Interactions and implications of halogens and VOCs on tropospheric oxidant cycles in the remote atmosphere

2020 ◽  
Author(s):  
Eric C. Apel
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Model Development ◽  
Tropospheric Chemistry ◽  
Chemical Mechanism ◽  
Chemical Production ◽  
Four Seasons ◽  
The Pacific ◽  
Volatile Organic ◽  
Remote Troposphere

<p>Reactive halogens have wide-ranging consequences on tropospheric chemistry including ozone destruction, HOx and NOx partitioning, oxidization of volatile organic compounds (VOCs) and initiation of new particle formation. Of particular note and importance, the tropospheric Ox loss due to halogens is estimated to be between 10-20% globally, and up to 50% in some local marine environments. In this work, we include a state-of-the-art coupled halogen and VOCs chemical mechanism into the CAM-Chem global model. Complementing the model development and providing the opportunity to test the model are recent results from the NASA Atmospheric Tomography (ATom) experiment.  ATom was conducted with a heavily instrumented NASA DC-8 aircraft over the course of two and a half years, transecting the lengths of the Pacific and Atlantic Oceans during four seasons, constantly profiling from the surface (200 m) to the upper troposphere/lower stratosphere (12000 m). The ATom payload included instruments that measured both inorganic halogens and organic halogen-containing very short-lived substances (VSLS), as well as those that measured additional volatile organic compounds (VOCs), including hydrocarbons and oxygenated VOCs (OVOCs), both of which react with halogens. Modeled BrO is sensitive to the inclusion of reactions between Br and OVOCs, particularly the aldehydes, which rapidly convert Br to HBr, a far less reactive form of Br<sub>y</sub>. These reactions can have large implications in the remote troposphere where the ATom measurements have revealed significant emissions and chemical production of low molecular weight aldehydes over the remote marine environment. A version of CAM-chem, updated to include aldehyde emissions from the ocean to close the gap between models and measurements, is used in these analyses. Comparisons between measured and modeled halogen containing species, both organic and inorganic, is presented along with a summary of the implications of our findings on the overall budgets of tropospheric halogens and ozone.</p>

scholarly journals Aerosol mass yields of selected biogenic volatile organic compounds – a theoretical study with nearly explicit gas-phase chemistry

2019 ◽  
Vol 19 (22) ◽  
pp. 13741-13758
Author(s):  
Carlton Xavier ◽  
Anton Rusanen ◽  
Putian Zhou ◽  
Chen Dean ◽  
Lukas Pichelstorfer ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Gas Phase ◽  
Organic Compounds ◽  
Chemical Mechanism ◽  
Biogenic Volatile Organic Compounds ◽  
Gas Phase Chemistry ◽  
Mass Load ◽  
Volatile Organic ◽  
Phase Chemistry ◽  
Good Agreement

Abstract. In this study we modeled secondary organic aerosol (SOA) mass loadings from the oxidation (by O3, OH and NO3) of five representative biogenic volatile organic compounds (BVOCs): isoprene, endocyclic bond-containing monoterpenes (α-pinene and limonene), exocyclic double-bond compound (β-pinene) and a sesquiterpene (β-caryophyllene). The simulations were designed to replicate an idealized smog chamber and oxidative flow reactors (OFRs). The Master Chemical Mechanism (MCM) together with the peroxy radical autoxidation mechanism (PRAM) were used to simulate the gas-phase chemistry. The aim of this study was to compare the potency of MCM and MCM + PRAM in predicting SOA formation. SOA yields were in good agreement with experimental values for chamber simulations when MCM + PRAM was applied, while a stand-alone MCM underpredicted the SOA yields. Compared to experimental yields, the OFR simulations using MCM + PRAM yields were in good agreement for BVOCs oxidized by both O3 and OH. On the other hand, a stand-alone MCM underpredicted the SOA mass yields. SOA yields increased with decreasing temperatures and NO concentrations and vice versa. This highlights the limitations posed when using fixed SOA yields in a majority of global and regional models. Few compounds that play a crucial role (>95 % of mass load) in contributing to SOA mass increase (using MCM + PRAM) are identified. The results further emphasized that incorporating PRAM in conjunction with MCM does improve SOA mass yield estimation.

scholarly journals Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

2002 ◽  
Vol 2 (6) ◽  
pp. 1847-1903 ◽  
Author(s):  
S. M. Saunders ◽  
M. E. Jenkin ◽  
R. G. Derwent ◽  
M. J. Pilling
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Good Description ◽  
Field Studies ◽  
Companion Paper ◽  
Chemical Mechanism ◽  
North West ◽  
Radical Intermediates ◽  
Volatile Organic ◽  
Master Chemical Mechanism

Abstract. Kinetic and mechanistic data relevant to the tropospheric degradation of volatile organic compounds (VOC), and the production of secondary pollutants, have previously been used to define a protocol which underpinned the construction of a near-explicit Master Chemical Mechanism. In this paper, an update to the previous protocol is presented, which has been used to define degradation schemes for 107 non-aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3). The treatment of 18 aromatic VOC is described in a companion paper. The protocol is divided into a series of subsections describing initiation reactions, the reactions of the radical intermediates and the further degradation of first and subsequent generation products. Emphasis is placed on updating the previous information, and outlining the methodology which is specifically applicable to VOC not considered previously (e.g. a- and b-pinene). The present protocol aims to take into consideration work available in the open literature up to the beginning of 2001, and some other studies known by the authors which were under review at the time. Application of MCM v3 in appropriate box models indicates that the representation of isoprene degradation provides a good description of the speciated distribution of oxygenated organic products observed in reported field studies where isoprene was the dominant emitted hydrocarbon, and that the a-pinene degradation chemistry provides a good description of the time dependence of key gas phase species in a-pinene/NOX photo-oxidation experiments carried out in the European Photoreactor (EUPHORE). Photochemical Ozone Creation Potentials (POCP) have been calculated for the 106 non-aromatic non-methane VOC in MCM v3 for idealised conditions appropriate to north-west Europe, using a photochemical trajectory model. The POCP values provide a measure of the relative ozone forming abilities of the VOC. Where applicable, the values are compared with those calculated with previous versions of the MCM.

scholarly journals Formaldehyde evolution in U.S. wildfire plumes during FIREX-AQ

2021 ◽  
Author(s):  
Jin Liao ◽  
Glenn M. Wolfe ◽  
Reem A. Hannun ◽  
Jason M. St. Clair ◽  
Thomas F. Hanisco ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Secondary Production ◽  
Chemical Production ◽  
Fire Plume ◽  
Field Campaign ◽  
Volatile Organic ◽  
Main Driver ◽  
Connect Space ◽  
Age Range

Abstract. Formaldehyde (HCHO) is one of the most abundant non-methane volatile organic compounds (VOCs) emitted by fires. HCHO also undergoes chemical production and loss as a fire plume ages, and it can be an important oxidant precursor. In this study, we disentangle the processes controlling HCHO by examining its evolution in wildfire plumes sampled by the NASA DC-8 during the FIREX-AQ field campaign. In nine of the twelve analyzed plumes, dilution-normalized HCHO increases with physical age (range 1–6 h). The balance of HCHO loss (mainly via photolysis) and production (via OH-initiated VOC oxidation) controls the sign and magnitude of this trend. Plume-average OH concentrations, calculated from VOC decays, range from −0.5 (±0.5) × 106 to 5.3 (±0.7) × 106 cm−3. Plume-to-plume variability in dilution-normalized secondary HCHO production correlates with OH abundance rather than normalized OH reactivity, suggesting that OH is the main driver of fire-to-fire variability in HCHO secondary production. Analysis suggests an effective HCHO yield of 0.33 (±0.05) per VOC molecule oxidized for the 12 wildfire plumes. This finding can help connect space-based HCHO observations to the oxidizing capacity of the atmosphere.

scholarly journals A mass balance-based emission inventory of non-methane volatile organic compounds (NMVOCs) for solvent use in China

2021 ◽  
Author(s):  
Ziwei Mo ◽  
Ru Cui ◽  
Bin Yuan ◽  
Huihua Cai ◽  
Brian C. McDonald ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Emission Inventory ◽  
Personal Care Products ◽  
Material Balance ◽  
Tropospheric Chemistry ◽  
Personal Care ◽  
Industrial Sectors ◽  
Volatile Organic ◽  
Solvent Use

Abstract. Non-methane volatile organic compounds (NMVOCs) are important precursors of ozone (O3) and secondary organic aerosol (SOA), which play key roles in tropospheric chemistry. A huge amount of NMVOCs emissions from solvent use are complicated by a wide spectrum of sources and species. This work presents a long-term NMVOCs emission inventory of solvent use during 2000–2017 in China. Based on a mass (material) balance method, NMVOCs emissions were estimated for six categories, including coatings, adhesives, inks, pesticides, cleaners and personal care products. The results show that NMVOC emissions from solvent use in China increased rapidly from 2000 to 2014 then kept stable after 2014. The total emission increased from 1.6 Tg (1.2–2.2 Tg at 95 % confidence interval) in 2000 to 10.6 Tg (7.7–14.9 Tg) in 2017. The substantial growth is driven by the large demand of solvent products in both industrial and residential activities. However, increasing treatment facilities on the solvent-related factories in China restrained the continued growth of solvent NMVOCs emissions in recent years. Rapidly developing and heavily industrialized provinces such as Jiangsu, Shandong and Guangdong contributed significantly to the solvent use emissions. Oxygenated VOCs, alkanes and aromatics were main components, accounting for 42 %, 28 % and 21 % of total NMVOCs emissions in 2017, respectively. Our results and previous inventories are generally comparable within the estimation uncertainties (−27 %–52 %). However, there exist significant differences in the estimates of sub-categories. Personal care products were a significant and quickly rising source of NMVOCs, which were probably underestimated in previous inventories. Emissions from solvent use were growing faster compared with transportation and combustion emissions which were relatively better controlled in China. Environmentally friendly products can reduce the NMVOCs emissions from solvent use. Supposing all solvent-based products were substituted by water-based products, it would result in 37 %, 41 % and 38 % reduction of emissions, OFP and SOAP, respectively. These results indicate there is still large room for NMVOCs reduction by reducing the utilization of solvent product and end-of-pipe control across industrial sectors.

scholarly journals Sources of volatile organic compounds and policy implications for regional ozone pollution control in an urban location of Nanjing, East China

2019 ◽  
Author(s):  
Qiuyue Zhao ◽  
Jun Bi ◽  
Zhenghao Ling ◽  
Qian Liu ◽  
Guofeng Shen ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Policy Implications ◽  
Chemical Mechanism ◽  
Effective Control ◽  
Urban Site ◽  
Biogenic Emissions ◽  
Industrial Emissions ◽  
Photochemical Pollution ◽  
Volatile Organic

Abstract. Understanding the composition, temporal variability, and source apportionment of volatile organic compounds (VOCs) is necessary for determining effective control measures to minimize VOCs and its related photochemical pollution. To provide a comprehensive analysis of VOC sources and their contributions to ozone (O3) formation in the Yangtze River Delta (YRD) – a region experiencing highest rates of industrial and economic development in China, we conducted a one-year sampling exercise for the first time at an urban site in Nanjing (JAES site). Alkanes were the dominant group at the JAES site, contributing ~ 53 % to the observed total VOCs, followed by aromatics (~ 17 %), acetylene (~ 17 %), and alkenes (~ 13 %). We identified seasonal variability in TVOCs with maximum and minimum concentrations in winter and summer, respectively. A morning and evening peak and a daytime trough were identified in the diurnal VOCs patterns. We identified the source apportionments of VOCs and their contributions to photochemical O3 formation using the Positive Matrix Factorization (PMF) and observation-based model together with a Master Chemical Mechanism (MCM). The PMF model identified five dominant VOC sources, with highest contributions from diesel vehicular exhausts (34 ± 5 %), followed by gasoline vehicular exhausts (27 ± 3 %), industrial emissions (19 ± 2 %), fuel evaporation (15 ± 2 %) and biogenic emissions (4 ± 1 %). The results from the OBM-MCM model simulation inferred photochemical O3 formation to be VOC-limited at the JAES site when considering both the reactivity and abundance of the individual VOC species in each source category. Further, VOCs from vehicular and industrial emissions were found to be the dominant control on O3 formation, particularly the VOC species m,p-xylene, toluene and propene, which top priorities should be given to the alleviation of photochemical smog. However, when considering the reactivity and abundance of VOC species, the contribution of biogenic emissions to O3 pollution was significantly reduced. Our results therefore highlight the need to consider both the abundance and reactivity of individual VOC species in order to develop effective control strategies to minimize photochemical pollution in Nanjing.

scholarly journals Missing OH Reactivity in the Global Marine Boundary Layer

2019 ◽  
Author(s):  
Alexander B. Thames ◽  
William H. Brune ◽  
David O. Miller ◽  
Hannah M. Allen ◽  
Eric C. Apel ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Dimethyl Sulfide ◽  
Marine Boundary Layer ◽  
Limit Of Detection ◽  
Chemical Species ◽  
Four Seasons ◽  
Volatile Organic ◽  
The Difference

Abstract. The hydroxyl radical (OH) reacts with thousands of chemical species in the atmosphere, initiating their removal and the chemical reaction sequences that produce ozone, secondary aerosols, and gas-phase acids. OH reactivity, which is the inverse of OH lifetime, influences the OH abundance and the ability of OH to cleanse the atmosphere. The NASA Atmospheric Tomography (ATom) campaign used instruments on the NASA DC-8 aircraft to measure OH reactivity and more than 100 trace chemical species. ATom presented a unique opportunity to test the completeness of the OH reactivity calculated from the chemical species measurements by comparing it to the measured OH reactivity over two oceans across four seasons. Although the calculated OH reactivity was below the OH reactivity instrument's limit-of-detection for much of the free troposphere, the OHR instrument was able to measure the OH reactivity in and just above the marine boundary layer. The average measured value of OH reactivity in the marine boundary layer across all latitudes and all ATom phases was 1.9 s−1, which 0.5 s−1 larger than the average calculated OH reactivity. Concurrently, missing OH reactivity, the difference between the measured and calculated OH reactivity, was measured to be ~ 0.5–2.0 s−1 at some locations in the tropics and midlatitudes. Correlations of missing OH reactivity with formaldehyde, dimethyl sulfide, butanal, and sea surface temperature suggest the presence of unmeasured or unknown volatile organic compounds or oxygenated volatile organic compounds associated with ocean emissions.

scholarly journals Emissions of Volatile Organic Compounds (VOCs) from an Open-Circuit Dry Cleaning Machine Using a Petroleum-Based Organic Solvent: Implications for Impacts on Air Quality

Atmosphere ◽  
2021 ◽  
Vol 12 (5) ◽  
pp. 637
Author(s):  
Hyeonji Lee ◽  
Kyunghoon Kim ◽  
Yelim Choi ◽  
Daekeun Kim
Keyword(s):  
Air Quality ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Organic Solvents ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Tropospheric Chemistry ◽  
Dry Cleaning ◽  
Volatile Organic ◽  
Vocs Emission

Volatile organic compounds (VOCs) are known to play an important role in tropospheric chemistry, contributing to ozone and secondary organic aerosol (SOA) generation. Laundry facilities, using petroleum-based organic solvents, are one of the sources of VOCs emissions. However, little is known about the significance of VOCs, emitted from laundry facilities, in the ozone and SOA generation. In this study, we characterized VOCs emission from a dry-cleaning process using petroleum-based organic solvents. We also assessed the impact of the VOCs on air quality by using photochemical ozone creation potential and secondary organic aerosol potential. Among 94 targeted compounds including toxic organic air pollutants and ozone precursors, 36 compounds were identified in the exhaust gas from a drying machine. The mass emitted from one cycle of drying operation (40 min) was the highest in decane (2.04 g/dry cleaning). Decane, nonane, and n-undecane were the three main contributors to ozone generation (more than 70% of the total generation). N-undecane, decane, and n-dodecane were the three main contributors to the SOA generation (more than 80% of the total generation). These results help to understand VOCs emission from laundry facilities and impacts on air quality.

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