科研成果

Hydroxyl radicals (OH) are the most important reagent for the oxidation of trace gases in the atmosphere. OH concentrations measured during recent field campaigns in isoprene-rich environments were unexpectedly large. A number of studies showed that unimolecular reactions of organic peroxy radicals (RO2) formed in the initial reaction step of isoprene with OH play an important role for the OH budget in the atmosphere at low mixing ratios of nitrogen monoxide (NO) of less than 100 pptv. It has also been suggested that similar reactions potentially play an important role for RO2 from other compounds. Here, we investigate the oxidation of methacrolein (MACR), one major oxidation product of isoprene, by OH in experiments in the simulation chamber SAPHIR under controlled atmospheric conditions. The experiments show that measured OH concentrations are approximately 50% larger than calculated by the Master Chemical Mechanism (MCM) for conditions of the experiments (NO mixing ratio of 90 pptv). The analysis of the OH budget reveals an OH source that is not accounted for in MCM, which is correlated with the production rate of RO2 radicals from MACR. In order to balance the measured OH destruction rate, 0.77 OH radicals (1 sigma error: +/- 0.31) need to be additionally reformed from each reaction of OH with MACR. The strong correlation of the missing OH source with the production of RO2 radicals is consistent with the concept of OH formation from unimolecular isomerization and decomposition reactions of RO2. The comparison of observations with model calculations gives a lower limit of 0.03 s(-1) for the reaction rate constant if the OH source is at-tributed to an isomerization reaction of MACR-1-OH-2-OO and MACR-2-OH-2-OO formed in the MACR + OH reaction as suggested in the literature (Crounse et al., 2012). This fast isomerization reaction would be a competitor to the reaction of this RO2 species with a minimum of 150 pptv NO. The isomerization reaction would be the dominant reaction pathway for this specific RO2 radical in forested regions, where NO mixing ratios are typically much smaller.

Hydroxyl radicals (OH) are the most important reagent for the oxidation of trace gases in the atmosphere. OH concentrations measured during recent field campaigns in isoprene-rich environments were unexpectedly large. A number of studies showed that unimolecular reactions of organic peroxy radicals (RO2) formed in the initial reaction step of isoprene with OH play an important role for the OH budget in the atmosphere at low mixing ratios of nitrogen monoxide (NO) of less than 100 pptv. It has also been suggested that similar reactions potentially play an important role for RO2 from other compounds. Here, we investigate the oxidation of methacrolein (MACR), one major oxidation product of isoprene, by OH in experiments in the simulation chamber SAPHIR under controlled atmospheric conditions. The experiments show that measured OH concentrations are approximately 50% larger than calculated by the Master Chemical Mechanism (MCM) for conditions of the experiments (NO mixing ratio of 90 pptv). The analysis of the OH budget reveals an OH source that is not accounted for in MCM, which is correlated with the production rate of RO2 radicals from MACR. In order to balance the measured OH destruction rate, 0.77 OH radicals (1σ error: ± 0.31) need to be additionally reformed from each reaction of OH with MACR. The strong correlation of the missing OH source with the production of RO2 radicals is consistent with the concept of OH formation from unimolecular isomerization and decomposition reactions of RO2. The comparison of observations with model calculations gives a lower limit of 0.03 s−1 for the reaction rate constant if the OH source is attributed to an isomerization reaction of MACR-1-OH-2-OO and MACR-2-OH-2-OO formed in the MACR + OH reaction as suggested in the literature (Crounse et al., 2012). This fast isomerization reaction would be a competitor to the reaction of this RO2 species with a minimum of 150 pptv NO. The isomerization reaction would be the dominant reaction pathway for this specific RO2 radical in forested regions, where NO mixing ratios are typically much smaller.

A particle-phase relative rates technique is used to investigate the heterogeneous reaction between OH radicals and tris-2-butoxyethyl phosphate (TBEP) at 298 K by combining aerosol time-of-flight mass spectrometry (C-ToF-MS) data and positive matrix factor (PMF) analysis. The derived second-order rate constants (k(2)) for the heterogeneous loss of TBEP is (4.44 +/- 0.45) x 10(-12) cm(3) molecule(-1) s(-1), from which an approximate particle-phase lifetime was estimated to be 2.6 (2.3-2.9) days. However, large differences in the rate constants for TBEP relative to a reference compound were observed when comparing internally and externally mixed TBEP/organic particles, and upon changes in the RH. The heterogeneous degradation of TBEP was found to be depressed or enhanced depending upon the particle mixing state and phase, highlighting the complexity of heterogeneous oxidation in the atmosphere. The effect of gas-particle partitioning on the estimated overall lifetime (gas C particle) for several organophosphate esters (OPEs) was also examined through the explicit modeling of this process. The overall atmospheric lifetimes of TBEP, tris-2-ethylhexyl phosphate (TEHP) and tris-1,3-dichloro-2-propyl phosphate (TDCPP) were estimated to be 1.9, 1.9 and 2.4 days respectively, and are highly dependent upon particle size. These results demonstrate that modeling the atmospheric fate of particle-phase toxic compounds for the purpose of risk assessment must include the gas-particle partitioning process, and in the future include the effect of other particulate components on the evaporation kinetics and/or the heterogeneous loss rates.

For the real-time and low-delay video surveillance and teleconferencing applications, the newly video coding standard HEVC can achieve much higher coding efficiency over H.264/AVC. However, we still argue that the hierarchical prediction structure in the HEVC low-delay encoder still does not fully utilize the special characteristics of surveillance and conference videos that are usually captured by stationary cameras. In this case, the background picture (G-picture), which is modeled from the original input frames, can be used to further improve the HEVC low-delay coding efficiency meanwhile reducing the complexity. Therefore, we propose an optimization method for the hierarchical prediction and coding in HEVC for these videos with background modeling. First, several experimental and theoretical analyses are conducted on how to utilize the G-picture to optimize the hierarchical prediction structure and hierarchical quantization. Following these results, we propose to encode the G-picture as the long-term reference frame to improve the background prediction, and then present a G-picture-based bit-allocation algorithm to increase the coding efficiency. Meanwhile, according to the proportions of background and foreground pixels in coding units (CUs), an adaptive speed-up algorithm is developed to classify each CU into different categories and then adopt different speed-up strategies to reduce the encoding complexity. To evaluate the performance, extensive experiments are performed on the HEVC test model. Results show our method can averagely save 39.09% bits and reduce the encoding complexity by 43.63% on surveillance videos, whereas those are 5.27% and 43.68% on conference videos.

Organochlorine pesticides (OCPs) in placental tissue have been reported to be associated with an increased risk for fetal neural tube defects (NTDs). Our case-control study was performed to explore the association between maternal serum OCP concentration and NTD risk in offspring. Serum samples were collected from 117 mothers who delivered NTD infants (case group) and 121 mothers who delivered healthy infants (control group). Only three of the 25 OCPs were detected in more than half of the maternal serum samples. The median concentration of total OCPs in the case group was significantly higher than that of the control group. However, no dose-response relationships between higher levels of any individual OCPs or total OCPs and the risk of NTDs or subtypes were observed in either the unadjusted binary unconditional logistic regression model or the model adjusted by potential confounders. We conclude that no clear association between maternal serum OCP residues and NTD risk in offspring was observed in this population. Capsule: No clear association between maternal serum levels of organochlorine pesticides and risk of neural tube defects in offspring was observed for a Chinese population. (C) 2014 Elsevier B.V. All rights reserved.

Exposure to ultrafine particles poses a potential health risk to school children. While many studies have focused on measuring ultrafine particle (UFP) concentrations in environments where children are at risk of high exposure, few studies have examined the particle deposition in the respiratory tract of children. This study aims to examine the particle deposition in the respiratory tract of school children in different microenvironments. UFP size distribution data were collected in residential homes, school buses, school classrooms, and from school outdoor air in both rural and urban areas of South Texas. The size distribution data were input to the Multiple Path Particle Dosimetry model to calculate regional and total particle deposition fraction. A 24-hour-school-day exposure was simulated by adding the time children spend in each microenvironment. The maximum pulmonary deposition fraction occurs at a diameter ranging from 18 to 40 nm, depending on condition. Age mostly affected the pulmonary region and the total lung deposition with the highest deposition fraction observed for younger children. In addition, comparison of size-dependent regional deposition and particle concentration establishes an accurate depiction of children's exposure and dose profiles. While children only spend 4% of the day in the home source environment, that environment may account for up to 77% of total daily dose intake. Higher deposition fraction occurs at smaller particle size. Younger children show increased levels of particle deposition than older children. Exposure period does not correlate to daily percentage of dose intake. This research can be used to assess children's accumulative exposure to UFPs.