Wet depositional fluxes of fossil fuel-derived carbon in East Asia: Dynamics of Brown carbon.

Over the past 50 years, fossil fuel consumption has increased dramatically, rising approximately eight-fold since 1950 and doubling since 1980. This surge has led to increased emissions of brown carbon (BrC) into the atmosphere, which are subsequently deposited onto oceans and land through dry or wet deposition processes. However, the source-specific fluxes of atmospheric organic carbon (OC) and BrC into the ocean are not adequately represented in the global carbon cycle. For the first time, we calculated BrC concentration using the optical intensity of organic matter and determined the global wet depositional flux of fossil fuel-derived BrC. Using the ratio of humic-like substances to OC fluxes, we estimated the global wet deposition of fossil fuel-derived BrC to be 2.0 ± 0.6 Tg C yr-1. Of this amount, the flux into oceans (0.7 ± 0.2 Tg C yr-1) represents 1.6% of the production rate of refractory dissolved organic carbon (RDOC) in the ocean (43 Tg yr-1). Notably, an increase in the proportion of fossil fuel-derived BrC in atmospheric OC may change the composition of OC in precipitation, resulting in a more refractory composition, which deviates from previously established paradigms. Our findings indicate that the flux of fossil fuel-derived RDOC from the atmosphere into the ocean, which is inadequately represented in current global DOC cycling models, may play a significant role in oceanic carbon cycles. These findings necessitate reconsidering our understanding of oceanic carbon cycling and highlight the need to improve existing models to better account for these newly identified processes and their potential impacts on global carbon dynamics.

Chemical composition of cloud and rainwater at a high-altitude mountain site in western India: source apportionment and potential factors.

This study focuses on the chemical composition of cloud water (CW) and rainwater (RW) collected at Sinhagad, a high-altitude station (1450 m AMSL) located in the western region of India. The samples were collected during the monsoon over two years (2016-2017). The chemical analysis suggests that the concentration of total ionic constituents was three times higher in CW than in RW, except for NH4+ (1.0) and HCO3- (0.6). Compared to RW, high concentrations of SO42- and NO3- were observed in CW. The weighted average RW pH (6.5 ± 0.3) was slightly more alkaline than CW pH (6.1 ± 0.5). This can be attributed to the high concentrations of neutralizing ions such as nss-Ca2+, nss-Mg2+, K+, and NH4+, indicating the greater extent of wet scavenging during rainfall. These ions counteract the acidity generated by SO42- and NO3-. A high correlation between Ca2+, Na+, K+, NO3-, and SO42- makes it difficult to estimate the contribution of SO42- from different sources. Anthropogenic sulfur emissions and soil dust significantly influence the ionic composition of clouds and rain. Positive matrix factorization (PMF) was used to identify the contribution of different sources to the samples. In the CW, the extracted factors were cooking and vehicles, aging sea salt, agriculture, and dust. In RW, the factors were industries, cooking and vehicles, agriculture and dust, and aging sea salt. The findings of this study have significant implications for the monsoon build-up, ecosystems, agriculture, and climate change.

[Evolution of Physical and Chemical Characteristics of Atmospheric Precipitation and Its Significant Impacts on the Environment in Beijing].

Atmospheric precipitation samples were collected in 2018, 2019, and 2021 in Beijing to study the concentrations and changes of the main metal elements and water-soluble ions； the wet deposition fluxes of heavy metals, water-soluble ions, dissolved inorganic nitrogen, and sulfur in the atmospheric precipitation and their impacts on the ecological environment； and the scavenging mechanisms of the typical precipitation to atmospheric pollutants during the study period. The results showed that the precipitation in Beijing during the study period was mostly neutral or alkaline, and the frequency of acid rain occurrence was very low, only accounting for 3.06%. The total concentrations of major metal elements in 2018, 2019, and 2021 were （4 787.46 ±4 704.31）, （7 663.07 ±8 395.05）, and （2 629.13 ±2 369.51） µg·L-1, respectively. The total equivalent concentrations of ions in 2018, 2019, and 2021 were （851.68 ±649.16）, （973.98 ±850.94）, and （644.31 ±531.16） µeq·L-1, respectively. The interannual changes in major metal elements and ions followed the order of 2019 > 2018 > 2021. The seasonal average total concentrations of major metal elements in spring, summer, autumn, and winter were （9 624.25 ±7 327.92）, （4 088.67 ±5 710.14）, （3 357.68 ±3 995.64）, and （6 203.19 ±3 857.43） µg·L-1, respectively, and the seasonal average total equivalent concentrations of ions in spring, summer, autumn, and winter were （1 014.71 ±512.21）, （729.83 ±589.90）, （724.35 ±681.40）, and （1 014.03 ±359.67） µeq·L-1, respectively, all presenting the order of spring > winter > summer > autumn. NO3- and SO42- were the main acid-causing ions in precipitation, whereas NH4+ and Ca2+ were the main acid-neutralizing ions. The wet deposition fluxes of the heavy metal Cd were very low [（0.05 ±0.01） mg·ï¼ˆm2·a）-1], only accounting for （0.13 ±0.04）% of the total wet deposition fluxes of main metal elements； however, its soil safety years were 291 years, significantly lower than those of other heavy metals, displaying that its ecological risk was relatively the highest. The total wet precipitation flux of water-soluble ions NH4+, Ca2+, NO3-, and SO42- accounted for （85.72 ±2.18）% of the wet precipitation flux of total ions, suggesting that their comprehensive impact on the ecological environment might have been higher. DIN wet deposition flux was mainly characterized by NH4+-N, which had a positive impact on the ecological environment in summer. SO42--S wet deposition flux was higher in summer, so its positive impact on the ecological environment was also greater. The scavenging effects of atmospheric precipitations to pollutants from the air were impacted by various factors, and the synergism effects of these factors could directly influence the scavenging mechanisms of precipitation to pollutants.

[Identification and Derivation of Emerging Contaminants in the Roof Rainwater Confluence].

To identify emerging contaminants （ECs） in rainwater is a topic that has gradually received widespread attention. Rainwater resources, specifically urban roofs, play a crucial role in utilizing rainwater efficiently by understanding the occurrence and migration characteristics of pollutants in precipitation. This study selected a typical roof and studied the differences in rainwater quality and pollution occurrence at different collection stages during six rainfall events from March to May in 2023. Principal component analysis （PCA） and correlation analysis were used to explore the distribution, migration, and transformation of ECs in the collection process of roof rainwater. The findings revealed the presence of 44/54 ECs in wet deposition, dry and wet deposition, and roof runoff processes, with a total concentration range of 63.0 to 432.4 ng·L-1 and an average concentration of 166.8 ng·L-1. Notably, bisphenol A （BPA） exhibited the highest concentration, ranging from 14.7 to 265.6 ng·L-1, with an average concentration of 62.5 ng·L-1, followed by ofloxacin （OFX） and ethylhexyl methoxycinnamate （EHMC）, with detected concentrations up to 45.5 ng·L-1 and 44.8 ng·L-1. Dissolved organic matter （DOM）, nitrogen pollutants, and particulate matter were important factors affecting the occurrence characteristics of ECs, with a mantel correlation coefficient of up to 0.98 （P<0.01）. Based on the analysis of different rainfall events and collection stages, variations were observed in the accumulation pathways and contribution ratios of different pollutants. The wet deposition exhibited the highest content of ECs in the initial stage, whereas the dry and wet deposition and roof runoff processes displayed higher ECs content in the later stages. Additionally, the average ECs contribution rates of dry and wet deposition to roof runoff were 21.48% and 78.52%, respectively. Due to the influence of roof material and surface roughness retention performance, over 30% of ECs, including pharmaceuticals and personal care products （PPCPs）, endocrine-disrupting compounds （EDCs）, and pesticides, were deposited on the roof during the runoff collection. The results of this research can provide the theoretical foundation and technical support for the identification and control of ECs in urban roof runoff and for the safe storage of rainwater.

Hydrochemical and isotopic characteristics on the southern and northern slopes of the Himalayas: spatio-temporal controls and source apportionment.

Water-soluble ions, inorganic nitrogen, and stable isotopes in precipitation were assessed from the southern (Koshi Tappu and Khandbari) and northern slopes (Lhasa and SET) of the Himalayas to understand the sources, chemistry of regional precipitation, and climatic processes. Water soluble ions showed distinct seasonal variation, with higher concentrations in the non-monsoon. The concentration of ionic species was highest in Koshi Tappu, followed by Lhasa, SET, and Khandbari. The sources were from the terrigenous (Ca2+, HCO3-), marine (Na+ and Cl-), anthropogenic (SO42-, NO3-, and NH4+), terrigenous and marine (Mg2+), and biomass-burning (K+). The southern slope, relative to the northern, was more prone to anthropogenic emissions with higher deposition. Among all sites, inorganic nitrogen deposition at Koshi Tappu was higher than the threshold value (10 kg ha-1 y-1). The isotopic composition during the study period was higher in non-monsoon, started declining from June, and depleted in July and August compared to other months, i.e., the monsoon mature phase, along the south-to-north transect. The diminished value of stable isotopes in precipitation with increasing altitude underlines the evidence of the orographic effect in isotopic composition. Our study delineated that the higher/lower d-excess value increased with altitude on the southern/northern slope of the Himalayas. The backward trajectory analysis and the National Centers for Environmental Prediction's Final (NCEP FNL) datasets identified that most of the trajectories arrived from warm and humid low-latitude regions during monsoon and westerlies in non-monsoon. Thus, the chemical characteristics and stable isotopic composition of precipitation differed on the southern and northern slopes of the Himalayas by orographic effect and various sources. This study provides new insights into the atmospheric environment and climatic control of stable isotopes in the Himalayan Tibetan Plateau and facilitates monitoring of transboundary air pollution.

Inversion of Critical Atmospheric 137Cs Emissions Following the Fukushima Accident by Resolving Temporal Formation from Total Deposition Data.

Understanding the transport of 137Cs emitted during the Fukushima accident is challenging because the critical emissions that produced the high-deposition area are not adequately resolved in existing source terms. This paper presents an objective inverse reconstruction of these emissions by fusing atmospheric concentrations with a-priori emissions extracted from total depositions. This extraction, previously considered impossible for complex real-world accidents, is achieved by identifying the critical temporal formation process of depositions in the high-deposition area and estimating the corresponding emissions by using an atmospheric transport model. The reconstructed source term reveals two emission peaks from 10:00-11:00 and 14:00-15:00 on March 15, which agree with the in situ pressure measurements and accident analysis, suggesting that they came from pressure drops in the primary containment vessels of Units 3 and 2, respectively. This finding explains the environmental observations of spherical 137Cs particles. The source term also objectively and independently confirms the widely used reverse estimate. The corresponding 137Cs transport simulations better match the various observations than those produced by other source terms, proving that the two-peak emission creates a high-deposition area. The proposed method outperforms the direct fusion of deposition and atmospheric concentration observations, providing a robust tool for multiobservation fusion.

Uncovering sources, distribution, and seasonal patterns of trace element deposition: the elemental puzzle of the western Himalayas.

The transport and deposition of atmospheric pollutants in the Himalayas have a adverse impact on the climate, cryosphere, ecosystem, and monsoon patterns. Unfortunately, there is a insufficiency of data on trace element concentrations and behaviors in the high-altitude Himalayan region, leading to limited research in this area. This study presents a comprehensive and detailed comprehension of trace element deposition, its spatial distribution, seasonal variations, and anthropogenic signals in the high-altitude Kashmir region of the Western Himalayas. Our investigation involved the analysis of 10 trace elements (Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb) in glacier ice, snow pits, surface snow, and rainwater collected at various sites including Kolahoi, Thajwas, Pahalgam (Greater Himalayan ranges), and Kongdori and Shopian (Pir Panjal Ranges) during 2021. The study reveals distinct ranges of concentrations for the trace elements at different sampling sites. Our analysis of trace element concentration depth profiles in snow pits reveals seasonal fluctuations during the deposition year. The highest concentrations were found in the autumn (below 20 cm) and summer (top layer), compared to the winter concentration (10-20 cm). The high enrichment factors (EFs) suggest the severity of human-induced trace metal deposition in the western Himalayan region, relative to surrounding regions. Surprisingly, the concentrations and EFs of trace elements showed seasonal contradictions, with lower concentration values and higher EFs during the non-monsoon season and vice versa. A source apportionment analysis using the positive matrix factorization (PMF) technique identified five sources of trace element deposition in the region, including crustal sources (32.33%), coal combustion (15.62%), biomass burning (17.63%), traffic emission (18.8%), and industrial sources (15.6%). Additionally, the study incorporated backward trajectories coupled with δ18O using the NOAA HYSPLIT model to estimate moisture sources in the region, which suggests atmospheric pollutants predominately deposited from the large-scale atmospheric circulation from westerlies (75%) during non-monsoon season. These findings underscore the urgent need for enhanced monitoring and research efforts in the future.

Air pollution in Bialowieza forest: Analysis of short-term trends from 2014 to 2021.

Air pollution caused by sulphur dioxide (SO2) and nitrogen oxides (NOx) has negative impacts on forest health and can initiate forest dieback. Long-term monitoring and analysis of these pollution are carried out in Bialowieza Forest in NE Poland due to the threats from abiotic, biotic and anthropogenic factors. The main objective of our study was to monitor the levels and trends of air pollutant deposition in Bialowieza Forest. During a short-term monitoring period over six years (2014-2021), the concentration of SO2 in the air decreased significantly (from 2.03 µg m-3 in December 2015 to 0.20 µg m-3 in July 2016), while the concentration of NO2 in the air showed a non-significant decrease (from 8.24 µg m-3 in December 2015 to 1.61 µg m-3 May 2016). There was no significant linear trend in the wet deposition of S-SO4 anions. Mean monthly S-SO4 deposition varies between 4.54 and 94.14 mg m-2month-1. Wet nitrogen deposition, including oxidized nitrogen (N-NO3) and reduced nitrogen (N-NH4), showed a non-significant increase. Mean monthly precipitation of N-NO3 and N-N H4 ranged from 1.91 to 451.73 mg m-2month-1. Neither did total sulphur deposition nor total nitrogen deposition exceed the mean deposition values for forests in Europe (below 6 ha-1yr-1 and 3-15 ha-1yr-1, respectively). Our results indicate that air pollutants originate from local sources (households), especially from the village of Bialowieza, as demonstrated by the level and spatial distribution of air pollutant deposition. This indicates that air pollutants from the village of Bialowieza could spread to other parts of Bialowieza Forest in the future and may have a negative impact on forest health and can initiate forest dieback. It is therefore important to continue monitoring air pollution to assess the threats to this valuable forest ecosystem.

Atmospheric wet and dry phosphorus deposition in Lake Erhai, China.

Lake Erhai is a potentially phosphorus (P)-limited lake and its water quality may have been affected by atmospheric P deposition. However, there have been few studies on atmospheric P deposition in this lake. In this study, we established five wet deposition monitoring sites and two dry deposition monitoring sites around Lake Erhai to quantify the wet and dry deposition of total phosphorus (TP), including dissolved inorganic phosphorus (DIP), dissolved organic phosphorus (DOP) and particulate phosphorus (PP) from July 2022 to June 2023. Wet deposition fluxes of P species were collected by automatic rainfall collection instrument, and dry deposition fluxes were estimated using airborne concentration measurements and inferential models. The results reveal that among the different P components, DOP had the highest contribution (50%) to wet TP deposition (average all sites 12.7 ± 0.7 mg P m2/yr), followed by PP (40%) and DIP (10%). Similarly, DOP (51%) was the major contributor to dry TP deposition (average two sites 2.4 ± 0.9 mg P m2/yr), followed by DIP (35%) and PP (14%). Wet deposition dominated the annual total TP deposition (wet plus dry), accounting for approximately 83%. The key seasons for dry deposition were spring and autumn, which accounted for 64% of the annual total dry TP deposition. In comparison, wet deposition was significantly higher in the summer, accounting for 73% of the annual total wet TP deposition. The results of the potential source contribution function and concentration-weighted trajectories analysis indicate that local source emission and long-range transport from surrounding cities jointly exerted a substantial influence on aerosol P concentrations, particularly in the eastern and northwestern regions of the lake. These findings provide a comprehensive understanding of the different P components in atmospheric deposition, which is beneficial for developing effective strategies to manage the P cycle in Lake Erhai.

Leveraging physics-based and explainable machine learning approaches to quantify the relative contributions of rain and air pollutants to wet deposition.

A quantitative understanding of the roles of rainfall and pollutant concentrations in wet deposition is important because they critically influence terrestrial and aquatic ecosystems. However, their relative contributions to wet deposition, which vary across regions, have not yet been identified. We propose two methods that quantitatively separate the contributions of rain and pollutant concentrations to wet deposition: one is based on simplified equations describing the wet scavenging of pollutants and the other is based on random forest models employing SHapley Additive exPlanations. Three-dimensional long-term air quality simulations from 2003 to 2019 are used as inputs for both the physics-based and machine learning models. Remarkably, the results drawn from the explainable machine learning model are consistent with those from the physics-based approach: overall, rain is a more important limiting factor than pollutant concentrations and the relative contribution of rain is larger than that of pollutants by up to a factor of 3-4 in polluted regions. In polluted regions, pollutant concentrations can remain relatively high even in the presence of precipitation owing to continuous and intense emissions; therefore, wet deposition is limited by rainfall. The contribution of rainfall is larger by 1.5-2.5 than that of pollutant concentrations in regions even with low emissions and this considerably large role of rain suggests that regional or transboundary pollutant transport plays a key role in modulating wet deposition. However, in very remote regions, once the rainfall amount exceeds a certain value, rainfall no longer contributes to increasing wet deposition because atmospheric pollutants are readily removed by rain. So, the contributions of the two factors are comparable in pristine regions. Our results can serve as a basis for explaining interannual variations in wet deposition and for future projections of wet deposition under emission control plans and climate change scenarios across regions.

Carbon wet deposition flux and river carbon output in a forest watershed in permafrost region of the Da Xing'an Mountains.

Carbon wet deposition and river carbon output in river basins are important components of global carbon cycle. The assessment of both properties is of great significance for regional carbon budget. However, research on these topics in high-latitude permafrost regions in China is still lacking. We conducted dynamic monitoring of carbon wet deposition and carbon output in the river from May 28th to October 30th, 2022, in Laoyeling watershed, a typical forested watershed in the Da Xing'an Mountains permafrost region. We analyzed the variations of carbon component concentrations and fluxes in precipitation and river water, and estimated the contribution of carbon wet deposition to carbon output in the watershed. The results showed that wet deposition fluxes of dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), and total dissolved carbon (TDC) in the Laoyeling watershed were 1354.86, 684.59, and 2039.45 kg·km-2, respectively. The fluxes of DOC, DIC, TDC, particulate organic carbon (POC), particulate inorganic carbon (PIC), and total carbon (TC) in the river were 601.75, 1977.30, 2579.05, 125.13, 21.99, and 2726.17 kg·km-2, respectively. The contribution of TDC wet deposition to the river TDC output was 9941.89 kg, accounting for 17.6% of total output. The DIC concentration in the river showed significant seasonal differences, with increased runoff resulting from precipitation leading to a decrease in DIC concentration in the river and showing a clear dilution effect, while the concentrations of DOC, POC, and PIC increased, mainly due to erosion effect. In conclusion, carbon wet deposition flux in the Laoyeling watershed was mainly determined by precipitation, and its contribution to river carbon output was relatively small compared to other factor. Runoff was the dominant factor affecting river carbon output. The results would provide important insights into carbon cycling and carbon budget balance in permafrost regions under climate change.

Fate and Transport of Mercury through Waterflows in a Tropical Rainforest.

Knowledge gaps of mercury (Hg) biogeochemical processes in the tropical rainforest limit our understanding of the global Hg mass budget. In this study, we applied Hg stable isotope tracing techniques to quantitatively understand the Hg fate and transport during the waterflows in a tropical rainforest including open-field precipitation, throughfall, and runoff. Hg concentrations in throughfall are 1.5-2 times of the levels in open-field rainfall. However, Hg deposition contributed by throughfall and open-field rainfall is comparable due to the water interception by vegetative biomasses. Runoff from the forest shows nearly one order of magnitude lower Hg concentration than those in throughfall. In contrast to the positive Δ199Hg and Δ200Hg signatures in open-field rainfall, throughfall water exhibits nearly zero signals of Δ199Hg and Δ200Hg, while runoff shows negative Δ199Hg and Δ200Hg signals. Using a binary mixing model, Hg in throughfall and runoff is primarily derived from atmospheric Hg0 inputs, with average contributions of 65 ± 18 and 91 ± 6%, respectively. The combination of flux and isotopic modeling suggests that two-thirds of atmospheric Hg2+ input is intercepted by vegetative biomass, with the remaining atmospheric Hg2+ input captured by the forest floor. Overall, these findings shed light on simulation of Hg cycle in tropical forests.

Organic carbon in wet deposition of an urbanized coastal bay, North China: Flux, sources and biogeochemical implications.

The process of atmospheric organic carbon (OC) entering the ocean through wet deposition plays a crucial role in the global carbon cycle. To gain insights into the biogeochemical dynamics of OC at the land-sea margin, we conducted an extensive four-year investigation on precipitation OC in Jiaozhou Bay (JZB). The results showed that the volume-weighted mean concentration of particulate OC (POC) and dissolved OC (DOC) in precipitation were 0.38 and 2.06 mg C L-1 with an average wet deposition flux of OC for 2666.5 mg C m-2 yr-1. The source of POC in precipitation is predominantly by the C3 plant emission and burning and fossil fuel combustion. Wet deposition contributed 986.6 t yr-1 of OC of which 506.3 t yr-1 of bioavailable DOC, which could have significant implications for carbon cycle in the JZB. This study could enhance the understanding of the marine atmospheric OC in coastal areas.

Organophosphate esters in the urban atmosphere of Thessaloniki city, Greece.

The occurrence of organophosphate esters (OPEs) in the atmosphere of the urban area of Thessaloniki city, Greece was studied. OPEs were determined in particulate matter (PM2.5) and precipitation during the period 2020-2021. ∑OPEs in rainwater ranged from 520 to 4719 ng L-11 (mean: 1662 ng L-1) with tris (2-butoxyethyl) phosphate (TBOEP) and tris (1-chloro-2-propyl) phosphate (TClPP) being the most abundant compounds. TBOEP and TClPP as well as triphenylphosphine oxide (TPPO) and tris (chloroethyl) phosphate (TCEP) were the dominant OPEs in PM2.5. Concentrations of ∑OPEs in PM2.5ranged from 2.82 to 13.3 ng m-3 (mean: 5.93 ng m-3). Wet deposition fluxes of OPEs were estimated and air mass back trajectories were used to elucidate possible source profiles. An overall low health risk for local population via inhalation of OPEs was revealed.

Atmospheric organic nitrogen deposition around the Danjiangkou Reservoir: Fluxes, characteristics and evidence of agricultural source.

Dissolved organic nitrogen (DON) deposition was the substantial component of dissolved total nitrogen (DTN) deposition in the world's nitrogen deposition hot spots areas. However, the information on the importance for DON deposition and its sources was still scarce, which limited the comprehensive assessment of the ecological threat from nitrogen deposition. Six sampling sites around the Danjiangkou Reservoir were set up to collect the dry and wet deposition samples from October 2017 to September 2021. The results showed that dry and wet DTN deposition averaged 34.72 kg ha-1 yr-1 and 22.27 kg ha-1 yr-1, respectively. Dry NH4+-N, NO3--N and DON deposition averaged 14.28 kg ha-1 yr-1, 5.91 kg ha-1 yr-1 and 14.53 kg ha-1 yr-1, respectively. Wet NH4+-N, NO3--N and DON deposition averaged 11.14 kg ha-1 yr-1, 3.89 kg ha-1 yr-1and 7.24 kg ha-1 yr-1, respectively. The contributions of DON to DTN were 41.85% (in dry deposition) and 32.50% (in wet deposition), respectively. Dry DON deposition varied between 26.44 kg ha-1 yr-1 and 9.11 kg ha-1 yr-1, and significantly differed among six sampling sites (P < 0.05). The different intensity of agricultural activities disturbance at the sampling sites was the important reason for the spatial variations of DON deposition. DON deposition was significantly correlated with ammonium nitrogen (NH4+-N) deposition (P < 0.05). According to the results of positive matrix factorization (PMF) model, agriculture source contributed significantly to the DON deposition, the contributions at six sampling sites ranged from 45.8% to 73.7% in dry deposition, and from 56.8% to 81.6% in wet deposition. In summary, our findings found that agricultural activities were the important factors influencing the spatial patterns of DON deposition around Danjiangkou Reservoir and provided new evidence for the anthropogenic source of DON deposition in China.

Multi-elemental stoichiometric ratios of atmospheric wet deposition in Chinese terrestrial ecosystems.

Intense human activities have significantly altered the concentrations of atmospheric components that enter ecosystems through wet and dry deposition, thereby affecting elemental cycles. However, atmospheric wet deposition multi-elemental stoichiometric ratios are poorly understood, hindering systematic exploration of atmospheric deposition effects on ecosystems. Monthly precipitation concentrations of six elements-nitrogen (N), phosphorus (P), sulfur (S), potassium (K), calcium (Ca), and magnesium (Mg)-were measured from 2013 to 2021 by the China Wet Deposition Observation Network (ChinaWD). The multi-elemental stoichiometric ratio of atmospheric wet deposition in Chinese terrestrial ecosystems was N: K: Ca: Mg: S: P = 31: 11: 67: 5.5: 28: 1, and there were differences between vegetation zones. Wet deposition N: S and N: Ca ratios exhibited initially increasing then decreasing inter-annual trends, whereas N: P ratios did not exhibit significant trends, with strong interannual variability. Wet deposition of multi-elements was significantly spatially negatively correlated with soil nutrient elements content (except for N), which indicates that wet deposition could facilitate soil nutrient replenishment, especially for nutrient-poor areas. Wet N deposition and N: P ratios were spatially negatively correlated with ecosystem and soil P densities. Meanwhile, wet deposition N: P ratios were all higher than those of ecosystem components (vegetation, soil, litter, and microorganisms) in different vegetation zones. High input of N deposition may reinforce P limitations in part of the ecosystem. The findings of this study establish a foundation for designing multi-elemental control experiments and exploring the ecological effects of atmospheric deposition.

Determining organic nitrogen emission sources and secondary formations in an urban coastal airshed via stable isotope techniques.

Organic nitrogen (ON) has been excluded in the majority of atmospheric N studies. However, dissolved organic nitrogen (DON) deposition influences coastal water quality and primary production creating an urgent need for comprehensive atmospheric ON characterization, especially in coastal airsheds. This study measured the concentration and isotopic composition of rainwater DON (δ15N-DON) and applied stable isotope mixing models to determine the ON emission source apportionments in a small-sized coastal city. The DON concentration averaged 10.6 ± 7.6 µM (n = 42), which was 29% of the total dissolved nitrogen in rainwater and produced a deposition flux of 1.5 kg N·ha-1·yr-1. The average rainwater δ15N-DON value was 8.3 ± 5.3‰ and isotope mixing model results suggested vehicles as a dominant source, overall contributing 35 ± 15% of ON emissions, followed by marine emissions (24 ± 16%), organic amines (18 ± 11%), organic nitrates (17 ± 11%), and biomass burning (8 ± 3%). Although secondary ON formations (i.e., organic amines and nitrates) had less contributions than primary emission sources (i.e., vehicles, marine, and biomass burning), it can be significant and rival primary emissions when the fertilizer application started. Our results fill knowledge gaps of ON wet deposition and emission sources in small-sized coastal cities and inform future atmospheric N mitigation strategies and coastal watershed restoration plans in similar regions. We call for further research determining the isotopic composition of ON emission sources and fractionation associated with primary emission and secondary formation in anticipation of creating a similar isotope-based foundation that has been used for decades to investigate inorganic nitrogen emissions.

Inter-comparison of measurements of inorganic chemical components in precipitation from NADP and CAPMoN at collocated sites in the USA and Canada during 1986-2019.

Wet deposition monitoring is a critical part of the long-term monitoring of acid deposition, which aims to assess the ecological impact of anthropogenic emissions of SO2 and NOx. In North America, long-term wet deposition has been monitored through two national networks: the Canadian Air and Precipitation Monitoring Network (CAPMoN) and the US National Atmospheric Deposition Program (NADP), for Canada and the USA, respectively. In order to assess the comparability of measurements from the two networks, collocated measurements have been made at two sites, one in each country, since 1986 (Sirois et al., in Environmental Monitoring and Assessment, 62, 273-303, 2000; Wetherbee et al., in Environmental Monitoring and Assessment, 1995-2004, 2010). In this study, we compared the measurements from NADP and CAPMoN instrumentation at the collocated sites at the Pennsylvania State University (Penn State), USA, from 1989 to 2016, and Frelighsburg, Quebec, Canada, from 2002 to 2019. We also included in the study the collocated daily-vs-weekly measurements by the CAPMoN network during 1999-2001 and 2016-2017 in order to evaluate the differences in wet concentration of ions due to sampling frequency alone. The study serves as an extension to two previous CAPMoN-NADP inter-comparisons by Sirois et al. (Environmental Monitoring and Assessment, 62, 273-303, 2000) and Wetherbee et al., in (Environmental Monitoring and Assessment, 1995-2004, 2010). At the Penn State University site, for 1986-2019, CAPMoN was higher than NADP for all ions, in terms of weekly concentration, precipitation-weighted annual mean concentration, and annual wet deposition. The precipitation-weighted annual mean concentrations were higher for SO42- (2%), NO3- (12%), NH4+ (16%), H+ (6%), and base cations and Cl- (11-15%). For annual wet deposition, CAPMoN was higher for SO4-2, NO3-, NH4+ and H+ (5-17%), and base cations and Cl- (12-17%) during 1986-2019. At the Frelighsburg site, NADP changed the sample collector in October 2011. For 2002-2011, the relative differences at the Frelighsburg site were positive and similar in magnitude to those at the Penn State site. For 2012-2019, the precipitation-weighted annual mean concentrations were 5-27% lower than NADP, except for H+, which was 23% higher. The change in sample collector by NADP had the largest effect on between-network biases. The comparisons of daily-vs-weekly measurements conducted by the CAPMoN network during 1999-2001 and 2016-2017 show that the weekly measurements were higher than the daily measurements by 1-3% for SO42-, NO3-, and NH4+; 3-9% for Ca2+, Mg2+, Na+, and Cl-; 10-24% for K+; and lower for H+ by 8-30% in terms of precipitation-weighted mean concentration. Thus, differences in sampling frequencies did not contribute to the systematically higher CAPMoN measurements. Understanding the biases in the data for these networks is important for interpretation of continental scale deposition models and transboundary comparison of wet deposition trends.

Refractory black carbon aerosols in rainwater in the summer of 2019 in Beijing: Mass concentration, size distribution and wet scavenging ratio.

Black carbon (BC) aerosols in the atmosphere play a significant role in climate systems due to their strong ability to absorb solar radiation. The lifetime of BC depends on atmospheric transport, aging and consequently on wet scavenging processes (in-cloud and below-cloud scavenging). In this study, sequential rainwater samples in eight rainfall events collected in 2 mm interval were measured by a tandem system including a single particle soot photometer (SP2) and a nebulizer. The results showed that the volume-weighted average (VWA) mass concentrations of refractory black carbon (rBC) in each rainfall event varied, ranging from 10.8 to 78.9 µg/L. The highest rBC concentrations in the rainwater samples typically occurred in the first fraction from individual rainfall events. The geometric mean median mass-equivalent diameter (MMD) decreased under precipitation, indicating that rBC with larger sizes was relatively aged and preferentially removed by wet scavenging. A positive correlation (R2 = 0.73) between the VWA mass concentrations of rBC in rainwater and that in ambient air suggested the important contribution of scavenging process. Additionally, the contributions of in-cloud and below-cloud scavenging were distinguished and accounted for 74% and 26% to wet scavenging, respectively. The scavenging ratio of rBC particles was estimated to be 0.06 on average. This study provides helpful information for better understanding the mechanism of rBC wet scavenging and reducing the uncertainty of numerical simulations of the climate effects of rBC.

Atmospheric wet deposition of trace metal elements: Monitoring and modelling.

Trace elements (TEs), a group of atmospheric pollutants, have attracted considerable attention from scientists and government administrators worldwide. The wet deposition fluxes of nineteen trace elements (NTE) were monitored at Wanqingsha, a coastal site in the Pearl River Delta, for three consecutive years (2016.9-2019.8). Significant seasonal differences in NTE between wet and dry seasons were observed. The fluxes of crustal elements (Ca, Na, Al, Mg, K, Fe, Zn and Ba) were significantly higher than those of anthropogenic elements, accounting for over 99 % of the total annual wet deposition of 19 elements. Analysis of PM2.5 and rainfall samples reveals that both the fraction of each TE in the PM2.5 (CQ) and the Apparent Scavengance Ratio for TE (ASR, defined as the concentration ratio in rain and PM2.5) follow lognormal distributions. The logCQ variation for each element is relatively small but shows substantial differences, with means ranging from -5.48 to -2.03, while the logASRs for all elements show similar means (varying from 5.86 to 7.64) and an extremely wide range of variation. The influences of meteorological factors on CQ and ASR were also investigated. A simple box model framework was constructed to reasonably simplify the TE removal process by precipitation. The corresponding regression analysis showed significant correlations between NTE and the precipitation rate, PM2.5 concentration, ASR, and CQ, with R2 ranging from 0.711 to 0.970. By substituting the effects of environmental factors on ASR and CQ into the above relationship, temporal variations in NTE can be predicted. The reliability of the model was demonstrated by comparing model simulations with observations over three years. For most elements, the models can predict the temporal variation of NTE quite accurately, and even for the worst predictions, such as Al, Mg, K, Co and Cd, where predictions exceed observations by only an order of magnitude.