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.     

Stability of the calcium sulphate ion pair at the ionic strength of seawater by potentiometry

The stability of the ion pair CaSO₄ was determined from measurement of the change in calcium ion activity with medium composition at constant ionic strength. A calcium selective PVC-matrix liquid membrane electrode was used to monitor the calcium ion activity. All measurements were performed at 1 atm, 25 ± 0.1°C and 0.7 M formal ionic strength. The evaluation of the stability constant depends on the degree of complexation between calcium and chloride and between sodium and sulphate. The dependence of K_CaSO4, on K_NaSO4 and K_CaCl can be described by the following relations:K_CaSO4=17.7 K_CaCl+16.5 (K_NaSO4=1.8)K_CaSO4=18.8 K_CaCl+17.3 (K_NaSO4=2) for K_CaCl=0–1A value of K_CaSO4=25.4 is suggested.     

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.     

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.     

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.     

Alkalinity determination in hypersaline solutions: a method for overcoming glass electrode errors

The non-ideality of commercially available glass pH electrode normally used for alkalinity determination by the Gran-type titration has been examined and its effect on the accuracy of the estimated alkalinity evaluated. It is found that slope errors of the glass electrode could be a limiting factor to the accuracy that can be obtained. This error source could be eliminated altogether by applying the proposed ‘slope correction’ algorithm which uses the titration data for in situ slope calibration of the glass electrode. Application of the proposed method eliminates the need for calibration of the glass electrode and the requirement for thermostating the test solution.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Pollution studies on Tolo Harbour,Hong Kong

Eight stations were chosen for this 14 month survey of Tolo Harbour in Hong Kong, four of them in the harbour proper and four in the estuaries of the major streams entering the harbour. Various chemical and physical factors were measured twice each month. Water samples were collected for nutrient, phytoplankton, chlorophyll and bacteriological analysis.The annual discharge of nutrients from the four streams into Tolo Harbour has been estimated, based on the nutrient analyses and computation of annual discharge (QA) values for these streams. The seasonal and spatial variations in nutrient content are discussed in relation to the increasing organic pollution of Tolo Harbour. Calculations of various ratios between SiO₃, PO₄, NO₃ and total inorganic N reveal that excessive amounts of phosphate are entering the harbour and subsequently accumulating in the bottom waters and sediments, leading to changes in the trophic condition of this water body and the development of anoxic conditions in the bottom layer.Significant correlation has been demonstrated between standing crop and various environmental parameters in both estuarine and marine waters and similarly between chlorophyll a concentration and various environmental parameters. However, no significant correlation values were obtained between either standing crop or chlorophyll a concentrations, SiO₃Si (the latter presumably due to the predominance of diatoms in the phytoplankton). Neither standing crop nor chlorophyll determinations reveal any evidence of alternating periods of high productivity and decomposition which could explain the deteriorating bottom water conditions. This again is taken as evidence that the high organic inputs are responsible for such deterioration.Increasing TC, FC and FS densities have been noted in Tolo Harbour as a direct result of the increasing organic pollution and ratios between FC and FS densities indicate that in 55% of the samples pollution was derived from human sewage. The bacterial levels well exceeded various international standards for bathing waters and shellfish collection for at least a part of the survey period and at a number of stations for the entire survey period. Pathogenic organisms were also present. This underlines the potential health risks in these waters.Finally, the future prospects for this harbour are discussed in relation to activities such as reclamation and the development of new towns and their impact on water quality.     

Sorption of Polycyclic aromatic hydrocarbons by natural estuarine colloids

The sorptive behaviour of natural estuarine colloids was investigated with benzene, naphthalene and anthracene. The equilibrium sorption isotherms were linear. Freundlich partition coefficients normalized to the organic content of the colloids for benzene, naphthalene, and anthracene were 920, 4060 and 510000, respectively. These values are at least an order of magnitude higher than those reported for corresponding soil/sediment systems. This suggests that hydrophobic compounds are more strongly bound to estuarine colloidal organic material.The effect of pH on sorption waas also studied. A significant decrease in sorption was observed when the ambient pH (8·01) of natural water was decreased by a factor of 2. The experimentally determined K_oc values were regressed against the water solubilities of PAHs and compared with a corresponding predictine relationship developed for a soil/sediment system. Such information greatly facilitates prediction of PAH phase partitioning in natural waters.     

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.