Search results

Title: In situ chemical mapping of dissolved iron and manganese in hydrothermal plumes,
Description: Hydrothermal vents along mid-ocean ridges are an important source of elements such as lithium, silicon, manganese and iron to the world's oceans. The venting produces both episodic and steady-state hydrothermal plumes with unique thermochemical signatures in the mid-water column. The particulate phases in these plumes (predominantly iron oxides and hydroxides) also scavenge phosphorus, vanadium, arsenic, lead, polonium and several rare-earth elements from sea water. Thus, on a global scale, hydrothermal plumes are both a source for some elements and a sink for others. Ultimately, the particulate metals precipitated from plumes form extensive regions of metalliferous sediments over the crests and flanks of mid-ocean ridges. Although the metalliferous sediment coverage is vast and well documented, only a tiny fraction of the vents responsible for these sediments have been located (Fig. 1a). To date, both the number and location of hydrothermal vents and the detailed distribution of chemical constituents within the resultant plumes are poorly understood because of under-sampling of the mid-ocean ridges and the overlying waters. Here we present the results of high-resolution mapping of the chemical and thermal characteristics of hydrothermal plumes in near real time using a novel submersible chemical analyser (Scanner) and a conductivity/temperature/depth/transmissometer instrument package (CTDT). We show that the kinetics of iron oxidation in the plume can be used to constrain estimates of the plume's age, and that variation in the ratio of manganese content to excess heat can be explained by the mixing of several different vent fluids., Cited By (since 1996):31, CODEN: NATUA, ,
Author: Coale, Chin, Massoth, Johnson, Baker
Date: 1991-01-01T00:00:00Z

Title: Benthic manganese fluxes along the Oregon-California continental shelf and slope
Description: Here we examine the factors that influence the manganese (Mn) benthic flux from eastern North Pacific marine sediments, with a primary emphasis on continental shelf locations off Oregon and California and studies that involve the use of in situ benthic chambers. Typical shelf-to-shallow margin (<~350m) sites have benthic Mn efflux rates that average ~8±5μmolm-2d-1. In contrast, for the Eel River continental shelf region the benthic Mn efflux can be an order of magnitude higher than other shelf settings with benthic effluxes exceeding ~50μmolm-2d-1. Based on prior work and some new results, continental margin and slope sites (350-~4000m) have benthic Mn efflux rates that average ~1±1μmolm-2d-1. The combination of the benthic flux and Mn solid-phase data, indicate that for the continental shelf off the Umpqua and Eel Rivers, approximately 15±10% of the total Mn that is delivered to the seafloor is remobilized. The compiled data set shows that the benthic Mn efflux co-varies with the organic carbon oxidation rate with a Mn to organic carbon oxidation (Cox) ratio of ~0.8mmol Mn mol-1. Although this ratio can be as high as ~5 for some Eel River sites, the generally close correspondence between Mn and organic carbon implies that the organic carbon oxidation rate exerts some primary control over the rate of the Mn efflux. The amount of organic carbon oxidized by Mn-oxides, however, represents a small fraction (i.e., generally <1%) of the total organic carbon oxidized in these seafloor sediments. © 2012 Elsevier Ltd., Cited By (since 1996):5, Oceanography, CODEN: CSHRD
Author: McManus, Berelson, Severmann, Johnson, Hammond, Roy, Coale
Date: 2012-01-01T00:00:00Z

Title: Spectrophotometric determination of dissolved manganese in natural waters with 1-(2-pyridylazo)-2-naphthol: Application to analysis in situ in hydrothermal plumes,
Description: A spectrophotometric method using the complexing reagent 1-(2-pyridylazo)-2-naphthol (PAN) was developed for the determination of dissolved manganese in seawater. A detection limit of approximately 22 nM was obtained when the analyses were performed in situ with a submersible chemical analyzer (Scanner). Color formation was rapid (less than 1 s), which permitted the technique to be used in flow injection and continuous flow systems. An investigation of possible interferences revealed that the only significant interferent to manganese determinations in seawater (hydrothermal plumes) was iron. The iron-specific chelating agent desferrioxamine B was used to mask this interference. Temperature and pressure did not adversely affect the sensitivity of the technique, which made it amenable to applications in situ to depths of 3000 m. This method was tested by measuring dissolved manganese concentrations in situ in submarine hydrothermal plumes using a Scanner. Scanner deployments over the Juan de Fuca Ridge produced the first near real time analyses of manganese from a hydrothermal plume environment. Estuarine samples have also been successfully analyzed in the laboratory and the results confirmed by an independent method. © 1992., Cited By (since 1996):22, Oceanography, CODEN: MRCHB, ,
Author: Chin, Johnson, Coale
Date: 1992-01-01T00:00:00Z

Title: The behaviour of iron and other trace elements during the IronEx-I and PlumEx experiments in the Equatorial Pacific,
Description: Dissolved (< 0.4 μm) and particulate (0.4-5 μm and > 5 μm, leachable and refractory) trace elements were measured during the IronEx I and PlumEx experiments in October and November 1993 near the Galapagos Islands. Iron was measured in the enriched patch and at control stations over a 9 day period following fertilization. The dissolved iron was initially depleted at a rate that gave an iron half-life of 28-40 h. The loss rate gradually decreased, and dissolved iron concentrations did not decrease below about 0.25 nmol kg-1 throughout the experiment. These results were most consistent with a kinetic model that was second order in iron concentration for the scavenging removal of each iron fraction. Other trace elements measured did not change significantly either in concentration or partitioning during the IronEx I experiment. Biological production tracked iron concentrations over time, which suggests that productivity within the fertilized patch was regulated by the availability of iron. The PlumEx study consisted primarily of two transects, a meridional course to the east of the Galapagos Islands and a zonal section to the west. Surface dissolved iron was very low at all stations except those near the Galapagos Islands. Sections of trace metal and other properties distinctly confirm the upwelling of the Equatorial Undercurrent as it intersects the islands. This upwelling has a great effect on the surface distributions of the trace metals on the west side of the islands. Productivity within the mixed layer of this region is highly correlated with iron and nitrate. West of the islands highest productivity is found at stations with the highest iron. North of the Equatorial front, in nitrate-depleted waters, elevated iron concentrations do not enhance productivity., Cited By (since 1996):58, Oceanography, CODEN: DSROE, ,
Author: Gordon, Johnson, Coale
Date: 1998-01-01T00:00:00Z

Title: The flux of iron from continental shelf sediments,
Description: The flux of dissolved iron from sediments to the water column was measured with flux chambers along the California coast over a five-year period. High fluxes were observed from sediments on the continental shelf. The measured fluxes were an average of 75 times larger than flux values derived from pore-water iron gradients. The iron flux was significantly correlated with the oxidation of organic matter, which allows an extrapolation to the global shelf. The input from shelf sediments is at least as significant as the global input of dissolved iron from aerosols, which has been presumed to be the dominant external iron source. Evidence of this input is seen 100's of kilometers offshore where it can enable the high productivity of broad coastal regions seen in satellite images. Copyright 2004 by the American Geophysical Union., Cited By (since 1996):125, Oceanography, CODEN: GPRLA, ,
Author: Elrod, Berelson, Coale, Johnson
Date: 2004-01-01T00:00:00Z

Title: A time series of benthic flux measurements from Monterey Bay, CA,
Description: In situ incubation chamber measurements of benthic nutrient recycling rates were made on the Monterey Bay shelf at 100m during various years and seasons. Variability in nutrient (Si, PO 4 2+, NH 3, NO 3 -) and trace metal (Mn, Fe (II), Cu) fluxes correlate with variability in the amount of organic carbon oxidized on the sea floor. Patterns of primary productivity show a mid-year maxima, consistent with the timing of increased rates of benthic C org and opal recycling. High rates of C org rain to the shelf promote nitrate consumption at a rate that equals or exceeds ammonia efflux. Low rates of C org rain promote greater efflux of DIN; thus these margin sediments provide a negative feedback to local productivity cycles. The efflux of iron (II) from shelf sediments is sufficient to support > 100% of new production, yet Fe flux is positively correlated with C org recycling which lags the maximum in new production. On account of this time lag, diagenetically recycled Fe is not likely a micro-nutrient trigger of new production, but could serve as a positive feedback. Bio-irrigation rates are seasonally variable by 30% but maximal during the maximum productivity months. © 2003 Elsevier Science Ltd. All rights reserved., Cited By (since 1996):65, CODEN: CSHRD, , , Oceanography
Author: Berelson, McManus, Coale, Johnson, Burdige, Kilgore, Colodner, Chavez, Kudela, Boucher
Date: 2003-01-01T00:00:00Z

Title: Phosphorus regeneration in continental margin sediments,
Description: Benthic incubation chambers have been deployed in a variety of geochemical environments along the California Continental Margin. These include both high and low oxygen environments and sites where the rate of organic matter oxidation on the seafloor (Cox) ranges from < 1 mmol m-2 day-1 to more than 7 mmol m-2 day-1 through a depth range of 100-3500 m. This range in the rate of organic matter oxidation along with variations in the concentration of bottom water oxygen allow us to elucidate the diagenetic conditions under which P regeneration may be decoupled from organic matter cycling. Under conditions where bottom water oxygen concentration is low (<50 μM), and the rate of organic matter oxidation is also low (< 1 mmol m-2 day-1), P regeneration may be less than that expected from the decay of organic debris and, in some cases, there is a flux of phosphate into the sediments. At stations where bottom water oxygen is low, and the degradation rate of organic material is greater than 1 mmol m-2 day-1, phosphate may be released at a rate exceeding the production expected from the oxidation of organic matter. At stations having high bottom water oxygen concentrations, rates of organic matter decomposition < ∼7 mmol m-2 day-1, and where benthic irrigation is not significant, P regeneration is consistent with that expected from the decomposition of organic debris. In addition, our data indicate that high benthic iron fluxes are observed in regions exhibiting a decoupling between organic matter and phosphate, whereas low to zero iron fluxes are observed in regions where P regeneration is either consistent with or less than that expected from the decomposition of organic material. These results support previous work suggesting a coupling between iron cycling and phosphate cycling in suboxic environments. Data presented here show that this coupling may result in either preferential phosphate burial or release relative to organic material in suboxic environments. Copyright © 1997 Elsevier Science Ltd., Cited By (since 1996):105, ,
Author: Mcmanus, Berelson, Coale, Johnson, Kilgore
Date: 1997-01-01T00:00:00Z

Title: Determination of subnanomolar levels of iron(II) and total dissolved iron in seawater by flow injection analysis with chemiluminescence detection
Description: A highly sensitive technique for the rapid determination of Fe( I I) and total dlssolved iron in seawater has been developed. The technlque employs flow Injection analysis and chemiluminescence detectlon (FIA-CL). The light Is emitted by the reaction of brilliant sulfoflavin with hydrogen peroxlde and Fe( I I ) in a neutral medlum. A cation-exchange column Is used to preconcentrate the Iron from seawater. The detection limit was 0.45 nmol/L when 4.4 mL of sample was passed through the column. Lower detectlon llmlts are attainable wlth larger sample volumes. The relative standard deviation is 2-5% for concentrations greater than 2.5 nmd/L. A typical analysis can be performed In 5 mln. The technique was determlned to be accurate based on the analysis of the trace metal standard seawater solutions NASS and CASS. Shipboard analyses provided oceanographically consistent profiles for total iron and also revealed some of the first profiles for Fe(I1) in hydrothermal plume samples. A typical profile of 12 samples, together with blanks and standards, can be analyzed In triplicate in 4.5 h.
Author: Elrod, Johnson, Coale

Title: Iron deficiency and phytoplankton growth in the equatorial Pacific,
Description: Several experiments were conducted in the equatorial Pacific at 140°W during the Joint Global Ocean Flux Study, equatorial Pacific, 1992 Time-series I (TS-I, 23 March-9 April). Time-series II (TS-II, 2-20 October) and FeLINE II cruises (10 March-14 April), to investigate the effects of added Fe on phytoplankton communities. Seven series of deckboard iron-enrichment experiments were performed, with levels of added Fe ranging from 0.13 to 1000 nM. Time-course measurements included nutrients, chlorophyll a and HPLC pigments. Results of these experiments showed that subnanomolar (sub-nM) additions of Fe increased net community specific growth rates, with resultant chlorophyll a increases and nutrient decreases. Community growth rates followed Michaelis Menten type kinetics resulting in maximum rates of 0.99 doublings per day and a half-saturation constant of 0.12 nM iron. The dominant group responding to iron enrichment was diatoms., Cited By (since 1996):62, CODEN: DSROE, ,
Author: Fitzwater, Coale, Gordon, Johnson, Ondrusek
Date: 1996-01-01T00:00:00Z

Title: A time series of benthic flux measurements from Monterey Bay, CA,
Description: , , , In situ incubation chamber measurements of benthic nutrient recycling rates were made on the Monterey Bay shelf at 100 m during various years and seasons. Variability in nutrient (Si, PO42+, NH3, NO3−) and trace metal (Mn, Fe (II), Cu) fluxes correlate with variability in the amount of organic carbon oxidized on the sea floor. Patterns of primary productivity show a mid-year maxima, consistent with the timing of increased rates of benthic Corg and opal recycling. High rates of Corg rain to the shelf promote nitrate consumption at a rate that equals or exceeds ammonia efflux. Low rates of Corg rain promote greater efflux of DIN; thus these margin sediments provide a negative feedback to local productivity cycles. The efflux of iron (II) from shelf sediments is sufficient to support >100% of new production, yet Fe flux is positively correlated with Corg recycling which lags the maximum in new production. On account of this time lag, diagenetically recycled Fe is not likely a micro-nutrient trigger of new production, but could serve as a positive feedback. Bio-irrigation rates are seasonally variable by 30% but maximal during the maximum productivity months., ,
Author: Berelson, McManus, Coale, Johnson, Burdige, Kilgore, Colodner, Chavez, Kudela, Boucher
Date: 2003-01-01T00:00:00Z

Title: The flux of iron from continental shelf sediments: A missing source for global budgets
Description: The flux of dissolved iron from sediments to the water column was measured with flux chambers along the California coast over a five-year period. High fluxes were observed from sediments on the continental shelf. The measured fluxes were an average of 75 times larger than flux values derived from pore-water iron gradients. The iron flux was significantly correlated with the oxidation of organic matter, which allows an extrapolation to the global shelf. The input from shelf sediments is at least as significant as the global input of dissolved iron from aerosols, which has been presumed to be the dominant external iron source. Evidence of this input is seen 100’s of kilometers offshore where it can enable the high productivity of broad coastal regions seen in satellite images.
Author: Elrod, Berelson, Coale, Johnson

Title: Organic matter diagenesis in the sediments of the San Pedro Shelf along a transect affected by sewage effluent,
Description: A study was conducted to examine the rate of organic matter degradation within the sediments adjacent to the Whites Point Los Angeles County sewage outfall system on the San Pedro Shelf. Benthic chamber deployments were made at three stations in a transect away from the outfall pipe during three cruise periods (October 1990, February and October 1991). The fluxes of phosphate, silicate and radon-222 showed the most significant difference (factor of 3) between stations proximal and distal to the sewage effluent outfall pipe; the fluxes of nitrate, ammonia, alkalinity and TCO2 showed some gradient (a factor of 1.5-2) and the uptake of oxygen showed no variability between sites. Carbon oxidation in these sediments is driven primarily by net oxygen consumption and secondarily by net sulfate reduction. Net sulfate reduction accounts for about 30% of the carbon oxidation near the outfall pipe and 10-15% at the distal sites. Measurements of radon-222 fluxes and radon emanation rates from sediments indicate that the intensity of bio-irrigation is greater by a factor of 2 at sites away from the outfall pipe, but also shows that bio-irrigation does take place at the site adjacent to the pipe. The total amount of particulate organic carbon (POC) oxidized in the sediments around the outfall is ∼2 × 107 g C/d. An estimate of carbon burial in this region is 4 × 107 g C/d. The outfall system could supply ∼3 × 107 g C/d of which 12-20% is estimated to have been deposited in the region. Hence, effluent-derived POC, although it may be a part of the total organic carbon pool undergoing diagenesis and burial on the sea floor, is not likely the only source of carbon to this system. Primary productivity in the surface ocean could supply 9-13 × 107 g C/d to the sea floor. A balanced carbon budget requires that half the primary production is exported to the sea floor, although this budget does not account for other sources of POC to the region. © 2002 Elsevier Science Ltd. All rights reserved., Cited By (since 1996):13, CODEN: CSHRD, ,
Author: Berelson, Johnson, Coale, Li
Date: 2002-01-01T00:00:00Z

Title: Iron distributions in the equatorial Pacific: Implications for new production,
Description: Several recent studies have shown that phytoplankton growth rate and production at 0°, 140°W is physiologically limited by iron. Therefore, changes in iron supply to the euphotic zone will result in variations in phytoplankton growth. We show that the flux of iron to this region is dominated by upwelling of the iron-rich Equatorial Undercurrent waters. Variations in the depth and strength of upwelling and changes in iron concentrations at the base of the euphotic zone will account for variations in primary and new production in this region. We determined dissolved and particulate iron profiles for the upper water column of the eastern equatorial Pacific including a vertical section from 9°N to 3°S along 140°W. One of the more prominent features of the section was a peak in dissolved and particulate iron associated with the Equatorial Undercurrent. The possible lithogenic origin of this iron is substantiated by the vertical section of particulate aluminum and manganese, which is consistent with a shallow hydrothermal source in the western equatorial Pacific. A simple one-dimensional model was used to calculate iron fluxes into the euphotic zone at the equator. Upwelling rates and dissolved iron concentrations were coupled to estimate the upwelling iron flux at 120 m (0.1% light level). Diffusive and atmospheric inputs of iron were also considered but were less significant than the upwelling flux. Iron-based potential new production was estimated to be 10-82 mmol C m-2 d-1 with C: Fe ratios of 100,000500,000: 1. In a similar manner, nitrate-based potential new production was 99-106 mmol C m-2 d-1. This demonstrates that iron supply limits new production to only 9-83% of the nitrate-based potential., Cited By (since 1996):103, CODEN: LIOCA, , , Downloaded from: aslo.org/lo/toc/vol_42/issue_3/0419.pdf (9 June 2014).
Author: Gordon, Coale, Johnson
Date: 1997-01-01T00:00:00Z

Title: Oxidation kinetics of manganese (II) in sea water at nanomolar concentrations,
Description: Manganese oxidation rates were determined at low (∼20 nM) concentrations in seawater by measuring dissolved manganese (Mn(II)) using flow injection analysis with chemiluminescence detection. Mn(II) was measured in samples that had been filtered (0.2 μm) and kept in the dark under controlled temperature and pH conditions for time periods up to 6 months. Eight 9 L carboys with mean pH values ranging from 8 to 8.7 were held at 25°C, another carboy (pH = 9.32) was kept at 5°C. Oxidation followed the Morgan (1967) homogeneous rate equation (d[Mn(II)]/dt = k1 [O2][OH-]2 [Mn(II)]). The mean rate constant k1 = 1.7 ± 0.7 × 1012 M-3 d-1 (95% CI), determined using hydroxide ion activities determined with pH measurements on the NBS scale, was in agreement with work by Morgan (1967; k1 = 4 × 1012 M-3 d-1) and Davies and Morgan (1989; k1 = 1.1 × 1012 M-3 d-1) in dilute solutions. The rate constant at 5°C was 1.3 ± 0.3 × 1012 M-3 d-1. If free hydroxide concentrations (based on the free proton pH scale) are used, then the rate constant at 25°C was k*1 = 0.34 ± 0.14 × 1012 M-3 d-1. Autocatalytic increases in Mn(II) oxidation rates, as predicted by a heterogeneous reaction mechanism (Morgan, 1967) (d[Mn(II)]/dt = k′2[Mn(II)][MnO2]) were not observed, indicating that the homogeneous reaction dominates Mn(II) oxidation at low nM concentrations in seawater. Bacteria were enumerated by 4′,6-diamidino-2-phenylindole (DAPI) staining during the experiments. No significant correlation between bacterial concentrations and Mn(II) oxidation rates was found. Copyright © 1997 Elsevier Science Ltd., Cited By (since 1996):26, ,
Author: Von Langen, Johnson, Coale, Elrod
Date: 1997-01-01T00:00:00Z

Title: On the formation of the manganese maximum in the oxygen minimum,
Description: A simple model that accounts for the formation of the Mn maximum in the oxygen minimum is presented here. In this model, Mn is proposed to cycle in a constant proportion to carbon, as do nitrogen and phosphorous. Superimposed on the Mn-carbon cycle is the removal of Mn(II) via scavenging onto sinking particles and transport by vertical diffusion. Scavenging is assumed to follow the rate law observed in the laboratory for Mn(II) oxidation. Manganese (II) concentrations were calculated with the model at stations in the Pacific and Atlantic Oceans and compared with measurements of dissolved Mn. All parameters in the model were based on laboratory measurements or field observations. The model reproduced Mn(II) maxima of the correct concentration and at the correct depth. This agreement was observed at a range of oxygen concentrations. The calculations demonstrate that the Mn maximum can form because of a reduction in the pseudo-first order scavenging rate constant (k′) within the oxygen minimum. The value of k′ will decrease in regions of the water column with low oxygen and pH (k′ = k0 [O2] {OH-}2). These regions will accumulate higher dissolved Mn(II) concentrations before the rate of Mn(II) removal, k′ [Mn(II)], equals the input from remineralization of POC and a steady state is reached. An additional source of Mn, such as flux from continental margin sediments or dissolution of Mn oxides, is not necessary to account for formation of the Mn maximum., Cited By (since 1996):51, ,
Author: Johnson, Coale, Berelson, Gordon
Date: 1996-01-01T00:00:00Z

Title: Determination of zinc in seawater using flow injection analysis with fluorometric detection,
Description: A sensitive technique for the shipboard determination of zinc in seawater has been developed. The technique couples flow injection analysis with fluorometric detection (FIA-FL). A cation exchange column was used to separate zinc from interfering alkali and alkaline earth ions and to concentrate Zn from seawater. The organic indicator ligand, p-tosyl-8-aminoquinoline, was used to form a complex with zinc, the fluorescence of which was determined with a flow-through fluorometer. The detection limit (defined as three times the standard deviation of the blank, n = 4) was 0.1 nM for a 4.4-mL sample. The precision based on the replicate analysis of samples containing 4.3 nM Zn was ±6% (n = 5). A single sample can be analyzed in 6 min. The technique was determined to be accurate on the basis of analysis of the standard seawater solutions CASS-2 and N ASS-2 and by comparison with previous reliable investigations. A typical profile of 12 samples along with standards and blanks can be completed in triplicate in 5.5 h., Cited By (since 1996):31, CODEN: ANCHA, ,
Author: Nowicki, Johnson, Coale, Elrod, Lieberman
Date: 1994-01-01T00:00:00Z

Title: What controls dissolved iron concentrations in the world ocean?,
Description: Dissolved (<0.4 μm) iron has been measured in 354 samples at 30 stations in the North and South Pacific, Southern Ocean and North Atlantic by the Trace Metals Laboratory at Moss Landing Marine Laboratories. These stations are all more than 50 km from a continental margin. The global distribution of dissolved iron, which is derived from these profiles, is remarkable for several reasons. The dissolved iron profiles have a uniform shape with a nutrient-like profile at each station. Concentrations at the surface are all <0.2 nmol kg-1 and average 0.07 nmol kg-1. Below 500 m, the average concentration is 0.76 nmol kg-1. The largest value in the data set is 1.38 nmol kg-1. There is no inter-ocean fractionation, which is unique for an element with a nutrient-like profile. Published estimates of the iron residence time are on the order of 100 to 200 yr, indicative of rapid removal. Other elements with such short residence times are characterized by vertical profiles that decrease with depth and deep concentrations that decrease with age as water passes from the Atlantic to the Pacific. This is not the case for iron. The largest horizontal changes in dissolved iron are observed in gradients from the continental margin. There is only a factor of three difference between the minimum (0.4 nmol kg-1) and maximum (1.3 nmol kg-1) value in the data set at a depth near 750 m, where variability is at a maximum. The minimum concentrations are found at stations in the remote central Pacific and the maximum values occur at stations adjacent to the continental margin. The major source of iron in the deep sea is generally aeolian deposition. Integrated (surface to 500 m) concentrations of iron at each station are only weakly correlated with the aeolian iron deposition flux, however. This contrasts with other elements such as lead that also have strong atmospheric sources. These observations lead us to conclude that the nutrient-like profile is maintained by a mechanism that reduces the scavenging rate of dissolved iron at concentrations less than 0.6 nmol kg-1. This mechanism may be complexation by strong iron binding ligands, which have been found in both the Atlantic and Pacific at concentrations near 0.6 nM. This apparent solubility would act to diminish inter-ocean fractionation. It would allow a nutrient-like profile to develop before scavenging began to remove iron. In order to test the concept, we developed a numerical model to make quantitative predictions of dissolved iron concentrations from place to place. The dissolved iron source in the ocean interior is remineralization from sinking particulate organic matter. Scavenging removes dissolved iron only at concentrations greater than the apparent solubility. The only geographically variable parameter in the model is the export flux of carbon from the surface layer, which carries iron with it. The model generated dissolved iron profiles, based on measured or estimated values of the carbon export flux, are in remarkable agreement with the observed profiles at all stations from the North Atlantic through the Southern Ocean to the North Pacific., Cited By (since 1996):386, CODEN: MRCHB, Oceanography, , ,
Author: Johnson, Michael Gordon, Coale
Date: 1997-01-01T00:00:00Z

Title: Biogenic matter diagenesis on the sea floor,
Description: Benthic chamber measurements of the reactants and products involved with biogenic matter diagenesis (oxygen, ammonium, nitrate, silicate, phosphate, TCO2, alkalinity) were used to define fluxes of these solutes into and out of the sediments off southern and central California. Onshore to offshore transects indicate many similarities in benthic fluxes between these regions. The pattern of benthic organic carbon oxidation as a function of water depth, combined with published sediment trap records, suggest that the supply of organic carbon from vertical rain can just meet the sedimentary carbon oxidation + burial demand for the central California region between the depths 100-3500 m. However, there is not enough organic carbon raining through the upper water column to support its oxidation and burial in the basins off southern California. Lateral transport and focusing of refractory carbon within these basins is proposed to account for the carbon buried. The organic carbon burial efficiency is greater off southern California (40-60%) compared to central California (2-20%), even though carbon rain rates are comparable. Oxygen uptake rates are not sensitive to bottom water oxygen concentrations nor to the bulk wt. % organic carbon in surficial sediments. Nitrate uptake rates are well defined by the depth of oxygen penetration into the sediments and the overlying water column nitrate concentration. Nitrate uptake accounts for about 50% of the total denitrification taking place in shelf sediments and denitrification (0.1-1.0 mmolN/m2d) occurs throughout the entire study region. The ratio of carbon oxidized to opal dissolved on the sea floor is constant (0.8 ± 0.2) through a wide range of depths, supporting the hypothesis that opal dissolution kinetics may be dominated by a highly reactive phase. Sea floor carbonate dissolution is negligible within the oxygen minimum zone and reaches maximal rates just above and below this zone (0.2-2.0 mmol/m2d)., Cited By (since 1996):72, Oceanography, ,
Author: Berelson, McManus, Coale, Johnson, Kilgore, Burdige, Pilskaln
Date: 1996-01-01T00:00:00Z

Title: IronEx-I, an in situ iron-enrichment experiment,
Description: An in situ iron-enrichment experiment near the Galapagos Islands was performed in October 1993. Here we report the theoretical and practical considerations of creating such a patch of iron-enriched surface water, as well as the strategies employed for the detection of the patch and the biological and chemical signals which developed, in an area dominated by advective processes. Physical and chemical models were used to predict the speciation, solubility, and the final concentration of iron in surface waters injected with acidic iron sulfate. A trial injection off the California coast in which 800 L of a 0.5 M FeSO4 were introduced into the ship's wake over a 1.5 km2 area, was used to test these predictions. Iron concentrations were determined continually onboard during the initial experiment as the ship steamed in transects through the enriched patch. The results indicate excellent spatial agreement with model predictions and final concentrations that were consistent with the chemical model. However, the use of a Cartesian coordinate system during rejection resulted in an extremely compressed, heterogeneous patch. Results from this preliminary experiment were then applied towards the development and implementation of the first open ocean iron enrichment experiment (IronEx I) near the Galapagos Islands in October 1993. The development and results of these methodologies are presented. In the IronEx I equatorial experiment, a Lagrangian coordinate system was established using a drogued buoy (equipped with GPS and packet radio) and the iron-enriched area (64 km2 containing 443 kg of Fe) was tagged with the inert chemical tracer sulfurhexafluoride (SF6). This strategy resulted in a fairly rectangular, homogeneous enriched patch initially detectable by both Fe and SF6 determination. Shipboard analysis and airborne observations confirmed good spatial agreement between the Lagrangian drifter and the biological and chemical signatures in the patch. Biological and chemical sampling of the enriched area showed an increase in chlorophyll, primary production, biomass and photosynthetic energy conversion efficiency relative to waters outside the patch, supporting the hypothesis that iron limits phytoplankton growth and biomass in a 'bottom up' manner in this area. The ability to create a coherent patch and track it over time led to this first open-ocean test of the iron hypothesis., Cited By (since 1996):42, CODEN: DSROE, ,
Author: Coale, Johnson, Fitzwater, Blain, Stanton, Coley
Date: 1998-01-01T00:00:00Z

Title: Geochemistry of barium in marine sediments,
Description: Variations in the accumulation rate of barium in marine sediments are thought to be indicative of variations in marine biological productivity through time. However, the use of Ba as a proxy for paleoproductivity is partly dependent upon its being preserved in the sediment record in a predictable or consistent fashion. Arguments in favor of high Ba preservation are partly based on the assumption that sediment porewaters are generally at saturation with respect to pure barite. The idea is that because nondetrital sedimentary Ba predominantly exists as barite, porewater saturation would promote burial. We present sediment porewater, sediment solid phase, and benthic incubation chamber data suggesting that solid-phase Ba preservation may be compromised in some geochemical settings. We propose that under suboxic diagenetic conditions, characterized by low bottom water oxygen and high organic carbon respiration rates, Ba preservation may be reduced. Independent of the mechanism, if this assertion is true, then it becomes important to know when the Ba record is unreliable. We present evidence demonstrating that the sedimentary accumulation of authigenic U may serve as a proxy for when the Ba record is unreliable. We then provide an example from the Southern Ocean during the last glacial period where high authigenic U concentrations coincide with high Pa:Th ratios and high accumulation rates of biogenic opal, but we find low accumulation rates of sedimentary Ba. Thus, for the study sites presented here during the last glacial, we conclude that Ba is an unreliable productivity proxy., Cited By (since 1996):163, ,
Author: McManus, Berelson, Klinkhammer, Johnson, Coale, Anderson, Kumar, Burdige, Hammond, Brumsack, McCorkle, Rushdi
Date: 1998-01-01T00:00:00Z

Title: Southern Ocean Iron Enrichment Experiment,
Description: The availability of iron is known to exert a controlling influence on biological productivity in surface waters over large areas of the ocean and may have been an important factor in the variation of the concentration of atmospheric carbon dioxide over glacial cycles. The effect of iron in the Southern Ocean is particularly important because of its large area and abundant nitrate, yet iron-enhanced growth of phytoplankton may be differentially expressed between waters with high silicic acid in the south and low silicic acid in the north, where diatom growth may be limited by both silicic acid and iron. Two mesoscale experiments, designed to investigate the effects of iron enrichment in regions with high and low concentrations of silicic acid, were performed in the Southern Ocean. These experiments demonstrate iron's pivotal role in controlling carbon uptake and regulating atmospheric partial pressure of carbon dioxide., Cited By (since 1996):316, Oceanography, CODEN: SCIEA, ,
Author: Coale, Johnson, Chavez, Buesseler, Barber, Brzezinski, Cochlan, Millero, Falkowski, Bauer, Wanninkhof, Kudela, Altabet, Hales, Takahashi, Landry, Bidigare, Wang, Chase, Strutton, Friederich, Gorbunov, Lance, Hilting, Hiscock, Demarest, Hiscock, Sullivan, Tanner, Gordon, Hunter, Elrod, Fitzwater, Jones, Tozzi, Koblizek, Roberts, Herndon, Brewster, Ladizinsky, Smith, Cooper, Timothy, Brown, Selph, Sheridan, Twining, Johnson
Date: 2004-01-01T00:00:00Z

Title: Cadmium flux in Los Angeles/Long Beach harbours and at sites along the California continental margin,
Description: Fluxes of dissolved cadmium were measured in situ using benthic flux chambers at stations in Los Angeles/Long Beach harbour and at sites on the California continental margin. Cadmium fluxes ranged from -0.212 to 0.118 μmol m-2 d-1 indicating that Cd flux may either be into or out of sediments. Correlations between Cd flux and carbon oxidation rate and between carbon oxidation rate and sulfate reduction indicate that anaerobic microbial degradation was the major process controlling both the sign and the magnitude of cadmium fluxes at stations in Los Angeles and Long Beach harbours. A simple box model based on sediment fluxes and water column concentrations indicates cadmium has a residence time of 47 days within the Los Angeles/Long Beach harbour system, similar to the hydraulic residence time. Sedimentary flux is, therefore, sufficient to account for water column cadmium concentration in inner harbour areas, suggesting that the sediments are the dominant source and sink of cadmium in these areas of the harbour. Comparison of the cadmium: phosphate ratio for the Los Angeles/Long Beach harbour water column with those reported for the northeast Pacific suggests that distributions of Cd in the study area were elevated over expected values but appear to be dominated by natural physical and biogeochemical processes. © 2001 Academic Press., Cited By (since 1996):9, Oceanography, CODEN: ECSSD, ,
Author: Colbert, Coale, Berelson, Johnson
Date: 2001-01-01T00:00:00Z

Title: Developing standards for dissolved iron in seawater
Description: Cited By (since 1996):114
Author: Johnson, Boyle, Bruland, Coale, Measures, Moffett, Aguilar-Islas, Barbeau, Bergquist, Bowie, Buck, Cai, Chase, Cullen, Doi, Elrod, Fitzwater, Gordon, King, Laan, Laglera-Baquer, Landing, Lohan, Mendez, Milne, Obata, Ossiander, Plant, Sarthou, Sedwick, Smith, Sohst, Tanner, Van den Berg, Wu
Date: 2007-01-01T00:00:00Z

Title: Direct ultraviolet spectrophotometric determination of total sulfide and iodide in natural waters,
Description: A technique is described that allows the determination of total dissolved sulfide in natural waters using direct ultraviolet detection of the HS- ion. The concentration of bisulfide is determined by measuring absorption from 214 to 300 nm and then deconvolution of the HS- spectra from the complex spectrum of natural fluids. A nonlinear least-squares fitting approach is used for the deconvolution. At a pH near 8, where >95% of total sulfide is present as HS-, the results are indistinguishable from total sulfide measured using the methylene blue method in a wide range of sample types and matrixes including freshwater from groundwater wells, marine hydrothermal vent fluids, and marine sediment porewaters. The method allows simultaneous determination of other UV-absorbing ions, including nitrate, bromide, and iodide, in samples with low total sulfide concentrations. Bisulfide concentrations can be determined in samples with low background absorption, such as well water and hydrothermal fluids, with a detection limit of <1 μM. The detection limit for bisulfide in sediment porewaters that have a high organic loading, which produces background absorbances of ∼0.5 A at 260 nm in a 1-cm cuvette, is 5 μM. The only chemical manipulation required is buffering acidic samples to pH > 7 and filtration of particulate-rich samples., Cited By (since 1996):36, Oceanography, CODEN: ANCHA, ,
Author: Guenther, Johnson, Coale
Date: 2001-01-01T00:00:00Z

Title: Manganese flux from continental margin sediments in a transect through the oxygen minimum,
Description: The flux of manganese from continental margin sediments to the ocean was measured with a free-vehicle, benthic flux chamber in a transect across the continental shelf and upper slope of the California margin. The highest fluxes were observed on the shallow continental shelf. Manganese flux decreased linearly with bottom water oxygen concentration, and the lowest fluxes occurred in the oxygen minimum zone (at a depth of 600 to 1000 meters). Although the flux of manganese from continental shelf sediments can account for the elevated concentrations observed in shallow, coastal waters, the flux from sediments that intersect the oxygen minimum cannot produce the subsurface concentration maximum of dissolved manganese that is observed in the Pacific Ocean., Cited By (since 1996):47, Oceanography, CODEN: SCIEA, ,
Author: Johnson, Berelson, Coale, Coley, Elrod, Fairey, Iams, Kilgore, Nowicki
Date: 1992-01-01T00:00:00Z

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