Multiphase Reactions between Organic Peroxides and Sulfur Dioxide in Internally Mixed Inorganic and Organic Particles: Key Roles of Particle Phase Separation and Acidity.

Organic peroxides (POs) are ubiquitous in the atmosphere and particularly reactive toward dissolved sulfur dioxide (SO2), yet the reaction kinetics between POs and SO2, especially in complex inorganic-organic mixed particles, remain poorly constrained. Here, we report the first investigation of the multiphase reactions between SO2 and POs in monoterpene-derived secondary organic aerosol internally mixed with different inorganic salts (ammonium sulfate, ammonium bisulfate, or sodium nitrate). We find that when the particles are phase-separated, the PO-S(IV) reactivity is consistent with that measured in pure SOA and depends markedly on the water content in the organic shell. However, when the organic and inorganic phases are miscible, the PO-S(IV) reactivity varies substantially among different aerosol systems, mainly driven by their distinct acidities (not by ionic strength). The second-order PO-S(IV) rate constant decreases monotonically from 5 × 105 to 75 M-1 s-1 in the pH range of 0.1-5.6. Both proton catalysis and general acid catalysis contribute to S(IV) oxidation, with their corresponding third-order rate constants determined to be (6.4 ± 0.7) × 106 and (6.9 ± 4.6) × 104 M-2 s-1 at pH 2-6, respectively. The measured kinetics imply that the PO-S(IV) reaction in aerosol is an important sulfate formation pathway, with the reaction kinetics dominated by general acid catalysis at pH > 3 under typical continental atmospheric conditions.

Isomer-Resolved Reactivity of Organic Peroxides in Monoterpene-Derived Secondary Organic Aerosol.

Organic peroxides play a vital role in the formation, evolution, and health impacts of atmospheric aerosols, yet their molecular composition and fate in the particle phase remain poorly understood. Here, we identified, using iodometry-assisted liquid chromatography mass spectrometry, a large suite of isomer-resolved peroxide monomers (C8-10H12-18O5-8) and dimers (C15-20H22-34O5-14) in secondary organic aerosol formed from ozonolysis of the most abundant monoterpene (α-pinene). Combining aerosol isothermal evaporation experiments and multilayer kinetic modeling, bulk peroxides were found to undergo rapid particle-phase chemical transformation with an average lifetime of several hours under humid conditions, while the individual peroxides decompose on timescales of half an hour to a few days. Meanwhile, the majority of isomeric peroxides exhibit distinct particle-phase behaviors, highlighting the importance of the characterization of isomer-resolved peroxide reactivity. Furthermore, the reactivity of most peroxides increases with aerosol water content faster in a low relative humidity (RH) range than in a high RH range. Such non-uniform water effects imply a more important role of water as a plasticizer than as a reactant in influencing the peroxide reactivity. The high particle-phase reactivity of organic peroxides and its striking dependence on RH should be considered in atmospheric modeling of their fate and impacts on aerosol chemistry and health effects.

Acylperoxy Radicals as Key Intermediates in the Formation of Dimeric Compounds in α-Pinene Secondary Organic Aerosol.

High molecular weight dimeric compounds constitute a significant fraction of secondary organic aerosol (SOA) and have profound impacts on the properties and lifecycle of particles in the atmosphere. Although different formation mechanisms involving reactive intermediates and/or closed-shell monomeric species have been proposed for the particle-phase dimers, their relative importance remains in debate. Here, we report unambiguous experimental evidence of the important role of acyl organic peroxy radicals (RO2) and a small but non-negligible contribution from stabilized Criegee intermediates (SCIs) in the formation of particle-phase dimers during ozonolysis of α-pinene, one of the most important precursors for biogenic SOA. Specifically, we find that acyl RO2-involved reactions explain 50-80% of total oxygenated dimer signals (C15-C20, O/C ≥ 0.4) and 20-30% of the total less oxygenated (O/C < 0.4) dimer signals. In particular, they contribute to 70% of C15-C19 dimer ester formation, likely mainly via the decarboxylation of diacyl peroxides arising from acyl RO2 cross-reactions. In comparison, SCIs play a minor role in the formation of C15-C19 dimer esters but react noticeably with the most abundant C9 and C10 carboxylic acids and/or carbonyl products to form C19 and C20 dimeric peroxides, which are prone to particle-phase transformation to form more stable dimers without the peroxide functionality. This work provides a clearer view of the formation pathways of particle-phase dimers from α-pinene oxidation and would help reduce the uncertainties in future atmospheric modeling of the budget, properties, and health and climate impacts of SOA.

The use of stable oxygen and nitrogen isotopic signatures to reveal variations in the nitrate formation pathways and sources in different seasons and regions in China.

Nitrate (NO3-) is one of the most important inorganic ions in fine particulate (PM2.5) and drives regional haze formation; however, the NO3- sources and formation mechanisms in different seasons and regions are still debated. Here, PM2.5 samples were collected from Kunming and Nanning in southwestern China from September 1, 2017, to February 28, 2018 (spanning warm and cold months). We measured the daily O and N isotopic compositions of NO3- (δ18O-NO3- and δ15N-NO3-), estimated the δ18O-HNO3 values produced by different oxidation pathways, and quantified the NO3- formation pathways based on the isotope mass-balance equation. Our results showed that the δ18O-NO3- values in Kunming (65.3 ± 7.6‰) and Nanning (67.7 ± 10.1‰) are close to the δ18O-HNO3 values arising from the OH radical pathway (POH, 54.7 ± 1.2‰ to 61.2 ± 1.8‰), suggesting that the δ18O-NO3- values are mainly influenced by POH, which showed a contribution greater than 74%. Stronger surface solar radiation and higher air temperatures in low-latitude regions and warm months increased the amount of HNO3 produced by POH and reduced the amount of HNO3 produced by PN2O5, which produced low δ18O-NO3- values. Increased air pollution emissions decreased the contribution from POH and increased the contribution from N2O5 and NO3 pathways (PN2O5+NO3). The δ15N-NO3- values of PM2.5 in Kunming (7.3 ± 2.8‰) were slightly higher than those in Nanning (2.8 ± 2.7‰). The increased NOx emissions with positive isotopic values led to high δ15N-NO3- values in northern China and during cold months. A higher fNO2 (fNO2 = NO2/(NO + NO2), temperature, and contribution of POH produced lower N isotope fractionation between NOx and δ15N-NO3-, which was found to further decrease the δ15N-NO3- values in southwestern China and during warm months.

Abiotic and Biological Degradation of Atmospheric Proteinaceous Matter Can Contribute Significantly to Dissolved Amino Acids in Wet Deposition.

Atmospheric proteinaceous matter is characterized by ubiquity and potential bioavailability. However, little is known about the origins, secondary production processes, and biogeochemical role of proteinaceous matter in wet deposition. Precipitation samples were collected in suburban Guiyang (southwestern China) over a 1 year period to investigate their chemical components, mainly including dissolved combined amino acids (DCAAs), dissolved free AAs (DFAAs), and nonleachable particulate AAs (PAAs). Glycine was most abundant in the DFAAs, while the dominant species in DCAAs and PAAs was glutamic acid (including deaminated glutamine). The total DCAA, DFAA, and PAA concentrations peaked on average in spring (min. in summer). On average, the contribution of DCAA-nitrogen (median of 3.44%) to dissolved organic nitrogen was 5-fold higher than that of DFAA-nitrogen (median of 0.60%). Correlation analyses of AAs with ozone, nitrogen dioxide, and the quantitative degradation index suggest that DC(/F)AAs are linked with both abiotic and biological degradation of proteinaceous matter. Moreover, the high FAA scavenging ratios indicate the presence of postdepositional degradation of atmospheric proteinaceous matter. Further, the positive matrix factorization results suggest that the degradation of atmospheric proteinaceous matter markedly contributes to DCAAs and DFAAs in precipitation. Overall, the results suggest that the secondary processes involved in the degradation of atmospheric proteinaceous matter significantly promote direct bioavailability of AA-nitrogen.

Effects of cadmium stress on growth and amino acid metabolism in two Compositae plants.

Cadmium, a high toxic heavy metal, is one of the most serious contaminants in soil and a potential threat to plant growth and human health. Amino acid metabolism has the central role in heavy metal stress resistance of plants. In this paper, a pot experiment was carried out to study the effects of different concentrations of cadmium (0, 3, 6, 12, 30 mg kg-1) on the growth, Cd accumulation and amino acid metabolism in two Compositae plants (Ageratum conyzoides L. and Crassocephalum crepidioides). The results showed that under cadmium stress, C. crepidioides accumulated more Cd in its shoot and was tolerant to Cd, whereas its low Cd-accumulating relative, A. conyzoides, suffered reduced growth. The Cd content in the aerial part of C. crepidioides exceeded the threshold of Cd-hyperaccumulator. Furthermore, the bioaccumulation factor (BCF) and biological transfer factor (BTF) values for Cd in C. crepidioides were > 1. Thus, C. crepidioides can be regarded as Cd-hyperaccumulator. The comparison between both studied plants indicated that Cd stress resulted in a differential but coordinated response of amino acid levels, which are playing a significant role in plant adaptation to Cd stress. Glu, Gln, Asp, Asn, Gaba, Val and Ala dominated the major amino acids. Higher Cd tolerance and Cd accumulation in C. crepidioides was associated with greater accumulation of free amino acids, especially for Gln and Asn, in C. crepidioides than in A. conyzoides.

Heavy metal contents and enrichment characteristics of dominant plants in wasteland of the downstream of a lead-zinc mining area in Guangxi, Southwest China.

A field investigation on the content of heavy metals in soils and 17 kinds of dominant plants from wasteland of the downstream of a Pb-Zn mine in Northwest Guangxi Zhuang Autonomous Region was carried out. The absorption and accumulation characteristics of heavy metals between plants and soil were compared, and the candidate species for ecosystem restoration of the area were selected. The results indicated that the soils had been subjected to pollution of heavy metals in varying degrees. The concentrations of Cd, Pb, Zn were 46.5, 57.3 and 23.7 times higher than their corresponding background values, respectively. The contents of Cd, Pb and Zn in the most analyzed plants exceed the normal ranges and the phytotoxic level. C. crepidioides, S. nigrum, B. pilosa, C. Canadensis, A. conyzoides, I. denticulata and E. crusgali showed strong capability in accumulation and transport of Cd, and they could be used as good candidates for Cd- phytoextraction. Among which, Cd concentration in the aerial part of C. crepidioides exceeded the threshold of Cd-hyperaccumulator. Thus, C. crepidioides demonstrated the basic characteristics of a Cd-hyperaccumulator. The lower translocation ratios for Cd, Cu, Zn and Pb in P. vittata and C. chinensis make them suitable for phytostabilization in the study area.

Sources and influences of atmospheric nonpolar organic compounds in Nanchang, central China: Full-year monitoring with a focus on winter pollution episodes.

Nonpolar organic compounds (NPOCs) are found in atmospheric aerosols and have significant implications for environmental and human health. Although many studies have quantitatively estimated the sources of NPOCs in different cities, few have evaluated their main influencing factors (e.g., emissions and meteorological conditions) at relatively long (e.g., different seasons) and short timescales (e.g., several days during pollution episodes). A better understanding of this issue could optimise strategies for dealing with organic contamination in atmospheric particulate matter. NPOCs (including n-alkanes, PAHs and hopanes) in fine particulate matter (PM2.5) were sampled daily at Nanchang, China, from 1 November 2020 to 31 October 2021. Analyses of specific biomarkers and diagnostic ratios indicate that the NPOCs mainly had anthropogenic sources. The quantitative estimates of a positive matrix factorization model show that fossil fuel and biomass combustion were the main sources of n-alkanes (contributing 64.8 %), while vehicle exhaust was the main source of PAHs (47.0 %) and hopanes (52.3 %). Seasonally, the contributions from coal and/or biomass combustion were higher in autumn and winter (40.2-56.3 %) than in spring and summer (25.7-44.3 %), while contributions from natural plants, petroleum volatilization and vehicle exhaust were higher in spring and summer (14.7-63.5 %) than in autumn and winter (8.1-48.9 %). Redundancy analysis shows that increased emissions, especially from coal and/or biomass combustion, are the main cause of increases in NPOCs, during both annual sampling periods and winter pollution episodes. Over the year, higher temperature and longer sunshine hours correspond to lower NPOC concentrations. In winter pollution episodes, increases in temperature and relative humidity correspond to increases in NPOC concentrations. Our results suggest that controlling primary emissions, especially from coal and biomass combustion, may be an effective way to prevent increases in NPOC concentrations.

Characterizing leaf-deposited particles: Single-particle mass spectral analysis and comparison with naturally fallen particles.

The size and composition of particulate matter (PM) are pivotal in determining its adverse health effects. It is important to understand PM's retention by plants to facilitate its atmospheric removal. However, the distinctions between the size and composition of naturally fallen PM (NFPM) and leaf-deposited PM (LDPM) are not well-documented. Here we utilize a single-particle aerosol mass spectrometer, coupled with a PM resuspension chamber, to analyze these differences. We find that LDPM particles are 6.8-97.3 % larger than NFPM. Employing a neural network algorithm based on adaptive resonance theory, we have identified distinct compositional profiles: NFPM predominantly consists of organic carbon (OC; 31.2 %) and potassium-rich components (19.1 %), whereas LDPM are largely composed of crustal species (53.9-60.6 %). Interestingly, coniferous species retain higher OC content (11.5-13.7 %) compared to broad-leaved species (0.5-1.2 %), while the levoglucosan content exhibit an opposite trend. Our study highlights the active role of tree leaves in modifying PM composition beyond mere passive capture, advocating for a strategic approach to species selection in urban greening initiatives to enhance PM mitigation. These insights provide guidance for urban planners and environmentalists in implementing nature-based solutions to improve urban air quality.

Multiphase interactions between sulfur dioxide and secondary organic aerosol from the photooxidation of toluene: Reactivity and sulfate formation.

There is growing evidence that the interactions between sulfur dioxide (SO2) and organic peroxides (POs) in aerosol and clouds play an important role in atmospheric sulfate formation and aerosol aging, yet the reactivity of POs arising from anthropogenic precursors toward SO2 remains unknown. In this study, we investigate the multiphase reactions of SO2 with secondary organic aerosol (SOA) formed from the photooxidation of toluene, a major type of anthropogenic SOA in the atmosphere. The reactive uptake coefficient of SO2 on toluene SOA was determined to be on the order of 10-4, depending strikingly on aerosol water content. POs contribute significantly to the multiphase reactivity of toluene SOA, but they can only explain a portion of the measured SO2 uptake, suggesting the presence of other reactive species in SOA that also contribute to the particle reactivity toward SO2. The second-order reaction rate constant (kII) between S(IV) and toluene-derived POs was estimated to be in the range of the kII values previously reported for commercially available POs (e.g., 2-butanone peroxide and 2-tert-butyl hydroperoxide) and the smallest (C1-C2) and biogenic POs. In addition, unlike commercial POs that can efficiently convert S(IV) into both inorganic sulfate and organosulfates, toluene-derived POs appear to mainly oxidize S(IV) to inorganic sulfate. Our study reveals the multiphase reactivity of typical anthropogenic SOA and POs toward SO2 and will help to develop a better understanding of the formation and evolution of atmospheric secondary aerosol.

Pollution characteristics, sources, and health risks of phthalate esters in ambient air: A daily continuous monitoring study in the central Chinese city of Nanchang.

In recent years, the atmospheric pollution caused by phthalate esters (PAEs) has been increasing due to the widespread use of PAE-containing materials. Existing research on atmospheric PAEs lacks long-term continuous observation and samples from cities in central China. To investigate the pollution characteristics, sources, and health risks of PAEs in the ambient air of a typical city in central China, daily PM2.5 samples were collected in Nanchang from November 2020 to October 2021. In this study, the detection and quantification of six significant PAE contaminants, namely diethyl phthalate (DEP), di-n-butyl phthalate (DnBP), diisobutyl phthalate (DIBP), Di-2-ethylhexyl phthalate (DEHP), di-n-octyl phthalate (DnOP), and diisodecyl phthalate (DIDP), were accomplished using gas chromatography and mass spectrometry. The results revealed that the concentrations of DEP, DnBP, DEHP, and DnOP were relatively high. Higher temperatures promote the volatilization of PAEs, leading to an increase in the gaseous and particulate PAE concentrations in warm seasons and winter pollution scenarios. The results of principal component analysis show that PAEs mainly come from volatile products and polyvinylchloride plastics. Using positive matrix factorization analysis, it is shown that these two sources contribute 67.0% and 33.0% in atmosphere PAEs, respectively. Seasonally, the contribution of volatile products to both gaseous and particulate PAEs substantially increases during warm seasons. The residents in Nanchang exposed to PAEs have a negligible non-cancer risk and a potential low cancer risk. During the warm seasons, more PAEs are emitted into the air, which will increase the toxicity of PAEs and their impact on human health.

Kinetic nitrogen isotope effects of 18 amino acids degradation during burning processes.

Understanding the nitrogen isotopic variations of individual amino acids (AAs) is essential for utilizing the nitrogen isotope values of individual amino acids (δ15N-AA) as source indicators to identify proteinaceous matter originating from biomass combustion processes. However, the nitrogen isotope effects (ε) associated with the degradation of individual amino acids during combustion processes have not been previously explored. In this study, we measured the nitrogen isotope values of residual free amino acids -following a series of controlled combustion experiments at temperatures of 160-240 °C and durations of 2 min to 8 h, as described in Part 1. δ15N values of proline, aspartate, alanine, valine, glycine, leucine, and isoleucine are more positive than their initial δ15N values after prolonged combustion. Variations in δ15N values of the most AAs conform to the Rayleigh fractionation during combustion and their nitrogen isotope effects (ε) are greatly impacted by their respective combustion degradation pathways. This is the first time the ε values associated with the degradation pathways of AAs during combustion have been characterized. Only the ε values associated with Pathway 1 (dehydration to form dipeptide) and 2 (simultaneous deamination and decarboxylation) are found to be significant and temperature-dependent, ranging from + 2.9 to 6.4‰ and + 0.9‰ to + 3.8‰, respectively. Conversely, ε values associated with other pathways are minor. This improves the current understanding on the degradation mechanisms of protein nitrogen during biomass burning.

Enhanced aerosols over the southeastern Tibetan Plateau induced by open biomass burning in spring 2020.

The Tibetan Plateau is the third pole of the world, with an essential role in regulating Northern Hemisphere climate. Previous studies showed that atmospheric aerosols over the Tibetan Plateau are influenced by biomass burning (BB) products from South and Southeast Asia. In fact, open biomass burning (OBB) is also an important form of BB in Southeast Asian countries, causing serious springtime air pollution yearly. However, there are still scientific gaps in the contribution of OBB to surrounding regional aerosols, especially on the Tibetan Plateau. In order to quantify this contribution, we collected samples of fine particulate matter and derived the concentrations of major water soluble ion, water soluble organic carbon (WSOC), and total carbon (TC) and total nitrogen (TN) as well as the dual isotopic compositions of carbon and nitrogen (δ13C and δ15N) during March-June on the southeastern Tibetan Plateau. δ13C and δ15N showed no significant difference (p > 0.05) between the OBB and non-OBB periods. Furthermore, both δ13C and δ15N (-25.7 ± 0.7 ‰ and 8.0 ± 3.6 ‰) values calculated during the whole sampling period were similar to the BB value, indicating that the primary source of TC and TN in aerosols was BB, whether OBB or non-OBB burning periods. TC and TN concentrations during the OBB period (6.5 ± 2.9 µg m-3 and 1.2 ± 0.4 µg m-3, respectively) were significantly higher than during the non-OBB period (4.1 ± 1.7 µg m-3, with p = 0.014, and 0.7 ± 0.3 µg m-3, with p = 0.013, respectively). Active fire data and surface smoke concentrations further indicated that BB emissions from Southeast Asia were higher during the OBB period. This suggests that OBB-related high BB emissions significantly enhanced atmospheric aerosols concentrations on the southeastern Tibetan Plateau.

Tracing sources of coal combustion using stable sulfur isotope ratios in epilithic mosses and coals from China.

In China, coal combustion is the most important source of atmospheric sulfur pollution. Moss sulfur isotopic signatures have been believed to hold source-specific information that can serve as a fingerprint to identify atmospheric sulfur sources. In cities where only local coals were combusted, we observed a good correspondence of average sulfur isotope ratios in urban mosses (Haplocladium microphyllum) to the values of local coals (δ(coals) = 1.455δ(mosses)- 3.945, R(2) = 0.975, p = 0.01). But if different types of coals were combusted, we did not know whether moss sulfur isotope ratios can indicate mixed coals. To confirm this, using a mixing model we estimated the ratios of imported coal to local coals at cities where both coals were used. We found that the estimated ratios at large cities (>1 million people) where both coals were used were similar to the reported ratios in their respective provinces. For small cities (<0.5 million people) in Jiangxi Province and other provinces, the estimated ratios were higher than the reported ratios because the relatively cheaper local coals were less used in all the small cities except in cities where local coal deposits were found nearby. The comparison results showed that moss sulfur isotope is a useful tool for indicating coal-derived sulfur even in cities where mixed coals were combusted.

Evaluation of black carbon source apportionment based on one year's daily observations in Beijing.

Combustion-derived black carbon (BC) is increasingly recognized as a significant pollutant that can have adverse effects on the atmospheric environment, human health, and regional climate. Fossil fuel combustion is the main source of BC, yet understanding of the relative contributions to BC from coal and liquid fuel combustion remains incomplete. Moreover, few studies have assessed the relative contributions based on long-term continuous daily field observations. This study adopted a Bayesian model of a three-dimensional array of a stable carbon isotope and the ratios of non-sea-salt K+ to BC and ΔBC/ΔCO of one year's daily observations (from September 1, 2017 to August 31, 2018) to constrain source apportionment of BC in Beijing (China). Results showed that both the BC and the carbon isotope concentrations exhibited strong seasonal variability, and that the annual BC concentration has decreased significantly in recent years. The Bayesian model results also revealed that the relative contributions from the combustion of coal, liquid fuel, and biomass were 42% ± 18%, 42% ± 18%, and 16% ± 11%, respectively, with a larger contribution from coal (liquid fuel) combustion in winter and spring (summer and autumn). The seasonal variation of source appointment was attributed to local and regional fuel combustion coupled with meteorological conditions. With increasing PM2.5 level, the BC concentration derived from biomass burning increased fastest, followed by that derived from coal combustion. But concentration of secondary inorganic ions increased faster than BC as PM2.5 increased.

Isotopic source analysis of nitrogen-containing aerosol: A study of PM2.5 in Guiyang (SW, China).

The source of fine particulate matter (PM2.5) has been a longstanding subject of debate, the nitrogen-15 isotope (δ15N) has been used to identify the major sources of atmospheric nitrogen. In this study, PM2.5 samples (n = 361) were collected from September 2017 to August 2018 in the urban area of Guiyang (SW, China), to investigate the chemical composition and potential sources of PM2.5. The results showed an average PM2.5 of 33.0 µg m-3 ± 20.0 µg m-3. The concentration of PM2.5 was higher in Winter, lower in Summer. The major water resolved inorganic ions (WSIIs) were Ca2+, NH4+, Na+, SO42-, NO3-, Cl-. Nitrogen-containing aerosols (i.e., NO3- and NH4+) suddenly strengthened during the winter, when NO3- became the dominant contributor. Over the sampling period, the molar ratio of NH4+/(NO3- + 2 × SO42-) ranged from 0.1 to 0.9, thus indicating the full fixation of NH4+ by existing NO3- and SO42- in PM2.5. The annual value of NOR was 0.1 while rised to 0.5 in Winter. The variations of NOR (Nitrogen oxidation ratio) (0.1-0.5) values suggest that the secondary formation of NO3- occurred every season and was most influential during the winter. The total particulate nitrogen (TN) δ15N value of PM2.5 ranged from -5.9‰ to 25.3‰ over the year with annual mean of +11.8‰ ± 4.7‰, whereas it was between -5.9‰ and 14.3‰ during the winter with mean of 7.0‰ ± 3.8‰. A Bayesian isotope mixing model (Stable Isotope Analysis in R; SIAR) was applied to analyze the nitrogen sources. The modeling results showed that 29%, 21%, and 40% of TN in PM2.5 during the winter in Guiyang was due to nitrogen-emissions from coal combustion, vehicle exhausts, and biomass burning, respectively. Our results demonstrate that biomass burning was the main contributor to PM during the winter, 80% of the air mass comes from rural areas of Guizhou border, this transport process can increase the risk of particulate pollution in Guiyang.

Oxidation and sources of atmospheric NOx during winter in Beijing based on δ18O-δ15N space of particulate nitrate.

The determination of both stable nitrogen (δ15N-NO3-) and stable oxygen (δ18O-NO3-) isotopic signatures of nitrate in PM2.5 has shown potential for an approach of assessing the sources and oxidation pathways of atmospheric NOx (NO+NO2). In the present study, daily PM2.5 samples were collected in the megacity of Beijing, China during the winter of 2017-2018, and this new approach was used to reveal the origin and oxidation pathways of atmospheric NOx. Specifically, the potential of field δ15N-NO3- signatures for determining the NOx oxidation chemistry was explored. Positive correlations between δ18O-NO3- and δ15N-NO3- were observed (with R2 between 0.51 and 0.66, p < 0.01), and the underlying environmental significance was discussed. The results showed that the pathway-specific contributions to NO3- formation were approximately 45.3% from the OH pathway, 46.5% from N2O5 hydrolysis, and 8.2% from the NO3+HC channel based on the δ18O-δ15N space of NO3-. The overall nitrogen isotopic fractionation factor (εN) from NOx to NO3- on a daily scale, under winter conditions, was approximately +16.1‰±1.8‰ (consistent with previous reports). Two independent approaches were used to simulate the daily and monthly ambient NOx mixtures (δ15N-NOx), respectively. Results indicated that the monthly mean values of δ15N-NOx compared well based on the two approaches, with values of -5.5‰ ± 2.6‰, -2.7‰ ± 1.9‰, and -3.2‰ ± 2.2‰ for November, December, and January (2017-2018), respectively. The uncertainty was in the order of 5%, 5‰ and 5.2‰ for the pathway-specific contributions, the εN, and δ15N-NOx, respectively. Results also indicated that vehicular exhaust was the key contributor to the wintertime atmospheric NOx in Beijing (2017-2018). Our advanced isotopic perspective will support the future assessment of the origin and oxidation of urban atmospheric NOx.

The impacts of reservoirs on the sources and transport of riverine organic carbon in the karst area: A multi-tracer study.

Reservoirs have been constructed as clean energy sources in recent decades with various environmental impacts. Karst rivers typically exhibit high dissolved inorganic carbon (DIC) concentrations, whether and how reservoirs affect carbon cycling, especially organic carbon (OC)-related biogeochemical processes in karst rivers, are unclear. To fill this knowledge gap, multiple tracer methods (including fluorescence excitation-emission matrix (EEM), ultraviolet (UV) absorption, and stable carbon (δ13C) and radiocarbon (Δ14C) isotopes) were utilized to track composition and property changes of both particulate OC (POC) and dissolved OC (DOC) along river-transition-reservoir transects in the Southwest China karst area. The changes in chemical properties indicated that from the river to the reservoir, terrestrial POC is largely replaced by phytoplankton-derived OC, while gradual coloured dissolved organic matter (CDOM) removal and addition of phytoplankton-derived OC to the DOC pool occurred as water flowed to the reservoir. Higher primary production in the transition area than that in the reservoir area was observed, which may be caused by nutrient released from suspended particles. Within the reservoir, the production surpassed degradation in the upper 5 m, resulting in a net DIC transformation into DOC and POC and terrestrial DOM degradation. The primary production was then gradually weakened and microbial degradation became more important down the profile. It is estimated that ~3.1-6.3 mg L-1 (~15.5-31.5 mg-C m-2 (~10-21%)) DIC was integrated into the OC pool through the biological carbon pump (BCP) process in the upper 5 m in the transition and reservoir areas. Our results emphasize the reservoir impact on riverine OC transport, and due to their characteristics, karst areas exhibit a higher BCP potential which is sensitive to human activities (more nutrient are provided) than non-karst areas.

Changes in nitrate accumulation mechanisms as PM2.5 levels increase on the North China Plain: A perspective from the dual isotopic compositions of nitrate.

Nitrate (NO3-) has become recognized as the most important water-soluble ion in fine particulate (PM2.5), and has been proposed as a driving factor for regional haze formation. However, nitrate formation mechanisms are still poorly understood. In this study, PM2.5 samples were collected from September 2017 to August 2018 in Shijiazhuang, a city located on the North China Plain, and NO3-concentration, δ18O-NO3- and δ15N-NO3- values in PM2.5 were analyzed. NO3- concentrations increased as PM2.5 levels increased during both polluted and non-polluted days over the entire year. δ18O-NO3- values during cold months (63.5-103‰) were higher than those during warm months (50.3-85.4‰), these results suggested that the nitrate formation pathways shifted from the NO2 + OH (POH) in warm months to the N2O5 + H2O (PN2O5) and NO3 + VOCs (PNO3) pathways in cold months. Especially during cold months, δ18O-NO3- values increased from 65.2-79.9‰ to 80.7-96.2‰ when PM2.5 increased from ∼25 to >100 µg/m3, but when PM2.5 > 100 µg/m3, there were relatively small variations in δ18O-NO3-. These results suggested that nitrate formation pathways changed from POH to PN2O5 and PNO3 pathways when PM2.5 < 100 µg/m3, but that PN2O5 and PNO3 dominated nitrate production when PM2.5 > 100 µg/m3. Higher δ15N-NO3- values in warm months (-11.8-13.8‰) than in cold months (-0.7-22.6‰) may be attributed to differences in NOx emission sources and nitrogen isotopic fractionation among NOx and NO3-. These results provide information on the dual isotopic compositions of nitrate to understand nitrate formation pathways under different PM2.5 levels.

Methylmercury biomagnification in aquatic food webs of Poyang Lake, China: Insights from amino acid signatures.

As the dominant mercury species in fish, methylmercury (MeHg) biomagnifies during its trophic transfer through aquatic food webs. MeHg is known to bind to cysteine, forming the complex of MeHg-cysteine. However, relationship between MeHg and cysteine in large-scale food webs has not been explored and contrasted with MeHg biomagnification models. Here, we quantified the compound-specific nitrogen isotopic analysis of amino acids (CSIA-AA), MeHg, and amino acid composition in aquatic organisms of Poyang Lake, the largest freshwater lake in China. The trophic positions (TPAA) of organisms ranged from 1.0 ± 0.1-3.7 ± 0.2 based on CSIA-AA approach. The trophic magnification factor (TMF) of MeHg, derived from the regression slope of Log-transformed MeHg in organisms upon their TPAA for the entire food web was 9.5 ± 0.5. Significantly positive regression between MeHg and cysteine (R2 = 0.64, p < 0.01) was documented, suggesting MeHg-cysteine complex may potentially play a critical role in the bioaccumulation of MeHg. Furthermore, TMFs of MeHg calculated with and without cysteine normalization compared well (7.7-8.7) when excluding primary producers. Our results implied that MeHg may biomagnify as the complex of MeHg-cysteine and contribute to our understanding of MeHg trophic transfer at the molecular level.