Impact of the Mediterranean Outflow Water on particle dynamics in intermediate waters of the Northeast Atlantic, as revealed by Th and Th

Over the last decade ²³⁴Th has become increasingly used to study particle transport in the ocean on a timescale of weeks. The application of ²³⁴Th is mainly focused on the determination of particle and associated carbon fluxes from oceanic surface water. However, ²³⁴Th is also suitable for investigating particle dynamic from the upper ocean down to interface sediments, as illustrated by the present work which reports unexpected behavior of ²³⁴Th in intermediate waters associated with the Mediterranean Outflow Water (MOW). Concentration profiles of dissolved ²³⁸U and ²²⁸Ra, and dissolved and particulate ²³⁴Th and ²²⁸Th were measured in the Mediterranean Outflow Water (MOW) near the Gibraltar Straits and at two sites (36°30′N–15°35′W, Nicole; 36°27′N–10°35′W, Yseult) which had hydrographic characteristics of Meddies, i.e. MOW that propagates as eddies in the Northeastern Atlantic at intermediate depths.There are marked differences in the distribution of thorium between MOW and the surrounding Atlantic waters. At the youngest Meddy Nicole salinity maximum at 1000 m depth, ²³⁴Th(total) : ²³⁸U and ²²⁸Th(total) : ²²⁸Ra activity ratios are significantly lower than radioactive equilibrium, indicating an unusual deficit of short half-life thorium nuclides. This implies an export of thorium, presumably on particles, from intermediate Meddy Nicole waters. This process is supported by an increase of particulate thorium fluxes measured in sediment traps deployed for two weeks above and within Meddy Nicole. In contrast, offshore Meddy Yseult has more typical profiles of both thorium nuclides that are nearly in equilibrium with their parents. These results indicate that at intermediate depths, the presence of MOW affects the exchange of reactive elements between particles and dissolved forms and enhances the downward flux of particles from intermediate waters in the Northeast Atlantic.     

The influence of a mature cyclonic eddy on particle export in the lee of Hawaii

Mesoscale eddies may enhance primary production (PP) in the open ocean by bringing nutrient-rich deep waters into the euphotic zone, potentially leading to increased transport of particles to depth. This hypothesis remains controversial, however, due to a paucity of direct particle export measurements. In this study, we investigated particle dynamics using ²³⁴Th–²³⁸U disequilibria within a mesoscale cold-core eddy, Cyclone Opal, which formed in the lee of the Hawaiian Islands. ²³⁴Th samples were collected along two transects across Cyclone Opal as well as during a time-series within the eddy core during a decaying diatom bloom. Particulate carbon (PC), particulate nitrogen (PN) and biogenic silica (bSiO₂) fluxes at 150 m varied spatially and temporally within the eddy and strongly depended on the ²³⁴Th model formulation used (e.g., steady state versus non-steady state, inclusion of upwelling, etc.). Particle fluxes estimated from a steady state model assuming an upwelling rate of 2 m day⁻¹ yielded the best fit to sediment-trap data. These ²³⁴Th-derived particle fluxes ranged from 332±14 to 1719±53 μmol C m⁻² day⁻¹, 27±3 to 114±12 μmol N m⁻² day⁻¹, and 33±20 to 309±73 μmol Si m⁻² day⁻¹. Although PP rates within Cyclone Opal were elevated by a factor of 2–3, PC and PN fluxes were the same, within error, inside and outside of Cyclone Opal. The ratio of PC export to PP remained surprisingly low at <0.03 and similar to those measured in surrounding waters. In contrast, bSiO₂ fluxes within the eddy core were three times higher. Detailed analyses of ²³⁴Th depth profiles consistently showed excess ²³⁴Th at 100–175 m, associated with the remineralization and possible accumulation of suspended and dissolved organic matter from the surface. We suggest that strong microzooplankton grazing facilitated particulate organic matter recycling and resulted in the export of empty diatom frustules. Thus, while eddies may increase PP, they do not necessarily increase PC and PN export to deep waters. This may be a general characteristic of wind-driven cyclonic eddies of the North Pacific Subtropical Gyre and suggests that eddies may preferentially act as a silica pump, thereby playing an important role in promoting silicic-acid limitation in the region.     

台湾海峡铀的来源及保守性混合

Seawater samples are collected in the spring of 2013 from the Taiwan Strait for the analysis of uranium(U)concentrations and isotopic compositions using MC-ICP-MS, and the geochemical behavior patterns of U in the Taiwan Strait are then investigated. Average concentrations of individual U isotopes are(3.23±0.14) μg/kg for 238 U,(2.34±0.09)×10~(–2) μg/kg for ~(235)U and(2.05±0.07)×10~(–4) μg/kg for 234 U. Correspondingly, the U isotopic compositions are 155±18 for δ234U and 138±2 for 238U:235U. The U concentrations and isotopic ratios in the Taiwan Strait are similar to those of open ocean seawater, suggesting the dominance of the open ocean input to the strait's U pool.However, river input, as suggested by the slightly lower salinity than that of the open ocean, also affected the U concentrations and isotopic compositions in the strait. From a compilation of U concentrations in the Taiwan Strait and adjacent areas, including the Jiulong Estuary and Zhujiang Estuary, the Xiamen Bay and the northern South China Sea, a strong and significant relationship between U concentration and salinity [U:S; U=(0.093 4±0.002 4)S+(0.092 0±0.061 5)] is revealed, suggesting conservative mixing of U in the Taiwan Strait. To better understand the U geochemistry in the Taiwan Strait, a multiple endmembers mixing model is applied to estimate the contributions of potential sources. The open ocean seawater contributed 69%–95% of U in the Taiwan Strait, with river water approximately 2%, and dust deposition only around 0.13%. Therefore, the model results supported the open ocean input source and the conservative mixing behavior of U derived from the observation of U concentrations and isotopic ratios and U:S ratios. The sediment interstitial water may be an important source of U to the Taiwan Strait with a possible contribution of 3%–29%, consistent with previous investigations based on radium isotopes.However, further investigations are warranted to examine the U concentration in the sediment interstitial water and its input to the overlying seawater in the Taiwan Strait.     

Particle fluxes associated with mesoscale eddies in the Sargasso Sea

We examined the impact of a cyclonic eddy and mode-water eddy on particle flux in the Sargasso Sea. The primary method used to quantify flux was based on measurements of the natural radionuclide, ²³⁴Th, and these flux estimates were compared to results from sediment traps in both eddies, and a ²¹⁰Po/²¹⁰Pb flux method in the mode-water eddy. Particulate organic carbon (POC) fluxes at 150 m ranged 1–4 mmol C m⁻² d⁻¹ and were comparable between methods, especially considering differences in integration times scales of each approach. Our main conclusion is that relative to summer mean conditions at the Bermuda Atlantic Time-series Study (BATS) site, eddy-driven changes in biogeochemistry did not enhance local POC fluxes during this later, more mature stage of the eddy life cycle (>6 months old). The absence of an enhancement in POC flux puts a constraint on the timing of higher POC flux events, which are thought to have caused the local O₂ minima below each eddy, and must have taken place >2 months prior to our arrival. The mode-water eddy did enhance preferentially diatom biomass in its center, where we estimated a factor of three times higher biogenic Si flux than the BATS summer average. An unexpected finding in the highly depth-resolved ²³⁴Th data sets is narrow layers of particle export and remineralization within the eddy. In particular, a strong excess ²³⁴Th signal is seen below the deep chlorophyll maxima, which we attribute to remineralization of ²³⁴Th-bearing particles. At this depth below the euphotic zone, de novo particle production in the euphotic zone has stopped, yet particle remineralization continues via consumption of labile sinking material by bacteria and/or zooplankton. These data suggest that further study of processes in ocean layers is warranted not only within, but below the euphotic zone.     

Th sorption and export models in the water column: A review

Over the past few decades, the radioisotope pair of ²³⁸U / ²³⁴Th has been widely and increasingly used to describe particle dynamics and particle export fluxes in a variety of aquatic systems. The present paper is one of five review articles dedicated to ²³⁴Th. It is focused on the models associated with ²³⁴Th whereas the companion papers (same issue) are focused on present and future methodologies and techniques (Rutgers van der Loeff et al.), C / ²³⁴Th ratios (Buesseler et al.), ²³⁴Th speciation (Santschi et al.) and present and future applications of ²³⁴Th [Waples, J.T., Benitez-Nelson, C.R., Savoye, N., Rutgers van der Loeff, M., Baskaran, M., Gustafsson, Ö., this issue. An Introduction to the application and future use of ²³⁴Th in aquatic systems. Marine Chemistry, FATE special issue]. In this paper, we review current ²³⁴Th scavenging models and discuss the relative importance of the non-steady state and physical terms associated with the most commonly used model to estimate ²³⁴Th flux. Based on this discussion we recommend that for future work the use of models should be accompanied by a discussion of the effect that model and data uncertainty have on the model results. We also suggest that future field work incorporate repeat occupations of sample sites on time scales of 1–4 weeks in order to evaluate steady state versus non-steady state estimates of ²³⁴Th export, especially during high flux events (> ca. 800 dpm m^− 2 d^− 1). Finally, knowledge of the physical oceanography of the study area is essential, particularly in ocean margins and in areas of established upwelling (e.g., Equatorial Pacific). These suggestions will greatly enhance the application of ²³⁴Th as a tracer of particle dynamics and flux in more complicated regimes.     

The POC / Th ratio of settling particles isolated using split flow-thin cell fractionation (SPLITT)

The common assumption that the ratio between particulate organic carbon (POC) and particulate ²³⁴Th obtained from shallow sediment traps and filterable particles are representative of the ratio in the total particle settling flux should be treated with caution in view of well-known biases associated with tethered shallow sediment traps and the decoupling between size and settling velocity of many natural particle regimes. To make progress toward reliably constraining the POC / ²³⁴Th ratio on truly settling particles, we have tested here a settling collection technique designed to remove any hydrodynamic bias; split flow-thin cell fractionation (SPLITT). These first results from a North Sea fjord and an open Baltic Sea time-series station indicates that the POC / ²³⁴Th ratio on the more complete particle-settling spectrum, isolated with SPLITT, was higher than the POC / ²³⁴Th ratio obtained simultaneously from tethered shallow sediment traps in seven out of seven parallel deployments with an average factor of 210%. The POC / ²³⁴Th ratio from the SPLITT was either in the same range or higher than that obtained on filtered “bulk” particles. To explain this novel data we hypothesize that the slowest settling fraction is organic-matter rich and does not strongly complex ²³⁴Th (i.e., high POC / ²³⁴Th). We suggest that this ultra-slow sinking fraction is better collected by SPLITT than with tethered sediment traps because of minimized hydrodynamic bias.This was tested using the ratio of POC / Al as a tracer of detrital mineral-ballast influenced settling velocity. The higher POC / Al ratios in SPLITT samples relative to in traps is consistent with the hypothesis that SPLITT is better suited for collecting also the slow-settling component of sinking particles. This important slow-settling component appears to here consist primarily of non-APS/TEP components of plankton exudates or other less-strongly ²³⁴Th-complexing organic matter. Further applications of the SPLITT technique are likely to return increasingly new insights on the composition (including “truly settling” POC / ²³⁴Th) of the total spectrum of particles settling out of the upper ocean.     

Influence of salinity and humic substances on the uptake of trace metals by the marine macroalga, Ulva lactuca: Experimental observations and modelling using WHAM

Uptake of the trace metals, Pd, Cd, Hg and Pb, by the marine macroalga, Ulva lactuca, has been studied along a salinity gradient (S = 15–35; pH ~ 8.3) created by batch mixing of synthetic sea water and pure water, both in the absence and presence of humic substances. Factors defining the concentration ratio of metal taken up (w/w) to metal remaining in solution ranged from about 10² mL g^− 1 for Cd to 10³ mL g^− 1 for Pd and Hg. Within experimental error, only the biouptake of Cd appeared to exhibit a dependence on salinity, while the addition of 3 mg L^− 1 of humics resulted in a small suppression of Pd and Hg uptake and a moderate enhancement of Pb uptake compared with the humic-free system. Metal internalisation, evaluated from an EDTA wash of the alga, followed the sequence: Hg > Pd > Cd > Pb; and was notably inhibited in the presence of humics for Pb. Metal uptake (as adsorption and internalisation) was modelled using the Windermere Humic Aqueous Model (WHAM, v6) by encoding the macroalga as a polyelectrolytic binding phase whose properties were defaulted to those of aqueous humics in the software database. By setting the “activity” of the binding phase to about 0.1 and systematically reducing the default constants for metal binding, the magnitude of metal uptake by U. lactuca was reproduced. However, for all metals the model predicted a reduction in algal uptake as a function of salinity that was not always observed experimentally. Moreover, calculations performed in the presence of aqueous humic substances and using the earlier fitted constants significantly underestimated metal uptake by U. lactuca. Discrepancies between experimental observations and model calculations, which are attributed to the formation of ternary complexes at the algal surface, suggest that conventional equilibrium speciation considerations alone are not applicable for modelling metal interactions with marine macroalgae.     

Time-series measurements of Th in water column and sediment trap samples from the northwestern Mediterranean Sea

Disequilibrium between ²³⁴Th and ²³⁸U in water column profiles has been used to estimate the settling flux of Th (and, by proxy, of particulate organic carbon); yet potentially major non-steady-state influences on ²³⁴Th profiles are often not able to be considered in estimations of flux. We have compared temporal series of ²³⁴Th distributions in the upper water column at both coastal and deep-water sites in the northwestern Mediterranean Sea to coeval sediment trap records at the same sites. We have used sediment trap records of ²³⁴Th fluxes to predict temporal changes in water column ²³⁴Th deficits and have compared the predicted deficits to those measured to determine whether the time-evolution of the two coincide. At the coastal site (327 m water depth), trends in the two estimates of water column ²³⁴Th deficits are in fairly close agreement over the 1-month deployment during the spring bloom in 1999. In contrast, the pattern of water column ²³⁴Th deficits is poorly predicted by sediment trap records at the deep-water site (DYFAMED, 2300 m water depth) in both 2003 and 2005. In particular, the transition from a mesotrophic to an oligotrophic system, clearly seen in trap fluxes, is not evident in water column ²³⁴Th profiles, which show high-frequency variability. Allowing trapping efficiencies to vary from 100% does not reconcile the differences between trap and water column deficit observations; we conclude that substantial lateral and vertical advective influences must be invoked to account for the differences.Advective influences are potentially greater on ²³⁴Th fluxes derived from water column deficits relative to those obtained from traps because the calculation of deficits in open-ocean settings is dominated by the magnitude of the “dissolved” ²³⁴Th fraction. For observed current velocities of 5–20 cm s⁻¹, in one radioactive mean-life of ²³⁴Th, the water column at the DYFAMED site can reflect ²³⁴Th scavenging produced tens to hundreds of kilometers away. In contrast, most of the ²³⁴Th flux collected in shallow sediment traps at the DFYFAMED site was in the fraction settling >200 m d⁻¹; in effect the sediment trap can integrate the ²³⁴Th flux over distances 40-fold less than water column ²³⁴Th distributions. In some sense, sediment trap and water column sampling for ²³⁴Th provide complementary pictures of ²³⁴Th export. However, because the two methods can be dominated by different processes and are subject to different biases, their comparison must be treated with caution.     

Sediment trap and in-situ pump size-fractionated POC/234Th ratios in the Mediterranean Sea and Northwest Atlantic: Implications for POC export

Measurements of particle size-fractionated POC/²³⁴Th ratios and ²³⁴Th and POC fluxes were conducted using surface-tethered, free-floating, sediment traps and large-volume in-situ pumps during four cruises in 2004 and 2005 to the oligotrophic eastern Mediterranean Sea and the seasonally productive western Mediterranean and northwest Atlantic. Analysis of POC/²³⁴Th ratios in sediment trap material and 10, 20, 53, 70, and 100 μm size-fractionated particles indicate, for most stations, decreasing ratios with depth, a weak dependence on particle size, and ratios that converge to ～1–5 μmol dpm^?1 below the euphotic zone (～100–150 m) throughout the contrasting biogeochemical regimes. In the oligotrophic waters of the Aegean Sea, ²³⁴Th and POC fluxes estimated using sediment traps were consistently higher than respective fluxes estimated from water-column ²³⁴Th–²³⁸U disequilibrium, observations that are attributed to terrigenous particle scavenging of ²³⁴Th. In the more productive western Mediterranean and northwest Atlantic, ²³⁴Th and POC fluxes measured by sediment trap and ²³⁴Th–²³⁸U disequilibrium agreed within a factor of 2–4 throughout the water column. An implication of these results is that estimates of POC export by sediment traps and ²³⁴Th–²³⁸U disequilibrium can be biased differently because of differential settling speeds of POC and ²³⁴Th-carrying particles.     

The importance of tides for sediment dynamics in the deep sea—Evidence from the particulate-matter tracer 234Th in deep-sea environments with different tidal forcing

Key aspects of deep-ocean fluid dynamics such as basin-scale (residual) and tidal flow are believed to have changed over glacial/interglacial cycles, with potential relevance for climatic change. To constrain the mechanistic links, magnitudes and temporal succession of events analyses of sedimentary paleo-records are of great importance. Efforts have been underway for some time to reconstruct residual-flow patterns from sedimentary records. Attempts to reconstruct tidal flow characteristics from deep-sea sediment deposits, however, are at a very early stage and first require a better understanding of the reflection of modern tides in sediment dynamics. In this context internal (baroclinic) tides, which are formed by the surface (barotropic) tide interacting with seafloor obstacles, are believed to play a particularly important role. Here we compare two modern deep-sea environments with respect to the effect of tides on sediment dynamics. Both environments are influenced by kilometre-scale topographic features but with vastly different tidal forcing: (1) two sites in the Northeast Atlantic (NEA) being surrounded by, or located downstream of, fields of short seamounts (maximum barotropic tidal current velocities ～5 cm s^?1); and (2) a site next to the Anaximenes seamount in the Eastern Mediterranean (EMed) (maximum barotropic tidal current velocities ～0.5 cm s^?1). With respect to other key fluid-dynamical parameters both environments are very similar. Signals of sedimentary particle dynamics, as influenced by processes taking place in the bottom boundary layer, were traced by the vertical water-column distribution of radioactive disequilibria (daughter/parent activity ratios≠1) between the naturally occurring, short-lived (half-life: 24.1 d) particulate-matter tracer ²³⁴Th relative to its very long-lived and non-particle-reactive parent nuclide ²³⁸U. Activity ratios of ²³⁴Th/²³⁸U<1 in water samples collected near the seafloor indicate fast ²³⁴Th scavenging onto particles followed by fast settling of these particles from the sampled parcel of water and, therefore, imply active sediment resuspension and dynamics on time scales of up to several weeks. In the Northeast Atlantic study region tides (in particular internal tides) are very likely to locally push total current velocities near the seafloor across the critical current velocity threshold for sediment erosion or resuspension whereas in the Eastern Mediterranean the tides are much too weak for this to happen. This difference in tidal forcing is reflected in a difference of the frequency of the occurrence of radioactive disequilibria <1 between total ²³⁴Th and ²³⁸U: In the near-bottom water column of the Northeast Atlantic region 59% of samples had detectable ²³⁴Th/²³⁸U disequilibria whereas at the Eastern Mediterranean site this fraction was only 7% (including a few disequilibria >1). The results of this study, therefore, add to the evidence suggesting that tides in the deep sea of the open oceans are more important for sediment dynamics than previously thought. It is hypothesised that (a) tide/seamount interactions in the deep open ocean control the local distribution of erosivity proxies (e.g., distributions of sediment grain sizes, heavy minerals and particle-reactive radionuclides) in sedimentary deposits and (b) the aforementioned topographically controlled sedimentary imprints of (internal) tides are useful in the reconstruction of past changes of tidal forcing in the deep sea.     

Precipitation of authigenic uranium in suboxic continental margin sediments from the Okinawa Trough

Concentrations of U and Th isotopes in Okinawa Trough and East China Sea sediment cores were determined by isotope dilution inductively coupled plasma-mass spectrometry (ID-ICP-MS) to investigate the behavior of redox sensitive uranium in suboxic hemipelagic sediments and determine their significance in oceanic uranium balance. ²³⁸U concentrations and ²³⁸U/²³²Th activity ratios in the East China Sea sediments showed no remarkable variation with depth. However, ²³⁸U and ²³⁸U/²³²Th ratios in the Okinawa Trough sediments were low in the surface oxidizing layer but increased where the suboxic condition was encountered. The distribution profiles of ²³⁰Th and ²³²Th concentrations were relatively constant with depth in both the Okinawa Trough and East China Sea sediment cores. These results suggested that there has been post-depositional precipitation of authigenic uranium within the suboxic Okinawa Trough sediment column. The post-depositional precipitation rates of authigenic uranium were estimated to be 47 ± 5 to >62 ± 8 ng cm⁻² yr⁻¹; these rates were comparable to those previously reported for several anoxic sediments. A mechanism controlling precipitation of uranium may be the downward diffusion of uranium U(VI), reduction to U(IV) and finally precipitation onto the solid phase. The accumulation rate of uranium for the Okinawa Trough sediments was approximately eight times higher than the world average rate reported for suboxic sediments. This removal of uranium in the oceanic budget increases the importance of the suboxic sediment sink.     

Factors influencing benthic bacterial abundance, biomass, and activity on the northern continental margin and deep basin of the Gulf of Mexico

As part of a larger project on the deep benthos of the Gulf of Mexico, an extensive data set on benthic bacterial abundance (n>750), supplemented with cell-size and rate measurements, was acquired from 51 sites across a depth range of 212–3732 m on the northern continental slope and deep basin during the years 2000, 2001, and 2002. Bacterial abundance, determined by epifluorescence microscopy, was examined region-wide as a function of spatial and temporal variables, while subsets of the data were examined for sediment-based chemical or mineralogical correlates according to the availability of collaborative data sets. In the latter case, depth of oxygen penetration helped to explain bacterial depth profiles into the sediment, but only porewater DOC correlated significantly (inversely) with bacterial abundance (p<0.05, n=24). Other (positive) correlations were detected with TOC, C/N ratios, and % sand when the analysis was restricted to data from the easternmost stations (p<0.05, n=9–12). Region-wide, neither surface bacterial abundance (3.30–16.8×10⁸ bacteria cm⁻³ in 0–1 cm and 4–5 cm strata) nor depth-integrated abundance (4.84–17.5×10¹³ bacteria m⁻², 0–15 cm) could be explained by water depth, station location, sampling year, or vertical POC flux. In contrast, depth-integrated bacterial biomass, derived from measured cell sizes of 0.027–0.072 μm³, declined significantly with station depth (p<0.001, n=56). Steeper declines in biomass were observed for the cross-slope transects (when unusual topographic sites and abyssal stations were excluded). The importance of resource changes with depth was supported by the positive relationship observed between bacterial biomass and vertical POC flux, derived from measures of overlying productivity, a relationship that remained significant when depth was held constant (partial correlation analysis, p<0.05, df=50). Whole-sediment incubation experiments under simulated in situ conditions, using ³H-thymidine or ¹⁴C-amino acids, yielded low production rates (5–75 μg C m⁻² d⁻¹) and higher respiration rates (76–242 μg C m⁻² d⁻¹), with kinetics suggestive of resource limitation at abyssal depths. Compared to similarly examined deep regions of the open ocean, the semi-enclosed Gulf of Mexico (like the Arabian Sea) harbors in its abyssal sediments a greater biomass of bacteria per unit of vertically delivered POC, likely reflecting the greater input of laterally advected, often unreactive, material from its margins.     

Rhenium in rivers and estuaries of India: Sources,transport and behaviour

The concentration of dissolved and particulate Re have been measured in the Narmada, Tapi and the Mandovi estuaries in the Arabian Sea and the Hooghly estuary in the Bay of Bengal. Re concentration in water and particulate matter of these estuaries is highly variable. Re in river waters analysed varies from 1 to 41 pmol/kg, the lowest in the Mandovi and the highest in the Mahi river. Re concentrations in the rivers analysed except in the Mandovi river are higher than the average global riverine Re concentration of 2.1 pmol/kg. Based on this study and the available data, the contemporary global annual flux of dissolved riverine Re is estimated to be ~ 350 × 10³ mol with an average concentration of ~ 9.2 pmol/kg, much higher than the earlier estimates. Residence time of Re in the oceans based on this estimate is 175,000 years, ~ 4 times lower compared to earlier estimates. Re behaves conservatively in all the estuaries studied. Re concentrations of seawater in the Bay of Bengal and in the Arabian Sea, estimated from the data of the Hooghly and the Mandovi estuaries respectively are ~ 40 pmol/kg, similar to the open ocean Re values of the Arabian Sea measured in this study and the values reported for in other oceanic regions. However, the dissolved Re in the Gulf of Cambay is 2 to 5 times higher, consistent with the high Re measured in the Mahi estuary and in the coastal waters of the Gulf of Cambay. The source of high Re in the Gulf of Cambay seems to be anthropogenic, measurements of Re in rivers and industrial waste waters draining into the Gulf supply amount to ~ 2300 mol of Re annually. This anthropogenic supply coupled with high residence time of water in the Gulf contribute to its high Re. Re concentration in suspended sediments of the Narmada estuary varies from 1 to 2 pmol/g, and does not show any discernible trend with salinity.The contemporary global riverine Re supply to the oceans estimated in this study is ~ 2–4 times higher compared to its removal in the reducing (anoxic/suboxic) sediments, indicating non-steady state of Re in the ocean. High dissolved riverine Re flux coupled with high Re content in the Gulf of Cambay highlights the need of a detailed study of Re in the various global rivers and in oceans including coastal regions and semi enclosed basins of the world to understand its behaviour in various reservoirs and to constrain the residence time of Re in the ocean.     

Depositional environments of the Mediterranean “Lower Evaporites” of the Messinian salinity crisis: Constraints from quantitative analyses

We use simple quantitative analyses to evaluate controversial water level scenarios for the Mediterranean “Lower Evaporites” of the Messinian salinity crisis. Our results indicate that a shallow-water scenario for the Lower Gypsum units – with Mediterranean water level lower than the sill at Gibraltar – would imply unrealistic salt thicknesses on the order of 3 km. Some outflow to the open ocean must have persisted, implying that the Mediterranean was a deep-water basin during Lower Gypsum formation. Since glacio-eustatic fluctuations do not seem to have had a major influence on Lower Gypsum deposits, Mediterranean water level was even substantially higher than the Gibraltar sill. Our analyses furthermore show that precessional changes in the freshwater budget may explain the observed cyclic lithological changes of gypsum and non-evaporitic sediments. Potential precipitation of gypsum in the deep Mediterranean basins would have critically depended on the availability of oxygen and thus on the stratification of the water column. Finally, our results indicate that the deep Mediterranean halite units could have been deposited under shallow conditions, assuming that they correspond to the ~ 70 kyr time interval between glacials TG12 and TG14, when Mediterranean outflow to the Atlantic was blocked.     

Quantum yield for the photochemical production of dissolved inorganic carbon in seawater

The direct photooxidation of coloured dissolved organic matter (CDOM) to dissolved inorganic carbon (DIC) may provide a significant sink for organic carbon in the ocean. To calculate the rate of this reaction on a global scale, it is essential to know its quantum yield, or photochemical efficiency. We have determined quantum yield spectra, φ(λ), (moles DIC/mole photons absorbed) for 14 samples of seawater from environments ranging from a turbid, eutrophic bay to the Gulf Stream. The spectra vary among locations, but can be represented quite well by three pooled spectra for zones defined by location and salinity: inshore φ(λ)=e^{−(6.66+0.0285(λ−290))}; coastal φ(λ)=e^{−(6.36+0.0140(λ−290))}; and open ocean φ(λ)=e^{−(5.53+0.00914(λ−290))}. Production efficiency increases offshore, which suggests that the most highly absorbing and quickly faded terrestrial chromophores are not those directly responsible for DIC photoproduction.     

Impact of halides on the photobleaching of dissolved organic matter

Understanding absorbance photobleaching of marine dissolved organic matter (DOM) is important because DOM chromophores impact oceanic primary productivity by affecting the depth of the photic zone, absorb UV radiation and affect ocean color used in remote sensing. However, the fundamental mechanisms which account for this bleaching are largely unknown. Controlled laboratory studies demonstrated that the presence of seawater concentrations of chloride and bromide ions enhanced absorbance photobleaching reaction rates by ~ 40%, regardless of DOM source or the presence or absence of carbonate ions. In contrast, halide ions generally did not affect fluorescence bleaching rates. Variations in ionic strength did not alter the enhancement in absorbance photobleaching by halide ions. Accordingly, the enhancement in absorbance photobleaching was specific to halide ions, rather than a generalized salinity effect. We confirmed the formation of hydroxyl radical (HO^•) in illuminated samples, and its significant scavenging in the presence of halide salts. Gamma-radiolysis experiments and associated modeling indicated that a small component (~ 12%) of the photobleaching enhancement by halides was consistent with the hypothesis that halide scavenging of HO^• will form reactive halogen radicals that target electron-rich chromophores within DOM more selectively than HO^•. The mechanism responsible for the major component of absorbance photobleaching rate enhancement by halides remains unresolved.     

Variability of the apparent quantum efficiency of CO photoproduction in the Gulf of Maine and Northwest Atlantic

The photochemical oxidation of colored, dissolved organic matter (CDOM) is important for carbon cycling in the ocean. This oxidation process produces a number of products, including carbon monoxide (CO). While the photochemical production efficiency of CO (apparent quantum yield, AQY, defined in terms of CDOM absorbance) has been reported to be similar for many water types, a full evaluation of the observed natural variability in CO AQY requires additional study. Here we use a polychromatic irradiation system to determine twenty AQY spectra at sea on fresh samples ranging from the near coastal waters of the Gulf of Maine to the offshore waters of the Northwest Atlantic. Despite the geographic variability of these marine samples the AQY of CO production in the Gulf of Maine and Northwest Atlantic exhibited only a small degree of variability, none of which was not correlated with measured environmental parameters. Consequently, a single aggregate AQY spectrum _λ = e^{(−(9.134+0.0425(λ−290)))+e(−(11.316+0.0142(λ−290)))} was found to adequately represent the entire data set. Significantly, the accuracy of an AQY spectrum determined using this multispectral/statistical technique was confirmed with data obtained from a monochromatic irradiation technique on a single open ocean sample. Taken together, the AQY spectra determined in this study were similar in magnitude and shape to those previously published for marine samples and, overall, were somewhat lower than those previously reported for freshwater studies.     

Influence of basin-scale and mesoscale physical processes on biological productivity in the Bay of Bengal during the summer monsoon

Physical forcing plays a major role in determining biological processes in the ocean across the full spectrum of spatial and temporal scales. Variability of biological production in the Bay of Bengal (BoB) based on basin-scale and mesoscale physical processes is presented using hydrographic data collected during the peak summer monsoon in July–August, 2003. Three different and spatially varying physical processes were identified in the upper 300 m: (I) anticyclonic warm gyre offshore in the southern Bay; (II) a cyclonic eddy in the northern Bay; and (III) an upwelling region adjacent to the southern coast. In the warm gyre (>28.8 °C), the low salinity (33.5) surface waters contained low concentrations of nutrients. These warm surface waters extended below the euphotic zone, which resulted in an oligotrophic environment with low surface chlorophyll a (0.12 mg m⁻³), low surface primary production (2.55 mg C m⁻³ day⁻¹) and low zooplankton biovolume (0.14 ml m⁻³). In the cyclonic eddy, the elevated isopycnals raised the nutricline upto the surface (NO₃–N > 8.2 μM, PO₄–P > 0.8 μM, SiO₄–Si > 3.5 μM). Despite the system being highly eutrophic, response in the biological activity was low. In the upwelling zone, although the nutrient concentrations were lower compared to the cyclonic eddy, the surface phytoplankton biomass and production were high (Chl a – 0.25 mg m⁻³, PP – 9.23 mg C m⁻³ day⁻¹), and mesozooplankton biovolume (1.12 ml m⁻³) was rich. Normally in oligotrophic, open ocean ecosystems, primary production is based on ‘regenerated’ nutrients, but during episodic events like eddies the ‘production’ switches over to ‘new production’. The switching over from ‘regenerated production’ to ‘new production’ in the open ocean (cyclonic eddy) and establishment of a new phytoplankton community will take longer than in the coastal system (upwelling). Despite the functioning of a cyclonic eddy and upwelling being divergent (transporting of nutrients from deeper waters to surface), the utilization of nutrients leading to enhanced biological production and its transfer to upper trophic levels in the upwelling region imply that the energy transfer from primary production to secondary production (mesozooplankton) is more efficient than in the cyclonic eddy of the open ocean. The results suggest that basin-scale and mesoscale processes influence the abundance and spatial heterogeneity of plankton populations across a wide spatial scale in the BoB. The multifaceted effects of these physical processes on primary productivity thus play a prominent role in structuring of zooplankton communities and could consecutively affect the recruitment of pelagic fisheries.     

A numerical study of sea level and current responses to Hurricane Frederic using a coastal ocean model for the Gulf of Mexico

A three-dimensional, nonlinear, primitive equation ocean general circulation model is used to study the response of the Gulf of Mexico to Hurricane Frederic. The model has free surface dynamics and a second order turbulence closure scheme for the mixed layer. Realistic coastlines, bottom topography and open boundary conditions are used in the study. The model has a vertical sigma coordinate with 18 levels, and a horizontal resolution of 0.2°×0.2° for the entire Gulf. The study focuses on hurricane generated sea level, current, and coastally trapped wave (CTW) responses of the Gulf. Time series of sea levels from U.S. coastal tide gauge stations and the numerical model simulation of sea levels and currents on the shelf are used to study sea level, current and CTW responses. Both model sea levels and observations from tide gauge stations show a westward progression of the surge as a CTW response. The results of the study of sea levels and currents indicate that CTW propagate to the west with phase speeds of 7–10 m s^–1. There is also a strong nonlinear interaction between the Loop Current and hurricane induced currents. The surface current attains a maximum of 200 cm s^–1 in the eastern Gulf. The model surface elevation at several locations is compared with tide gauge data. The current meter data at three moorings are also compared with the model currents. The model simulations show good agreement with observed data for the hurricane induced coastally trapped wave, storm surge, and current distribution in the Gulf.     

Measuring low concentrations of Th in water and sediment

²³⁴Th/²³⁸U disequilibria have been used extensively in studies of particle dynamics and the fate and transport of particle-reactive matter in marine environments. Similar work in low salinity, estuarine, and freshwater systems has not occurred primarily because the lower concentrations of both parent and daughter nuclides that are typical of these systems often render established methods for the analysis of ²³⁴Th inadequate. The application of this radionuclide tracer technique to these systems, however, has great potential. To this end, we present a method for measuring low activities of ²³⁴Th in relatively small samples (<200 l) using low background gas-flow proportional counters, a ²²⁹Th yield monitor, and empirical corrections for the interferences from real and apparent betas that are emitted by other thorium isotopes and their progeny. For samples with low ²³⁴Th/²²⁸Th activity ratios, we improve upon current beta counting methodologies that rely on immediate sample counting, weak beta absorption, or multiple beta counts so that, using the analytical approach outlined here, it should be possible to measure ²³⁴Th activities (i) as low as 1.5 dpm/total sample, (ii) up to 2 weeks after radiochemical purification of thorium, and (iii) with only one sample count for alpha and beta activity.