potentials dropped by 72 and 83%, respectively. Ethanol blending appears to reduce genotoxic emissions on this specific flex-fuel GDI vehicle; however, other GDI vehicle types should be analyzed.

Biofuel-Promoted Polychlorinated Dibenzodioxin/furan Formation in an Iron-Catalyzed Diesel Particle Filter.

Iron-catalyzed diesel particle filters (DPFs) are widely used for particle abatement. Active catalyst particles, so-called fuel-borne catalysts (FBCs), are formed in situ, in the engine, when combusting precursors, which were premixed with the fuel. The obtained iron oxide particles catalyze soot oxidation in filters. Iron-catalyzed DPFs are considered as safe with respect to their potential to form polychlorinated dibenzodioxins/furans (PCDD/Fs). We reported that a bimetallic potassium/iron FBC supported an intense PCDD/F formation in a DPF. Here, we discuss the impact of fatty acid methyl ester (FAME) biofuel on PCDD/F emissions. The iron-catalyzed DPF indeed supported a PCDD/F formation with biofuel but remained inactive with petroleum-derived diesel fuel. PCDD/F emissions (I-TEQ) increased 23-fold when comparing biofuel and diesel data. Emissions of 2,3,7,8-TCDD, the most toxic congener [toxicity equivalence factor (TEF) = 1.0], increased 90-fold, and those of 2,3,7,8-TCDF (TEF = 0.1) increased 170-fold. Congener patterns also changed, indicating a preferential formation of tetra- and penta-chlorodibenzofurans. Thus, an inactive iron-catalyzed DPF becomes active, supporting a PCDD/F formation, when operated with biofuel containing impurities of potassium. Alkali metals are inherent constituents of biofuels. According to the current European Union (EU) legislation, levels of 5 µg/g are accepted. We conclude that risks for a secondary PCDD/F formation in iron-catalyzed DPFs increase when combusting potassium-containing biofuels.

Releases of chlorobenzenes, chlorophenols and dioxins during fireworks.

In fireworks, organic additives with high chlorine content such as hexachlorobenzene (HCB) are used for the improvement of illumination effects. In the course of a monitoring campaign for the detection of HCB in fireworks, atmospheric concentrations of chlorobenzenes (CBs), chlorophenols (CPs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), were measured during the Swiss National holiday August 1, 2011 which is celebrated with fireworks nationwide. Samples were collected in the city of Zurich using high-volume air samplers equipped with quartz fiber filters and poly-urethane foam plugs. With one sampling period of 3h, a peak HCB concentration of 297 pg m(-3) was detected. Maximum total concentrations of pentachlorophenol and PCDD/Fs were 218 pg m(-3) and 61 fg I-TEQ m(-3), respectively. These levels are in the order of ten times above background concentrations measured one week before and two weeks after the event. Atmospheric emissions of HCB and CPs were quantified using a multimedia mass balance model to interpret the field measurements resulting in total emissions of HCB and CPs during the event of 23 g and 25 g, respectively. Based on per capita amounts this corresponds to total annual emissions from fireworks of 1.5 kg for each of the two pollutants in Switzerland. Starting from an estimation of the total worldwide emissions of HCB, in Switzerland emissions from fireworks may represent about 2-14% of total HCB releases.

Formation of PBDD/F from PBDE in electronic waste in recycling processes and under simulated extruding conditions.

The increasing volumes of waste electrical and electronic equipment (WEEE) in Europe and developing economies demand for efficient disposal solutions. However, WEEE also contains toxic compounds and, therefore, there is a need for recycling technologies for WEEE that creates revenue without causing environmental harm. Among other fast developing economies, South Africa is tempting to make use of recycled plastic. Brominated flame retardants (BFRs) are additives used to protect plastic materials in electrical and electronic equipment (EEE) against ignition. Some BFRs are known persistent organic pollutants (POPs) and some BFRs can be transformed into highly toxic compounds such as polybrominated dibenzofurans and dioxins (PBDD/Fs). In this study, the contents of critical BFRs, i.e. polybrominated diphenyl ethers, and highly toxic PBDD/Fs were measured in WEEE material from Switzerland and South Africa. The formation of PBDD/Fs has been observed in two South African recycling processes and under controlled laboratory conditions. Total PBDE-contents in the South African and Swiss plastic waste varied between 1×10(3) and 7×10(6) µg kg(-1). A few WEEE plastic fractions exceeded the RoHS limit of 1×10(6) µg kg(-1) for PBDEs and thus they could not be used for recycling products without special treatment. The total content of ∑PBDFs was around 1×10(3) µg kg(-1). Such contents in materials do not pose a risk for consumer under normal conditions. Workers at recycling plants might be at risk. The measured formation rates of PBDFs were between 2×10(-5) and 2×10(-4)∑PBDE(-1) min(-1).

Release and environmental impact of silver nanoparticles and conventional organic biocides from coated wooden façades.

This study represents for the first time a comprehensive assessment of functionality and environmental impacts of metallic silver nanoparticles (Ag-NP) compared to conventional organic biocides. Four different transparent, hydrophobic coatings of wooden outdoor façades were tested during one year outdoor weathering. The total silver release from products with Ag-NP was proportional to the overall erosion of the coating. The results indicate that the Ag-NPs are likely transformed to silver complexes, which are considerably less toxic than ionic silver. The protective effect of the silver containing coatings against mold, blue stain and algae was insufficient, even in immaculate and non-weathered conditions. The release of organic biocides from conventional coatings was dependent on the weather conditions, the type of biocide and the use in the base or top coat. The conventional coating showed a good overall performance free from mold, blue stain and algae until the end of the test period.

PCDD/F formation in an iron/potassium-catalyzed diesel particle filter.

Catalytic diesel particle filters (DPFs) have evolved to a powerful environmental technology. Several metal-based, fuel soluble catalysts, so-called fuel-borne catalysts (FBCs), were developed to catalyze soot combustion and support filter regeneration. Mainly iron- and cerium-based FBCs have been commercialized for passenger cars and heavy-duty vehicle applications. We investigated a new iron/potassium-based FBC used in combination with an uncoated silicon carbide filter and report effects on emissions of polychlorinated dibenzodioxins/furans (PCDD/Fs). The PCDD/F formation potential was assessed under best and worst case conditions, as required for filter approval under the VERT protocol. TEQ-weighted PCDD/F emissions remained low when using the Fe/K catalyst (37/7.5 µg/g) with the filter and commercial, low-sulfur fuel. The addition of chlorine (10 µg/g) immediately led to an intense PCDD/F formation in the Fe/K-DPF. TEQ-based emissions increased 51-fold from engine-out levels of 95 to 4800 pg I-TEQ/L after the DPF. Emissions of 2,3,7,8-TCDD, the most toxic congener (TEF = 1.0), increased 320-fold, those of 2,3,7,8-TCDF (TEF = 0.1) even 540-fold. Remarkable pattern changes were noticed, indicating a preferential formation of tetrachlorinated dibenzofurans. It has been shown that potassium acts as a structural promoter inducing the formation of magnetite (Fe3O4) rather than hematite (Fe2O3). This may alter the catalytic properties of iron. But the chemical nature of this new catalyst is yet unknown, and we are far from an established mechanism for this new pathway to PCDD/Fs. In conclusion, the iron/potassium-catalyzed DPF has a high PCDD/F formation potential, similar to the ones of copper-catalyzed filters, the latter are prohibited by Swiss legislation.

Effects of a combined Diesel particle filter-DeNOx system (DPN) on reactive nitrogen compounds emissions: a parameter study.

The impact of a combined diesel particle filter-deNO(x) system (DPN) on emissions of reactive nitrogen compounds (RNCs) was studied varying the urea feed factor (α), temperature, and residence time, which are key parameters of the deNO(x) process. The DPN consisted of a platinum-coated cordierite filter and a vanadia-based deNO(x) catalyst supporting selective catalytic reduction (SCR) chemistry. Ammonia (NH3) is produced in situ from thermolysis of urea and hydrolysis of isocyanic acid (HNCO). HNCO and NH3 are both toxic and highly reactive intermediates. The deNO(x) system was only part-time active in the ISO8178/4 C1cycle. Urea injection was stopped and restarted twice. Mean NO and NO2 conversion efficiencies were 80%, 95%, 97% and 43%, 87%, 99%, respectively, for α = 0.8, 1.0, and 1.2. HNCO emissions increased from 0.028 g/h engine-out to 0.18, 0.25, and 0.26 g/h at α = 0.8, 1.0, and 1.2, whereas NH3 emissions increased from <0.045 to 0.12, 1.82, and 12.8 g/h with maxima at highest temperatures and shortest residence times. Most HNCO is released at intermediate residence times (0.2-0.3 s) and temperatures (300-400 °C). Total RNC efficiencies are highest at α = 1.0, when comparable amounts of reduced and oxidized compounds are released. The DPN represents the most advanced system studied so far under the VERT protocol achieving high conversion efficiencies for particles, NO, NO2, CO, and hydrocarbons. However, we observed a trade-off between deNO(x) efficiency and secondary emissions. Therefore, it is important to adopt such DPN technology to specific application conditions to take advantage of reduced NO(x) and particle emissions while avoiding NH3 and HNCO slip.

Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization.

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.

Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of beta-HBCD racemization.

Hexabromocyclododecanes (HBCDs) are high production volume chemicals currently produced in quantities exceeding 20000ty(-1). They are used as flame retardants for plastics and textiles. HBCDs are thermally labile compounds, rapidly decomposing at temperatures above 250 degrees C to form bromine radicals, which scavenge other radicals formed during pyrolysis. But certain HBCD stereoisomers must reach the environment without decomposition, because their levels in soils, sediments, and biota are increasing worldwide. The fate of individual HBCD stereoisomers during production, product use, disposal, and transformation in the environment remains unclear. Herein we report on the thermally induced, highly selective isomerization of (+) and (-)beta-HBCD. Regio- and stereoselective migration of only two of the six bromine atoms resulted in the racemization of both beta-HBCDs. First order rate constants (k(rac)) increased from 0.005, 0.011, 0.021, to 0.055min(-1) at 130, 140, 150, and 160 degrees C, corresponding to half life times tau(1/2) of 143, 63, 29, and 14min, respectively. From the deduced kinetic model, we conclude that any thermal treatment of enantiomerically enriched beta-HBCDs in the range of 100-160 degrees C will result in a loss of most optical activity within few hours. The simultaneous inversion of two asymmetric centers occurred with perfect stereocontrol. Selectively, vicinal dibromides with the RR- and the SS-configurations migrated at these temperatures. An intramolecular reaction mechanism with a four-center transition state is postulated, based on the obtained stereoisomer pattern and the observed reaction kinetics. Crystal structure analysis revealed that all vicinal dibromides in beta-HBCDs prefer synclinal (gauche) conformations. However, an antiperiplanar (staggered) conformation is assumed to facilitate the concerted 1.2-shifts of both bromine atoms, resulting in an inversion of both neighboring carbon atoms. First experiments with other HBCD stereoisomers suggest that the presented isomerization mechanism is of relevance for those stereoisomers as well.

Solid-state conformations and absolute configurations of (+) and (-) alpha-, beta-, and gamma-hexabromocyclododecanes (HBCDs).

Hexabromocyclododecanes (HBCDs) are high production volume chemicals used as flame retardants for plastics and textiles. They are currently produced in quantities exceeding 20,000 t/y. Despite this fact, the correct stereochemistry of most HBCDs is still not known. Six stereocenters are formed during bromination of cyclododecatrienes, resulting in mixtures of different stereoisomers. Considering all elements of symmetry, 16 different stereoisomers including six pairs of enantiomers as well as 4 meso forms are possible theoretically. Recently, we isolated 8 of the 16 possible stereoisomers from a technical HBCD mixture and assigned their relative configurations. Herein, we report on the isolation of 6 enantiomerically pure alpha-, beta-, and gamma-HBCDs, obtained from preparative chiral-phase liquid chromatography, and we present their absolute configurations, which were determined from X-ray diffraction analysis. The absolute configuration of (-) alpha-HBCD was found to be (1R,2R,5S,6R,9R,10S), while the one of (+) beta-HBCD is assigned to (1S,2S,5S,6R,9S,10R), whereas the one of (-) gamma-HBCD corresponds to (1S,2S,5S,6R,9R,10S). The given structural information allows the unambiguous identification of the six most important HBCD stereoisomers, which typically account for more than 95% of technical HBCDs. In addition, we compared the solid-state conformations of racemic and enantiomerically pure alpha-, beta-, and gamma-HBCDs. In all cases, vicinal dibromides adopted a synclinal (sc) conformation with torsion angles of 69+/-6 degrees. A unique structural motive was common to all examined HBCD solid-state conformations. This conserved structure was described as an extended triple turn consisting of an arrangement of three pairs of synclinal and two antiperiplanar torsion angles.

Crystal structure analysis of enantiomerically pure (+) and (-) beta-hexabromocyclododecanes.

The molecular structures of individual HBCD stereoisomers are not elucidated yet. Recently, we isolated 8 of the 16 possible stereoisomers from a technical HBCD mixture and tentatively assigned their relative configurations. Herein we report on the isolation of enantiomerically pure (+) and (-) beta-HBCDs, both obtained from preparative chiral-phase liquid chromatography, and we present their absolute configurations determined from X-ray diffraction analysis. The absolute configuration of (+) beta-HBCD was found to be (1S,2S,5S,6R,9S,10R), while the one of (-) beta-HBCD was assigned to (1R,2R,5R,6S,9R,10S). The given structural information allows, for the first time, the unambiguous identification of these two important HBCD stereoisomers, which are typically found in technical products at proportions of about 3-5% for each enantiomer.