Presence In Seawater Research Articles

Micro(nano)plastics from synthetic oligomers persisting in Mediterranean seawater: Comprehensive NMR analysis, concerns and origins

The presence in seawater of low-molecular-weight polyethylene (PE) and polydimethylsiloxane (PDMS), synthetic polymers with high chemical resistance, has been demonstrated in this study for the first time by developing a novel methodology for their recovery and quantification from surface seawater. These synthetic polymer debris (SPD) with very low molecular weights and sizes in the nano- and micro-metre range have escaped conventional analytical methods. SPD have been easily recovered from water samples (2 L) through filtration with a nitrocellulose membrane filter with a pore size of 0.45 μm. Dissolving the filter in acetone allowed the isolation of the particulates by centrifugation followed by drying. The isolated SPD were analysed by 1H nuclear magnetic resonance spectroscopy (1H NMR), identifying PE and PDMS. These polymers are thus persisting on seawater because of their low density and the ponderal concentrations were quantified in mg/m3. This method was used in an actual case study in which 120 surface seawater samples were collected during two sampling campaigns in the Mediterranean Sea (from the Gulf of Salerno to the Gulf of Policastro in South Italy). The developed analytical protocol allowed achieving unprecedented simplicity, rapidity and sensitivity. The 1H and 13C NMR structural analysis of the PE debris indicates the presence of oxidised polymer chains with very low molecular weights. Additionally, the origin of those low molecular weight polymers was investigated by analysing influents and effluents from a wastewater treatment plant (WWTP) in Salerno as a hot spot for the release of SPD: the analysis indicates the presence of low molecular weight polymers compatible with wax-PE, widely used for coating applications, food industry, cosmetics and detergents. Moreover, the origin of PDMS debris found in surface seawater can be ascribed to silicone-based antifoamers and emulsifiers.

Bioaccumulation and fate of pharmaceuticals in a Mediterranean coastal lagoon: Temporal variation and impact of a flash flood event

Coastal ecosystems are particularly vulnerable to terrestrial inputs from human-impacted areas. The prevalence of wastewater treatment plants, unable to remove contaminants such as pharmaceuticals (PhACs), leads to their continuous input into the marine environment. In this paper, the seasonal occurrence of PhACs in a semi-confined coastal lagoon (the Mar Menor, south-eastern Spain) was studied during 2018 and 2019 by evaluating their presence in seawater and sediments, and their bioaccumulation in aquatic organisms. Temporal variation in the contamination levels was evaluated by comparison to a previous study carried out between 2010 and 2011 before the cessation of permanent discharges of treated wastewater into the lagoon. The impact of a flash flood event (September 2019) on PhACs pollution was also assessed. A total of seven compounds (out of 69 PhACs analysed) were found in seawater during 2018–2019, with a limited detection frequency (<33%) and concentrations (up to 11 ng/L of clarithromycin). Only carbamazepine was found in sediments (ND–1.2 ng/g dw), suggesting an improved environmental quality in comparison to 2010–2011 (when 24 and 13 compounds were detected in seawater and sediments, respectively). However, the biomonitoring of fish and molluscs showed a still remarkable accumulation of analgesic/anti-inflammatory drugs, lipid regulators, psychiatric drugs and β-blocking agents, albeit not higher than in 2010. The flash flood event from 2019 increased the prevalence of PhACs in the lagoon, compared to the 2018–2019 sampling campaigns, especially in the upper water layer. After the flash flood the antibiotics clarithromycin and sulfapyridine yielded the highest concentrations ever reported in the lagoon (297 and 145 ng/L, respectively), alongside azithromycin in 2011 (155 ng/L). Flash flood events associated with sewer overflows and soil mobilisation, which are expected to increase under climate change scenarios, should be considered when assessing the risks posed by pharmaceuticals to vulnerable aquatic ecosystems in the coastal areas.

Rapid Biotic and Abiotic Transformation of Toxins produced by Ostreopsis. cf. ovata.

The dinoflagellate Ostreopsis cf. ovata produces several families of toxic polyketides. Despite only a few field measurements of these phycotoxins in seawater and aerosols, they are believed to be responsible for dermatitis and the toxic inhalations reported during blooms of this species. Therefore, the stability of these compounds in seawater is essential to understanding the causes of these symptoms, however, this has never been assessed. In the current study, the optimization of a solid phase extraction (SPE) procedure was first performed to ensure the most efficient extraction of all phycotoxins known to be produced by this strain, including the recently described liguriatoxins. The SPE cartridge SDBL® under non acidified conditions offered the best option. The stability of the ovatoxins and the liguriatoxins under biotic and abiotic stress was assessed by exposing the spent medium of a culture of Ostreopsis cf. ovata to its bacterial consortium and natural sunlight. A rapid biotic transformation was detected for both families of compounds. When exposed to bacteria, the half-lives of the ovatoxins were reached before 10 h and at 36 h, 97% of these toxins had been transformed. The half-lives of the liguriatoxins were 10 h under these conditions. Photolysis (abiotic degradation) of the ovatoxins (T1/2 < 36 h) was faster than for the liguriatoxins (T1/2 > 62 h). Although none of the catabolites of these phycotoxins were thoroughly identified, an untargeted metabolomics approach combined with molecular networking highlighted the presence of several compounds exhibiting structural similarities with the ovatoxins. Additional work should confirm the preliminary findings on these potential ovatoxins’ catabolites and their biological properties. The rapid transformation of O. cf. ovata’s phycotoxins introduces questions concerning their presence in seawater and their dispersion in the sea spray aerosols. The compounds involved in the toxic inhalations and dermatitis often experienced by beachgoers may stem from the catabolites of these toxins or even unrelated and as yet unidentified compounds.

First ecotoxicological characterization of paraffin microparticles: a biomarker approach in a marine suspension-feeder, Mytilus sp

Microplastics are one of the main environmental pollutants in marine ecosystems, and their presence in seawater is a consequence of the widespread use of plastic materials in modern commodities. This wide usage of plastics includes the employment of microspheres in common personal care products, which end up being ultimately released into the aquatic compartment. Known ecotoxicological effects of microplastics favoured the search for technologically viable and environmentally safer alternatives, such as paraffin wax microparticles, whose ecotoxicological risks have not been entirely characterized. To address this gap, the present study exposed mussels (Mytilus sp.) for 96h to three densities (5mg/L, 20mg/L and 80mg/L) of four size ranges (100-300μm, 300-500μm, 400-850μm, and 800-1200μm) of paraffin wax particles. Toxicological endpoints were the activities of four enzymes involved in key cellular processes, including antioxidant defence (catalase (CAT), glutathione reductase (GRed) and glutathione peroxidase (GPx)) and phase II metabolism (glutathione S-transferases (GSTs)), as well as lipid content and fatty acid profiles of the digestive gland. Significant interactions between the presence/absence of food and paraffin particle density were found, as food sometimes worked as a confounding factor in the analysed biomarkers. Despite this uncertainty, some overall patterns emerged. In general, smaller paraffin wax particles (100-300μm) caused little effects on the activity of the four enzymes tested, whereas larger particles (800-1200μm) caused significant effects on almost all biomarkers. CAT activity was enhanced in animals exposed to larger paraffin particles, whilst GPx activity was depressed; GRed activity was not affected by the exposure to paraffin particles. The activity of GSTs was enhanced, but only in one tested condition. No effects were observed in terms of the total lipid content and fatty acids of exposed animals. Overall, data obtained in this work suggest that, at densities of paraffin wax particles comparable to the levels found in the environment for microplastic beads, no toxicity is expected to occur in the tested mussel species, by measuring the here-assessed toxicological endpoints.

An eDNA/eRNA-based approach to investigate the life cycle of non-cultivable shellfish micro-parasites: the case of Bonamia ostreae, a parasite of the European flat oyster Ostrea edulis.

SummaryEnvironmental DNA approaches are increasingly used to detect microorganisms in environmental compartments, including water. They show considerable advantages to study non‐cultivable microorganisms like Bonamia ostreae, a protozoan parasite inducing significant mortality in populations of flat oyster Ostrea edulis. Although B. ostreae development within the host has been well described, questions remain about its behaviour in the environment. As B. ostreae transmission is direct, seawater appears as an interesting target to develop early detection tools and improve our understanding of disease transmission mechanisms. In this context, we have developed an eDNA/eRNA approach allowing detecting and quantifying B. ostreae 18S rDNA/rRNA as well as monitoring its presence in seawater by real‐time PCR. B. ostreae DNA could be detected up to 4 days while RNA could be detected up to 30 days, suggesting a higher sensitivity of the eRNA‐based tool. Additionally, more than 90% of shed parasites were no longer detected after 2 days outside the oysters. By allowing B. ostreae detection in seawater, this approach would not only be useful to monitor the presence of the parasite in oyster production areas but also to evaluate the effect of changing environmental factors on parasite survival and transmission.

Effects of Cobalt on Spore Germination, Gametophyte Growth and Gametogenesis of Undaria pinnatifida (Phaeophyceae).

With rapid development of the construction of nuclear power plants along the coast, the concern of negative effects of potentially unexpected release of nuclides on marine organisms has increased. Cobalt (Co) is one of the crucial nuclides in nuclear polluted seawater. The effect of its presence in seawater on life cycle of macroalgae has seldom been studied. In this investigation, a series of Co concentrations including 1, 10, 100μgL-1, and 1, 10mgL-1 (the background concentration of Co in culture seawater was determined to be at the level of 0.75 ± 0.11μgL-1) were used to test the effects of their presence on spore germination, gametophyte growth and gametogenesis of the important brown macroalga Undaria pinnatifida. It was found that the spore germination rate of 10mgL-1 group was significantly lower than that of the control group after 1- and 2days exposure. The gametophyte sizes of 1 and 10mgL-1 groups were much smaller than that of the control group after 6- and 12-days exposure. Oogonia and juvenile sporophytes were observed to appear in 1, 10μgL-1 and the control groups after 12 and 15days, respectively, but not in the higher concentration groups. In the recovery test, sporophytes appeared in the 100μgL-1 group on the 5th day, but not in 1 and 10mgL-1 groups. These results demonstrate that presence of Co at high concentrations in seawater disturbs the life cycle by suppressing both the gametophyte growth and gametogenesis in U. pinnatifida.

Development of a two-step, non-probed multiplex real-time PCR for surveilling Vibrio anguillarum in seawater.

Vibrio anguillarum is an aggressive and halophilic bacterial pathogen most commonly originating from seawater. Vibrio anguillarum presence in fisheries and aquaculture facilities causes significant morbidity and mortality among aquaculture species primarily from haemorrhaging of the body and skin of the infected fish that eventually leads to death, collectively recognized as the disease vibriosis. This study served to develop a non-probe, multiplex real-time PCR assay to rapidly detect V.anguillarum presence in seawater. Specific primers targeting genes vah1, empA and rpoN of V.anguillarum were selected for multiplex reaction among 11 different primer sets and the extension step was eliminated. Primer concentration, denaturation time as well as annealing time and temperature of DNA amplification were optimized, thus reducing reaction duration. The two-step, non-probed multiplex real-time PCR set forth by this study detects as little as 3CFUmL(-1) of V.anguillarum presence in sea water, without enrichment cultivation, in 70min with molecular precision and includes melting curve confirmation.

Enzymatic methods for the determination of pollution in seawater using salt resistant alkaline phosphatase from eggs of the sea urchin Strongylocentrotus intermedius

A new salt resistant alkaline phosphatase from eggs of the sea urchin Strongylocentrotus intermedius (StAP) has been shown to have a unique property to hydrolyze substrate in seawater without loss of enzymatic activity. The enzyme has pH optimum at 8.0–8.5. Model experiments showed various concentrations of copper, zinc, cadmium and lead added to seawater or a standard buffer mixture to inhibit completely the enzyme activity at the concentrations of 15–150μg/l. StAP sensitivity to the presence in seawater of metals, pesticides, detergents and oil products appears to be considerably less. Samples of seawater taken from aquatic areas of the Troitsy Bay of the Peter the Great Bay, Japan Sea have been shown to inhibit the enzyme activity; the same was shown for the samples of fresh waters. The phosphatase inhibition assay developed proved to be highly sensitive, technically easy-to use allowing to test a great number of samples.

Toxicity of Metal Pyrithione Photodegradation Products to Marine Organisms with Indirect Evidence for Their Presence in Seawater

We evaluated the acute toxicities of the metal pyrithiones (MePTs)--copper pyrithione (CuPT) and zinc pyrithione (ZnPT)--to four species of marine algae and a marine crustacean (Tigriopus japonicus). We also performed acute toxicity tests using six of the main MePT photodegradation products: pyridine-N-oxide (PO); 2-mercaptopyridine (HPS); pyridine-2-sulfonic-acid (PSA); 2-mercaptopyridine-N-oxide (HPT); 2,2'-dithio-bis-pyridine ([PS](2)); and 2,2'-dithio-bis-pyridine-N-oxide ([PT](2))-and three marine organisms representing three trophic levels: an alga (Skeletonema costatum), a crustacean (T. japonicus), and a fish (Pagrus major). The acute toxicity values (72-h EC(50)) of CuPT, ZnPT, HPT, (PT)(2), (PS)(2), HPS, PO, and PSA for S. costatum, which was the most sensitive of the test organisms to the chemicals tested, were 1.5, 1.6, 1.1, 3.4, 65, 730, >100,000, and >100,000 microg l(-1), respectively. CuPT was detected in the growth media used for S. costatum tests and in seawater containing HPT or (PT)(2); the concentration of CuPT in seawater containing HPT was highly dependent on the Cu(2+) concentration. These results indicate that in the presence of sufficient Cu(2+), the toxicities of HPT and (PT)(2) should be assessed as CuPT because in Japan MePTs are most frequently used as antifouling booster biocides in conjunction with cuprous oxide.

Influence of temperature, salinity and nutrient limitation on yessotoxin production and release by the dinoflagellate Protoceratium reticulatum in batch-cultures

The toxic dinoflagellate Protoceratium reticulatum (Claparède & Lachmann) Buetschli is recurrently present in the Adriatic sea. It is the producing organism of yessotoxin (YTX) and some of its analogues and thus its presence in seawater often results in shellfish farm closure for long periods. However, molluscs become highly toxic also at the presence of low cell concentrations, due to the high YTX content present in most algal strains. As no data were available on the environmental conditions favouring growth and YTX production by Adriatic P. reticulatum strains, in the present work, we investigated the effect of nutrient limitation, salinity and temperature on growth and YTX content in P. reticulatum cultures. Liquid chromatography–mass spectrometry (LC–MS) analyses were carried out to determine YTX production as well as the difference between the YTX amount retained in cells and that released in growth medium, in order to relate cell content to excretion mechanisms. The toxin content was determined in cells collected at the stationary phase, since both toxin production and release were found to be higher in this growth stage than in the exponential phase. As for nutrient-effect, a severe P-limitation strongly affected cell growth and favoured toxin accumulation, as consequences of both impaired cell division and lower toxin release. N-limited cultures, on the contrary, had a toxin content similar to controls and the highest percentage of release. P. reticulatum was confirmed to be tolerant towards salinity changes as it could grow at salinity values in the range of 22–42. The highest YTX production was observed at intermediate salinity values (32) whereas toxin release, expressed as percentage of the total amount produced, decreased as salinity increased. P. reticulatum growth was impaired in cultures kept at 26 °C in respect to those grown at 16 and 20 °C. YTX release decreased as temperature increased; however, cells kept at 26 °C displayed a very high YTX content. The environmental implications of these physiological behaviours highlight that farmed molluscs can become less toxic in colder waters at lower salinity values.

Rate of Mass Deposition of Scaling Compounds from Seawater on the Outer Surface of Heat Exchangers in MED Evaporators

The scaling problem in Multi Effect Distillation (MED) evaporators is investigated by the experimental measurement of the deposition rate under different operating conditions. The measurements are conducted in a batch vessel containing artificial seawater, which is allowed to contact the outer surface of a hot pipe under controlled temperature, salinity and pH. The rate of mass deposition is higher at elevated temperature. The salinity of the seawater also influences the scaling process - an increase in salinity from 47-59 g/L leads to an increase of 75.6 % in the deposition rate. Decreasing the pH value of seawater to 2.01 results in a complete inhibition of scaling, whereas the severity of the scaling increases in neutral and basic mediums. Polyacrylic acid is tested as an antifoulant and it was found that its presence in seawater reduces the scaling process. The nature of the heat transfer surface material also plays an important role in the scaling process. It is found experimentally that the rate of scaling is higher in the case of a Cu-Ni alloy as the surface material of the tube rather than stainless steel.

Clustering of sex hormone disruptors in Singapore's marine environment.

Abnormal sexual differentiation and other reproductive abnormalities in marine animals indicate the presence in seawater of endocrine-disrupting compounds (EDCs) that perturb the function of the sex hormone signaling pathways. However, most studies to date have reported on EDC effects in freshwater and sewage samples, and there is a paucity of bioassay data on the effects of EDCs in marine waters. Our aims in this study were to devise robust methodologies suitable for extracting potential EDCs and to measure their summated effects on activities of androgen receptors (ARs) and estrogen receptors (ER-alpha and ER-beta) in marine samples from Singapore's coastal waters. In this study, we examined the ability of C18, hydrophilic and lipophilic balance, and diol cartridges to extract potential EDCs from seawater samples. Extracts from C18 cartridges exhibited the highest sex hormone bioactivities in reporter gene assays based on a human cell line expressing AR, ER-alpha, and ER-beta. Examination of extracts from 20 coastal locations showed high androgenic and estrogenic agonist activities in confined clusters closest to the main island of Singapore. Sex hormone activity declined rapidly in clusters farther from the main coastline and in more open waters. Unexpectedly, surface and mid-depth samples from the confined high-activity clusters, in the presence of hormone, exhibited AR and ER-alpha activities that were 200-900% higher than those observed for the cognate hormone alone. This enhanced sex hormone activity suggests that analyses of complex seawater mixtures may uncover unusual bioactivities that may not be obvious by studying individual compounds. Our data present a "snapshot" of the sex hormone disruptor activity in Singapore's marine environment and indicate that C18 extraction for EDCs used in conjunction with reporter gene bioassays represents a robust and sensitive methodology for measuring summated androgenic and estrogenic activities in seawater.

Photoproduction of nonmethane hydrocarbons (NMHCs) in seawater

Abstract Nonmethane hydrocarbons (NMHCs) are emitted into the atmosphere from the ocean's surface. Although the oceanic contribution to the global NMHC budget is considered minor relative to other sources, it is one of the least well measured or understood. The major compounds emitted are a series of C2–C4 alkenes. Due to their ubiquitous presence in seawater, their high reactivity in the atmosphere, and the important role they play in the atmospheric chemistry in remote regions of the globe, the processes responsible for their formation and fate warrant examination. To ascertain the role of photoprocesses in NMHC formation in surface waters, laboratory experiments were conducted to determine the magnitude and wavelength dependence of NMHC photoproduction for a range of water types. Photochemical transformation of dissolved organic matter (DOM) present in surface seawater results in the production of the C2–C4 alkenes in the surface ocean with the UV portion (295–340 nm) of the solar spectrum controlling the bulk of this production. Under summer sunlight intensities in Miami, FL, net photoproduction rates for ethene, the dominant photoproduced NMHC in surface seawater, varied from 0.220 pmol l−1 min−1 for transparent oligotrophic waters to 6.11 pmol l−1 min−1 for highly colored estuarine waters. Apparent quantum yields of photoproduction varied from 10−9 to 10−7 depending on water type, wavelength of light and individual compound.

Amplification of DNA polymerase gene fragments from viruses infecting microalgae.

Nested PCR with three highly degenerate primers was used for amplification and identification of DNA polymerase (pol) genes from viruses which infect three genera of microalgae. Group-specific primers (AVS1 and AVS2) were designed on the basis of inferred amino acid sequences unique to the DNA pol genes of viruses (PBCV-1 and NY-2A) that infect an endosymbiotic Chlorella-like alga (Chlorophyceae) and a virus (MpV-SP1) which infects the photosynthetic flagellate Micromonas pusilla (Prasinophyceae). In addition, a nested primer (POL) was designed on the basis of the highly conserved amino acid sequence YGDTDS found in most B-family (alpha-like) DNA pol genes. These primers were used to amplify DNA from the three viruses, PBCV-1, NY-2A, and MpV-SP1, for which the primers were designed, as well as eight clonal isolates of genetically distinct viruses which infect M. pusilla and others which infect Chrysochromulina spp. (Prymnesiophyceae), suggesting that these are a group of related viruses. In contrast, no product resulted from using DNA from viruses which infect the marine brown algae Ectocarpus siliculosis and Feldmannia sp. (Phaeophyceae), suggesting that these viruses may not be closely related to those that infect microalgae. These primers were also used to amplify DNA from natural virus communities. Our results indicate that nested PCR, even under low-stringency conditions, can be used as a rapid method to verify the presence in seawater of a group of related viruses which infect microalgae. Sequence analysis of these fragments should provide information on the genetic diversity and potentially the phyletic relationships among these viruses.(ABSTRACT TRUNCATED AT 250 WORDS)

A microwave exposure system for marine animals: Dosimetry and reflectometric observations

An aquatic system is described in which marine biota can be exposed under natural conditions for indefinite periods of time to dose‐determinate levels of microwave radiation. A source of 2450‐MHz CW energy is used to feed a standard‐gain horn that radiates a glass‐faced aquarium in the far field; source and aquarium are located in a microwave‐anechoic chamber. Seawater in the 95‐liter aquarium can be maintained at a desired temperature by a high‐capacity heat‐exchange system. By caging sets of one or more small aquatic animals at various distances from the glass face, determinate SARs at different levels can be achieved simultaneously within the aquarium. Reflectometric data on a small marine animal, the mollusc Aplysia californica, reveal that its presence in seawater does not appreciably change the load that is seen by incident RF waves. The system should prove useful in studying effects of long‐term microwave exposures in animals that are otherwise maintained in a natural environment.

38.—Development of Ideas concerning the Carbon Dioxide System in Sea Water up to 1940.

SynopsisMarcet reported in 1822 that sea salt contained lime, and several investigators confirmed its presence in sea water in the 1830s. Darondeau found dissolved CO2in sea water in 1838, and von Bibra in 1851 considered sea water to be slightly alkaline. Tornöe in 1880 pointed out that this condition required part of the CO2to be bound chemically, and Hamberg applied the mass action law to the CO2-system in sea water in 1885. For nearly 50 years, however, despite the development of the concepts of pH and activity, attempts to apply the law in detail failed, first because the behaviour of H2CO3and HCO3−as weak acids is strikingly different in pure water, sea water or NaCl solutions, and secondly because the presence and role of another weak acid, boric acid, was not recognised fully until 1933. Investigators often attributed their failures to some mysterious ability of the sea to disregard or evade the laws of physical chemistry. Buch in 1933 and 1938 finally laid this hobgoblin to rest, and his results are still accepted with only minor modifications.

Galvanic Relationships between Aluminum Alloys and Magnesium Alloys: II . Aluminum Claddings on Magnesium

The cladding of magnesium AZ31A alloy with 99.99% aluminum greatly improves its resistance to saline environments. The protective ability of the cladding is little changed by incorporation therein of magnesium, silicon, or manganese, but it is impaired greatly by iron and copper and more mildly by zinc. The presence in seawater of soluble magnesium salts greatly diminishes the effects of iron, copper, and zinc from that seen in sodium chloride solution. This decrease is probably due to decreased cathodic attack of the aluminum at the lower equilibrium pH of the seawater environment.