John M. Edmond

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.

Ridge crest hydrothermal activity and the balances of the major and minor elements in the ocean: The Galapagos data

Samples collected by the deep submersible “Alvin” from four hot spring fields (T = 3–13°C) on the crest of the Galapagos spreading ridge show pronounced and varied compositional anomalies. If it is assumed that these have a general significance, that they are associated with hydrothermal reactions between seawater and basalt wherever new oceanic crust is being produced then global fluxes can be computed. These are large. For Mg and SO4 they balance the river input. For Li and Rb they exceed it by factors of between five and ten. Calcium is supplied at a rate equivalent to that of non-carbonate Ca from the continents. The additions of K, Ba and Si are between one third and two thirds of the river load. There are large positive and negative anomalies for Cl and Na indicating that substantial amounts of Cl may be taken up by the newly formed crust and transported deep into the subduction zones. Where there are data in common, the field measurements agree with the experimental findings at low (<5) water/rock ratios.

Chemistry of submarine hydrothermal solutions at 21 °N, East Pacific Rise

Abstract The three hydrothermal fields at 21°N latitude, East Pacific Rise, were resampled and an additional one was discovered. Maximum fluid temperatures observed were within a few degrees of 350°C and these waters had concentrations of Mg and sulfate indistinguishable from zero. One field, NGS, which had active 350°C springs in 1979, was inactive when first located in 1981. However, when a chimney was broken open during sampling, water issued at 273°C and continued to flow for at least five days. The chemical composition strongly suggests that these waters cooled conductively from 350°C in the sealed conduit. The major ion data are consistent with the estimates based on extrapolation of the original measurements made on the hot springs from the Galapagos Spreading Center ( Edmond et al ., 1979a). The fluids have a pH of 3.5 and the sulfide-forming element concentrations show significant inter-field variations. Fe levels range from 0.8 to 2.4 mmoles/kg; the ratio Fe:Mn varies from 0.9 to 2.9 similar to metalliferous sediments on the ridge flanks, but much higher than observed at Galapagos (where sub-surface precipitation of iron sulfides occurs) indicating that the overwhelming proportion of the mass flux from hydrothermal systems occurs at high temperatures. Zn ranges from 40 to 106 μmoles/kg with Cu being substantially lower. Since the ratio of these elements in tholeiites is about unity, there is strong net preferential mobilization of Zn. Lead ranges from 183 to 359 nmoles/kg. Nickel and Be are highly immobile relative to the other trace elements. The abundance of H 2 S is about three times that of the total sulfide-forming cations. These data demonstrate that acid solutions at elevated temperatures can transport substantial amounts of ore-forming elements in the presence of large excesses of sulfide.

The strontium isotope budget of the modern ocean

Abstract We have measured the Sr concentration and isotopic composition of most of the worlds major rivers. These data greatly extend the range of geologic, tectonic and climatic drainage basin environments that have been studied and, overall, constitute a doubling of the fluvial Sr isotope data base. This has produced a more accurate estimate for the87Sr/86Sr ratio of global runoff of 0.7119; this is distinctly higher than obtained from previous studies. We have also determined the Sr concentration and87Sr/86Sr ratio of oceanic hydrothermal vent waters from diverse tectonic and volcanogenic environments that have allowed us to further constraint the Sr isotope systematic of this source. These new data have been combined with previously published riverine data and values for the diagenetic benthic flux of Sr from deep-sea sediments to obtain a contemporary oceanic Sr isotope budget. The results of steady-state calculations give a best estimate for the flux of seawater through high-temperature ridge crest hydrothermal system of1.2 ± 0.3 × 1014 kg/yr; this is substantially higher than recent estimates.

The mechanism of iron removal in estuaries

Abstract A survey of U.S. east coast estuaries confirms that large-scale rapid removal of iron from river water is a general phenomenon during estuarine mixing. The river-borne ‘dissolved’ iron consists almost entirely of mixed iron oxide-organic matter colloids, of diameter less than 0.45 μm, stabilized by the dissolved organic matter. Precipitation occurs on mixing because the seawater cations neutralize the negatively charged iron-bearing colloids allowing flocculation. The process has been duplicated in laboratory experiments using both natural filtered and unfiltered river water and a synthetic colloidal goethite in 0.05 μm filtered water. The colloidal nature of the iron has been further confirmed by ultracentrifugation and ultrafiltration. A major consequence of the precipitation phenomena is to reduce the effective input of ‘dissolved’ iron to the ocean by about 90% of the primary river value, equivalent to a concentration of less than 1 μmol per liter of river water.

Volcanic eruption of the mid-ocean ridge along the East Pacific Rise crest at 9°45-52'N: direct submersible observations of seafloor phenomena associated with an eruption event in April, 1991

In April, 1991, we witnessed from the submersible Alvin a suite of previously undocumented seafloor phenomena accompanying an in-progress eruption of the mid-ocean ridge on the East Pacific Rise crest at 9°45′N–52′N. The volume of the eruption could not be precisely determined, although comparison of pre- and post-eruption SeaBeam bathymetry indicate that any changes in ridge crest morphology resulting from the eruption were < 10 m high. Effects of the eruption included: (1) increased abundance and redistribution of hydrothermal vents, disappearance of numerous vent communities, and changes in characteristics of vent fauna and mineral deposits within the eruption area since December, 1989; (2) murkiness of bottom waters up to tens of meters above the seafloor due to high densities of suspended mineral and biogenic particulates; (3) destruction of a vent community by lava flows, mass wasting, and possible hydrovolcanic explosion at a site known as ‘Tubeworm Barbecue’ in the axial summit caldera (ASC) at 9°50.6′N; (4) near-critical temperatures of hydrothermal vent fluids, ranging up to 403°C; (5) temporal variations over a 2 week interval in both temperatures and chemical/isotopic compositions of hydrothermal fluids; (6) unusual compositions of end-member vent fluids, with pH values ranging to a record low of 2.5, salinities ranging as low as 0.3 wt% NaCl (one-twelfth that of seawater), and dissolved gases reaching high concentrations (> 65 mmol/l for both CO2 and H2S); (7) venting at temperatures above 380°C of visually detectable white vapor that transformed to plumes of gray smoke a few centimeters above vent orifices; (8) disorganized venting of both high-temperature fluids (black and gray smoke) and large volumes of cooler, diffuse hydrothermal fluids directly from the basaltic seafloor, rather than from hydrothermal mineral constructions; (9) rapid and extensive growth of flocculent white bacterial mats (species unknown) on and under the seafloor in areas experiencing widespread venting of diffuse hydrothermal fluid; and (10) subseafloor downslope migration of magma normal to the ridge axis in a network of small-scale (1–5 m diameter) lava tubes and channels to distances at least 100–200 m outside the ASC. We suggest that, in April, 1991, intrusion of dikes in the eruption area to < 200 m beneath the ASC floor resulted in phase separation of fluids near the tops of the dikes and a large flux of vapor-rich hydrothermal fluids through the overlying rubbly, cavernous lavas. Low salinities and gas-rich compositions of hydrothermal fluids sampled in the eruption area are appropriate for a vapor phase in a seawater system undergoing subcritical liquid-vapor phase separation (boiling) and phase segregation. Hydrothermal fluids streamed directly from fissures and pits that may have been loci of lava drainback and/or hydrovolcanic explosions. These fissures and pits were lined with white mats of a unique fast-growing bacteria that was the only life associated with the brand-new vents. The prolific bacteria, which covered thousands of square meters on the ridge crest and were also abundant in subseafloor voids, may thrive on high levels of gases in the vapor-rich hydrothermal fluids initially escaping the hydrothermal system. White bacterial particulates swept from the seafloor by hydrothermal vents swirled in an unprecedented biogenic ‘blizzard’ up to 50 m above the bottom. The bacterial proliferation of April, 1991 is likely to be a transient bloom that will be checked quickly either by decline of dissolved gas concentrations in the fluids as rapid heat loss brings about cessation of boiling, and/or by grazing as other organisms are re-established in the biologically devastated area.

Boron isotope exchange between seawater and the oceanic crust

Abstract Dissolved boron in seawater from the Atlantic and Pacific is isotopically homogeneous at 39.5 per mil ( 11 B 10 B ratios are expressed as per mil deviations from NBS SRM 951). Unaltered mid-ocean ridge basalts (MORE) from the crest of the East Pacific Rise (EPR) at 21° and 13°N have B contents of 0.39 ± 0.03 and 0.46 ± 0.03 ppm (about one order of magnitude lower than previous estimates) and δ11B of −3.6 ± 0.4 and −2.2 ± 0.6 per mil respectively. Large scale B exchange between seawater and the oceanic crust has been demonstrated at both high and low temperature. Hydrothermal solutions from nine separate vent fields at 21° and 13°N (EPR) have variable B enrichments, relative to seawater (416 μmoles/kg), of between 8 and 32% and have δ11B values between 30.0 ± 0.4 and 36.8 ± 0.4 per mil. Boron has been extracted from the basalts with no resolvable isotopic fractionation. High temperature water rock ratios, based on the B concentrations, are between 0.28 and 3.0. The hydrothermal flux of B into the oceans is between 0.4 and 0.8 × 109 moles/yr, assuming that only pristine basalts are present in the reaction zone. Basalts altered at low temperature and serpentinites are variably enriched in B. The B content of altered whole rocks correlates strongly with δ18O, and increases with degree of alteration. Altered basalts (n = 7) containing between 8.9 and 69 ppm B have δ11B between 0.1 and 9.2 ± 0.4 per mil. Model calculations give water rock ratios greater than 100 for rocks recovered from DSDP Hole 418A. Serpentinized peridotites (n = 4) with between 50 and 81 ppm B have δ11B between 8.3 ± 0.4 and 12.6 ± 0.4 per mil. The flux of B into the crust during low temperature alteration is about 13 × 109 moles/yr. The maximum diffusive flux of B into the crust from sediment pore waters is 0.8 × 109 moles/yr with a δ11B less than 43 per mil.

Chemistry of submarine hydrothermal solutions at Guaymas Basin, Gulf of California

Abstract Reconnaisance ALVIN dives in the sediment-filled southern trough of the Guaymas Basin found active hot springs with temperatures ranging up to 315°C. High temperature activity is generally restricted to the crests of large mounds that rise out of the flat-lying basin sediments. The chemistry of the hydrothermal waters is distinctly different from that characteristic of sediment-starved, open ocean ridge axes in that the solutions are alkaline, contain ammonium as a major ion and are strongly depleted in the “ore-forming” metals. These compositions are interpreted as the result of reaction of a primary solution, similar in composition to those as 21°N, EPR, with the biogenous sediments overlying the intrusion zone. The pH of this fluid is raised both by the dissolution of carbonate and the addition of ammonium from thermocatalytic cracking of immature planktonic carbon. Metal sulfides are consequently precipitated at depth in the sediment column. The Guaymas Basin is thus the site of active formation of a sediment-hosted massive sulfide mineral deposit; the exiting waters are the “spent” ore-forming fluid. The ammonium data demonstrate that organic carbon (black shale) is, by itself, a sufficient source of alkalinity to induce the precipitation of sulfides from ascending solutions. Since ammonium does not participate directly in these reactions but does form secondary aluminosilicate minerals these latter should constitute a valuable exploration tool in the search for shale hosted deposits.

The Trace Element Geochemistry of Marine Biogenic Particulate Matter.

Abstract Plankton samples have been carefully collected from a variety of marine environments for major and trace-chemical analysis. The samples were collected and handled under the rigorous conditions necessary to prevent contamination of the trace elements. Immediately after collection, the samples were subjected to a series of physical and chemical leaching-decomposition experiments designed to identify the major and trace element composition of the biogenic particulate matter. Emphasis was placed on the determination of the trace element/major element ratios in the various biogenic phases important in biogeochemical cycling. The majority of the trace elements in the samples were directly associated with the non-skeletal organic phases of the plankton. These associations include a very labile fraction which was rapidly released into seawater immediately after collection and a more refractory component which involved specific metal-organic binding. Calcium carbonate and opal were not significant carriers for any of the trace elements studied. A refractory phase containing aluminum and iron in terrigenous ratios was present in all samples, even from remote pelagic environments. This non-biogenic carrier contributed insignificant amounts to the other trace elements studied. The plankton samples were collected from surface waters with a wide range in the dissolved trace element/nutrient ratios, however, the same elemental ratios in the bulk plankton samples were relatively constant in all these environments. The bulk compositions and the rapid release of the metals and nutrient elements (specifically phosphorus) from the plankton after collection were used to examine the systematics of depletions of the dissolved elements from surface waters. These elemental ratios were combined with known fluxes of the major biogenic materials to estimate the significance of the plankton in the vertical flux of the trace elements. In parallel with the major surface ocean cycles of carbon and nitrogen, significant fractions of the trace elements taken up by primary producers must be rapidly regenerated in order to explain the observed elemental compositions and fluxes.

On the chemical mass-balance in estuaries

Abstract A general model is presented for mixing processes between river and ocean water in which are established criteria for the identification of any non-conservative behavior of the dissolved constituents involved. A review of previous data shows that in no case has removal of silica been demonstrated unambiguously in estuarine regimes. New data for iron which show highly non-conservative behavior are used in an example of the application of the model.