Three-wavelength nephelometer suitable for aircraft measurement of background aerosol scattering coefficient

A new nephelometer suitable for aircraft measurements of aerosol scattering extinction coefficient (σ_sp) has been constructed and operated under field conditions. This instrument is vacuum tight for operation in a pressurized aircraft cabin and is capable of measuring background tropospheric σ_sp at an averaging time of 1 min. For example, in a typical atmospheric profile the instrument can measure values of about 10⁻⁴ m⁻¹ with a time resolution of 2 s in a polluted region, and about 10⁻⁷ m⁻¹ with a time resolution of 1 min in a clean region. This sensitivity is made possible by: (1) subtracting in real time the air Rayleigh scattering from the total scattering signal by continuously measuring pressure and temperature in the sampling volume of the instrument; (2) correcting for the dark count and sensitivity of the photomultipliers using a rotating shutter; and (3) using a beam splitter arrangement to allow simultaneous detection by three photomultipliers. A laboratory measurement of instrument noise suggests a 550-nm noise level of about 5 × 10⁻⁸ m⁻¹ at an averaging time of 1 min.     

Wintertime measurements of aerosol acidity and trace elements in Wuhan,a city in central China

A 2-week intensive ambient aerosol study was conducted in December 1988 in Wuhan (Hubei Province), a city of nearly 2 million located on the Yangtze River in central China (P.R.C.). This is an industrial region where soft coal burning is widespread, and emission controls for vehicles and industrial facilities are minimal. The sampling site was located in one of the civic centers where residential and commercial density is highest. An Andersen dichotomous sampler was operated with Teflon membrane filters to collect fine (d_p < 2.5 μmad) and coarse (2.5 ⩽ d_p < 10 μmad) particles for total mass and element determinations. An annular denuder system (ADS) was used to collect fine fraction aerosols for analyses of ionic species including strong acidity (H⁺).The study was conducted between 18 and 30 December, which was rainless, consistently cool (3–10°C) and overcast, but without fog or acute stagnation. Fine particulate mass (PM, as μ m⁻³) averaged 139 (range 54–207); coarse PM averaged 86 (range 29–179). Trace element concentrations were also high. Crustal elements (Si, Al, Ca and Fe) were found primarily in the coarse fraction, while elements associated with combustion (S, K, Cl, Zn and Se) were enriched in the fine fraction. The concentrations of arsenic and selenium were evidence of a large source of coal burning, while vanadium levels (associated with fuel oil use) were not especially enriched.Despite the seemingly high PM loadings, ionic concentrations were not especially high. The average composition of soluble fine aerosol species (in neq m⁻³) were SO₄²⁻: 520 (range 180–980), NO₃⁻: 225 (range 50–470), Cl⁻: 215 (range 20–640), and NH₄⁺: 760 (range 280–1660). A deficit in accountable FP components (total mass compared to the total of ionic plus element masses) as well as the black appearance of collected materials indicate an abundance of carbonaceous aerosol, as high as 100 μ m⁻³. (total mass compared to the total of ionic plus element masses) as well as the black appearance of collected materials indicate an abundance of carbonaceous aerosol, as high as 100 μ m⁻³Aerosol acidity was negligible during most monitoring periods, H⁺: 14 (range 0–50 neq m⁻³, equivalent to 0–2.5 μm m⁻³ as H₂SO₄). Sulfur dioxide, measured by the West-Gaeke method for part of the study, concentrations were low. Although not directly measured, the aerosol measurments suggested that gaseous HCl (from refuse incineration) and NH₃ (animal wastes) concentrations might have been high. Higher aerosol acidity might be expected if HCl sources were more prominent and not neutralized by local ammonia or other base components.     

Measurements of ammonia flux to a spruce stand in Denmark

This work demonstrates the existence of a linear relation between the deposition velocity of ammonia and the friction velocity measured above a spruce stand in the western part of Denmark. In order to estimate the ammonia deposition velocity and flux to a Norway spruce forest, concentration gradients of ammonia and several meteorological parameters were measured in a meteorology tower during two periods, 1 week in spring and 1 week in late summer 1991. The estimated deposition velocities lie in the range −0.125 to 0.201 m s⁻¹, with a mean of 0.026 m s⁻¹. The deposition velocity and the flux were generally largest in the afternoon. On the basis of 24-h measurements of ammonia and routine meteorological measurements the relation between deposition velocity and friction velocity is extrapolated to an estimate of the average flux for the growing season May to September 1991. The estimate gave an average flux of 87 μg NH₃N m⁻² h⁻¹ (=0.02 μg NH₃N m⁻² s⁻¹). The average deposition velocity for the period was 0.045 m s⁻¹.     

Real-time,in situ measurements of atmospheric optical absorption in the visible via photoacoustic spectroscopy—IV. Visibility degradation and aerosol optical properties in Los Angeles

Aerosol light absorption (b_abs) has been measured in real-time in Los Angeles with a validated photoacoustic technique, and its impact on visibility degradation has been examined. These measurements were collected during ten days in the summer of 1987 for the Southern California Air Quality Study (SCAQS). Aerosol b_abs (λ = 514.5 nm) varied from an hourly average value of 7 × 10⁻⁶ m⁻¹ in the 3–4 and 4–5 a.m. periods of 13 July to 9 × 10⁻⁵ m⁻¹ in the 7–8 a.m. period of both 28 August and 3 September. This b_abs, which is due solely to elemental carbon (EC) showed a distinct diurnal pattern with low values at night, increasing around sunrise to higher values through mid-afternoon. Comparison of these data with aerosol light scattering data clearly illustrates that the contribution of aerosol light absorption to visibility degradation increases in importance under less polluted conditions. Other urban and rural studies show similar results.     

Methane,nitrous oxide and ammonia emissions during storage and after application of dairy cattle slurry and influence of slurry treatment

Slurries are a significant source of CH₄, NH₃ and N₂O emissions to the atmosphere. The research project aimed at quantifying CH₄, NH₃ and N₂O emissions from liquid manure stores and after manure application under field conditions. The influence of the manure treatment options “no treatment”, “slurry separation”, “anaerobic digestion”, “slurry aeration” and “straw cover” on the emission level was investigated. Approximately 10 m³ of differently treated slurry were stored in pilot scale slurry tanks. Emissions were followed for c. 80 days. After the storage period, slurries were applied to permanent grassland. Greenhouse gas emissions from slurry were mainly caused by methane emissions during storage and by nitrous oxide emissions after field application of manures. Mitigation of GHG emissions can be achieved by a reduction in slurry dry matter and easily degradable organic matter content. Ammonia emissions mainly occurred after field application. Untreated slurry emitted 226.8 g NH₃ m⁻³ and 92.4 kg CO₂ eq. m⁻³ (storage and field application). Slurry separation (liquid fraction and composting of the solid fraction) resulted in NH₃ losses of 402.9 g m⁻³ and GHG losses of 58.5 kg CO₂ eq. m⁻³. Anaerobic digestion was a very effective means to reduce GHG emissions. 37.9 kg CO₂ eq. m⁻³ were lost. NH₃ emissions were similar to those from untreated slurry. Covering the slurry store with a layer of chopped straw instead of a wooden cover increased NH₃ emissions to 320.4 g m⁻³ and GHG emissions to 119.7 kg CO₂ eq. m⁻³. Slurry aeration nearly doubled NH₃ emissions compared to untreated slurry. GHG emissions were reduced to 53.3 kg CO₂ eq. m⁻³.     

Characterization of atrazine degradation and nitrate reduction by Pseudomonas sp. strain ADP

Concomitant atrazine degradation and nitrate reduction by a pure culture of Pseudomonas sp. strain ADP were studied. Under anoxic conditions, Ps ADP grew well and degraded atrazine efficiently in the presence of nitrate. Similar atrazine degradation rates were observed under both anoxic and aerobic conditions: 30.7±2.83 and 36.2±0.44 mg atrazine g⁻¹ cell h⁻¹, respectively. A high denitrification rate of 90.8±8.22 mg NO₃⁻-N g⁻¹ cell h⁻¹ was also observed using Ps ADP with citrate as the electron donor. The required citrate to nitrate ratio for complete denitrification was 5.11±0.15 g citrate g⁻¹ NO₃⁻-N.     

Dairy farm CH4 and N2O emissions,from one square metre to the full farm scale

The greenhouse gas emissions from agricultural systems contribute significantly to the national budgets for most countries in Europe. Measurement techniques that can identify and quantify emissions are essential in order to improve the selection process of emission reduction options and to enable quantification of the effect of such options. Fast box emission measurements and mobile plume measurements were used to evaluate greenhouse gas emissions from farm sites. The box measurement technique was used to evaluate emissions from farmyard manure and several other potential source areas within the farm. Significant (up to 250 g CH₄ m⁻² day⁻¹and 0.4 g N₂O m⁻² day⁻¹) emissions from ditches close to stables on the farm site were found.Plume emission measurements from individual manure storages were performed at three sites. For a manure storage with 1200 m³ dairy slurry in Wageningen emission factors of 11 ± 5 g CH₄ m⁻³ manure day⁻¹ and 14 ± 8 mg N₂O m⁻³ manure day⁻¹ were obtained in February 2002.Mobile plume measurements were carried out during 4 days at distances between 30 and 300 m downwind of 20 different farms. Total farm emissions levels ranged from 14 to 95 kg CH₄ day⁻¹ for these sites. Expressed as emission per animal the levels were 0.7 ± 0.4 kg CH₄ animal⁻¹ day⁻¹ for conventional farms. For three farms that used straw bedding for the animals1.4 ± 0.2 kg CH₄ animal⁻¹ day⁻¹ was obtained. These factors include both respired methane and emission from manure in the stable and the outside storages.For a subset of these farms the CH₄ emission was compared with monthly averaged model emission calculations using FarmGHG. This model calculates imports, exports and flows of all products through the internal chains on the farm using daily time steps. The fit of modelled versus measured data has a slope of 0.97 but r² = 0.27. Measurements and model emission estimates agree well on average, for large farms within 30%. For small farms the differences can be up to a factor of 3. CH₄ emissions during winter seem to be underestimated.     

Monitoring the dry deposition of SO2 in the Netherlands: Results for grassland and heather vegetation

An automated system based on the micrometeorological gradient technique has been developed to measure the dry deposition of SO₂ on a routine basis. Measurements were made at two locations in the Netherlands. From these results dry deposition fluxes, dry deposition velocities and surface resistances for a heathland and for an agricultural grassland site were estimated using a selected set of data and a calculation procedure based on micrometeorological considerations. An extensive analysis was made to determine uncertainties in the resulting deposition parameters. From this analysis it has been concluded that the uncertainty in these parameters is almost completely determined by the random errors in measured concentrations. The meteorological surface exchange parameters can be estimated sufficiently accurately (<20% uncertainty). At the grassland site, average surface resistances to deposition of 6(±8) and 13(±12) s m⁻¹ were calculated for wet and dry conditions, respectively. At the heathland site, a similar distinct difference between R_c values for wet and dry conditions was found. These values are 20(±21) and 70(±90) s m⁻¹, respectively. The yearly average dry deposition flux for SO₂ at the grassland site amounts to 585(±330) mol ha⁻¹ yr⁻¹, while at the heathland site the yearly average flux was 300(±270) mol ha⁻¹ yr⁻¹. The yearly average dry deposition velocity at 4 m height was 1.2(±0.3) cm s⁻¹ at the grassland site and 0.8(±0.4) cm s⁻¹ at the heathland site.     

Seasonal variation and source apportionment of organic and inorganic compounds in PM2.5 and PM10 particulates in Beijing, China

The distribution and source of the solvent-extractable organic and inorganic components in PM 2.5(aerodynamics equivalent diameter below 2.5 microns),and PM 10(aerodynamics equivalent diameter below 10 microns) fractions of airborne particles were studied weekly from September 2006 to August 2007 in Beijing.The extracted organic and inorganic compounds identified in both particle size ranges consisted of n-alkanes,PAHs(polycyclic aromatic hydrocarbons),fatty acids and water soluble ions.The potential emission sources of these organic compounds were reconciled by combining the values of n-alkane carbon preference index(CPI),%waxC n,selected diagnostic ratios of PAHs and principal component analysis in both size ranges.The mean cumulative concentrations of n-alkanes reached 1128.65ng/m3 in Beijing,74% of which(i.e.,831.7ng/m3) was in the PM 2.5 fraction,PAHs reached 136.45ng/m3(113.44ng/m3 or 83% in PM 2.5),and fatty acids reached 436.99ng/m3(324.41ng/m3 or 74% in PM 2.5),which resulted in overall enrichment in the fine particles.The average concentrations of SO42-,NO3-,and NH4+ were 21.3±15.2,6.1±1.8,12.5±6.1μg/m3 in PM 2.5,and 25.8±15.5,8.9±2.6,16.9±9.5μg/m3 in PM 10,respectively.These three secondary ions primarily existed as ammonium sulfate((NH4)2SO4),ammonium bisulfate(NH4HSO4) and ammonium nitrate(NH4NO3).The characteristic ratios of PAHs revealed that the primary sources of PAHs were coal combustion,followed by gasoline combustion.The ratios of stearic/palmitic acid indicated the major contribution of vehicle emissions to fatty acids in airborne particles.The major alkane sources were biogenic sources and fossil fuel combustion.The major sources of PAHs were vehicular emission and coal combustion.     

燃料油和原油乳化液在缢蛏（Sinonovacula constricta）体内的富集动力学研究

应用半静态双箱动力学模型在室内模拟了缢蛏(Sinonovacula constricta)对燃料油(0#柴油)和东海平湖原油乳化液的生物富集实验,通过对富集与释放过程中缢蛏体内石油烃的动态检测以及对检测结果的非线性曲线拟合,获得缢蛏对0#柴油、原油乳化液的吸收速率常数k1、释放速率常数k2、生物富集因子BCF、平衡状态下缢蛏体内石油烃含量C Amax、生物学半衰期B1/2等动力学参数.拟合结果得到的各动力学参数平均值分别为:缢蛏对0#柴油乳化液的吸收速率常数k1为10.67、k2为0.0795、BCF为122.56、C Amax为129.07 mg·kg-1、B1/2为9.61 d;缢蛏对原油乳化液的吸收速率常数k1为7.79、k2为0.0948、BCF为89.38、C Amax为110.68 mg·kg-1、B1/2为7.88 d.缢蛏对0#柴油、原油乳化液的吸收速率常数k1、BCF均随外部水体中石油烃浓度的增大而减少,对0#柴油、原油乳化液的释放速率常数k2与外部水体中石油烃浓度无明显相关性,C Amax随外部水体中石油烃浓度的增大而增大.对模型的拟合优度检验结果显示,模型的拟合优度良好.0#柴油在缢蛏体内的富集量高于原油乳化液、释放量低于原油乳化液,其原因与不同种类石油的烃类组分有关.     

Seasonal contrasts in modelled and observed dry deposition velocities of O3, SO2 and NO2 over three surfaces

Results of modelled and observed deposition velocities (V_d) for O₃, SO₂ and NO₂ for time-averaged diurnal cycles and sometimes for a collection of hourly values taken from different days are discussed for different seasons. From the observations, it was found that the O₃V_d values over a deciduous forest had a daytime representative value of 1.0 cm s⁻¹ in the summer and 0.3 cm s⁻¹ in the winter. For SO₂ over the same forest and over a carrot field the daytime values ranged from 0.0 to 0.65 cm s⁻¹ in the autumn, and for SO₂ over a snow surface the V_d ranged from 0.0 to 0.15 cm s⁻¹. The NO₂V_d was mostly negative over the forest and the carrot field in the autumn and had a range of 0.0-0.15 cm s⁻¹ over snow. From the model, it was found that for the three seasons the V_d values over all the land-use types were much larger than the observations. The model could not simulate the observed negative values of the NO₂V_d. The impact of the V_d model and its modified version on the concentrations of O₃ and SO₂ were tested with a comprehensive Eulerian air quality model.     

Nitrous oxide emissions from a dung heap measured by chambers and plume methods

Dung heaps provide a large, spatial and temporal variable, source of the greenhouse gas N₂O. In this paper emission rates measured by static and flow through chamber methods, which enclose only a small area of the heap, were compared with Gaussian plume and tracer ratio methods, which measure the emissions from the entire dung heap. The dung heap was a 300 m³ heap, composed of material from nearby cattle sheds. From the flow through and static chambers it was estimated that the dung heap emitted 315 and 51 g N₂ON m⁻³ day⁻¹, respectively. The spatial variability between the chambers and chamber methods was large. Standard deviations of the mean fluxes were >75% of the average flux. The smaller emissions were measured on the slopes of the heap and the larger emissions on the ridge. The plume of N₂O was measured downwind of the dung heap by (1) tunable diode laser spectroscopy and calculation of the N₂O source strength of the heap using Gaussian plume theory and (2) tracer ratio method releasing SF₆ from the heap summit and capture in Tedlar bags downwind with subsequent analysis by gas chromatography. The Gaussian plume theory calculated an average N₂O source strength of 5.3 g N₂ON m⁻³ day⁻¹ (1.4–6.7 g N₂ON m⁻³ day⁻¹). The tracer ratio method calculated a slightly larger average emission rate of 14.4 g N₂ON m⁻³ day⁻¹ (7.4–38.6 g N₂ON m⁻³ day⁻¹). Both methods were successfully validated by point release of SF₆ and N₂O, which suggests that the micrometeorological methods provided a good estimate of the source strength of the heap, whereas the few chamber measurements overestimated its source strength.     

Heterogeneous sulfur conversion in sea-salt aerosol particles: the role of aerosol water content and size distribution

Meteorological and chemical conditions during the July 1988 Bermuda-area sampling appear to have been favorable for conversion of sulfur gases to particulate excess sulfate (XSO₄). Observed average XSO₄ and SO₄ concentrations of 11 and 2.1 nmol m⁻³, respectively, at 15 m a.s.l. in the marine boundary layer (MBL) upwind of Bermuda, indicate that conversion of SO₂ to XSO₄, over and above homogeneous conversion, may be necessary to explain the > 5.0 average molar ratio of XSO₄ to SO₂. Given an observed cloud cover of <15% over the region and the <3 nmol m⁻³ SO₃ concentrations observed by aircraft, heterogeneous conversion mechanisms, in addition to cloud conversion of SO₂, are necessary to explain the observed 11 nmol XSO₄ m⁻³.Aerosol water content, estimated as a function of particle size distribution plus consideration of SO₂ mass transfer for the observed particle size distribution, shows that SO₂ was rapidly transferred to the sea-salt aerosol particles. Assuming that aqueous-phase SO₂ reaction kinetics within the high pH sea-salt aerosol water are controlled by O₃ oxidation, and considering mass-transfer limitations, SO₂ conversion to XSO₄ in the sea-salt aerosol water occurred at rates of approximately 5% h⁻¹ under the low SO₂ concentration, Bermuda-area sampling conditions. All of the 2 nmol XSO₄ m⁻³ associated with sea-salt aerosol particles during low-wind-speed, Bermuda-area sampling can be explained by this conversion mechanism. Higher wind speed, greater aerosol water content and higher SO₂ concentration conditions over the North Atlantic are estimated to generate more than 4 nmol XSO₄ m⁻³ by heterogeneous conversion of SO₂ in sea-salt aerosol particles.     

The variability of biogenic sulfur flux from a temperate salt marsh on short time and space scales

Three emission chambers were deployed simultaneously to measure rates of emission of dimethyl sulfide, methane thiol and carbonyl sulfide within or across vegetation zones in a New Hampshire salt marsh. Short term (a few hours) variation in fluxes of all S gases from replicate sites were small within a monospecific stand of either Spartina alterniflora or S. patens. The quantity of emergent biomass and the type of vegetation present were the primary factors regulating the rate of emission. Dimethyl sulfide fluxes from the S. alterniflora soils ranged from 800 to 18,000 nmol m⁻² h⁻¹ compared to emissions of 25–120 nmol m⁻² h⁻¹ from S. patens. This difference was probably due to the presence of the dimethyl-sulfide precursor dimethylsulfoniopropionate which is an osmoregulator in S. alterniflora but not in S. patens. Methane thiol emissions from S. alterniflora were 20–280 nmol m⁻² h⁻¹ and they displayed a similar diel trend as dimethyl sulfide, although at much lower rates, suggesting that methane thiol is produced primarily by leaves. Methane thiol emissions from S. patens were 20–70 nmol m⁻² h⁻¹. Net uptake of carbonyl sulfide of 25–40 nmol m⁻² h⁻¹ occurred in stands of S. alterniflora while net efflux of 10–36 nmol m⁻² h⁻¹ of carbonyl sulfide occurred in stands of S. patens. In general, ranges of emissions of sulfur gases were similar to most other published values.     

Chemical characterization of acid precipitation in Albany,New York

Chemical composition of precipitation in Albany, NY from July 1986 to December 1988 has been studied. Mean volume-weighted concentrations (μeq^ℓ−1) were: acidity, 104.0; alkalinity, −63.7; SO₄²⁻, 52.8; NO₃⁻, 29.8; Cl⁻, 5.6; F⁻, 0.50; NH₄⁺, 19.3; Ca²⁺, 6.5; Mg²⁺, 2.8; Na⁺, 3.5; and K⁺, 1.4. Mean pH was 4.2 . Seasonal patterns were pronounced for most species. Concentrations of H⁺, SO₄²⁻, NO₃⁻, NH₄⁺ and Ca²⁺ peaked in the summer and spring. Deposition was related to rainfall amount by a power law relationship in which the exponent of the equation was ∮.6. Wet SO₄²⁻ deposition was 2.35 keq ha⁻¹ over a 30-month period. The SO₄²⁻ and NO₃⁻ deposition rates observed at Albany indicate that transport from midwestern sources have a major influence at this site. On the average, free H⁺ ion concentrations determined from pH measurements accounted for 51% of the measured total acidity. There were unknown species, most likely organic acids, that could contribute to the acidity. Correlation and regression analyses indicated that major anions, SO₄²⁻ and NO₃⁻, were closely associated with H⁺ and NH₄⁺ ions. Factor analysis revealed four common factors which are related to fossil-fuel combustion, sea spray, cement factory and biomass burning.     

经典等温吸附模型在重金属离子/硅藻土体系中的应用及存在问题

为了深入了解天然硅藻土对常见重金属离子Cu2+、Zn2+、Pb2+、Cd2+、Mn2+、Fe3+的吸附属性,同时也为了发现经典等温吸附模型应用于液/固体系时存在的问题,开展了系列等温吸附研究.结果表明,最适于描述天然硅藻土对Pb2+、Cd2+、Cu2+、Zn2+、Mn2+、Fe3+吸附的模型分别为Tenkin、Tenkin、Langmuir、Tenkin、Freundlich和Freundlich模型.各离子在天然硅藻土上的吸附以物理过程为主,吸附反应容易进行.液/固体系中,应用经典等温吸附模型对试验数据进行线性拟合时,发现平衡吸附量q e不是离子平衡浓度c e的唯一函数,而是c e与吸附剂浓度W0两个变量的函数,q e与c e/W0具有一一对应的函数关系.经典等温吸附模型存在明显的吸附剂浓度效应,参数值不稳定,模拟值与实测值差异显著,缺乏实际指导意义.试验证明新的四组分模型可用于描述天然硅藻土-水溶液体系中单一离子的吸附行为,新模型参数k与q m值也具有唯一性,可用于给定体系的实际定量计算.     

Statistical theory of the Marshall-Palmer distribution of raindrops

A statistical model is developed for the large-sample-averaged raindrop size spectrum. Under the condition that the “instant” spectrum can be fitted with a gamma distribution, n(D) = N₀D^μe^−λD, it is proven that the averaged spectrum approaches the Marshall-Palmer distribution, n(D) = N₀e^−λD, with the sample number increasing.     

Laboratory studies of some halogenated ethanes and ethers: Measurements of rates of reaction with OH and of infrared absorption cross-sections

We have measured, using a conventional discharge-flow resonance-fluorescence technique, the rates of reaction between the hydroxyl radical and a series of halogenated ethanes and ethers for the temperature range 230–423 K. Our measurements gave the following Arrhenius expressions (units are cm³ molecule⁻¹ s⁻¹): CF₂HCH₃ (HFC-152), 14.2 × 10⁻¹³ exp-(1050/T); CF₂ClCH₃ (HCFC-142b), 2.6 × 10⁻¹³ exp-(1230/T); CFCl₂CH₃ (HCFC-141b), 5.8 × 10⁻¹³ exp-(1100/T); CF₃CFH₂ (HFC-134a), 5.8 × 10⁻¹³ exp-(1350/T); CF₃CF₂H (HFC-125), 2.8 × 10⁻¹³ exp-(1350/T); CF₃CCl₂H (HCFC-123), 11.8 × 10⁻¹³ exp-(900/T); CF₂HOCF₂CFClH, (enflurane), 6.1 × 10⁻¹³ exp-(1080/T); CFH₂OCH(CF₃)₂, (sevoflurane), 15.3 × 10⁻¹³ exp-(900/T). In two cases, we measured rate constants only at room temperature: CF₃CClBrH (halothane), 6 × 10⁻¹⁴ and CF₂HOCClHCF₃ (isoflurane), 2.1 × 10⁻¹⁴.We also report the following values for the integrated absorption cross-sections of the compounds in the spectral region 800–1200 cm⁻¹ in units of cm⁻² atm⁻¹: CF₂HCH₃, 1155; CF₂ClCH₃, 1422; CFCl₂CH₃, 1995; CF₃CFH₂, 2686; CF₃CF₂H, 1970, CF₃CCl₂H, 1411; CF₃CClBrH, 1400; CF₂HOCF₂CFClH, 4800; CF₂HOCClHCF₃, 3900; CFH₂OCH(CF₃)₂, 2550. We use our measurements to calculate ozone depletion potentials and greenhouse warming potentials relative to CFCl₃ for each compound.     

Effects of temperature,TSP and per cent non-exchangeable material in determining the gas-particle partitioning of organic compounds

The temperature dependence of the measured, gas-particle partitioning ratio (F_T/TSP)/A_T has been examined for the case when a constant fraction x (%) of a compound is assumed to be bound within the particulate matter, and non-exchangeable with the gas phase. The parameter F_T is the total (exchangeable + non-exchangeable) measured concentration in the atmosphere (ng m⁻³), A_T is the gaseous concentration (ng m⁻³), and TSP is the level of suspended atmospheric particulate matter (μg m⁻³). It is assumed that the true thermodynamic constant K_p depends upon 1/T according to log K_p = m_p/T + b_p where m_p depends on the enthalpy of desorption of the compound of interest, b_p depends in part on other properties of the compound as well as the specific surface area of the particulate matter, and T is the temperature (Kelvin). When K_p or TSP are low, the difference between the measured quantity (F_T/TSP)/A_T and K_p can be significant even when the non-exchangeable fraction x is as low as a few per cent. This approach has been used to examine the PAH data set of Yamasaki et al. [(1982) Env. Sci. Technol.16, 189–194]. It was found that the Yamasaki data set does not allow estimates of x that are consistent with the current understanding of the temperature dependence of log K_p values. A likely reason for this result is some dependence of m_p and b_p on the exact nature of the particulate matter and atmospheric conditions such as relative humidity. It is concluded that estimates of x values for a given compound on actual particulate matter may only be possible by the direct examination of individual particulate matter samples.