Mapping gaseous dimethylamine, trimethylamine, ammonia, and their particulate counterparts in marine atmospheres of China ’ s marginal seas: Part 1 Differentiating marine emission from continental transport

. To study sea-derived gaseous amines, ammonia, and primary particulate aminium ions in the marine atmosphere of China’s marginal seas, an onboard URG-9000D Ambient Ion Monitor-Ion chromatography (AIM-IC, Thermo Fisher) was set up on the front deck of the R/V Dongfanghong 3 to semi-continuously measure the spatiotemporal variations in the concentrations of atmospheric trimethylamine (TMA gas ), dimethylamine (DMA gas ), and ammonia (NH 3gas ) along with their particulate matter (PM 2.5 ) counterparts. In this study, we differentiated marine emissions of the gas species from continental 15 transport using data obtained from December 9 to 22, 2019 during the cruise over the Yellow and Bohai seas, facilitated by additional short-term measurements collected at a coastal site near the Yellow Sea during summer, fall, and winter of 2019. The data obtained from the cruise and coastal sites demonstrated that the observed TMA gas and protonated trimethylamine (TMAH + ) in PM 2.5 over the Yellow and Bohai seas overwhelmingly originated from marine sources. During the cruise, no significant correlation (P>0.05) was observed between the simultaneously measured TMAH + and TMA gas concentrations. 20 Additionally, the concentrations of TMAH + in the marine atmosphere varied around 0.28±0.18 μg m -3 (average ± standard deviation), with several particulate DMAH + in PM 2.5 were estimated. The estimated average values of each species contributed to 16%, 34%, and 65% of the observed average concentrations for non-sea-derived DMA gas , NH 3gas and non-sea-spray particulate DMAH + in PM 2.5 , respectively. Uncertainties remained in the estimations, as TMAH + may decompose into smaller molecules in seawater to varying extents. The non-sea-derived gases and non-sea-spray particulate DMAH + likely originated from long- 30 range transport from the upwind continents based on the recorded offshore winds and increased concentrations of non-sea-salt SO 42- (nss-SO 42- ) and NH 4+ in PM 2.5 . The lack of a detectable increase in particulate DMAH + , NH 4+ , and nss-SO 42-concentrations in several SO 2 plumes did not support the secondary formation of particulate DMAH + in the marine atmosphere.


Introduction
Gaseous amines and their particulate counterparts are vital for reduced nitrogen compounds in the marine atmosphere (Facchini et al., 2008;Müller et al., 2009;Hu et al., 2015;Hu et al., 2018;van Pinxteren et al., 2015;van Pinxteren et al., 2019;Yu et al., 2016;Xie et al., 2018;Zhou et al., 2019) and are primarily derived from seawater, where glycine betaine (GBT), trimethylamine N-oxide (TMAO), and choline are the three major precursors (Burg and Ferraris, 2008;Lidbury et al., 40 2015a;Lidbury et al., 2015b;Jameson et al., 2016;Taubert et al., 2017). GBT, TMAO, and choline are critical for maintaining the osmotic pressure in marine organisms. When released into the environment, they can be degraded by bacteria to trimethylamine (TMA), dimethylamine (DMA), or methylamines (MA) (Lidbury et al., 2015a;Lidbury et al., 2015b). Gaseous DMA, TMA, and MA may be vital in the formation of secondary particles in the atmosphere by nucleation (Almeida et al., 2013;Chen et al., 2016;Zhu et al., 2019). In addition to biogenic amines, anthropogenic 45 emissions are known as important sources of amines in the continental atmosphere, but not in the marine atmosphere (Ge et al., 2011). Modeling studies have shown that the continental amine species in gas and/or particle phases can be transported regionally, including downwind marine atmospheres (Yu and Luo, 2014;Mao et al., 2018). Simultaneous real-time measurement of gaseous amines and their particulate counterparts in the marine atmosphere over the ocean remains challenging because of artifact signals related to self-vessel emissions and amine-contained dew evaporation; however, this 50 is not the case in the continental atmosphere (VandenBoer et al., 2011). The lack of direct measurements restricts the determination of their sources and the relationship between the reduced nitrogen compounds and acid-base neutralization reactions in the marine atmosphere.
Reduced nitrogen compounds in the ocean can finally decompose into ammonium ions (NH4 + ) and other smaller molecules.
NH4 + in surface seawater releases to the marine atmosphere as atmospheric ammonia (NH3gas) under favorable conditions 55 (Johnson et al., 2008;Carpenter et al., 2012;Paulot et al., 2015). The ocean is an important source of NH3gas, contributing to approximately 40% of the natural NH3 emissions on Earth (Carpenter et al., 2012;Paulot et al., 2015). In the literature, large uncertainties remain in estimating NH3 emissions from the ocean; for example, the annual emission flux ranges from 2 to 23 Tg N a -1 (Clarke and Porter, 1993;Dentener and Crutzen, 1994;Sutton et al., 2013;Paulot et al., 2015). These uncertainties are primarily derived from two factors: 1) the major marine sources of NH3gas are still disputed, such as seawater, sea birds, 60 or the photolysis of marine organic nitrogen at the ocean surface or in the atmosphere; and 2) direct NH3gas observations in marine atmospheres are restricted as onboard ambient NH3gas measurement techniques sometimes suffer from large artifacts from NH3gas contamination associated with onboard human activities, dew evaporation, and water vapor interference (Quinn et al., 1990;Clarke and Porter, 1993;Johnson et al., 2008;Keene et al., 2009;Wentworth et al., 2016;Teng et al., 2017).
To identify and characterize sea-derived gaseous amines, ammonia, and sea-spray particulate aminium ions, as well as secondary particulate aminium ions from continental transport in the atmospheres of China's marginal seas, we conducted two cruise campaigns: one over the Yellow and Bohai seas in China from December 9 to 22, 2019 (Campaign A), and another over the Eastern China and Yellow seas from December 27, 2019 to January 16, 2020 (Campaign B). Winter cruise 70 campaigns provide great opportunities for observational studies due to the following: 1) higher concentrations of nutrients in the seas at lower sea surface water temperatures, which may favor higher primary production (Guo et al., 2020) and subsequently increase marine emissions of gaseous amines and/or aminum-contained sea-spray aerosols; 2) periodically 4 enhanced air-sea exchanges driven by the strong winter Asian monsoon every 4-10 days ; and 3) periodically enhanced long-range transport of anthropogenic pollutants from continents to the seas, which may enhance the 75 formation of secondary ammonium and aminium aerosols (Guo et al., 2016;Yu et al., 2016;Xie et al., 2018;Wang et al., 2019).
In this study, an onboard URG-9000D Ambient Ion Monitor-Ion chromatography (AIM-IC, Thermo Fisher) instrument was used to simultaneously measure the spatiotemporal variations in the concentrations of gaseous amines and NH3gas, along with their counterparts in PM2.5. Semi-continuous measurement data were analyzed to identify the study targets. This study was 80 divided into two parts. In this section, we distinguish the marine sources from the continental transport of reduced nitrogen compounds in marine atmospheres and subsequently quantify each contribution to the observed species during the December 9-22, 2019 campaign. In the companion paper (Gao et al., 2021), we analyzed the spatiotemporal heterogeneity and related causes, and subsequently delivered a hypothesis regarding the marine emissions of reduced nitrogen compounds using the data from the two campaigns and an additional cruise campaign previously reported by Hu et al. (2015). 85 2. Experimental

Sampling periods, locations, and instruments
Campaign A was conducted from December 9 to 19, 2019 on the R/V Dongfanghong-3 with a displacement tonnage of 5000.
The research vessel was still within its testing period and used state-of-the-art combustion technology with low-sulfur diesel.
Campaign B started from December 27, 2019 to January 17, 2020, and was organized by another research team. During 90 December 20-22, the vessel was anchored at the port while the sampling continued. The 44 hours were referred to as the transition period between campaigns A and B. A standard-sized air-conditioned container was set up on the front deck to house a suite of instruments including the AIM-IC, a fast-mobility particle sizer (FMPS, Tsi), a cloud condensation nuclei counter (CCN-100, Droplet MT), and a single particle aerosol mass spectrometer (SPAMS 05,Hexin). No human activities occurred on the front deck during cruising, excluding anchoring at the port. Even during the anchoring period, human 95 activity on the front deck was rare. The use of the container on the front deck effectively minimized the self-vessel contamination by NH3gas and gaseous amines. The front deck was approximately 10 m above sea level, and the container 5 height was 2.8 m.
To ensure that the onboard AIM-IC was operated properly, it was housed in a mobile air-conditioned mini-container, which was further placed in a standard container with a 1 m stainless steel sampling probe connected to the ambient air. The inlet of 100 the sampling probe extended from the top corner of the standard container facing the sea. The AIM-IC consists of two major parts: an ambient air sampling system and an ion chromatography analysis system. For the sampling system, the AIM-IC was equipped with a PM2.5 cyclone and operated at a rate of 3 L/min. The sampled gases and particles in the water solution were stored in two syringes prior to their injection for analysis. The ion chromatography analysis system measured the semicontinuous concentrations of chemically reactive gases. These included NH3gas, gaseous amines, and acidic gases such as 105 SO2 and HNO3, along with their particulate counterparts, at a temporal resolution of 1 h. This facilitated the identification of possible interference from onboard dew evaporation, which typically occurs with sunrise (Teng et al., 2017). An automatic weather system providing real-time meteorological data is available on the R/V Dongfanghong-3. The heading wind was corrected to determine the true wind speed and direction. The surface seawater temperature was not measured during this cruise campaign, and typically had a delay of a few hours compared to the ambient air temperature (Deng et al., 110 2014).
On August 1-9, September 12 to October 1, and November 16 to December 1, 2019, the AIM-IC was set up at a coastal site in Qingdao (36.34°N, 120.67°E) to conduct routine measurements (Fig. 1). Coastal measurement data were obtained from two weeks to four months before the winter cruise campaign. The sampling site was located in a new high-technology zone near the Yellow Sea, with the shortest distance from the sea being approximately 1 km in the south. The AIM-IC was housed 115 in a research lab on the fifth floor of a building, approximately 16 m above ground level. The sampling probe extended out of the window and was directly connected to the ambient air. Typically, higher biogenic emissions of reduced nitrogen compounds over the continents are expected in the summer than in the winter owing to the temperature effect (Yu et al., 2016;Teng et al., 2017). 120
Methanesulfonic acid solution (5 mM) was used as the eluent for cation analysis, while potassium hydroxide solution 125 (varying from 3 to 40 mM) was used as the gradient eluent for anion analysis. Each analysis took 26-28 mins to obtain a complete ion spectrum. The volume of the injection loop installed on the low-pressure valve was 250 μL, which substantially reduced the limits of detection for all ions. The limits of detection for NH4 + , DMAH + , and TMAH + were 0.0004, 0.004, and 0.002 μg m -3 , respectively, in ambient air. The limits of detection for NO3and SO4 2were 0.05 and 0.015 μg m -3 , respectively, in ambient air. The ICS-1100 was calibrated onboard prior to obtaining regular measurements, and the second 130 calibration was conducted when the vessel was anchored at the port. The AIM-IC analysis was not affected by ambient water vapor, as the device directly measured the ions. Detailed information regarding the AIM-IC analysis is provided in Teng et al. (2017) and Xie et al. (2018). Notably, strong K + interference occurred unexpectedly and occasionally, and then disappeared during different campaigns. When the interference occurred, DMAH + and TMAH + were undetectable because of the increased baseline at the corresponding residence time in the ion chromatograph (Fig. S1); consequently, some PM2.5 135 DMAH + and TMAH + concentration data are unavailable in Fig. 1. However, the concentrations of gaseous amines were still detected correctly, with a low baseline at the residence. K + interference remains to be investigated. Additionally, a few surface seawater samples were collected from different sea zones. The NH4 + and aminium ion concentrations in the samples were not measured, as the analytical methods were still hindered by high sea-salt ion contents.

Temporal variations in the concentrations of basic gases and their PM2.5 counterparts in the coastal atmosphere
Before analyzing the basic gases and their counterparts in the marine atmosphere, we initially presented their continental concentrations at the coastal site facing the Yellow Sea as important evidence to facilitate the analysis of the contributors to these species in the marine atmosphere. Figs. 1a & b show that the TMAgas and TMAH + concentrations in PM2.5 were mostly below the detection limit, varying at approximately 0.001±0.001 μg m -3 (average ± standard deviation), regardless of the 145 presence of offshore or onshore winds during short-term measurements in the three seasons of 2019. The DMAgas and 7 DMAH + concentrations varied at 0.018±0.021 and 0.017±0.013 μg m -3 , respectively, which were approximately one order of magnitude larger than those of TMAgas and TMAH + . TMAgas and TMAH + concentrations in the upwind continental and coastal atmospheres were substantially lower than those reported in the literature, by up to a few tens of ng m -3 (Ge et al., 2011). However, Gibb et al. (1999) reported a low average TMAgas (0.5 ng m -3 ) and particulate TMAH + (0.5 ng m -3 ) in the 150 marine atmosphere over the Arabian Sea on November 16 to December 19, 1994. Xie et al. (2018 reported that TMAH + concentrations were comparable to those of DMAH + in atmospheric particles collected at two other coastal sites located approximately 20 km from the study area, as listed in Table S1. The cause of this change is beyond the scope of this study, but may be due to the large decrease in manure application, based on our recent survey in the Qingdao area. The DMAgas and DMAH + concentrations in PM2.5 with offshore winds from the north were substantially higher than those 155 with onshore winds from the south or southeast (top of Fig. 1a Fig. 2c). Peaks 1 and 2 were generally associated with offshore winds, while peak 3 was mostly associated with onshore winds (Fig. 2b). The peaks lasted from tens to dozens of hours and were not induced by the onboard dew evaporation at sunrise. For example, the highest value (0.060 μg m -3 ) occurred at 23:00 165 on December 16. The observed TMAgas concentrations were one order of magnitude higher than those measured in the coastal atmosphere during the summer, fall, and winter. This suggested that the TMAgas observed during Campaign A was largely derived from marine sources rather than from long-range continental transport. The same conclusion can be drawn by analyzing the three peaks of TMAgas and its temporal variations during the anchoring port period. For example, during peak 1 (Fig. 2a), the concentrations of TMAgas increased by approximately 100% from 20:00 on December 9 to 11:00 on 170 8 December 10, with an approximately 30% decrease in the non-sea-salt SO4 2-(nss-SO4 2-) concentration (from 22 to 16 µg m -3 ; Fig. 2b). Moreover, the peaks in the TMAgas concentrations corresponded to troughs in the nss-SO4 2concentrations during peak 3, as shown in Figs. 2c & d. The self-vessel emissions of nss-SO4 2in PM2.5 were negligible because of the use of lowsulfur diesel, which is discussed later. The increased nss-SO4 2concentrations in PM2.5 may be a good indicator of continental transport, and vice versa.

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The concentrations of DMAgas varied at approximately 0.006±0.006 μg m -3 (Fig. 2d) and were significantly higher than those of TMAgas (P<0.01). Unlike TMAgas, continental transport was likely an important contributor to the DMAgas and NH3gas observed in the marine atmosphere, particularly during peak 1, when higher nss-SO4 2concentrations were observed in PM2.5 (Figs. 2c-e). The DMAgas and NH3gas concentrations were negatively correlated with those of TMAgas during peak 1; namely, R 2 =0.35 (P<0.01) between TMAgas and DMAgas, and R 2 =0.17 (P<0.01) between TMAgas and NH3gas. This suggested that 180 most of the DMAgas and NH3gas were likely derived from continental transport, rather than marine sources. During peak 2, increased TMAgas, DMAgas, and NH3gas concentrations were concurrently observed with increasing nss-SO4 2concentrations, suggesting that both marine emissions and continental transport simultaneously contributed to the observed DMAgas and NH3gas. During the port-anchoring period from December 20-22, the DMAgas and NH3gas concentrations varied slightly, and were moderate and low, respectively. However, the TMAgas concentrations continuously increased by over 100% as the 185 ambient temperature increased (Figs. 2c and f). Additionally, the nss-SO4 2concentrations of PM2.5 varied greatly and followed a bell-shaped pattern during the port-anchoring period.
As the TMAH + concentrations were approximately two orders of magnitude higher than those observed at the coastal site during the three seasons of 2019, the observed TMAH + was largely derived from marine sources. The TMAH + concentrations 205 followed a spatiotemporal pattern that clearly differed from those of DMAH + and NH4 + , while the latter two ions exhibited a similar spatiotemporal pattern during most periods of Campaign A (Figs. 3a-c). A significant negative correlation (P<0.01) was observed between the concentrations of TMAH + and NH4 + in PM2.5 (not shown). The spatiotemporal pattern of the TMAH + concentration also significantly differed from those of nss-SO4 2- (Fig. 2d) and SO2 (Fig. 3b), which are regarded as tracers of long-range transported continental pollutants and fresh vessel plumes. For example, extremely strong TMAH + 210 peaks occurred concurrently with low nss-SO4 2-, NH4 + , and SO2 concentrations, accompanied by high Na + concentrations under high wind speeds, which are common indicators of sea spray aerosols (Feng et al., 2017). Moreover, the TMAH + concentrations were approximately one order of magnitude larger than those of TMAgas, and no significant correlation was observed between them (P>0.05). This suggests that the observed TMAH + may not be derived from the neutralization reactions of TMAgas with acids in the marine atmosphere, and may have been derived from primary sea-spray organic 215 aerosols (Hu et al., 2015. Primary sea-spray organic aerosols mainly contain primary and degraded biogenic organics (Ault et al., 2013;Prather et al., 2013;Quinn et al., 2015;Dall'Osto et al., 2019).
The DMAH + concentrations varied at approximately 0.065±0.068 μg m -3 from December 9-22; however, they varied at approximately 0.10 ±0.04 μg m -3 during the port-anchoring period. The 25th percentile value of DMAH + during Campaign A was 0.021 μg m -3 , suggesting a low background concentration in the marine area. The DMAH + concentrations were 220 significantly correlated with those of NH4 + (R 2 =0.71, P<0.01; data not shown). When the data obtained at 03:00-05:59 and 14:00-16:59 on December 18 (strong peaks of TMAH + with a simultaneous increase in DMAH + ) were removed for correlation, the R 2 value improved to 0.78. Unlike TMAH + , the observed DMAH + may have been partially derived from acid-basic neutralization reactions in the ambient air, in addition to the primary sea-spray organic aerosols. For example, a large increase in DMAH + concentrations occurred concurrently with strong peaks in the TMAH + concentrations (gray 225 shadowed peak 4 in Figs. 3a & b).
The NH4 + concentrations of PM2.5 varied greatly at approximately 4.7±7.2 g m -3 during Campaign A (Fig. 3c). However, the 25 th percentile values were as low as 0.21 g m -3 , suggesting low marine background values. The 50 th percentile value was also only 1.2 g m -3 , which was considerably smaller than the average owing to the presence of strong peaks in NH4 + concentrations. The increased NH4 + concentrations associated with NO3and nss-SO4 2during Campaign A were likely due 230 to the long-range transport from the upwind continents.

Effects of temperature on the observed basic gases in the marine atmosphere
As mentioned above, the observed TMAgas likely originated from marine sources. We plotted the concentrations of TMAgas against the ambient air temperature (T) in Fig. 4a, which generally increased with increasing T. We further separated the 235 average hourly wind speeds (WS) into three categories: WS 5.0, 5.0 < WS 9.0, and WS > 9.0 m s -1 . At WS > 9.0 m s -1 , the data obtained from 15:00 on December 16 to 01:00 on December 19, including peaks 3 and 4, were separately considered as half-full symbols in Fig. 4a. The concentrations of TMAgas (half-full symbols) generally exceeded those of the other gases at the same T, with which they exhibited a moderately good exponent correlation ([TMAgas] = 0.03  e 0.04T with R 2 =0.72).
From 15:00 on December 16 to 01:00 on December 19, stronger emission potentials of TMAgas to the marine atmosphere 240 were expected in the corresponding marine zone. However, the measured concentrations of TMAH + and seawater pH in surface seawater are required to confirm this.
Following the same approach, the DMAgas and NH3gas concentrations were plotted against T, as shown in Figs. 4b & c, respectively. These values generally increased with increasing T. The NH3gas concentrations (half-full symbols) were strongly correlated with T ([NH3gas] = 0.05  e 0.3T with R 2 =0.96). As lower concentrations of nss-SO4 2-, NH4 + , and SO2 were 245 generally observed simultaneously, the continental transport of NH3gas was greatly reduced; therefore, the observed NH3gas was mainly derived from the seas. Therefore, the seas were the net source of NH3gas at the time of measurement. However, at the same T, the NH3gas concentrations (half-full symbols) were generally lower than those during other periods in this study.
The concentrations of NH4 + in surface seawater may have been lower at the time of measurement. However, this may not be the case, as higher concentrations of TMAH + were expected. Alternatively, the continental transport of NH3gas may have 250 made an important contribution to the observed NH3gas during most other periods when the seas were the net NH3gas sink.
DMAgas exhibited an extremely good exponent correlation with T (half-full symbols) at the measurement time ([DMAgas] = 0.001  e 0.3T with R 2 =0.91). At the same T, the DMAgas concentrations (half-full symbols) were not always higher or lower than the others. We considered these two hypotheses: In hypothesis 1, the observed DMAgas concentrations exceeded those predicted by the regression equation using the ambient T as the input; the seas were the net sinks of DMAgas. In hypothesis 2, 255 including all others, measurements of DMAH + in the surface seawater were required to confirm whether the seas were net sources or sinks of DMAgas.

Estimating the sea-derived DMAgas and NH3gas in the marine atmosphere
To estimate the sea-derived DMAgas and NH3gas concentrations in the marine atmosphere, we plotted the DMAgas and NH3gas concentrations against TMAgas, as shown in Figs. 5a and b. The purple-red and dark-green markers represent the data 260 obtained, with increasing concentrations of the three species from 10:00 on December 14 to 23:00 on December 16 (increasing period), and with decreasing concentrations from 23:00 on December 16 to 19:59 on December 17 (decreasing period) during peak 3, respectively; these were analyzed separately. A good correlation was obtained between DMAgas and TMAgas during the increasing period ([DMAgas] = 0.64  [TMAgas] -0.01, R 2 =0.86, and P<0.01). The good correlation suggested that DMAgas was likely released with TMAgas from the seawater and facilitated the estimation of non-sea-derived 265 DMAgas (DMAgas # ) concentrations using the regression equation. We assumed that any data beyond the purple-red dashed line reflected the non-sea-derived DMAgas, which can be attributed to continental transport. Therefore, we assumed that the DMAgas # concentrations were equal to the observed values of DMAgas minus the predicted values obtained using [DMAgas] = 0.64  [TMAgas] -0.01; the calculated DMAgas # values are shown in Fig. 5c. During peak 1, the calculated DMAgas # contributed to over 40% of the observed DMAgas for 12 h. Similar calculated results for DMAgas # were obtained during peak 270 2.
However, the equation for the decreasing period was as follows: [DMAgas] = 1.4[TMAgas] -0.05, R 2 =0.84, and P<0.01. The decreasing R 2 value and the increasing slope suggest that the TMAH + in the surface seawater may decompose into DMAH + to different extents (Lidbury et al., 2015a;Lidbury et al., 2015b;Xie et al., 2018). The two regression curves (purple-red and dark-green dashed lines in Figs. 5a and b) created a large triangular zone that likely reflected the different ratios of 275 DMAgas/TMAgas in primary marine emissions on the cruise route. Based on the triangular zone in Fig. 5a, the aforementioned calculations should be considered as the lower limit of DMAgas # .
The same approach was employed to analyze the NH3gas results, as shown in Figs. 5b and d. During peak 1, the calculated non-sea-derived NH3gas (NH3gas # ) contributed to over 40% of the observed NH3gas for 17 h. During peak 2, the calculated NH3gas # contributed to over 40% of the observed NH3gas for 24 h.

Estimation of non-sea-spray particulate DMAH + in the marine atmosphere
We plotted the concentrations of DMAH + against those of TMAH + in PM2.5 (Fig. 6a) using the data obtained from 15:00 on December 16 to 01:00 on December 19 ([DMAH + ]PM2.5 =0.13  [TMAH + ]PM2.5, R 2 =0.91, P<0.01). During this period, largely increased concentrations of DMAH + and TMAH + were observed under high wind speeds of 9-13 m s -1 . The good correlation suggested that the observed DMAH + was likely released with TMAH + as amines-contained sea spray aerosols in the 290 atmosphere, and facilitated the calculation of sea-derived DMAH + using TMAH + as a tracer of sea-spray aerosols. Thus, the 13 non-sea-derived DMAH + concentrations in PM2.5, marked as DMAH +# , were assumed to be equal to the observed DMAH + values minus the predicted values (sea-derived DMAH + ) using the regression equation. The calculated DMAH +# values are shown in Fig. 6b. The DMAH +# concentrations varied at approximately 0.0420.070 μg m -3 throughout Campaign A, during which the calculated average DMAH +# accounted for 65% of the observed average. Additionally, the calculated DMAH +# 295 values accounted for over 80% of the observed values in 26% of the Campaign A period. The estimations suggested that the observed DMAH + originated predominantly from long-range continental transport and/or secondary formation in the marine atmosphere. The analysis was supported by the good correlation between the concentrations of DMAH +# and those of NH4 + ; namely, [DMAH +# ]PM2.5 = 0.0089× [NH4 + ]PM2.5, (R 2 =0.82, P<0.01; Fig. 6c). The slope of 0.0089 was approximately 50% larger than that obtained in the coastal atmosphere (0.0059), suggesting more DMAgas partitioning in PM2.5 in the marine 300 atmosphere than in the coastal atmosphere (Pankow, 2015;Xie et al., 2018).
Moreover, the decomposition of TMAH + to DMAH + may have occurred in surface seawater and/or the marine atmosphere, to an extent, and the estimated DMAH +# should be considered as the upper limit. Notably, the NH4 + and TMAH + concentrations were negatively correlated during Campaign A, and no primary particulate NH4 + from sea-spray aerosols were identified.

Formation and chemical conversion of aminium ions in the transported and self-vessel SO2 plumes
When the sea-spray particulate DMAH + was deducted, the increased concentrations of DMAH +# were generally associated with increased nss-SO4 2and SO2 concentrations. Combining this with the moderate correlation between DMAH +# and NH4 + , we inferred that DMAH +# likely originated from concurrent secondary formation with NH4 + . However, we separated the air pollutant plumes into two groups. Group 1 represented an increase in nss-SO4 2and NH4 + together with SO2, while group 2 310 represented an increase in SO2 without increases in nss-SO4 2and NH4 + . Group 1 likely reflected the transport of aged air pollutant plumes from the continents, while group 2 may reflect self-vessel SO2 plumes. As shown in Figs. 6b and 3b-c, the concentrations of DMAH +# and NH4 + in the self-vessel SO2 plumes did not increase in the intervals between peaks 1 and 2 and between peaks 2 and 3. Therefore, no fresh formation of DMAH +# and NH4 + in the self-vessel emissions was detected.
However, the concentrations of TMAH + decreased in some self-vessel SO2 plumes. The TMAH + concentrations were 315 14 approximately one order of magnitude higher than those of TMAgas in the marine atmosphere. Assuming that the decreased TMAH + was released from PM2.5 to the gas phase, a simultaneous large spike in TMAgas should be observed. However, this was not the case, as shown in Fig. 1c. The decreased TMAH + may persist in PM2.5, but could not be detected by AIM-IC.

Conclusion and Implication
In continental China upwind of the Yellow Sea, the TMAgas and TMAH + concentrations in PM2.5 were extremely low 320 (0.001±0.001 µg m -3 ), mostly below the detection limit of the AIM-IC. Considering the observations as a reference, the largely increased TMAgas (0.031±0.009 μg m -3 ) and particulate TMAH + (0.28±0.18 μg m -3 ) concentrations in the marine atmosphere were attributed to marine emissions. Therefore, TMAgas and particulate TMAH + can be used as unique tracers to quantify the marine emissions of DMAgas, NH3gas, and particulate DMAH + , as well as the long-range transport from upwind continental China.

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Through comprehensive comparison and correlation analyses, the high concentrations of TMAH + in PM2.5 observed over the Yellow and Bohai seas, with episodic hourly averages exceeding 1 μg m -3 , were inferred to originate from strong primary sea-spray aerosol emissions. Moreover, the TMAgas concentrations generally increased with increasing ambient temperature and sea surface wind speeds, suggesting that the observed TMAgas was likely released from the surface seawater. However, the TMAgas concentrations were substantially lower than those of particulate TMAH + , and were not significantly correlated.

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Although different mechanisms have been reported in the literature for the release of TMAgas and particulate TMAH + from the seas, the lack of a significant correlation between them was surprising and was explored in the companion study.
The DMAgas and NH3gas concentrations varied at approximately 0.006±0.006 and 0.53±0.53 μg m -3 during Campaign A, wherein at least 16% and 34% of the observational values were derived from continental transport, respectively. The seaderived DMAgas and NH3gas were likely released with TMAgas as they peaked simultaneously. The DMAH + concentrations in 335 PM2.5 varied at approximately 0.065±0.068 μg m -3 during Campaign A, 65% of which was derived from continental transport.
Our analysis results did not support the occurrence of photolysis of marine organic nitrogen to generate NH3gas in the marine atmosphere during winter, as there was no correlation between the sea-derived NH3gas and particulate TMAH + concentrations.

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Additionally, peaks 2 and 3 of NH3gas persisted for dozens of hours under strong winds and were therefore unlikely to be 340 derived from seabird emissions. A good exponent correlation was observed between the observed NH3gas concentrations and T during the period without continental air pollutant transport, suggesting that the observed NH3gas was released from seawater. NH3 emissions from seabirds were unlikely contributors to the observed NH3gas in the marine atmosphere during winter; however, this may not have been the case during other seasons.
Additionally, no formation of particulate NH4 + and DMAH + in the self-vessel SO2 plume was observed in the marine 345 atmosphere. However, the particulate TMAH + concentration clearly decreased in the self-vessel SO2 plume without a simultaneous increase in the TMAgas concentration. Chemical conversion of particulate TMAH + likely occurred in the plume, while AIM-IC could not detect the products. This requires further investigation.
Data availability. The data of this paper are available upon request (contact: Xiaohong Yao, xhyao@ouc.edu.cn).