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.     

Rational approximations in the parabolic equation method for water waves

Approximations based on minimax principles are developed in order to allow for large-angle propagation in the parabolic equation method. Numerical studies show that the minimax approximations do not cause any significant degradation of accuracy at small angles of incidence when compared with an existing model based on a (1,1) Padé approximant, and that they allow for much more successful treatment of large angles of incidence than is possible using the previously available methods.     

Glucuronidation in the polar bear (Ursus maritimus)

Polar bears bioaccumulate lipophilic pollutants, including polychlorinated biphenyls (PCBs), into their bodies from their exclusive diet of marine organisms. Hydroxylated PCB metabolites (OH-PCBs) have been found in plasma, presumably due to CYP-dependent biotransformation of PCBs in liver. Little is known about the phase 2 metabolism of hydroxylated xenobiotics in polar bears. The objective of this study was to examine UDP-glucuronosyltransferase (UGT) activity with OH-PCBs and a hydroxylated polycyclic aromatic hydrocarbon, 3-hydroxy-benzo(a)pyrene (3-OH-BaP), in polar bear liver. Samples of frozen polar bear liver were used to prepare microsomes. UGT activity with 3-OH-BaP in Brij-treated microsomes, measured by a fluorescence assay, was readily measurable with protein concentrations in assay tubes of up to 10 g/ml, but dropped off very sharply at higher protein concentrations. The apparent Km for 3-OH-BaP was 1.71 +/- 0.04 microM, and Vmax 1.26 +/- 0.16 nmol/min/mg protein (mean +/- SD, n=3). UGT activities with a model tetrachloro-OH-PCB (4'-OH-CB72) and a model hexachloro-OH-PCB (4'-OH-CB159) were assayed with [14-C]-UDPGA and separation of the [14-C]-glucuronide by ion-pair extraction and thin-layer chromatography. [14-C]-glucuronide conjugates were readily formed by polar bear liver microsomes in the absence of added substrate, apparently from contaminants present in liver. This phenomenon was not observed using hepatic microsomes from laboratory-held catfish. Glucuronidation efficiency was much higher with 4'-OH-CB72 (Km 7.3 microM; Vmax 1.55 nmol/min/mg) than 4'-OH-CB159 (Km 16.1 microM; Vmax 0.46 nmol/min/mg). The identities of the aglycones present in polar bear liver are not known, but could include OH-PCBs or hydroxylated metabolites of other persistent organic pollutants. This study demonstrates that UGT with high activity for 3-OH-BaP and other substrates is present in polar bear liver.     

Tracking the last sea-level cycle: seafloor morphology and shallow stratigraphy of the latest Quaternary New Jersey middle continental shelf

Seafloor geomorphology and surficial stratigraphy of the New Jersey middle continental shelf provide a detailed record of sea-level change during the last advance and retreat of the Laurentide ice sheet (120 kyr B.P. to Present). A NW–SE-oriented corridor on the middle shelf between water depths of 40 m (the mid-shelf “paleo-shore”) and 100 m (the Franklin “paleo-shore”) encompasses 500 line-km of 2D Huntec boomer profiles (500–3500 Hz), an embedded 4.6 km² 3D volume, and a 490 km² swath bathymetry map. We use these data to develop a relative stratigraphy. Core samples from published studies also provide some chronological and sedimentological constraints on the upper <5 m of the stratigraphic succession.The following stratigraphic units and surfaces occur (from bottom to top): (1) “R”, a high-amplitude reflection that separates sediment >46.5 kyr old (by AMS ¹⁴C dating) from overlying sediment wedges; (2) the outer shelf wedge, a marine unit up to 50 m thick that onlaps “R”; (3) “Channels”, a reflection sub-parallel to the seafloor that incises “R”, and appears as a dendritic system of channels in map view; (4) “Channels” fill, the upper portion of which is sampled and known to represent deepening-upward marine sediments 12.3 kyr in age; (5) the “T” horizon, a seismically discontinuous surface that caps “Channels” fill; (6) oblique ridge deposits, coarse-grained shelly units comprised of km-scale, shallow shelf bedforms; and (7) ribbon-floored swales, bathymetric depressions parallel to modern shelf currents that truncate the oblique ridges and cut into surficial deposits.We interpret this succession of features in light of a global eustatic sea-level curve and the consequent migration of the coastline across the middle shelf during the last 120 kyr. The morphology of the New Jersey middle shelf shows a discrete sequence of stratigraphic elements, and reflects the pulsed episodicity of the last sea-level cycle. “R” is a complicated marine/non-marine erosional surface formed during the last regression, while the outer shelf wedge represents a shelf wedge emplaced during a minor glacial retreat before maximum Wisconsin lowstand (i.e., marine oxygen isotope stage 3.1). “Channels” is a widespread fluvial subarial erosion surface formed at the late Wisconsin glacial maximum 22 kyr B.P. The shoreline migrated back across the mid-shelf corridor non-uniformly during the period represented by “Channels” fill. Oblique ridges are relict features on the New Jersey middle shelf, while the ribbon-floored swales represent modern shelf erosion. There is no systematic relationship between modern seafloor morphology and the very shallowly buried stratigraphic succession.     

Functional responses for zooplankton feeding on multiple resources: a review of assumptions and biological dynamics

Modelers often need to quantify the rates at which zooplankton consume a variety of species, size classes and trophic types. Implicit in the equations used to describe the multiple resource functional response (i.e. how nutritional intake varies with resource densities) are assumptions that are not often stated, let alone tested. This is problematic because models are sensitive to the details of these formulations. Here, we enable modelers to make more informed decisions by providing them with a new framework for considering zooplankton feeding on multiple resources. We define a new classification of multiple resource responses that is based on preference, selection and switching, and we develop a set of mathematical diagnostics that elucidate model assumptions. We use these tools to evaluate the assumptions and biological dynamics inherent in published multiple resource responses. These models are shown to simulate different resource preferences, implied single resource responses, changes in intake with changing resource densities, nutritional benefits of generalism, and nutritional costs of selection. Certain formulations are further shown to exhibit anomalous dynamics such as negative switching and sub-optimal feeding. Such varied responses can have vastly different ecological consequences for both zooplankton and their resources; inappropriate choices may incorrectly quantify biologically-mediated fluxes and predict spurious dynamics. We discuss how our classes and diagnostics can help constrain parameters, interpret behaviors, and identify limitations to a formulation's applicability for both regional (e.g. High-Nitrate-Low-Chlorophyll regions comprising large areas of the Pacific) and large-scale applications (e.g. global biogeochemical or climate change models). Strategies for assessing uncertainty and for using the mathematics to guide future experimental investigations are also discussed.     

The reliability of analytical data for tributyltin (TBT) in sea water and its implications on water quality criteria

To investigate the reliability of analytical data for tributyltin (TBT) in sea water, split water samples were distributed to ten laboratories in six countries. The sub-surface samples comprised: (i) an offshore (0·5 km) water sample, (ii) the same sample but spiked with an undisclosed quantity of TBT standard compound (175 ng TBT⁺ liter⁻¹), and (iii) a sample taken from a yacht marina. The seven acceptable data sets were in good agreement for the spiked sample (178 ± 26 ng TBT⁺ liter⁻¹) but showed a greater variation in concentrations reported for the yacht marina sample (366 ± 93 ng TBT⁺ liter⁻¹). Atomic absorption and gas chromatographic-flame photometric detection techniques produced results of similar accuracy and precision. Samples acidified with 1 ml of 10% (v/v) acetic acid appeared stable for more than 2 weeks when stored refrigerated and in darkness. Analyses of the offshore seawater sample revealed TBT contamination (9 ± 7 ng TBT⁺ liter⁻¹) indicating dispersion of the compound to the shelf waters off Monaco. The spread in values reported by the laboratories demonstrates inherent difficulties in obtaining good precision below approximately 20 ng TBT⁺ liter⁻¹. This observation is discussed with respect to the setting and enforcing of water quality standards.     

Seasonal methyltin and (3-dimethylsulphonio)propionate concentrations in leaf tissue of Spartina alterniflora of the Great Bay estuary (NH)

Concentrations of total recoverable inorganic tin (TRISn), monomethyltin (MeSn³⁺), dimethyltin (Me₂Sn²⁺), trimethyltin (Me₃Sn⁺) and (3-dimethylsulphonio)propionate (DMSP) were determined in leaves of Spartina alterniflora from three sites in the Great Bay estuary (NH) from 8 May to 15 September 1989. Total methyltin concentration increased from 8·9 ng g⁻¹ (fresh weight) on 8 May to 472 ng g⁻¹ on 23 May, decreased to 52 ng g⁻¹ on 7 June and 16ng g⁻¹ on 20 June, and remained low until the last sample on 18 September. Statistical calculations showed that methyltin concentrations varied significantly with sampling week, but not with site. DMSP concentrations showed very different behaviour. During the same sampling period DMSP concentrations varied only from 7·5 to 26 μmol g⁻¹ (fresh weight). DMSP concentrations varied significantly for site, but not sampling week.     

Thermodynamic characterization of the partitioning of iron between soluble and colloidal species in the Atlantic Ocean

Recent electrochemical measurements have shown that iron (Fe) speciation in seawater is dominated by complexation with strong organic ligands throughout the water column and have provided important thermodynamic information about these compounds. Independent work has shown that iron exists in both soluble and colloidal fractions in the Atlantic Ocean. Here we have combined these approaches in samples collected from a variety of regimes within the Atlantic Ocean. We measured the partitioning of Fe between soluble (< 0.02 μm) and colloidal (0.02 to 0.4 μm) size classes and characterized the concentrations and conditional stability constants of Fe ligands within these size classes. Results suggest that equilibrium partitioning of Fe between soluble and colloidal ligands is partially responsible for the distribution of Fe between soluble and colloidal size classes. However, a significant fraction of the colloidal Fe was inert to ligand exchange as soluble Fe concentrations were generally lower than values predicted by a simple equilibrium partitioning model.In surface waters, strong ligands with conditional stability constants of 10¹³ relative to total inorganic Fe appeared to dominate speciation in both the soluble and colloidal fractions. In deep waters these ligands were absent, and instead we found ligands with stability constants 12–15 fold smaller that were predominantly in the soluble pool. Nevertheless, significant levels of colloidal Fe were found in these samples, which we inferred must be inert to coordination exchange.