Field tests of a passive sampler for atmospheric ozone at California mountain forest locations

Field tests of a colorant-based ozone passive sampler have been carried out during the 1990 smog season at five mountain forest locations in California. Co-located measurements of ambient ozone were made at all field sites using the passive sampler and a reference method, ultraviolet (u.v.) photometry. The sampling duration ranged from 3 to 30 days. Nitrogen dioxide, aldehydes and the phytotoxic oxidants peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) were measured at one location to assess possible interferences. The average precision of the measurements, calculated from data for 42 sets of colocated passive samplers, was 12%. Data for all field locations could be reduced to a single equation relating color change (ΔE units) to ozone dose (units: ppb-days). This polynomial equation could be reduced to a linear equation for color changes not exceeding 8 ΔE units (equivalent to sampling durations of up to 15 days), with good agreement between field data and earlier calibration results obtained in the laboratory. Both polynomial and linear equations can be used to obtain quantitative, time-integrated measurements of ambient ozone. The performance of the passive sampler showed no dependence on changes in ambient temperature and humidity. Interferences from air pollutants other than ozone contributed a total positive bias of less than 5% to the measured ozone concentrations: 3% for NO₂, 1.3% for PAN, 0.2% for PPN, and 0.% or less for formaldehyde and acetaldehyde.     

Sulfur dioxide,hydrogen sulfide,total reduced sulfur,chlorinated hydrocarbons and photochemical oxidants in southern California museums

Indoor and outdoor concentrations of the air pollutants ozone, NO₂, SO₂, H₂S, total reduced sulfur (TRS), peroxyacetyl nitrate (PAN), methyl chloroform and tetrachloroethylene, have been measured at three southern California museums. Indoor maxima were 175 ppb for NO₂, 77 ppb for O₃, 0.7 ppb for PAN, 1.2 ppb for C₂Cl₄, >6.3 ppb for CH₃CCl₃, 2.5 ppb for SO₂, 1.4 ppb for TRS, and 46 ppt for H₂S. Indoor levels and indoor/outdoor (I/O) ratios for the chlorinated hydrocarbons pointed out to indoor sources. Outdoor and indoor levels of SO₂ and TRS were low at all three museums, but I/O ratios for SO₂ were high and averaged 0.89. H₂S concentrations were low, 16–46 ppt at one museum and less than 6 ppt at the other two museums. I/O ratios for the air pollutants with outdoor sources (ozone, PAN and NO₂) showed substantial variations, from low values of 0.02–0.33 at locations without influx of outdoor air to high values of 0.85–0.88 at locations experiencing high influx of outdoor air. Of the 10 institutions we have surveyed in southern California to date, eight exhibit high I/O ratios, e.g. 0.60–1.00 for PAN. Of the four museums surveyed that were equipped with HVAC and chemical filtration, only two yielded the expected low I/O ratios.     

Biogenic volatile organic compound analyses by PTR-TOF-MS: Calibration, humidity effect and reduced electric field dependency

Green leaf volatiles(GLVs) emitted by plants after stress or damage induction are a major part of biogenic volatile organic compounds(BVOCs). Proton transfer reaction time-of-flight mass spectrometry(PTR-TOF-MS) is a high-resolution and sensitive technique for in situ GLV analyses, while its performance is dramatically influenced by humidity, electric field,etc. In this study the influence of gas humidity and the effect of reduced field(E/N) were examined in addition to measuring calibration curves for the GLVs. Calibration curves measured for seven of the GLVs in dry air were linear, with sensitivities ranging from 5 to10 ncps/ppbv(normalized counts per second/parts per billion by volume). The sensitivities for most GLV analyses were found to increase by between 20% and 35% when the humidity of the sample gas was raised from 0% to 70% relative humidity(RH) at 21°C, with the exception of(E)-2-hexenol. Product ion branching ratios were also affected by humidity,with the relative abundance of the protonated molecular ions and higher mass fragment ions increasing with humidity. The effect of reduced field(E/N) on the fragmentation of GLVs was examined in the drift tube of the PTR-TOF-MS. The structurally similar GLVs are acutely susceptible to fragmentation following ionization and the fragmentation patterns are highly dependent on E/N. Overall the measured fragmentation patterns contain sufficient information to permit at least partial separation and identification of the isomeric GLVs by looking at differences in their fragmentation patterns at high and low E/N.     

Biogenic volatile organic compound analyses by PTR-TOF-MS: Calibration,humidity effect and reduced electric field dependency

Green leaf volatiles (GLVs) emitted by plants after stress or damage induction are a major part of biogenic volatile organic compounds (BVOCs). Proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) is a high-resolution and sensitive technique for in situ GLV analyses, while its performance is dramatically influenced by humidity, electric field, etc. In this study the influence of gas humidity and the effect of reduced field (E/N) were examined in addition to measuring calibration curves for the GLVs. Calibration curves measured for seven of the GLVs in dry air were linear, with sensitivities ranging from 5 to 10 ncps/ppbv (normalized counts per second/parts per billion by volume). The sensitivities for most GLV analyses were found to increase by between 20% and 35% when the humidity of the sample gas was raised from 0% to 70% relative humidity (RH) at 21°C, with the exception of (E)-2-hexenol. Product ion branching ratios were also affected by humidity, with the relative abundance of the protonated molecular ions and higher mass fragment ions increasing with humidity. The effect of reduced field (E/N) on the fragmentation of GLVs was examined in the drift tube of the PTR-TOF-MS. The structurally similar GLVs are acutely susceptible to fragmentation following ionization and the fragmentation patterns are highly dependent on E/N. Overall the measured fragmentation patterns contain sufficient information to permit at least partial separation and identification of the isomeric GLVs by looking at differences in their fragmentation patterns at high and low E/N.     

Effects of emissions from a coal-fired power plant on surface soil trace element concentrations

Increase in trace element (As, Cd, Cr, Cu and Hg) concentrations in surface soils caused by deposition of emissions from a power plant was evaluated through field studies and model calculations. The enrichment discrimination factor (EDF) was used as an indication of the effects. Model calculations estimated that the maximum deposition of the elements would be located at a site 3 km north of the plant. The increase in EDF, ΔE, at the ssite due to cumulative depositions over 25 years was evaluated to be As:0.06, Cd:0.20, Cr:0.02, Cu:0.13 and Hg:0.08, respectively. In contrast, observed EDFs of each element at 30 sites within a 10 km radius from the plant fluctuated within the range far beyond the ΔE, and there was no statistically significant correlation among the EDFs as a function of distance or direction from the plant, suggesting that the effects of emissions lie concealed in normal ambient fluctuation of the element concentrations.     

Heterogeneous oxidation of SO2 by O3-aged black carbon and its dithiothreitol oxidative potential

Ozone (O₃) is an important atmospheric oxidant. Black carbon (BC) particles released into the atmosphere undergo an aging process via O₃ oxidation. O₃-aged BC particles may change their uptake ability toward trace reducing gases such as SO₂ in the atmosphere, leading to different environmental and health effects. In this paper, the heterogeneous reaction process between O₃-aged BC and SO₂ was explored via in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Combined with ion chromatography (IC), DRIFTS was used to qualitatively and quantitatively analyze the sulfate product. The results showed that O₃-aged BC had stronger SO₂ oxidation ability than fresh BC, and the reactive species/sites generated on the surface had an important role in the oxidation of SO₂. Relative humidity or 254 nm UV (ultraviolet) light illumination enhanced the oxidation uptake of SO₂ on O₃-aged BC. The oxidation potentials of the BC particles were detected via dithiothreitol (DTT) assay. The DTT activity over BC was decreased in the process of SO₂ reduction, with the consumption of oxidative active sites.     

Formic acid and acetic acid measurements during the Southern California Air Quality Study

As part of the Southern California Air Quality Study (SCAQS), ambient levels of gas phase formic acid and acetic acid have been measured at four locations: a ‘control’ site (San Nicholas Island), a source-dominated coastal site (Long Beach) and two inland smog receptor sites (Claremont and Palm Springs). Samples were collected on alkaline traps and were analyzed by size exclusion liquid chromatography with ultraviolet detection. Levels of gas phase formic acid (up to 19 ppb) and acetic acid (up to 17 ppb) exhibited diurnal (frequent night-time maxima), spatial and seasonal variations. During summer smog episodes, concentrations increased from 0.6 ppb at the ‘control’ site to up to 13–19 ppb at the inland smog receptor sites reflecting primary emissions and in situ formation during transport inland. The acetic acid/formic acid (A/F) ratio decreased from coastal to inland sites. At the coastal site levels of both acids and the A/F ratio were substantially higher during the fall than during the summer.     

An analysis of surface ozone data measured at the end of the 19th century in Zagreb,Yugoslavia

A 12-year record of surface ozone data collected by means of Schoenbein's method in Zagreb, Croatia, Yugoslavia, 1889–1900 is analyzed and calibrated. The data were collected twice a day. To convert the original data into absolute units the Montsouris regression modified by Bojkov has been used. The statistical parameters of daytime and night-time data samples show a significant difference. The annual run of daytime data contains a primary maximum at the transition from spring to summer and a secondary at the beginning of autumn. The annual run of night-time values contain one maximum only, situated at the transition from spring to summer. A comparison of old ozone data (1893–1900) with present ozone measurements over a 5-month warm period (1975), shows an increase of volume fractions from 36 to 67 ppb for daytime and from 30 to 56 ppb for night-time. It should be taken into account that many uncertainties exist in the data.     

Micelle dyeing with low liquor ratio for reactive dyes using dialkyl maleic acid ester surfactants

Micelle dyeing with low liquor ratio is novel fabric dyeing method for cleaner production. Preparation and interaction of dye-surfactant micelles using dibutyl maleic acid ester sodium sulfate surfactant were investigated by UV-Vis spectra. Dyeing properties of cellulose fabrics using micelle dyeing with low liquor ratio were discussed by color yields (K/S), color differences (ΔE), exhaustion (E), fixation (F) and reactivity (R) of three reactive dyes. The results show that reactive dye molecules could be solved in surfactant micelles and form stable dye-surfactant micelles. Micelles formed by dibutyl maleic acid ester sodium sulfate had good anti-agglomeration effect on dye solutions. Liquor ratio of micelle dyeing for cellulose fabrics could be reduced from 1:15 to 1:5. Leveling properties of three reactive dyes using micelle dyeing were good. The exhaustion, fixation and reactivity of all three dyes using micelle dyeing were similar with the conventional dyeing technology. Wet rubbing, washing and perspiration fastnesses of dyed samples using micelle dyeing were also good. Micelle dyeing with low liquor ratio can save a large amount of water and energy.     

Urban air pollution in Brazil: Acetaldehyde and other carbonyls

We have measured ambient levels of carbonyls in three major urban areas of Brazil: Sao Paulo, Rio de Janeiro and Salvador. The most abundant carbonyls were acetaldehyde (up to 63 μg m⁻³, or 35 ppb) followed by formaldehyde (up to 42 μg m⁻³, or 34 ppb), and acetone (up to 20 ppb). Levels of 10 other aliphatic and aromatic carbonyls were in the range 0–5 ppb. Total carbonyl concentrations were in the range 11–75 ppb. Indoor levels were also measured at several locations in Salvador. High levels of acetaldehyde, 430 μg m⁻³ or 240 ppb, were measured in a highway tunnel.Using carbonyl/CO concentration ratios, mobile source emissions of carbonyls are estimated for the Sao Paulo area. Ambient levels of acetaldehyde and acetaldehyde/formaldehyde concentration ratios in Brazil are compared to those for other urban areas, and are briefly discussed in relation with the large scale use of ethanol as a vehicle fuel.     

Adsorption of lead on multi-walled carbon nanotubes with different outer diameters and oxygen contents: Kinetics, isotherms and thermodynamics

The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes (MWCNTs) were investigated in an aqueous solution and lead was chosen as a model metal ion. The results indicated that the percentage removal and adsorption capacity of lead remarkably increased with decreasing outer diameter due to larger specific surface area (SSA). The SSA-normalized maximum adsorption capacity (qm /SSA) and SSA-normalized adsorption coefficient (Kd /SSA) were strongly positively correlated with surface oxygen content, implying that lead adsorption onto MWCNTs significantly increases with the rise of oxygen content and decreases with decreasing SSA. The calculated thermodynamic parameters indicated that adsorption of lead on MWCNTs was endothermic and spontaneous. When the oxygen content of MWCNTs increased from 2.0% to 5.9%, the standard free energy (△ G0 ) became more negative, which implied that the oxygenated functional groups increased the adsorption affinity of MWCNTs for lead. Through calculation of enthalpy (△ H0 ), G0 and free energy of adsorption (Ea ), lead adsorption onto MWCNTs was recognized as a chemisorption process. The chemical interaction between lead and the phenolic groups of MWCNTs could be one of the main adsorption mechanisms due to highly positive correlations between the phenolic groups and K d /SSA or q m /SSA.     

杭州灰霾天气超细颗粒浓度分布特征

利用快速迁移率粒径谱仪(FMPS)对杭州2013年12月6～11日连续灰霾天气和灰霾消退过程超细颗粒进行监测,分析颗粒物浓度变化和粒径谱分布特征及其与气象的相关性.结果表明,颗粒物日变化特征为夜晚数浓度较高,凌晨数浓度开始降低,08:00和18:00上下班高峰期出现一个小峰值,体现出明显的交通源峰值,表明交通排放对大气污染影响较大.灰霾天气下颗粒物最高数浓度达到8.0×104cm-3.粒径谱呈双峰分布,峰值粒径分别为15 nm和100 nm,粒径在100 nm附近的粒子占大多数,粒子以爱根核模态和积聚模态为主,平均数量中位径CMD(count medium diameter)为85.89 nm.而在灰霾消退过程,颗粒物数浓度降低,峰值粒径向小粒径演变,粒径在100 nm附近的粒子逐渐减少,核模态粒子增多,大于积聚模态,平均CMD为58.64 nm.气象因素中能见度和风力与数浓度主要呈负相关,相关系数R分别为-0.225和-0.229,相对湿度与数浓度正相关,相关系数R为0.271,冬季大气比较稳定,水平温度与数浓度的相关性较小.研究灰霾天气数浓度分布和气象因素的综合影响对其形成机制及控制有重要意义.     

Mechanism of spring high oxidant episode— A meteorological analysis in and around the Hokuriku district,Japan

In order to clarify the mechanism of spring surface level high oxidant episodes, both upper and surface level ozone observations were carried out from April to June 1983. The results were analyzed using aerological data and AMeDAS (Automated Meteorological Data Acquisition System) data.During the observation period, there were 11 days with high oxidant episodes which were defined as when the recorded ozone concentration exceeded 100 ppb at any of five stations. Meteorological conditions under which the surface episodes occurred were examined for three cases when upper level ozone distributions were observed, and the mechanism of the episode were investigated. In this paper, the analysis for one case is explained in detail. For this case: (i) the peak time of oxidant (ozone) concentration at each surface station was controlled by the transition pattern of photochemical oxidant under the local wind system and (ii) the stratospheric air with high concentrations of ozone intruded into the troposphere through the tropopause gap (tropopause folding) behind the cyclone and continued to descend gradually. In the lower troposphere, it descended further due to the influence of topography, and contributed to high surface oxidant episodes. The descent of stratospheric ozone was related to the position of both cyclones and anticyclones. The other two cases had similar upper meteorological conditions but different surface wind systems such as land and sea breeze.     

Experimental study on drying and moisture re-adsorption kinetics of an Indonesian low rank coal

The drying kinetics of an Indonesian low rank coal and moisture re-adsorption of the dried coal using a thermobalance and a climatic chamber were investigated. Results show that the drying kinetics is best represented by two stages, as a constatnt rate stage followed by a rate decay stage. The water removal rate is dependent mainly on drying temperature and coal sample size. The apparent activation energy (E) of drying was 26.58 kJ/mol. A rate equation for drying of the coal was obtained from the experimental data. The moisture re-adsorption rate was dependent on drying temperature, coal particle size, and relative humidity of the atmosphere.     

Carbonyl compounds in dining areas, kitchens and exhaust streams in restaurants with varying cooking methods in Kaohsiung, Taiwan

Eighteen carbonyl species in C₁–C₁₀ were measured in the dining areas, kitchens and exhaust streams of six different restaurant types in Kaohsiung, southern Taiwan. Measured results in the dining areas show that Japanese barbecue (45.06 ppb) had the highest total carbonyl concentrations (sum of 18 compounds), followed by Chinese hotpot (38.21 ppb), Chinese stir-frying (8.99 ppb), Western fast-food (8.22 ppb), Chinese–Western mixed style (7.38 ppb), and Chinese buffet (3.08 ppb), due to their different arrangements for dining and cooking spaces and different cooking methods. On average, low carbon-containing species (C₁–C₄), e.g., formaldehyde, acetaldehyde, acetone and butyraldehyde were dominant and contributed 55.01%–94.52% of total carbonyls in the dining areas of all restaurants. Meanwhile, Chinese–Western mixed restaurants (45.48 ppb) had high total carbonyl concentrations in kitchens mainly because of its small kitchen and poor ventilation. However, high carbon-containing species (C₅–C₁₀) such as hexaldehyde, heptaldehyde and nonanaldehyde (16.62%–77.00% of total carbonyls) contributed comparatively with low carbon-containing compounds (23.01%–83.39% of total carbonyls) in kitchens. Furthermore, Chinese stir-frying (132.10 ppb), Japanese barbecue (125.62 ppb), Western fast-food (122.67 ppb), and Chinese buffet (119.96 ppb) were the four restaurant types with the highest total carbonyl concentrations in exhaust streams, indicating that stir-frying and grilling are inclined to produce polluted gases. Health risk assessments indicate that Chinese hotpot and Japanese barbecue exceeded the limits of cancer risk (10^− 6) and hazard index (= 1), mainly due to high concentrations of formaldehyde. The other four restaurants were below both limits.     

Characteristics and recent trends of sulfur dioxide at urban, rural, and background sites in North China: Effectiveness of control measures

SO₂ measurements made in recent years at sites in Beijing and its surrounding areas are performed to study the variations and trends of surface SO₂ at different types of sites in Northern China. The overall average concentrations of SO₂ are (16.8 ± 13.1) ppb, (14.8 ± 9.4) ppb, and (7.5 ± 4.0) ppb at China Meteorological Administration (CMA, Beijing urban area), Gucheng (GCH, relatively polluted rural area, 110 km to the southwest of Beijing urban area), and Shangdianzi (SDZ, clean background area, 100 km to the northeast of Beijing urban area), respectively. The SO₂ levels in winter (heating season) are 4-6 folds higher than those in summer. There are highly significant correlations among the daily means of SO₂ at different sites, indicating regional characteristics of SO₂ pollution. Diurnal patterns of surface SO₂ at all sites have a common feature with a daytime peak, which is probably caused by the downward mixing and/or the advection transport of SO₂-richer air over the North China Plain. The concentrations of SO₂ at CMA and GCH show highly significant downward trends (-4.4 ppb/yr for CMA and -2.4 ppb/yr for GCH), while a less significant trend (-0.3 ppb/yr) is identified in the data from SDZ, reflecting the character of SDZ as a regional atmospheric background site in North China. The SO₂ concentrations of all three sites show a significant decrease from period before to after the control measures for the 2008 Olympic Games, suggesting that the SO₂ pollution control has long-term effectiveness and benefits. In the post-Olympics period, the mean concentrations of SO₂ at CMA, GCH, and SDZ are (14.3 ± 11.0) ppb, (12.1 ± 7.7) ppb, and (7.5 ± 4.0) ppb, respectively, with reductions of 26%, 36%, and 13%, respectively, compared to the levels before. Detailed analysis shows that the differences of temperature, relative humidity, wind speed, and wind direction were not the dominant factors for the significant differences of SO₂ between the pre-Olympics and post-Olympics periods. By extracting the data being more representative of local or regional characteristics, a reduction of up to 40% for SO₂ in polluted areas and a reduction of 20% for regional SO₂ are obtained for the effect of control measures implemented for the Olympic Games.     

Sex pheromone component ratios and mating isolation among three Lygus plant bug species of North America

The plant bugs Lygus hesperus, Lygus lineolaris, and Lygus elisus (Hemiptera: Miridae) are major pests of many agricultural crops in North America. Previous studies suggested that females release a sex pheromone attractive to males. Other studies showed that males and females contain microgram amounts of (E)-4-oxo-2-hexenal, hexyl butyrate, and (E)-2-hexenyl butyrate that are emitted as a defense against predators. Using gas chromatography–mass spectrometry, we found that female L. lineolaris and L. elisus have a 4:10 ratio of hexyl butyrate to (E)-2-hexenyl butyrate that is reversed from the 10:1 ratio in female L. hesperus (males of the three species have ~10:1 ratio). These reversed ratios among females of the species suggest a behavioral role. Because both sexes have nearly equal amounts of the major volatiles, females should release more to attract males. This expectation was supported because L. hesperus females released more hexyl butyrate (mean of 86 ng/h) during the night (1800–0700 hours) than did males (<1 ng/h). We used slow-rotating pairs of traps to test the attraction of species to blends of the volatiles with a subtractive method to detect synergism. Each species’ major butyrate ester was released at 3 μg/h, the minor butyrate according to its ratio, and (E)-4-oxo-2-hexenal at 2 μg/h. The resulting catches of only Lygus males suggest that (E)-4-oxo-2-hexenal is an essential sex pheromone component for all three species, (E)-2-hexenyl butyrate is essential for L. elisus and L. lineolaris, and hexyl butyrate is essential for L. hesperus. However, all three components are recognized by each species since ratios of the butyrate esters are critical for conspecific attraction and heterospecific avoidance by males and thus play a role in reproductive isolation among the three species. Because L. hesperus males and females are known to emit these major volatiles for repelling ant predators, our study links defensive allomones in Lygus bugs with an additional use as sex pheromones.     

Nitrogenous air pollutants at a southern California mountain forest smog receptor site

Ambient levels of the nitrogenous pollutants NO, NO₂, nitric acid, nitrous acid, ammonia, particulate nitrate, particulate ammonium, peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) have been measured at a southern California mountain forest location severely impacted by urban photochemical smog. Air quality at the mountain forest location was characterized by high levels of nitric acid (up to 18 ppb) and the phytotoxic peroxyacyl nitrates PAN (up to 22 ppb) and PPN (up to 5 ppb). Alkyl nitrates were below our detection limits of 0.05–0.5 ppb. The (PAN + PPN)/NO₂ ratios varied substantially (range 0.03–2.27) and were generally large, with typical 24-h averages of 0.19–0.50. Diurnal variations of the (PAN/PPN)/NO₂ ratio exhibited both nighttime and daytime maxima reflecting diurnal variations in PAN (and PPN) thermal stability and photochemical production rates, respectively. Organic nitrogen-containing oxidation products (PAN + PPN) were more abundant than inorganic nitrate (HNO₃ + NO₃⁻), with an average organic/inorganic concentration ratio of 2.5 (daytime ratio 1.0; nighttime ratio 3.7). The four oxidation products PAN, PPN, HNO₃ and NO₃⁻ together accounted for 0.26 of the total reactive nitrogen. The results are discussed with respect to diurnal and seasonal variations and in terms of NO₂ atmospheric oxidation pathways. Deposition fluxes and velocities to ponderosa pine have been measured for inorganic nitrate and for ammonium and have been compared with those obtained at other mountain forest locations.     

Numerical simulation of transport from a point source: error analysis

The techniques used to represent point sources in numerical air pollution models have received little attention.However, an inadequate representation of these sources can lead to significant loss of solution accuracy. Kasibhatla et al. (1988, Atmospheric Environment22, 75–82) have performed a parametric error analysis for the two-dimensional transport of an inert species from an infinite line source. This paper extends the analysis to three-dimensional problems.Numerical results for an inert plume emanating from a single point source shown that the radio of the advection time scale to the turbulent time scale in the vertical direction, K_zΔx/uΔy², as well as the ratio of the advection time scale to the turbulent diffusion time scale in the cross-wind direction, K_yΔx/uδy², have an effect on solution accuracy. In addition, comparisons between the volume-averaged representation of a point source and the use of an irregular grid for point source representation demonstrate that, near the source, improved results can be obtained by placing a node at the source location. Numerical results for the case in which the wind velocity vector is not aligned with tghe grid lines indicate that the cross-derivative diffusion term can be negleted without loss of accuracy.