scholarly journals Contribution of dust inputs to dissolved organic carbon and water transparency in Mediterranean reservoirs

2012 ◽  
Vol 9 (12) ◽  
pp. 5049-5060 ◽  
Author(s):  
I. de Vicente ◽  
E. Ortega-Retuerta ◽  
R. Morales-Baquero ◽  
I. Reche

Abstract. The Mediterranean reservoirs receive frequent atmospheric Saharan dust inputs with soil-derived organic components mostly during the stratification periods, when run-off inputs are particularly limited. Here, we quantified and optically characterized the water-soluble organic carbon (WSOC) of the (dry and wet) atmospheric deposition in collectors placed near three reservoirs from the western Mediterranean Basin. In addition, we determined the WSOC contribution to the pool of dissolved organic carbon (DOC) in the reservoirs and the influence of dust-derived chromophoric organic components on the water transparency during their stratification periods. We found synchronous dynamics in the WSOC atmospheric inputs among the three collectors and in the DOC concentrations among the three reservoirs. The DOC concentrations and the WSOC atmospheric inputs were positive and significantly correlated in the most oligotrophic reservoir (Quéntar) and in the reservoir with the highest ratio of surface area to mixing water depth (Cubillas). Despite these correlations, WSOC atmospheric inputs represented less than 10% of the total DOC pool, suggesting that indirect effects of dust inputs on reservoir DOC may also promote these synchronous patterns observed in the reservoirs. Chromophoric components from dust inputs can significantly reduce the water transparency to the ultraviolet radiation (UVR). The depths where UVR at λ = 320 nm was reduced to ten percent of surface intensity (Z10%) decreased 27 cm in Béznar, 49 cm in Cubillas, and 69 cm in Quéntar due to the dust inputs. Therefore, the increasing dust export to the atmosphere may have consequences for the water transparency of aquatic ecosystems located under the influence of the global dust belt.

2012 ◽  
Vol 9 (7) ◽  
pp. 8307-8336
Author(s):  
I. de Vicente ◽  
E. Ortega-Retuerta ◽  
R. Morales-Baquero ◽  
I. Reche

Abstract. Mediterranean reservoirs receive frequent Saharan dust inputs with soil-derived organic compounds mostly during stratification periods, when run-off inputs are particularly limited. Here, we quantified and optically characterized the water-soluble organic carbon (WSOC) of the (dry and wet) atmospheric deposition in collectors located near three reservoirs from the Western Mediterranean Basin. In addition, we determined, during the stratification period, the WSOC contribution to the pool of dissolved organic carbon (DOC) and the influence of the chromophoric organic compounds from the dust on water transparency. We found synchrony both in the WSOC atmospheric inputs among collectors and in the DOC dynamics among the three reservoirs. DOC concentrations and WSOC atmospheric inputs were positive and significantly correlated in the two reservoirs more sensitive to atmospheric inputs: the most oligotrophic reservoir (Quentar) and the reservoir with the highest ratio of surface area to mixing water depth (Cubillas). Nevertheless, WSOC atmospheric inputs, during the stratification period, represented less than 10 % of the total DOC pool, suggesting that indirect effects of dust inputs such as primary productivity stimulation may also induce these synchronic patterns. Chromophoric compounds from dust inputs can significantly reduce water transparency to ultraviolet radiation (UVR). The depths where UVR at λ = 320 nm is reduced to ten percent of surface intensity (Z10 %) decreased 15 cm (about 24 %) in Beznar, 17 cm (about 27 %) in Cubillas, and 43 cm (about 39 %) in Quéntar due to dust inputs.


2021 ◽  
Vol 21 (10) ◽  
pp. 8067-8088
Author(s):  
Vincent Michoud ◽  
Elise Hallemans ◽  
Laura Chiappini ◽  
Eva Leoz-Garziandia ◽  
Aurélie Colomb ◽  
...  

Abstract. The characterization of the molecular composition of organic carbon in both gaseous and aerosol is key to understanding the processes involved in the formation and aging of secondary organic aerosol. Therefore a technique using active sampling on cartridges and filters and derivatization followed by analysis using a thermal desorption–gas chromatography–mass spectrometer (TD–GC–MS) has been used. It is aimed at studying the molecular composition of organic carbon in both gaseous and aerosol phases (PM2.5) during an intensive field campaign which took place in Corsica (France) during the summer of 2013: the ChArMEx (Chemistry and Aerosol Mediterranean Experiment) SOP1b (Special Observation Period 1B) campaign. These measurements led to the identification of 51 oxygenated (carbonyl and or hydroxyl) compounds in the gaseous phase with concentrations between 21 and 3900 ng m−3 and of 85 compounds in the particulate phase with concentrations between 0.3 and 277 ng m−3. Comparisons of these measurements with collocated data using other techniques have been conducted, showing fair agreement in general for most species except for glyoxal in the gas phase and malonic, tartaric, malic and succinic acids in the particle phase, with disagreements that can reach up to a factor of 8 and 20 on average, respectively, for the latter two acids. Comparison between the sum of all compounds identified by TD–GC–MS in the particle phase and the total organic matter (OM) mass reveals that on average 18 % of the total OM mass can be explained by the compounds measured by TD–GC–MS. This number increases to 24 % of the total water-soluble OM (WSOM) measured by coupling the Particle Into Liquid Sampler (PILS)-TOC (total organic carbon) if we consider only the sum of the soluble compounds measured by TD–GC–MS. This highlights the important fraction of the OM mass identified by these measurements but also the relative important fraction of OM mass remaining unidentified during the campaign and therefore the complexity of characterizing exhaustively the organic aerosol (OA) molecular chemical composition. The fraction of OM measured by TD–GC–MS is largely dominated by di-carboxylic acids, which represent 49 % of the PM2.5 content detected and quantified by this technique. Other contributions to PM2.5 composition measured by TD–GC–MS are then represented by tri-carboxylic acids (15 %), alcohols (13 %), aldehydes (10 %), di-hydroxy-carboxylic acids (5 %), monocarboxylic acids and ketones (3 % each), and hydroxyl-carboxylic acids (2 %). These results highlight the importance of polyfunctionalized carboxylic acids for OM, while the chemical processes responsible for their formation in both phases remain uncertain. While not measured by the TD–GC–MS technique, humic-like substances (HULISs) represent the most abundant identified species in the aerosol, contributing for 59 % of the total OM mass on average during the campaign. A total of 14 compounds were detected and quantified in both phases, allowing the calculation of experimental partitioning coefficients for these species. The comparison of these experimental partitioning coefficients with theoretical ones, estimated by three different models, reveals large discrepancies varying from 2 to 7 orders of magnitude. These results suggest that the supposed instantaneous equilibrium being established between gaseous and particulate phases assuming a homogeneous non-viscous particle phase is questionable.


2020 ◽  
Author(s):  
Vincent Michoud ◽  
Elise Hallemans ◽  
Laura Chiappini ◽  
Eva Leoz-Garziandia ◽  
Aurélie Colomb ◽  
...  

Abstract. The characterization of the molecular composition of organic carbon in both gaseous and aerosol is key to understand the processes involved in the formation and aging of secondary organic aerosol. Therefore a technique using active sampling on cartridges and filters and derivatization followed by analysis using a Thermal Desorption-Gas Chromatography/mass spectrometer (TD-GC/MS) has been used to study the molecular composition of organic carbon in both gaseous and aerosol phases during an intensive field campaign which took place in Corsica during the summer 2013: the ChArMEx (Chemistry and Aerosol Mediterranean Experiment) SOP1b (Special Observation Period 1B) campaign. These measurements led to the identification of 51 oxygenated (carbonyl and or hydroxyl) compounds in the gaseous phase with concentrations comprised between 21 ng m−3 and 3900 ng m−3 and of 85 compounds in the particulate phase with concentrations comprised between 0.3 and 277 ng m−3. Comparisons of these measurements with collocated data using other techniques have been conducted showing fair agreement in general for most species except for glyoxal in the gas phase and malonic, tartaric, malic and succinic acids in the particle phase with disagreements that can reach up to a factor of 8 and 20 on average, respectively for the latter two acids. Comparison between the sum of all compounds identified by TD-GC/MS in particle phase with the total Organic Matter (OM) mass reveal that 18 % of the total OM mass can be explained by the compounds measured by TD-GC/MS for the whole campaign. This number increase to 24 % of the total Water Soluble OM (WSOM) measured by PILS-TOC if we consider only the sum of the soluble compounds measured by TD-GC/MS. This highlights the non-negligible fraction of the OM mass identified by these measurements but also the relative important fraction of OM mass remaining unidentified during the campaign and therefore the complexity of characterizing exhaustively the Organic Aerosol (OA) molecular chemical composition. The fraction of OM measured by TD-GC/MS is largely dominated by di-carboxylic acids which represents 49 % of the PM2.5 content detected and quantified by this technique. Other contributions to PM2.5 composition measured by TD-GC/MS are then represented by tri-carboxylic acids (15 %), alcohols (13 %), aldehydes (10 %), di-hydroxy-carboxylic acids (5 %), monocarboxylic acids and ketones (3 % each) and hydroxyl-carboxylic acids (2 %). These results highlight the importance of poly functionalized carboxylic acids for OM while the chemical processes responsible for their formation in both phases remain uncertain. While not measured by TD-GC/MS technique, HUmic-LIke Substances (HULIS) represent the most abundant identified species in the aerosol, contributing for 59 % of the total identified OM mass on average during the campaign. 14 compounds were detected and quantified in both phases allowing the calculation of experimental partitioning coefficient for these species. The comparison of these experimental partitioning coefficients with theoretical ones, estimated by three different models, reveals large discrepancies varying from 2 to 7 orders of magnitude. These results suggest that the supposed instantaneous equilibrium being established between gaseous and particulate phases assuming a homogeneous non-viscous particle phase is questionable.


2013 ◽  
Vol 13 (10) ◽  
pp. 5117-5135 ◽  
Author(s):  
B. Ervens ◽  
Y. Wang ◽  
J. Eagar ◽  
W. R. Leaitch ◽  
A. M. Macdonald ◽  
...  

Abstract. Cloud and fog droplets efficiently scavenge and process water-soluble compounds and, thus, modify the chemical composition of the gas and particle phases. The concentrations of dissolved organic carbon (DOC) in the aqueous phase reach concentrations on the order of ~ 10 mgC L−1 which is typically on the same order of magnitude as the sum of inorganic anions. Aldehydes and carboxylic acids typically comprise a large fraction of DOC because of their high solubility. The dissolution of species in the aqueous phase can lead to (i) the removal of species from the gas phase preventing their processing by gas phase reactions (e.g., photolysis of aldehydes) and (ii) the formation of unique products that do not have any efficient gas phase sources (e.g., dicarboxylic acids). We present measurements of DOC and select aldehydes in fog water at high elevation and intercepted clouds at a biogenically-impacted location (Whistler, Canada) and in fog water in a more polluted area (Davis, CA). Concentrations of formaldehyde, glyoxal and methylglyoxal were in the micromolar range and comprised ≤ 2% each individually of the DOC. Comparison of the DOC and aldehyde concentrations to those at other locations shows good agreement and reveals highest levels for both in anthropogenically impacted regions. Based on this overview, we conclude that the fraction of organic carbon (dissolved and insoluble inclusions) in the aqueous phase of clouds or fogs, respectively, comprises 2–~ 40% of total organic carbon. Higher values are observed to be associated with aged air masses where organics are expected to be more highly oxidised and, thus, more soluble. Accordingly, the aqueous/gas partitioning ratio expressed here as an effective Henry's law constant for DOC (KH*DOC) increases by an order of magnitude from 7 × 103 M atm−1 to 7 × 104 M atm−1 during the ageing of air masses. The measurements are accompanied by photochemical box model simulations. These simulations are used to contrast two scenarios, i.e., an anthropogenically vs. a more biogenically impacted one as being representative for Davis and Whistler, respectively. Since the simplicity of the box model prevents a fully quantitative prediction of the observed aldehyde concentrations, we rather use the model results to compare trends in aldehyde partitioning and ratios. They suggest that the scavenging of aldehydes by the aqueous phase can reduce HO2 gas phase levels significantly by two orders of magnitude due to a weaker net source of HO2 production from aldehyde photolysis in the gas phase. Despite the high solubility of dicarbonyl compounds (glyoxal, methylglyoxal), their impact on the HO2 budget by scavenging is < 10% of that of formaldehyde. The overview of DOC and aldehyde measurements presented here reveals that clouds and fogs can be efficient sinks for organics, with increasing importance in aged air masses. Even though aldehydes, specifically formaldehyde, only comprise ~ 1% of DOC, their scavenging and processing in the aqueous phase might translate into significant effects in the oxidation capacity of the atmosphere.


2016 ◽  
Vol 16 (14) ◽  
pp. 8749-8766 ◽  
Author(s):  
Julie Vincent ◽  
Benoit Laurent ◽  
Rémi Losno ◽  
Elisabeth Bon Nguyen ◽  
Pierre Roullet ◽  
...  

Abstract. Previous studies have provided some insight into the Saharan dust deposition at a few specific locations from observations over long time periods or intensive field campaigns. However, no assessment of the dust deposition temporal variability in connection with its regional spatial distribution has been achieved so far from network observations over more than 1 year. To investigate dust deposition dynamics at the regional scale, five automatic deposition collectors named CARAGA (Collecteur Automatique de Retombées Atmosphériques insolubles à Grande Autonomie in French) have been deployed in the western Mediterranean region during 1 to 3 years depending on the station. The sites include, from south to north, Lampedusa, Majorca, Corsica, Frioul and Le Casset (southern French Alps). Deposition measurements are performed on a common weekly period at the five sites. The mean dust deposition fluxes are higher close to the northern African coasts and decrease following a south–north gradient, with values from 7.4 g m−2 year−1 in Lampedusa (35°31′ N, 12°37′ E) to 1 g m−2 year−1 in Le Casset (44°59′ N, 6°28′ E). The maximum deposition flux recorded is of 3.2 g m−2 wk−1 in Majorca with only two other events showing more than 1 g m−2 wk−1 in Lampedusa, and a maximum of 0.5 g m−2 wk−1 in Corsica. The maximum value of 2.1 g m−2 year−1 observed in Corsica in 2013 is much lower than existing records in the area over the 3 previous decades (11–14 g m−2 year−1). From the 537 available samples, 98 major Saharan dust deposition events have been identified in the records between 2011 and 2013. Complementary observations provided by both satellite and air mass trajectories are used to identify the dust provenance areas and the transport pathways from the Sahara to the stations for the studied period. Despite the large size of African dust plumes detected by satellites, more than 80 % of the major dust deposition events are recorded at only one station, suggesting that the dust provenance, transport and deposition processes (i.e. wet vs. dry) of dust are different and specific for the different deposition sites in the Mediterranean studied area. The results tend to indicate that wet deposition is the main form of deposition for mineral dust in the western Mediterranean basin, but the contribution of dry deposition (in the sense that no precipitation was detected at the surface) is far from being negligible, and contributes 10 to 46 % to the major dust deposition events, depending on the sampling site.


2020 ◽  
Author(s):  
Jesús Yus-Díez ◽  
Marina Ealo ◽  
Marco Pandolfi ◽  
Noemí Perez ◽  
Gloria Titos ◽  
...  

Abstract. Accurate measurements of the horizontal and vertical distribution of atmospheric aerosol particle optical properties are key for a better understanding of their impact on the climate. Here we present the results of a measurement campaign based on instrumented flights over NE Spain. We measured vertical profiles of size segregated atmospheric particulate matter (PM) mass concentrations and multi-wavelength scattering and absorption coefficients in the Western Mediterranean Basin (WMB). The campaign took place during typical summer conditions, characterized by the development of a vertical multi-layer structure, under both summer regional pollution episodes (REG) and Saharan dust events (SDE). REG patterns in the region form under high insolation and scarce precipitation in summer, favoring layering of highly-aged fine PM strata in the lower few km a.s.l. The REG scenario prevailed during the entire measurement campaign. Additionally, African dust outbreaks and plumes from North African wildfires influenced the study area. The vertical profiles of climate relevant intensive optical parameters such as single scattering albedo (SSA), asymmetry parameter (g), scattering, absorption and SSA Angstrom exponents (SAE, AAE, SSAAE), and PM mas scattering and absorption cross sections (MSC and MAE) were derived from the measurements. Moreover, we compared the aircraft measurements with those performed at two GAW/ACTRIS surface measurement stations located in NE Spain, namely: Montseny (MSY; regional background) and Montsec d'Ares (MSA; remote site). Airborne in-situ measurements and ceilometer ground-based remote measurements identified aerosol air masses at altitude up to more than 3.5 km a.s.l. The vertical profiles of the optical properties markedly changed according to the prevailing atmospheric scenarios. During SDE the SAE was low along the profiles, reaching values  2.0 and the asymmetry parameter g was rather low (0.5–0.6) due to the prevalence of fine PM which were characterized by an AAE close to 1.0 suggesting a fossil fuel combustion origin. During REG, some of the layers featured larger AAE (> 1.5), relatively low SSA at 525 nm ( 9 m2 g−1) and were associated to the influence of PM from wildfires. Overall, the SSA and MSC near the ground ranged around 0.85 and 3 m2 g−1, respectively and increased at higher altitudes, reaching values above 0.95 and up to 9 m2 g−1. The PM, MSC and MAE were on average larger during REG compared to SDE due to the larger scattering and absorption efficiency of fine PM compared with dust. The SSA and MSC had quite similar vertical profiles and often both increased with height indicating the progressive shift toward PM with larger scattering efficiency with altitude. This study contributes to our understanding of regional aerosol vertical distribution and optical properties in the WMB and the results will be useful for improving future climate projections and remote sensing/satellite retrieval algorithms.


2012 ◽  
Vol 223 (7) ◽  
pp. 4075-4088 ◽  
Author(s):  
Y. G. Yang ◽  
Z. L. He ◽  
Y. B. Wang ◽  
Y. L. Liu ◽  
Z. B. Liang ◽  
...  

2012 ◽  
Vol 12 (12) ◽  
pp. 33083-33125 ◽  
Author(s):  
B. Ervens ◽  
Y. Wang ◽  
J. Eagar ◽  
W. R. Leaitch ◽  
A. M. Macdonald ◽  
...  

Abstract. Cloud and fog droplets efficiently scavenge and process water-soluble compounds and thus modify the chemical composition of the gas and particle phases. The concentrations of dissolved organic carbon (DOC) in the aqueous phase reach concentrations on the order of ~10 mg C L−1 which is typically on the same order of magnitude as the sum of inorganic anions. Aldehydes and carboxylic acids typically comprise a large fraction of DOC because of their high solubility. The dissolution of species in the aqueous phase can lead to (i) the removal of species from the gas phase preventing their processing by gas phase reactions (e.g. photolysis of aldehydes) and (ii) the formation of unique products that do not have any efficient gas phase sources (e.g. dicarboxylic acids). We present measurements of DOC and select aldehydes in fog water at high elevation and intercepted clouds in a biogenically-impacted location (Whistler, Canada) and in fog water in a more polluted area (Davis, CA). Concentrations of formaldehyde, glyoxal and methylglyoxal were in the micromolar range and comprised ≤2% each individually of the DOC. Comparison of the DOC and aldehyde concentrations to those at other locations shows good agreement and reveals highest levels for both in anthropogenically impacted regions. Based on this overview, we conclude that the fraction of organic carbon (dissolved and insoluble inclusions) in the aqueous phase comprises 1–~40% of total organic carbon. Higher values are observed to be associated with aged air masses where organics are expected to be more highly oxidized and thus more soluble. Accordingly, the aqueous/gas partitioning ratio expressed here as an effective Henry's law constant for DOC (KH*DOC) increases by an order of magnitude from 7×103 M atm−1 to 7×104 M atm−1 during the ageing of air masses. The measurements are accompanied by photochemical box model simulations. They suggest that the scavenging of aldehydes by the aqueous phase can reduce HO2 gas phase levels by two orders of magnitude due to a weaker net source of HO2 production from aldehyde photolysis in the gas phase. Despite the high solubility of dialdehydes (glyoxal, methylglyoxal), their impact on the HO2 budget by scavenging is <10% of that of formaldehyde. The overview of DOC and aldehyde measurements presented here reveals that clouds and fogs can be efficient sinks for organics, with increasing importance in aged air masses. Even though aldehydes, specifically formaldehyde, only comprise ~1% of DOC, their scavenging and processing in the aqueous phase might translate into significant effects on the oxidation capacity of the atmosphere.


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