Janine Schindelka

Sulfate radical-initiated formation of isoprene-derived organosulfates in atmospheric aerosols

Recent studies show that isoprene-derived organosulfates are an important fraction of ambient secondary organic aerosol (SOA), adding up to 20% to the organic mass. Organosulfates with m/z of 199 and 183 relating to C4 compounds are found in ambient and laboratory generated SOA and a sulfate radical induced oxidation of methacrolein (MACR) and methyl vinyl ketone (MVK) has been shown to be a possible formation mechanism. In the present study, experiments on the sulfate radical-induced oxidation of methacrolein and methyl vinyl ketone were performed in bulk aqueous phase, as well as in an aerosol chamber, and finally compared with ambient PM10 samples collected at a rural East German village during the summer 2008, to investigate their relevance in aqueous phase SOA formation. Samples from aqueous phase experiments and extracts from filters were analysed with UPLC/(-)ESI-IMS-QTOFMS. All the samples showed the abundance of highly oxidised organosulfates with m/z 153, 155, 167, 183 and 199 corresponding to the species found in ambient particle samples. In the bulk phase studies with laser-induced sulfate radical formation, the signal intensities increased with increasing number of laser pulses, indicating the sulfate radical-induced formation of these organosulfates. Additionally, the chamber experiments showed a particle mass growth of about 10 microg m(-3) and 4 microg m(-3) for experiments on the reactive uptake of MACR and MVK with a sulfate radical precursor (K2S2O8) in the seed particles. Correlations of the C2 to C5 organosulfate species (including the m/z 215, C5H11O7S-), detected in the ambient samples were found to be very strong (r > 0.8), indicating that these compounds are formed from similar mechanisms and under equal environmental conditions. This study shows that sulfate radical-induced oxidation in the aqueous particle phase provides a reasonable explanation for the formation of these organosulfates from methacrolein and methyl vinyl ketone.

Compound specific stable isotope analysis (CSIA) to characterize transformation mechanisms of α-hexachlorocyclohexane

A systematic investigation of environmentally relevant transformation processes of alpha-hexachlorocyclohexane (α-HCH) was performed in order to explore the potential of compound specific stable isotope analysis (CSIA) to characterize reaction mechanisms. The carbon isotope enrichment factors (ɛC) for the chemical transformations of α-HCH via direct photolysis, indirect photolysis (UV/H2O2), hydrolysis, electro-reduction or reduction by Fe(0) were quantified and compared to those previously published for biodegradation. Hydrogen abstraction by hydroxyl radicals generated by UV/H2O2 led to ɛC of -1.9 ± 0.2 ‰ with an apparent kinetic carbon isotope effect (AKIEC) of 1.012 ± 0.001. Dehydrochlorination by alkaline hydrolysis yielded ɛC of -7.6 ± 0.4 ‰ with AKIEC of 1.048 ± 0.003. Dechlorination either by homolytic bond cleavage in direct photolysis (ɛC=-2.8 ± 0.2 ‰) or single-electron transfer in electro-reduction (ɛC=-3.8 ± 0.4 ‰) corresponded to AKIEC of 1.017 ± 0.001 and 1.023 ± 0.003, respectively. Dichloroelimination catalyzed by Fe(0) via two-electron transfers resulted in ɛC of -4.9 ± 0.1 ‰. AKIEC values assuming either a concerted or a stepwise mechanism were 1.030 ± 0.0006 and 1.015 ± 0.0003, respectively. Contrary to biodegradation, no enantioselectivity of α-HCH was observed in chemical reactions, which might be used to discriminate chemical and biological in situ transformations.

Investigation of Humic Substance Photosensitized Reactions via Carbon and Hydrogen Isotope Fractionation

Humic substances (HS) acting as photosensitizers can generate a variety of reactive species, such as OH radicals and excited triplet states ((3)HS*), promoting the degradation of organic compounds. Here, we apply compound-specific stable isotope analysis (CSIA) to characterize photosensitized mechanisms employing fuel oxygenates, such as methyl tert-butyl ether (MTBE) and ethyl tert-butyl ether (ETBE), as probes. In oxygenated aqueous media, Λ (Δδ(2)H/Δδ(13)C) values of 23 ± 3 and 21 ± 3 for ETBE obtained by photosensitization by Pahokee Peat Humic Acid (PPHA) and Suwannee River Fulvic Acid (SRFA), respectively, were in the range typical for H-abstraction by OH radicals generated by photolysis of H2O2 (Λ = 24 ± 2). However, (3)HS* may become a predominant reactive species upon the quenching of OH radicals (Λ = 14 ± 1), and this process can also play a key role in the degradation of ETBE by PPHA photosensitization in deoxygenated media (Λ = 11 ± 1). This is in agreement with a model photosensitization by rose bengal (RB(2-)) in deoxygenated aqueous solutions resulting in one-electron oxidation of ETBE (Λ = 14 ± 1). Our results demonstrate that the use of CSIA could open new avenues for the assessment of photosensitization pathways.

Analyzing sites of OH radical attack (ring vs. side chain) in oxidation of substituted benzenes via dual stable isotope analysis (δ13C and δ2H)

OH radicals generated by the photolysis of H2O2 can degrade aromatic contaminants by either attacking the aromatic ring to form phenolic products or oxidizing the substituent. We characterized these competing pathways by analyzing the carbon and hydrogen isotope fractionation (εC and εH) of various substituted benzenes. For benzene and halobenzenes that only undergo ring addition, low values of εC (-0.7‰ to -1.0‰) were observed compared with theoretical values (-7.2‰ to -8‰), possibly owing to masking effect caused by pre-equilibrium between the substrate and OH radical preceding the rate-limiting step. In contrast, the addition of OH radicals to nitrobenzene ring showed a higher εC (-3.9‰), probably due to the lower reactivity. Xylene isomers, anisole, aniline, N,N-dimethylaniline, and benzonitrile yielded normal εH values (-2.8‰ to -29‰) indicating the occurrence of side-chain reactions, in contrast to the inverse εH (11.7‰ to 30‰) observed for ring addition due to an sp(2) to sp(3) hybridization change at the reacting carbon. Inverse εH values for toluene (14‰) and ethylbenzene (30‰) were observed despite the formation of side-chain oxidation products, suggesting that ring addition has a larger contribution to isotope fractionation. Dual element isotope slopes (∆δ(2)H/∆δ(13)C) therefore allow identification of significant degradation pathways of aromatic compounds by photochemically induced OH radicals. Issues that should be addressed in future studies include quantitative determination of the contribution of each competing pathway to the observed isotope fractionation and characterization of physical processes preceding the reaction that could affect isotope fractionation.

Characterizing chemical transformation of organophosphorus compounds by 13C and 2H stable isotope analysis

Continuous and excessive use of organophosphorus compounds (OPs) has led to environmental contaminations which raise public concerns. This study investigates the isotope fractionation patterns of OPs in the aquatic environment dependence upon hydrolysis, photolysis and radical oxidation processes. The hydrolysis of parathion (EP) and methyl parathion (MP) resulted in significant carbon fractionation at lower pH (pH2-7, εC=-6.9~-6.0‰ for EP, -10.5~-9.9‰ for MP) but no detectable carbon fractionation at higher pH (pH12). Hydrogen fractionation was not observed during any of the hydrolysis experiments. These results indicate that compound specific isotope analysis (CSIA) allows distinction of two different pH-dependent pathways of hydrolysis. Carbon and hydrogen isotope fractionation were determined during UV/H2O2 photolysis of EP and tris(2-chloroethyl) phosphate (TCEP). The constant δ2H values determined during the OH radical reaction of EP suggested that the rate-limiting step proceeded through oxidative attack by OH radical on the PS bond. The significant H isotope enrichment suggested that OH radical oxidation of TCEP was caused by an H-abstraction during the UV/H2O2 processes (εH=-56±3‰). Fenton reaction was conducted to validate the H isotope enrichment of TCEP associated with radical oxidation, which yielded εH of -34±5‰. Transformation products of OPs during photodegradation were identified using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS). This study highlights that the carbon and hydrogen fractionation patterns have the potential to elucidate the transformation of OPs in the environment.