Historical polycyclic aromatic and petrogenic hydrocarbon loading in Northern Central Gulf of Mexico shelf sediments

The distribution of selected hydrocarbons within ten dated sediment cores taken from the Mississippi River Bight off coastal Louisiana suggests a chronic contaminant loading from several sources including the river itself, oil and gas exploration in the central Gulf of Mexico (GOM) shelf area, and natural geologic hydrocarbon seeps. Data were grouped as either total polycyclic aromatic hydrocarbons (PAH's), which were indicative of pyrogenic PAH's; or estimated total hopanes (indicative of petrogenic hydrocarbons). The total PAH concentrations and estimated total hopanes begin increasing above background levels (approximately 200 ng g(-1)) after the 1950s. The distribution of these hydrocarbons and hopanes within the dated sediment cores suggests that the Mississippi River is a regional source of pyrogenic PAH's, and that the hopanes are from natural geologic hydrocarbon seeps, oil and gas exploration in the GOM, or both.     

Predicting summer hypoxia in the northern Gulf of Mexico: riverine N, P, and Si loading

We conducted a statistical analysis to discern the relative strengths of the loading of various forms of nitrogen, phosphorus, dissolved silicate and their molar ratios on the variance in the size of the summertime low oxygen zone found off the Mississippi River, northern Gulf of Mexico. A stable statistical model that included Year and riverine nitrate+nitrite loading for the 2 months prior to the measurement of hypoxic zone size described 82% of its variation in size from 1978 to 2004. The usefulness of the term Year is consistent with the documented increase in carbon stored in sediments after the 1970s, which is when the hypoxic zone is predicted to have become a regular feature on the shelf and to have expanded westward. The increased carbon storage is anticipated to cause a sedimentary respiratory demand influencing the size of the zone, and whose temporal influence is cumulative and transcends the annual variations in nitrogen loading. The variable Year is negatively correlated with the TN:TP ratio in a way that suggests N, not P, has become more important as a factor limiting phytoplankton growth in the last 20 years. Nitrogen, in particular nitrate+nitrite, and not phosphorus, dissolved silicate, or their molar ratios, appears to be the major driving factor influencing the size of the hypoxic zone on this shelf. This conclusion is consistent with cross-system analyses that conclude that the TN:TP ratio in the Mississippi River, currently fluctuating around 20:1, is indicative of nitrogen, not phosphorus, limitation of phytoplankton growth. Nutrient management that places stronger emphasis on reducing nitrogen loading as compared to phosphorus loading, is justified.     

A modeling study of the physical processes affecting the development of seasonal hypoxia over the inner Louisiana-Texas shelf: Circulation and stratification

The physical processes affecting the development of seasonal hypoxia over the Louisiana-Texas shelf were examined using a high-resolution, three-dimensional, unstructured-grid, Finite Volume Coastal Ocean Model (FVCOM). The model was forced with the observed freshwater fluxes from the Mississippi and Atchafalaya Rivers, surface winds, heat fluxes, tides and offshore conditions. The simulations were carried out over a six-month period, from April to September 2002, and the model performance was evaluated against several independent series of observations that included tidal gauge data, Acoustic Doppler Current Profiler (ADCP) data, shipboard measurements of temperature and salinity, vertical salinity and sigma-t profiles, and satellite imagery. The model accurately described the offshore circulation mode generated over the Louisiana-Texas shelf by the westerly winds during summer months, as well as the prevalent westward flow along the coast caused by the easterly winds during the rest of the study period. The seasonal cycle of stratification also was well represented by the model. During 2002, the stratification was initiated in early spring and subsequently enhanced by the intensity and phasing of riverine freshwater discharges. Strong stratification persisted throughout the summer and was finally broken down in September by tropical storms. The model simulations also revealed a quasi-permanent anticyclonic gyre in the Louisiana Bight region formed by the rotational transformation of the Mississippi River plume, whose existence during 2002 was supported by the satellite imagery and ADCP current measurements. Model simulations support the conclusion that local wind forcing and buoyancy flux resulting from riverine freshwater discharges were the dominant mechanisms affecting the circulation and stratification over the inner Louisiana-Texas shelf.     

Discriminating sources of PCB contamination in fish on the coastal shelf off San Diego, California (USA)

Management of coastal ecosystems necessitates the evaluation of pollutant loading based on adequate source discrimination. Monitoring of sediments and fish on the shelf off San Diego has shown that some areas on the shelf are contaminated with polychlorinated biphenyls (PCBs). Here, we present an analysis of PCB contamination in fish on the shelf off San Diego designed to discriminate possible sources. The analysis was complicated by the variability of species available for analysis across the shelf, variable affinities of PCBs among species, and non-detects in the data. We utilized survival regression analysis to account for these complications. We also examined spatial patterns of PCBs in bay and offshore sediments and reviewed more than 20 years of influent and effluent data for local wastewater treatment facilities. We conclude that most PCB contamination in shelf sediments and fish is due to the ongoing practice of dumping contaminated sediments dredged from San Diego Bay.     

Chemical composition of short sediment cores from Thermaikos Gulf (Eastern Mediterranean): Sediment accumulation rates, trawling and winnowing effects

Four cores recovered within the framework of the INTERPOL Project have been analysed for their grain size and geochemistry; sediment accumulation rates (SARs) were also determined from ²¹⁰Pb and ¹³⁷Cs profiles. Two cores are representative of the Axios and Aliakmon Rivers depositional environment, whilst the third core represents the Pinios River province; the fourth core represents an environment of outer shelf relict sands. Apparent SARs ranged between 0.667 g cm⁻² yr⁻¹ (Axios and Aliakmon Rivers) and 0.414 g cm⁻² yr⁻¹ (Pinios River). Trawling activities and biomixing are critical processes that may be responsible for the mixing of the surface sediments, as observed from the excess ²¹⁰Pb profiles. The thickness of the surface mixed layer was 4.5 cm in the vicinity of Axios and Aliakmon Rivers and in the area of Pinios River, 3.75 cm on the outer shelf and 1 cm in the area where no trawling was observed. Sediment accumulation appeared to be regulated by variations in the riverine discharge, shelf transport pathways and winnowing processes. Major element variations, such as Si, Al, Ti, V and Ni, were dominated by terrigenous supply as aluminosilicate minerals and quartz, whereas most Ca and Sr were biogenic. Si/Al and Ca/Al ratios have been used to express changes in sediment accumulation and winnowing. Redox processes were depicted by Mn, which showed an increase in the depth of its redoxcline, from 1 cm in inshore stations to 2 cm on the outer shelf. Si/Al ratios follow the Ca/Al ratios and can be used to assess percentage winnowing in the sediment. Increases in these ratios indicate a decrease in sediment input rates and are seen in the upper parts of most of the cores. Anthropogenic or ‘excess’ metal contents have been calculated from Zn/V and Pb/V ratios. Their distributions in the cores showed that by far the highest contamination is associated with the Axios River output, whilst sediments influenced by the Pinios River were relatively uncontaminated.     

Dispersal of Mississippi and Atchafalaya sediment on the Texas-Louisiana shelf: Model estimates for the year 1993

A three-dimensional coupled hydrodynamic-sediment transport model for the Texas-Louisiana continental shelf was developed using the Regional Ocean Modeling System (ROMS) and used to represent fluvial sediment transport and deposition for the year 1993. The model included water and sediment discharge from the Mississippi River and Atchafalaya Bay, seabed resuspension, and suspended transport by currents. Input wave properties were provided by the Simulating WAves Nearshore (SWAN) model so that ROMS could estimate wave-driven bed stresses, critical to shallow-water sediment suspension. The model used temporally variable but spatially uniform winds, spatially variable seabed grain size distributions, and six sediment tracers from rivers and seabed.At the end of the year 1993, much of the modeled fluvial sediment accumulation was localized with deposition focused near sediment sources. Mississippi sediment remained within 20-40 km of the Mississippi Delta. Most Atchafalaya sediment remained landward of the 10-m isobath in the inner-most shelf south of Atchafalaya Bay. Atchafalaya sediment displayed an elongated westward dispersal pattern toward the Chenier Plain, reflecting the importance of wave resuspension and perennially westward depth-averaged currents in the shallow waters (<10 m). Due to relatively high settling velocities assumed for sediment from the Mississippi River as well as the shallowness of the shelf south of Atchafalaya Bay, most sediment traveled only a short distance before initial deposition. Little fluvial sediment could be transported into the vicinity of the “Dead Zone” (low-oxygen area) within a seasonal-annual timeframe. Near the Mississippi Delta and Atchafalaya Bay, alongshore sediment-transport fluxes always exceeded cross-shore fluxes. Estimated cumulative sediment fluxes next to Atchafalaya Bay were episodic and “stepwise-like” compared to the relatively gradual transport around the Mississippi Delta. During a large storm in March 1993, strong winds helped vertically mix the water column over the entire shelf (up to 100-m isobath), and wave shear stress dominated total bed stress. During fair-weather conditions in May 1993, however, the freshwater plumes spread onto a stratified water column, and combined wave-current shear stress only exceeded the threshold for suspending sediment in the inner-most part of the shelf.     

Environmental monitoring in a gas production area on the northwestern Black-Sea shelf

The results of long-term seasonal oceanographic observations conducted by YugNIRO from 1955 to 1991 in standard cross-sections on the northwestern shelf of the Black Sea and data obtained by monitoring oil and chemical pollution of the marine environment from 1987 to 1993 in the area of gas deposit development are systematized and statistically treated. The oceanographic conditions of pollution field formation in this region are studied. The dynamics and distribution of total concentrations of oil products and microelements (Hg, Cu, Pb, Cd, and Cr) in water and bottom sediments are examined in the areas in Karkinitskii Bay where permanent offshore platforms are operated. The obtained results are compared with data on the background environmental pollution of the Black Sea and World Ocean. A hypothesis is offered to elucidate the possible causes and mechanisms through which offshore gas production affects the hydrochemical conditions on the shelf. The monitoring data are said to be a necessary information basis for the prediction of pollution dynamics in Karkinitskii Bay with the use of a box-type hydroecological model of petroleum hydrocarbon biotransformations in water, and approaches for the use of these data for this purpose are outlined.     

Sources of organic matter in surface sediments of the Louisiana Continental margin: Effects of major depositional/transport pathways and Hurricane Ivan

Lignin and pigment biomarkers were analyzed in surface sediments of the Louisiana Continental margin (LCM) to distinguish differences in the degradative state of sedimentary organic matter along and between two major depositional pathways (along shore and offshore to the Mississippi Canyon) from Southwest (SW) Pass in July 2003. Barataria Bay, an inter-distributary estuary, was also assessed as a potential source of terrestrial organic matter to the LCM. Sediment signatures taken along the same pathways after Hurricane Ivan (October 2004) were compared with the pre-Ivan signature to elucidate carbon dynamics after major hurricane events. Density fractions were investigated at key stages across the LCM. Mississippi Canyon sediments are a depocenter for labile and refractory organic matter derived from river and previously deposited shelf sediments. Barataria Bay material may be a contributing source of sedimentary organic matter in shallow shelf areas bordering the bay and is thus potentially important in carbon cycling in sediments of these shallow areas; however, our results show that organic matter inputs from the bay were likely rapidly decomposed and/or diluted. Hurricane Ivan mobilized sedimentary organic carbon (SOC) offshore and homogenized terrestrial sediment parameters and gradients. As observed through pigment concentrations sediments tended to equilibrate to a more steady-state condition within months of the disturbance. Insights from density fractions show that selective degradation and aggregation/flocculation processes were also very important processes during cross-shelf transport. Zooplankton grazing, largely on diatoms and other algae, was a shelf wide phenomenon, however, grazing products dominated the marine-derived SOC in margin sediments west of the birdsfoot delta indicated by the abundance of steryl chlorin esters (SCEs).     

Stratigraphic spatial variation on the inner shelf of a high-yield river,Waiapu River,New Zealand: Implications for fine-sediment dispersal and preservation

The inner shelves of active, energetic continental margins are frequently defined as regions of sediment segregation and fine-sediment bypassing. The Waiapu River, North Island, New Zealand presents an opportunity to study fine-sediment segregation and strata formation in a spatially constrained, highly energetic, aggradational setting, with one of the highest sediment yields on earth. We present evidence that the inner shelf of the Waiapu River plays a significant role in both the fate of fine-grained (<63 μm) riverine sediments and the formation of continental margin stratigraphy. Results obtained from high-resolution interferometric bathymetry and high-frequency seismic mapping ground-truthed by cores show significant stratigraphic spatial variation preserved on the Waiapu inner shelf. This spatial variation is likely controlled by spatially-distinct sediment deposition and resuspension processes as well as antecedent geology. Two distinct depositional regions are interpreted as: (1) surface plume-dominated with partial resuspension, characterized by acoustically transparent seismic reflection profiles and muddy sands; and (2) event-layer dominated, characterized by thickly laminated sediments. A modern-day bathymetric low overlying an observed paleochannel may influence the fate of hyperpycnal flows transiting the shelf via bathymetric steering. Fining-upward sequences found over the entire shelf are interpreted to represent deforestation-induced sedimentation that has overwhelmed the ability of the energetic system to resuspend and segregate fine sediments. We conclude that the primary control on strata formation on the inner shelf of the Waiapu River is local sediment supply.     

Efficient trapping of organic carbon in sediments on the continental margin with high fluvial sediment input off southwestern Taiwan

Accumulation rates of marine and terrigenous organic carbon in the continental margin sediments off southwestern Taiwan were estimated from the measured concentrations and isotopic compositions of total organic carbon (TOC) and previously reported sedimentation rates. Surficial sediments were collected from the study area spanning from the narrow shelf near the Kaoping River mouth to the deep slope with depths reaching almost 3000 m. The average sediment loading of Kaoping River is 17 Mt/yr, which yields high sediment accumulation rates ranging from 0.08 to 1.44 g cm⁻² yr⁻¹ in the continental margin. About half of the discharged sediments were deposited on the margin within 120 km of the river mouth. Carbon isotopic compositions of terrestrial and marine end-members of organic matter were determined, respectively, based on suspended particulate matter (SPM) collected from three major rivers in the southwestern Taiwan and from an offshore station. All samples were analyzed for the TOC content and its isotopic composition (δ¹³C_org). The SPM samples were also analyzed for the total nitrogen (TN) content. TOC content in marine sediments ranges from 0.45% to 1.35% with the highest values on the upper slope near the Kaoping River mouth. The TOC/TN ratio of the SPM samples from the offshore station is 6.8±0.6, almost identical to the Redfield ratio, indicating their predominantly marine origin; their δ¹³C_org values are also typically marine with a mean of −21.5±0.3‰. The riverine SPM samples exhibit typical terrestrial δ¹³C_org values around −25‰. The δ¹³C_org values of surficial sediments range from −24.8‰ to −21.2‰, showing a distribution pattern influenced by inputs from the Kaoping River. The relative contributions from marine and terrestrial sources to sedimentary organic carbon were determined by the isotope mixing model with end-member compositions derived from the riverine and marine SPM. High fluvial sediment inputs lead to efficient trapping of organic carbon over a wide range of water depth in this continental margin. The marine organic accumulation rate ranges from 1.6 to 70 g C m⁻² yr⁻¹ with an area weighted mean of 4.2 g C m⁻² yr⁻¹, which is on a par with the mean terrestrial contribution and accounts for 2.3% of mean primary production. The depth-dependent accumulation rate of marine organic carbon can be simulated with a function involving primary productivity and mineral accumulation rate, which may be applicable to other continental margins with high sedimentation rates. Away from the nearshore area, the content of terrigenous organic carbon in surficial sediments decreases with distance from the river mouth, indicating its degradation in marine environments.     

Origin and distribution of surface sediments and human impacts on recent sedimentary processes. The case of the Amvrakikos Gulf (NE Ionian Sea)

The sedimentology of the floor of the Amvrakikos Gulf, a river influenced, semi-enclosed relatively shallow-silled embayment, lying along the northeastern Hellenic coast of the Ionian Sea (eastern Mediterranean Sea), is investigated with respect to its origin (terrigenous and/or biogenic), the prevailing oceanographic conditions and human interference. Nearshore (water depths approximately <10 m) sediments, especially along the northern margin of the Gulf, consist mostly of biogenic sands, as the result of water exchange between the freshwater lagoonal waters and the surface waters of the Gulf. An exception to this is the mouth area of the Arachthos River, which is dominated by the terrigenous riverine sediment influx. The offshore (water depths >10 m) bottom surficial sediments are fine-grained (silty and clayey) of terrigenous origin (>70%); this is attributed to the inter-seasonal, strong two-layer stratification of the water column in the Gulf which restricts benthic productivity by inhibiting the downward flux of surface eutrophic waters and the development of nearbed disoxic conditions in water depths >40 m. River damming has reduced also the riverine terrigenous sediment supply; this is more profound in the case of the Arachthos River where not only the deltaic evolution has been affected, but also the textural character of the seabed sediments of the mouth area has been altered; this is expected to influence the benthic communities of prodeltaic surficial sediment.     

Isotopic signature of nitrate in river waters of the lower Mississippi and its distributary,the Atchafalaya

Periodic summer hypoxia occurring in the Northern Gulf of Mexico has been attributed to large nutrient inputs, especially nitrate‐nitrogen, from the Mississippi–Atchafalaya River system. The 2008 Gulf Hypoxia Action Plan calls for river corridor wetland restoration to reduce nitrate loads, but it is largely unknown how effective riverine wetland systems in the lower Mississippi River are for nitrate removal. We carried out an intensive isotope study to address this question by comparing nitrate isotopic signatures of the well‐channelized Mississippi River with those of the Atchafalaya River, which has extensive floodplains and backwater swamps. We investigated changes in δ¹⁵N_NO3 and δ¹⁸O_NO3 for water samples collected biweekly to monthly over a 2‐year period at the Atchafalaya River outlets (Morgan City and Wax Lake) and on the Mississippi River at Baton Rouge. In addition, in situ water quality parameters including temperature, dissolved oxygen and pH were recorded for each sampling date. Waters from both rivers showed moderately high nitrate concentration (>1 mg l^?1) and undetectable (< 0.01 mg l^?1) nitrite throughout the study period. The Mississippi River had slightly, but significantly higher (p=0.01) mean nitrate concentrations (1.5 mg l^?1) and higher δ¹⁵N_NO3 (7.7‰) than the Atchafalaya (1.1 mg l^?1, 7.0‰); while no difference in δ¹⁸O_NO3 (4.6‰) was found between the rivers. Flux‐weighted mean isotope values were overall lower than mean values for both the Mississippi and Atchafalaya Rivers, with a greater difference between the two rivers (7.4‰ versus 6.5‰, respectively). River flooding and hurricane storm surge also appeared to affect nitrate isotopic values. The lack of large difference in isotopic values between the Atchafalaya and Mississippi Rivers suggests that the majority of nitrate is transported through the Atchafalaya River with relatively little processing, and that riverine floodplains and wetlands are not effective sinks for nitrate, as previously assumed, because of insufficient residence time and well‐oxygenated river waters. Copyright © 2012 John Wiley & Sons, Ltd.     

Barium in the Antarctic Ocean and implications regarding the marine geochemistry of Ba and226Ra

Ba distribution in the ocean correlates linearly with that of ²²⁶Ra, reflecting little fractionation of the two elements in their uptake by marine organisms. The weight ratio of ²²⁶Ra/Ba is estimated to be (0.714 ± 0.08) × 10^?8. A wide range of Ba/Si and Ra/Si values is noted in siliceous plankton collected from different oceans. This corraborates with the observations that, although silica co-varies with Ba and²²⁶Ra, the Ba/Si and²²⁶Ra/Si ratios in seawater vary from one area to another. Sediment pore water contains higher Ba concentrations than the overlying seawater. The resulting diffusive flux of Ba through the sediment-sea interface is estimated to be no more than 20% of the river input. The apparent oversaturation of dissolved Ba in pore fluids with respect to barite supports the idea that complexing of Ba with organic ligands may be important. Box model calculations show that: (1) on a per unit area basis, ²²⁶Ra flux from the continental shelf sediments is higher than that from the deep sea floor; (2) in the deep ocean, the magnitude of diffusive input of ²²⁶Ra from sediments is about equal to the loss due to radioactive decay.     

The Ba/Ca record of corals from the Southern Gulf of Mexico: Contributions from land-use changes, fluvial discharge and oil-drilling muds

The Ba/Ca in the growth bands of Montastraea faveolata from the Veracruz Reef System was used to reconstruct the long-term environmental change associated to anthropogenic activity in the Southern Gulf of Mexico (SGM). The 168-yr coral record shows two periods of distinct Ba concentrations: a pre-industrial period (1835-1965: 7.54 μmol/mol) followed by an industrial one (1966-2000: 8.57 μmol/mol). As human population quadrupoled during the latter, sediment load in the fluvial discharge also increased due to changes in land-use, yielding a 14% increase in the Ba-levels. A remarkable finding is that the periods at which the coral Ba/Ca ratio losses its correlation with fluvial discharge coincide exactly with peak periods of high barite consumption (used for oil drilling) in the Northern Gulf of Mexico, and the onset of oil drilling in the SGM. This finding suggests that barite may be one of the dominant sources for dissolved-Ba in the SGM.     

Distribution and origins of polycyclic aromatic hydrocarbons (PAHs) in riverine, estuarine, and marine sediments in Thailand

To assess the status of polycyclic aromatic hydrocarbon (PAH) contamination in coastal and riverine environments in Thailand, we collected 42 surface sediment samples from canals, a river, an estuary, and coastal areas in Thailand in 2003 and analyzed them for PAHs with 3-7 benzene rings by gas chromatography-mass spectrometry (GC-MS). The total concentration of PAHs ranged from 6 to 8399 ng/g dry weight. The average total PAH concentrations were 2290+/-2556 ng/g dry weight (n=8) in canals, 263+/-174 (n=11) in the river, 179+/-222 (n=9) in the estuary, and 50+/-56 (n=14) in coastal areas. Comparison of the concentration range with a worldwide survey of sedimentary PAH concentrations ranked PAH contamination in Thai sediments as low to moderate. The ratio of the sum of methylphenanthrenes to phenanthrene (MP/P ratio) allows discrimination of PAH sources between petrogenic (>2) and pyrogenic (<0.5) origins. Sediments from urban canals in Bangkok showed the highest PAH concentrations and petrogenic signatures (MP/P=1.84+/-0.98 [n=6] in canal sediments) with abundant alkylated PAHs, indicating major sources of petrogenic PAHs in the city. To identify the sources of the petrogenic inputs in Thailand, we analyzed triterpanes, biomarkers of petroleum pollution, in the sediment samples and in potential source materials. Hopane profiles were remarkably uniform throughout the nation, suggesting a diffuse single source (e.g. automobiles). Molecular profiles of hopanes and PAHs in sediments from the urban canals were similar to those in street dust, indicating that street dust is one of the major sources of petrogenic PAHs in the urban area. On the other hand, low levels of PAHs (approximately 50 ng/g) with a pyrogenic signature (MP/P ratio approximately 0.5) were widely recorded in remote areas of the coast and the Chao Phraya River. These pyrogenic PAHs may be atmospherically transported throughout the nation. Middle and lower reaches of the Chao Phraya River, the river mouth, and the upper Gulf of Thailand showed intermediate concentrations and profiles of PAHs, indicating mixtures of petrogenic and pyrogenic origins. Perylene was abundant in sediments, representing up to approximately 60% of total identified PAHs. High inputs of soil due to frequent heavy rains could contribute to the high perylene abundance in the sediments. Sedimentary PAH concentrations decreased offshore with a half distance of approximately 10 km in the upper Gulf off the mouth of the Chao Phraya River. This is probably due to active deposition of laterally transported riverborne particles.     

The effect of an oil drilling operation on the trace metal concentrations in offshore bottom sediments of the Campos Basin oil field,SE Brazil

The concentrations of Al, Fe, Mn, Zn, Cu, Pb, Ni, Cr, Ba, V, Sn and As in offshore bottom sediments from the Bacia de Campos oil field, SE Brazil, were measured at the beginning and at 7 months after completion of the drilling operation. Concentrations of Al, Fe, Ba, Cr, Ni and Zn were significantly higher closer to the drilling site compared to stations far from the site. Average concentrations of Al, Cu, and in particular of Ni, were significantly higher at the end of the drilling operation than at the beginning. Comparison between drilling area sediments with control sediments of the continental platform, however, showed no significant difference in trace metal concentrations. Under the operation conditions of this drilling event, the results show that while changes in some trace metal concentrations do occur during drilling operations, they are not significantly large to be distinguished from natural variability of the local background concentrations.     

Transport and deposition of plutonium in the ocean: evidence from Gulf of Mexico sediments

A study of sediments in the Gulf of Mexico shows dramatic gradients in Pu content and isotope ratios from the continental shelf to the Sigsbee Abyssal Plain. In terms of predicted direct fallout inventory of Pu, one shelf core contains 745% of the predicted inventory, while abyssal plain sediments contain only 15–20% of the predicted value. Absolute Pu concentrations of shelf sediments are also conspicuously high, up to 110 dpm/kg, compared to 13.5 dpm/kg in Mississippi River suspended sediment. There is no evidence of Pu remobilization in Gulf of Mexico shelf sediments, based on comparison of Pu profiles with Mn/Al and Fe/Al profiles. Horizontal transport of fallout nuclides from the open ocean to removal sites in ocean margin sediments is concluded to be the source of both the high concentrations and high inventories of Pu reported here.The shelf sediments show²⁴⁰Pu/²³⁹Pu ratios close to 0.179, the average stratospheric fallout value, but the ratios decrease progressively across the Gulf to low values of 0.06 in abyssal plain sediments. The source of low-ratio Pu in deep-water sediments may be debris from low yield tests transported in the troposphere. Alternatively, it may represent a fraction of the Pu from global stratospheric fallout which has been separated in the water column from the remainder of the Pu in the ocean. In either case, the low-ratio material must have been removed rapidly to the sea floor where it composes a major fraction of the Pu in abyssal plain sediments. Pu delivered by global atmospheric fallout from the stratosphere has apparently remained for the most part in the water or has been transported horizontally and removed into shallow-water sediments.     

Origin and Extent of Fresh Paleowaters on the Atlantic Continental Shelf, USA

While the existence of relatively fresh groundwater sequestered within permeable, porous sediments beneath the Atlantic continental shelf of North and South America has been known for some time, these waters have never been assessed as a potential resource. This fresh water was likely emplaced during Pleistocene sea-level low stands when the shelf was exposed to meteoric recharge and by elevated recharge in areas overrun by the Laurentide ice sheet at high latitudes. To test this hypothesis, we present results from a high-resolution paleohydrologic model of groundwater flow, heat and solute transport, ice sheet loading, and sea level fluctuations for the continental shelf from New Jersey to Maine over the last 2 million years. Our analysis suggests that the presence of fresh to brackish water within shallow Miocene sands more than 100 km offshore of New Jersey was facilitated by discharge of submarine springs along Baltimore and Hudson Canyons where these shallow aquifers crop out. Recharge rates four times modern levels were computed for portions of New England's continental shelf that were overrun by the Laurentide ice sheet during the last glacial maximum. We estimate the volume of emplaced Pleistocene continental shelf fresh water (less than 1 ppt) to be 1300 km³ in New England. We also present estimates of continental shelf fresh water resources for the U.S. Atlantic eastern seaboard (10⁴ km³) and passive margins globally (3 × 10⁵ km³). The simulation results support the hypothesis that offshore fresh water is a potentially valuable, albeit nonrenewable resource for coastal megacities faced with growing water shortages.     

Cytochrome P4501A expression,chemical contaminants and histopathology in roach,goby and sturgeon and chemical contaminants in sediments from the Caspian Sea,Lake Balkhash and the Ily River Delta,Kazakhstan

Roach, goby and sturgeon were examined for cytochrome P4501A (CYP1A) expression and histopathology, in relation to contaminant burdens in fish and sediment. Gradients of induction of CYP1A were observed. Roach from the Ural and Ily River Deltas and roach and goby from the two stations nearest the Caspian Sea oil fields displayed higher levels of CYP1A expression in several organs than was observed in fish from further offshore. Great sturgeon and Russian sturgeon showed higher levels of CYP1A expression than was seen in starred sturgeon and gobies in the Ural delta. No fish showed evidence of contaminant-related histopathologies in the organs examined, despite the elevated CYP1A levels. Low levels of polychlorinated biphenyls and elevated levels of inshore and riverine petroleum hydrocarbons from these habitats suggest that this ongoing hydrocarbon exposure, and that from natural sources and long-term oil exploration on the Northeastern Caspian shore, contributed to the CYP1A induction observed.     

On the processes that influence the transport and fate of Mississippi waters under flooding outflow conditions

The Mississippi River (MR) freshwater outflow is a major circulation forcing mechanism for the Northern Gulf of Mexico. We investigate the transport and fate of the brackish waters under flood conditions. The largest outflow in history (45,000 m³/s in 2011) is compared with the second largest outflow in the last 8 years (41,000 m³/s in 2008). Realistically forced simulations reveal the synergistic effect of enhanced discharge, winds, stratification of ambient shelf waters, and offshore circulation over the transport of plume waters. The strongest impact is attributed to the evolution of the Loop Current (LC) and associated frontal cyclonic eddies and anticyclonic rings, which exhibited distinctly different influence during the two study periods. The northward LC intrusion in the summer of 2011 weakened and blocked the buoyancy-driven downstream (westward) transport of brackish waters. The 2011 flood was thus characterized by upstream (eastward) flow and an extensive coverage of the Mississippi–Alabama–Florida shelf. An immediate response between the LC and the brackish offshore eastward spreading is computed during and after this historic event. The absence of a LC northward intrusion during the 2008 flood, in combination with wind effects, promotes downstream advection of MR waters towards the Louisiana–Texas shelf; large amounts of buoyant waters are also retained near the Delta, subject to local offshore advection under the synergistic action of LC-associated counter-rotating eddies.