Speciation of Water‐Soluble Inorganic, Organic, and Total Nitrogen in a Background Marine Environment: Cloud Water, Rainwater, and Aerosol Particles

Cloud water, rainwater, and aerosol particles were collected in Puerto Rico from December 2004 to March 2007 in order to investigate their chemical composition, relation to sources, and removal processes. The species analyzed were inorganic ions, metals, total and dissolved organic carbon (TOC, DOC), total nitrogen (TN), and organic acids. For all samples, the dominant species were marine (Na+, Cl−), representing about 50%–65% of total content. Non‐sea‐salt fraction was dominated by SO42− (17%–25%), followed by water‐soluble organic (2%–8%) and total nitrogen (2% –6%) compounds. Organic acids represented contributions to the organic fraction in cloud water of 20% and 6% for aerosol particles. Inorganic species were predominant in total nitrogen portion. The chemical composition of cloud water, rainwater, and aerosol particles were observed to be sensitive to transport patterns. Air masses from northwest Africa showed the highest concentrations of nss‐Ca2+, Fe, and Al, suggesting a crustal origin. The pH values for cloud water and rainwater observed under this transport pattern were higher than background conditions, probably due to the alkalinity associated with nss‐Ca2+. The highest concentrations of Cl− and SO42−, with lower pH, were measured during periods of influence from Soufriere Hills volcano eruptions, most likely due to emitted SO2 and HCl. Air masses from North America had an anthropogenic influence, where levels of nss‐SO42−, TOC, and TN were higher (∼4 times) than in clean air masses. These results suggest that long‐range transport could be an extra source of metals and organic/nitrogen species to the Caribbean region ecosystems

Classifying aerosol type using in situ surface spectral aerosol optical properties

Knowledge of aerosol size and composition is important for determining radiative forcing effects of aerosols, identifying aerosol sources and improving aerosol satellite retrieval algorithms. The ability to extrapolate aerosol size and composition, or type, from intensive aerosol optical properties can help expand the current knowledge of spatiotemporal variability in aerosol type globally, particularly where chemical composition measurements do not exist concurrently with optical property measurements. This study uses medians of the scattering Ångström exponent (SAE), absorption Ångström exponent (AAE) and single scattering albedo (SSA) from 24 stations within the NOAA/ESRL Federated Aerosol Monitoring Network to infer aerosol type using previously published aerosol classification schemes. Three methods are implemented to obtain a best estimate of dominant aerosol type at each station using aerosol optical properties. The first method plots station medians into an AAE vs. SAE plot space, so that a unique combination of intensive properties corresponds with an aerosol type. The second typing method expands on the first by introducing a multivariate cluster analysis, which aims to group stations with similar optical characteristics and thus similar dominant aerosol type. The third and final classification method pairs 3-day backward air mass trajectories with median aerosol optical properties to explore the relationship between trajectory origin (proxy for likely aerosol type) and aerosol intensive parameters, while allowing for multiple dominant aerosol types at each station. The three aerosol classification methods have some common, and thus robust, results. In general, estimating dominant aerosol type using optical properties is best suited for site locations with a stable and homogenous aerosol population, particularly continental polluted (carbonaceous aerosol), marine polluted (carbonaceous aerosol mixed with sea salt) and continental dust/biomass sites (dust and carbonaceous aerosol); however, current classification schemes perform poorly when predicting dominant aerosol type at remote marine and Arctic sites and at stations with more complex locations and topography where variable aerosol populations are not well represented by median optical properties. Although the aerosol classification methods presented here provide new ways to reduce ambiguity in typing schemes, there is more work needed to find aerosol typing methods that are useful for a larger range of geographic locations and aerosol populations

UNDERSTANDING THE TRANSPORT AND IMPACT OF AFRICAN DUST ON THE CARIBBEAN BASIN

Every year huge quantities of soil dust are carried by winds from Africa, across the Atlantic, and to the Caribbean. No other ocean region is so extensively and persistently impacted by such high concentrations of dust, a region that extends over 7000 km from the coast of Africa to the Caribbean and to the bounding continental shores of the Americas. In effect, the Caribbean Basin can be thought of as the receptor site of the Saharan dust source, a source that accounts for over half of global dust emissions. It is generally recognized that on a global scale mineral dust can affect many aspects of climate, marine biogeochemical processes, soil fertility, air quality, and human health. However, it is difficult to assess the impact on the Caribbean Basin because of the dearth of studies in this region. A better understanding is needed of the factors that affect the transport of dust, the physical and chemical properties of the transported materials, and how these might change during transport. Of particular interest is how climate change might affect dust transport in the future. Presented here is a brief overview of research relevant to the region and issues in dust-related research that need to be addressed

Organic Carbon, Total Nitrogen, and Water-Soluble Ions in Clouds from a Tropical Montane Cloud Forest in Puerto Rico

Chemical characterization to determine the organic and nitrogen fractions was performed on cloud water samples collected in a mountaintop site in Puerto Rico. Cloud water samples showed average concentrations of 1.09 mg L−1 of total organic carbon (TOC), of 0.85 mg L−1 for dissolved organic carbon (DOC) and of and 1.25 mg L−1 for total nitrogen (TN). Concentrations of organic nitrogen (ON) changed with the origin of the air mass. Changes in their concentrations were observed during periods under the influence of African dust (AD). The ON/TN ratios were 0.26 for the clean and 0.35 for the AD periods. Average concentrations of all these species were similar to those found in remote environments with no anthropogenic contribution. In the AD period, for cloud water the concentrations of TOC were 4 times higher and TN were 3 times higher than during periods of clean air masses associated with the trade winds. These results suggest that a significant fraction of TOC and TN in cloud and rainwater is associated to airborne particulate matter present in dust. Functional groups were identified using proton nuclear magnetic resonance (1H NMR) spectroscopy. This characterization led to the conclusion that water-soluble organic compounds in these samples are mainly aliphatic oxygenated compounds, with a small amount of aromatics. The ion chromatography results showed that the ionic species were predominantly of marine origin, for air masses with and without African dust influence, with cloud water concentrations of NO3− and NH4+ much lower than from polluted areas in the US. An increase of such species as SO42−, Cl−, Mg2+, K+ and Ca2+ was seen when air masses originated from northwest Africa. The changes in the chemical composition and physical properties of clouds associated with these different types of aerosol particles could affect on cloud formation and processes

Water-Soluble Organic and Nitrogen Levels in Cloud and Rainwater in a Background Marine Environment Under Influence of Different Air Masses

Chemical characterization was performed on cloud and rainwater samples collected as part of the Rain In Cumulus over the Ocean Experiment (RICO). This experiment took place at a mountaintop site (East Peak) in Puerto Rico from December 2004 to March 2007 in order to determine water-soluble organic and nitrogen fractions in a marine background environment. For cloud water, similar average concentrations of 1.0 (±0.3) mg/L were found for total organic carbon (TOC) and total nitrogen (TN) and an average concentration of 0.8 (±0.2) mg/L was found for dissolved organic carbon (DOC). In rainwater, these concentrations were lower, ranging from 0.3 to 0.5 (±0.1) mg/L. Changes in the concentrations of these species were observed in periods under the influence of anthropogenic, African dust, and volcanic ash air masses. In these periods the concentrations of TOC, DOC, and TN were 2 to 4 times higher than in periods under the influence of trade winds. The insoluble organic material arriving during African dust events showed total carbon (TC) concentrations on averaging 1.5 mg/L for cloud water. The TC was composed mainly of organic carbon with polar compounds from low to high molecular weight (MW). The polar compounds with high MW were probably associated with pollution (e.g., fossil fuel combustion) from other regions. Crustal species (Al and Fe) dominated particles associated with dust episodes, confirming the soil origin. Our results suggested that a fraction (40–80%) of TOC and (\u3c100%) of TN in Puerto Rican cloud/rainwater could be originated from long-range transport of dust, ash and/or pollution

Air Quality in Puerto Rico in the Aftermath of Hurricane Maria: A Case Study on the Use of Lower-Cost Air Quality Monitors

In the aftermath of Hurricane Maria, the electricity grid in Puerto Rico was devastated, with over 90% of the island without electricity; as of December 2017, about 50% of the island lacked electricity, and power outages were common elsewhere. Backup generators are widely used, sometimes as the main source of electricity. The hurricane also damaged the island’s existing air monitoring network and the University of Puerto Rico’s observing facilities. We deployed four lower-cost air quality monitors (Real-time Affordable Multi-Pollutant or RAMP monitors) and a black carbon (BC) monitor in the San Juan Metro Area in November 2017. The first month of data collected with the RAMPs showed high sulfur dioxide (SO2) and carbon monoxide (CO) concentrations of varying magnitudes each night. SO2 and CO are strongly correlated (r2 >0.9) at two sites ~5 km apart (University of Puerto Rico and an industrial area, Puerto Nuevo), suggesting a single source type. BC measured at the UPR site is also well correlated with CO and SO2. While the RAMPs are not certified as a federal equivalent method, the RAMP SO2 data suggest that the EPA’s daily 1-hour threshold for SO2 (75 ppb) was exceeded on almost 80% of the first 30 days of deployment (November-December 2017). The widespread reliance on generators for regular electric supply in the aftermath of Hurricane Maria appears to have increased air pollution in San Juan

Do Cloud Properties in a Puerto Rican Tropical Montane Cloud Forest Depend on Occurrence of Long-Range Transported African Dust?

We investigated cloud properties of warm clouds in a tropical montane cloud forest at Pico del Este (1,051 m a.s.l.) in the northeastern part of Puerto Rico to address the question of whether cloud properties in the Caribbean could potentially be affected by African dust transported across the Atlantic Ocean. We analyzed data collected during 12 days in July 2011. Cloud droplet size spectra were measured using the FM-100 fog droplet spectrometer that measured droplet size distributions in the range from 2 to 49 µm, primarily during fog events. The droplet size spectra revealed a bimodal structure, with the first peak (D < 6 µm) being more pronounced in terms of droplet number concentrations, whereas the second peak (10 µm < D < 20 µm) was found to be the one relevant for total liquid water content (LWC) of the cloud. We identified three major clusters of characteristic droplet size spectra by means of hierarchical clustering. All clusters differed significantly from each other in droplet number concentration (�� tot), effective diameter (ED), and median volume diameter (MVD). For the cluster comprising the largest droplets and the lowest droplet number concentrations, we found evidence of inhomogeneous mixing in the cloud. Contrastingly, the other two clusters revealed microphysical behavior, which could be expected under homogeneous mixing conditions. For those conditions, an increase in cloud condensation nuclei—e.g., from processed African dust transported to the site—is supposed to lead to an increased droplet concentration. In fact, one of these two clusters showed a clear shift of cloud droplet size spectra towards smaller droplet diameters. Since this cluster occurred during periods with strong evidence for the presence of long-range transported African dust, we hypothesize a link between the observed dust episodes and cloud characteristics in the Caribbean at our site, which is similar to the anthropogenic aerosol indirect effect.ISSN:0033-4553ISSN:1420-9136ISSN:1557-736

Aerosol inorganic composition at a tropical site: Discrepancies between filter-based sampling and a semi-continuous method

The concentrations of the water-soluble inorganic aerosol species, ammonium (NH4+), nitrate (NO3-), chloride (Cl-), and sulfate (SO42-), were measured from September to November 2002 at a pasture site in the Amazon Basin (Rondnia, Brazil) (LBA-SMOCC). Measurements were conducted using a semi-continuous technique (Wet-annular denuder/Steam-Jet Aerosol Collector: WAD/SJAC) and three integrating filter-based methods, namely (1) a denuder-filter pack (DFP: Teflon and impregnated Whatman filters), (2) a stacked-filter unit (SFU: polycarbonate filters), and (3) a High Volume dichotomous sampler (HiVol: quartz fiber filters). Measurements covered the late dry season (biomass burning), a transition period, and the onset of the wet season (clean conditions). Analyses of the particles collected on filters were performed using ion chromatography (IC) and Particle-Induced X-ray Emission spectrometry (PIXE). Season-dependent discrepancies were observed between the WAD/SJAC system and the filter-based samplers. During the dry season, when PM2.5 (D-p <= 2.5 mu m) concentrations were similar to 100 mu g m(-3), aerosol NH4+ and SO42- measured by the filter-based samplers were on average two times higher than those determined by the WAD/SJAC. Concentrations of aerosol NO3- and Cl- measured with the HiVol during daytime, and with the DFP during day- and nighttime also exceeded those of the WAD/SJAC by a factor of two. In contrast, aerosol NO3- and Cl- measured with the SFU during the dry season were nearly two times lower than those measured by the WAD/SJAC. These differences declined markedly during the transition period and towards the cleaner conditions during the onset of the wet season (PM2.5 similar to 5 mu g m(-3)); when filter-based samplers measured on average 40-90% less than the WAD/SJAC. The differences were not due to consistent systematic biases of the analytical techniques, but were apparently a result of prevailing environmental conditions and different sampling procedures. For the transition period and wet season, the significance of our results is reduced by a low number of data points. We argue that the observed differences are mainly attributable to (a) positive and negative filter sampling artifacts, (b) presence of organic compounds and organosulfates on filter substrates, and (c) a SJAC sampling efficiency of less than 100%

Spread of SARS-CoV-2 through Latin America and the Caribbean region: A look from its economic conditions, climate and air pollution indicators

We have evaluated the spread of SARS-CoV-2 through Latin America and the Caribbean (LAC) region by means of a correlation between climate and air pollution indicators, namely, average temperature, minimum temperature, maximum temperature, rainfall, average relative humidity, wind speed, and air pollution indicators PM10, PM2.5, and NO2 with the COVID-19 daily new cases and deaths. The study focuses in the following LAC cities: Mexico City (Mexico), Santo Domingo (Dominican Republic), San Juan (Puerto Rico), Bogotá (Colombia), Guayaquil (Ecuador), Manaus (Brazil), Lima (Perú), Santiago (Chile), São Paulo (Brazil) and Buenos Aires (Argentina). The results show that average temperature, minimum temperature, and air quality were significantly associated with the spread of COVID-19 in LAC. Additionally, humidity, wind speed and rainfall showed a significant relationship with daily cases, total cases and mortality for various cities. Income inequality and poverty levels were also considered as a variable for qualitative analysis. Our findings suggest that and income inequality and poverty levels in the cities analyzed were related to the spread of COVID-19 positive and negative, respectively. These results might help decision-makers to design future strategies to tackle the spread of COVID-19 in LAC and around the world