In this study, perfluoroalkylated substances (PFASs) were analyzed in 92 surface seawater samples taken during the Malaspina 2010 expedition which covered all the tropical and subtropical Atlantic, ...Pacific and Indian oceans. Nine ionic PFASs including C6–C10 perfluoroalkyl carboxylic acids (PFCAs), C4 and C6–C8 perfluoroalkyl sulfonic acids (PFSAs) and two neutral precursors perfluoroalkyl sulfonamides (PFASAs), were identified and quantified. The Atlantic Ocean presented the broader range in concentrations of total PFASs (131–10900 pg/L, median 645 pg/L, n = 45) compared to the other oceanic basins, probably due to a better spatial coverage. Total concentrations in the Pacific ranged from 344 to 2500 pg/L (median = 527 pg/L, n = 27) and in the Indian Ocean from 176 to 1976 pg/L (median = 329, n = 18). Perfluorooctanesulfonic acid (PFOS) was the most abundant compound, accounting for 33% of the total PFASs globally, followed by perfluorodecanoic acid (PFDA, 22%) and perfluorohexanoic acid (PFHxA, 12%), being the rest of the individual congeners under 10% of total PFASs, even for perfluorooctane carboxylic acid (PFOA, 6%). PFASAs accounted for less than 1% of the total PFASs concentration. This study reports the ubiquitous occurrence of PFCAs, PFSAs, and PFASAs in the global ocean, being the first attempt, to our knowledge, to show a comprehensive assessment in surface water samples collected in a single oceanic expedition covering tropical and subtropical oceans. The potential factors affecting their distribution patterns were assessed including the distance to coastal regions, oceanic subtropical gyres, currents and biogeochemical processes. Field evidence of biogeochemical controls on the occurrence of PFASs was tentatively assessed considering environmental variables (solar radiation, temperature, chlorophyll a concentrations among others), and these showed significant correlations with some PFASs, but explaining small to moderate percentages of variability. This suggests that a number of physical and biogeochemical processes collectively drive the oceanic occurrence and fate of PFASs in a complex manner.
The bioaccumulation of perfluoroalkylated substances (PFASs) in plankton has previously been evaluated only in freshwater and regional seas, but not for the large oligotrophic global oceans. Plankton ...samples from the tropical and subtropical Pacific, Atlantic and Indian Oceans were collected during the Malaspina 2010 circumnavigation expedition, and analyzed for 14 ionizable PFASs, including perfluorooctanoate (PFOA), perfluorooctanesulfonate (PFOS) and their respective linear and branched isomers. PFOA and PFOS concentrations in plankton ranged from 0.1 to 43 ng gdw –1 and from 0.5 to 6.7 ng gdw –1, respectively. The relative abundance of branched PFOA in the northern hemisphere was correlated with distance to North America, consistent with the historical production and coherent with previously reported patterns in seawater. The plankton samples showing the highest PFOS concentrations also presented the largest relative abundances of branched PFOS, suggesting a selective cycling/fractionation of branched PFOS in the surface ocean mediated by plankton. Bioaccumulation factors (BAFs) for plankton were calculated for six PFASs, including short chain PFASs. PFASs Log BAFs (wet weight) ranged from 2.6 ± 0.8 for perfluorohexanesulfonic acid (PFHxS), to 4.4 ± 0.6 for perfluoroheptanoic acid (PFHpA). The vertical transport of PFASs due to the settling of organic matter bound PFAS (biological pump) was estimated from an organic matter settling fluxes climatology and the PFAS concentrations in plankton. The global average sinking fluxes were 0.8 ± 1.3 ng m–2d–1 for PFOA, and 1.1 ± 2.1 ng m–2d–1 for PFOS. The residence times of PFAS in the surface ocean, assuming the biological pump as the unique sink, showed a wide range of variability, from few years to millennia, depending on the sampling site and individual compound. Further process-based studies are needed to constrain the oceanic sink of PFAS.
The atmospheric dry deposition fluxes of 16 polycyclic aromatic hydrocarbons (PAHs) have been measured, for the first time, in the tropical and subtropical Atlantic, Pacific, and Indian Oceans. ...Depositional fluxes for fine (0.7–2.7 μm) and coarse (>2.7 μm) aerosol fractions were simultaneously determined with the suspended aerosol phase concentrations, allowing the determination of PAH deposition velocities (v D). PAH dry deposition fluxes (F DD) bound to coarse aerosols were higher than those of fine aerosols for 83% of the measurements. Average F DD for total (fine + coarse) Σ16PAHs (sum of 16 individual PAHs) ranged from 8.33 ng m–2d–1 to 52.38 ng m–2d–1. Mean F DD for coarse aerosol’s individual PAHs ranged between 0.13 ng m–2d–1 (Perylene) and 1.96 ng m–2d–1 (Methyl Pyrene), and for the fine aerosol fraction these ranged between 0.06 ng m–2d–1 (Dimethyl Pyrene) and 1.25 ng m–2d–1 (Methyl Chrysene). The estimated deposition velocities went from the highest mean v D for Methyl Chrysene (0.17–13.30 cm s–1), followed by Dibenzo(ah)Anthracene (0.29–1.38 cm s–1), and other high MW PAHs to minimum values of v D for Dimethyl Pyrene (<0.04 cm s–1) and Pyrene (<0.06 cm s–1). Dry depositional processes depend on the concentration of PAHs in the suspended aerosol, but also on physicochemical properties and environmental variables (vapor pressure, wind speed, and on the affinity of aerosols for depositing to the sea surface). Empirical parametrizations are proposed to predict the dry depositional velocities of semivolatile organic compounds to the global oceans.
Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) were measured in plankton samples from the Atlantic, Pacific, and Indian Oceans collected ...during the Malaspina circumnavigation cruise. The concentrations of PCDD/Fs and dl-PCBs in plankton averaged 14 and 240 pg gdw –1, respectively, but concentrations were highly variable. The global distribution of PCDD/Fs and dl-PCBs was not driven by proximity to continents but significantly correlated with plankton biomass, with higher plankton phase PCDD/F and dl-PCB concentrations at lower biomass. These trends are consistent with the interactions between atmospheric deposition, biomass dilution, and settling fluxes of organic matter in the water column (biological pump), as key processes driving POPs plankton phase concentrations in the global oceans. The application of a model of the air–water–plankton diffusive exchange reproduces in part the influence of biomass on plankton phase concentrations and suggests future modeling priorities. The estimated oceanic sink (Atlantic, Pacific, and Indian Oceans) due to settling fluxes of organic matter bound PCDD/Fs and dl-PCBs is of 400 and 10,500 kg y–1, respectively. The atmospheric inputs due to gross diffusive absorption and dry deposition are nearly 3 and 10 times larger for PCDD/Fs and dl-PCBs, respectively, than the oceanic sink. These observations suggest that the coupling of atmospheric deposition with water column cycling supports and drives the accumulation of dl-PCBs and PCDD/Fs in plankton from the global oligotrophic oceans.
Organophosphate esters (OPEs) are widely used as flame retardants and plasticizers and have been detected ubiquitously in the remote atmosphere. Fourteen OPEs were analyzed in 115 aerosol phase ...samples collected from the tropical and subtropical Atlantic, Pacific, and Indian Oceans during the MALASPINA circumnavigation campaign. OPEs were detected in all samples with concentrations ranging from 360 to 4400 pg m–3 for the sum of compounds. No clear concentration trends were found between the Northern and Southern hemispheres. The pattern was generally dominated by tris(1-chloro-2-propyl) phosphate (TCPP), although tri-n-butyl phosphate (TnBP) had a predominant role in samples close to continents and in those influenced by air masses originating in continents. The dry deposition fluxes of aerosol phase ∑14OPE ranged from 4 to 140 ng m–2 d–1. An estimation of the OPE gas phase concentration and gross absorption fluxes by using three different sets of physical chemical properties suggested that the atmosphere–ocean diffusive exchange of OPEs could be 2–3 orders of magnitude larger than dry deposition. The associated organic phosphorus inputs coming from diffusive OPE fluxes were estimated to potentially trigger up to 1.0% of the reported primary production in the most oligotrophic oceanic regions. However, the uncertainty associated with these calculations is high and mostly driven by the uncertainty of the physical chemical properties of OPEs. Further constraints of the physical chemical properties and fluxes of OPEs are urgently needed, in order to estimate their environmental fate and relevance as a diffusive source of new organic phosphorus to the ocean.
Intensive aquaculture is an important source of organic waste and antibiotics into the marine environment. Yet, their impacts on benthic marine ecosystems are poorly understood. Here, we investigated ...the ecological impacts of fish feed waste alone and in combination with three different antibiotics (i.e., oxytetracycline, florfenicol and flumequine) in benthic ecosystems of the Mediterranean Sea by performing a field experiment. We assessed the fate of the antibiotics in the sediment and their accumulation in wild fauna after two weeks of exposure. Moreover, we investigated the impact of the feed waste alone and in combination with the antibiotics on sediment physico-chemical properties, on benthic invertebrates, as well as on the microbiota and resistome of the sampled sediments. One week after the last antibiotic application, average oxytetracycline and flumequine concentrations in the sediment were <1% and 15% of the applied dose, respectively, while florfenicol was not detected. Flumequine concentrations in wild invertebrates reached 3 μg g−1, while concentrations of oxytetracycline were about an order of magnitude lower, and florfenicol was not detected. Feed waste, with and without antibiotics, increased the concentration of fine particulate matter, affected the pH and redox conditions, and significantly reduced the biodiversity and abundance of benthic invertebrates. Feed waste also had a significant influence on the structure of sediment microbial communities, while specific effects related to the different antibiotics ranged from insignificant to mild. The presence of antibiotics significantly influenced the normalized abundance of the measured antibiotic resistance genes. Florfenicol and oxytetracycline contributed to an increase of genes conferring resistance to macrolides, tetracyclines, aminoglycosides and chloramphenicol, while flumequine had a less clear impact on the sediment resistome. This study demonstrates that feed waste from aquaculture farms can rapidly alter the habitat and biodiversity of Mediterranean benthic ecosystems, while antibiotic residual concentrations can contribute to the enrichment of bacterial genes resistant to antibiotic classes that are of high relevance for human medicine.
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•Effects of aquaculture feed waste and antibiotics were assessed on benthic ecosystems.•Oxytetracycline and flumequine accumulated in sediments and wild invertebrates.•Feed waste altered habitat conditions and decreased macroinvertebrate diversity.•Feed waste significantly influenced the structure of microbial communities.•Florfenicol and oxytetracycline correlated with resistance to several antibiotics.
The atmosphere plays a fundamental role in the transport of microbes across the planet but it is often neglected as a microbial habitat. Although the ocean represents two thirds of the Earth's ...surface, there is little information on the atmospheric microbial load over the open ocean. Here we provide a global estimate of microbial loads and air-sea exchanges over the tropical and subtropical oceans based on the data collected along the Malaspina 2010 Circumnavigation Expedition. Total loads of airborne prokaryotes and eukaryotes were estimated at 2.2 × 10
and 2.1 × 10
cells, respectively. Overall 33-68% of these microorganisms could be traced to a marine origin, being transported thousands of kilometres before re-entering the ocean. Moreover, our results show a substantial load of terrestrial microbes transported over the oceans, with abundances declining exponentially with distance from land and indicate that islands may act as stepping stones facilitating the transoceanic transport of terrestrial microbes.The extent to which the ocean acts as a sink and source of airborne particles to the atmosphere is unresolved. Here, the authors report high microbial loads over the tropical Atlantic, Pacific and Indian oceans and propose islands as stepping stones for the transoceanic transport of terrestrial microbes..
The ubiquitous occurrence of perfluoroalkyl substances (PFAS) in the open ocean has been previously documented, but their vertical transport and oceanic sinks have not been comprehensively ...characterized and quantified at the oceanic scale. During the Malaspina 2010 circumnavigation expedition, 21 PFAS were measured at the surface and at the deep chlorophyll maximum (DCM) in the Atlantic, Indian and Pacific oceans. In this work, we report an extended data set of PFAS dissolved phase concentrations at the DCM. ∑PFAS at the DCM varied from 130 to 11 000 pg L
, with a global average value of 500 pg L
. Perfluorooctanesulfonate (PFOS) abundance contributed 39% of ∑PFAS, followed by perfluorodecanoate (PFDA, 17%), and perfluorohexanoate (PFHxA, 12%). The relative contribution of the remaining compounds was below 10%, with perfluorooctanoate (PFOA) contributing only 5% to PFAS measured at the DCM. Estimates of vertical diffusivity, derived from microstructure turbulence observations in the upper (<300 m) water column, allowed the derivation of PFAS eddy diffusive fluxes from concurrent field measurements of eddy diffusivity and PFAS concentrations. The PFAS concentrations at the DCM predicted from an eddy diffusivity model were lower than field-measured concentrations, suggesting a relevant role of other vertical transport mechanisms. Settling fluxes of organic matter bound PFAS (biological pump), oceanic circulation and potential, yet un-reported, biological transformations are discussed.
Antibiotics used in marine aquaculture have been reported to accumulate in sediments and non-target aquatic organisms, modifying the biodiversity and the environmental conditions in areas close to ...the fish farms. Improved analytical methods are required to assess the spread and the impacts of aquaculture antibiotics in the marine environment, as well as to estimate resistance development risks. In this study, we have optimized a method for simultaneous quantitative determination of oxytetracycline, florfenicol and flumequine in marine samples using liquid chromatography coupled to time-of-flight high resolution mass spectrometry (LC-TOF/MS). The method optimization was carried out for seawater, sediment and biological samples (biofilm and two benthic invertebrate species: Gammarus aequicauda and Monodonta articulata). Special attention was paid to the optimization of the extraction and purification steps, testing: liquid-liquid and solid-liquid extractions, the use of silica and other commercial sorbents' clean-up, and single and tandem solid phase extraction procedures. The limits of quantification (MQLs) achieved with the developed method are 0.1–0.5 μg L-1 in seawater; 1–5 μg kg−1 in marine sediments; 5–25 μg kg−1 in biofilm; and 100–500 μg kg−1 in invertebrates, with good accuracy and precision. Method recoveries in spiked samples are 65–120% in seawater and sediment samples, and 63–110% in the biological samples. The method has been successfully implemented for the determination of antibiotic concentrations in sediment and invertebrate samples collected from a Mediterranean bay in south-east Spain. These represent significant advances in the analysis of antibiotics in environmental samples, especially for wild marine taxa, and attend for a proper assessment of the environmental fate and side effects of aquaculture antibiotics in the marine environment.
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•LC-TOF MS determination of antibiotics in several marine samples•Antibiotic extraction from environmental samples is based on SPE tandem purification.•The methods show a high sensitivity and reproducibility.•MQLs of 0.1–0.5 μg L−1 in seawater; 0.3–50 μg/kg in sediments and biota samples•Measurable concentrations of oxytetracycline and flumequine were found.
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