Atmospheric corrosion effects of HNO3—Influence of temperature and relative humidity on laboratory-exposed copper

The effect of HNO₃ on the atmospheric corrosion of copper has been investigated at varied temperature (15–35 °C) and relative humidity (0–85% RH). Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction (XRD) confirmed the existence of cuprite and gerhardtite as the two main corrosion products on the exposed copper surface. For determination of the corrosion rate and for estimation of the deposition velocity (V_d) of HNO₃ on copper, gravimetry and ion chromatography has been employed. Temperature had a low effect on the corrosion of copper. A minor decrease in the mass gain was observed as the temperature was increased to 35 °C, possibly as an effect of lower amount of cuprite due to a thinner adlayer on the metal surface at 35 °C. The V_d of HNO₃ on copper, however, was unaffected by temperature. The corrosion rate and V_d of HNO₃ on copper was the lowest at 0% RH, i. e. dry condition, and increased considerably when changing to 40% RH. A maximum was reached at 65% RH and the mass gain remained constant when the RH was increased to 85% RH. The V_d of HNO₃ on copper at ⩾65% RH, 25 °C and 0.03 cm s⁻¹ air velocity was as high as 0.15±0.03 cm s⁻¹ to be compared with the value obtained for an ideal absorbent, 0.19±0.02 cm s⁻¹. At sub-ppm levels of HNO₃, the corrosion rate of copper decreased after 14 d and the growth of the oxide levelled off after 7 d of exposure.     

Photooxidation of methylhydroperoxide and ethylhydroperoxide in the aqueous phase under simulated cloud droplet conditions

The photooxidation of methylhydroperoxide (MHP) and ethylhydroperoxide (EHP) was studied in the aqueous phase under simulated cloud droplet conditions. The kinetics and the reaction products of direct photolysis and OH-oxidation were studied for both compounds. The photolysis frequencies obtained were J_MHP=4.5 (±1.0)×10⁻⁵ s⁻¹ and J_EHP=3.8 (±1.0)×10⁻⁵ s⁻¹ for MHP and EHP respectively at 6 °C. The rate constants of OH-oxidation of MHP at 6 °C were 6.3 (±2.6)×10⁸ M⁻¹ s⁻¹ and 5.8 (±1.9)×10⁸ M⁻¹ s⁻¹ relative to ethanol and 2-propanol respectively, and the rate constant of OH-oxidation of EHP was 2.1 (±0.6)×10⁹ M⁻¹ s⁻¹ relative to 2-propanol at 6 °C. The reaction products obtained were not only the corresponding aldehydes, but also the corresponding acids, and hydroxyhydroperoxides as primary reaction products. The yields for these products were sensitive to the pH value. The carbon balance was higher than 85% for all experiments, showing that most reaction products were detected. A chemical mechanism was proposed for each reaction, and the atmospheric implications were discussed.     

Measurement and analysis of atmospheric ammonia emissions from anaerobic lagoons

Ammonia-nitrogen flux (NH₃-N=(14/17)NH₃) was determined from six anaerobic swine waste storage and treatment lagoons (primary, secondary, and tertiary) using the dynamic chamber system. Measurements occurred during the fall of 1998 through the early spring of 1999, and each lagoon was examined for approximately one week. Analysis of flux variation was made with respect to lagoon surface water temperature (∼15 cm below the surface), lagoon water pH, total aqueous phase NH_x(=NH₃+NH₄⁺) concentration, and total Kjeldahl nitrogen (TKN). Average lagoon temperatures (across all six lagoons) ranged from approximately 10.3 to 23.3^°C. The pH ranged in value from 6.8 to 8.1. Aqueous NH_x concentration ranged from 37 to 909 mg N l⁻¹, and TKN varied from 87 to 950 mg N l⁻¹. Fluxes were the largest at the primary lagoon in Kenansville, NC (March 1999) with an average value of 120.3 μg N m⁻² min⁻¹, and smallest at the tertiary lagoon in Rocky Mount, NC (November 1998) at 40.7 μg N m⁻² min⁻¹. Emission rates were found to be correlated with both surface lagoon water temperature and aqueous NH_x concentration. The NH₃-N flux may be modeled as ln(NH₃-N flux)=1.0788+0.0406T_L+0.0015([NH_x]) (R²=0.74), where NH₃-N flux is the ammonia flux from the lagoon surface in μg N m⁻² min⁻¹, T_L is the lagoon surface water temperature in ^°C, and [NH_x] is the total ammonia-nitrogen concentration in mg N l⁻¹.     

Effect of copper(II) on biodegradation of benzo[a]pyrene by Stenotrophomonas maltophilia

Benzo[a]pyrene (BaP) biodegradation by Stenotrophomonas maltophilia was studied under the influence of co-existed Cu(II) ions. About 45% degradation was achieved within 3 d when dealing with 1 mg L^?1 BaP under initial natural pH at 30 °C; degradation reached 48% in 2 d at 35 °C. Efficacy of BaP biodegradation reached the highest point at pH 4. In the presence of 10 mg L^?1 Cu(II) ions, the BaP removal ratio was 45% on 7th day, and maintained stable from 7 to 14 d at 30 °C under natural pH. The favorable temperature and pH for BaP removal was 25 °C and 6.0 respectively, when Cu(II) ions coexisted in the solutions. Experiments on cometabolism indicated that S. maltophilia performed best when sucrose was used as an additional carbon source. GC–MS analysis revealed that the five rings of BaP opened, producing compounds with one or two rings which were more bioavailable.     

Volatile organic compound emissions from Siberian larch

We determined hourly emissions of isoprene, monoterpenes and sesquiterpenes from Siberian larch, one of the major tree species in Siberian forests. Summer volatile organic compounds (VOCs) emission from Siberian larch consisted mainly of monoterpenes (about 90%). The monoterpene emission spectrum remained constant during the measurement period, almost half was sabinene and other major monoterpenes were Δ³-carene, β- and α-pinene. During spring and summer, about 10% of the VOCs were sesquiterpenes, mainly α-farnesene. The sesquiterpene emissions declined to 3% in the fall. Isoprene, 2-methyl-3-buten-2-ol (MBO) and 1,8-cineole contributed to less than 3% of the VOC emission during the whole period. The diurnal variation of the emissions could be explained using a temperature-dependent parameterization. Emission potentials normalized to 30 °C were 5.2–21 μg g_dw⁻¹ h⁻¹ (using β-value of 0.09 °C⁻¹) for monoterpenes and 0.4–1.8 μg g_dw⁻¹ h⁻¹ (using β-value of 0.143 °C⁻¹, mean of determined values) for sesquiterpenes. Normalized monoterpene emission potentials were highest in late summer and elevated again in late fall. Sesquiterpene emission potentials were also highest in late summer, but decreased towards fall.     

Isoprene and monoterpene emission from the coniferous species Abies Borisii-regis—implications for regional air chemistry in Greece

The emission of isoprene has been studied from a forest of Abies Borisii-regis, a Mediterranean fir species previously thought to emit only monoterpenes. Emission studies from two independent enclosure experiments indicated a standardised isoprene emission rate of (18.4±3.8) μg g_dry-weight⁻¹ h⁻¹, similar in magnitude to species such as eucalyptus and oak which are considered to be strong isoprene emitters. Isoprene emission depended strongly on both leaf temperature (2°C–34°C) and photosynthetically active radiation (PAR) below 250 μmol m⁻² s⁻¹, becoming saturated with respect to PAR above this value. The annual isoprene emission rate was estimated to be (132±29) kT yr⁻¹ for those trees growing within Greece, comparable to current estimates of the total isoprene budget of Greece as a whole, and contributing significantly to regional ozone and carbon monoxide budgets. Monoterpene emission exhibited exponential temperature dependence, with 1,8-cineole, α-pinene, β-pinene and limonene forming the primary emissions. A standardised total monoterpene emission rate of (2.7±1.1) μg g_dry-weight⁻¹ h⁻¹ was calculated, corresponding to an annual monoterpene emission rate of (24±12) kT yr⁻¹. Research was conducted as part of the AEROBIC’97 (AEROsol formation from BIogenic organic Carbon) series of field campaigns.     

A laboratory study of the effect of NO2 on the atmospheric corrosion of zinc

Studies on the effect of NO_x on zinc corrosion are scarce and their results are variable and at times seemingly contradictory. This paper reports laboratory tests involving the dry deposition on zinc surfaces of 800 μg m⁻³ NO₂, alone and in combination with 800 μg m⁻³ SO₂, at temperatures of 35 and 25 °C and relative humidities of 90% and 70%. From the gravimetric results obtained and from the characterisation of the corrosion products by optical microscopy, scanning electron microscopy (SEM/EDX), grazing incidence X-ray diffraction (GIXD) and X-ray photoelectron spectroscopy (XPS), it has been verified that the corrosive action of NO₂ alone is negligible compared with SO₂. However, an accelerating effect has been observed when NO₂ acts in conjunction with SO₂ at 25 °C and 90% RH. At 35 °C and 90% RH, the accelerating effect is smaller, and at low relative humidities (70%), the synergistic effect is only slight, which suggests it may be favoured by the presence of moisture. In those cases where an accelerating effect has been observed, a greater proportion of sulphate ions has been found in the corrosion products, and nitrogen compounds have not been detected, indicating that NO₂ participates indirectly as a catalyst of the oxidation of SO₂ to sulphate.     

Interaction of temperature and an environmental stressor: Moina macrocopa responds with increased body size,increased lifespan,and increased offspring numbers slightly above its temperature optimum

For organisms, temperature is one of the most important environmental factors and gains increasing importance due to global warming, since increasing temperatures may pose organisms close to their environmental tolerance limits and, thus, they may become more vulnerable to environmental stressors. We analyzed the temperature-dependence of the water-soluble antioxidant capacity of the cladoceran Moina macrocopa and evaluated its life trait variables with temperature (15, 20, 25, 30 °C) and humic substance (HS) concentrations (0, 0.18, 0.36, 0.90, 1.79 mM DOC) as stressors. Temperatures below and above the apparent optimum (20 °C) reduced the antioxidative capacity. Additions of HSs increased body length, but decreased mean lifespan at 15 and 20 °C. There was no clear HS-effect on offspring numbers at 15, 20, and 30 °C. At 25 °C with increasing HS-concentration, lifespan was extended and offspring numbers increased tremendously, reaching 250% of the control. Although the applied HS preparation possesses estrogenic and antiandrogenic activities, a xenohormone mechanism does not seem plausible for the reproductive increase, because comparable effects did not occur at other temperatures. A more convincing explanation appears to be the mitohormesis hypothesis which states that a certain increase of reactive oxygen production leads to improved health and longevity and, with Moina, also to increased offspring numbers. Our results suggest that at least with the eurythermic M. macrocopa, a temperature above the optimum can be beneficial for several life trait variables, even when combined with a chemical stressor. Temperatures approximately 10 °C above its optimum appear to adversely affect the lifespan and reproduction of M. macrocopa. This indicates that this cladoceran species seems to be able to utilize temperature as an ecological resource in a range slightly above its thermal optimum.     

Feasibility of a simple laboratory approach for determining temperature influence on SPMD–air partition coefficients of selected compounds

Semipermeable membrane devices (SPMDs) are a widely used passive sampling methodology for both waterborne and airborne hydrophobic organic contaminants. The exchange kinetics and partition coefficients of an analyte in a SPMD are mediated by its physicochemical properties and certain environmental conditions. Controlled laboratory experiments are used for determining the SPMD–air (K_sa's) partition coefficients and the exchange kinetics of organic vapors. This study focused on determining a simple approach for measuring equilibrium K_sa's for naphthalene (Naph), o-chlorophenol (o-CPh) and p-dichlorobenzene (p-DCB) over a wide range of temperatures. SPMDs were exposed to test chemical vapors in small, gas-tight chambers at four different temperatures (−16, −4, 22 and 40 °C). The exposure times ranged from 6 h to 28 d depending on test temperature. K_sa's or non-equilibrium concentrations in SPMDs were determined for all compounds, temperatures and exposure periods with the exception of Naph, which could not be quantified in SPMDs until 4 weeks at the −16 °C temperature. To perform this study the assumption of constant and saturated atmospheric concentrations in test chambers was made. It could influence the results, which suggest that flow through experimental system and performance reference compounds should be used for SPMD calibration.     

Kinetics of the gas-phase reactions of NO3 radicals with ethyl acrylate,n-butyl acrylate,methyl methacrylate and ethyl methacrylate

The relative rate method has been used to determine the rate constants for the gas-phase reactions of NO₃ radicals with a series of acrylate esters: ethyl acrylate (k₁), n-butyl acrylate (k₂), methyl methacrylate (k₃) and ethyl methacrylate (k₄) at 298 ± 1 K and 760 Torr. The obtained rate constants are k₁ = (1.8 ± 0.25) × 10^?16 cm³ molecule^?1 s^?1, k₂ = (2.1 ± 0.33) × 10^?16 cm³ molecule^?1 s^?1, k₃ = (3.6 ± 1.2) × 10^?15 cm³ molecule^?1 s^?1, k₄ = (4.9 ± 1.7) × 10^?15 cm³ molecule^?1 s^?1. The experimental rate constants are in good agreement with theoretical rate constants calculated by an algorithm of the correlation between the rate constants and the orbital energies for the reactions of unsaturated VOCs with NO₃ radicals. In addition, the atmospheric lifetimes of the compound against NO₃ attack are estimated and the results show that NO₃ reactions contribute little to the atmospheric losses of acrylate esters except in polluted regions.     

The influence of aerosols on photochemical smog in Mexico City

Aerosols in the Mexico City atmosphere can have a non-negligible effect on the ultraviolet radiation field and hence on the formation of photochemical smog. We used estimates of aerosol optical depths from sun photometer observations in a detailed radiative transfer model, to calculate photolysis rate coefficients (J_NO2) for the key reaction NO₂+hν→NO+O (λ<430 nm). The calculated values are in good agreement with previously published measurements of J_NO2at two sites in Mexico City: Palacio de Minerı́a (19°25′59″N, 99°07′58″W, 2233 masl), and IMP (19°28′48″N, 99°11′07″W, 2277 masl) and in Tres Marias, a town near Mexico City (19°03′N, 99°14′W, 2810 masl). In particular, the model reproduces very well the contrast between the two urban sites and the evidently much cleaner Tres Marias site. For the measurement days, reductions in surface J_NO2 by 10–30% could be attributed to the presence of aerosols, with considerable uncertainty due largely to lack of detailed data on aerosol optical properties at ultraviolet wavelengths (esp. the single scattering albedo). The potential impact of such large reductions in photolysis rates on surface ozone concentrations is illustrated with a simple zero-dimensional photochemical model.     

Aerosol scattering properties in northern China

The aerosol scattering properties were investigated at two continental sites in northern China in 2004. Aerosol light scattering coefficient (σ_sp) at 525 nm, PM₁₀, and aerosol mass scattering efficiencies (α) at Dunhuang had a mean value of 165.1±148.8 M m⁻¹, 157.6±270.0 μg m⁻³, and 2.30±3.41 m² g⁻¹, respectively, while these values at Dongsheng were, respectively, 180.2±151.9 M m⁻¹, 119.0±112.9 μg m⁻³, and 1.87±1.41 m² g⁻¹. There existed a seasonal variability of aerosol scattering properties. In spring, at Dunhuang PM₁₀, σ_sp, and α were 184.1±211.548 μg m⁻³, 126.3±89.6 M m⁻¹, and 1.05±0.97 m² g⁻¹, respectively, and these values at Dongsheng were 146.4±142.1 μg m⁻³, 183.4±81.7 M m⁻¹, and 1.98±1.52 m² g⁻¹, respectively. However, in winter at Dunhuang PM₁₀, σ_sp, and α were 158.1±261.4 μg m⁻³, 303.3±165.2 M m⁻¹, and 3.17±1.93 m² g⁻¹, respectively, and these values at Dongsheng were 155.7±170.1 μg m⁻³, 304.4±158.1 M m⁻¹, and 2.90±1.72 m² g⁻¹, respectively. σ_sp and α in winter were higher than that in spring at both the sites, which coincides with the characteristics of dust aerosol and pollution aerosol. Overall, the dominant aerosol types in spring and winter at both sites in northern China are dust aerosol and pollution aerosol, respectively.     

Isoprene and monoterpene fluxes measured above Amazonian rainforest and their dependence on light and temperature

Canopy scale emissions of isoprene and monoterpenes from Amazonian rainforest were measured by eddy covariance and eddy accumulation techniques. The peak mixing ratios at about 10 m above the canopy occurred in the afternoon and were typically about 90 ppt_v of α-pinene and 4–5 ppb_v of isoprene. α-pinene was the most abundant monoterpene in the air above the canopy comprising ≈50% of the total monoterpene mixing ratio. Measured isoprene fluxes were almost 10 times higher than α-pinene fluxes. Normalized conditions of 30°C and 1000 μmol m⁻² s⁻¹ were associated with an isoprene flux of 2.4 mg m⁻² h⁻¹ and a β-pinene flux of 0.26 mg m⁻² h⁻¹. Both fluxes were lower than values that have been specified for Amazon rainforests in global emission models. Isoprene flux correlated with a light- and temperature-dependent emission activity factor, and even better with measured sensible heat flux. The variation in the measured α-pinene fluxes, as well as the diurnal cycle of mixing ratio, suggest emissions that are dependent on both light and temperature. The light and temperature dependence can have a significant effect on the modeled diurnal cycle of monoterpene emission as well as on the total monoterpene emission.     

Effects of aqueous stable fullerene nanocrystals (nC60) on Daphnia magna: Evaluation of sub-lethal reproductive responses and accumulation

Concerns exist regarding the inadvertent release of engineered nanomaterials into natural systems, and the possible negative ecosystem response that may occur. Understanding sub-lethal effects may be particularly important to determining ecosystem responses as current levels of nanomaterial release are low compared to levels projected for the future. In this work, the sub-lethal effects and bioaccumulation of water stable, nanocrystalline fullerenes as C₆₀, (termed nC₆₀) were studied in Daphnia magna, a globally distributed, parthenogenetic zooplankton. Sub-lethal concentrations were first determined for both mature mother (LD₅₀ = 0.4 mg L⁻¹) and neonate (gestating) daphnids (0.2 mg L⁻¹) in standard 48 h exposure tests. Subsequent experiments focused on the accumulation and effects (at temperatures of 18–28 °C) of nC₆₀, during the D. magna reproductive cycle. The results demonstrate that upon sub-lethal exposure, the mortality rates of gestating daphnids increased with time and developmental stage. The maturation of daughter daphnids was negatively impacted. The mother daphnids were unable to reproduce again after exposure during pregnancy, and differential bioaccumulation occurred as a function of lipid content in the daphnia with the highest accumulation level of 7000 mg kg⁻¹ wet weight. Taken together, these results not only describe the accumulation and sub-lethal effects of nC₆₀ on exposed daphnia, but also highlight the importance of sub-lethal exposure scenarios, which are critical to fully understanding the potential impact of fullerenes and other engineered nanoscale materials on natural systems.     

Decolorization of azo dye reactive black B by Bacillus cereus strain HJ-1

Reactive black B (RBB) is a group of azo dyes that are widely used in the textile industry. In this study, a new microbial strain was isolated from azo dye contaminated river sediment which is capable of degrading RBB. The strain was identified as Bacillus cereus strain HJ-1 by 16S rRNA gene sequences analysis. The optimal conditions for RBB decolorization by B. cereus strain HJ-1 are: 25 °C, pH 8, 1 CMC of triton X-100, 0.15 g L^?1 of added yeast extract, 0.125 g L^?1 of added glucose and static culture. Then the toxicity of RBB on the green algae Chlorella vulgaris was determined. The results showed that the median effective concentration (EC₅₀) of RBB for C. vulgaris is 48 mg L^?1 and toxicity will really decrease after decolorization. In the end, B. cereus strain HJ-1 was amended into the origin river sediment and analyzed the whole microbial community structure of river sediment samples by PCR-DGGE technique. The result showed that B. cereus strain HJ-1 could survive in the river sediment after 12 d of incubation. Based on this work, we hope that these findings could provide some useful information for applying the decolorization of RBB in our environment.     

Ozone response to precursor controls: comparison of data analysis methods with the predictions of photochemical air quality simulation models

Comparisons were made between the predictions of six photochemical air quality simulation models (PAQSMs) and three indicators of ozone response to emission reductions: the ratios of O₃/NO_z and O₃/NO_y and the extent of reaction. The values of the two indicator ratios and the extent of reaction were computed from the model-predicted mixing ratios of ozone and oxidized nitrogen species and were compared to the changes in peak 1 and 8 h ozone mixing ratios predicted by the PAQSMs. The ozone changes were determined from the ozone levels predicted for base-case emission levels and for reduced emissions of volatile organic compounds (VOCs) and oxides of nitrogen (NO_x). For all simulations, the model-predicted responses of peak 1 and 8 h ozone mixing ratios to VOC or NO_x emission reductions were correlated with the base-case extent of reaction and ratios of O₃/NO_z and O₃/NO_y. Peak ozone values increased following NO_x control in 95% (median over all simulations) of the high-ozone (>80 ppbv hourly mixing ratio in the base-case) grid cells having mean afternoon O₃/NO_z ratios less than 5 : 1, O₃/NO_y less than 4 : 1, or extent less than 0.6. Peak ozone levels decreased in response to NO_x reductions in 95% (median over all simulations) of the grid cells having peak hourly ozone mixing ratios greater than 80 ppbv and where mean afternoon O₃/NO_z exceeded 10 : 1, O₃/NO_y was greater than 8 : 1, or extent exceeded 0.8. Ozone responses varied in grid cells where O₃/NO_z was between 5 : 1 and 10 : 1, O₃/NO_y was between 4 : 1 and 8 : 1, or extent was between 0.6 and 0.8. The responses in such grid cells were affected by ozone responses in upwind grid cells and by the changes in ozone levels along the upwind boundaries of the modeling domains.     

Extent of H-atom abstraction from OH + p-cymene and upper limits to the formation of cresols from OH + m-xylene and OH + p-cymene

Aromatic hydrocarbons are important constituents of vehicle exhaust and of non-methane volatile organic compounds in ambient air in urban areas. It has recently been proposed that dealkylation is a significant pathway for the OH radical-initiated reactions, leading to the formation of phenolic compounds and/or oxepins (Noda, J., Volkamer, R., Molina, M.J., 2009. Dealkylation of alkylbenzenes: a significant pathway in the toluene, o-, m-, and p-xylene + OH reaction. Journal of Physical Chemistry A 113, 9658–9666.). We have investigated the formation of cresols from the reactions of OH radicals with m-xylene and p-cymene, and obtain upper limits of <1% for formation of each cresol isomer from OH + m-xylene and <2% for formation of each cresol isomer from OH + p-cymene. In addition, we have measured the formation yield of 4-methylacetophenone (the major product formed subsequent to H-atom abstraction from the CH(CH₃)₂ group) in the OH + p-cymene reaction to be 14.8 ± 3.2%, and estimate that H-atom abstraction from the CH₃ and CH(CH₃)₂ groups in p-cymene accounts for 20 ± 4% of the overall OH radical reaction. We also used a relative rate technique to measure the rate constant for the reaction of OH radicals with 4-methylacetophenone to be (4.50 ± 0.43) × 10^?12 cm³ molecule^?1 s^?1 at 297 ± 2 K.     

Effect of natural compounds on reducing formaldehyde emission from plywood

The effects of natural compounds on reducing formaldehyde emission from plywood were investigated. Urea, catechin and vanillin were examined as the natural formaldehyde reducers. The microemission cell, with an internal volume of 35 ml, the maximum exposed test surface area of 177 cm² and an air purge flow rate of 50 ml min⁻¹, was used to measure specific emission rate (SER). In the case of no reducer treatment, formaldehyde emission from plywood was fast and SERs were 4.4 mg m⁻² h⁻¹ at 30 °C and 15 mg m⁻² h⁻¹ at 60 °C. When this plywood was treated with the natural compounds, the SERs of formaldehyde were decreased at all temperatures. In the case of urea treatment, the SERs of formaldehyde decreased to 0.30 mg m⁻² h⁻¹ at 30 °C and 0.65 mg m⁻² h⁻¹ at 60 °C. When the urea treatment was applied to the inside of kitchen cabinet (made from plywood; 270 cm wide, 60 cm deep, 250 cm high), the concentration of formaldehyde was reduced substantially from 1600 to 130 μg m⁻³. The reducing effect of formaldehyde continued during the observation period (6 months), with a mean concentration of 100 μg m⁻³. Reducers in the plywood would react with released formaldehyde. Application of natural compounds such as urea, catechin and vanillin could provide a simple and effective approach for suppressing formaldehyde emission from plywood.     

Laboratory studies on the uptake of aromatic hydrocarbons by ice crystals during vapor depositional crystal growth

Uptake of aromatic hydrocarbons (AH) by ice crystals during vapor deposit growth was investigated in a walk-in cold chamber at temperatures of 242, 251, and 260 K, respectively. Ice crystals were grown from ambient air in the presence of gaseous AH namely: benzene (C₆H₆), toluene (methylbenzene, C₇H₈), the C₈H₁₀ isomers ethylbenzene, o-, m-, p-xylene (dimethylbenzenes), the C₉H₁₂ isomers n-propylbenzene, 4-ethyltoluene, 1,3,5-trimethylbenzene (1,3,5-TMB), 1,2,4-trimethylbenzene (1,2,4-TMB), 1,2,3-trimethylbenzene (1,2,3-TMB), and the C₁₀H₁₄ compound tert.-butylbenzene. Gas-phase concentrations calculated at 295 K were 10.3–20.8 μg m⁻³. Uptake of AH was detected by analyzing vapor deposited ice with a very sensitive method composed of solid-phase micro-extraction (SPME), followed by gas chromatography/mass spectrometry (GC/MS).Ice crystal size was lower than 1 cm. At water vapor extents of 5.8, 6.0 and 8.1 g m⁻³, ice crystal shape changed with decreasing temperatures from a column at a temperature of 260 K, to a plate at 251 K, and to a dendrite at 242 K. Experimentally observed ice growth rates were between 3.3 and 13.3×10⁻³ g s⁻¹ m⁻² and decreased at lower temperatures and lower value of water vapor concentration. Predicted growth rates were mostly slightly higher.Benzene, toluene, ethylbenzene, and xylenes (BTEX) were not detected in ice above their detection limits (DLs) of 25 pg g_ice⁻¹ (toluene, ethylbenzene, xylenes) and 125 pg g_ice⁻¹ (benzene) over the entire temperature range. Median concentrations of n-propylbenzene, 4-ethyltoluene, 1,3,5-TMB, tert.-butylbenzene, 1,2,4-TMB, and 1,2,3-TMB were between 4 and 176 pg g_ice⁻¹ at gas concentrations of 10.3–10.7 μg m⁻³ calculated at 295 K. Uptake coefficients (K) defined as the product of concentration of AH in ice and density of ice related to the product of their concentration in the gas phase and ice mass varied between 0.40 and 10.23. K increased with decreasing temperatures. Values of Gibbs energy (ΔG) were between −4.5 and 2.4 kJ mol⁻¹ and decreased as temperatures were lowered. From the uptake experiments, the uptake enthalpy (ΔH) could be determined between −70.6 and −33.9 kJ mol⁻¹. The uptake entropy (ΔS) was between −281.3 and −126.8 J mol⁻¹ K⁻¹. Values of ΔH and ΔS were rather similar for 4-ethlytoluene, 1,3,5-TMB and tert.-butylbenzene, whereas 1,2,3-TMB showed much higher values.     

HNO3 analyzer by scrubber difference and the NO–ozone chemiluminescence method

A fast response analyzer for HNO₃ in highly polluted air is described. The time resolution attainable was 12 s. The method is based on the difference in a technique for HNO₃-scrubbed and non-scrubbed air and the reduction of HNO₃ to NO with the use of a line of catalytic converters and a method for the subsequent NO-ozone chemiluminescence. A sample air stream, in which particulates are removed with a Teflon filter, is divided into two channels. CH-1 is directly connected to the converter line, and CH-2 contains a HNO₃ scrubber packed with a nylon fiber that goes to another converter line. Each converter line is composed of a hot quartz-bead converter (QBC) and a molybdenum converter (MC) in a series. A QBC reduces HNO₃ to (NO+NO₂), which is called NO_x. The MC reduces the NO_x to NO.For CH-1, the analyzer detects most compounds that typically comprise NO_y (J. Geophys. Res. 91 (1986) 9781). These CH-1 compounds are called NO_y′ hereafter (NO_y-particulate nitrate) because the particulates are removed by the filter. A difference in the detector signal for the two channels indicates HNO₃. For a blank test, atmospheric air in which HNO₃ was pre-scrubbed by an extra nylon fiber was introduced to the analyzer. Variations in the blank value were 0.38±0.42 and 0.34±0.55 ppb during the high readings (NO_y′-HNO₃ ) (called NO_y^* hereafter) (111±12 ppb, N=180), and low NO_y^* readings (62±8 ppb, N=180), respectively, indicating that the lowest detection limit of the analyzer is 1.1 ppb (2σ). When the data obtained with the analyzer is compared to the data using the denuder method, a linear correlation with the regression of Y=0.973X+0.077 (r²=0.916 (N=20)) in the range of 0–6.5 ppb HNO₃ is obtained, which is an excellent agreement. Atmospheric monitoring was carried out at Kobe. Although the average concentration of HNO₃ was 2.6±1.3 ppb, ca.10 ppb for a HNO₃ concentration was occasionally observed when the NO_y^* concentration was high, i.e., more than 100 ppb.