Jack Dymond

Submarine Thermal Springs on the Galápagos Rift

The submarine hydrothermal activity on and near the Gal�pagos Rift has been explored with the aid of the deep submersible Alvin. Analyses of water samples from hydrothermal vents reveal that hydrothermal activity provides significant or dominant sources and sinks for several components of seawater; studies of conductive and convective heat transfer suggest that two-thirds of the heat lost from new oceanic lithosphere at the Gal�pagos Rift in the first million years may be vented from thermal springs, predominantly along the axial ridge within the rift valley. The vent areas are populated by animal communities. They appear to utilize chemosynthesis by sulfur-oxidizing bacteria to derive their entire energy supply from reactions between the seawater and the rocks at high temperatures, rather than photosynthesis.

Barium in Deep-Sea Sediment: A Geochemical Proxy for Paleoproductivity

We used sediment traps to define the particulate fluxes of barium and organic carbon and investigate the use of barium as a proxy for ocean fertility. Strong correlations between Corg and Ba fluxes indicate a link between upper ocean biological processes and barium flux to the seafloor. The ratio of organic carbon to barium decreases systematically with water depth. Data from 10 sites indicate that organic debris settling from the 200-m depth has a Corg /Ba ratio of approximately 200. The systematic decrease in this ratio with increasing water depth results from the simultaneous decay of organic matter and uptake of Ba in settling particles. This behavior provides additional evidence that the formation of barite in oceanic particles is a consequence of decomposition/uptake in microenvironments rather than the secretion of barite by specific organisms. The decrease of the Corg/Ba ratio with depth is greatest in the North Pacific followed by the equatorial Pacific and is lowest in the western Atlantic. Since this spatial pattern is consistent with the variations in the deep-ocean barium contents which increase along the path of bottom water flow from the Atlantic to the North Pacific, it suggests that the particulate barium uptake and flux is enhanced by higher barium contents in the intermediate and deep waters of the ocean. Consequently, we have combined our particle flux data with existing water column Ba data to define an algorithm relating new productivity, dissolved barium contents, water depth, and particulate barium flux. This relationship provides a basis of applying barium flux measurements in sediments to estimating new production. In order to use barium as an indicator of productivity, it will be necessary to evaluate inputs from hydrothermal and aluminosilicate sources and xenophyophors. The application of a sequential leach procedure to the trap material indicates that 50-70% of the Ba in settling particles is in the form of barite and the remaining is adsorbed or bound to carbonates. Normative analysis demonstrates that in nearshore areas the contribution of barium from aluminosilicate sources can dominate that from biogenic inputs. It appears that normative estimates of biogenic barium contents can be made with accuracy if less than 50% of the Ba is associated with aluminosilicates; i.e., is of terrigenous origin. Since diagenetic mobilization of Ba can occur in reduced and suboxic sediments, highly productive nearshore areas also are likely to be inappropriate sites to use Ba measurements as productivity indicators. Comparisons between the rain rates of particulate Ba to the seafloor and the burial rate indicate that approximately 30% of the Ba rain is preserved. Although the preservation factor does not appear to be constant, it may be possible to predict the extent of preservation from an empirical relationship with the mass accumulation rate. These observations indicate that measurement of Ba burial fluxes in sediments can provide quantitative information on the paleoproductivity of the oceans. Joining the relationship between barium rain and burial with the barium and organic carbon algorithm, we make estimates of the new production in the northern California Current during the last 18,000 years. This calculation suggests that new production was at least a factor of 2 lower at this site during the last glacial maximum.

A review of the Si cycle in the modern ocean: recent progress and missing gaps in the application of biogenic opal as a paleoproductivity proxy

Abstract Due to the major role played by diatoms in the biological pump of CO2, and to the presence of silica-rich sediments in areas that play a major role in air–sea CO2 exchange (e.g. the Southern Ocean and the Equatorial Pacific), opal has a strong potential as a proxy for paleoproductivity reconstructions. However, because of spatial variations in the biogenic silica preservation, and in the degree of coupling between the marine Si and C biogeochemical cycles, paleoreconstructions are not straitghtforward. A better calibration of this proxy in the modern ocean is required, which needs a good understanding of the mechanisms that control the Si cycle, in close relation to the carbon cycle. This review of the Si cycle in the modern ocean starts with the mechanisms that control the uptake of silicic acid (Si(OH)4) by diatoms and the subsequent silicification processes, the regulatory mechanisms of which are uncoupled. This has strong implications for the direct measurement in the field of the kinetics of Si(OH)4 uptake and diatom growth. It also strongly influences the Si:C ratio within diatoms, clearly linked to environmental conditions. Diatoms tend to dominate new production at marine ergoclines. At depth, they also succeed to form mats, which sedimentation is at the origin of laminated sediments and marine sapropels. The concentration of Si(OH)4 with respect to other macronutrients exerts a major influence on diatom dominance and on the rain ratio between siliceous and calcareous material, which severely impacts surface waters pCO2. A compilation of biogenic fluxes collected at about 40 sites by means of sediment traps also shows a remarkable pattern of increasing BSi:Corg ratio along the path of the “conveyor belt”, accompanying the relative enrichment of waters in Si compared to N and P. This observation suggests an extension of the Si pump model described by Dugdale and Wilkerson (Dugdale, R.C., Wilkerson, F.P., 1998. Understanding the eastern equatorial Pacific as a continuous new production system regulating on silicate. Nature 391, 270–273.), giving to Si(OH)4 a major role in the control of the rain ratio, which is of major importance in the global carbon cycle. The fate of the BSi produced in surface waters is then described, in relation to Corg, in terms of both dissolution and preservation mechanisms. Difficulties in quantifying the dissolution of biogenic silica in the water column as well as the sinking rates and forms of BSi to the deep, provide evidence for a major gap in our understanding of the mechanisms controlling the competition between retention in and export from surface waters. The relative influences of environmental conditions, seasonality, food web structure or aggregation are however explored. Quantitatively, assuming steady state, the measurements of the opal rain rate by means of sediment traps matches reasonably well those obtained by adding the recycling and burial fluxes in the underlying abyssal sediments, for most of the sites where such a comparison is possible. The major exception is the Southern Ocean where sediment focusing precludes the closing of mass balances. Focusing in fact is also an important aspect of the downward revision of the importance of Southern Ocean sediments in the global biogenic silica accumulation. Qualitatively, little is known about the duration of the transfer through the deep and the quality of the material that reaches the seabed, which is suggested to represent a major gap in our understanding of the processes governing the early diagenesis of BSi in sediments. The sediment composition (special emphasis on Al availability), the sedimentation rate or bioturbation are shown to exert an important control on the competition between dissolution and preservation of BSi in sediments. It is suggested that a primary control on the kinetic and thermodynamic properties of BSi dissolution, both in coastal and abyssal sediments, is exerted by water column processes, either occuring in surface waters during the formation of the frustules, or linked to the transfer of the particles through the water column, which duration may influence the quality of the biogenic rain. This highlights the importance of studying the factors controlling the degree of coupling between pelagic and benthic processes in various regions of the world ocean, and its consequences, not only in terms of benthic biology but also for the constitution of the sediment archive. The last section, first calls for the end of the “NPZD” models, and for the introduction of processes linked to the Si cycle, into models describing the phytoplankton cycles in surface waters and the early diagenesis of BSi in sediments. It also calls for the creation of an integrated 1-D diagnostic model of the Si:C coupling, for a better understanding of the interactions between surface waters, deep waters and the upper sedimentary column. The importance of Si(OH)4 in the control of the rain ratio and the improved parametrization of the Si cycle in the 1-D diagnostic models should lead to a reasonable incorporation of the Si cycle into 3-D regional circulation models and OGCMs, with important implications for climate change studies and paleoreconstructions at regional and global scale.

Export production of particles to the interior of the equatorial Pacific Ocean during the 1992 EqPac experiment

Abstract Twenty-four time-series, moored sediment traps were deployed between 2/2/92 and 1/27/93 along 140°W at 9°N, 5°N, 2°N, 0°, 2°S, 5°S and 12°S at water depths of approximately 1200 m and 2200 m, and 700 m above the bottom. The opening/closing of the traps was synchronized at 17-day periods, for 21 events, covering a total of 357 days. The average annual particle flux in the oceans interior (2.2 to 4.4 km deep) from 5°N to 5°S was 28.5 g m−2 year−1, with 34.8 g−2 year−1 the maximum annual flux at the equator. Sixty-six per cent of settling particles were carbonate; 24% biogenic SiO2 and 5% organic carbon. The onset of tropical instability waves, marking the years El Nino/post-El Nino boundary, was associated with a succession of intervals with greater organic carbon and opal at 5°N, 2°S and 5°S that occurred synchronously with a meridional oscillation of instability waves, while net carbon flux during El Nino and post-El Nino periods did not change. Although organic carbon flux increased at 5°N, 2°S and 5°S during the post-El Nino period, it was counterbalanced by decreases at the upwelling stations (2°N and the equator), resulting in no net carbon flux increase across the 5°N to 5°S region. In February/March 1992, only 0.34% of the organic carbon fixed by primary production over the 5°N to 5°S zone arrived in the oceans interior. In August/September that year, zonal average of organic carbon flux increased slightly to 0.5% of primary production. Very little carbon reached the interior depths of the upwelling stations; however, the fraction of export was higher at the 5°N, 2°S and 5°S stations. The pattern of variability of particle flux at the shallow depths was observed also in deeper traps, without temporal offsets, suggesting a settling particle residence time shorter than the 17-day timeseries resolution during most of this experiment.

The chemistry of hydrothermal mounds near the Galapagos Rift

Abstract Samples dredged from the sediment mounds have a unique chemistry and mineralogy which reveals details of the hydrothermal processes that produce these deposits. The mounds form primarily by deposition of Fe, Mn and Si from hydrothermal fluids which circulate through the basalt crust and the overlying sediments. The Mn, Fe and Si are strongly fractionated in the process; the Fe and Si precipitate within the mounds under slightly reducing conditions as nontronite, while the Mn is deposited as Mn oxyhydroxides at the seawater-sediment interface. The nontronite is exceptionally well crystallized, and contains less than 200 ppm Al. The Mn minerals, todorokite and birnessite, also have exceptional crystallinity and the distribution of trace elements Cu, Ni, Zn, Co, Ca and Ba in these phases agrees with predictions made on the basis of models of their crystal structure. The environment of deposition which produces this suite of minerals — slow percolation of hydrothermal fluids through pelagic sediments — may not be unique to the Galapagos Rift, as the same suite of minerals has been found in similar setting in the Gulf of Aden and on the Mid-Atlantic Ridge.

Ferromanganese nodules from MANOP Sites H, S, and R-Control of mineralogical and chemical composition by multiple accretionary processes

Abstract The chemical composition of ferromanganese nodules from the three nodule-bearing MANOP sites in the Pacific can be accounted for in a qualitative way by variable contributions of distinct accretionary processes. These accretionary modes are: 1. (1) hydrogenous, i.e., direct precipitation or accumulation of colloidal metal oxides in seawater, 2. (2) oxic diagenesis which refers to a variety of ferromanganese accretion processes occurring in oxic sediments; and 3. (3) suboxic diagenesis which results from reduction of Mn+4 by oxidation of organic matter in the sediments. Geochemical evidence suggests processes (1) and (2) occur at all three MANOP nodule-bearing sites, and process (3) occurs only at the hemipelagic site, H, which underlies the relatively productive waters of the eastern tropical Pacific. A normative model quantitatively accounts for the variability observed in nearly all elements. Zn and Na, however, are not well explained by the three end-member model, and we suggest that an additional accretionary process results in greater variability in the abundances of these elements. Variable contributions from the three accretionary processes result in distinct top-bottom compositional differences at the three sites. Nodule tops from H are enriched in Ni, Cu, and Zn, instead of the more typical enrichments of these elements in nodule bottoms. In addition, elemental correlations typical of most pelagic nodules are reversed at site H. The three accretionary processes result in distinct mineralogies. Hydrogenous precipitation produces δMnO2. Oxic diagenesis, however, produces Cu-Ni-rich todorokite, and suboxic diagenesis results in an unstable todorokite which transforms to a 7 A phase (“birnessite”) upon dehydration. The presence of Cu and Ni as charge-balancing cations influence the stability of the todorokite structure. In the bottoms of H nodules, which accrete dominantly by suboxic diagenesis, Na+ and possibly Mn+2 provide much of the charge balance for the todorokite structure. Limited growth rate data for H nodules suggest suboxic accretion is the fastest of the three processes, with rates at least 200 mm/106 yr. Oxic accretion is probably 10 times slower and hydrogenous 100 times slower. Since these rates predict more suboxic component in bulk nodules than is calculated by the normative analysis, we propose that suboxic accretion is a non-steady-state process. Variations in surface water productivity cause pulses of particulate flux to the sea floor which result in transient Mn reduction in the surface sediments and reprecipitation on nodule surfaces.

Origin of Metalliferous Sediments from the Pacific Ocean

Sediments from near the basement of a number of Deep Sea Drilling Project (DSDP) sites, from the Bauer Deep, and from the East Pacific Rise have unusually high transition metal-to-aluminum ratios. Similarities in the chemical, isotopic, and mineralogical compositions of these deposits point to a common origin. All the sediments studied have rare-earth-element (REE) patterns strongly resembling the pattern of sea water, implying either that the REEs were coprecipitated with ferromanganese hydroxyoxides (hydroxyoxides denote a mixture of unspecified hydrated oxides and hydroxides), or that they are incorporated in small concentrations of phosphatic fish debris found in all samples. Oxygen isotopic data indicate that the metalliferous sediments are in isotopic equilibrium with sea water and are composed of varying mixtures of two end-member phases with different oxygen isotopic compositions: an iron-manganese hydroxyoxide and an iron-rich montmorillonite. A low-temperature origin for the sediments is supported by mineralogical analyses by x-ray diffraction which show that goethite, iron-rich montmorillonite, and various manganese hydroxyoxides are the dominant phases present. Sr87/Sr86 ratios for the DSDP sediments are indistinguishable from the Sr87/Sr86 ratio in modern sea water. Since these sediments were formed 30 to 90 m.y. ago, when sea water had a lower Sr87/Sr86 value, the strontium in the poorly crystalline hydroxyoxides must be exchanging with interstitial water in open contact with sea water. In contrast, uranium isotopic data indicate that the metalliferous sediments have formed a closed system for this element. The sulfur isotopic compositions suggest that sea-water sulfur dominates these sediments with little or no contribution of magmatic or bacteriologically reduced sulfur. In contrast, ratios of lead isotopes in the metalliferous deposits resemble values for oceanic tholeiite basalt, but are quite different from ratios found in authigenic marine manganese nodules. Thus, lead in the metalliferous sediments appears to be of magmatic origin. The combined mineralogical, isotopic, and chemical data for these sediments suggest that they formed from hydrothermal solutions generated by the interaction of sea water with newly formed basalt crust at mid-ocean ridges. The crystallization of solid phases took place at low temperatures and was strongly influenced by sea water, which was the source for some of the elements found in the sediments.

Genesis and transformation of metalliferous sediments from the East Pacific Rise, Bauer Deep, and Central Basin, northwest Nazca plate

Analytical data for northwest Nazca plate sediments can be described in terms of a mixture of hydrothermal, detrital, hydrogenous, and biogenous material. Fe, Mn, Cu, Zn, Ni, Ba, Si, and Al are more than 50 percent hydrothermal in East Pacific Rise samples from lat 10° to 25 °S. The first four elements are dominantly hydrothermal in the Bauer Deep and Central Basin as well. Seventy to 80 percent of the Ni, 60 to 80 percent of the Ba, and 30 to 60 percent of the Cu and Zn in Bauer Deep and Central Basin sediments are hydrogenous. Si, Ba, and Zn are dominantly biogenous on the northern East Pacific Rise crest, where more than one-third of the Cu also is derived from this source. Detrital Al and Si are dominant away from the rise crest, particularly in the Central Basin, where about 40 percent of the Fe and 15 percent of the Zn may also be detrital. Much of the hydrothermal Fe and biogenous Si have been transformed to an iron-rich smectite. The proportion of total Fe bound in this phase varies from less than 20 percent on the southern rise crest to about 40 percent in the Bauer Deep. The distribution of each element is governed by (1) supply from the four basic sources; (2) lateral transport by bottom currents moving east and then south across the northern East Pacific Rise and Bauer Deep to the Central Basin and moving west from the Peru Basin to the Central Basin; and (3) transformation of the unstable metalliferous hydroxides into more stable smectite and ferromanganese oxyhydroxides.

A biomarker perspective on prymnesiophyte productivity in the northeast pacific ocean

Abstract Long-chain alkenones derived from prymnesiophyte algae were analysed in 1-year sediment trap time series (September 1987–1988) from three sites along a 630 km offshore transect at ∼42°N in the northeast Pacific Ocean. Biomarker flux monitored at 1000 m water depth was evident throughout the year at all sites and showed a consistent seasonal maximum in late spring which increased in amplitude with distance offshore. The integrated annual biomarker flux was constant along the transect, despite differences in seasonality between sites. Alkenone unsaturation patterns were remarkably uniform throughout the time series, reflecting an algal growth temperature of 10.6 ± 1.1°C. This value corresponds to regional water temterature at the sea-surface in winter. It recurs in seasonal upwelling near the coast and at the depth of the subsurface chlorophyll maximum offshore during seasons of stratification. These biomaker observations, interpreted in view of trap data for total organic (TOC) and inorganic carbon and ancillary hydrographic information, help to clarify seasonal productivity patterns for alkenone-producing prymnesiophytes in the northeast Pacific Ocean. Sediments accumulating with distance offshore along the sampling transect change from suboxic and Mn-reducing at the water-sediment interface to aerobic throughout the depths penetrated by box coring. Comparison of alkenone and TOC accumulation rates in surface (0–1 cm) sediments with corresponding annual fluxes integrated by the trap time series, shows that the fraction of both properties accounted at the seafloor is highest and similar under sub-oxic conditions (∼25%), and declines steeply and disproportionately as aerobic conditions are encountered farther offshore. Only 0.25 and 3.1% of the annual inventory for alkenones and TOC in traps are accountable in surface sediments from the slowest accumulating, most oxidizing site farthest offshore. Despite major loss of biomarker to early diagenesis, surface sediments and trap particles display consistent alkenone unsaturation patterns. Results from this study provide a necessary background for palaeoceanographic reconstruction of the northeast Pacific Ocean from stratigraphic analysis of alkenone abundances, unsaturation patterns and isotopic compositions in sediment cores.

Particulate barium fluxes and their relationships to biological productivity

Abstract To understand better the processes that control the transport of particulate barium through the water column and its preservation in marine sediments, we measured particulate barium fluxes along an equatorial transect at 140°W using moored sediment traps. The fluxes of barium correlate strongly with the fluxes of organic carbon; however, this relationship is non-linear—higher carbon fluxes have proportionately less associated barium. As a result we observe spatial and temporal variations of roughly a factor of three in the barium-to-organic carbon ratio. Understanding this variability may help to define the processes that determine the geochemical behavior of Ba in the oceans. Several hypotheses that could influence the flux of Ba and its relationship to organic carbon flux have been proposed: barite formation in barium- and sulfate-enriched microenvironments formed during particle settling; lateral advection of carbon and barium from continental margins; the influence of seawater barium concentration; and Ba scavenging by aluminosilicates. Our study reveals temporal variability in the Ba/Corg values that occurs over timescales of less than one month. Also, depth profiles of carbon and Ba fluxes show that the variability originates at depths less than 1200 m and is conveyed throughout the water column. Both the rapid changes and the upper water column origin of the signals point to upper-ocean biological processes as the predominant cause of the variability in the barium-to-organic carbon ratios. We also observe, however, a 25% increase in Ba flux below 1200 m. The deep sources of Ba could result from barite formation linked to continued organic carbon degradation or from lateral sources of particulate barium. Because the spatial and temporal changes in Ba/Corg values correlated to changes in particulate opal and organic carbon fluxes, ocean ecology appears to have an important influence on barium fluxes. A better understanding of the processes that contribute to the particulate barium flux is needed before the accumulation of barium in marine sediments can be used as a quantitative proxy for ocean productivity.