Reduction of biogenic VOC sampling losses from ozone via trans-2-butene addition

The continuous addition of trans-2-butene to air containing ozone-reactive volatile and semivolatile organic compounds prior to sampling on Tenax-TA adsorbent was found to be an effective means of removing ozone and reducing analyte losses of ozone reactive biogenic volatile organic compounds (BVOCs). To allow sufficient time for ozone scavenging to occur, the reacting mixture is passed through a heated (40 degrees C) coil of Sulfinert (Restek Corp., Bellefonte, PA) treated stainless steel tubing. The method was evaluated using a test mixture consisting of terpenes, terpenoid alcohols, and sesquiterpenes at part per trillion (pptv) levels in air in the presence of 100 parts per billion (ppbv) of ozone. The continuous addition of trans-2-butene to produce 600 ppm (ppmv) was found to be completely effective in controlling VOC losses on Tenax-TA as long as (1) sufficient time is allowed for the ozone scavenging to occur before the VOCs are adsorbed and (2) analyte enrichment on the adsorbentdoes not approach the hydroxyl radical scavenging capacity of the trans-2-butene. A manganese dioxide (MnO2) coated copper screen ozone scrubber was also tested and found to be of very limited utility.     

Research Watch: VOC sampling bag losses

Measurements.     

Measurement of atmospheric ozone by cavity ring-down spectroscopy

Ozone plays a key role in both the Earth's radiative budget and photochemistry. Accurate, robust analytical techniques for measuring its atmospheric abundance are of critical importance. Cavity ring-down spectroscopy has been successfully used for sensitive and accurate measurements of many atmospheric species. However, this technique has not been used for atmospheric measurements of ozone, because the strongest ozone absorption bands occur in the ultraviolet spectral region, where Rayleigh and Mie scattering cause significant cavity losses and dielectric mirror reflectivities are limited. Here, we describe a compact instrument that measures O3 by chemical conversion to NO2 in excess NO, with subsequent detection by cavity ring-down spectroscopy. This method provides a simple, accurate, and high-precision measurement of atmospheric ozone. The instrument consists of two channels. The sum of NO2 and converted O3 (defined as Ox) is measured in the first channel, while NO2 alone is measured in the second channel. NO2 is directly detected in each channel by cavity ring-down spectroscopy with a laser diode light source at 404 nm. The limit of detection for O3 is 26 pptv (2 sigma precision) at 1 s time resolution. The accuracy of the measurement is ±2.2%, with the largest uncertainty being the effective NO2 absorption cross-section. The linear dynamic range of the instrument has been verified from the detection limit to above 200 ppbv (r2>99.99%). The observed precision on signal (2 sigma) with 41 ppbv O3 is 130 pptv in 1 s. Comparison of this instrument to UV absorbance instruments for ambient O3 concentrations shows linear agreement (r2=99.1%) with slope of 1.012±0.002.     

Effects of atmospheric cold plasma and ozone on prebiotic orange juice

In this study, the effect of plasma and ozone treatments on the quality of orange juice was evaluated. The juice was directly and indirectly exposed to a plasma field at 70 kV for different treatment times: 15, 30, 45 and 60 s. For ozone processing, different loads (0.057, 0.128 and 0.230 mg/O₃ mL of juice) were evaluated. After the treatments, the oligosaccharides were quantified by HPLC. The juice pH, color, total phenolic content and total antioxidant activity were also determined. Both processes promoted a partial degradation of the oligosaccharides in the juice. However, the juice maintained an enough amount of oligosaccharides to be classified as a prebiotic food. The phenolic content and antioxidant capacity of the treated samples was also well preserved as the pH and color. Thus, atmospheric cold plasma and ozone are suitable non-thermal alternatives for prebiotic orange juice treatment.Industrial relevanceConsumers are looking for safe food products with high quality. Thus, the food industry is currently considering non-thermal processes as an alternative to reduce the nutrient loss in processed foods. Despite atmospheric cold plasma and ozone are technologies already evaluated as an efficient non-thermal alternative for pathogens inactivation in orange juice, no previous studies on their effects on the oligosaccharides in functional fruit juice was published. This study is of industrial relevance because it demonstrates that after plasma and ozone treatment the overall quality of prebiotic orange juice was preserved and the product maintained its functional appeal.     

宁德市大气臭氧污染现状及影响因素

以宁德市蕉城区农机局、市监测站国控监测点2016年1月到2017年7月臭氧8小时监测值为基础,研究臭氧浓度的日变化、月变化趋势及臭氧相关影响因素,结果表明:在高温、低湿、低风速、晴朗无云的情况下,易形成高浓度臭氧;低温、高湿、少日照不利于臭氧的生成.现实情况中可能存在跨区域输送或区域内生成等情况都会导致臭氧污染的生成不...     

Oxidation of atmospheric humic like substances by ozone: a kinetic and structural analysis approach

This work explores the heterogeneous reaction between HUmic-LIke Substances (so-called HULIS) and ozone. Genuine atmospheric HULIS were extracted from aerosol samples collected in Chamonix (France) in winter and used in coated flow tube experiments to evaluate heterogeneous uptake of O? on such mixtures. The uptake coefficient (γ) was investigated as a function of pH (from 2.5 to 10), O? concentration (from 8 to 33 × 1011 molecules cm?3), relative humidity (20 to 65%) and photon flux (from 0 to 1.66 × 101? photons cm?2 s?1). Reactive uptake was found to increase in the irradiated experiment with pH, humidity and photon flux. The extract was characterized before and after exposure to O? and/or UV light in the attempt to elucidate the effect of the photochemical aging. Carbon content measurements, UV-vis spectroscopy and functional groups analysis revealed a decrease of the UV absorbance as well as of the carbon mass content, while the functionalization rate (COOH and C═O) and therefore the polarity increased during the simulated photochemical exposure.     

Novel algorithm for tomographic reconstruction of atmospheric chemicals with sparse sampling

Numerical studies were performed to evaluate a new air monitoring method for reconstructing chemical exposures and source emissions, based upon optical remote sensing (ORS) and computed tomography (CT). With an ORS-CT system, two-dimensional maps of chemical concentrations can be created that have good spatial and temporal resolution. The mathematical algorithm used to compute the distribution is critical for accurate and useable reconstructions of the concentrations. In this research, a novel reconstruction method was tested that uses maximum likelihood expectation maximization (MLEM) combined with two techniques called grid-translation and multi-grid (GT-MG). To evaluate this method, computer simulations were performed using 120 test maps of varying complexity and a simulated ORS system with four instruments and a total of 40 path-integrated measurements. The results were quantitatively compared with two previously used reconstruction methods (single-grid and grid-translation). Results using the GT-MG method were dramatically improved over previously used methods. Quantitatively, peak exposure errors were reduced by up to 85% and artifacts were dramatically minimized.     

Physicochemical characteristics and biological activities of seasonal atmospheric particulate matter sampling in two locations of Paris

Fine particulate matter present in urban areas seems to be incriminated in respiratory disorders. The aim of this study was to relate physicochemical characteristics of PM2.5 (particulate matter collected with a 50% efficiency for particles with an aerodynamic diameter of 2.5 microm) to their biological activities toward a bronchial epithelial cell line 16-HBE. Two seasonal sampling campaigns of particles were realized, respectively, in a kerbside and an urban background station in Paris. Sampled-PM2.5 mainly consist of particles with a size below 1 microm and are mainly composed of soot as assessed by analytical scanning electron microscopy. The different PM2.5 samples contrasted in their PAH content, which was the highest in the kerbside station in winter, as well as in their metal content. Kerbside station samples were characterized by the highest Fe and Cu content, which appears correlated to their hydroxyl radical generating properties measured by electron paramagnetic resonance. Particles were compared by their capacity to induce cytotoxicity, intracellular ROS production, and proinflammatory cytokine release (GM-CSF and TNF-alpha). At a concentration of 10 microg/cm2, all samples induced peroxide production and cytokine release to the similar extent in the absence of cytotoxicity. In conclusion, whereas the PM2.5 samples differ by their PAH and metal composition, they induce the same biological responses likely either due to components bioavailability and/ or interactions between PM components.     

Research Watch: Urban trees and ozone

Air.     

Synergistic effect of tannic acid and modified atmospheric packaging on the prevention of lipid oxidation and quality losses of refrigerated striped catfish slices

Chemical, microbiological and sensorial changes of striped catfish (Pangasius hypophthalmus) slices treated without and with tannic acid (100 and 200 mg/kg) were determined during 15 days of storage at 4 °C in air and under modified atmospheric packaging (MAP, 60% N₂/35% CO₂/5% O₂). The slices consisted of 9.2 g lipid/100 g and the lipid contained 64.55% unsaturated fatty acids and 33.87% saturated fatty acids. During the storage, the sample treated with 200 mg/kg tannic acid and stored under MAP (M₂) had the lowest peroxide value (PV) and thiobarbituric acid-reactive substances (TBARS) with the coincidental lowest non-haem iron content, indicating the retarded lipid oxidation. Fourier transform infrared (FTIR) spectra indicated the formation of primary oxidation products and free fatty acids in M₂ sample after 15 days. Conversely, these compounds were found at lower contents in the control samples kept in air without tannic acid treatment (A₀), suggesting that the deterioration was more advanced. Myosin heavy chain of A₀ was degraded by 17.85% after 15 days of storage, whereas no change was noticeable in M_2, compared with the fresh sample (F). Based on microbiological acceptability limit (10⁷ cfu/g), the shelf-life of A₀ and M₂ was estimated to be 3 and 15 days, respectively. M₂ had the acceptable scores for all sensory attributes up to 15 days, while A₀ was acceptable when stored for 9 days. Therefore, tannic acid exhibited a synergistic effect with MAP on retarding lipid oxidation and microbial growth, thereby increasing the shelf-life of striped catfish slices during refrigerated storage.     

Reduction of radiation-induced vitamin E- and B1- losses by irradiation of foodstuffs at low temperature and by exclusion of atmospheric oxygen

The protective effect of low temperatures during irradiation on vitamin B1 and E levels in foods is not abolished by subsequent storage or heating. Egg powder irradiated at 1 Mrad in the presence of air and stored for 4 months at ambient temperature lost 68% of its thiamin content when irradiated at 20 degrees C, 33% when irradiated at -30 degrees C. Sunflower oil irradiated at 3 Mrad in the presence of air and subsequently heated for 1 hour at 180 degrees C lost 98% of its alpha-tocopherol content when irradiated at 20 degrees C, 65% when irradiated at -30 degrees C. Exclusion of atmospheric oxygen by packaging under nitrogen reduced the loss of alpha-tocopherol in irradiated (0.1 Mrad) rolled oats after 8 months of storage from 56 to 5% and the loss of thiamin from 86 to 26%. Vacuum packaging was equally effective during the first 3 months and somewhat less effective during the following 5 months. Packaging under carbon dioxide showed no advantage over packaging in air. Sensory evaluation of rolled oats, raw or cooked, 1 and 3 months after irradiation with 0.1 Mrad indicated no significant quality difference between unirradiated and irradiated samples packaged under nitrogen.     

Tedlar bag sampling technique for vertical profiling of carbon dioxide through the atmospheric boundary layer with high precision and accuracy

Carbon dioxide is the most important greenhouse gas other than water vapor, and its modulation by the biosphere is of fundamental importance to our understanding of global climate change. We have developed a new technique for vertical profiling of CO2 and meteorological parameters through the atmospheric boundary layer and well into the free troposphere. Vertical profiling of CO2 mixing ratios allows estimates of landscape-scale fluxes characteristic of approximately100 km2 of an ecosystem. The method makes use of a powered parachute as a platform and a new Tedlar bag air sampling technique. Air samples are returned to the ground where measurements of CO2 mixing ratios are made with high precision (< or =0.1%) and accuracy (< or =0.1%) using a conventional nondispersive infrared analyzer. Laboratory studies are described that characterize the accuracy and precision of the bag sampling technique and that measure the diffusion coefficient of CO2 through the Tedlar bag wall. The technique has been applied in field studies in the proximity of two AmeriFlux sites, and results are compared with tower measurements of CO2.     

Degradation of ozone-refractory organic phosphates in wastewater by ozone and ozone/hydrogen peroxide (peroxone): the role of ozone consumption by dissolved organic matter

Ozonation is very effective in eliminating micropollutants that react fast with ozone (k > 10(3) M(-1) s(-1)), but there are also ozone-refractory (k < 10 M(-1) s(-1)) micropollutants such as X-ray contrast media, organic phosphates, and others. Yet, they are degraded upon ozonation to some extent, and this is due to (?)OH radicals generated in the reaction of ozone with organic matter in wastewater (DOM, determined as DOC). The elimination of tri-n-butyl phosphate (TnBP) and tris-2-chloroisopropyl phosphate (TCPP), added to wastewater in trace amounts, was studied as a function of the ozone dose and found to follow first-order kinetics. TnBP and TCPP concentrations are halved at ozone to DOC ratios of ～0.25 and ～1.0, respectively. The (?)OH rate constant of TCPP was estimated at (7 ± 2) × 10(8) M(-1) s(-1) by pulse radiolysis. Addition of 1 mg H(2)O(2)/L for increasing the (?)OH yield had very little effect. This is due to the low rate of reaction of H(2)O(2) with ozone at wastewater conditions (pH 8) that competes unfavorably with the reaction of ozone with wastewater DOC. Simulations based on the reported (No?the et al., ES&T 2009, 43, 5990-5995) (?)OH yield (13%) and (?)OH scavenger capacity of wastewater (3.2 × 10(4) (mgC/L)(-1) s(-1)) confirm the experimental data. Based on a typically applied molar ratio of ozone and H(2)O(2) of 2, the contribution of H(2)O(2) addition on the (?)OH yield is shown to become important only at high ozone doses.     

粮食储藏中粮堆温度与大气温度之关系

本文着重阐述了已通过国家科技部验收的国家“九五”重点科技攻关计划项目-智能化粮情检测分析控制系统专题（96-615-05-02）实施过程中,使用统计软件SAS对辽宁沈阳,丹东,广西梧州,河南漯河等粮库的粮情检测数据进行分析的方法及结果。通过对粮堆温度与大气温度资料进行的相关分析。结果表明粮堆温度与大气温度间存在着明显的相关关系。但这种相关关系并非是纯线性的,而是随着测温点位置的不同,粮堆温度的变化表现出相对大气温度变化的滞后,这一相关系数随着测温点位置与外界距离的加大而呈现出递减趋势。     

Air quality impacts of climate mitigation: UK policy and passenger vehicle choice

In 2001-2002 the UK began taxing vehicles according to CO2 emission rates. Since then, there has been a significant increase in consumer choice of small cars and diesel engines. We estimate CO2 reductions and air quality impacts resulting from UK consumers switching from petrol to diesel cars from 2001 to 2020. Annual reductions of 0.4 megatons (Mt) of CO2 and 1 million barrels of oil are estimated from switching to diesels. However, diesels emit higher levels of particulate matter estimated to result in 90 deaths annually (range 20-300). We estimate 570, 460, and 0 additional deaths per Mt of CO2 abated, for Euro III, Euro IV, and post-Euro IV emission class vehicles, respectively. CO2 policies are suspected to have contributed substantially to diesel growth, but the magnitude of impact has yet to be quantified rigorously. To the extent that CO2 policies contribute to diesel growth, coordinating CO2 controls with tightening of emission standards would save lives. This research shows that climate policy, while reducing fuel use and CO2, does not always ensure ancillary health benefits. Lessons from the UK can help inform policies designed elsewhere which strive to balance near-term ambient air quality and health with long-term climate mitigation.