Photochemical Oxidation Products Research Articles

Life cycle assessment and life cycle costing of hydrogen production from biowaste and biomass in Sweden

In this study, an environmental and economic assessment of hydrogen production from biowaste and biomass is performed from a life cycle perspective, with a high degree of primary life cycle inventory data on materials, energy, and investment flows. Using SimaPro LCA software and CML-IA, 2001 impact assessment method, ten environmental impact categories are analyzed for environmental analysis. Economic analysis includes capital and operational expenditures and monetization cost of life cycle environmental impacts. The hydrogen production from biowaste has a high climate impact, photochemical oxidant, and freshwater eutrophication than biomass while it performs far better in ozone depletion, terrestrial ecotoxicity, abiotic depletion-fossil, abiotic depletion, human toxicity, and freshwater ecotoxicity. The sensitivity analysis of LCA results indicates that feedstock to biogas/pyrolysis-oil yields ratio and the type of energy source for the reforming process can significantly influence the results, particularly climate change, abiotic depletion, and human toxicity. The life cycle cost (LCC) of 1 kg hydrogen production has been accounted as 0.45–2.76 € with biowaste and 0.54–3.31 € with biomass over the plant's lifetime of 20 years. From the environmental impacts of climate change, photochemical oxidant, and freshwater eutrophication hydrogen production from biomass is a better option than biowaste while from other included impact categories and LCC perspectives it’s biowaste. This research contributes to bioresources to hydrogen literature with some new findings that can be generalized in Europe and even globally as it is in line with and endorse existing theoretical and simulation software-based studies.

Observed versus simulated OH reactivity during KORUS-AQ campaign: Implications for emission inventory and chemical environment in East Asia

We present a holistic examination of tropospheric OH reactivity (OHR) in South Korea using comprehensive NASA DC-8 airborne measurements collected during the Korea–United States Air Quality field study and chemical transport models. The observed total OHR (tOHR) averaged in the planetary boundary layer (PBL, <2.0 km) and free troposphere was 5.2 s−1 and 2.0 s−1 during the campaign, respectively. These values were higher than the calculated OHR (cOHR, 3.4 s−1, 1.0 s−1) derived from trace-gas observations, indicating missing OHR fractions in the PBL and free troposphere of 35% and 50%, respectively. Incorporating nonobserved secondary species from the observationally constrained box model increased cOHR to 4.0 s−1 in the PBL and 1.3 s−1 in the free troposphere. Simulated OHR (sOHR, 2.7 s−1, 0.8 s−1) was substantially lower than both tOHR and cOHR by as much as 60%. This underestimate was substantial in the free troposphere and marine boundary layer of the marginal sea (Yellow Sea). We then discuss the potential causes of unaccounted OHR. First, we suggest improving the accuracy of tropospheric reaction kinetics, which vary significantly in the available literature. Second, underestimated emissions of anthropogenic CO and oxygenated volatile organic compounds in East Asia contributed to the discrepancy between tOHR and sOHR. In addition, oxygenated and biogenic volatile organic compounds emitted from the marginal sea may contribute substantially to the regional OHR. Typical chemical transport models underestimate these sources, leading to a large missing OHR fraction. Despite this discrepancy, we found that simulated OH concentrations were comparable with those observed during the campaign because of slow OH recycling rates in the models; therefore, the models predicted less formation of photochemical oxidation products such as ozone.

Pathways to Highly Oxidized Products in the Δ3-Carene + OH System.

Oxidation of the monoterpene Δ3-carene (C10H16) is a potentially important and understudied source of atmospheric secondary organic aerosol (SOA). We present chamber-based measurements of speciated gas and particle phases during photochemical oxidation of Δ3-carene. We find evidence of highly oxidized organic molecules (HOMs) in the gas phase and relatively low-volatility SOA dominated by C7-C10 species. We then use computational methods to develop the first stages of a Δ3-carene photochemical oxidation mechanism and explain some of our measured compositions. We find that alkoxy bond scission of the cyclohexyl ring likely leads to efficient HOM formation, in line with previous studies. We also find a surprising role for the abstraction of primary hydrogens from methyl groups, which has been calculated to be rapid in the α-pinene system, and suggest more research is required to determine if this is more general to other systems and a feature of autoxidation. This work develops a more comprehensive view of Δ3-carene photochemical oxidation products via measurements and lays out a suggested mechanism of oxidation via computationally derived rate coefficients.

Modeling of a Solar Heterogeneous Photocatalytic Reactor with TiO2 for Treatment of Wastewater Contaminated By Albendazole

Albendazole is an anthelmintic drug with antiangiogenic properties, which means that inhibits the development of new blood vessels. This causes a serious risk for the growth of fetus during pregnancy as a result. Heterogeneous photocatalysis has been proposed as an alternative for removal of this contaminant. In this study, a solar compound parabolic collector (CPC) photocatalytic reactor was modeled and simulated in order to describe the total organic carbon (TOC) degradation of commercial albendazole. The Six Flux Model approach (SFM) was used to estimate the Local Velocity Volumetric Rate of Photon Absorption (LVRPA) coupled with a Langmuir-Hinshelwood (L-H) kinetic model in order to describe the photocatalytic degradation of the TOC content of the contaminant and its photochemical oxidation products. The parameters of the L-H model were estimated from experimental data obtained with a catalyst loading of 0.6 g/l, initial pH of 5.0 and three different initial TOC concentrations of the commercial albendazole (159.95, 75.58 and 40 ppm). The rate constant (kT) and adsorption constant (K1), estimated from the parameter fitting, were 9.28×10-4 m1.5ppmW-0.5 s-1 and 3.02 × 10-2 ppm-1, respectively. The model was validated with experimental results, achieving a TOC removal of 40% with the lowest concentration of the contaminant. By simulating the process with different catalyst loadings, the maximum TOC removal was achieved with 0.21 g/L of TiO2.

Effects of ocean acidification and short-term light/temperature stress on biogenic dimethylated sulfur compounds cycling in the Changjiang River Estuary

Environmental contextContinuous anthropogenic CO2 emissions have led to an increase in seawater acidity, potentially affecting the growth of phytoplankton and their production of the climate-moderating biogenic gas, dimethyl sulfide. Our simulation experiments showed that ocean acidification, coupled with light and temperature changes, had a significant influence on dimethyl sulfide concentrations. This research provides fundamental data for predicting the biogeochemical cycle of dimethyl sulfide under various global change scenarios. AbstractOcean acidification (OA) affects marine primary productivity and community structure. Therefore, OA may influence the biogeochemical cycles of volatile biogenic dimethyl sulfide (DMS), and its precursor dimethylsulfoniopropionate (DMSP) and photochemical oxidation product dimethyl sulfoxide (DMSO). A 23-day shipboard incubation experiment investigated the short-term response of the production and cycling of biogenic sulfur compounds to OA in the Changjiang River Estuary to understand the effects of OA on biogenic sulfur compounds. Phytoplankton abundance and community composition showed a marked difference at three different pH levels at the late stage of the experiment. Significant reductions in chlorophyll a (Chl-a), DMS, particulate DMSP (DMSPp) and dissolved DMSO (DMSOd) concentrations were identified under high CO2 levels. Moreover, minimal changes were observed in the productions of dissolved DMSP (DMSPd) and particulate DMSO (DMSOp) among the treatments. The ratios of DMS, total DMSP (DMSPt) and total DMSO (DMSOt) to Chl-a were not affected by a change in pH. Furthermore, the concentrations of DMS and DMSOd were closely related to the mean bacterial abundance at the three pH levels. Additional short-term (8h) incubation experiments on the light and temperature effects showed that the influence of pH on the production of dimethylated sulfur compounds also depended on solar radiation and temperature. Under natural and UVB light, DMS photodegradation rates increased by 1.6 to 4.2 times at low pH levels. Thus, OA may lead to decreasing DMS concentrations in surface seawater. Light and temperature conditions also play important roles in the production and cycling of biogenic sulfur compounds.

Diurnal variation in the proinflammatory activity of urban fine particulate matter (PM 2.5) by in vitro assays.

Background: Ambient particulate matter (PM) smaller than 2.5 µm in diameter (PM 2.5) undergoes diurnal changes in chemical composition due to photochemical oxidation. In this study we examine the relationships between oxidative activity and inflammatory responses associated with these diurnal chemical changes. Because secondary PM contains a higher fraction of oxidized PM species, we hypothesized that PM 2.5 collected during afternoon hours would induce a greater inflammatory response than primary, morning PM 2.5. Methods: Time-integrated aqueous slurry samples of ambient PM 2.5 were collected using a direct aerosol-into-liquid collection system during defined morning and afternoon time periods. PM 2.5 samples were collected for 5 weeks in the late summer (August-September) of 2016 at a central Los Angeles site. Morning samples, largely consisting of fresh primary traffic emissions (primary PM), were collected from 6-9am (am-PM 2.5), and afternoon samples were collected from 12-4pm (pm-PM 2.5), when PM composition is dominated by products of photochemical oxidation (secondary PM). The two diurnally phased PM 2.5 slurries (am- and pm-PM 2.5) were characterized for chemical composition and BV-2 microglia were assayed in vitro for oxidative and inflammatory gene responses. Results: Contrary to expectations, the am-PM 2.5 slurry had more proinflammatory activity than the pm-PM 2.5 slurry as revealed by nitric oxide (NO) induction, as well as the upregulation of proinflammatory cytokines IL-1β, IL-6, and CCL2 (MCP-1), as assessed by messenger RNA production. Conclusions: The diurnal differences observed in this study may be in part attributed to the greater content of transition metals and water-insoluble organic carbon (WIOC) of am-PM 2.5 (primary PM) vs. pm-PM 2.5 (secondary PM), as these two classes of compounds can increase PM 2.5 toxicity.

Diurnal variation in the proinflammatory activity of urban fine particulate matter (PM 2.5) by in vitro assays

Background: Ambient particulate matter (PM) smaller than 2.5 µm in diameter (PM 2.5) undergoes diurnal changes in chemical composition due to photochemical oxidation. In this study we examine the relationships between oxidative activity and inflammatory responses associated with these diurnal chemical changes. Because secondary PM contains a higher fraction of oxidized PM species, we hypothesized that PM 2.5 collected during afternoon hours would induce a greater inflammatory response than primary, morning PM 2.5. Methods: Time-integrated aqueous slurry samples of ambient PM 2.5 were collected using a direct aerosol-into-liquid collection system during defined morning and afternoon time periods. PM 2.5 samples were collected for 5 weeks in the late summer (August-September) of 2016 at a central Los Angeles site. Morning samples, largely consisting of fresh primary traffic emissions (primary PM), were collected from 6-9am (am-PM 2.5), and afternoon samples were collected from 12-4pm (pm-PM 2.5), when PM composition is dominated by products of photochemical oxidation (secondary PM). The two diurnally phased PM 2.5 slurries (am- and pm-PM 2.5) were characterized for chemical composition and BV-2 microglia were assayed in vitro for oxidative and inflammatory gene responses. Results: Contrary to expectations, the am-PM 2.5 slurry had more proinflammatory activity than the pm-PM 2.5 slurry as revealed by nitric oxide (NO) induction, as well as the upregulation of proinflammatory cytokines IL-1β, IL-6, and CCL2 (MCP-1), as assessed by messenger RNA production. Conclusions: The diurnal differences observed in this study may be in part attributed to the greater content of transition metals and water-insoluble organic carbon (WIOC) of am-PM 2.5 (primary PM) vs. pm-PM 2.5 (secondary PM), as these two classes of compounds can increase PM 2.5 toxicity.

Diurnal variation in the proinflammatory activity of urban fine particulate matter (PM2.5) by in vitro assays

Background: Ambient particulate matter (PM) smaller than 2.5 µm in diameter (PM2.5) undergoes diurnal changes in chemical composition due to photochemical oxidation. In this study we examine the relationships between oxidative activity and inflammatory responses associated with these diurnal chemical changes. Because secondary PM contains a higher fraction of oxidized PM species, we hypothesized that PM2.5 collected during afternoon hours would induce a greater inflammatory response than primary, morning PM2.5. Methods: Time-integrated aqueous slurry samples of ambient PM2.5 were collected using a direct aerosol-into-liquid collection system during defined morning and afternoon time periods. PM2.5 samples were collected for 5 weeks in the late summer (August-September) of 2016 at a central Los Angeles site. Morning samples, largely consisting of fresh primary traffic emissions (primary PM), were collected from 6-9am (am-PM2.5), and afternoon samples were collected from 12-4pm (pm-PM2.5), when PM composition is dominated by products of photochemical oxidation (secondary PM). The two diurnally phased PM2.5 slurries (am- and pm-PM2.5) were characterized for chemical composition and BV-2 microglia were assayed in vitro for oxidative and inflammatory gene responses. Results: Contrary to expectations, the am-PM2.5 slurry had more proinflammatory activity than the pm-PM2.5 slurry as revealed by nitric oxide (NO) induction, as well as the upregulation of proinflammatory cytokines IL-1β, IL-6, and CCL2 (MCP-1), as assessed by messenger RNA production. Conclusions: The diurnal differences observed in this study may be in part attributed to the greater content of transition metals and water-insoluble organic carbon (WIOC) of am-PM2.5 (primary PM) vs. pm-PM2.5 (secondary PM), as these two classes of compounds can increase PM2.5 toxicity.

Diurnal variation in the proinflammatory activity of urban fine particulate matter (PM 2.5) by in vitro assays.

Background: Ambient particulate matter (PM) smaller than 2.5 µm in diameter (PM 2.5) undergoes diurnal changes in chemical composition due to photochemical oxidation. In this study we examine the relationships between oxidative activity and inflammatory responses associated with these diurnal chemical changes. Because secondary PM contains a higher fraction of oxidized PM species, we hypothesized that PM 2.5 collected during afternoon hours would induce a greater inflammatory response than primary, morning PM 2.5. Methods: Time-integrated aqueous slurry samples of ambient PM 2.5 were collected using a direct aerosol-into-liquid collection system during defined morning and afternoon time periods. PM 2.5 samples were collected for 5 weeks in the late summer (August-September) of 2016 at a central Los Angeles site. Morning samples, largely consisting of fresh primary traffic emissions (primary PM), were collected from 6-9am (am-PM 2.5), and afternoon samples were collected from 12-4pm (pm-PM 2.5), when PM composition is dominated by products of photochemical oxidation (secondary PM). The two diurnally phased PM 2.5 slurries (am- and pm-PM 2.5) were characterized for chemical composition and BV-2 microglia were assayed in vitro for oxidative and inflammatory gene responses. Results: Contrary to expectations, the am-PM 2.5 slurry had more proinflammatory activity than the pm-PM 2.5 slurry as revealed by nitric oxide (NO) induction, as well as the upregulation of proinflammatory cytokines IL-1β, IL-6, and CCL2 (MCP-1), as assessed by messenger RNA production. Conclusions: The diurnal differences observed in this study may be in part attributed to the greater content of transition metals and water-insoluble organic carbon (WIOC) of am-PM 2.5 (primary PM) vs. pm-PM 2.5 (secondary PM), as these two classes of compounds can increase PM 2.5 toxicity.

High-effective cultivation of Halobacterium salinarum providing with bacteriorhodopsin production under controlled stress

Submerged growth of Halobacterium salinarum and therefore synthesis of bacteriorhodopsin (BR) and carotenoids depend greatly on products of both chemical and/or photochemical oxidation of medium components and cellular metabolism which act as inhibitors. Some cultivation variants which allowed eliminating an adverse effect of inhibitors on biomass accumulation and BR synthesis are reviewed. The application of activated charcoal or ion exchange resin as adsorbents at preparing inoculums and the main cultivation stages was shown to allow controlling, namely lowering overstress of the halobacterial cells by metabolites. The halobacterial biomass was accumulated up to 45gL−1 during eight-day cultivation with recycling cell suspension through adsorbent in a fed-batch mode. Such biomass contained up to 1,750mgL−1 BR and a minimum amount of carotenoids; thus the latter contributed to an easier isolation and purification of bacteriorhodopsin. To control BR biosynthesis the express method of BR quantification based on colour shades of cell suspension was developed.

Characterization of the organic matter in submicron urban aerosols using a Thermo-Desorption Proton-Transfer-Reaction Time-of-Flight Mass Spectrometer (TD-PTR-TOF-MS)

Organic matter is the most complicated and unresolved major component of atmospheric aerosol particles. Its sources and global budget are still highly uncertain and thereby necessitate further research efforts with state-of-the-art instrument. This study employed a Thermo-Desorption Proton-Transfer-Reaction Time-of-Flight Mass Spectrometer (TD-PTR-TOF-MS) for characterization of ambient organic aerosols. First, five authentic standard substances, which include phthalic acid, levoglucosan, arabitol, cis-pinonic acid and glutaric acid, were utilized to examine the response of the instrument. The results demonstrated the linearity of the TD-PTR-TOF-MS signals against a range of mass loading of specific species on filters. However, it was found that significant fragmentation happened to those challenging compounds, although the proton-transfer-reaction (PTR) was recognized as a soft ionization technique. Consequently, quantitative characterization of aerosols with the TD-PTR-TOF-MS depended on the availability of the fragmentation pattern in mass spectra and the recovery rate with the quantification ion peak(s). The instrument was further deployed to analyze a subset of submicron aerosol samples collected at the TARO (Taipei Aerosol and Radiation Observatory) in Taipei, Taiwan during August 2013. The results were compared with the measurements from a conventional DRI thermo-optical carbon analyzer. The inter-comparison indicated that the TD-PTR-TOF-MS underestimated the mass of total organic matter (TOM) in aerosol samples by 27%. The underestimation was most likely due to the thermo-decomposition during desorption processes and fragmentation in PTR drift tube, where undetectable fragments were formed. Besides, condensation loss of low vapor pressure species in the transfer components was also responsible for the underestimation to a certain degree. Nevertheless, it was showed that the sum of the mass concentrations of the major detected ion peaks correlated strongly with the TOM determined by DRI analyzer (R2 = 0.8578), suggesting that the TD-PTR-TOF-MS measurements explained more than 85% of the variance in the time series of TOM. In addition to identification by comparing with the fragmentation pattern obtained from the mass spectra of the authentic substances, most of the major ions were attributed to protonated or acylium ions of specific parent compounds. Amongst the quantified species with full calibration with authentic standard, phthalic acid was found accounting for 7.0% of the mass loading of TOM. In addition, a high-end estimation of 9.4% was suggested for the mass contribution from glutaric acid, which was made by assuming that the ion with m/z of 73.027 was totally produced from fragmentation of glutaric acid as characterization of authentic standard despite of the formation of protonated methyl-glyoxal ion. Moreover, a substantial contribution from ions corresponding to protonated acetic acid and acetone was measured, which could be produced from fragmentation of larger oxygenated molecules. The TD-PTR-TOF-MS measurements suggested that low molecular weight carboxylic acid (LMWCA), products of photochemical oxidation of gaseous hydrocarbons and fatty acids, constituted a major fraction of secondary organic aerosols in Taipei, Taiwan, a typical subtropical urban area.

Seasonal and longitudinal distributions of atmospheric water‐soluble dicarboxylic acids, oxocarboxylic acids, and α‐dicarbonyls over the North Pacific

AbstractIn order to assess the seasonal variability of atmospheric abundances of dicarboxylic acids, oxocarboxylic acids, and α‐dicarbonyls over the North Pacific and Sea of Japan, aerosol samples were collected along the longitudinal transacts during six cruises between Canada and Japan. The back trajectory analyses indicate that aerosol samples collected in winter and spring are influenced by the East Asian outflow, whereas summer and fall samples are associated with the pristine maritime air masses. Molecular distributions of water‐soluble organics in winter and spring samples show the predominance of oxalic acid (C2) followed by succinic (C4) and malonic acids (C3). In contrast, summer and fall marine aerosols are characterized by the predominance of C3 over C4. Concentrations of dicarboxylic acids were higher over the Sea of Japan than the North Pacific. With a lack of continental outflow, higher concentrations during early summer are ascribed to atmospheric oxidation of organic precursors associated with high biological activity in the North Pacific. This interpretation is further supported by the high abundances of azelaic acid, which is a photochemical oxidation product of biogenic unsaturated fatty acids, over the Bering Sea in early summer when surface waters are characterized by high biological productivity. We found higher ratios of oxalic acid to pyruvic and glyoxylic acids (C2/Pyr and C2/ωC2) and glyoxal and methylglyoxal (C2/Gly and C2/MeGly) in summer and fall than in winter and spring, suggesting a production of C2 from the aqueous‐phase oxidation of oceanic isoprene. In this study, dicarboxylic acids account for 0.7–38% of water‐soluble organic carbon.

Differences in ozone photochemical characteristics between the megacity Tianjin and its rural surroundings

Ground level ozone and its precursors were measured from July 10 to September 30, 2009 within Tianjin. The data were used to analyze differences in ozone photochemical oxidant production in urban and rural areas. Results showed more pronounced risk of O3 exposure at the rural site, Wuqing. During the observation period, ozone varied monthly, peaking in Jul. and reaching a minimum in Sep. The daily maximum ozone concentration was found to exceed 80 ppb for 28 days 100 ppb for 12 days, 120 ppb for 7 days at Wuqing, while it exceeded 80 ppb for 10 days, 100 ppb for 2 days, and 120 ppb for 1 day at the urban site, Tieta. The daily maximum ozone concentrations at Wuqing and Tieta were 193.7 ppb and 130.4 ppb. The daily maximum ozone concentration occurred at noon in Tieta and at 14:00 in Wuqing. NO and NOx peaked in September and reached minimum values in Jul., CO showed little variation at both sites. NOx and CO showed similar double-peak diurnal cycles resulted from a combination of diurnal variation of emission and the Planetary Boundary Layer During the VOCs (volatile organic compounds) sampling period, the average total VOCs concentration showed considerable day to day variation, which was 87.91 ppb with a range of 27.2 ppb–437.3 ppb at Tieta, and the average total VOCs was 197.95 ppb with a range of 63.48 ppb–473.97 ppb at Wuqing. A sensitivity study performed with the NCAR-MM model showed alkenes to be the most numerous contributors to O3 production, accounting for 53.3% of the total. Aromatics and alkanes accounted for 35.1% and 9.2%, respectively.

Thermal and photochemical oxidation of 2-acetylcyclopentanone with atmospheric oxygen

The major products of thermal (acetone, CaCl2 excess, reflux) and photochemical (acetone or CCl4, room temperature) oxidation of 2-acetylcyclopentanone with atmospheric oxygen are 2-acetyl-2-hydroxycyclopentanone, 2-acetyl-2-hydroxymethylcyclopentanone, 1,1′-diacetyl-1,1′-bicyclopentyl-2,2′-dione, 2-acetoxycyclopentanone, 5,6-dioxoheptanoic acid, glutaric acid, and glutaric anhydride. The formation of 2-acetyl-2-hydroxycyclopentanone is the first example of the direct α-hydroxylation of β-dicarbonyl compound under the conditions described.

Glyoxal processing by aerosol multiphase chemistry: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles

Abstract. This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions that form secondary organic aerosol (SOA) in aqueous aerosol particles. Recent laboratory results on glyoxal reactions are reviewed and a consistent set of empirical reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds. Products of these processes include (a) oligomers, (b) nitrogen-containing products, (c) photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud) chemistry for the same conditions (liquid water content, particle size). The application of the new module including detailed chemical processes in a box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the predicted atmospheric relevance of SOA formation from glyoxal. During day time, a photochemical (most likely radical-initiated) process is the major SOA formation pathway forming ∼5 μg m−3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt). During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids) contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5 < pH < 7). Glyoxal uptake into ammonium sulfate seed under dark conditions can be represented with a single reaction parameter keffupt that does not depend on aerosol loading or water content, which indicates a possibly catalytic role of aerosol water in SOA formation. However, the reversible nature of uptake under dark conditions is not captured by keffupt, and can be parameterized by an effective Henry's law constant including an equilibrium constant Kolig = 1000 (in ammonium sulfate solution). Such reversible glyoxal oligomerization contributes <1% to total predicted SOA masses at any time. Sensitivity tests reveal five parameters that strongly affect the predicted SOA mass from glyoxal: (1) time scales to reach equilibrium states (as opposed to assuming instantaneous equilibrium), (2) particle pH, (3) chemical composition of the bulk aerosol, (4) particle surface composition, and (5) particle liquid water content that is mostly determined by the amount and hygroscopicity of aerosol mass and to a lesser extent by the ambient relative humidity. Glyoxal serves as an example molecule, and the conclusions about SOA formation in aqueous particles can serve for comparative studies of other molecules that form SOA as the result of multiphase chemical processing in aerosol water. This SOA source is currently underrepresented in atmospheric models; if included it is likely to bring SOA predictions (mass and O/C ratio) into better agreement with field observations.

Mesocosm trials of bioremediation of contaminated soil of a petroleum refinery: comparison of natural attenuation, biostimulation and bioaugmentation

Contamination with petroleum hydrocarbons (PHC) is a global problem with environmental implications. Physico-chemical treatments can be used for soil cleanup, but they are expensive, and can have implications for soil structure and environment. Otherwise, biological remediation treatments are cost-effective and restore soil structure. Several remediation experiments have been carried out in the lab and in the field; however, there is the challenge to achieve as good or better results in the field as in the laboratory. In the ambit of a project aiming at investigating suitable biological remediation approaches for recovering a refinery contaminated soil, we present here results obtained in bioremediation trials. The approaches biostimulation and bioaugmentation were tested, in parallel, and compared with natural attenuation. For this purpose, mesocosm experiments were carried out inside the refinery area, which constitutes a real asset of this work. Soil contaminated with crude oil was excavated, re-contaminated with turbine oil, homogenised and used to fill several 0.5 m(3) high-density polyethylene containers. The efficiency of procedures as follows: (1) natural attenuation; (2) manual aeration; (3) biostimulation by adding (3.1) only nutrients; and (3.2) nutrients and a non-ionic surfactant; and (4) bioaugmentation in the presence of added (4.1) nutrients or (4.2) nutrients and a non-ionic surfactant were evaluated after a 9-month period of experiment. For bioaugmentation, a commercial bacterial product was used. In addition to physico-chemical characterization, initial and final soil contents in total petroleum hydrocarbons (TPH) (by Fourier transform infrared spectrophotometry) and the total number of bacteria (by total cell counts) were carried out. For TPH degradation evaluation the soil was divided in four fractions corresponding to different depths: 0-5; 5-10; 10-15; and 15-20 cm. Mean values of percentages of PHC degradation varied between 20 and 50% at surface and between 10 and 35% below 5-cm depth. Natural attenuation was as efficient as most of the tested treatments (about 30% TPH degradation) being exceeded only by bioaugmentation combined with nutrient and surfactant amendments (about 50% TPH degradation). Higher TPH degradation at surface suggests that a combination of sufficient dioxygen, propitious for aerobically degradation, with sunlight required for production of strong photochemical oxidants like ozone, contributed for enhancing degradation. Indeed, the atmosphere of the refineries is relatively rich in volatile organic compounds and nitrogen dioxide (a side-product of the combustion of residual volatile PHC released by the chimneys), which are precursors of O(3) and other photochemical oxidants produced in sunny days, which are very common in Portugal. The fact that natural attenuation was as efficient as most of the soil treatments tested was very probably a result of the presence, in the initial soil, of physiologically adapted native microorganisms, which could be efficient in degrading PHC. A cost-effective way to reduce half-life for the degradation of PHC of contaminated soil of the refinery will be a periodic revolving of the soil, like tillage, in order to expose to the oxidative atmosphere the different layers of contaminated soil. A combination of soil revolving with bioaugmentation together with nutrients and surfactant amendments may result in an additional improvement of PHC degradation rate. However, this last procedure will raise markedly the price of the remediation treatment.

Guanine sulphinate is a major stable product of photochemical oxidation of DNA 6-thioguanine by UVA irradiation

The DNA of patients taking the immunosuppressant and anticancer drugs azathioprine or 6-mercaptopurine contains 6-thioguanine (6-TG). The skin of these patients is selectively sensitive to ultraviolet A radiation (UVA) and they suffer an extremely high incidence of sunlight-induced skin cancer with long-term treatment. DNA 6-TG interacts with UVA to generate reactive oxygen species, which oxidize 6-TG to guanine sulphonate (GSO3). We suggested that GSO3 is formed via the reactive electrophilic intermediates, guanine sulphenate (GSO) and guanine sulphinate (GSO2). Here, GSO2 is identified as a significant and stable UVA photoproduct of free 6-TG, its 2′-deoxyribonucleoside, and DNA 6-TG. Mild chemical oxidation converts 6-TG into GSO2, which can be further oxidized to GSO3—a stable product that resists further reaction. In contrast, GSO2 is converted back to 6-TG under mild conditions. This suggests that cellular antioxidant defences might counteract the UVA-mediated photooxidation of DNA 6-TG at this intermediate step and ameliorate its biological effects. In agreement with this possibility, the antioxidant ascorbate protected DNA 6-TG against UVA oxidation and prevented the formation of GSO3.

Ozone photochemical production in urban Shanghai, China: Analysis based on ground level observations

Ozone and its precursors were measured from 15 June 2006 to 14 June 2007 at an urban site in Shanghai and used to characterize photochemical oxidant production in this region. During the observation period, ozone displays a seasonal variation with a maximum in spring. Observed nitrogen oxides (NOx) and carbon monoxide (CO) reached a maximum in winter and a minimum in summer. NOx and CO has a similar double‐peak diurnal cycle, implying that they are largely of motor vehicle origin. Total nonmethane organic compounds (NMOC) concentrations averaged over the morning, and the 24‐hour periods have a large day‐to‐day variation with no apparent seasonal cycle. Aromatics play a dominant role in contributing to total NMOC reactivity and ozone‐forming potential. Anthropogenic NMOC of diverse sources are major components of total NMOC and consist mainly of moderate and low reactivity species. In contrast, relatively low levels of biogenic NMOC concentrations were observed in urban Shanghai. The early morning NMOC/NOx ratios are typically below 8:1 with an average of around 4:1, indicating that the sampling location is situated in a NMOC‐limited regime. Model simulations confirm that potential photochemical ozone production in Shanghai is NMOC‐sensitive. It is presently difficult to predict the impact of future human activities, such as the increase of automobiles and vegetation‐covered landscapes and the reduction of aerosol on ozone pollution in the fast developing megacities of China, and additional studies are needed to better understand the highly nonlinear ozone problem.

Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol

Abstract. Isoprene is the largest single VOC emission to the atmosphere. Although it is primarily oxidized photochemically during daylight hours, late-day emissions that remain in the atmosphere at sunset undergo oxidation by NO3 in regionally polluted areas with large NOx levels. A recent aircraft study examined isoprene and its nocturnal oxidants in a series of night flights across the Northeast US, a region with large emissions of both isoprene and NOx. Substantial amounts of isoprene that were observed after dark were strongly anticorrelated with measured NO3 and were the most important factor determining the lifetime of this radical. The products of photochemical oxidation of isoprene, methyl vinyl ketone and methacrolein, were more uniformly distributed, and served as tracers for the presence of isoprene at sunset, prior to its oxidation by NO3. A determination of the mass of isoprene oxidized in darkness showed it to be a large fraction (>20%) of emitted isoprene. Organic nitrates produced from the NO3+isoprene reaction, though not directly measured, were estimated to account for 2–9% of total reactive nitrogen. The mass of isoprene oxidized by NO3 was comparable to and correlated with the organic aerosol loading for flights with relatively low organic aerosol background. The contribution of nocturnal isoprene oxidation to secondary organic aerosol was determined in the range 1–17%, and isoprene SOA mass derived from NO3 was calculated to exceed that due to OH by approximately 50%.

Photochemical oxidation of thiophene by O2 in an organic two-phase liquid-liquid extraction system

Photochemical oxidation products and the kinetics of thiophene in an n-octane/acetonitrile extraction system using O2 as an oxidant was studied. The results could be used as a reference for the oxidative desulfurization of gasoline because thiophene is one of the main components containing sulfur in a fluid catalytic cracking (FCC) gasoline. Thiophene dissolved in n-octane was photodecomposed and removed into the water phase at an ambient temperature and atmospheric pressure. A 500-W high-pressure mercury lamp (main wavelength 365 nm, 0.22 kW m−2) was used as the light source for irradiation and air was introduced by a gas pump to supply O2. Thiophene could be photooxidized to SO4 2− and CO2. The desulfurization yield of thiophene in n-octane is 65.2% for a 5-h photoirradiation under the conditions of air flow at 150 m min−1 and V(n-octane): V(acetonitrile) = 1:1. It can be improved to 96.5% by adding 1.5 g L−1 artificial zeolite, which is an absorbent for O2. Under such conditions, the photooxidation kinetics of thiophene with O2 is of the first order with an apparent rate constant of 0.6297 h−1 and a half time of 1.10 h. The sulfur content can be depressed from 800 to 28 ppm.