Do aerosols act as catalysts in the OH radical initiated atmospheric oxidation of volatile organic compounds?

Smog chamber/FTIR techniques were used to study the relative reactivity of OH radicals with methanol, ethanol, phenol, C₂H₄, C₂H₂, and p-xylene in 750 Torr of air diluent at 296±2 K. Experiments were performed with, and without, 500–8000 μg m⁻³ (4000–50 000 μm² cm⁻³ surface area per volume) of NaCl, (NH₄)₂SO₄ or NH₄NO₃ aerosol. In contrast to the recent findings of Oh and Andino (Atmospheric Environment 34 (2000) 2901, 36 (2002) 149; International Journal of Chemical Kinetics 33 (2001) 422) there was no discernable effect of aerosol on the rate of loss of the organic compounds via reaction with OH radicals. Gas kinetic theory arguments cast doubt upon the findings of Oh and Andino. The available data suggest that the answer to the title question is “No”. As part of this work the rate constants for reactions of OH radicals with methanol, ethanol, and phenol in 750 Torr of air at 296 K were determined to be: k_OH+CH3OH=(8.12±0.54)×10⁻¹³, k_OH+C2H5OH=(3.47±0.32)×10⁻¹² and k_OH+phenol=(3.27±0.31)×10⁻¹¹ cm³ molecule⁻¹ s⁻¹.     

Diffusion of HTO, Cl and I in Opalinus Clay samples from Mont Terri: Effect of confining pressure

Diffusion coefficients (T=23±2 °C) and accessible porosities for HTO, ³⁶Cl⁻ and ¹²⁵I⁻ were measured on Opalinus Clay (OPA) samples from the Mont Terri Underground Rock Laboratory (URL) using the through-diffusion technique. The direction of transport (diffusion) was perpendicular to bedding. Special cells that allowed the application of confining pressure were designed and constructed. The pressures ranged from 1 to 5 MPa, the latter value simulating the overburden at the Mont Terri URL (about 200 m). The test solution used in the experiments was a synthetic version of the Opalinus Clay pore water, which has Na⁺ and Cl⁻ as the main components (I=0.42 M).The measured values of the effective diffusion coefficients (D_e) and rock capacity factors (α) are: D_e=1.2–1.5×10⁻¹¹ m² s⁻¹ and α=0.09–0.11 for HTO, D_e=4.0–5.5×10⁻¹² m² s⁻¹ and α=0.05 for ³⁶Cl⁻ and D_e=3.2–4.6×10⁻¹² m² s⁻¹ and α=0.07–0.10 for ¹²⁵I⁻. For non-sorbing tracers (HTO, ³⁶Cl) the rock capacity factor α is equal to the diffusion-accessible porosity . The experimental results showed that pressure only had a small effect on the value of the diffusion coefficients. Increasing the pressure from 1 to 5 MPa resulted in a decrease of the diffusion coefficient of 17% for HTO, 28% for ³⁶Cl⁻ and 30% for ¹²⁵I⁻. Moreover, the diffusion coefficients for ³⁶Cl⁻ and ¹²⁵I⁻ are smaller than for HTO, which is consistent with an effect arising from anion exclusion.The diffusion coefficients of HTO and ¹²⁵I⁻ measured in this study are in good agreement with recent measurements at three other laboratories performed within the framework of a laboratory comparison exercise. The values of the diffusion-accessible porosities show a larger degree of scatter.     

Long-term variation of PM2.5 levels and composition at rural, urban, and roadside sites in Hong Kong: Increasing impact of regional air pollution

Long-term study of air pollution plays a decisive role in formulating and refining pollution control strategies. In this study, two 12-month measurements of PM_2.5 mass and speciation were conducted in 00/01 and 04/05 to determine long-term trend and spatial variations of PM_2.5 mass and chemical composition in Hong Kong. This study covered three sites with different land-use characteristics, namely roadside, urban, and rural environments. The highest annual average PM_2.5 concentration was observed at the roadside site (58.0±2.0 μg m⁻³ (average±2σ) in 00/01 and 53.0±2.7 μg m⁻³ in 04/05), followed by the urban site (33.9±2.5 μg m⁻³ in 00/01 and 39.0±2.0 μg m⁻³ in 04/05), and the rural site (23.7±1.9 μg m⁻³ in 00/01 and 28.4±2.4 μg m⁻³ in 04/05). The lowest PM_2.5 level measured at the rural site was still higher than the United States’ annual average National Ambient Air Quality Standard of 15 μg m⁻³. As expected, seasonal variations of PM_2.5 mass concentration at the three sites were similar: higher in autumn/winter and lower in summer. Comparing PM_2.5 data in 04/05 with those collected in 00/01, a reduction in PM_2.5 mass concentration at the roadside (8.7%) but an increase at the urban (15%) and rural (20%) sites were observed. The reduction of PM_2.5 at the roadside was attributed to the decrease of carbonaceous aerosols (organic carbon and elemental carbon) (>30%), indicating the effective control of motor vehicle emissions over the period. On the other hand, the sulfate concentration at the three sites was consistent regardless of different land-use characteristics in both studies. The lack of spatial variation of sulfate concentrations in PM_2.5 implied its origin of regional contribution. Moreover, over 36% growth in sulfate concentration was found from 00/01 to 04/05, suggesting a significant increase in regional sulfate pollution over the years. More quantitative techniques such as receptor models and chemical transport models are required to assess the temporal variations of source contributions to ambient PM_2.5 mass and chemical speciation in Hong Kong.     

An aerosol flow tube study of the interaction of N2O5 with calcite, Arizona dust and quartz

The interaction of N₂O₅ with dispersed samples of Arizona Test Dust (ATD), Calcite (CaCO₃) and quartz (SiO₂) was investigated at varying relative humidity using an aerosol flow reactor. Reactive uptake coefficients, γ, obtained at close to zero relative humidity were (4.8 ± 0.7) × 10⁻³ for CaCO₃, (8.6 ± 0.6) × 10⁻³ for Quartz and (9.8 ± 1.0) × 10⁻³ for ATD. In the case of calcite, evidence was obtained for an enhanced rate of uptake at relative humidities above ≈ 50%. The results are compared to literature values obtained using bulk substrates and to previous aerosol uptake data on Saharan dust.     

Acute and chronic effects of nano- and non-nano-scale TiO2 and ZnO particles on mobility and reproduction of the freshwater invertebrate Daphnia magna

Among the emerging literature addressing the biological effects of nanoparticles, very little information exists, particularly on aquatic organisms, that evaluates nanoparticles in comparison to non-nanocounterparts. Therefore, the potential effects of nano-scale and non-nano-scale TiO₂ and ZnO on the water flea, Daphnia magna, were examined in 48-h acute toxicity tests using three different test media, several pigment formulations – including coated nanoparticles – and a variety of preparation steps. In addition, a 21-d chronic Daphnia reproduction study was performed using coated TiO₂ nanoparticles. Analytical ultracentrifugation analyses provided evidence that the nanoparticles were present in a wide range of differently sized aggregates in the tested dispersions. While no pronounced effects on D. magna were observed for nano-scale and non-nano-scale TiO₂ pigments in 19 of 25 acute (48-h) toxicity tests (EC50 > 100 mg L⁻¹), six acute tests with both nano- and non-nano-scale TiO₂ pigments showed slight effects (EC10, 0.5–91.2 mg L⁻¹). For the nano-scale and non-nano-scale ZnO pigments, the acute 48-h EC50 values were close to the 1 mg L⁻¹ level, which is within the reported range of zinc toxicity to Daphnia. In general, the toxicity in the acute tests was independent of particle size (non-nano-scale or nano-scale), coating of particles, aggregation of particles, the type of medium or the applied pre-treatment of the test dispersions. The chronic Daphnia test with coated TiO₂ nanoparticles demonstrated that reproduction was a more sensitive endpoint than adult mortality. After 21 d, the NOEC for adult mortality was 30 mg L⁻¹ and the NOEC for offspring production was 3 mg L⁻¹. The 21-d EC10 and EC50 values for reproductive effects were 5 and 26.6 mg L⁻¹, respectively. This study demonstrates the utility of evaluating nanoparticle effects relative to non-nano-scale counterparts and presents the first report of chronic exposure to TiO₂ nanoparticles in D. magna.     

Kinetics of OH-initiated oxidation of oxygenated organic compounds in the aqueous phase: new rate constants, structure–activity relationships and atmospheric implications

The kinetics of OH oxidation of several organic compounds of atmospheric relevance were measured in the aqueous phase. Relative kinetics were performed using various organic references and OH sources. After validation of the protocol, temperature-dependent rate constants for the reactions of OH radical with ethyl ter-butyl ether (, E_a/R=580 (±560) K), n-butyl acetate ( (±0.4)×10⁹ M⁻¹ s⁻¹, E_a/R=1000 (±200) K), acetone ( (±0.05)×10⁹ M⁻¹ s⁻¹, E_a/R=1400 (±500) K), methyl ethyl ketone (, E_a/R=1200 (±200) K), methyl iso-butyl ketone (, E_a/R=1200 (±300) K) and methylglyoxal (, E_a/R=1100 (±300) K) were determined. A non-Arrhenius behavior was found for phenol, in good agreement with the contribution of an OH addition to the mechanism, which also includes H-abstraction by OH radicals. Global rate constants of acetaldehyde, propionaldehyde, butyraldehyde and valeraldehyde were studied at 298 K only, as these compounds partly hydrate in the aqueous phase. All the obtained data (except those of phenol) complemented by literature data were used to investigate three methods to estimate rate constants for H-abstraction reactions of OH radicals in aqueous solutions when measured data were not available: Evans-Polanyi-type correlations, comparisons with gas-phase data, structure activity relationships (SAR). The results show that the SAR method is promising; however, the data set is currently too small to extend this method to temperatures other than 298 K. The atmospheric impact of aqueous phase OH oxidation of water-soluble organic compounds is discussed with the determination of their global atmospheric lifetimes, taking into account both gas- and aqueous-phase reactivities. The results show that atmospheric droplets can act as powerful photoreactors to eliminate soluble organic compounds from the atmosphere.     

Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, α-thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

Cation exchange in a glacial till drumlin at a road salt storage facility

At a former wood preservation plant severely contaminated with coal tar oil, in situ bulk attenuation and biodegradation rate constants for several monoaromatic (BTEX) and polyaromatic hydrocarbons (PAH) were determined using (1) classical first order decay models, (2) Michaelis–Menten degradation kinetics (MM), and (3) stable carbon isotopes, for o-xylene and naphthalene. The first order bulk attenuation rate constant for o-xylene was calculated to be 0.0025 d^− 1 and a novel stable isotope-based first order model, which also accounted for the respective redox conditions, resulted in a slightly smaller biodegradation rate constant of 0.0019 d^− 1. Based on MM-kinetics, the o-xylene concentration decreased with a maximum rate of k_max = 0.1 µg/L/d. The bulk attenuation rate constant of naphthalene retrieved from the classical first order decay model was 0.0038 d^− 1. The stable isotope-based biodegradation rate constant of 0.0027 d^− 1 was smaller in the reduced zone, while residual naphthalene in the oxic part of the plume further downgradient was degraded at a higher rate of 0.0038 d^− 1. With MM-kinetics a maximum degradation rate of k_max = 12 µg/L/d was determined. Although best fits were obtained by MM-kinetics, we consider the carbon stable isotope-based approach more appropriate as it is specific for biodegradation (not overall attenuation) and at the same time accounts for the dominant electron-accepting process. For o-xylene a field based isotope enrichment factor ε_field of − 1.4 could be determined using the Rayleigh model, which closely matched values from laboratory studies of o-xylene degradation under sulfate-reducing conditions.     

Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions

This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH₂ linkage in J, with a rate constant derived from the quantum chemical results of 1 × 10¹⁵ exp(−68 kcal/mol/RT) s⁻¹ for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 10¹² exp(−53 kcal/mol/RT) s⁻¹ over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.     

Microbial characterization of nitrification in a shallow, nitrogen-contaminated aquifer, Cape Cod, Massachusetts and detection of a novel cluster associated with nitrifying Betaproteobacteria

Groundwater nitrification is a poorly characterized process affecting the speciation and transport of nitrogen. Cores from two sites in a plume of contamination were examined using culture-based and molecular techniques targeting nitrification processes. The first site, located beneath a sewage effluent infiltration bed, received treated effluent containing O₂ (> 300 µM) and NH₄⁺ (51–800 µM). The second site was 2.5 km down-gradient near the leading edge of the ammonium zone within the contaminant plume and featured vertical gradients of O₂, NH₄⁺, and NO₃⁻ (0–300, 0–500, and 100–200 µM with depth, respectively). Ammonia- and nitrite-oxidizers enumerated by the culture-based MPN method were low in abundance at both sites (1.8 to 350 g^− 1 and 33 to 35,000 g^− 1, respectively). Potential nitrifying activity measured in core material in the laboratory was also very low, requiring several weeks for products to accumulate. Molecular analysis of aquifer DNA (nested PCR followed by cloning and 16S rDNA sequencing) detected primarily sequences associated with the Nitrosospira genus throughout the cores at the down-gradient site and a smaller proportion from the Nitrosomonas genus in the deeper anoxic, NH₄⁺ zone at the down-gradient site. Only a single Nitrosospira sequence was detected beneath the infiltration bed. Furthermore, the majority of Nitrosospira-associated sequences represent an unrecognized cluster. We conclude that an uncharacterized group associated with Nitrosospira dominate at the geochemically stable, down-gradient site, but found little evidence for Betaproteobacteria nitrifiers beneath the infiltration beds where geochemical conditions were more variable.     

Simulation of aerosol radiative properties with the ORISAM-RAD model during a pollution event (ESCOMPTE 2001)

The aim of this study is to present the organic and inorganic spectral aerosol module-radiative (ORISAM-RAD) module, allowing the 3D distribution of aerosol radiative properties (aerosol optical depth, single scattering albedo and asymmetry parameter) from the ORISAM module. In this work, we test ORISAM-RAD for one selected day (24th June) during the ESCOMPTE (expérience sur site pour contraindre les modèles de pollution atmosphérique et de transport d’emissions) experiment for an urban/industrial aerosol type. The particle radiative properties obtained from in situ and AERONET observations are used to validate our simulations. In a first time, simulations obtained from ORISAM-RAD indicate high aerosol optical depth (AOD)0.50–0.70±0.02 (at 440 nm) in the aerosol pollution plume, slightly lower (10–20%) than AERONET retrievals. In a second time, simulations of the single scattering albedo (ω_o) have been found to well reproduce the high spatial heterogeneities observed over this domain. Concerning the asymmetry parameter (g), ORISAM-RAD simulations reveal quite uniform values over the whole ESCOMPTE domain, comprised between 0.61±0.01 and 0.65±0.01 (at 440 nm), in excellent agreement with ground based in situ measurements and AERONET retrievals. Finally, the outputs of ORISAM-RAD have been used in a radiative transfer model in order to simulate the diurnal direct radiative forcing at different locations (urban, industrial and rural). We show that anthropogenic aerosols strongly decrease surface solar radiation, with diurnal mean surface forcings comprised between −29.0±2.9 and −38.6±3.9 W m⁻², depending on the sites. This decrease is due to the reflection of solar radiations back to space (−7.3±0.8<ΔF_TOA<−12.3±1.2 W m⁻²) and to its absorption into the aerosol layer (21.1±2.1<ΔF_ATM<26.3±2.6 W m⁻²). These values are found to be consistent with those measured at local scale.     

Influence of temperature on the chemical removal of 3-methylbutanal,trans-2-methyl-2-butenal,and 3-methyl-2-butenal by OH radicals in the troposphere

Absolute rate coefficients for the gas-phase reactions of OH radical with 3-methylbutanal (k₁), trans-2-methyl-2-butenal (k₂), and 3-methyl-2-butenal (k₃) have been obtained with the pulsed laser photolysis/laser-induced fluorescence technique. Gas-phase concentration of aldehydes was measured by UV absorption spectroscopy at 185 nm. Experiments were performed over the temperature range of 263–353 K at total pressures of helium between 46.2 and 100 Torr. No pressure dependence of all k_i (i = 1–3) was observed at all temperatures. In contrast, a negative temperature dependence of k_i (i.e., k_i increases when temperature decreases) was observed in that T range. The resulting Arrhenius expressions (±2σ) are: k₁(T) = (5.8 ± 1.7)×10^?12 exp{(499 ± 94)/T} cm³ molecule^?1 s^?1, k₂(T)=(6.9 ± 0.9)×10^?12 exp{(526 ± 42)/T} cm³ molecule^?1 s^?1, k₃(T)=(5.6 ± 1.2)×10^?12 exp{(666 ± 54)/T} cm³ molecule^?1 s^?1.The tropospheric lifetimes derived from the above OH-reactivity trend are estimated to be higher for 3-methylbutanal than those for the unsaturated aldehydes. A comparison of the tropospheric removal of these aldehydes by OH radicals with other homogeneous degradation routes leads to the conclusion that this reaction can be the main homogeneous removal pathway. However, photolysis of these aldehydes in the actinic region (λ > 290 nm) could play an important role along the troposphere, particularly for 3-methyl-2-butenal. This process could compete with the OH reaction for 3-methylbutanal or be negligible for trans-2-methyl-2-butenal in the troposphere.     

Effective diffusivity of the uranyl ion in a granite from Inada, Ibaraki, Japan

The effective diffusivity of uranium(VI) in Inada granite has been determined by through-diffusion. Experiments were performed at room temperature (20–25°C) in a 0.1 mol 1⁻¹ KCl solution where uranium is present predominantly as the poorly sorbing UO₂²⁺. An effective diffusivity (D_e) of (3.6 ± 1.6) × 10⁻¹⁴ m² s⁻¹ was obtained, close to that for uranine (nonsorbing organic tracer), but one order of magnitude lower than those obtained for Sr²⁺ and NpO₂⁺, and two orders of magnitude lower than that obtained for I⁻. According to well established theory, a proportional relationship exists between D_e and the diffusivity in the bulk of the solution (D_v). The effective diffusivity obtained in granite was not proportional to D_v. This agrees with results obtained for effective diffusivity in a Swedish granite. The ratio D_e/D_v was found to be not constant but increased with D_e or D_v. This result suggests a limit to the application of the theory.     

Comportement photochimique du nitro-4 phenol en solution aqueuse

The quantum yield of the phototransformation of 4-nitrophenol has been evaluated as 4.5×10⁻⁵±0.6×10⁻⁵ at pH=2; at 3.0×10⁻⁵±0.6×10⁻⁵ at pH=5.5; 1.8×10⁻⁵±0.5×10⁻⁵ at pH=8.3. However the half-life is relatively low and no accumulation of aromatic or quinonic products was observed. Hydroquinone (QH₂) is the main organic primary product formed when an air-saturated or degassed solution was irradiated in 365 nm monochromatic light (about 80% of the 4-nitrophenol initially converted at pH=5.5 in the absence of oxygen). In air-saturated neutral or acidic solution, the formation of NO⁻₃ ions accounted for about 80% of the 4-nitrophenol converted, but in degassed medium a mixture NO : NO⁻₂ : NO⁻₃ is formed. An heterolytical mechanism of photohydrolysis with primary formation of QH₂ and HNO₂ is suggested. Several by-products as benzoquinone, 4-nitrosophenol, 4-nitrocatechol and nitrohydroquinone are formed according to the conditions. Many secondary reactions are involved as the disproportionation or the oxidation of HNO₂, the oxidation of QH₂ by HNO₂ and oxidations induced by excitation of NO⁻₂ and NO⁻₃.     

Net ecosystem CO2 exchange over a larch forest in Hokkaido, Japan

Larch forests are distributed extensively in the east Eurasian continent and are expected to play a significant role in the terrestrial ecosystem carbon cycling process. In view of the fact that studies on carbon exchange for this important biome have been very limited, we have initiated a long-term flux observation in a larch forest ecosystem in Hokkaido in northern Japan since 2000. The net ecosystem CO₂ exchange (NEE) showed large seasonal and diurnal variation. Generally, the larch forest ecosystem released CO₂ in nighttime and assimilated CO₂ in daytime during the growing season from May to October. The ecosystem started to become a net carbon sink in May, reaching a maximum carbon uptake as high as 186 g C m⁻² month⁻¹ in June. With the yellowing, senescing and leaf fall, the ecosystem turned into a carbon source in November. During the non-growing season, the larch forest ecosystem became a net source of CO₂, releasing an average of 16.7 g C m⁻² month⁻¹. Overall, the ecosystem sequestered 141–240 g C m⁻² yr⁻¹ in 2001. The NEE was significantly influenced by environmental factors. Respiration of the ecosystem, for example, was exponentially dependent on air temperature, while photosynthesis was related to the incident PAR in a manner consistent with the Michaelis–Menten model. Although the vapor pressure deficit (VPD) was scarcely higher than 15 hPa, the CO₂ uptake rate was also depressed when VPD surpassed 10 hPa.     

The ratio between nitrogen oxides and carbon monoxide total emissions as precursors of tropospheric hydroxyl content evolution

The Main Geophysical Observatory 2D channel photochemical model is used to study the behavior of tropospheric OH within the 30–60°N zonal belt in relation to changing NO_X and CO emissions. The changes of tropospheric OH as a function of the contributions by NO_X and CO emissions during the period 1850–2050 are calculated. Our estimations show that the largest annual increment of total tropospheric OH within the belt considered occurs in the 1985–1995 period, about 0.27% yr⁻¹. Based on scenarios of tropospheric pollution emissions in the first half of 21st century, the total tropospheric OH content will increase more slowly, by 0.12–0.15% yr⁻¹. The maximum growth of OH concentration occurs close to air pollution locations—in the lower troposphere during 1850–1995 but in the upper troposphere in the 21st century when the NO_X source from subsonic aircraft increases faster than the surface source.     

Adsorption of uranium(VI) on amorphous ferric oxyhydroxide at high concentrations of dissolved carbon(IV) and sulfur(VI)

Amorphous ferric oxyhydroxide is being used to treat groundwater contaminated with uranium(VI); the compound also has potential for use as a component in in situ chemical barriers. To quantitatively evaluate its effectiveness in such applications, adsorption of uranium(VI) onto amorphous ferric oxyhydroxide was experimentally investigated under a wide range of uranium(VI) (8.40·10⁻⁷−2.10·10⁻³ mol L⁻¹; 0.2–500 mg L⁻¹), sulfur(VI) (0–0.07 mol L⁻¹; 0–2240 mg L⁻¹) and carbon(IV) (0–0.0195 mol L⁻¹; 0–234 mg L⁻¹) concentrations, and pH-values (4–9.6). The adsorption behavior of uranium(VI) (uranyl ion and its complexes) is similar to that of other cations; it exhibits a sharp rise in the extent of adsorption with increasing pH. Interactions among uranyl complexes and surface sites are interpreted using a site complexation model. Although the model does not incorporate electrostatics and includes only a single type of adsorption site, it provides a reasonable match to measured adsorption and proton exchange data. The simplicity of the model and the resulting reduction in computational demand allow its efficient incorporation into coupled reaction-transport models.     

Emissions of organophosphate and brominated flame retardants from selected consumer products and building materials

The emissions of selected flame retardants were measured in 1- and 0.02-m³ emission test chambers and 0.001-m³ emission test cells. Four product groups were of interest: insulating materials, assembly foam, upholstery/mattresses, and electronics equipment. The experiments were performed under constant environmental conditions (23°C, 50% RH) using a fixed sample surface area and controlled air flow rates. Tris (2-chloro-isopropyl)phosphate (TCPP) was observed to be one of the most commonly emitted organophosphate flame retardants in polyurethane foam applications. Depending on the sample type, area-specific emission rates (SER_a) of TCPP varied between 20 ng m⁻² h⁻¹ and 140 μg m⁻² h⁻¹.The emissions from electronic devices were measured at 60°C to simulate operating conditions. Under these conditions, unit specific emission rates (SER_u) of organophosphates were determined to be 10–85 ng unit⁻¹ h⁻¹. Increasing the temperature increased the emission of several flame retardants by up to a factor of 500. The results presented in this paper indicate that emissions of several brominated and organophosphate flame retardants are measurable. Polybrominated diphenylethers exhibited an SER_a of between 0.2 and 6.6 ng m⁻² h⁻¹ and an SER_u of between 0.6 and 14.2 ng unit⁻¹ h⁻¹. Because of sink effects, i.e., sorption to chamber components, the emission test chambers and cells used in this study have limited utility for substances low vapour pressures, especially the highly brominated compounds; hexabromocyclododecane had an SER_a of between 0.1 and 29 ng m⁻² h⁻¹ and decabromodiphenylether was not detectable at all.     

Levels and composition of volatile organic compounds on commuting routes in Detroit, Michigan

Vehicle emissions can constitute a major share of ambient concentrations of many volatile organic compounds (VOCs) and other air pollutants in urban areas. Especially high concentrations may occur at curbsides, vehicle cabins, and other microenvironments. Such levels are not reflected by monitoring at fixed sites. This study reports on measurements of VOCs made from buses and cars in Detroit, MI. A total of 74 adsorbent tube samples were collected on 40 trips and analyzed by GC-MS for 77 target compounds. Three bus routes, selected to include residential, commercial and heavily industrialized areas, were sampled simultaneously on four sequential weeks during morning and afternoon rush hour periods. Nineteen compounds were regularly detected and quantified, the most prevalent of which included hexane/2-methyl pentane (15.6±5.8 μg m⁻³), toluene (10.2±7.9 μg m⁻³), m,p-xylene (6.8±4.7 μg m⁻³), benzene (4.5±3.0 μg m⁻³), 1,2,4-trimethylbenzene (4.0±2.6 μg m⁻³), o-xylene (2.2±1.6 μg m⁻³), and ethylbenzene (2.1±1.5 μg m⁻³). VOC levels in bus interiors and outdoor levels along the roadway were similar. Despite the presence of large industrial sources, route-to-route variation was small, but temporal variation was large and statistically significant. VOC compositions and trends indicate the dominance of vehicle sources over the many industrial sources in Detroit with the possible exceptions of styrene and several chlorinated VOCs. In-bus levels exceeded concentrations at fixed site monitors by a factor of 2–4. VOC concentrations in Detroit traffic are generally comparable to levels measured elsewhere in the US and Canada, but considerably lower than measured in Asia and Europe.