Mixed-function oxygenases as biological monitors around petroleum hydrocarbon development sites: Potential for induction by diesel and other drilling mud base oils containing reduced levels of polycyclic aromatic hydrocarbons

The use of oil-based drilling muds has been discouraged in hydrocarbon exploration and production in the marine environment but these muds are presently being used to a considerable degree in the United Kingdom and Norwegian sectors of the North Sea. Field studies in the North Sea have demonstrated only localized impacts around individual drilling sites,^1,2 even including those sites where ‘toxic’ diesel oils were employed as base fluids in drilling muds. Yet the question of disposal of cuttings contaminated with oil from drilling muds remains somewhat controversial. The induction of mixed-function oxygenases (MFO) has been validated on a number of occasions in the field as a sensitive index of low level hydrocarbon exposure (reviewed by Payne),³ including sites in the North Sea where diesel-based muds were used.⁴ The present study demonstrates that any potential for induction by hydrocarbon contaminated cuttings will probably be reduced by substitution of low-aromatic base oils for diesel in drilling mud formulations.     

Circulation

Low-frequency current and temperature variability on the southeast US continental shelf during summer conditions of weak wind forcing and vertical stratification was found to be similar in many aspects to previous findings for winter, when stronger wind forcing and vertical homogeneity prevails. Subtidal variability in the outer shelf is dominated by the weekly occurrence of Gulf Stream frontal eddies and meanders. These baroclinic events strongly affect the balance of momentum in the outer shelf, but not at mid-shelf. A negative alongshore sea level slope of order −10⁻⁷ is required to balance mean along-shelf momentum at the shelf edge, similar to oceanic estimates, and can contribute to the observed northward mean flow over the shelf.Low-frequency flow at mid-shelf and coastal sea level fluctuations appear to occur as a forced wave response to local alongshore wind stress events that are coherent over the shelf domain. Momentum balances indicate a trapped wave response similar to the arrested topographic wave found in the mid-Atlantic Bight (CSANADY, 1978). Density driven currents from river discharge do not appear to be significant at mid-shelf. Cold, subsurface intrusions of deeper, nutrient rich Gulf Stream waters can occasionally penetrate to mid- and inner-shelf regions north of Cape Canaveral, causing strong phytoplankton and zooplankton responses. These events were observed following the simultaneous occurrence of upwellings from northward winds and Gulf Stream frontal eddies at the shelf break during periods when the Stream was in an onshore position. Subsurface Gulf Stream intrusions to mid-shelf occur only during the summer, when the shelf is vertically stratified and cross-shelf density gradients do not present a barrier as in winter.     

Upwelling in the Black Sea by the results of numerical experiments and satellite data

The paper analyses results of the numerical simulation of upwelling events in the north-western part of the Black Sea, mostly near the South Crimea. The calculations were performed using a numerical model based on primitive hydrodynamics equations. Emphasis is laid on the case when a salinity front simulating the Black Sea rim current is prescribed in the initial conditions. The interaction of the Black Sea rim current's stream with the coastline and bottom topography leads to the development of an upwelling near the Crimea's coast, even in the absence of wind forcing. The paper discusses the structure of the three-dimensional circulation of waters in the shelf area of the NW Black Sea. Numerical modelling results are matched up with the satellite data obtained by the HRPT receiving station. Translated by Vladimir A. Puchkin.     

The Amphipod Community as a Bioindicator in Algeciras Bay (Southern Iberian Peninsula) Based on a Spatio-Temporal Distribution

Abstract. The amphipod population associated with Bugula neritina (L.), a verycommon bryozoan species in Algeciras Bay (Strait of Gibraltar), was studied on a spatio-temporal scale, in order to define its role as a bioindicator. Samples were collected in December, March, June and September along a transect running from the external to the internal sampling stations.
Fifty-three species belonging to 22 families were identified; the most abundant species were Jassa marmorata H olmes , Ischyrocerus inexpectatus (R uffo ) and Phtisica marina S labber .
The spatial evolution of the amphipod community reflected the physico-chemical conditions of Algeciras Bay, yielding a clear gradient from the outer to the inner stations. The stations located at the mouth of the bay, characterised by high hydrodynamism and low sedimentation, had a higher diversity and species richness than the inner stations with low water movement and higher sedimentation. Eight species preferred for the outer stations, while another nine species were typical of the inner harbours.
The most notable aspect of the seasonal evolution was the increased dominance of the tube-builder and deposit-suspension feeder Jassa marmorota .
Structural and ordination analyses corroborate the outer-inner gradient in the bay and illustrate the importance of hydrodynamic forces and sedimentation in the amphipod community.     

Sedimentology and morphodynamics of a macrotidal beach, Pendine Sands, SW Wales

The foreshore of Pendine Sands forms the seaward part of an extensive, sandy coastal barrier in a shallow Carmarthen Bay, SW Wales. The sedimentological features of the macrotidal foreshore reflect a tide-induced modification of nearshore wave characteristics. As the tide ebbs, the breaker height may decrease, the surf zone widens and becomes increasingly dissipative, and swash/backwash velocities diminish. A concomitant change from plunging to spilling breakers and increasingly symmetrical swash zone flows are associated with a decreasing beach gradient.

A zero net transport model demonstrates that the beach profile is self-stabilising in the short-term, and periodic levelling has shown that the beach is in long-term equilibrium with prevailing conditions, though this does not preclude a significant dynamic response to changing tides and waves.

The flow regimes of wave-generated currents decline as the tide ebbs, and normal beach processes do not usually affect the lower foreshore. Accordingly, there is an overall seaward-fining of the primary framework component of the sands. In more detail, this framework component displays a slight seaward-coarsening across an upper foreshore dominated by high water swash and surf; a rapid seaward-fining across the mid-foreshore in response to the ebb-attenuating swash zone flow velocities; and a slight seaward-fining across the lower foreshore under the action of nearshore shoaling waves. Bedforms vary from a swash/backwash emplaced flat bed across the upper foreshore to the small ripples of nearshore asymmetric oscillatory flows across the lower foreshore.

The surface sediment veneer is not representative of the subsurface sediments which form in response partly to fairweather conditions, partly to storms. The upper foreshore is characterised by swash/backwash emplaced plane bedding in fine sands frequently disrupted by bubble cavities. The mid-foreshore is composed of coarser-grained shelly traction clogs arranged as landward- and seaward-dipping large-scale cross bedding and/or plane bedding; these are probably storm breaker/surf deposits. The lower foreshore, though partially and sometimes totally bioturbated, shows landward-dipping small-scale cross bedding in very fine sands sorted by nearshore shoaling waves.

Tide- and storm-induced modification of the nearshore flow regimes therefore produces a distinctive shore-normal array of sedimentary facies. Each facies is characterised by diagnostic textural and structural signatures. A prograding sequence of such macrotidal deposits would be similar to, but more extensive than, a comparable microtidal sequence.     

On the sulphur chemistry of a super-anoxic fjord, Framvaren, South Norway

The concentrations of total carbonate (C_t), sulphate, sulphide, thiols and oxygen, the ratio between the stable sulphur isotopes ³⁴S and ³²S in sulphate and sulphide, and the density (used to calculate salinity) were determined on samples from the water column of Framvaren, a superanoxic fjord in southern Norway. From a depth of 18m (the oxic-anoxic boundary) the initial sulphate concentration, ([SO₄]_init), as calculated from salinity, is significantly higher than the sum of the measured sulphur species. This is attributed to a loss of sulphur from the water column. The amount of total carbonate produced, corrected for the initial concentration (C_t - 2.4 Sal/35) is found to be proportional to the amount of sulphate consumed, ([SO₄]_init - [SO₄]), according to the following relation C_t- 2.4 Sal/35 = 1.84 ([SO₄]_init - [SO₄]). Isotopic fractionation caused by bacterial sulphate reduction in the anoxic part of the water column produces sulphide with a δ³⁴S 40‰ lower than the δ³⁴S for sulphate at corresponding depths. The isotopic fractionation also results in δ³⁴S value for the remaining sulphate at depths below 80 m being considerably higher than the mean value for ocean water, which is close to + 20‰. The δ³⁴S values for sulphate at depths between 10 and 50 m were lower than + 20‰ which indicates oxidation of sulphide, which follows upon diffusion of sulphide from deeper parts of the water column and inflow of oxygenated seawater over the sill into the anoxic water of the fjord. A conclusive scenario of the Framvaren sulphur chemistry is presented.     

Analysis of Triphenyltin in Fish

A procedure to analyse triphenyltin and other organotins in fish tissues is described. The method consists of the following steps: homogenization of the fish, extraction by heating under reflux in a water/hexane mixture, centrifugation, separation of the hexane layer followed by reduction of the volume by evaporation, methylation of the organotin with a Grignard reaction, clean-up of the fish extract by column chromatography, and detection by gas chromatography with flame photometric detection. The extraction was carried out without adding acid or base to the aqueous phase, as the extraction efficiency was independent of pH. The methylation was successfully carried out in the fish extract. For clean-up of the fish extract a florisil column was used, from which the triphenylmethyltin was eluted with hexane. Using this method, triphenyltin has a recovery of 77 ± 10%, with a limit of detection of 0·8 ng/g for 0·1 g fish samples.     

On the relevance of iron adsorption to container materials in small-volume experiments on iron marine chemistry: Fe-aided assessment of capacity, affinity and kinetics

Iron chemistry in seawater has been extensively studied in the laboratory, mostly in small-volume sample bottles. However, little has been reported about iron wall sorption in these bottles. In this paper, radio-iron ⁵⁵Fe was used to assess iron wall adsorption, both in terms of capacity, affinity and kinetics. Various bottle materials were tested. Iron sorption increased from polyethylene/polycarbonate to polymethylmetacrylate (PMMA)/high-density polyethylene/polytetrafluoroethylene to glass/quartz, reaching equilibrium in a 25–70 h period. PMMA was studied in more detail: ferric iron (Fe(III)) adsorbed on the walls of the bottles, whereas ferrous iron (Fe(II)) did not. Considering that in seawater the inorganic iron pool mostly consists of ferric iron, the wall will be a factor that needs to be considered in bottle experiments.The present data indicate that for PMMA with specific surface (S)-to-volume (V) ratio S/V, both iron capacity (42 ± 16 × 10^− 9 mol/m² or 1.7 × 10^− 9 mol/L recalculated for the S/V-specific PMMA bottles used) and affinity (log K_Fe'W = 11.0 ± 0.3 m²/mol or 12.4 ± 0.3 L/mol, recalculated for the S/V-specific PMMA bottles used) are of similar magnitude as the iron capacity and -affinity of the natural ligands in the presently used seawater and thus cannot be ignored.Calculation of rate constants for association and dissociation of both Fe'L (iron bound to natural occurring organic ligands) and Fe'W (iron adsorbed on the wall of vessels) suggests that the two iron complexes are also of rather similar kinetics, with rate constants for dissociation in the order of 10 ⁻⁴–10^− 5 L/s and rate constants for association in the order of 10⁸ L/(mol s). This makes that iron wall sorption should be seriously considered in small-volume experiments, both in assessments of shorter-term dynamics and in end-point observations in equilibrium conditions. Therefore, the present data strongly advocate making use of iron mass balances throughout in experiments in smaller volume set-ups on marine iron (bio) chemistry.