Marine chemistry

Sediment traps were deployed on the Northwest Shelf (NWS) of Australia in November 1996, to determine fluxes of organic matter and inorganic elements from the photic zone to deeper waters in a transect extending from Exmouth Shelf to Exmouth Plateau. Infiltrex II water samplers collected particulate and dissolved organics from the water column near the trap sites. Surface sediments and sediment cores were also collected over the study region. Lipid biomarkers were used to determine the sources of organic carbon and its cycling processes on the NWS.Dry weight fluxes from the traps ranged from 124 to 616 mg m−2 day−1and particulate organic carbon (POC) fluxes ranged from 22 to 42 mg m−2 day−1. The biogenic lipids consisted of biomarkers indicative of marine zooplankton, phytoplankton and bacteria, plus traces of land plant markers. A large contribution of unresolved complex material (UCM), which is indicative of petroleum, was detected at four times the biogenic hydrocarbon flux at shallow stations, and up to seven times the biogenic hydrocarbon flux at the most offshore station.There is essentially no river input, and only trace aeolian-derived material to contribute to primary production on the NWS of Australia. Most of the organic matter produced are rapidly recycled in the water column and the small fraction of lipids that settle to the sediments is already partially degraded and undergoes further rapid degradation in the surface sediments. Natural oil seeps also provide utilisable organic carbon to the system. The production and vertical flux rates of organics determined in this study are comparable to those reported in studies of shallow traps in oceanic areas from long-term studies in the Arabian Sea, and other coastal margins such as the Bay of Biscay (France) and California (USA).In offshore areas, most “living” lipid materials passed through the GFF filters thus invalidating POC estimates based on high volume sampling. To adequately assess living (particulate) carbon, gentle filtration of low volume seawater samples is more accurate, as shown by this solid phase absorption study of individual lipid biomarkers.

Polychlorinated biphenyls (PCBs) were quantified in bulk seawater (3.1 ± 1.0 ngl−1, N = 3) in 1976, in plankton (2.9 ± 3.3 ng g−1 wet weight, N = 176) in 1976 and 1977 and in fish (155 ± 194 ng g−1 wet weight, N = 135) in 1977 collected from St. Georges Bay in the southern Gulf of St. Lawrence. PCB concentrations in the plankton of the entire water column varied seasonally by ten times, with the highest values occurring in spring, lowest during summer and variable levels in late fall. The lower PCB levels in the total summer community coincide with a reduced biomass in certain size fractions in the Bay rather than a decrease in PCB concentration of the plankton. PCBs were concentrated in the middle-sized fractions of the planktonic community and this is attributed to the greater biomass present in these categories. PCB concentrations in plankton were most highly correlated with their lipid content at the time of sampling. Seasonal reductions of lipid in the plankton per m3 resulted in a higher concentration of PCB per unit lipid in the remaining community. Planktonic PCB concentrations, expressed on a lipid basis, are found to be correlated with cumulative rainfall 21 d before sampling for both years combined.Adult fish were more contaminated by PCBs than either their egg or juvenile stages. Mature gaspereau, herring and smelt had higher concentrations of PCB contamination than mackerel, capelin, white hake and silversides. No difference was found between PCB contamination of the sexes of fish species analyzed. PCBs were transferred from mother to offspring in fish, but at lower levels than the level present in the parent; and the maximum accumulation from the environment occurred between immature and adult fish. The best predictors of PCB contamination in fish in St. Georges Bay are lipid content followed by size and age.PCB concentrations in plankton, normalized to lipid content, did not increase with size or trophic level. PCB concentrations in fish increased with size and on average were ten times the levels found in plankton. Marine mammals collected by other researchers in the region during the 1970s had accumulated up to several orders-of-magnitude higher concentrations than those found in fish, with a more gradual increase with size of organism. Lipid content and age or exposure period appear to be the main factors which determine PCB concentrations in the marine food chain in the southern Gulf of St. Lawrence.

Pesticides have been extensibility used in the control of agricultural and sanitary pests. From World War II onward, more efficient and cheaper synthetic pesticides, such as organochlorine pesticides (OCPs), including DDT, lindane, or endosulfan, replaced the relatively environmentally friendly pesticides. OCPs were widely used worldwide; however, in the 1970s these compounds were began banned due to their harmful effects on both, biota and humans. Nevertheless, half a century later, due to their high persistence and the existence of some active sources, OCPs remain a problem for the health of marine ecosystems. Once in the environment, their distribution depends on the interaction of several factors -explained in detail in this chapter- such as the physical-chemical properties of each compound; interactions with the matrix; characteristics of the environment; and intensity, distance, and seasonality of the source, between others. This chapter reviews current levels, environmental behavior and fate, and effects on biota of organochlorine pesticides in global marine coastal environments, noting that these compounds are still detectable and could be harmful to marine biota

This study provides a comprehensive and quantitative discussion of the inventory and mass balance of dissolved thallium (Tl) in the oceans. The calculations are based on a critical evaluation of recently published analytical data. Thallium is estimated to have a mean seawater concentration of 65 pmol/kg and this implies a total oceanic inventory of about 8.76×104 Mmol Tl. The five

A direct, spectrophotometric method has been adapted for quantitative determination of nitrate concentrations in seawater. The method is based on nitration of resorcinol in acidified seawater, resulting in a color product. The absorption spectrum obtained for the reaction product shows a maximum absorption at 505 nm, with a molar absorptivity of 1.7 × 104 L mol− 1 cm− 1. This method has a detection limit of 0.5 μM and is linear up to 400 μM for nitrate. The advantage of this method is that all reagents are in aqueous solutions without involving cadmium granules as a heterogeneous reactant, as in conventional methods, and therefore is simple to implement. Application of the resorcinol to seawater analysis demonstrated that the results obtained are in good agreement with the conventional approach involving the reduction of nitrate by cadmium followed by diazotization.

Algae and marine sponges have been the targets of important scientific researches in the last 50 years, with a large number of secondary metabolites isolated and identified, showing a wide structural variety where certain compounds are useful in characterizing classes of algae and sponges – fact of great importance for chemists, taxonomists and ecologists. These substances exhibit many biological activities, such as defense against consumers and competitors, and colonial and pathogen organisms; or they display reproductive function. This thesis describes the results from the chemical study of Sargassum polyceratium Montagne, a seaweed from the Sargassaceae family, and Aplysina fistularis Pallas, a marine sponge from the Aplysinidae family. Both species had their chemical constituents identified by spectroscopic methods such as IR, mass and 1H and 13C-1D and -2D NMR, and by comparison with literature. The following porphirinic derivatives were isolated from S. polyceratium: 132-hydroxy-(132-R)-phaephytin a, 132-hydroxy-(132-S)-phaeophytin a, phaeophytin a and the steroid fucosterol. The chemical study of A. fistularis led us to the reisolation of the alkaloid and acetamide: 2-(3,5-dibromo-4-methoxyphenyl)-N,N,Ntrimethylethanamonium and (3,5-dibromo-4-ethoxy-1-hydroxy-4-methoxycyclohexa-2,5-dienyl) acetamide, and to the isolation of alkaloid 3,5-dibromo-4-[3’dimethylamonium]propoxyphenyl]-N,N,N-trimethylethanamonium (aplysfistularine), reported for the first time. The ethanolic extract from S. polyceratium was evaluated for psicopharmacological effects, showing behavioral changes of CNS depressant type. The ethanolic, hexanic and dichloromethanic extracts as well as the mixture (132-hydroxy-(132-R)-phaephytin a and 132-hydroxy-(132-S)-phaeophytin a) were not capable of inhibiting the growth of the tested lineages, showing negative antimicrobial activity. However they were capable of modifying the antibiotic activity, modulating the bacterial resistance between 2x to 4x. The isolated compounds from A. fistularis show inhibition of the DNA enzyme Topoisomerase II-
, with further biological studies needed for determining the compounds potency. Therefore, the present results contribute for the chemical study of marine organisms from species S. polyceratium and A. fistularis.

A modified procedure has been proposed for the colorimetric determination of dissolved oxygen in seawater to improve its precision and accuracy. When a pickled sample is acidified, iodine liberated in the iodometric reaction is measured by direct spectrophotometry at 456 nm. ...

Systematic water sampling for characterization of chromophoric dissolved organic matter (CDOM) in the coastal South Atlantic Bight, was conducted as part of the long term Coastal Ocean Research and Monitoring Program (CORMP). Water samples were collected ...

Phosphorus Near Edge X-ray Fluorescence Spectroscopy (P-NEXFS) data were collected on phosphorus containing phases including organic and inorganic compounds and minerals. Although phases containing P in the plus five oxidation state P(V) in a tetrahedral PO4 structure have similar primary fluorescence peak positions, the size, shape, and positions of secondary spectral features are diagnostic for different compounds and minerals. In particular, calcium phosphates exhibited a notable post-peak shoulder at 2154.5 eV, while oxidized iron phosphates had a distinctive pre-peak feature at 2148 eV. Polyphosphates have a broad secondary peak located approximately 2 eV higher in energy than a similar feature in phosphate esters and diesters. Compounds containing P(V) in structures other than PO4 tetrahedra such as phosphonates have a primary peak shifted about 1 eV lower than corresponding organo-phosphates. Organo-phosphates with P in the plus three oxidation state P(III) such as phosphines...

... Rivers alone discharge sufficient DOC to support the turnover of DOC throughout the ocean (Williams and Druffel, 1987) and enough POC to account for all the organic carbon now being buried in marine sediments (Berner, 1989; Hedges and Keil, 1995). ...