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1.
OH formation from the ozonolysis reactions of seven internal alkenes with 4–6 carbons, styrene, trans-β-methyl styrene, and α-methyl styrene was studied using complementary techniques. A small-ratio relative-rate technique in which small quantities of OH tracers are added to monitor OH formation yields provided the following results: trans-2-butene, 0.64±0.12; cis-2-butene, 0.33±0.05; trans-2-pentene, 0.46±0.08; cis-2-pentene, 0.29±0.06; trans-3-hexene, 0.53±0.08; cis-3-hexene, 0.36±0.07; and 2-methyl-2-butene, 0.98±0.24. For styrene, trans-β-methyl styrene, and α-methyl styrene, OH yields of 0.07±0.04, 0.22±0.09, and 0.23±0.12 were measured, respectively. A second method, which monitors product formation from the OH reaction with 2-butanol was used to derive OH formation yields from 2,3-dimethyl-2-butene, 2-methyl-2-butene and cis-2-pentene, and provided yields of 0.91±0.14, 0.80±0.12, and 0.27±0.07, respectively. The results are briefly discussed in terms of the relationship between structures of these alkenes and OH formation.  相似文献   

2.
The US EPA has exempted t-butyl acetate from VOC regulations, which increases the likelihood that it may replace other solvents in some settings. This investigation probes its chemosensory properties. In Study 1, subjects (n = 29) sought to detect the odor of t-butyl acetate and of n-butyl acetate in forced-choice testing of stable concentrations, analytically confirmed. Subjects sniffed from cones with a high enough volumetric flow to insure against dilution by nonodorized air. A subject made hundreds of judgments, enough for a psychometric function for each material. The points of 50% detection above chance (“threshold”) occurred at 8 and 2 ppb for t-butyl acetate and n-butyl acetate, respectively. In study 2, subjects (n = 26) sought to detect vapor with the eye via chemesthesis (sensory irritation) in 10-s exposures. Detection at 50% occurred at 177 and 113 ppm for t-butyl acetate and n-butyl acetate, respectively, more than 10,000 times above that for odor detection. The protocols produced results of uncommon precision compared to those in often-misleading archival databases. The nose exhibits much higher sensitivity than the databases indicate. The collections rarely exhibit accuracy better than ±1000%. Collection of accurate data for a VOC can ironically bring on stricter regulation for just it, a situation that calls for a strategy to improve the database by collection of new data, importation of better data, and development of quantitative structure–activity modeling.  相似文献   

3.
In August 2012, eight rainwater samples were collected and analyzed for pH and metal ions, viz., iron, copper, and manganese. The pH was within the range 6.84–7.65. The rate of oxidation of dissolved sulfur dioxide was determined using these rainwater samples as reaction medium. Kinetics was defined by the rate law: ?d[S(IV)]/dt = R o = k o[S(IV)]], where k o is the first-order rate constant and R o is the rate of the reaction. The effect of two volatile organic compounds—ethanol and 2-butanol—was examined and found to inhibit the oxidation as defined by the rate law: k obs = k o/(1 + B [Inh]), where k obs is the first-order rate constant in the presence of the inhibitor, [Inh] is the concentration of the inhibitor, and B is the inhibitor parameter—an empirical constant. In the pH range of collected rainwater samples, the values of first-order rate constants ranged from 3.1?×?10?5 to 1.5?×?10?4 s?1 at 25 °C. The values of inhibition parameter were found to be (5.99?±?3.91?×?104) (ethanol) and (3.95?±?2.36)?×?104 (2-butanol) at 25 °C.  相似文献   

4.
Absolute rate coefficients for the reaction of OH radical with a series of saturated and unsaturated aliphatic aldehydes were measured with the pulsed laser photolysis/laser-induced fluorescence technique at room temperature and as a function of total pressure (pT=100–400 Torr). No pressure dependence of the rate coefficients was observed. The weighted average values obtained, kOH±2σ, in units of 10−11 cm3 molecule−1 s−1, were 2.88±0.26 for n-butanal, 2.48±0.24 for n-pentanal, 2.60±0.21 for n-hexanal, 2.96±0.23 for n-heptanal, 3.51±0.71 for crotonaldehyde, 2.35±0.32 for trans-2-pentenal, 2.95±0.45 for trans-2-hexenal and 2.45±0.30 for trans-2-heptenal, respectively. The results are compared with previous data when available and with the corresponding coefficients for the reactions with NO3 and O3. The dominant tropospheric chemical loss process for these aliphatic aldehydes is the daytime reaction with OH, except in the case of trans-2-heptenal where the estimated lifetime for the reaction with NO3 radical is smaller than the corresponding value for the OH reaction.  相似文献   

5.
Airborne concentrations of benzene, toluene and the xylenes have been measured inside passenger cars whilst driven along major roads in the city of Birmingham, UK, as well as immediately outside the car, and at the roadside. A comparison of concentrations measured in the car with those determined from immediately outside showed little difference, with a mean ratio for benzene of 1.17±0.34 and for toluene 1.11±0.16 (n=53). The ratio of in-car to roadside concentration was rather higher at 1.55±0.68 for benzene and 1.54±0.72 for toluene (n=53). The roadside concentrations were typically several-fold higher than those measured at a background suburban monitoring station within Birmingham, although much variation was seen between congested and uncongested roads, with concentrations adjacent to uncongested roads similar to those measured at the background monitoring station. Measurements of benzene and toluene in a car driven on a rural road outside the city showed very comparable in-car and out-of-car concentrations strengthening the conclusion that pollution inside the car is derived from pollutants outside entering with ventilation air. The exceptions were an older car where in-car concentrations appreciably exceeded those outside (in-to out-vehicle ratio=2.3 for benzene and 2.2 for toluene where n=5) indicating probable self-contamination, and a very new car which built up increased VOC concentrations when stationary without ventilation (in-to out-vehicle ratio=2.4 for benzene and 3.3 for toluene where n=5). A further set of measurements inside London taxi cabs showed concentrations to be influenced by the area within which the taxi was driven, the traffic density and the presence of passengers smoking cigarettes.  相似文献   

6.
In order to assist in assessing potential odor problems arising from chemical manufacturing operations, the odor thresholds of 53 commercially important odorant chemicals have been determined using a standardized and defined procedure. The odor threshold data previously available have shown wide variation reflecting the diversity of procedures and techniques used. Factors that may affect the odor threshold measurement include the mode of presentation of the stimulus to the observer, the influence of extraneous odorants in the presentation system, the type of observer used, the definition of the odor response, the treatment of the data obtained, and the chemical purity of the odorant. The experimental approach used has minimized these variations. The odorants were presented to a trained odor panel in a static air system utilizing a low odor background air as the dilution medium. The odor threshold is defined as the first concentration at which all panel members can recognize the odor. The effect of chemical purity has been determined by measuring the odor threshold of materials representing different modes of manufacture or after purification by gas chromatographic procedures. The threshold concentrations range over six orders of magnitude. Trimethylamine exhibited the lowest threshold (0.00021 ppm volume); methylene chloride was not recognizable below 214 ppm. Of the 53 chemicals, sulfur bearing compounds exhibit low threshold values on the order of parts per billion. Aside from the sulfides, it is not possible to anticipate the odor threshold of a material based on its chemical structure or functionality.  相似文献   

7.
The reproducibility of odor thresholds determined by forced-choice dynamic triangle olfactometry was studied employing panels of 23- 45 subjects who tested 12 odorants, with four replications for one (1-butanol). Depending on the selection of panelists, their number, and between-session differences in olfactometer variables, the standard deviation of log(threshold) values ranged from 0.12 (same session, different panels of nine) to 0.37 (different sessions, different panels of nine).

Among the demographic factors, only age was found significant; those below age of 30 were 1.6-3 times more sensitive than the older group. No systematic sensitivity difference was found between females and males, and nonsmokers and smokers.

Suspicion has been raised in the literature that the method used here, ASTM E679, yields biased results. It is shown for panels of 6-45 members that such biases are inconsequential if the range of concentration presented to the panelists is large enough, and the group threshold is well within that range. The Hall-Ellis method of calculation may have a slight advantage for panels of less than eight subjects, but such small panels are not advisable because of their high variability. The method based on the detectability index exhibited more scatter and would need an impracticaliy large number of measurements.  相似文献   

8.
Converting lipid-extracted microalgal wastes to methane (CH4) via anaerobic digestion (AD) has the potential to make microalgae-based biodiesel platform more sustainable. However, it is apparent that remaining n-hexane (C6H14) from lipid extraction could inhibit metabolic pathway of methanogens. To test an inhibitory influence of residual n-hexane, this study conducted a series of batch AD by mixing lipid-extracted Chlorella vulgaris with a wide range of n-hexane concentration (~10 g chemical oxygen demand (COD)/L). Experimental results show that the inhibition of n-hexane on CH4 yield was negligible up to 2 g COD/L and inhibition to methanogenesis became significant when it was higher than 4 g COD/L based on quantitative mass balance. Inhibition threshold was about 4 g COD/L of n-hexane. Analytical result of microbial community profile revealed that dominance of alkane-degrading sulfate-reducing bacteria (SRB) and syntrophic bacteria increased, while that of methanogens sharply dropped as n-hexane concentration increased. These findings offer a useful guideline of threshold n-hexane concentration and microbial community shift for the AD of lipid-extracted microalgal wastes.  相似文献   

9.
Industrial activity such as burning of fossil fuels produces magnetically enhanced particulates. These particulates consist of coarse-grained multidomain and stable single domain magnetic minerals. Two threshold values of low field magnetic susceptibility (χLF) and frequency dependent susceptibility percentage (χFD%) discriminate ferrimagnetic minerals of these sizes and can act as a tracer of magnetic pollution. Application of the thresholds to a magnetic topsoil data set (n = 5656 across England and Wales) revealed 637 samples potentially dominated by pollution particulates. The magnetic parameters of these samples display a negative correlation with distance to urban areas and positive correlations with metals associated with anthropogenic activity (Cu, Pb, and Zn). Results of experimentation with threshold values and modelling of magnetic anomalies suggest that regional factors such as geology and potential for pedogenic secondary magnetic enhancement should be considered when setting threshold values.  相似文献   

10.
An aquatic biomonitoring of Giardia cysts and Cryptosporidium oocysts in river water corresponding to five villages situated in three states in peninsular Malaysia was determined. There were 51.3 % (20/39) and 23.1 % (9/39) samples positive for Giardia and Cryptosporidium (oo)cysts, respectively. Overall mean concentration between villages for Giardia cysts ranged from 0.10 to 25.80 cysts/l whilst Cryptosporidium oocysts ranged from 0.10 to 0.90 oocysts/l. Detailed results of the river samples from five villages indicated that Kuala Pangsun 100 % (9/9), Kemensah 77.8 % (7/9), Pos Piah 33.3 % (3/9) and Paya Lebar 33.3 % (1/3) were contaminated with Giardia cysts whilst Cryptosporidium (oo)cysts were only detected in Kemensah (100 %; 9/9) and Kuala Pangsun (66.6 %; 6/9). However, the water samples from Bentong were all negative for these waterborne parasites. Samples were collected from lower point, midpoint and upper point. Midpoint refers to the section of the river where the studied communities are highly populated. Meanwhile, the position of the lower point is at least 2 km southward of the midpoint and upper point is at least 2 km northward of the midpoint. The highest mean concentration for (oo)cysts was found at the lower points [3.15?±?6.09 (oo)cysts/l], followed by midpoints [0.66?±?1.10 (oo)cysts/l] and upper points [0.66?±?0.92 (oo)cysts/l]. The mean concentration of Giardia cysts was highest at Kuala Pangsun (i.e. 5.97?±?7.0 cysts/l), followed by Kemensah (0.83?±?0.81 cysts/l), Pos Piah (0.20?±?0.35 cysts/l) and Paya Lebar (0.10?±?0.19 cysts/l). On the other hand, the mean concentration of Cryptosporidium oocysts was higher at Kemensah (0.31?±?0.19 cysts/l) compared to Kuala Pangsun (0.03?±?0.03cysts/l). All the physical and chemical parameters did not show significant correlation with both protozoa. In future, viability status and molecular characterisation of Giardia and Cryptosporidium should be applied to identify species and genotypes/subgenotypes for better understanding of the epidemiology of these waterborne parasites.  相似文献   

11.
The mass concentration of carbonaceous species, organic carbon (OC), and elemental carbon (EC) using a semicontinuous thermo-optical EC-OC analyzer, and black carbon (BC) using an Aethalometer were measured simultaneously at an urban mega city Delhi in Ganga basin from January 2011 to May 2012. The concentrations of OC, EC, and BC exhibit seasonal variability, and their concentrations were ~2 times higher during winter (OC 38.1?±?17.9 μg m?3, EC 15.8?±?7.3 μg m?3, and BC 10.1?±?5.3 μg m?3) compared to those in summer (OC 14.1?±?4.3 μg m?3, EC 7.5?±?1.5 μg m?3, and BC 4.9?±?1.5 μg m?3). A significant correlation between OC and EC (R?=?0.95, n?=?232) indicate their common emission sources with relatively lower OC/EC ratio (range 1.0–3.6, mean 2.2?±?0.5) suggests fossil fuel emission as a major source of carbonaceous aerosols over the station. On average, mass concentration of EC was found to be ~38 % higher than BC during the study period. The measured absorption coefficient (babs) was significantly correlated with EC, suggesting EC as a major absorbing species in ambient aerosols at Delhi. Furthermore, the estimated mass absorption efficiency (σabs) values are similar during winter (5.0?±?1.5 m2 g?1) and summer (4.8?±?2.8 m2 g?1). Significantly high aerosol loading of carbonaceous species emphasize an urgent need to focus on air quality management and proper impact assessment on health perspective in these regions.  相似文献   

12.
This study sampled six times of river water, sediment, and tilapia (Oreochromis niloticus) in the Dan-Shui River, Taipei, Taiwan; 10 feminizing compounds were analyzed using ultra-performance liquid chromatography-tandem mass spectrometry. Bisphenol A (508?±?634 ng/L, geometric mean (GM) 303 ng/L) and nonylphenol (491?±?570 ng/L, GM 328 ng/L) were the most abundant among analytes in the river water. Nonylphenol (770?±?602 ng/g wet weight, GM 617 ng/g wet weight) was also the highest in sediment. Fish may uptake nonylphenol and nonylphenol ethoxylates from river water and sediment because there were significant correlations between the concentrations in these matrixes and those in fish tissues (r s ranged from 0.21 to 0.49, p?相似文献   

13.
Interactions between volatile organic compounds (VOCs) and vinyl flooring (VF), a relatively homogenous, diffusion-controlled building material, were characterized. The sorption/desorption behavior of VF was investigated using single-component and binary systems of seven common VOCs ranging in molecular weight from n-butanol to n-pentadecane. The simultaneous sorption of VOCs and water vapor by VF was also investigated. Rapid determination of the material/air partition coefficient (K) and the material-phase diffusion coefficient (D) for each VOC was achieved by placing thin VF slabs in a dynamic microbalance and subjecting them to controlled sorption/desorption cycles. K and D are shown to be independent of concentration for all of the VOCs and water vapor. For the four alkane VOCs studied, K correlates well with vapor pressure and D correlates well with molecular weight, providing a means to estimate these parameters for other alkane VOCs. While the simultaneous sorption of a binary mixture of VOCs is non-competitive, the presence of water vapor increases the uptake of VOCs by VF. This approach can be applied to other diffusion-controlled materials and should facilitate the prediction of their source/sink behavior using physically-based models.  相似文献   

14.
The atmospheric oxidation of several terpenes appears to be a potentially relevant source of acetone in the atmosphere. Proton-transfer-reaction mass spectrometry was used as an on-line analytical method in a chamber study to measure acetone and other gas phase products from the oxidation of α- and β-pinene initiated by OH radicals in air and in the presence of NOx.Acetone may be formed promptly, following attack by the OH radical on the terpene, via a series of highly unstable radical intermediates. It can also be formed by slower processes, via degradation of stable non-radical intermediates such as pinonaldehyde and nopinone.Primary acetone and pinonaldehyde molar yields of 11±2% (one σ) and 34±9% (one σ), respectively, were found from the reaction between α-pinene and the OH radical. After all α-pinene had been consumed, an additional formation of acetone due to the degradation of stable non-radical intermediates was observed. The total amount of acetone formed was 15±2% (one σ) of the reacted α-pinene. An upper limit of 12±3% (one σ) for the acetone molar yield from the oxidation of pinonaldehyde was established.From the reaction between β-pinene and the OH radicals, primary acetone and nopinone molar yields of 13±2% (one σ) and 25±3% (one σ), respectively, were observed. Additional amounts of acetone were formed by the further degradation of the primary product, such as the most abundant product nopinone. The total amount of acetone formed was 16±2% (one σ) of the reacted β-pinene. An upper limit of 12±2% (one σ) for the acetone molar yield from the oxidation of nopinone was established.The observed product yields from α- and β-pinene are in good agreement with other studies using mass-spectrometric and gas chromatographic analytical techniques, but differ significantly from previous studies using spectroscopic methods. Possible reasons for the discrepancies are discussed.  相似文献   

15.
This study examines the characteristics of volatile organic compounds (VOCs) and their major emission sources at the Bulgwang site in Seoul, Korea. The annual levels of VOCs (96.2–121.1 ppb C) have shown a decreasing trend from 2004 to 2008. The most abundant component in Seoul was toluene, which accounted for over 23.5 % of the total VOCs on the parts per billion on a carbon basis, and the portions of alkanes with two to six carbons constituted the largest major lumped group, ranging from 40.1 to 48.4 % (45.3?±?3.7 %) of the total VOCs. Major components of the solvent (toluene, m/p-xylene, o-xylene, and ethylbenzene) showed high in daytime and summer and low in nighttime and winter due mainly to the variation of the ambient temperature. The species mostly emitted from gasoline vapor (i/n-butane, i/n-pentane, n-hexane, and 2-methylpentane) and vehicular exhaust (ethylene, acetylene, and benzene) showed bimodal peaks in the diurnal variation around the commuting hours because of the high traffic volume. For the 14 out of 15 highest concentration species, the weekend effect was only evident on Sundays because of the stepwise implementation of the 5-day work-week system. Principal components analysis (PCA) was applied in order to identify the sources of the 15 highest concentration VOCs and, as a result, three principal components such as gasoline vapor (48.9 %), vehicular exhaust (17.9 %), and evaporation of solvents (9.8 %) were obtained to explain a total of 76.6 % of the data variance. Most influential contributing sources at the sampling site were traffic-related ones although the use of solvent was the dominant emission source based on the official emission inventory.  相似文献   

16.
The knowledge on the distribution of hydrophobic organic contaminants in soils can provide better understanding for their fate in the environment. In the present study, the n-butanol extraction and humic fractionation were applied to investigate the impact of SOM on the distribution of polycyclic aromatic hydrocarbons (PAHs). The results indicated that 80.5%-94.8% of the target PAHs could be extracted by n-butanol and 63.1%-94.6% of PAHs were associated with fulvic acid (FA). Concentrations of un-extracted PAHs increased significantly with the increasing soil organic matter (SOM), however, such an association was absent for the extractable fractions. The results suggested that the sequestration played a critical role in the accumulation of PAHs in soils. SOM also retarded the diffusion of PAHs into the humin fractions. It implied that sequestration in SOM was critical for PAH distribution in soils, while the properties of PAH compounds also had great influences.  相似文献   

17.
The levels of organochlorine pesticides (OCPs) in the water, suspended solids, and sediments from Lake Chaohu during the high water level period were measured by a solid-phase extraction gas chromatograph–electron capture detector. The spatial distributions of the three phases and the water/suspended solids and sediment/water partition coefficients were analyzed. The results showed the following: (1) The mean contents of OCPs in the water, suspended solids, and sediments were 132.4?±?432.1 ng/L, 188.1?±?286.7 ng/g dry weight (dw), and 13.7?±?9.8 ng/g dw, respectively. The dominant OCP components were isodrin (85.1 %) for the water, DDTs (64.4 %) for the suspended solids, and both isodrin (48.5 %) and DDTs (31.8 %) for the sediments. (2) β-HCH was the primary isomer of HCHs in the water and sediments, and the proportions were 61.7 and 41.3 %; γ-HCH was the primary isomer in the suspended solids, accounting for 49.3 %; p,p′-DDT was the dominant content of DDTs in the water and suspended solids, whereas p,p′-DDD was the main metabolite of DDTs in the sediments. (3) The concentrations of contaminants in the water from the western lake were greater than those from the eastern lake, but the concentrations in the suspended solids from the western lake were less than those from the eastern lake. (4) There was no significant correlation between the water–suspended solids partition coefficient K d and the n-octanol–water partition coefficient K ow, and between the sediment–water organic-C weighted sorption coefficients K oc and K ow.  相似文献   

18.
The Mediterranean fanworm, Sabella spallanzanii Gmelin 1791, was first detected in the Southern Hemisphere in the 1990s and is now abundant in many parts of southern Australia and in several locations around northern New Zealand. Once established, it can proliferate rapidly, reaching high densities with potential ecological and economic impacts. Early detection of new S. spallanzanii incursions is important to prevent its spread, guide eradication or control efforts and to increase knowledge on the species’ dispersal pathways. In this study, we developed a TaqMan probe real-time polymerase chain reaction assay targeting a region of the mitochondrial cytochrome oxidase I gene. The assay was validated in silico and in vitro using DNA from New Zealand and Australian Sabellidae with no cross-reactivity detected. The assay has a linear range of detection over seven orders of magnitude with a limit of detection reached at 12.4 × 10?4 ng/μL of DNA. We analysed 145 environmental (water, sediment and biofouling) samples and obtained positive detections only from spiked samples and those collected at a port where S. spallanzanii is known to be established. This assay has the potential to enhance current morphological and molecular-based methods, through its ability to rapidly and accurately identify S. spallanzanii in environmental samples.  相似文献   

19.
Ambient speciated mercury concentrations including total gaseous mercury (TGM), gaseous divalent mercury (Hg(II)), and particulate mercury (Hg(p)) were measured on the roof of the Graduate School of Public Health building in Seoul, Korea from February 2005 to February 2006. The average concentrations were 3.22 ± 2.10 ng m?3, 27.2 ± 19.3 pg m?3, and 23.9 ± 19.6 pg m?3 for TGM, Hg(II), and Hg(p), respectively. Hg(II) and Hg(p) concentrations were higher during the daytime than during the nighttime, probably because of high photochemical activity. Hg0 concentrations were not significantly correlated with ozone however a positive correlation between ozone and Hg(II) was found during periods of high humidity. Eighteen days were characterized as pollution events with 24 h average PM2.5 concentrations >65 μg m?3. The average concentrations of TGM and Hg(p) during these events were 1.4–2 times higher than those during non-pollution events. In order to identify the contribution of long-range transported mercury to the enhanced mercury concentrations in Korea, an episode was defined as a period with hourly average TGM and CO concentrations higher than the monthly average TGM and CO concentrations and with significant enhancement of both TGM and CO concentrations for at least 10 h. A total of 70 episodes were identified during the sampling period: 36 local episodes and 34 long-range transport episodes. The mean ΔTGM/ΔCO slope for all episodes was 0.0063 ng m?3 ppbv?1 which agreed well with the slope (0.0036–0.0074 ng m?3 ppbv?1) found in previous studies that identified long-range transport of TGM from China. The mean slope during non-events was 0.0011 ng m?3 ppbv?1. Back-trajectory analysis showed that during episodes, air parcels arrived mostly from the major industrial areas in China (n = 25, 73%), followed by Japan (n = 4, 12%), Yellow Sea (n = 3, 9%), and Russia (n = 2, 6%).  相似文献   

20.
Measurements of atmospheric electricity began at Kew Observatory, London (51°28′N, 0°19′W) in 1843, with recording apparatus installed by Lord Kelvin in 1861. The measured electric potential gradient (PG) at Kew has always been influenced by smoke pollution, causing a December PG maximum and July minimum. Theory links PG variations with aerosol concentrations, and the 20th century smoke measurements made at Kew permit smoke concentrations to be retrieved from 19th century PG data. Absolute calibration of the 1862–1864 PG is achieved by considering changes in the global electric circuit, for which the geomagnetic aa-index is used as a proxy. The mean annual PG in 1863 is estimated as 363±29 V m−1, and the mean smoke concentration found is 0.17±0.05 mg m−3. Diurnal variations in smoke pollution differ between the seasons, and change in their character after the advent of motor traffic.  相似文献   

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