Christopher I. Measures

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.

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 role of atmospheric deposition in the biogeochemistry of the Mediterranean Sea

Abstract Estimates of atmospheric inputs to the Mediterranean and some coastal areas are reviewed, and uncertainities in these estimates considered. Both the magnitude and the mineralogical composition of atmospheric dust inputs indicate that eolian deposition is an important (50%) or even dominant (>80%) contribution to sediments in the offshore waters of the entire Mediterranean basin. Model data for trace metals and nutrients indicate that the atmosphere delivers more than half the lead and nitrogen, one-third of total phosphorus, and 10% of the zinc entering the entire basin. Measured data in sub-basins, such as the north-western Mediterranean and northern Adriatic indicate an even greater proportions of atmospheric versus riverine inputs. When dissolved fluxes are compared (the form most likely to impinge on surface water biogeochemical cycles), the atmosphere is found to be 5 to 50 times more important than rivers for dissolved zinc and 15 to 30 times more important for lead fluxes. Neglecting co-limitation by other nutrients, new production supported by atmospheric nitrogen deposition ranges from 2–4 g C m−2 yr−1, whereas atmospheric phosphorus deposition appears to support less than 1 g C m−2 yr−1. In spite of the apparently small contribution of atmospheric deposition to overall production in the basin it has been suggested that certain episodic phytoplankton blooms are triggered by atmospheric deposition of N, P or Fe. Future studies are needed to clarify the extent and causal links between these episodic blooms and atmospheric/oceanographic forcing functions. A scientific program aimed at elucidating the possible biogeochemical effects of Saharan outbreaks in the Mediterranean through direct sampling of the ocean and atmosphere before and after such events is therefore highly recommended.

THE FLUVIAL GEOCHEMISTRY AND DENUDATION RATE OF THE GUAYANA SHIELD IN VENEZUELA, COLOMBIA, AND BRAZIL

Abstract The Guayana Shield is composed of Early to Mid-Precambrian igneous and metamorphic basement rocks with a quartzitic platform cover. The complete absence of limestones and evaporites allows a clear chemical expression in the stream data of the primary weathering of the basement in a humid tropical environment. Total erosion rates are extremely slow, ∼10 m/m.y., with equal contributions from the dissolved and suspended loads. However, the former is largely silica with ratios of Si to total cation equivalents [Si:TZ+] ranging to in excess of three. Weathering is “complete” to kaolinite and gibbsite, i.e., the environment is one of active laterisation with a penetration rate of the weathering front into the fresh substrate about twice the denudation rate. In basins of relatively homogeneous lithology, Rb/Sr isochrons constructed from the river data agree with the whole-rock ages from the drainages; thus, all the common, refractory, Rb-containing minerals (K-feldspar, mica) are completely dissolved. The thick, lateritic regolith that is accumulating as a result of this intense weathering is a common relict feature on other Southern Hemisphere Shields. In the absence of active tectonics or greatly accelerated mechanical erosion, the weathering rates of these basement rocks must be quite insensitive to environmental change.

On the formation of metal-rich deposits at ridge crests

Data from the hot springs at the Galapagos spreading center (T = 3–13°C) show depletions of the exiting waters in Cu, Ni, Cd, Se, Cr and U relative to ambient seawater. Manganese is strongly enriched. Iron shows highly variable behavior between vent fields but is in general low. The data confirm the occurrence of extensive subsurface mixing between the primary high-temperature, acid, reducing hydrothermal fluids and “groundwater”. The composition of the latter is indistinguishable from that of the free water column adjacent to the ridge axis. The final solutions are on the boundary between those forming MnO2 crusts and those producing iron-manganese rich sediments. The suite of metal rich deposits observed at ridge crests — Mn-O, Fe-Mn-O, Fe-S — can be explained as the manifestation of the degree of subsurface mixing, decreasing from 100 : <1 to <1 : 1 across the series (assuming an end-member temperature of 350°C).

Developing standards for dissolved iron in seawater

In nearly a dozen open- ocean fertilization experiments conducted by more than 100 researchers from nearly 20 countries, adding iron at the sea surface has led to distinct increases in photosynthesis rates and biomass. These experiments confirmed the hypothesis proposed by the late John Martin [Martin, 1990] that dissolved iron concentration is a key variable that controls phytoplankton processes in ocean surface waters. However, the measurement of dissolved iron concentration in seawater remains a difficult task [Bruland and Rue, 2001] with significant interlaboratory differences apparent at times. The availability of a seawater reference solution with well- known dissolved iron (Fe) concentrations similar to open- ocean values, which could be used for the calibration of equipment or other tasks, would greatly alleviate these problems [National Research Council (NRC), 2002]. The Sampling and Analysis of Fe (SAFe) cruise was staged from Honolulu, Hawaii, to San Diego, Calif., between 15 October and 8 November 2004 to collect data and samples that were later used to provide this reference material. Here we provide a brief report on the cruise results, which have produced a tenfold improvement in the variability of iron measurements, and announce the availability of the SAFe dissolved Fe in seawater standards.

Determination of iron in seawater by flow injection analysis using in-line preconcentration and spectrophotometric detection

A highly sensitive flow injection analysis (FIA) method for determining the concentration of iron in seawater has been developed. The technique is a modification of the catalytic batch method previously reported by Hirayama and Unohara. By optimising the chemistry for FIA and incorporating in-line preconcentration of the iron from seawater onto a column of resin-immobilised 8-hydroxyquinoline, the detection limit of the method has been reduced to 0.025 nM. The typical precision of the method for a 0.35 nM Fe sample is 2.5% (n = 6). The method has been used at sea in its preconcentration mode to determine iron in open ocean water samples from the equatorial Pacific and the North Atlantic. It has also been used in a direct injection mode for hydrothermal plume samples from around Loihi Seamount in the Central Pacific.

On the use of dissolved aluminum in surface waters to estimate dust deposition to the ocean

The concentration of dissolved Al in surface waters from various oceanic regimes is used in a simple model to calculate the annual amount of dust deposited to the surface ocean. Calculated values range from 0.015 to 9.9 g dust m−2 yr−1. Comparison of these calculated dust depositions with independent dust deposition estimates obtained from direct measurements, suspended atmospheric dust loads, or sediment traps show remarkably good agreement over approximately 3 orders of magnitude. In regions where the agreement between the model and other estimates is weakest, it is anticipated that local scaling of model parameters such as mixed layer depth and surface water residence time, will lead to improved agreement. Since surface water Al concentrations appear to be driven primarily by dust deposition, the distribution of dissolved Al in surface waters can be used to investigate the systematics of the delivery of other biologically important trace elements, for example, Fe, to the surface of the remote ocean by this route. In addition, temporal variations in surface water Al concentrations can be used to investigate the biogeochemical consequences to the surface ocean of large-scale changes in atmospheric dust loads driven by decadal-scale climatic variations.

Fluvial geochemistry of the eastern slope of the northeastern Andes and its foredeep in the drainage of the Orinoco in Colombia and Venezuela

Abstract The fluvial geochemistry of the tributaries of the Orinoco draining the eastern branch of the northern Andes in Colombia and Venezuela is determined by lithology and ranges from rivers dominated by aluminosilicate weathering, mainly of shales and mafic rocks, to those bearing the signatures of dissolution of marine limestones and evaporites and of continental playa deposits. These left bank tributaries of the Orinoco provide the overwhelming proportion of the suspended and dissolved loads transported by the main stem although feeding only half the discharge. However, due to the extreme severity of weathering on the Guayana Shield, the right bank tributaries supply about half the silica and 40% of the K carried by the Orinoco. There is a similar partitioning between the Andes and the lowlands in the Amazon drainage. In contrast the Mackenzie, which drains the northern extremity of the continental arc of the Western Americas, is completely dominated by the weathering of limestones and evaporites and transports very little silica. This, again, appears to be a reflection of lithology since the Yukon, in similar latitudes and terrain, has silica concentrations comparable to the Tropical systems. In addition, a conservative deconvolution of the data gives estimates of the net consumption of atmospheric CO 2 by aluminosilicate weathering that follows the same pattern. Thus, the available evidence from the Western Americas indicates that exposure and lithology, rather than the climatic variables, temperature, and runoff, dominate the weathering yields in active orogenic belts. These observations contradict the conventional view of weathering processes and their controls and are at complete variance with the assumptions parameterised in most models of the geochemical cycle.