ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2024
·
IF 10.8
Wangjin Yang,Hui Ji,Fu Li,Xue He,Shan Zhang,Xiangli Nan,Tao Du,Kun Li,Chong Han
Nitrites (NO2–/HONO), as the primary source of hydroxyl radicals (•OH) in the atmosphere, play a key role in atmospheric chemistry. However, the current understanding of the source of NO2–/HONO is insufficient and therefore hinders the accurate quantification of atmospheric oxidation capacity. Herein, we highlighted an overlooked HONO source by the reaction between nitrophenols (NPs) and •OH in the aqueous phase and provided kinetic data to better evaluate the contribution of this process to atmospheric HONO. Three typical NPs, including 4-nitrophenol (4NP), 2-nitrophenol (2NP), and 4-nitrocatechol (4NC), underwent a denitration process to form aqueous NO2– and gaseous HONO through the •OH oxidation, with the yield of NO2–/HONO varied from 15.0 to 33.5%. According to chemical composition and structure analysis, the reaction pathway, where the ipso addition of •OH to the NO2 group on 4NP generated hydroquinone, can contribute to more than 61.9% of the NO2–/HONO formation. The aqueous photooxidation of NPs may account for HONO in the atmosphere, depending on the specific conditions. The results clearly suggest that the photooxidation of NPs should be considered in the field observation and calculation to better evaluate the HONO budget in the atmosphere.
研究领域:
大气化学
·
环境科学
✓ 已验证
DOI
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2024
·
IF 10.8
Qiong Li,Shuaishuai Ma,Qiuyue Ge,Xinyuan Wu,Yu Liu,Xiang Tu,Liwu Zhang,Hongbo Fu
Significant discrepancies persist between field observations and model simulations regarding the strength of marine-derived HONO sources, underscoring the urgency to resolve unidentified HONO sources. In this study, sodium dodecyl sulfate (SDS) was chosen as a proxy for marine surfactants to investigate its impact on aqueous nitrate photolysis for the first time. Remarkable increases in HONO and NO2 production rates by factors of 3.3 and 5.6, respectively, along with a 1.9-fold rise in NO2– concentration, were observed at a very low SDS concentration of 0.01 mM, strongly illustrating the promoting effect on nitrate photolysis. Furthermore, at an SDS concentration of 2 mM, intriguingly aligned with the critical micelle concentration, there was an additional 41.7% increase in HONO production rates. Vertically resolved Raman measurements indicated that SDS anions at the aqueous-air interface attracted NO3– closer to the aqueous surfaces, increasing the amount of incompletely solvated surface nitrate. Importantly, the anionic surfactant exhibited a greater promoting effect on HONO production compared to other typical nitrate photochemistry systems with the addition of a marine dissolved organic matter proxy, halogen, photosensitizer, or OH scavenger. These findings offer new insights into marine-derived HONO sources and should be considered in model simulations concerning the budgets of NOx, OH, and O3.
研究领域:
大气化学
·
环境科学
·
海洋化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Frontiers in Environmental Science
·
2024
·
IF 3.3
Zhao Yilong,Liu Chengwei,Tu Xiang,Huang Wenkai,Liu Yu,Fu Hongbo
Field observations have confirmed that halide ions are widely distributed among aerosols from the marine boundary layer and on the surfaces of ice and snow in polar regions. Consequently, the coexistence of halide ions may play a more significant role in nitrate photolysis than previously thought. In this study, we simultaneously measured HONO, NO2, and NO2− in situ to gain a deeper understanding of the coexisting system, including the photogenerated nitrogen products and the effects on nitrate photolysis rates due to enhanced aqueous nitrite and HONO transfer rates by halides. The presence of halides significantly increased the photogenerated nitrogen products across various molar ratios ([X–]/[NO3−]) at pH 3.5. By eliminating oxygen flux, the transformation of the primary photogenerated products was affected, resulting in higher concentrations of N(III) as both HONO and NO2−. Experiments involving OH scavengers indicated that the attack from·OH initiated by halides leads to side reactions that enhance nitrate photolysis. Both theoretical calculations and nitrate actinometry were used to determine the photolysis rate of nitrate solutions, which together indicated that the presence of halides enhances nitrate photolysis. A newly developed model was used to determine the HONO transfer rate, finding that the presence of halides ([X–]/[NO3−] = 0.2) enhanced the evaporation of N(III) in solution by factors of 0.68, 0.95, and 1.27 for Cl−, Br−, and I−, respectively. To our knowledge, this is the first determination of halide effects on the mass transfer of HONO. The enhanced nitrate photolysis rate can be attributed to the differential surface effects of halides and parallel reactions initiated via ·OH stemming from nitrate photolysis, with varying rates leading to different quantities of nitrogenous products. Additionally, simultaneous measurements of photoproducts in both gas and condensed phases are recommended to better constrain the rate constants of NO3− photolysis.
研究领域:
环境科学
·
大气化学
✓ 已验证
DOI
高影响因子
Atmospheric Pollution Research
·
2025
·
IF 3.5
Peng Cheng,Baobin Han,Zhilin Tian,Zhen Liu,Wenda Yang,Jianwei Gu,Xiaofang Yu,Hongli Wang,Min Zhou
Nitrous acid (HONO) greatly impacts tropospheric chemistry by producing hydroxyl radical (OH) through photolysis, and yet our knowledge about sources of HONO remains elusive. Emissions of nitrogen (N) containing gases from soils have long been a subject of research in biogeochemistry. Soil emissions of HONO have received greater attention recently, helping explain a missing source of observed atmospheric HONO. We conducted laboratory experiments to simultaneously measure emission fluxes of HONO along with other N containing gases including nitric oxide (NO), nitrous oxide (N 2 O), and ammonia (NH 3 ) from lateritic red soil samples, and evaluated the contributions of microbiological processes to HONO emissions by conducting process inhibiting experiments. Results from monitoring emissions during a full wet-drying cycle showed that the emissions of HONO, NO and N 2 O have a strong dependance on soil water content, with maximum fluxes for HONO (125 ± 17 ng N m −2 s −1 ), NO (115 ± 11 ng N m −2 s −1 ) and N 2 O (453 ± 100 ng N m −2 s −1 ) observed at 17 % (HONO), 42 % (NO) and 94 % (N 2 O) water filled pore space (WFPS), respectively, while NH 3 emission remains at ∼16 ng N m −2 s −1 in majority of the WFPS range. Results from process inhibiting experiments suggested ammonia oxidation to be the dominant pathway for HONO production in the low water-content range, while reduction of nitrate to NO 2 − appeared dominant in the high water-content range. Our study demonstrates the feasibility of studying emissions of HONO along with other N containing gases as connected network of processes as a whole.
研究领域:
生态学
·
环境科学
·
生物地球化学
✓ 已验证
产品关联
DOI
高影响因子
ATMOSPHERIC ENVIRONMENT
·
2022
·
IF 5.755
Wangjin Yang,Di You,Xiangli Nan,Ning Tang,Tao Du,Chong Han
The effects of aromatic carbonyls (ACs), polycyclic aromatic hydrocarbons (PAHs) and phenols (PHs) on the photolysis of nitroaromatic compounds (ArNO 2 ) in the solid phase were explored. The reactive nitrogen gas formation by the photolysis process was investigated in a cylindrical reactor coupled to a NO x analyzer. These organics had an enhanced or inhibited influence on the nitrous acid (HONO) and NO formations by the photolysis of 1-nitropyrene (NPy) and 5-nitrosalicylic acid (NSA), depending on the hydrogen abstraction and donation abilities of organics. Based on the high-performance liquid chromatography (HPLC) results, methyl-2-benzoylbenzoate (MBB), fluoranthene (FLA) and syringaldehyde (SG) showed a promoted effect on the photodegradation of NPy and NSA, as shown by an increase in the photolysis frequency of ArNO 2 ( J ArNO 2 ) by a factor of 1.19–2.76. Based on experimental results, the HONO source strength by the photolysis of ArNO 2 in organic aerosols was estimated to be lower than 1 ppt h −1 .
研究领域:
环境科学
·
大气化学
✓ 已验证
DOI
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2026
·
IF 12.2
Yiqun Cao,Huiying Xuan,Jun Liu,Hao Li,Peng Zhang,Tianzeng Chen,Yonghong Wang,Biwu Chu,Pengfei Liu,Yujing Mu,Qingxin Ma,Hong He
H2O2 is a vital atmospheric oxidant, while its photolysis in the troposphere is negligible in conventional view. For the first time, we find that gas-phase H2O2 can undergo heterogeneous photolysis to produce OH radicals on the surfaces of particles such as SiO2, Fe2O3, and Na2SO4 under solar irradiation, which further convert NO to produce HONO and NO2. It is demonstrated that acidity can inhibit the formation of HONO and promote the formation of NO2 significantly. Moreover, the heterogeneous photolysis of H2O2 is dependent on the reactivity of particles, with inert surfaces being more conducive to the generation of OH radicals. A MCM box model indicates that the HONO formation rate via the H2O2 heterogeneous reaction can reach 0.10 ppb·h–1 at 9 a.m., and the relative contribution to the total daytime HONO production can account for approximately 5% at 1 p.m. Given the ubiquitous presence of SiO2 in mineral dust particles, glass curtain walls, and terrestrial soils, these findings indicate that heterogeneous photolysis of H2O2 on the particle surface could be a potential source of daytime HONO. Our research also underscores the importance of atmospheric interfacial chemistry and its contribution to unknown sources of atmospheric oxidizing capacity.
✓ 已验证
DOI
PubMed
高影响因子
Environmental Science & Technology Letters
·
2021
·
IF 7.653
Wangjin Yang,Di You,Chunhui Li,Chong Han,Ning Tang,He Yang,Xiangxin Xue
Nitrous acid (HONO) significantly contributes to OH radicals in the atmosphere, whereas the HONO sources need to be urgently further explored. The photolysis of solid nitroaromatic compounds (Ar-NO2), including nitrophenols (NPs) and nitro-polycyclic aromatic hydrocarbons (NPAHs), was investigated in a cylindrical reactor coupled to a NOx analyzer at the ambient pressure. The formation of HONO and NOx (NOx = NO2 + NO) by the photolysis of five NPs and four NPAHs was quantified. HONO and NO formations from Ar-NO2 were obviously enhanced under irradiation. For NPs, the Ar-NO2 photolysis frequency for HONO (JAr-NO2→HONO) and NO (JAr-NO2→NO) formations varied in the range of (0.34–4.16) × 10–7 and (0.38–3.21) × 10–7 s–1, respectively. For NPAHs, JAr-NO2→HONO and JAr-NO2→NO were measured to be (0.02–2.01) × 10–5 and (0.001–1.59) × 10–4 s–1, respectively. The photolysis of Ar-NO2 in aerosols was estimated to establish a HONO source strength lower than 17 ppt·h–1, suggesting that the photolysis of Ar-NO2 may not well explain daytime HONO source strength in the atmosphere.
研究领域:
环境科学
·
大气化学
·
光化学
✓ 已验证
DOI
高影响因子
Nano Research
·
2024
·Vol. 17
·期 6
·4815-4824
·
IF 9.5
You Xingchao,Xu Jiawei,Zhuang Zechao,Xia Junkai,Wang Suwen,Wei Haiyan,Li Yongfu,Cai Yanjiang,Xiang Hai,Yu Bing
Developing electrocatalysts that exhibit both high activity and ammonia selectivity for nitrate reduction is a significant and demanding challenge, primarily due to the complex nature of the multiple-electron reduction process involved. An encouraging approach involves coupling highly active precious metals with transition metals to enhance catalytic performance through synergy. Here, we report a ruthenium-nickel alloy catalyst with nanosheets (Ru-Ni NSs) structure that achieves a remarkable ammonia Faradaic efficiency of approximately 95.93%, alongside a yield rate of up to 6.11 g·h −1 ·cm −2 . Moreover, the prepared Ru-Ni NSs exhibit exceptional stability during continuous nitrate reduction in a flow reactor for 100 h, maintaining a Faradaic efficiency of approximately 90% and an ammonia yield of 37.4 mg·L −1 ·h −1 using 0.05 M nitrate alkaline electrolyte. Mechanistic studies reveal that the catalytic process follows a two-step pathway, in which HONO serves as a migration intermediate. The presence of a partially oxidized Ru (002) surface enhances the adsorption of nitrate and facilitates the release of the migration intermediate by adjusting the strength of the electrostatic and covalent interactions between the adsorbate and the surface, respectively. On the other hand, the Ni (111) surface promotes the utilization of the migration intermediate and requires less energy for NH 3 desorption. This tandem process contributes to a high catalytic activity of Ru-Ni NSs towards nitrate reduction.
研究领域:
电化学
·
催化
·
纳米材料
·
环境化学
·
能量转换
·
材料科学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）