Compounds In Marine Organisms Research Articles

The osteogenic and mineralogenic potential of the microalgae Skeletonema costatum and Tetraselmis striata CTP4 in fish models

Skeletal disorders are problematic aspects for the aquaculture industry as skeletal deformities, which affect most species of farmed fish, increase production costs and affect fish welfare. Following recent findings that show the presence of osteoactive compounds in marine organisms, we evaluated the osteogenic and mineralogenic potential of commercially available microalgae strains Skeletonema costatum and Tetraselmis striata CTP4 in several fish systems. Ethanolic extracts increased extracellular matrix mineralization in gilthead seabream (Sparus aurata) bone-derived cell cultures and promoted osteoblastic differentiation in zebrafish (Danio rerio) larvae. Long-term dietary exposure to both extracts increased bone mineralization in zebrafish and upregulated the expression of genes involved in bone formation (sp7, col1a1a, oc1, and oc2), bone remodeling (acp5a), and antioxidant defenses (cat, sod1). Extracts also improved the skeletal status of zebrafish juveniles by reducing the incidence of skeletal anomalies. Our results indicate that both strains of microalgae contain osteogenic and mineralogenic compounds, and that ethanolic extracts have the potential for an application in the aquaculture sector as dietary supplements to support fish bone health. Future studies should also identify osteoactive compounds and establish whether they can be used in human health to broaden the therapeutic options for bone erosive disorders such as osteoporosis.

Characteristics, sources and health risks of organotin compounds in marine organisms from the seas adjacent to the eastern ports of China

Organotin compounds (OTCs), being widely used as antifouling coatings on ships, are defined as endocrine-disrupting chemicals by the EPA due to their harmful effects on marine organisms. The eastern coast of China has developed abundant maritime transportation and fishery industries but the associated OTC pollution can pose potential health risks. In the present study, 20 species of marine organisms (including mollusks, crustaceans and fish) were collected from the seas adjacent to the eastern ports of China and 6 OTCs (ie, tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT) and triphenyltin (TPhT), diphenyltin (DPhT) and monophenyltin (MPhT)) were analyzed using GC-MS/MS. ∑OTCs in marine organisms ranged from 0.81 to 2900 ng Sn g−1 dw with the mean of 130 ng Sn g−1 dw, being at a comparatively moderate level across the world. PhTs were the dominant pollutants with the contribution up to 51%–87%. Spatially, the highest concentration of OTCs occurred in marine organisms from the ports in the Southeast Coast, and mollusks were more likely to accumulate OTCs than other species. BT concentrations in seafood decreased significantly after the implementation and enforcement of the TBT ban. The source analysis showed that BTs detected in current biota are mainly from historical exposure to antifouling coating on ships. However, PhTs may be closely associated with coastal aquaculture as well as terrestrial agriculture-related activities. The commercially important fishes were recovered a higher level of ∑OTCs than others suggesting a potential risk for protein uptake. Health risks via seafood consumption caused by OTCs were not high but children are exposed to the highest risk, followed by adolescents and adults respectively. In the future, continuous monitoring of OTCs, especially PhTs, in marine organisms from the eastern ports of China is still necessary, and effective measures to protect marine ecosystems and human health need to be taken.

Bisphenol Analogs in Aquatic Environments and Their Effects on Marine Species—A Review

Bisphenol A analogs are currently used in manufacturing and as plasticizers as a substitute for bisphenol A. This replacement is taking place because bisphenol A is recognized as an endocrine disruptor chemical (EDC) that can also cause oxidative stress and genotoxic effects in aquatic species. Bisphenol A analogs have a similar chemical structure to BPA, raising doubts about their use as safer substitutes. This review intends to summarize the concentrations of BPA analogs found in aquatic environments and the effects of these emerging compounds on marine species. Generally, studies indicate that BPA analogs have similar effects to their precursor, altering the neuroendocrine system in several marine species. Furthermore, BPA analogs can cause oxidative stress and developmental alterations. The available information on the biological effects of BPA analogs suggests that more effort should be performed to assess the effects of these compounds in marine organisms.

UV-Protective Compounds in Marine Organisms from the Southern Ocean.

Solar radiation represents a key abiotic factor in the evolution of life in the oceans. In general, marine, biota—particularly in euphotic and dysphotic zones—depends directly or indirectly on light, but ultraviolet radiation (UV-R) can damage vital molecular machineries. UV-R induces the formation of reactive oxygen species (ROS) and impairs intracellular structures and enzymatic reactions. It can also affect organismal physiologies and eventually alter trophic chains at the ecosystem level. In Antarctica, physical drivers, such as sunlight, sea-ice, seasonality and low temperature are particularly influencing as compared to other regions. The springtime ozone depletion over the Southern Ocean makes organisms be more vulnerable to UV-R. Nonetheless, Antarctic species seem to possess analogous UV photoprotection and repair mechanisms as those found in organisms from other latitudes. The lack of data on species-specific responses towards increased UV-B still limits the understanding about the ecological impact and the tolerance levels related to ozone depletion in this region. The photobiology of Antarctic biota is largely unknown, in spite of representing a highly promising reservoir in the discovery of novel cosmeceutical products. This review compiles the most relevant information on photoprotection and UV-repair processes described in organisms from the Southern Ocean, in the context of this unique marine polar environment.

Sterol Sulfates and Sulfotransferases in Marine Diatoms.

Sterol sulfates are widely occurring molecules in marine organisms. Their importance has been so far underestimated although many of these compounds are crucial mediators of physiological and ecological functions in other organisms. Biosynthesis of sterol sulfates is controlled by cytosolic sulfotransferases (SULTs), a varied family of enzymes that catalyze the transfer of a sulfo residue (-SO3H) from the universal donor 3'-phosphoadenosine-5'-phosphosulfate to the hydroxyl function at C-3 of the steroid skeleton. The absence of molecular tools has been the main impediment to the development of a biosynthetic study of this class of compounds in marine organisms. In fact, there is very limited information about these enzymes in marine environments. SULT activity has, however, been reported in several marine species, and, recently, the production of sterol sulfates has been linked to the control of growth in marine diatoms. In this chapter, we describe methods for the study of sterol sulfates in this lineage of marine microalgae. The main aim is to provide the tools useful to deal with the biosynthesis and regulation of these compounds and to circumvent the bottleneck of the lack of molecular information. The protocols have been designed for marine diatoms, but most of the procedures can be used for other marine organisms.

Screening for Anti-Cancer Compounds in Marine Organisms in Oman.

Marine organisms are a rich source of bioactive molecules with potential applications in medicine, biotechnology and industry; however, few bioactive compounds have been isolated from organisms inhabiting the Arabian Gulf and the Gulf of Oman. This study aimed to isolate and screen the anti-cancer activity of compounds and extracts from 40 natural products of marine organisms collected from the Gulf of Oman. This study was carried out between January 2012 and December 2014 at the Sultan Qaboos University, Muscat, Oman. Fungi, bacteria, sponges, algae, soft corals, tunicates, bryozoans, mangrove tree samples and sea cucumbers were collected from seawater at Marina Bandar Al-Rowdha and Bandar Al-Khayran in Oman. Bacteria and fungi were isolated using a marine broth and organisms were extracted with methanol and ethyl acetate. Compounds were identified from spectroscopic data. The anti-cancer activity of the compounds and extracts was tested in a Michigan Cancer Foundation (MCF)-7 cell line breast adenocarcinoma model. Eight pure compounds and 32 extracts were investigated. Of these, 22.5% showed strong or medium anti-cancer activity, with malformin A, kuanoniamine D, hymenialdisine and gallic acid showing the greatest activity, as well as the soft coral Sarcophyton sp. extract. Treatment of MCF-7 cells at different concentrations of Sarcophyton sp. extracts indicated the induction of concentration-dependent cell death. Ultrastructural analysis highlighted the presence of nuclear fragmentation, membrane protrusion, blebbing and chromatic segregation at the nuclear membrane, which are typical characteristics of cell death by apoptosis induction. Some Omani marine organisms showed high anti-cancer potential. The efficacy, specificity and molecular mechanisms of anti-cancer compounds from Omani marine organisms on various cancer models should be investigated in future in vitro and in vivo studies.

Determination of selenium and its compounds in marine organisms

In this study, we investigate the type and quantity of selenium compounds in fish and marine organisms, using ion-pair reversed phase LC–ICP-MS, developed and applied for the analysis of Atlantic cod, Atlantic salmon, Greenland halibut, Atlantic herring, blue mussel, common crab, scallop, calanus, and Euphasia super. Of the samples examined, the lowest level of selenium was found in farmed Atlantic salmon (0.17mgSekg−1dm). The total selenium extraction efficiency by phosphate buffer was 2.5 times higher in sea plankton and shellfish samples than in fish samples. Analysis of Se species in each hydrolysate obtained by proteolysis showed the presence of selenomethionine, which constituted 41.5% of the selenium compounds detected in hydrolysates of Atlantic herring and 98.4% of those in extracts of Atlantic salmon. Inorganic compounds, such as selenates and selenites, were detected mainly in sea plankton and shellfish samples (<0.13mgSekg−1wm), although no correlation was found between the presence of inorganic compounds and total selenium concentration. The accuracy of the total selenium determination was validated using a certified reference material (oyster tissue (NIST 1566b)). A lyophilised powder of cod (Gadus morhua) was used to validate speciation analysis, enzymatic hydrolysis of lyophilised powder of cod recovered 54±6% of total selenium, and SeMet constituted 83.5±5.28% of selenium detected in hydrolysates. The chromatographic detection limits were, respectively, 0.30ngmL−1, 0.43ngmL−1, 0.54ngmL−1, 0.55ngmL−1, 0.57ngmL−1 and 0.72ngmL−1 for selenate, selenomethionine, selenite, Se-methyl-selenocysteine, selenocystine and selenomethionine selenoxide.The data on selenium concentrations and speciation presented here could be useful in estimating levels of selenium intake by seafood consumption.

Antiproliferative activity of VLC fractions obtained from Asparagopsis armata associated bacteria

Event Abstract Back to Event Antiproliferative activity of VLC fractions obtained from Asparagopsis armata associated bacteria João F. Francisco1, Andre Horta1, Nádia S. Fino1, Susete Piteus1, Celso Alves1 and Rui Pedrosa1* 1 Marine Resources Research Group (GIRM), ESTM, Polytechnic Institute of Leiria, Portugal Many studies are showing the presence of bioactive compounds in marine organisms, such as algae and algae associated bacteria. Cancer is one of the major causes of death in the world, consequently research for new antitumor compounds is continuous and have high importance for the human health. The aim of this study was to evaluate the antitumor activity of Shewanella sp. associated bacteria from Asparagopsis armata. Crude extract of associated bacteria was obtained with methanol and dichloromethane (1:1) extraction. Then the crude extract was fractioned by vacuum liquid chromatography (VLC) using cyclohexane with increasing amounts of 25% of ethyl acetate, in order to isolate different compounds obtained five fractions (F1-F5). The cell viability and the cell proliferation studies were performed on human breast adenocarcinoma cell line (MCF-7 cells) according to MTT method. In cytotoxicity assay (1mg/ml; 24 hours), the highest reduction of MCF-7 viability was induced by F2 and F3 fractions (53.6% and 48.6% respectively). On the other hand in cell proliferation assay (1mg/ml; 24 hours), all fractions showed anti-proliferative activity (1mg/mL), however the highest inhibition of MCF-7 proliferation was exhibited by F3 and F5 fractions, 15% and 17,7%, respectively. These results suggest that the Shewanella sp. associated bacteria from Asparagopsis armata can be an interesting source of new antitumor drugs. Keywords: associated bacteria, algae, Marine compounds, antitumoral therapies, Natural Products, marine symbiosis Conference: IMMR | International Meeting on Marine Research 2014, Peniche, Portugal, 10 Jul - 11 Jul, 2014. Presentation Type: Poster Presentation Topic: BLUE BIOTECH Citation: Francisco JF, Horta A, Fino NS, Piteus S, Alves C and Pedrosa R (2014). Antiproliferative activity of VLC fractions obtained from Asparagopsis armata associated bacteria. Front. Mar. Sci. Conference Abstract: IMMR | International Meeting on Marine Research 2014. doi: 10.3389/conf.fmars.2014.02.00064 Copyright: The abstracts in this collection have not been subject to any Frontiers peer review or checks, and are not endorsed by Frontiers. They are made available through the Frontiers publishing platform as a service to conference organizers and presenters. The copyright in the individual abstracts is owned by the author of each abstract or his/her employer unless otherwise stated. Each abstract, as well as the collection of abstracts, are published under a Creative Commons CC-BY 4.0 (attribution) licence (https://creativecommons.org/licenses/by/4.0/) and may thus be reproduced, translated, adapted and be the subject of derivative works provided the authors and Frontiers are attributed. For Frontiers’ terms and conditions please see https://www.frontiersin.org/legal/terms-and-conditions. Received: 10 May 2014; Published Online: 18 Jul 2014. * Correspondence: Dr. Rui Pedrosa, Marine Resources Research Group (GIRM), ESTM, Polytechnic Institute of Leiria, Peniche, Portugal, rpedrosa@ipleiria.pt Login Required This action requires you to be registered with Frontiers and logged in. To register or login click here. Abstract Info Abstract The Authors in Frontiers João F Francisco Andre Horta Nádia S Fino Susete Piteus Celso Alves Rui Pedrosa Google João F Francisco Andre Horta Nádia S Fino Susete Piteus Celso Alves Rui Pedrosa Google Scholar João F Francisco Andre Horta Nádia S Fino Susete Piteus Celso Alves Rui Pedrosa PubMed João F Francisco Andre Horta Nádia S Fino Susete Piteus Celso Alves Rui Pedrosa Related Article in Frontiers Google Scholar PubMed Abstract Close Back to top Javascript is disabled. Please enable Javascript in your browser settings in order to see all the content on this page.

Mass spectrometric studies shed light on unusual oxidative transformations of 1,2‐dehydro‐N‐acetyldopa

Lamellarins are a group of over 70 plus bioactive marine natural compounds possessing a 6,7-dihydroxycoumarin moiety. Although they appear to derive from 3,4-dihydroxyphenylalanine (dopa), practically nothing is known about the metabolic fate of these compounds. Biochemical considerations indicate that they could arise from a N-acetyl-1,2-dehydrodopa precursor through oxidative cyclization reaction. To assess the above hypothesis, we synthesized N-acetyl-1,2-dehydrodopa and conducted oxidation studies with commercially available mushroom tyrosinase and evaluated the course of the reaction with reversed-phase liquid chromatography/mass spectrometry (LC/MS). Mushroom tyrosinase readily oxidized N-acetyl-1,2-dehydrodopa - not to the normally expected quinone - but to an unstable quinone methide isomer, which rapidly cyclized to produce the dihydroxycoumarin product, 3-aminoacetyl esculetin. Interestingly, 3-aminoacetyl esculetin was further oxidized to a second quinone methide derivative that exhibited an addition reaction with the parent dihydroxycoumarin generating dimeric and other oligomeric products in the reaction mixture. LC/MS analysis of the N-acetyl-1,2-dehydrodopa oxidation reaction reveals not only a possible novel oxidative cyclization route for the biosynthesis of coumarin-type dehydrodopa compounds in marine organisms, but also unusual oxidative transformations of dehydro dopa derivatives.

Bioaccumulation and trophic transfer of dioxins in marine copepods and fish

Despite the great concerns about dioxins in the marine environments, the biokinetics and bioaccumulation of these compounds in marine organisms remains little known. Using radioactive tracers the aqueous uptake, dietary assimilation efficiency, and elimination of dioxins were measured in marine phytoplankton, copepods and seabream. The calculated uptake rate constant of dioxins decreased with increasing trophic levels, whereas the dietary assimilation efficiency (AE) was 28.5–57.6% in the copepods and 36.6–70.2% in the fish. The dietary AE was highly dependent on the food concentrations and food type. The elimination rate constant of dioxin in the copepods varied with different exposure pathways as well as food concentration and food type. Biokinetic calculation showed that dietary accumulation was the predominant pathway for dioxin accumulation in marine copepods and fish. Aqueous uptake can be an important pathway only when the bioconcentration of dioxins in the phytoplankton was low.

Simultaneous determination nucleosides in marine organisms using ultrasound‐assisted extraction followed by hydrophilic interaction liquid chromatography–electrospray ionization time‐of‐flight mass spectrometry

A new method has been developed based on ultrasound-assisted extraction (UAE) followed by hydrophilic interaction chromatography (HILIC) and electrospray ionization time-of-flight mass spectrometry (ESI-TOF/MS) for the simultaneous determination of 16 nucleosides and nucleobases in medicinal extracts of various marine organisms. The separation was achieved on a Venusil HILIC column (250×4.6 mm id, 5 μm) and gradient elution using a solution of acetonitrile and buffer (0.20% formic acid and 20 mmol/L ammonium acetate) as the mobile phase. Identification of the 16 target nucleosides and nucleobases was based on the retention time, UV spectra, and mass measurements of the protonated molecules ([M+H](+)) and main fragment ions (ESI-TOF/MS). In addition, non-target compounds of 2'-deoxyinosine and four other amino acids were also tentatively identified by ESI-TOF/MS. The 16 target compounds were quantified by HILIC-ESI-TOF/MS under optimized mass conditions. All calibration curves showed good linearity (r(2)>0.9951). The recoveries were 84.72-124.10%, and the limits of detection of the 16 target compounds were 0.6-130.0 ng/mL. The developed method was applied to quantify the target compounds in 15 batches of various marine organisms. The method has potential applicability for the identification and determination of highly polar and low-concentration active compounds in marine organisms.

Arsenic cycling in marine systems: degradation of arsenosugars to arsenate in decomposing algae, and preliminary evidence for the formation of recalcitrant arsenic

Environmental context Despite high levels of complex organoarsenic compounds in marine organisms, arsenic in seawater is present almost entirely as inorganic species. We examine the arsenic products from a marine alga allowed to decompose under simulated natural coastal conditions, and demonstrate a multi-step conversion of organic arsenicals to inorganic arsenic. The results support the hypothesis that the arsenic marine cycle begins and ends with inorganic arsenic. Abstract Time series laboratory experiments were performed to follow the degradation of arsenic compounds naturally present in marine algae. Samples of the brown alga Ecklonia radiata, which contains three major arsenosugars, were packed into 12 tubes open to air at one end only, and allowed to naturally decompose under moist conditions. During the subsequent 25 days, single tubes were removed at intervals of 1–4 days; their contents were cut into four sections (from open to closed end) and analysed for arsenic species by HPLC/ICPMS following an aqueous methanol extraction. In the sections without direct contact with air, the original arsenosugars were degraded primarily to arsenate via two major intermediates, dimethylarsinoylethanol (DMAE) and dimethylarsinate (DMA). The section with direct contact with air degraded more slowly and significant amounts of arsenosugars remained after 25 days. We also report preliminary data suggesting that the amount of non-extractable or recalcitrant arsenic (i.e. insoluble after sequential extractions with water/methanol, acetone, and hexane) increased with time. Furthermore, we show that treatment of the pellet with 0.1-M trifluoroacetic acid at 95°C solubilises a significant amount of this recalcitrant arsenic, and that the arsenic is present mainly as a cationic species of currently unknown structure.

Sex differences in effects on sexual development in rat offspring after pre- and postnatal exposure to triphenyltin chloride

Consumers are exposed to organotin compounds (OTCs) via contaminated fish and seafood due to the accumulation of these compounds in marine organisms. Certain OTCs are immunotoxic and may also have endocrine disrupting properties resulting in adverse effects on the reproductive tract in mollusks and mammals. Since effects of in utero exposure to endocrine disrupting chemicals on the reproductive system are dependent on the critical window of exposure during its development, we conducted a comprehensive study with the aim to identify the most sensitive window of exposure to TPTCl and to investigate the effects of pre- and postnatal treatment on sexual development in rats. Male and female offspring rats were exposed to 2 or 6mg TPTCl/kg b.w. and day either in utero and during lactation (gestation day 6 until weaning on PND 21) or from gestation day 6 until termination. As previously reported, offspring in the 6mg TPTCl dose group exhibited high perinatal mortality and therefore no further evaluation was carried out at this dose level (Grote, K., Hobler, C, Andrade, A.J.M., Wichert Grande, S., Gericke, C., Talsness, C.E., Appel, K.E., Chahoud, I., 2007. Effects of in utero and lactational exposure to triphenyltin chloride on pregnancy outcome and postnatal development in rat offspring. Toxicology 238, 177–185). In the present paper, results on postnatal development obtained from surviving offspring of dams exposed to 2mg TPTCl/kg b.w. are reported. Male offspring were sacrificed on PND 64 or 65 and female offspring at first estrus after PND 58. A clear sex difference in response to treatment was observed. Male postnatal development was severely affected with decreases in body weight gain, reproductive organ weights and testosterone concentration as well as a significant delay in the age at preputial separation. In contrast, females exhibited a precocious completion of vaginal opening while all other endpoints were unaffected. Most of these effects were already present in animals that were only exposed until weaning indicating that these effects may be irreversible and continued treatment until termination had contributed less than expected to the severity of the observed effects. The results of the present study suggest that the sensitive window for the evaluated endpoints seems to be the period of prenatal development and that male offspring rats were more susceptible to treatment.

Comparison of two analytical methods for the determination of organotin compounds in marine organisms

Abstract Two analytical procedures were used for the determination of butyltin compounds in mussels. Both methods include extraction with methanol containing tropolone, derivatization, purification on Florisil and GC–MS analysis. The main difference between the procedures is in the derivatization step: one employs a Grignard reagent (n-pentylmagnesium bromide) while the other uses sodium tetraethylborate (STEB). Quantitative determinations were carried out in single ion monitoring using tripropyltin as internal standard. The accuracy of the procedures was verified on a certified reference material (ERM 477), providing good results for both methods. All the considered compounds showed lower detection limits with STEB derivatization; in particular for tributyltin (TBT), the difference between the two methods overcame one order of magnitude. An in vivo experiment was then performed, exposing mussels (Mytilus galloprovincialis) to known amount of TBT for 7 days; control and contaminated tissues were analyzed using the STEB derivatization method. Results showed the accumulation of TBT, especially in the gills.

Bioactive compounds in marine organisms

Bioactive compounds in marine organisms

Mapping of arsenic species and identification of a novel arsenosugar in giant clams Tridacna maxima and Tridacna derasa using advanced mass spectrometric techniques

Environmental context. Arsenic is known to accumulate in various marine organisms. The high acute toxicity of inorganic arsenic species and the potential chronic toxicity of some organoarsenic species require detailed knowledge about the occurrence and metabolism of arsenic compounds in marine organisms. The application of advanced analytical techniques still allows, even after decades of arsenic speciation, the identification of novel species. In addition, comprehensive mapping of all arsenic species present in marine organisms may allow for a more detailed understanding of arsenic metabolism. Abstract. Because of their symbiotic microalgae, giant clams (Tridacna species) exhibit a unique arsenic metabolism, which has been shown in previous studies to involve a large number of arsenic species. This study demonstrates the application of liquid chromatography (HPLC) online with electrospray tandem mass spectrometry (ES-MS/MS) as well as inductively coupled plasma mass spectrometry (ICP-MS) for arsenic speciation analysis in giant clam extracts. Selected reaction monitoring (SRM) was used for sensitive and selective detection of a large number of arsenic species in a single chromatographic run. Novel aspects are the analysis of 10 tissue fractions from one clam and the analysis of kidney extracts both from T. maxima and T. derasa with the same method thus offering the possibility for direct comparisons. Moreover, HPLC-ES-MS/MS in the precursor ion scan mode and product ion scan mode allowed the identification of a novel sulfonated dimethylarsenosugar and the partial characterisation of another unknown arsenic species. The results indicate that most arsenic species are accumulated in the kidneys. However, arsenobetaine was found at similar contents in all analysed tissue fractions of one T. maxima clam.

Tissue Distribution of Perfluorinated Chemicals in Harbor Seals (Phoca vitulina) from the Dutch Wadden Sea

Perfluorinated acids (PFAs) are today widely distributed in the environment, even in remote arctic areas. Recently, perfluorooctane sulfonate (PFOS) has been identified in marine mammals all over the world, but information on the compound-specific tissue distribution remains scarce. Furthermore, although longer perfluorinated carboxylic acids (PFCAs) are used in industry and were shown to cause severe toxic effects, still little is known on potential sources or their widespread distribution. In this study, we report for the first time on levels of longer chain PFCAs, together with some short chain PFAs, perfluorobutane sulfonate (PFBS) and perfluorobutanoate (PFBA), in liver, kidney, blubber, muscle, and spleen tissues of harbor seals (Phoca vitulina) from the Dutch Wadden Sea. PFOS was the predominant compound in all seal samples measured (ranging from 89 to 2724 ng/g wet weight); however, large variations between tissues were monitored. Although these are preliminary results, it is, to our knowledge, the first time that PFBS could be found at detectable concentrations (2.3 +/- 0.7 ng/g w wt) in environmental samples. PFBS was only detected in spleen tissue. PFCA levels were much lower than PFOS concentrations. The dominant PFCA in all tissues was PFNA (perfluorononanoic acid), and concentrations generally decreased in tissues for all other PFCA homologues with increasing chain length. No clear relationship between PFOS levels in liver and kidney was observed. Furthermore, hepatic PFDA (perfluorodecanoic acid) levels increased with increasing body length, but in kidney tissue, PFDA levels showed an inverse relationship with increasing body length. These data suggest large differences in tissue distribution and accumulation patterns of perfluorinated compounds in marine organisms.

Thio arsenosugars in freshwater mussels from the Danube in Hungary

In contrast to the large body of data on naturally-occurring arsenic compounds in marine organisms, relatively little is known about arsenic speciation in freshwater biota. We report an investigation using HPLC-ICPMS into the arsenic compounds in five species of freshwater mussels collected from five sites from the Danube in Hungary. Total arsenic concentrations in the mussels ranged from 3.8-12.8 mg As kg(-1). The arsenic speciation patterns were broadly similar for mussels representing each of the five species and five sites, but quite different from those reported for marine mussels. The major extractable arsenicals were two oxo arsenosugars (glycerol sugar and phosphate sugar), and their thio analogues (thio glycerol sugar and thio phosphate sugar). Arsenobetaine, usually the major arsenical in marine organisms, was not a significant compound in the freshwater mussels and was detected in only three of the 11 samples. This is the first report of thio arsenosugars in freshwater biota and suggests that these compounds may be common and widespread naturally-occurring arsenicals.

Volatile analytes formed from arsenosugars: determination by HPLC-HG-ICPMS and implications for arsenic speciation analyses.

It is generally accepted that the use of the hydride generation method to produce volatile analytes from arsenic compounds is restricted to the two inorganic forms (As(III) and As(V)) and the three simple methylated species methylarsonate (MA), dimethylarsinate (DMA), and trimethylarsine oxide. We report here that arsenosugars, major arsenic compounds in marine organisms, produce volatile analytes by the hydride generation (HG) method without a prior mineralization/oxidation step and that they can be quantitatively determined using HPLC-HG-ICPMS. The hydride generation efficiency depends on the type of hydride generation system and is influenced by the concentration of HCl and NaBH(4). For the four arsenosugars investigated, the hydride generation efficiencies were approximately 21-28% (or 4-6%, depending on the HG system) that obtained for As(III) under conditions optimized for As(III). This hydride efficiency was less than that shown by MA ( approximately 68% relative to As(III)) and DMA ( approximately 75%) but greater than that displayed by As(V) ( approximately 18%). Analysis of two species of brown algae, Fucus serratus and Hizikia fusiforme, by HPLC-HG-ICPMS produced results comparable with those obtained from other techniques used in our laboratory (HPLC-ICPMS and LC-ESMS for F. serratus) and with results from other laboratories taking part in a round robin exercise (H. fusiforme). This study shows for the first time the quantitative determination of arsenosugars using the hydride generation method without a decomposition step and has considerable implications for analytical methods for determining inorganic arsenic based on the formation of volatile hydrides.

Is the Mussel Test a good Indicator of Antifouling Activity? A Comparison Between Laboratory and Field Assays

Current antifouling technologies rely on metal-based paints, but due to their toxicity, an expected worldwide ban of organotin-containing paints is now prompting the quest for safe and effective alternatives. One of these is antifouling coatings whose active components are naturally occurring compounds in marine organisms. A number of laboratory bioassays has been designed to search for antifouling compounds. However, there is no evidence to date that these assays provide results reproducible through ecologically realistic field experiments. Natural concentrations of the extracts from the Brazilian seaweeds Laurencia obtusa and Stypopodium zonale were tested in the laboratory through the 'mussel test' and in the field through the 'phytagel method' in order to compare the efficiency of these methods in assessing antifouling activity. L. obtusa extract significantly inhibited fouling in both the laboratory and field assays, while S. zonale stimulated fouling in both assays. Major compounds from the extracts were identified. The findings suggest that the 'mussel test' is a reliable time and cost-saving screening method for antifouling substances, although field assays are more sensitive for detection of their activity spectrum.