Early diagenesis in sediments from the eastern equatorial Pacific,I. Pore water nutrient and carbonate results

Interstitial waters were extracted from cores at three locations in the eastern equatorial Pacific and analyzed for nutrients, dissolved carbonate species, Mn and Fe. From the depth variation in pore water chemistry, we infer that organic matter oxidation reactions occur with depth in the following sequence: O₂ reduction, NO₃^? and MnO₂ reduction, and then ferric iron reduction. From NO₃^? results we infer that O₂ is largely or totally consumed within the top few centimeters of sediment. NO₃^? is completely reduced at a sediment depth of 20 cm at a site near the crest of the East Pacific Rise, but is preserved at levels of 20–30 μmol/kg at 40 cm depth at a Guatemala Basin site.We have calculated the alkalinity for pore water samples assuming ions diffuse according to relative ionic diffusion coefficients, that the stoichiometry of organic matter oxidation reactions is that of “Redfield” organic matter, and that the pore waters are saturated throughout with respect to CaCO₃. The measured alkalinity increase is only about half of the predicted value. The difference is probably a result of either enhanced mixing of the pore water in the top few centimeters of sediments by biological or physical processes, or the occurrence of an inorganic reaction which consumes alkalinity.At depths of oxygen and nitrate reduction in the sediments, the ion concentration product of CaCO₃ is the same, within the analytical error, as the solubility product of Ingle et al. [34] at 1 atm and 4°C. This result indicates CaCO₃ resaturation on pressure change during coring. Where pore water Mn concentrations become measurable, the ion concentration product increases, indicating either supersaturation with respect to calcite or that another phase is controlling the carbonate solubility.     

Formation of Fe-oxyhydroxides from the East Pacific Rise near latitude 13°N: Evidence from mineralogical and geochemical data

The mineralogical and geochemical characteristics of Fe-oxyhydroxide samples from one dredge station (long. 103°54.48′W, lat. 12°42.30′N, water depth 2655 m) on the East Pacific Rise near lat 13°N were analyzed by XRD, ICP-AES, and ICP-MS. Most Fe-oxyhydroxides are amorphous, with a few sphalerite microlites. In comparison with Fe-oxyhydroxides from other fields, the variable ranges in the chemical composition of Fe-oxyhydroxide samples are very narrow; their Fe, Si, and Mn contents were 39.90%, 8.92%, and 1.59%, respectively; they have high Cu (0.88%–1.85%) and Co (65×10⁻⁶−704×10⁻⁶) contents, and contain Co+Cu+Zn+Ni> 1.01%. The trace-element (As, Co, Ni, Cu, Zn, Ba, Sr) and major-element (Fe, Ca, Al, Mg) contents of these samples are in the range of hydrothermal sulfide from the East Pacific Rise near 13°N, reflecting that this type of Fe-oxyhydroxide constitutes a secondary oxidation product of hydrothermal sulfide. The Fe-oxyhydroxide samples from one dredge station on the East Pacific Rise near 13°N are lower in ΣREE (5.44×10⁻⁶–17.01×10⁻⁶), with a distinct negative Ce anomaly (0.12–0.28). The Fe-oxyhydroxide samples have similar chondrite-normalized rare-earth-element (REE) patterns to that of seawater, and they are very different from the REE composition characteristics of hydrothermal plume particles and hydrothermal fluids, showing that the REEs of Fe-oxyhydroxide are a major constituent of seawater and that the Fe-oxyhydroxides can become a sink of REE from seawater. The quick settling of hydrothermal plume particles resulted in the lower REE content and higher Mn content of these Fe-oxyhydroxides, which are captured in part of the V and P from seawater by adsorption. The Fe-oxyhydroxides from one dredge station on the East Pacific Rise near 13°N were formed by secondary oxidation in a low temperature, oxygenated environment. In comparison with the elemental (Zn, Cd, Pb, Fe, Co, Cu) average content of hydrothermal sulfide samples from the East Pacific Rise near 13°N, the Zn, Cd, and Pb contents of the Fe-oxyhydroxides are lower, and their Fe, Co, and Cu contents are higher. Supported in part by the Pilot Project of Knowledge Innovation Project, Chinese Academy of Sciences (Grant No. KZCX3-SW-223), and the Special Foundation for the Tenth Five Plan of COMRA (Grant No. DY105-01-03-1)     

Phosphate removal from sea water by adsorption on volcanogenic ferric oxides

Chemical data presented in this paper indicate a good correlation between P₂O₅ and Fe₂O₃ in some iron-rich volcanogenic sediments from the East Pacific Rise. In addition, adsorption experiments and chemical analyses of deuterically altered and unaltered samples of submarine basalts strongly suggest that this association is due to the reaction of phosphate in sea water with poorly crystallized hydrous ferric oxides. East Pacific Rise sediments adsorb far greater amounts of phosphate from sea water than either carbonate or non-carbonate sediments from other areas of the ocean. From geochemical flux calculations it is concluded that an appreciable proportion of dissolved phosphate delivered to the oceans by rivers is removed by ridge crest volcanogenic iron oxides either as absorbed surface coatings or as discrete, but highly disordered, ferric phosphate phases. This process should be taken into consideration when considering oceanic phosphate budgets, both in the present and past oceans.     

Origin of metalliferous sediments from the East Pacific Rise

The distribution of several metals in East Pacific Rise sediments, when normalized to Al₂O₃, exhibit stronger maxima near the rise crest than when simply plotted on a carbonate-free basis. The similarity (1) between the distribution of metals in ridge sediments and previously measured mean heat flow values and (2) between the composition of crestal sediments and terrestrial ore bodies associated with greenstone belts, strongly supports a hydrothermal origin for rise crest sediments.     

Metallogenesis in the southeastern Pacific: A progress report on the IDOE Nazca Plate project

Under the auspices of the International Decade of Ocean Exploration, scientists from Oregon State University and the Hawaii Institute of Geophysics, along with representatives from the several South American countries which border the Nazca Plate, are intensively studying the origin and economic importance of metalliferous sediments which form extensive deposits on and near the East Pacific Rise. The sediments, enriched in iron, manganese, copper, nickel, zinc, silver, molybdenum, and lead are mineralogically and chemically similar to deposits cored by the “Glomar Challenger”, implying a common origin. The metalliferous sediments are especially abundant in an extensive basin, the Bauer Deep, which occurs about 800 km east of the East Pacific Rise. Elemental and isotopic data, supported by geologic information provided by cores and by geophysical instrumentation, suggest that the enriched elements in the sediments originate by the interplay of volcanism and sea water, by precipitation from sea water alone, and perhaps by the influence of deep-ocean physical processes acting on detritus transported from the continents or from the basaltic East Pacific Rise.An additional objective of the project is to define the possible relationship between marine metalliferous sediments of the plate to ore deposits of the Andean Cordillera. As pointed out by several writers, much of the earth's economic mineralization occurs along zones of convergence between subducted oceanic crust, including metalliferous sediments if present, and continental margins. Field and geochemical techniques are being applied to determine if sediments are in fact subducted beneath the Andean margin, and if they are remobilized into the continental ore deposits of the Andes. Isotopic tracers may prove most useful in testing this relation. Before the model can be tested rigorously, one must know not only the important chemical parameters of the ocean sediment that may be subducted, but also those of the pertinent rock and ore bodies of the South American Cordillera.     

Iron-rich metalliferous sediments on the East Pacific Rise: prototype of undifferentiated metalliferous sediments on divergent plate boundaries

Sediments in a zone on the East Pacific Rise with an especially high spreading rate were studied chemically, mineralogically, and microscopically. They consist of a mixture of metalliferous sediments and plankton tests. The metalliferous sediments were formed by an acidic, hydrothermal leaching of tholeiitic basalt with seawater and subsequent precipitation in contact with cold near-bottom seawater. We assume the precipitation from hydrothermal solutions in this part of the East Pacific rise to be undifferentiated due to the high spreading rate and the resulting rapid flow on the water through the basalt. Thus, these metalliferous sediments are an initial stage type that have not undergone differentiation.Mn, Mo, La, Cu, V, Ni, Fe, Zn, Co, and Y, all of which are leachable in acidic, hydrothermal solutions, are enriched in the metalliferous sediments in comparison to the tholeiitic basalts.Zr, Al, and Ti, on the other hand, which under the same conditions are not easily leached, are reduced in their concentrations.All components of the metalliferous sediments precipitated as hydroxides or as adsorbed ions on the hydroxides of other elements. This is due to the oxidizing conditions in the near-bottom seawater. The sedimentation rate is high; the almost 3-m-long cores reach only to the Late Pleistocene. The only distinctly observable diagenetic process for this period of time is the formation of goethite from amorphous iron oxides.Only for Na, K, and Rb does it seem possible that a distinct enrichment in the sediments by adsorption from the seawater could have taken place.Ca, Sr, Pb, and perhaps Sc, are primarily bound to the planktonic carbonate part of the sediments.     

Geochemical baselines of major, minor and trace elements in the tropical sediments of the Terengganu River basin, Malaysia

The geochemical baselines and distribution of 31 elements (Al, Fe, K, Na, Mg, Ca, Mn, Ba, Cr, Zr, Ni, Sr, Zn, Y, Li, Cu, Mo, Nb, Th, Co, Ga, W, Ta, Be, Ti, Ge, Se, Bi, Te, Sc and Re) and physico-chemical parameters of the tropical surface sediments of the Terengganu River basin, Malaysia, are reported. Sediments are sandy loam to sand in texture consisting of mostly quartz, low organic matter content (average-2.68%), low CEC (average-2.02 cmol(+)/kg) and mildly acidic pH1:5 (average-5.91). Concentrations of Mn, Fe, Ba, Cr, Ni, Cu, Mo and Se were measured to be above the environmental sediment quality criteria at various locations. Lake sediments registered significantly higher Al, Fe, Ti, Mg, Ca, Mn, Te and Sc concentrations as compared to the river sediments. Most of the elements investigated showed an association with silt size fraction (2-63 μm). Among the investigated metals, Mo and Fe concentrations showed an increasing (5-fold) and decreasing (3-fold) trend, respectively, along the river path from the upstream to the downstream depending on the stream pH-redox conditions. The enrichment factor values (EF 5) of Cr, Ni, Mo and Se indicated enrichment from anthropogenic activities. Alkali and alkali earth metals registered a significant depletion (EF values 0.7) as compared to the Earth's crust. Principal component analysis of the two main components (PC1, 87.4% and PC2, 8.7%) revealed a well-defined group of estuary sediments. Lake and river sediment sampling locations did not form defined groups revealing heterogeneity in the origin of geologic material and the in-stream geochemical processes. However, Cr, Ni, Mo and Se formed a separate group with elevated concentrations (e.g. Cr1,000 mg/kg) indicating contamination of sediments. This work presents the geochemical baselines of the tropical sediments as industrial development and urbanization along the north east coast of Peninsular Malaysia are advancing rapidly.     

Metal concentrations in water and sediments from tourist beaches of Acapulco, Mexico

A survey on the metal concentrations (As, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V, Zn) in beach water and sediments is reported from the tourist destination of Acapulco city on the Pacific coast of Mexico. The concentration of dissolved trace metals (DTMs) in beach water and acid leachable trace metals (ALTMs) in sediments indicated that they are anthropogenic in nature due to the increased tourist activities in the crowded beach locations. The statistical analysis indicates Fe and Mn play a major role as metal scavengers in both the medium (water and sediment) and the higher value of other metals is site specific in the study area, indicating that they are transported from the local area. Comparison results suggest that the beach water quality has deteriorated more than the sediments and special care needs to be taken to restore the beach quality.     

Metal accumulation rates in the Southeast Pacific and the origin of metalliferous sediments

Metal accumulation rates over the East Pacific Rise and Bauer Deep rule out normal authigenic precipitation of iron and manganese as the major mechanism of enrichment to the metalliferous sediments. A hydrothermal source located along the East Pacific Rise is compatible with the transition metal and aluminum accumulation rates. For the Bauer Deep the accumulation rate data suggest either that metal-bearing phases are being transported from the rise to the protected basins of the deep or that a second hydrothermal source exists within the Bauer Deep. A major portion of the minor elements being deposited in the Bauer Deep could result from authigenic precipitation, thus accounting for their distinctive chemical composition.     

Manganese in the North Pacific

A quantitative and precise method for determination of dissolved Mn at the nanomole(nmol)/kg level in seawater has been developed and used to study the distribution of Mn in the northeast Pacific. Mn concentrations in the surface mixed layer decrease from 1.0 to 0.6 nmol/kg between the central gyre and the western boundary of the California Current, then increase to values from 2 to 6 nmol/kg near the coastal boundary (in contrast to the distribution of²¹⁰Pb). Particulate Mn in the surface waters accounts for only about 1% of the total.Vertical distributions of Mn are characterized by surface maxima, minima near 300 m, maxima at mid-depth coinciding with the oxygen minimum and the labile nutrient maxima, and concentrations in Pacific bottom waters of approximately 0.2 nmol/kg. The oceanic distribution of Mn appears to be dominated by external inputs superimposed upon overall scavenging which can lead to Mn maxima in (1) the surface waters due to riverine and atmospheric sources; (2) the deep ocean as a result of hydrothermal injection and/or sediment resuspension; and (3) the oxygen minimum region resulting from in-situ breakdown of organic matter, in-situ MnO₂ reduction, and/or advective-diffusive transport of dissolved Mn from anoxic slope sediments.     

Speciation of heavy metals on suspended sediment under high flow conditions in the River Aire,West Yorkshire,UK

Concentrations of heavy metals (Cd, Cu, Pb and Zn) on suspended sediments during a flood event at Thwaite Mills, River Aire, were analysed using a five step sequential extraction technique to determine their major chemical associations (exchangeable, surface oxide and carbonate, Fe and Mn oxides, organic and residual metal ions). Total metal concentrations were lowest at higher discharges, resulting from dilution by clean sediment. The major transport fractions are the Fe and Mn oxides, which carry 29% of the total metals. Knowledge of the chemical forms of heavy metals on suspended sediment is essential for estimating their biological availability and physicochemical reactivity. © 1998 John Wiley & Sons, Ltd.     

Dynamics of microelement concentrations in bottom sediments of the marginal filter (Razdol’naya R.–Amur Bay)—Result of biogeochemical processes

Atomic-emission spectroscopy was used to determine the concentrations of Be, Ga, Nb, Ta, Y, Zr, Hf, Sc, Mo, U, and Th in subcolloidal, medium-pelite, coarse-pelite, fine-aleurite, and coarse-aleurite fractions of bottom sediments of Razdol’naya R. marginal filter. The concentrations of examined elements are maximal for the subcolloidal sediment fraction. The average concentration (n = 10) of elements in the soil and fluvial sediments (upstream of the mixing zone) were calculated and taken as background concentrations. The highest concentrations of Y, Be, U was shown to correspond to sediments in the zone of fresh and sea water mixing, which is accompanied by flocculation and sorption on Fe and Mn hydroxides and clay minerals (hydromica in fluvial sediments, and smectite in marine sediments).     

Chemistry of solutions from the 13°N East Pacific Rise hydrothermal site

Ten samples were recovered by the submersible “Cyana” submersible from two groups of hydrothermal vents located 2600 m deep along the East Pacific Rise at 13°N. The maximum measured temperature was 317°C and minimum pH 3.8. A systematic determination of major and trace elements has been carried out and mixing lines between a high-temperature component (HTC) and seawater are observed. The water chemistry of the HTC slightly differs for several elements at the two sites. This HTC is deprived of SO₄ and Mg and is greatly enriched in most other species. Maximum concentrations are (in units per kg):Cl = 0.72mol; Br = 1.1mmol; Na = 0.55mol; K = 29mmol; Rb = 14 μmol; Ca = 52mmol; Sr = 170 μmol; Mn = 750 μmol; Fe = 1mmol; Al = 15 μmol; Si = 21mmol. For many elements, the magnitude of the anomaly relative to seawater does not compare with the results obtained from the Galapagos or East Pacific Rise 21°N. The enrichment of cations relative to seawater is likely related to the huge Cl excess through charge balance. TheBr/Cl ratio is close to that for seawater. However, it is not clear whether the Cl excess is due to gas release or basalt hydration (formation of amphibole chlorite or epidote).P-T dependence of SiO₂ solubility suggests that water-rock interaction last occurred at a depth in excess of 1 km below the sea floor. A mixing line of⁸⁷Sr/⁸⁶Sr vs. Mg/Sr demonstrates that the HTCs have a nearly identical⁸⁷Sr/⁸⁶Sr ratio of 0.7041 for both sites. A water/rock ratio of about 5 is inferred, which differs from the 1.5 value obtained at 21°N.     

Grain-size distribution,morphoscopy and elemental chemistry of suspended sediments of Pindari Glacier,Kumaon Himalaya,India

Abstract

Suspended sediment concentrations in the meltwater of Pindari Glacier were determined at regular intervals in four ablation seasons. The late ablation periods (September 1994 and October 1995) were characterized by a reduced level of sediment concentration, while the sampling periods of early ablation (May 1994 and July 1995) showed very high concentrations of suspended sediment in the meltwater. Grain size distribution shows the dominance of medium and coarse silt fractions of the mean size of the suspended sediments between 4.35 and 5.82 ø. Clay size constitutes about 7% of the total size population. The majority of the samples are poorly sorted, symmetrically to finely skewed and mesokurtic in nature. The grain shows texture of mechanical and chemical origin, in which mechanical texture is predominant on most of the grains. It was observed that the grains were mostly subangular to subrounded in shape with variable size ranges. Bulk sediment chemistry consists mostly (>70%) of the five elements, Si, Al, K, Fe and Mg. Iron (Fe) and Mn are dominant heavy metals and sediments show the elemental abundance in the order of Fe > Mn > Zn > Cu > Ni > Pb. The Chemical Index of Alteration (CIA) of suspended sediments (57) is relatively higher than in the case of average unweathered upper continental crust (~50) indicating a higher degree of weathering due to glacier grinding and crushing action. Quartz is the most dominant mineral, followed by mica, illite, feldspar and kaolinite.     

Cyprus umbers: Chemical precipitates on a Tethyan ocean ridge

Iron-rich mudstones (umbers), directly overlying pillow lavas of the Troodos Massif, Cyprus, are interpreted as precipitates connected with late stages of volcanism on a Cretaceous ocean ridge. Chemical composition of the basal sediments allies them with the basal iron-rich sediments of the East Pacific Rise. Overlying radiolarites and chalks are more comparable to normal pelagic sediments. Sedimentary features and stratigraphic relations suggest rapid deposition of umbers, relative to the overlying sediments.     

Topography and evolution of the East Pacific Rise between 5°S and 20°S

In the absence of convincing magnetic anomaly information, topographic profiles have been used to infer the tectonic history of the East Pacific Rise between 5°S and 20°S. Profiles projected at right angles to the rise crest show a sharp drop in elevation at roughly the same distance on either side of the crest. Profiles to the east of the rise also show a second topographic high at 95°W. Comparison of these profiles with empirical depth versus age curves for the North Pacific suggests that this rise, the Galapagos Rise, is the fossil East Pacific Rise which terminated close to 6 mybp by the spreading center jumping 900 km to the west. The extreme youthfulness of the present East Pacific Rise, the step structure of its flanks, and the similarity in age of the top of this step and the crest of the Galapagos Rise substantiate this interpretation. This jump coincided with a similar readjustment involving the Mathematicians ridge at 5° to 20°N and the opening of the Gulf of California.     

Effects of reservoir stratification and watershed hydrology on manganese and iron in a dam‐regulated river

The presence of metals, including manganese (Mn) and iron (Fe), adversely impacts water quality. In seasonally stratified reservoirs, Mn and Fe can accumulate in the water column due to reducing conditions in sediments and be released to downstream rivers through dam discharge. In addition to reservoir stratification influences, the release of metals downstream is influenced by hydrologic conditions in the river. We examined the seasonal and spatial variability of Mn and Fe concentrations in a eutrophic, hydropower reservoir and the downstream river over a two‐year period. Overall, we found that reservoir stratification was a strong predictor of tailrace Mn and Fe concentrations but that tailrace Fe concentrations were also influenced by dam discharge. Downgradient of the tailrace, river discharge and suspended sediment were the dominant predictors of both Mn and Fe concentrations. Using our data, we develop a conceptual model of seasonal and hydrologic drivers of metal concentrations. The model can be modified for other systems aiding drinking water utilities and other water users in forecasting under what seasonal and hydrologic conditions that Mn and Fe concentrations in river systems are likely to be elevated.     

Bacterial contribution to mitigation of iron and manganese in mangrove sediments

The Mandovi and Chapora are two tropical estuaries lying in close geographic proximity on the west coast of India. Seasonal changes in down core variation of Fe, Mn and Total Organic Carbon (TOC) in the mangrove sediments adjoining these estuaries were studied to assess their influence on some of the representative benthic bacteria belonging to heterotrophic and autotrophic groups. Heterotrophic bacteria (HB) cultured on different nutrient concentrations (0.01%, 0.1% and 25%) together with nitrifiers (NtB; representating autotroph) were chosen to assess the influence of the above-mentioned abiotic parameters on the former. The experimental site located along the Mandovi is under the influence of extensive ferromanganese ore mining, while the control site at Chapora is relatively free from such influences. Geoaccumulation index computed for Mandovi showed that sediments (0-10cm) were 'uncontaminated to moderately contaminated' by Fe during the pre monsoon and monsoon seasons, while in the post monsoon season the 4-10cm fraction was almost completely restored from contamination. Similar computations for Mn showed that in pre monsoon, sediments fell in the 'moderately contaminated' and 'moderately to strongly contaminated' categories, while in the monsoon and post monsoon seasons all the sections were 'Uncontaminated'. The difference observed in correlation between Fe and Mn with the various fractions of heterotrophs and nitrifiers indicated that though these two elements shared a similar chemistry in the environment, microbes involved in biogeochemical processes might prefer them differentially. The relationship between TOC and HB enumerated on 0.01% dilute nutrient agar remained at r=0.50, p<0.05 throughout the year. Hence, it could be apparently linked to their preferred concentration of organic carbon requirement. A relationship of r=0.61, p<0.01 between manganese concentration and heterotrophs recovered on different strengths of nutrient agar is suggestive of their response to the metal enrichment. They could thus contribute towards maintaining the level of Mn at par with reference levels at Chapora. A positive correlation between Mn with NtB (n=10, p<0.05, r=0.58) at the experimental site during the non-monsoon months is suggestive of the latter's contribution to regulation of the metal concentration in the sediment probably through anaerobic nitrification at the expense of manganese. The study therefore supports our hypothesis that both autochthonous autotrophs and heterotrophs work in tandem to mitigate concentration of Mn and related metals in mangrove sediments.     

Noble gases in submarine pillow volcanic glasses

Fifteen submarine glasses from the East Pacific Rise (CYAMEX), the Kyushu-Palau Ridge (DSDP Leg 59) and the Nauru Basin (DSDP Leg 61) were analysed for noble gas contents and isotopic ratios. Both the East Pacific Rise and Kyushu-Palau Ridge samples showed Ne excess relative to Ar and a monotonic decrease from Xe to Ar when compared with air noble gas abundance. This characteristic noble gas abundance pattern (type 2, classified by Ozima and Alexander) is interpreted to be due to a two-stage degassing from a noble gas reservoir with originally atmospheric abundance. In the Kyushu-Palau Ridge sample, noble gases are nearly ten times more abundant than in the East Pacific Rise samples. This may be attributed to an oceanic crust contamination in the former mantle source.There is no correlation between the He content and that of the other noble gas in the CYAMEX samples. This suggests that He was derived from a larger region, independent from the other noble gases.Except where radiogenic isotopes are involved, all other noble gas isotopic ratios were indistinguishable from air noble gas isotopic ratios. The³He/⁴He in the East Pacific Rise shows a remarkably uniform ratio of (1.21±0.07)×10^?5, while the⁴⁰Ar/³⁶Ar ranges from 700 to 5600.