Role of eicosenoic and docosenoic fatty acids in fresh water and marine lipids

The isomeric compositions of the eicosenoic and docosenoic fatty acids of four freshwater fish oils (from sheepshead Aplodinotus grunniens, tullibee Coregonus artedii, maria Lota lota and alewife Alosa pseudoharengus, respectively) were examined by open-tubular gas—liquid chromatography. The 22:1ω11 isomer, usually the dominant isomer in marine-fish oils, was unimportant relative to 22:1ω9. The unsaponifiables lacked fatty alcohols and pristane and were mostly cholesterol. The probability that the 22:1ω1 in marine fish oils is strictly of an exogenous origin (primarily originating as the fatty alcohol in copepod wax esters) is reviewed and it is proposed that docosenoic acids have no obligatory role in the lipid biochemistry of either marine or freshwater fish.     

A convenient method for the determination of carbon in marine “net zooplankton”

Measurements of carbon in marine “net zooplankton” were made by use of a Leco 70 Second TC-12 Automatic Carbon Determinator. The instrument employs high-temperature (ca. 1600°C), dry-combustion and thermal-conductivity detection of the purified carbon-dioxide combustion product and oxygen carrier gas mixtures. The methodology developed in this study is convenient and rapid (ca. 70 sec per freeze-dried sample), with a mean error ($\text{±2σ/}\text{x}\text{·100}$) of ±4.4% at the 3 mg-C level and ±7.4% at the 10 mg-C level when benzoic acid is used as a standard, and ±9.2% at the 5 mg-C level and ±6.0% at the 10 mg-C level when casein is used as the standard. The technique was applied to the “splash zone” marine copepod Tigriopus californicus to obtain an average value of 38.6% C by weight. Concentrated samples of “net zooplankton” of varying size fractions were collected in the Monterey upwelling region over an eight-month period. Values up to 2000 mg-C/m² ocean surface (0–200 m) were observed in a seasonal cycle doubly peaked for some size fractions but not for others.     

A chemical investigation of the transport and fate of petroleum hydrocarbons in littoral and benthic environments: The TSESIS oil spill

The fate of saturated and aromatic hydrocarbons discharged into the coastal Baltic Sea environment from the TSESIS oil spill has been studied in the acute and postacute (one year) phases of the spill. Periodic samples of Mytilus edulis (mussels) from eight littoral zone stations and Macoma balthica from nine soft bottom stations were obtained as well as sediment trap samples and surface sediment samples. Glass capillary gas chromatography and gas chromatographic mass spectrometry were used as the analytical tools to determine saturated and aromatic hydrocarbon composition and concentrations in these samples.Sediment trap samples indicated that sizable quantities of chemically and microbially weathered oil were sedimented, and available for benthic uptake shortly after the spill. After initial uptake of sedimented oil (500 to 1000 μ/g dry weight), Macoma populations appear to have begun slow depuration through the first winter after the spill, but TSESIS oil was again introduced to the benthic stations studied during the following summer. Mytilus populations in the region were severely impacted by the oil. Initial depuration of spilled oil during the first month was rapid and nearly complete at all but the most heavily impacted stations one year after the spill. The post-spill depuration of assimilated hydrocarbons was characterised by a relative retention of alkylated dibenzothiophenes and alkylated phenanthrenes compared to their unsubstituted parent compounds and compared with the entire homologous naphthalene series.These data suggest that petroleum hydrocarbons from the TSESIS spill have become a chronic source of degraded saturated and aromatic hydrocarbons to the soft bottom benthic communities. Petroleum hydrocarbons in the benthic environment from this spill appear to reside in the difficulty sampled and mobile flucculent layer at the sediment/water interface and may affect epifaunal communities for an extended period of time.     

A comparison of lignin and stable carbon isotope compositions in quaternary marine sediments

Organic matter in four Quaternary sediment cores from the Gulf of Mexico and one core from the Washington State coast have been analyzed for lignin and stable carbon isotope compositions. Holocene sequences of all five cores contain organic matter with high relative abundances of ¹³C ($\text{δ}{}^{13}\text{C = ?19.0 to ?22.5\% versus PDB}$) and low lignin concentrations, both of which are consistent with a marine origin. Distinctly lower ¹³C concentrations ($\text{δ}{}^{13}\text{C = ?24.0 to ?25.5\%}$) occur in underlying glacial-age sequences from four of the five cores, including the core from the Washington coast where such trends are previously unreported. Although the carbon isotopic compositions of these Pleistocene sediments are typical of predominantly land-derived organic matter, they contain only about 5% of the lignin found in modern sediments of similar $\text{δ}{}^{13}\text{C}$ from adjacent continental shelves. The lignin-poor organic matter in the glacial-age deposits appears to be either marine-derived or terrigenous material that likely was depleted in vascular plant debris at the time of deposition.     

A priori determination of valid control sites: An example using marine meiobenthic nematodes

Proper control sites for nematode abundance, patch size and patch dispersion could not be defined prior to a manipulative oil pollution experiment despite the apparent physical similarity and proximity of two locations. Comparisons of abundance and patch size demonstrated that neither site could serve as a control for the other. Spectral analysis was not useful, in this case, in resolving patch dispersion in the range of 1·2 to 60 cm. These data indicated that in circumstances where a posteriori studies comparing two areas cannot be avoided, it is only with great caution that a single factor should be interpreted as causative of observed densities or distribution of organisms.     

Incorporation,distribution and fate of saturated petroleum hydrocarbons in sediments from a controlled marine ecosystem

A simulation of a chronic input of petroleum into an estuarine environment was investigated using the facilities at the Marine Ecosystems Research Laboratory at the University of Rhode Island. An oil-water dispersion of No. 2 fuel oil was added to the system (twice weekly for 24 weeks) and the saturated hydrocarbons from this oil were measured in suspended material and sediments. After the initial chronic oil addition, trace amounts of hydrocarbons were detected in the sediments within two weeks, but substantial accumulation was not detected for approximately 135 days. The oil appeared to enter the sediment via the suspended material, with most of the saturated hydrocarbons associated with smaller size sediment particles (< 45 μm to > 0·3 μm). With time, the fuel oil saturated hydrocarbons in the sediments were mixed to a depth of 3 to 4 cm. Although only 12% of the total saturated hydrocarbons added to the system were found in the sediments, these hydrocarbons appear to be relatively stable and were still detectable in these sediments for at least six months after the last oil addition.     

Relationship between hydrocarbons and bacterial activity in mediterranean sediments: Part 2—hydrocarbon degrading activity of bacteria from sediments

In marine sediments from the Mediterranean coast polluted by oil spills (Etang de Berre) high bacterial activity is responsible for self-purification, samples collected from these areas showing a bacterial density several orders of magnitude higher than samples from non-polluted areas (Isle des Embiez). Between 60 and 80 % of the heterotrophic bacteria in the polluted areas are hydrocarbon-degrading, compared with 0.01 % in the non-polluted area.Several strains of hydrocarbon utilisers were isolated, a mixture of strains from each biotope was taken to represent a ‘biotope population’ and their activity towards different types of hydrocarbons (n-alkanes, iso-alkanes, cycloalkanes, aromatics) was determined.With ammonia as the nitrogen source the ‘biotope population’ from the polluted area degraded hydrocarbons much more readily than the ‘biotope population’ from the non-polluted area. With nitrate as the nitrogen source the degradation was much reduced, and, for some hydrocarbons, ceased in both ‘populations’.Individual hydrocarbons encouraged the growth of individual strains in the ‘biotope population’. In natural mixtures of hydrocarbons all strains grew well and degraded aliphatics. There was a good correlation between the respiratory activity of the ‘biotope population’ and the ability of the ‘population’ to utilise hydrocarbons for growth.     

Degradation of alkyl-substituted benzenes and their photo-oxidation products by a marine mixed bacterial population

Oxidation of alkyl-substituted benzenes by a marine mixed bacterial population showed no accumulation of phenyl acetic and phenyl acrylic acids, although more than 90 % of the substrates were converted to microbial cells and carbon dioxide. Photo-oxidation products were also used by bacteria to form assimilable intermediates. These reactions with mixed population constitute an interesting example of favourable interaction between bacterial degradation and photo-oxidation and can explain the disappearance of compounds listed as recalcitrant substrates. Key intermediates have been identified by gas chromatography and mass spectrometry. A mechanism based on their chemical structure is proposed for the degradation of alkyl-substituted benzenes containing side chains with odd and even numbers of carbon atoms.     

Phosphorus and metals bound to organic matter in coastal sediments - An investigation of complexes of P,Cu, Zn,Fe, Mn,Ni, Co and Ti by inductively coupled plasma-atomic emission spectrometry with sephadex gel chromatography

Phosphorus and metals bound to organic matter were separated from coastal sediments of Harima Sound in Seto Inland Sea, Japan by extraction with NaOH and fractionated by Sephadex G-25 chromatography. Phosphorus and metals were determined in the eluates by a multi-channel, inductively coupled plasma-atomic emission spectrometer. Phosphorus and Cu, Zn, Fe, Mn, Ni, Cr, Co and Ti bound to organic matter with high molecular weights (OMHMW) (MW ? 5000) were found to be present in the sediments, but no Mo or V were found. The technique provides minimum estimates of the amounts of P and metals bound to organic matter. These organic complexes show surface enrichment in a sediment core (0–20 cm) and their contents decrease with depth. Also, the amounts of eighteen elements, namely: P, Fe, Mn, Zn, Cu, Si, Al, Ti, Pb, Co, Ni, Cr, Mo, V, Na, K, Ca and Mg, in H₂O, ammonium acetate at pH 7 and 5, hydrogen peroxide, hydroxylamine hydrochloride and hydrogen fluoric acid soluble fractions have been determined with a selective chemical leaching technique for the ²¹⁰Pb-dated sediment core sample. Considerable amounts of P (6–19%) and Cu (5–21%) were associated with organic matter, in contrast to other metals such as Fe, Mn, Zn, Ni, Cr, Co and Ti which were associated with sulfide and silicate.     

Lead in the North Sea and the north east Atlantic Ocean

Lead has been determined in 105 water samples from the north east Atlantic and from the North Sea. Rigorous precautions were applied to avoid contamination during sampling and analysis.Two different analytical methods were used: ASV and AAS. Determinations with ASV were carried out on board, directly after sampling. After two months storage, acidified samples were analysed by AAS after freon dithiocarbamate extraction and nitric acid back extraction. Particulate lead was determined by AAS after an acid digestion.The profiles of lead concentration versus depth show around 160 pM at the surface and around 20 pM at the bottom, both in the Atlantic and in the Norwegian Sea. The shapes of the profiles are different, however, depending on the hydrography of the area sampled. The profiles from the north east Atlantic coincide with a recently published profile from the north west Atlantic. Moreover, these profiles have lead concentrations about a factor of three higher than those in the Pacific.Considering the high lead input to the North Sea, the lead concentrations found there are remarkably low, probably because of scavenging effects in estuaries leading to a short residence time in the water column. The dominant lead input in offshore regions is from the atmosphere. The highest lead levels are found in the northern North Sea, around 300 pM in surface water.In the Atlantic, particulate lead is a minor part of the total lead whereas in the North Sea the particulate fraction is larger, up to 40%.     

Trace metals and hydrocarbons in sediments from the Southampton water region,with particular reference to the influence of oil refinery effluent

The concentrations of a number of trace metals (Co, Ni, Cu, Zn, Ag, Cd and Hg) have been determined in sediments from cores collected in the Southampton Water region. Measurements of total hydrocarbons were also made on several of the cores. Markedly elevated concentrations of copper, up to 362 μg/g dry wt, were found in sediments which were collected close to the discharge points of oil refinery outfalls and which also showed concentrations of total hydrocarbons considerably greater than the background levels for the estuary. The results of selective chemical extractions showed that much of the copper was present in the non-lattice fraction of the sediment. Although the concentrations of Co, Ni, Zn and Cd were significantly correlated with those of copper in the core showing the highest concentrations of this element, these metals were not enhanced in comparison with the levels found in several other parts of the estuary. Variations in concentrations of metals in sediments throughout the estuary were not correlated with differences in organic carbon content.     

Intercomparison of different methods for the determination of trace metals in seawater

During a cruise on the North Sea and the North East Atlantic, about 90 samples were obtained from various depths. Concentrations of cadmium, copper, lead, nickel and zinc were determined by atomic absorption spectroscopy after separation/concentration using two different extraction methods. One, using APDC and MIBK, was applied directly on board while the other, using a mixture of dithiocarbamates and freon, was applied after storage under acid conditions. About half of the samples were also analysed for cadmium, copper and lead using ASV. The results of these determinations are intercompared. Consistent results were obtained for cadmium with the two extraction methods and for lead with the freon extraction method and ASV. In the other cases discrepancies were found.     

The fate of polyaromatic hydrocarbons in an intertidal sediment exposure system: Bioavailability to macoma inquinata (mollusca: Pelecypoda) and abarenicola pacifica (annelida: Polychaeta)

Macoma inquinata, a detritus feeding clam, was exposed for 60 days to coarse-grained, and Abarenicola pacifica, a burrowing polychaete, to fine-grained, sediment. Each sediment contained ¹⁴-C-labelled phenanthrene, chrysene or benzo(a)pyrene. Over 70% of the chrysene and benzo(a)pyrene, but only 8% of the phenanthrene, remained in the coarse sediment during the exposure. Essentially all of the chrysene and benzo(a)pyrene and 70% of the phenanthrene remained in the fine sediment. The concentrations of chrysene and benzo(a)pyrene in the clams rose steadily, reaching levels 11·6 and 5·2 times as high as those in the sediment. The tissue phenanthrene concentration rose for 3 days, then fell to one-eighth of the initial concentration. The concentrations of each of the aromatic hydrocarbons in Abarenicola tissue increased for 2 weeks to four to six times the sediment levels. The tissue concentration of chrysene remained constant thereafter, but the levels of phenanthrene and benzo(a)pyrene fell to three-quarters of their peak values. No intermediate degradation products of any of the hydrocarbons were identified in extracts of sediment from either exposure system, or in solvent extracts of tissue or of tissue digestates.Significant ¹⁴C-activity, associated with non-solvent extractable compounds, remained in tissue digestates of individuals of both species exposed to phenanthrene.     

Investigation of a eutrophic tidal basin: part 2nutrients and environmental aspects

The eutrophication of Langstone Harbour, a large tidal basin, has been studied by statistically designed nutrient surveys. Rates of input of nutrients from the sea, from effluent discharges and from other sources, have been estimated. Sediment/water interactions have been shown to be important in the phosphate budget of the basin, but they are less important in the nitrogen budget. Deductions were made about the relative importance of the various inputs and processes affecting concentrations of nutrients in the water column.It is concluded that ecologically or aesthetically detrimental growths of macroalgae are unlikely to occur in Langstone Harbour in the foreseeable future and that the removal of nutrient inputs, formerly thought to be necessary, will not, in fact, be required.The principles of the experimental design and of interpreting the data are of general applicability to tidal waters where the ratio of natural to man-made inputs needs to be known, where eutrophication is, or is expected to become, a problem, or where the progressive accumulation of nutrients by recycling is suspected.     

Theory of interaction intensities,buffer capacities,and pH stability in aqueous systems,with application to the pH of seawater and a heterogeneous model ocean system

The choice of convenient basic constituents for evaluating pH stability of aqueous systems is discussed, and two useful interaction parameters are defined and related to the buffer capacity: the interaction capacity, $\text{δ′}{}_{\mathrm{X,Y}}\text{=}\text{?}\text{p}\text{X}\text{?}\text{TOT}\text{Y}$, and the interaction intensity, $\text{δ}{}_{\mathrm{X,\; Y}}\text{=}\text{?}\text{p}\text{X}\text{?}\text{pTOT}\text{Y}$; for pH and TOTH, δ′_{H, H} = ?β_H^?1, where β_H is the pH buffer capacity. A method is presented for the computation of exact values of all interaction capacities and intensities through inversion of the Jacobian matrix of the system of non-linear equations describing the aqueous system. The major species of an aqueous system (H₂O, H⁺, solid phases, gases, and the most abundant solute species) are shown to constitute a useful set of basic constituents for evaluation of approximate pH buffer capacities according to a simple rule: the major-minor species rule for zeroth order pH-TOTH interaction. The concepts of buffering and pH-statting are examined and contrasted; it is demonstrated that the buffer capacity of an aqueous system cannot be infinite: it is limited by the concentration of solutes in solution. The effect upon pH of variations in constituents other than H⁺ is described in terms of first order interactions via complex formation and solid formation; approximate formulas for calculation are derived. Higher order interactions are derived from combinations of first order ones. The pH stability of the ocean system is examined in terms of an aqueous phase model including ion-association reactions and a heterogeneous model incorporating CO₂ in the gas phase, quartz, kaolinite, calcite, chlorite, and illite, in addition to the aqueous phase. There is an approximately three-fold enhancement of buffer capacity in the aqueous model as a consequence of ion-association. Only a few interaction pathways are of quantitative significance in establishing the buffer capacity. Results for the heterogeneous ocean model lend quantitative support to Sillén's notion of pH stability: the buffer capacity is about four hundred times greater than that of the aqueous phase model.     

Distribution of stable organic molecules in the marine environment: physical chemical aspects. Chlorinated hydrocarbons

The relative concentrations of non-polar organic compounds in seawater and suspended particulate matter can be explained by an equilibrium sorption mechanism. The value of the quasi-equilibrium constant, K, was calculated with reasonable accuracy for polychlorinated biphenyls from a relatively simple equation which relies on both measurable physical parameters and a number of molecular terms estimated from fundamental physical chemical considerations. This model represents an approach to defining the accumulation of stable organic molecules on marine particulate interfaces within a coherent theoretical framework. As such, it provides a guide for selecting appropriate ecosystem parameters which influence the distribution and accumulation potential of these chemicals in the marine environment.     

Distribution of total Al,Cd, Co,Cu, Ni and Zn in the tongue of the ocean and the northwestern Atlantic Ocean

The elements Al, Cd, Co, Cu, Ni and Zn were concentrated from seawater using tetraethylenepentamine resin and analysed by atomic absorption spectrophotometry. The spatial distribution of these elements in the northwest Atlantic Ocean is discussed with respect to possible riverine inputs to the area from Puerto Rico.