How do certain atmospheric aerosols affect Cu-binding organic ligands in the oligotrophic coastal sea surface microlayer?

It is still unclear how the chemical speciation of Cu in surface seawater is impacted by aerosols from various sources deposited on the sea surface, which is surprising, considering the environmental importance of Cu. Therefore, we used voltammetry to investigate Cu complexing capacity (CuCC) in the sea surface microlayer (SML) and in the underlying water (ULW) of the oligotrophic middle Adriatic Sea during February-July 2019. The focus was on the impacts of specific atmospheric processes such as open-fire biomass burning (BB), pollination season and Saharan dust intrusion. The presence of ligand class L2 (19.9-392.0, average 63.8, median 43.1) nM; log K2 (8.3-10.2, average 9.6, median 9.6) was observed in all samples, while ligand class L1 (40.5-76.1, average 53.6, median 48.9) nM; log K1 (10.3-11.1, average 10.6, median 10.5) was found in only 25% of SML samples. Throughout the period, the SML was enriched with organic ligands by a factor of up to 9.1 compared to the ULW, mainly due to the high sensitivity of the SML to specific atmospheric depositions. In addition, measurements with corresponding specific model aerosols were conducted to analyse their impacts on CuCC. Pollen directly affected CuCC in the SML by increasing the concentration of allochthonous ligands such as proteins. The deposition of BB aerosols rich in nutrients and trace metals stimulated the biological production of organic ligands, showing an indirect effect on CuCC delayed by up to two weeks. Finally, Saharan dust had a negligible impact on CuCC. This study illustrates the susceptibility of oligotrophic coastal area to the effects of pollen and open-fire BB aerosols in altering the Cu-binding organic ligands in the SML.

Sources, Ionic Composition and Acidic Properties of Bulk and Wet Atmospheric Deposition in the Eastern Middle Adriatic Region.

Atmospheric bulk and wet deposition samples were collected simultaneously at the background coastal site in the Eastern Middle Adriatic region in order to assess the impact of major ions (Cl-, NO3-, SO42-, Na+, K+, NH4+, Mg2+, Ca2+) on deposition acidity and distinguish the main sources. Higher ion levels were observed during the cold period, especially for Cl-, Na+, Mg2+ and K+. Dust intrusion caused significant increases in levels of Ca2+, Mg2+ and K+, while open-fire events increased the levels of K+. Deposition acidity showed seasonal differences as well as the influence of dust intrusion. Low ionic balance ratios indicated acidic deposition properties and the presence of organic anions. The highest neutralization ability was found for Ca2+, Na+ and NH4+. Several natural (marine, crustal) and anthropogenic sources were determined, as well as the formation of secondary aerosols. Wet deposition was characterized by higher contribution of sea salt fraction compared to bulk deposition and lower contribution of crustal fraction.

The size distribution of SARS-CoV-2 genetic material in airborne particles sampled in hospital and home care environments occupied by COVID-19 positive subjects.

Characterizing the size distribution of airborne particles carrying SARS-CoV-2 virus is essential for understanding and predicting airborne transmission and spreading of COVID-19 disease in hospitals as well as public and home indoor settings. Nonetheless, few data are currently available on virus-laden particle size distribution. Thus, the aim of this study is reporting the total concentrations and size distributions of SARS-CoV-2- genetic material in airborne particles sampled in hospital and home environments. A nanoMOUDI R122 cascade impactor (TSI, USA) was used to collect size-segregated aerosol down to the sub-micron range in home and in three different hospital environments in presence of infected patients in order to provide the concentration of airborne SARS-CoV-2 genetic material for each particle size range at different sampling locations. Providing one of the largest datasets of detailed size-fractionated airborne SARS-CoV-2 RNA to date, we found that 45.2 % of the total sub- and super-micrometric fractions were positive for SARS-CoV-2 with its genetic material being present in 17.7 % of sub-micrometric (0.18-1 µm) and 81.9 % of super-micrometric (>1 µm) fractions. The highest concentration of SARS-CoV-2 genetic material in total suspended particles (5.6 ± 3.4 RNA copies m-3) was detected in the room occupied with patients with more severe COVID-19 symptoms collected during the patients' high flow nasal oxygen therapy. The highest concentration at certain particle size fraction strongly depends on the sampling environment. However, the contribution of SARS-CoV-2 genetic material was in favour of super-micrometric compared to sub-micrometric particle size range. The evaluation of the individual risk of infection was carried out on the basis of the obtained data considering a hypothetical exposure scenario. The obtained results indicate the necessity of the protective masks in presence of infected subjects, especially while staying for longer period of time in the hospital environments.

Lipids of different phytoplankton groups differ in sensitivity to degradation: Implications for carbon export.

The future of life on Earth depends on how the ocean might change, as it plays an important role in mitigating the effects of global warming. The main role is played by phytoplankton. Not only are phytoplankton the base of the oceans' food web, but they also play an important role in the biological carbon pump (BCP), the process of forming organic matter (OM) and transporting it to the deep sea, representing a sink of atmospheric CO2 . Lipids are considered important vectors for carbon sequestration. A change in the phytoplankton community composition as a result of ocean warming is expected to affect the BCP. Many predictions indicate a dominance of small at the expense of large phytoplankton. To gain insight into interplay between the phytoplankton community structure, lipid production and degradation, and adverse environmental conditions, we analyzed phytoplankton composition, particulate organic carbon (POC) and its lipid fraction in the northern Adriatic over a period from winter to summer at seven stations with a gradient of trophic conditions. We found that at high salinity and low nutrient content, where nanophytoplankton prevailed over diatoms, the newly fixed carbon is substantially directed toward the synthesis of lipids. Lipids produced by nanophytoplankton, coccolithophores, and phytoflagellates, are more resistant to degradation than those produced by diatoms. The difference in lipid degradability is discussed as a difference in the size of the cell phycosphere. We hypothesize that the lipids of nanophytoplankton are less degradable due to the small phycosphere with a poorer bacterial community and consequently a lower lipid degradation rate compared with diatoms. The lipid chemical composition of the different phytoplankton groups could have a different susceptibility to degradation. Results suggest a successful lipid carbon sink of nanophytoplankton and, thus, a negative feedback on global warming.

Interfacial photochemistry of marine diatom lipids: Abiotic production of volatile organic compounds and new particle formation.

The global importance of abiotic oceanic production of volatile organic compounds (VOCs) still presents a source of high uncertainties related to secondary organic aerosol (SOA) formation. A better understanding of the photochemistry occurring at the ocean-atmosphere interface is particularly important in that regard, as it covers >70% of the Earth's surface. In this work, we focused on the photochemical VOCs production at the air-water interface containing organic material from authentic culture of marine diatom Chaetoceros pseudocurvisetus. Abiotic VOCs production upon irradiation of material originating from total phytoplankton culture as well as the fraction containing only dissolved material was monitored by means of PTR-ToF-MS. Furthermore, isolated dissolved lipid fraction was investigated after its deposition at the air-water interface. All samples acted as a source of VOCs, producing saturated oxygenated compounds such as aldehydes and ketones, as well as unsaturated and functionalized compounds. Additionally, a significant increase in surfactant activity following irradiation experiments observed for all samples implied biogenic material photo-transformation at the air-water interface. The highest VOCs flux normalized per gram of carbon originated from lipid material, and the produced VOCs were introduced into an atmospheric simulation chamber, where particle formation was observed after its gas-phase ozonolysis. This work clearly demonstrates abiotic production of VOCs from phytoplankton derived organic material upon irradiation, facilitated by its presence at the air/water interface, with significant potential for affecting the global climate as a precursor of particle formation.

How do open coastal fire episodes' impact sea surface microlayer neuston communities?

Human-induced climate change is expected to increase the frequency and severity of vegetation fires. The Mediterranean region is considered particularly prone to fire episodes in summer. It is well known that pyrogenic particles are an important source of external nutrients for the marine environment, especially in oligotrophic areas. In this study, the plankton components of the sea surface layers were integrated to evaluate, for the first time, their dynamics over six months and their response to fire events in a typical coastal area of the Adriatic Sea. Concentrations of nutrients and organic compounds, together with plankton communities were significantly higher in the sea surface microlayer (SML, < 1 mm thick), than in the underlying water from 1 m depth. The piconeuston community and chlorophyll a responded with extreme abundance and concentration to the most intense fire event that enriched the SML with NH4+. Phytoneuston abundance increased with a delay of 2 weeks, while diversity indices decreased slightly after the fire events. The large abundances of the studied piconeuston parameters could be explained by the high availability of organic compounds and the immediate availability of NH4+, while the phytoneuston community responded to an increased NO3- concentration, triggered by the fire events. We confirmed that fast-acting marine heterotrophs are important members of biogeochemical cycles associated with fire events and that, together with phytoplankton, they are unavoidable parameters to detect environmental changes.

Variabilities of biochemical properties of the sea surface microlayer: Insights to the atmospheric deposition impacts.

Atmospheric deposition (AD) of nutrients and its impact on the sea surface requires consideration of interfacial processes within the sea surface microlayer (SML), the ocean-atmosphere boundary layer of major importance for many global biogeochemical and climate-related processes. This study comprised a comprehensive dataset, including dissolved NO3-, NH4+ and PO43- in ambient aerosol particles, wet deposition and sea surface samples collected from February to July 2019 at a central Adriatic coastal site. The aerosol mean concentration of dissolved nitrogen (DIN = NO3- + NH4+) and PO43- were 48.8 ± 82.8 µmol m-3 and 0.8 ± 0.6 µmol m-3, respectively, while their total fluxes (dry + wet) ranged from 24.2 to 212.3 µmol m-2 d-1 (mean 123.2 ± 53.2 µmol m-2 d-1) and from 1.2 to 2.1 µmol m-2 d-1 (mean 1.5 ± 0.3 µmol m-2 d-1), respectively. Intensive local episodes of open biomass burning (BB) significantly increased aerosol DIN concentrations as well as DIN deposition fluxes, particularly altering the molar DIN/PO43- ratio of atmospheric samples. The DIN temporal patterns showed high variability in the SML (range 0.2-24.6 µmol L-1, mean 5.0 ± 7.1 µmol L-1) in contrast to the underlying water samples (range 0.5-4.2 µmol L-1, mean 1.9 ± 1.2 µmol L-1), with significant increases during BB periods. Variability in abundance of heterotrophic bacteria and autotrophs in the SML along with concentrations of bulk dissolved and particulate organic carbon as well as dissolved and particulate lipids and carbohydrates, gel particles and surfactants followed DIN enhancements with a two-week delay. This study showed that AD can affect the short-term scale enrichments of organic matter in the SML, especially when accompanied by BB emissions typical of the overall Mediterranean coastal environment. This could have strong implications for global air-sea exchange processes, including those of climate relevant gases, mediated by the SML.

Seasonal variability of nitroaromatic compounds in ambient aerosols: Mass size distribution, possible sources and contribution to water-soluble brown carbon light absorption.

Nitroaromatic compounds (NACs) as important constituents of atmospheric humic-like substances (HULIS) and brown carbon (BrC) affect the Earth's climate and pose a serious environmental hazard. We investigated seasonal size-segregated NACs in aerosol samples from the urban background environment in Ljubljana, Slovenia. Total concentrations of twenty NACs in PM15.6 were on average from 0.51 ng m-3 (summer) to 109 ng m-3 (winter), and contributed the most to submicron aerosols (more than 74%). Besides 4-nitrocatechol (4NC) as the prevailing species, methylnitrocatechols (MNCs) and nitrophenols (NPs), we reported on some very rarely mentioned, but also on five novel NACs (i.e., 3H4NBA: 3-hydroxy-4-nitrobenzoic acid, 3MeO4NP: 3-methoxy-4-nitrophenol, 4Et5NC: 4-ethyl-5-nitrocatechol, 3Et5NC: 3-ethyl-5-nitrocatechol and 3MeO5NC: 3-methoxy-5-nitrocatechol). Concentrations of 3MeO5NC, 4Et5NC and 3Et5NC were enhanced during cold seasons, contributing up to 11% to total NAC in winter. In cold season, NAC size distributions were characterized with the peaks in the broader size range of 0.305-1.01 µm (accumulation mode), with 4NC and alkyl-nitrocatechols (∑(M/Et)NC) as the most abundant, followed by 4-nitrosyringol, nitrophenols and nitroguaiacols. In spring, a pronounced peak of ∑(M/Et)NC was observed in the accumulation mode (0.305-0.56 µm) as well as in the coarse one. A strong correlation of all NACs with ∑(M/Et)NC and levoglucosan indicates that primary emissions of wood burning were the most important source of NACs, but their secondary formation (e.g., aqueous-phase at higher ambient RH) in cold season could also be a significant one. In warmer season, NACs may be mostly derived from traffic-related aromatic VOCs. The contribution of NACs to the light absorption of the aqueous extracts was up to 10-times higher (contribution to Abs365 up to 31%) than their mass contributions to WSOC (up to 3%) of corresponding size-segregated aerosols, confirming that most of the identified NACs are strong BrC chromophores.

A study of cobalt (II) complexes involved in marine biogeochemical processes: Co(II)-1,10-Phenanthroline and Co(II)-1,10-Phenanthroline-L-α-Phosphatidylcholine.

The cell membrane is structured so that the surface layer is composed of lipid molecules with selective permeability for micronutrients and organic ligands. Binding of Co (II) to natural lipid phosphatidylcholine (PC) has been studied to identify a possible mechanism of Co (II) entry through the cell membrane of the biota in detail, by voltammetry followed by checking the system at the air-water boundary, by Langmuir method. Binding of cobalt (II) ions to the PC molecules was enabled by the Co(II)-1,10-Phenanthroline (Phen) complex formation as an intermediate. Co(II)-Phen-PC complex reduction was recorded in the pH range from 5 to 9.5. The reduction was identified as a two-electron irreversible reaction at about -1.5 V, with the reactant adsorption followed dissociation (EC mechanism). The Co(II)-Phen-PC complex electrode surface concentration (Γ) was calculated to be (1.45 ± 0.12) × 10-10 mol.cm-2. Conditional stability constants log KCo(II)Phen2PC = 23.02 ± 0.26 and log KCo(II)Phen2PC2 = 29.31 ± 0.17 (Ic = 0.55) were calculated by CLE/ACSV method. Pressure-area (π-A) isotherms obtained at water-air interface by Langmuir monolayer technique indicated penetration of Co(II)-Phen into the PC monolayer, supporting electrochemical results. The equilibrium constants of the Co (II)-PC system (1:1) at the air-water interface was calculated to be K1 = 2.4 × 10-2 m3 mol-1, while for Co(II)-Phen-PC K2 = 4.86 × 1010 m2 mol-1.

Pollution levels and deposition processes of airborne organic pollutants over the central Adriatic area: Temporal variabilities and source identification.

First data on polycyclic aromatic hydrocarbons (PAHs) and nitro-aromatic compounds (NACs) in aerosols as well as of PAHs, polychlorinated biphenyls (PCBs) and NACs in bulk and wet atmospheric deposition samples were simultaneously obtained during 6-month-long field campaign at the costal central Adriatic area. Special attention was given to open-fire biomass burning episodes as extreme events common for the overall Mediterranean coastal area in order to gain a better understanding of the atmospheric variabilities and potential sources of trace organic pollutants in coastal environments. Diesel and gasoline combustion related to land and maritime traffic as well as occasional open-fire episodes (forest fires) were found to be the dominant pollution sources of PAHs in PM10 particles. NACs were determined almost exclusively in samples affected by biomass burning episodes. Open-fire episodes had a strong contribution to the overall NACs atmospheric deposition fluxes. Several chlorinated congeners of PCBs were predominantly contributed in deposition samples.

Atmospheric deposition of biologically relevant trace metals in the eastern Adriatic coastal area.

Aerosol (PM10), bulk deposition, sea surface microlayer (SML) and underlying water (ULW) samples were collected simultaneously during a field campaign at the middle Adriatic coastal site between February and July 2019, to assess the impact of atmospheric deposition (AD) of biologically relevant trace metals (TM) (Zn, Cu, Co, Ni, Cd and Pb) on the sea surface responses in an oligotrophic coastal region. Anthropogenic emissions from continental Europe, alongside local/regional domestic heating, likely affected the concentrations of Zn, Cd and Pb in aerosols during winter-early spring, while traffic emissions during the tourist season impacted Ni, Co and Cu aerosol concentrations. Additionally, open-fire biomass burning (BB) episodes caused considerable TM concentration increases, while Saharan dust intrusion in spring led to a 10-fold increase in Co concentrations in PM10 samples. These intensive episodes significantly affected the bulk deposition fluxes of TMs, showing that a small number of such extreme events, common to Mediterranean coastal areas, could be responsible for most of the AD. Enrichments and concentrations of total TMs in SML samples collected following BB events indicated that such events, along with high precipitation, influenced TM partitioning in surface water layers. We estimated that AD represents a significant source of TM to the shallow middle Adriatic coastal area, highlighting the need to further explore the atmosphere-sea surface links, to expand our understanding of the biogeochemistry of these important micronutrients and pollutants, including their impact on the aquatic community.

Chemical characterization of fine aerosols in respect to water-soluble ions at the eastern Middle Adriatic coast.

Fine particulate matter (PM2.5) concentrations at the Middle Adriatic coastal site of Croatia were affected by different air-mass inflows and/or local sources and meteorological conditions, and peaked in summer. More polluted continental air-mass inflows mostly affected the area in the winter period, while southern marine pathways had higher impact in spring and summer. Chemical characterization of the water-soluble inorganic and organic ionic constituents is discussed with respect to seasonal trends, possible sources, and air-mass inputs. The largest contributors to the PM2.5 mass were sea salts modified by the presence of secondary sulfate-rich aerosols indicated also by principal component analysis. SO42- was the prevailing anion, while the anthropogenic SO42- (anth-nssSO42-) dominantly constituted the major non-sea-salt SO42- (nssSO42-) fraction. Being influenced by the marine origin, its biogenic fraction (bio-nssSO42-) increased particularly in the spring. During the investigated period, aerosols were generally acidic. High Cl- deficit was observed at Middle Adriatic location for which the acid displacement is primarily responsible. With nssSO42- being dominant in Cl- depletion, sulfur-containing species from anthropogenic pollution emissions may have profound impact on atmospheric composition through altering chlorine chemistry in this region. However, when accounting for the neutralization of H2SO4 by NH3, the potential of HNO3 and organic acids to considerably influence Cl- depletion is shown to increase. Intensive open-fire events substantially increased the PM2.5 concentrations and changed the water-soluble ion composition and aerosol acidity in summer of 2015. To our knowledge, this work presents the first time-resolved data evaluating the seasonal composition of water-soluble ions and their possible sources in PM2.5 at the Middle Adriatic area. This study contributes towards a better understanding of atmospheric composition in the coastal Adriatic area and serves as a basis for the comparison with future studies related to the air quality at the coastal Adriatic and/or Mediterranean regions.

Concentrations and Adsorption Isotherms for Amphiphilic Surfactants in PM1 Aerosols from Different Regions of Europe.

Predicting the activation of submicrometer particles into cloud droplets in the atmosphere remains a challenge. The importance of surface tension, σ (mN m-1), in these processes has been evidenced by several works, but information on the "surfactants" lowering σ in actual atmospheric particles remains scarce. In this work, PM1 aerosols from urban, coastal, and remote regions of Europe (Lyon, France, Rogoznica, Croatia, and Pallas, Finland, respectively) were investigated and found to contain amphiphilic surfactants in concentrations up to 2.8 µg m-3 in the air and 1.3 M in the particle dry volume. In Pallas, correlations with the PM1 chemical composition showed that amphiphilic surfactants were present in the entire range of particle sizes, supporting recent works. This implied that they were present in hundreds to thousands of particles cm-3 and not only in a few large particles, as it has been hypothesized. Their adsorption isotherms and critical micelle concentration (CMC) were also determined. The low CMC obtained (3 × 10-5-9 × 10-3 M) implies that surface tension depression should be significant for all the particles containing these compounds, even at activation (growth factor ∼ 10). Amphiphilic surfactants are thus likely to enhance the CCN ability of submicrometer atmospheric particles.

Size-Resolved Surface-Active Substances of Atmospheric Aerosol: Reconsideration of the Impact on Cloud Droplet Formation.

Our current understanding of the importance of surface-active substances (SAS) on atmospheric aerosol cloud-forming efficiency is limited, as explicit data on the content of size-resolved ambient aerosol SAS, which are responsible for lowering the surface tension (σ) of activating droplets, are not available. We report on the first data comprising seasonal variability of size-segregated SAS concentrations in ambient aerosol particulate matter (PM). To assess the impact of SAS distribution within PM on cloud droplet activation and growth, a concept of surfactant activity was adopted and a parametrization developed; i.e., surfactant activity factor (SAF) was defined, which allowed translation of experimental data for use in cloud parcel modeling. The results show that SAS-induced σ depression during cloud activation may affect droplet number ( Nd) as much as a 2-fold increase in particle number, whereas by considering also the size distribution of particulate SAS, Nd may increase for another 10%. This study underscores the importance of size-resolved SAS perspective on cloud activation, as data typically obtained from aqueous extracts of PM2.5 and PM10 may result in misleading conclusions about droplet growth due to large mass fractions of supermicron particles with SAS deficit and little or no influence on CCN and Nd.

Copper-phospholipid interaction at cell membrane model hydrophobic surfaces.

Detailed investigation of Cu (II) binding with natural lipid phosphatidylglycerol (PG) in aqueous solution was carried out by voltammetric measurements at the mercury drop electrode, complemented by monolayer studies in a Langmuir trough and electrophoretic measurements, all used as models for hydrophobic cell membranes. Penetration of copper ions into the PG layer was facilitated by the formation of hydrophilic Cu-Phenanthroline (Phen) complex in the subphase, followed by the mixed ligand Cu-Phen-PG complex formation at the hydrophobic interface. Electrophoretic measurements indicated a comparatively low abundance of the formed mixed ligand complex within the PG vesicles, resulting it the zeta potential change of +0.83mV, while monolayer studies confirmed their co-existence at the interface. The Cu-Phen-PG complex was identified in the pH range from 6 to 9. The stoichiometry of the complex ([PhenCuOHPG]), as well as its stability and kinetics of formation, were determined at the mercury drop electrode. Cu-Phen-PG reduces quasireversibly at about -0.7V vs. Ag/AgCl including reactant adsorption, followed by irreversible mixed complex dissociation, indicating a two-electron transfer - chemical reaction (EC mechanism). Consequently, the surface concentration (γ) of the adsorbed [PhenCuOHPG] complex at the hydrophobic electrode surface was calculated to be (3.35±0.67)×10-11molcm-2. Information on the mechanism of Cu (II) - lipid complex formation is a significant contribution to the understanding of complex processes at natural cell membranes.

Quantum Chemical Calculations Resolved Identification of Methylnitrocatechols in Atmospheric Aerosols.

Methylnitrocatechols (MNCs) are secondary organic aerosol (SOA) tracers and major contributors to atmospheric brown carbon; however, their formation and aging processes in atmospheric waters are unknown. To investigate the importance of aqueous-phase electrophilic substitution of 3-methylcatechol with nitronium ion (NO2(+)), we performed quantum calculations of their favorable pathways. The calculations predicted the formation of 3-methyl-5-nitrocatechol (3M5NC), 3-methyl-4-nitrocatechol (3M4NC), and a negligible amount of 3-methyl-6-nitrocatechol (3M6NC). MNCs in atmospheric PM2 samples were further inspected by LC/(-)ESI-MS/MS using commercial as well as de novo synthesized authentic standards. We detected 3M5NC and, for the first time, 3M4NC. In contrast to previous reports, 3M6NC was not observed. Agreement between calculated and observed 3M5NC/3M4NC ratios cannot unambiguously confirm the electrophilic mechanism as the exclusive formation pathway of MNCs in aerosol water. However, the examined nitration by NO2(+) is supported by (1) the absence of 3M6NC in the ambient aerosols analyzed and (2) the constant 3M5NC/3M4NC ratio in field aerosol samples, which indicates their common formation pathway. The magnitude of error one could make by incorrectly identifying 3M4NC as 3M6NC in ambient aerosols was also assessed, suggesting the importance of evaluating the literature regarding MNCs with special care.

Improved separation and analysis of glycolipids by Iatroscan thin-layer chromatography-flame ionization detection.

We demonstrate improved power of Iatroscan thin layer chromatography/flame ionization detection (TLC-FID) technique for analysis of complex marine lipid mixture by developing protocol for the separation and analysis of glycolipids including sulfoquinovosyldiacylglycerols (SQDG), monogalactosyldiacylglycerols (MGDG) and digalactosyldiacylglycerols (DGDG). We have modified the common protocol used so far for the analysis of lipid classes by replacing the elution step which uses pure acetone for the elution of acetone mobile polar lipids, with the elution step containing chloroform-acetone (72:28, v:v) for separation of MGDG and DGDG. To separate SQDG from the complex lipid matrix we introduced solvent mixture acetone-chloroform-methanol-formic acid (33:33:33:0.6, v:v:v:v). Quantification of glycolipid classes was performed after calibration with glycolipid standards for the masses between 0.2 and 2.7-5.0µg. With this new protocol we have successfully separated three glycolipids from the complex particulate lipid mixture of the seawater samples. Such an approach extends the power of existing protocol for the analysis of lipids which altogether ensure detection and quantification of 18 lipid classes what was demonstrated on seawater samples. This enables to gain a very broad system overview of the particularly complex environments as are seas, oceans and freshwaters.

Adaptation of marine plankton to environmental stress by glycolipid accumulation.

A systematic investigation of non-phosphorus containing glycolipids (GL) was conducted in the northern Adriatic Sea during two years at two stations with different nutrient loads. GL concentration varied both spatially and temporally, with values of 1.1-21.5 µg/L and 0.4-44.7 µg/L in the particulate and the dissolved fraction, respectively. The highest concentrations were measured during summer in surface waters and at the more oligotrophic station, where GL yields (% of total lipids) were often higher than 20% and 50% in the particulate and dissolved fractions, respectively. To obtain more insight into factors governing GL accumulation autotrophic plankton community structure (pico-, nano- and microplankton fractions), chlorophyll a, heterotrophic bacteria and nutrient concentrations were measured together with hydrographic parameters and sunlight intensity. During the investigated period smaller autotrophic plankton cells (pico- and followed by nanoplankton) prevailed in abundance over larger cells (microplankton), which were found in large numbers in freshened surface samples. Several major findings resulted from the study. Firstly, during PO4 limitation, particularly at the oligotrophic station, enhanced glycolipid instead of phospholipid accumulation takes place, representing an effective phosphate-conserving mechanism. Secondly, results suggest that at seawater temperatures >19 °C autotrophic plankton considerably accumulate GL, probably to achieve thermal stability. Thirdly, high sunlight intensities seem to influence increased GL accumulation; GL possibly plays a role in cell mechanisms that prevent/mitigate photooxidation. And finally, substantial accumulation of GL detected in the dissolved fraction could be related to the fact that GL do not contain biologically relevant elements, like phosphorus, which makes them an unattractive substrate for enzyme activity. Therefore, substantial portion of CO2 could be removed from the atmosphere in P-limited regions during summer via its capture by plankton and conversion to GL.

Physicochemical signatures of natural sea films from Middle Adriatic stations.

Monolayer studies and a force-area quantification approach, in combination with electrochemical methods, are applied for physicochemical characterization of surface active substances (SAS) of the sea surface microlayers (MLs) from Middle Adriatic stations. Higher primary production during late spring-early autumn was reflected in the presence of MLs of higher surfactant activity containing on average molecules of lower molecular masses (M(w) = 0.65 ± 0.27 kDa) and higher miscibility (y = 6.46 ± 1.33) and elasticity (E(isoth) = 18.33 ± 2.02 mN m(-1)) modulus in comparison to structural parameters (average M(w) = 2.15 ± 1.58 kDa; y = 3.51 ± 1.46; E(isoth) = 6.41 ± 1.97 mN m(-1)) obtained for MLs from a period of lower production. A higher inhibition effect on the reduction process of Cd(2+) was observed for SAS abundant MLs from a more productive period. This kind of distribution is explained as the consequence of competitive adsorption of hydrophobic lipid-like substances of lower M(w) that act as end-members, highly influencing the surface structural properties of the natural air-water interface forming there segregated surface films during more productive period.