The monosaccharide spectra of natural waters

Monosaccharides were determined in waters and sediment pore waters from a wide variety of environments and locations. Desalting was performed by electrodialysis and concentrated extracts were analyzed by two forms of liquid chromatography. At least 12 sugars were identified. Glucose and fructose were the dominant monosaccharides in nearly all samples examined. Analyses of over 150 seawater and sediment pore water samples showed that fructose is highly significantly correlated (>0.99) with glucose concentrations. Laboratory kinetic experiments on the epimerization reaction, glucose ? fructose, in sterilized natural seawater in the dark, yielded a forward rate constant, k₁, of 1.2 × 10^?5 h^?1 at 25°C and 1.6 × 10^?7 h^?1 at 2°C. The approximate time required to attain equilibrium at 25°C was 1.1 y and at 2°C, 15.4 y; the measured equilibrium constant was in the range 0.3–0.4. The actual ratio of fructose to glucose in natural water samples was usually in the range 1.0–1.4/l, independent of the total monosaccharide concentrations, which varied in the samples by a factor of ～100. Several possible explanations for the apparent discrepancy in the determined and found ratios are discussed: the presence of universal, as yet, undiscovered major biological sources for fructose in marine environments; preferential utilization of glucose; preferential incorporation of fructose into or onto inorganic colloids; and preferential formation of fructose-transition metal ion associations.     

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.     

Mass solubility and aqueous activity coefficients of stable organic chemicals in the marine environment: polychlorinated biphenyls

The solubilities and aqueous activity coefficients of polychlorinated biphenyls were measured in distilled and saline water (30? salinity). Solubilities in distilled water ranged from 3 · 10^?4 g/l for dichlorobiphenyls to 6 · 10^?6 g/l for heptachlorobiphenyls; values in artificial seawater were about five times lower than the corresponding values in distilled water. In both cases, the solubilities decreased regularly with increasing degree of chlorination. The corresponding activity coefficients are inversely proportional to the chlorine content and range from 4 · 10⁷ to 4 · 10⁹ in distilled water and from 3 · 10⁸ to 1.5 · 10¹⁰ in saline water. Both the solubilities and activity coefficients agree well with those predicted from additivity considerations. The physical chemical aspects discussed in this paper can be applied in determining the solubility behavior of other stable organic molecules in the marine environment.     

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.     

Chemical comparison of dissolved organic matter isolated from different oceanic environments

Dissolved organic matter was isolated from coastal and open-ocean surface waters having a wide range of biological productivities, and from seawater of intermediate depths. Approximately 50% of the organic matter was recovered by the use of activated-charcoal chromatography. The organic matter isolated from different types of water masses exhibited varying spectroscopic characteristics, and stable carbon-isotope compositions. The ability of the isolated organic matter to interact with copper ions also varied, but over a relatively narrow range which was not exceeded by more than a factor of two by similarly isolated terrigenous organic matter.     

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.     

The effects of used ferrochrome lignosulphonate drilling muds from a Santa Barbara channel oil well on the development of starfish embryos

The effects of water-soluble fractions (WSF) of thirteen used ferrochrome lignosulphonate muds on developing embryos of Patiria miniata were studied. The muds were collected during the drilling of a single slant well from Platform Hondo in the Santa Barbara Channel, California, at drilling depths of 4220 to 9858 ft. None of the embryos survived 48 hours' exposure in 25 % WSF of the muds (25,000 ppm mud added (v/v)). Significant reduction in growth and high abnormalities (up to 100%) were observed in the 15% WSF. In lesser concentrations the effects varied from significant reduction of growth, down to 0·5% for three muds, to significant enhancement of growth for several muds in some dilutions. The EC₅₀'s ranged from 5% to greater than 15% WSF. In the 5% WSF, decreased embryo growth was correlated with increasing Cr concentrations and possibly also with total organic carbon (TOC). Although experiments carried out with NaOH addition to simulate the strong alkalinity of the muds showed increased abnormalities and decreased embryo growth with increasing pH, in the chemically complex WSF (5% dilution) the opposite effect occurred. Dissociation of chrome lignosulphonate molecules from particulates may occur with increasing acidity and explain the relationship between pH and toxicity in dilute WSF. The results of these experiments are discussed in terms of the effects of dispersions of drilling muds in the oceanic environment. It is concluded that water column effects on organisms during the dumping of such muds are only likely within short distances of the discharge pipes of offshore drill rigs.     

Stability constants of NaSO4−, MgSO4, MgF+, MgCl+ ion pairs at the ionic strength of seawater by potentiometry

The stability of the ion pair NaSO₄ was determined by measuring the change in sodium activity with medium composition at constant ionic strength, using a sodium-sensitive glass electrode. The stability constants of MgSO₄ and MgCl⁺ were determined indirectly from measurements of the stability of MgF⁺ in different media. All measurements were performed at 1 atm pressure, 25 ± 0.1 °C and 0.7 M formal ionic strength. The stability constants for NaSO₄^?, MgSO₄, MgF⁺ and MgCl⁺ are 1.8 ± 0.1, 6.3 ± 0.1, 22.9 ± 0.1 and 0.34 ± 0.02 M^?1, respectively.     

Quantitative adsorption of organic matter from seawater on solid matrices

The influence of several operational parameters, including pH, flow rate, total volume of water passed, and choice of eluants, upon the efficiency of extraction of organic matter from seawater by two forms of commercially-available resin, XAD-2 and XAD-8, is considered. The overall efficiency of adsorption is at best 40%. The main factor determining the adsorption efficiency of XAD resin for natural organic matter is pH. The efficiency at normal seawater pH is only half that at pH 2.0. Although the efficiency decreases with increasing flow rate, the decrease is not great up to 3 bed vol./min. With increasing volume of water passed, the adsorption capacity of the resin initially drops, but reaches an approximately constant level after 1000 bed volumes. Alkaline solutions, either NH₄OH or NaOH, followed by methanol, completely recover adsorbed organic material from the resin. There is no significant advantage of XAD-8 over XAD-2 for seawater extractions, and the materials adsorbed by the two forms of resin are not substantially different.A new separation method combining XAD-2 resin and activated carbon as adsorbents in series in a column has been developed. Efficiencies of up to 90% were obtained in the extraction of acidified seawater. When the volume of water passed was less than 500 bed volumes, the adsorption as measured by UV-oxidation was quantitative. Elution of 90–100% of the adsorbed organic carbon was possible when ammonium hydroxide (7 M), methanol and an ammonium hydroxide—methanol mixture were used sequentially.     

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.     

Amino acid composition of sediments from a deltaic environment

Nineteen amino acids in sediments from the Ebro Delta (Spain) have been determined by HPLC. According to quantitative and qualitative data it is suggested that the distributions reflect organic autochthonous contributions and are constrained by environmental conditions of deposition.In the more reducing areas (8.7–11.6 mg total amino acids/g of dry sediment) hydroxyproline, threonine, glycine and glutamic acid are the major amino acids, while in the off-shore stations (1.0–2.7 mg total amino acids/g of dry sediment) ornithine, lysine, phenylalanine, serine and valine are dominant. In these samples absolute concentrations decrease with water depth.The analysis of two cores has shown that sulfur-containing and neutral branched-chain amino acids are the least resistant to geochemical degradation. Within the basic fraction, which appeared to be the most stable, ornithine is produced geochemically and preferentially in the more oxic sediments.     

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%.