Isoprene is an important reactive gas that is produced mainly in terrestrial ecosystems but is also produced in marine ecosystems. In the marine environment, isoprene is produced in the seawater by ...various biological processes. Here, we show that photosensitized reactions involving the sea-surface microlayer lead to the production of significant amounts of isoprene. It is suggested that H-abstraction processes are initiated by photochemically excited dissolved organic matter which will the degrade fatty acids acting as surfactants. This chemical interfacial processing may represent a significant abiotic source of isoprene in the marine boundary layer.
Aerosol particles acting as cloud condensation nuclei (CCN) or ice-nucleating particles (INPs) play a major role in the formation and glaciation of clouds. Thereby they exert a strong impact on the ...radiation budget of the Earth. Data on abundance and properties of both types of particles are sparse, especially for remote areas of the world, such as the Southern Ocean (SO). In this work, we present unique results from ship-borne aerosol-particle-related in situ measurements and filter sampling in the SO region, carried out during the Antarctic Circumnavigation Expedition (ACE) in the austral summer of 2016–2017. An overview of CCN and INP concentrations over the Southern Ocean is provided and, using additional quantities, insights regarding possible CCN and INP sources and origins are presented.
CCN number concentrations spanned 2 orders of magnitude, e.g. for a supersaturation of 0.3 % values ranged roughly from 3 to 590 cm−3.
CCN showed variable contributions of organic and inorganic material (inter-quartile range of hygroscopicity parameter κ from 0.2 to 0.9).
No distinct size dependence of κ was apparent, indicating homogeneous composition across sizes (critical dry diameter on average between 30 and 110 nm).
The contribution of sea spray aerosol (SSA) to the CCN number concentration was on average small.
Ambient INP number concentrations were measured in the temperature range from −5 to −27 ∘C using an immersion freezing method. Concentrations spanned up to 3 orders of magnitude, e.g. at −16 ∘C from 0.2 to 100 m−3.
Elevated values (above 10 m−3 at −16 ∘C) were measured when the research vessel was in the vicinity of land (excluding Antarctica), with lower and more constant concentrations when at sea. This, along with results of backward-trajectory analyses, hints towards terrestrial and/or coastal INP sources being dominant close to ice-free (non-Antarctic) land.
In pristine marine areas INPs may originate from both oceanic sources and/or long-range transport.
Sampled aerosol particles (PM10) were analysed for sodium and methanesulfonic acid (MSA). Resulting mass concentrations were used as tracers for primary marine and secondary aerosol particles, respectively.
Sodium, with an average mass concentration around 2.8 µg m−3, was found to dominate the sampled, identified particle mass.
MSA was highly variable over the SO, with mass concentrations up to 0.5 µg m−3 near the sea ice edge.
A correlation analysis yielded strong correlations between sodium mass concentration and particle number concentration in the coarse mode, unsurprisingly indicating a significant contribution of SSA to that mode.
CCN number concentration was highly correlated with the number concentration of Aitken and accumulation mode particles. This, together with a lack of correlation between sodium mass and Aitken and accumulation mode number concentrations, underlines the important contribution of non-SSA, probably secondarily formed particles, to the CCN population. INP number concentrations did not significantly correlate with any other measured aerosol physico-chemical parameter.
Ambient concentrations of ice-forming particles measured during ship expeditions are collected and summarised with the aim of determining the spatial distribution and variability in ice nuclei in ...oceanic regions.
The presented data from literature and previously unpublished data from over 23 months of ship-based measurements stretch from the Arctic to the Southern Ocean and include a circumnavigation of Antarctica. In comparison to continental observations, ship-based measurements of ambient ice nuclei show 1 to 2 orders of magnitude lower mean concentrations. To quantify the geographical variability in oceanic areas, the concentration range of potential ice nuclei in different climate zones is analysed by meridionally dividing the expedition tracks into tropical, temperate and polar climate zones. We find that concentrations of ice nuclei in these meridional zones follow temperature spectra with similar slopes but vary in absolute concentration. Typically, the frequency with which specific concentrations of ice nuclei are observed at a certain temperature follows a log-normal distribution. A consequence of the log-normal distribution is that the mean concentration is higher than the most frequently measured concentration. Finally, the potential contribution of ship exhaust to the measured ice nuclei concentration on board research vessels is analysed as function of temperature. We find a sharp onset of the influence at approximately −36 ∘C but none at warmer temperatures that could bias ship-based measurements.
Considering solely ocean-atmosphere transfer and neglecting atmospheric processing, high FAA enrichment factors were found in both aerosol particles in the submicron range (EF.sub.aer(âFAA) : ...2x10.sup.3 -6x10.sup.3) and medium enrichment factors in the supermicron range (EF.sub.aer(âFAA) : 1x10.sup.1 -3x10.sup.1). In addition, indications for a biogenic FAA formation were observed. Furthermore, one striking finding was the high and varying FAA cloud water concentration (11.2-489.9 ng m.sup.-3 ), as well as enrichments (EF.sub.CW : 4x10.sup.3 and 1x10.sup.4 compared to the SML and ULW, respectively), which were reported here for the first time. The abundance of inorganic marine tracers (sodium, methanesulfonic acid) in cloud water suggests an influence of oceanic sources on marine clouds. Finally, the varying composition of the FAAs in the different matrices shows that their abundance and ocean-atmosphere transfer are influenced by additional biotic and abiotic formation and degradation processes. Simple physicochemical parameters (e.g., surface activity) are not sufficient to describe the concentration and enrichments of the FAAs in the marine environment. For a precise representation in organic matter (OM) transfer models, further studies are needed to unravel their drivers and understand their composition.
Agro-industrial areas are frequently affected by various sources of atmospheric pollutants that have a negative impact on public health and ecosystems. However, air quality in these areas is ...infrequently monitored because of their smaller population compared to large cities, especially in developing countries. The Cauca River valley (CRV) is an agro-industrial region in southwestern Colombia, where a large fraction of the area is devoted to sugarcane and livestock production. The CRV is also affected by road traffic and industrial emissions. This study aims to elucidate the chemical composition of particulate matter fine mode (PM2.5) and to identify the main pollutant sources before source attribution. A sampling campaign was carried out at a representative site in the CRV region, where daily averaged mass concentrations of PM2.5 and the concentrations of water-soluble ions, trace metals, organic and elemental carbon, and various fractions of organic compounds (carbohydrates, n alkanes, and polycyclic aromatic hydrocarbons – PAHs) were measured. The mean PM2.5 was 14.4±4.4 µg m−3, and the most abundant constituent was organic material (52.7 % ± 18.4 %), followed by sulfate (12.7 % ± 2.8 %), and elemental carbon (7.1 % ± 2.5 %), which indicates the presence of secondary aerosol formation and incomplete combustion. Levoglucosan was present in all samples, with a mean concentration of (113.8±147.2 ng m−3), revealing biomass burning as a persistent source. Mass closure using the elemental carbon (EC) tracer method explained 88.4 % on PM2.5, whereas the organic tracer method explained 70.9 % of PM2.5. We attribute this difference to the lack of information of specific organic tracers for some sources, both primary and secondary. Organic material and inorganic ions were the dominant groups of species (79 % of PM2.5). OMprim and OMsec contribute 24.2 % and 28.5 % to PM2.5. Inorganic ions as sulfate, nitrate, and ammonia constitute 19.0 %, EC 7.1 %, dust 3.5%, particle-bounded water (PBW) 5.3 %, and trace element oxides (TEOs), 0.9 % of PM2.5. The aerosol was acidic, with a pH of 2.5±0.4, mainly because of the abundance of organic and sulfur compounds. Diagnostic ratios and tracer concentrations indicate that most PM2.5 was emitted locally and had contributions of both pyrogenic and petrogenic sources, that biomass burning was ubiquitous during the sampling period and was the main source of PAHs, and that the relatively low PM2.5 concentrations and mutagenic potentials are consistent with low-intensity, year-long biomass burning (BB) and sugarcane pre-harvest burning in the CRV.
Silicone rod and silicone tube sorptive extraction van Pinxteren (née Schellin), Manuela; Paschke, Albrecht; Popp, Peter
Journal of Chromatography A,
04/2010, Letnik:
1217, Številka:
16
Journal Article
Recenzirano
This review focuses on the applications of silicone in the form of tubes or rods for sorptive extraction of organic compounds as sample preparation method in combination with various chromatographic ...techniques. Silicone rods (SRs) and silicone tubes (STs) have the advantage of being inexpensive, flexible and robust. SRs and STs with different sizes and volumes of silicone (8–635
μL) have so far been applied for the extraction/preconcentration of a large variety of organic micropollutants from different matrices. The theoretical principle of SR and ST extraction in comparison with similar microextraction techniques is presented as well as a summary of the published applications of SR and ST extraction in combination with gas chromatography (GC) or liquid chromatography (LC). Furthermore, the use of SRs and STs for time-integrated (passive) sampling is reported.
Carbohydrates, originating from marine microorganisms, enter the atmosphere as part of sea spray aerosol (SSA) and can influence fog and cloud microphysics as cloud condensation nuclei (CCN) or ...ice-nucleating particles (INP). Particularly in the remote Arctic region, significant knowledge gaps persist about the sources, the sea-to-air transfer mechanisms, atmospheric concentrations, and processing of this substantial organic group. In this ship-based field study conducted from May to July 2017 in the Fram Strait, Barents Sea, and central Arctic Ocean, we investigated the sea-to-air transfer of marine combined carbohydrates (CCHO) from concerted measurements of the bulk seawater, the sea surface microlayer (SML), aerosol particles and fog. Our results reveal a wide range of CCHO concentrations in seawater (22–1070 µg L−1), with notable variations among different sea-ice-related sea surface compartments. Enrichment factors in the sea surface microlayer (SML) relative to bulk water exhibited variability in both dissolved (0.4–16) and particulate (0.4–49) phases, with the highest values in the marginal ice zone (MIZ) and aged melt ponds. In the atmosphere, CCHO was detected in super- and submicron aerosol particles (CCHOaer,super: 0.07–2.1 ng m−3; CCHOaer,sub: 0.26–4.4 ng m−3) and fog water (CCHOfog,liquid: 18–22 000 µg L−1; CCHOfog,atmos: 3–4300 ng m−3). Enrichment factors for sea–air transfer varied based on assumed oceanic emission sources. Furthermore, we observed rapid atmospheric aging of CCHO, indicating both biological/enzymatic processes and abiotic degradation. This study highlights the diverse marine emission sources in the Arctic Ocean and the atmospheric processes shaping the chemical composition of aerosol particles and fog.
This study examines carbohydrates, amino acids, and lipids as important contributors to organic carbon (OC) in the tropical Atlantic Ocean at the Cape Verde Atmospheric Observatory (CVAO). The above ...compounds were measured in both surface seawater and in ambient sub-micron aerosol particles to investigate their sea-to-air transfer, including their enrichment in the sea surface microlayer (SML), potential atmospheric in situ formation or degradation, and their oceanic contribution to the ambient marine aerosol particles.
Recent studies pointed to a high ice nucleating activity (INA) in the Arctic sea surface microlayer (SML). However, related chemical information is still sparse. In the present study, INA and free ...glucose concentrations were quantified in Arctic SML and bulk water samples from the marginal ice zone, the ice-free ocean, melt ponds, and open waters within the ice pack. T 50 (defining INA) ranged from −17.4 to −26.8 °C. Glucose concentrations varied from 0.6 to 51 μg/L with highest values in the SML from the marginal ice zone and melt ponds (median 16.3 and 13.5 μg/L) and lower values in the SML from the ice pack and the ice-free ocean (median 3.9 and 4.0 μg/L). Enrichment factors between the SML and the bulk ranged from 0.4 to 17. A positive correlation was observed between free glucose concentration and INA in Arctic water samples (T 50(°C) = (−25.6 ± 0.6) + (0.15 ± 0.04)·Glucose(μg/L), R P = 0.66, n = 74). Clustering water samples based on phytoplankton pigment composition resulted in robust but different correlations within the four clusters (R P between 0.67 and 0.96), indicating a strong link to phytoplankton-related processes. Since glucose did not show significant INA itself, free glucose may serve as a potential tracer for INA in Arctic water samples.
Ice-nucleating particles (INPs) in the troposphere can form ice in clouds via heterogeneous ice nucleation. Yet, atmospheric number concentrations of INPs (N.sub.INP) are not well characterized, and, ...although there is some understanding of their sources, it is still unclear to what extend different sources contribute or if all sources are known. In this work, we examined properties of INPs at Cabo Verde (a.k.a. Cape Verde) from different environmental compartments: the oceanic sea surface microlayer (SML), underlying water (ULW), cloud water and the atmosphere close to both sea level and cloud level.
PDF
