Insights into tropical cloud chemistry in Réunion (Indian Ocean): results from the BIO-MAÏDO campaign

We present here the results obtained during an intensive field campaign conducted in the framework of the French “BIO-MAÏDO” (Bio-physico-chemistry of tropical clouds at Maïdo (Réunion Island): processes and impacts on secondary organic aerosols' formation) project. This study integrates an exhaustive chemical and microphysical characterization of cloud water obtained in March–April 2019 in Réunion (Indian Ocean). Fourteen cloud samples have been collected along the slope of this mountainous island. Comprehensive chemical characterization of these samples is performed, including inorganic ions, metals, oxidants, and organic matter (organic acids, sugars, amino acids, carbonyls, and low-solubility volatile organic compounds, VOCs). Cloud water presents high molecular complexity with elevated water-soluble organic matter content partly modulated by microphysical cloud properties. As expected, our findings show the presence of compounds of marine origin in cloud water samples (e.g. chloride, sodium) demonstrating ocean–cloud exchanges. Indeed, Na+ and Cl− dominate the inorganic composition contributing to 30 % and 27 %, respectively, to the average total ion content. The strong correlations between these species (r2 = 0.87, p value: < 0.0001) suggest similar air mass origins. However, the average molar Cl-/Na+ ratio (0.85) is lower than the sea-salt one, reflecting a chloride depletion possibly associated with strong acids such as HNO3 and H2SO4. Additionally, the non-sea-salt fraction of sulfate varies between 38 % and 91 %, indicating the presence of other sources. Also, the presence of amino acids and for the first time in cloud waters of sugars clearly indicates that biological activities contribute to the cloud water chemical composition. A significant variability between events is observed in the dissolved organic content (25.5 ± 18.4 mg C L−1), with levels reaching up to 62 mg C L−1. This variability was not similar for all the measured compounds, suggesting the presence of dissimilar emission sources or production mechanisms. For that, a statistical analysis is performed based on back-trajectory calculations using the CAT (Computing Atmospheric Trajectory Tool) model associated with the land cover registry. These investigations reveal that air mass origins and microphysical variables do not fully explain the variability observed in cloud chemical composition, highlighting the complexity of emission sources, multiphasic transfer, and chemical processing in clouds. Even though a minor contribution of VOCs (oxygenated and low-solubility VOCs) to the total dissolved organic carbon (DOC) (0.62 % and 0.06 %, respectively) has been observed, significant levels of biogenic VOC (20 to 180 nmol L−1) were detected in the aqueous phase, indicating the cloud-terrestrial vegetation exchange. Cloud scavenging of VOCs is assessed by measurements obtained in both the gas and aqueous phases and deduced experimental gas-/aqueous-phase partitioning was compared with Henry's law equilibrium to evaluate potential supersaturation or unsaturation conditions. The evaluation reveals the supersaturation of low-solubility VOCs from both natural and anthropogenic sources. Our results depict even higher supersaturation of terpenoids, evidencing a deviation from thermodynamically expected partitioning in the aqueous-phase chemistry in this highly impacted tropical area.

Understanding the Extratropical Liquid Water Path Feedback in Mixed-Phase Clouds with an Idealized Global Climate Model

A negative shortwave cloud feedback associated with higher extratropical liquid water content in mixed-phase clouds is a common feature of global warming simulations, and multiple mechanisms have been hypothesized. A set of process-level experiments performed with an idealized global climate model (a dynamical core with passive water and cloud tracers and full Rotstayn-Klein single-moment microphysics) show that the common picture of the liquid water path (LWP) feedback in mixed-phase clouds being controlled by the amount of ice susceptible to phase change is not robust. Dynamic condensate processes—rather than static phase partitioning—directly change with warming, with varied impacts on liquid and ice amounts. Here, three principal mechanisms are responsible for the LWP response, namely higher adiabatic cloud water content, weaker liquid-to-ice conversion through the Bergeron-Findeisen process, and faster melting of ice and snow to rain. Only melting is accompanied by a substantial loss of ice, while the adiabatic cloud water content increase gives rise to a net increase in ice water path (IWP) such that total cloud water also increases without an accompanying decrease in precipitation efficiency. Perturbed parameter experiments with a wide range of climatological LWP and IWP demonstrate a strong dependence of the LWP feedback on the climatological LWP and independence from the climatological IWP and supercooled liquid fraction. This idealized setup allows for a clean isolation of mechanisms and paints a more nuanced picture of the extratropical mixed-phase cloud water feedback than simple phase change.

Increasing Cloud Water Resource in a warming world

Under global warming, terrestrial water resource regulated by precipitation may become more unevenly distributed across space, and some regions are likely to be highly water-stressed. From the perspective of the hydrological cycle, we propose a method to quantify the water resource with potential precipitation capacity in the atmosphere, or hydrometeors which remain suspended in the atmosphere without contributing to precipitation, namely Cloud Water Resource (CWR). Analyzing the characteristics of CWR during 2000-2017, CWR mainly concentrates in the middle-high latitudes which is the cold zone of the Köppen classification. In a warming world, CWR shows a significant increase, especially in the cold zone. Climate change with Arctic amplification and enhanced meridional circulation both contribute to the change of CWR through influencing hydrometeor inflow. By studying the characteristics of CWR and its influencing mechanisms, we demonstrate a perspective for human intervention with potential CWR in the atmosphere to alleviate terrestrial water resource shortages in the future.

The optical properties and in-situ observational evidence for the formation of brown carbon in cloud

Atmospheric brown carbon (BrC) makes a substantial contribution to aerosol light-absorbing and thus the global radiative forcing. Although BrC may change the lifetime of the cloud and ultimately affect precipitation, little is known regarding the optical properties and formation of BrC in the cloud. In the present study, the light-absorption properties of cloud droplet residual (cloud RES) were measured by coupled a ground-based counterflow virtual impactor (GCVI) and an Aethalometer (AE-33), in addition to the cloud interstitial (cloud INT) and ambient (cloud-free) particles by PM2.5 inlet-AE-33, at Mt. Tianjing (1690 m a.s.l.), a remote mountain site in southern China, from November to December 2020. Meanwhile, the light-absorption and fluorescence properties of water-soluble organic carbon (WSOC) in the collected cloud water and PM2.5 samples were also obtained, associated with the concentration of water-soluble ions. The mean light-absorption coefficient (Abs370) of the cloud RES, cloud INT, and cloud-free particles were 0.25 ± 0.15, 1.16 ± 1.14, and 1.47 ± 1.23 Mm−1, respectively. The Abs365 of WSOC was 0.11 ± 0.08 Mm−1 in cloud water and 0.40 ± 0.31 Mm−1 in PM2.5, and the corresponding mass absorption efficiency (MAE365) was 0.17 ± 0.07 and 0.31 ± 0.21 m2·g−1, respectively. A comparison of the light-absorption coefficient between BrC in the cloud RES/cloud INT and WSOC in cloud water/PM2.5 indicates a considerable contribution (48–75 %) of water-insoluble BrC to total BrC light-absorption. Secondary BrC estimated by minimum R squared (MRS) method dominated the total BrC in cloud RES (67–85 %), rather than in the cloud-free (11–16 %) and cloud INT (9–23 %) particles. It may indicate the formation of secondary BrC during cloud processing. Supporting evidence includes the enhanced WSOC and dominant contribution of secondary formation/biomass burning factor (> 80 %) to Abs365 in cloud water provided by Positive Matrix Factorization (PMF) analysis. In addition, we showed that the light-absorption of BrC in cloud water was closely related to humic-like substances and tyrosine/proteins-like substances (r > 0.63, p < 0.01), whereas only humic-like substances for PM2.5, as identified by excitation-emission matrix fluorescence spectroscopy.

High number concentrations of transparent exopolymer particles (TEP) in ambient aerosol particles and cloud water – A case study at the tropical Atlantic Ocean

Transparent exopolymer particles (TEP) exhibit the properties of gels and are ubiquitously found in the world oceans. Possibly, TEP may enter the atmosphere as part of sea spray aerosol. Here, we report number concentrations of TEP (diameter > 4.5 µm) in ambient aerosol and cloud water samples from the tropical Atlantic Ocean as well as in generated aerosol particles using a plunging waterfall tank that was filled with the ambient sea water. The ambient TEP concentrations ranged between 7 × 102 and 3 × 104 #TEP m−3 in supermicron aerosol particles and correlations to sodium (Na+) and calcium (Ca2+) (R2 = 0.5) suggested some contribution via bubble bursting. Cloud water TEP concentrations were between 4 × 106 and 9 × 106 #TEP L−1 corresponding to equivalent air concentrations of 2–4 × 103 #TEP m−3. The TEP concentrations in the tank-generated aerosol particles, produced from the same waters and sampled with an equivalent system, were significantly lower (4 × 102–2 × 103 #TEP m−3) compared to the ambient concentrations. Based on Na+ concentrations in seawater and in the atmosphere, the enrichment factor for TEP in the atmosphere was calculated. The tank-generated TEP were enriched by a factor of 50 compared to sea water and, therefore, in-line with published enrichment factors for supermicron organic matter in general and TEP specifically. TEP enrichment in the ambient atmosphere was on average 1 × 103 in cloud water and 9 × 103 in ambient aerosol particles and therefore about two orders of magnitude higher than the corresponding enrichment from the tank study. Such high enrichment of supermicron particulate organic constituents in the atmosphere is uncommon and we propose that atmospheric TEP concentrations resulted from a combination of enrichment during bubble bursting transfer from the ocean and TEP in-situ formation in atmospheric phases. Abiotic in-situ formation might have occurred from aqueous reactions of dissolved organic precursors that were present in particle and cloud water samples, while biotic formation involves bacteria, which were abundant in the cloud water samples. The ambient TEP number concentrations were two orders of magnitude higher than recently reported ice nucleating particle (INP) concentrations measured at the same location. As TEP likely possess good properties to act as INP, in future experiments it is worth studying if a certain part of TEP contributes a fraction of the biogenic INP population.

Measurement report: Molecular characteristics of cloud water in southern China and insights into aqueous-phase processes from Fourier transform ion cyclotron resonance mass spectrometry

Characterizing the molecular composition of cloud water could provide unique insights into aqueous chemistry. Field measurements were conducted at Mt. Tianjing in southern China in May, 2018. There are thousands of formulas (C5–30H4–55O1–15N0–2S0–2) identified in cloud water by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). CHON formulas (formulas containing C, H, O, and N elements; the same is true for CHO and CHOS) represent the dominant component (43.6 %–65.3 % of relative abundance), followed by CHO (13.8 %–52.1%). S-containing formulas constitute ∼5 %–20 % of all assigned formulas. Cloud water has a relative-abundance-weighted average O/C of 0.45–0.56, and the double bond equivalent of 5.10–5.70. Most of the formulas (>85 %) are assigned as aliphatic and olefinic species. No statistical difference in the oxidation state is observed between cloud water and interstitial PM2.5. CHON with aromatic structures are abundant in cloud water, suggesting their enhanced in-cloud formation. Other organics in cloud water are mainly from biomass burning and oxidation of biogenic volatile organic compounds. The cloud water contains more abundant CHON and CHOS at night, which are primarily contributed by −N2O5 function and organosulfates, demonstrating the enhanced formation in dark aqueous or multi-phase reactions. While more abundant CHO is observed during the daytime, likely due to the photochemical oxidation and photolysis of N- or S-containing formulas. The results provide an improved understanding of the in-cloud aqueous-phase reactions.

Assimilating Cloud Optical Depth for Applications to Extreme Weather Events

This paper reports the assimilation of cloud optical depth datasets into a variational data assimilation system to improve cloud ice, cloud water, rain, snow, and graupel analysis in extreme weather events for improving forecasts. A cloud optical depth forward operator was developed and implemented in the Space and Time Multiscale Analysis System (STMAS), a multiscale three-dimensional variational analysis system. Using this improved analysis system, the NOAA GOES-15 DCOMP (Daytime Cloud Optical and Microphysical Properties) cloud optical depth products were assimilated to improve the microphysical states. For an eight-day period of extreme weather events in September 2013 in Colorado, the United States, the impact of the cloud optical depth assimilation on the analysis results and forecasts was evaluated. The DCOMP products improved the cloud ice and cloud water predictions significantly in convective and lower levels. The DCOMP products also reduced errors in temperature and relative humidity data at the top (250–150 hPa) and bottom (850–700 hPa) layers. With the cloud ice improvement at higher layers, the DCOMP products provided better forecasts of cloud liquid at low layers (900–700 hPa), temperature and wind at all layers, and relative humidity at middle and bottom layers. Furthermore, for this extreme weather event, both equitable threat score (ETS) and bias were improved throughout the 12 h period, with the most significant improvement observed in the first 3 h. This study will raise the expectation of cloud optical depth product assimilation in operational applications.