Estimation of atmospheric nutrient inputs to the Atlantic Ocean from 50°N to 50°S based on large-scale field sampling: Iron and other dust-associated elements

Atmospheric inputs of mineral dust supply iron and other trace metals to the remote ocean and can influence the marine carbon cycle due to iron's role as a potentially limiting micronutrient. Dust generation, transport, and deposition are highly heterogeneous, and there are very few remote marine locations where dust concentrations and chemistry (e.g., iron solubility) are routinely monitored. Here we use aerosol and rainwater samples collected during 10 large-scale research cruises to estimate the atmospheric input of iron, aluminum, and manganese to four broad regions of the Atlantic Ocean over two 3 month periods for the years 2001–2005. We estimate total inputs of these metals to our study regions to be 4.2, 17, and 0.27 Gmol in April–June and 4.9, 14, and 0.19 Gmol in September–November, respectively. Inputs were highest in regions of high rainfall (the intertropical convergence zone and South Atlantic storm track), and rainfall contributed higher proportions of total input to wetter regions. By combining input estimates for total and soluble metals for these time periods, we calculated overall percentage solubilities for each metal that account for the contributions from both wet and dry depositions and the relative contributions from different aerosol types. Calculated solubilities were in the range 2.4%–9.1% for iron, 6.1%–15% for aluminum, and 54%–73% for manganese. We discuss sources of uncertainty in our estimates and compare our results to some recent estimates of atmospheric iron input to the Atlantic.

A massive phytoplankton bloom induced by an ecosystem-scale iron fertilization experiment in the equatorial Pacific Ocean

The seeding of an expanse of surface waters in the equatorial Pacific Ocean with low concentrations of dissolved iron triggered a massive phytoplankton bloom which consumed large quantities of carbon dioxide and nitrate that these microscopic plants cannot fully utilize under natural conditions. These and other observations provide unequivocal support for the hypothesis that phytoplankton growth in this oceanic region is limited by iron bioavailability.

The biogeochemical structuring role of horizontal stirring: Lagrangian perspectives on iron delivery downstream of the Kerguelen Plateau

Field campaigns are instrumental in providing ground truth for understanding and modeling global ocean biogeochemical budgets. A survey however can only inspect a fraction of the global oceans, typically a region hundreds of kilometers wide for a temporal window of the order of (at most) several weeks. This spatiotemporal domain is also the one in which the mesoscale activity induces through horizontal stirring a strong variability in the biogeochemical tracers, with ephemeral, local contrasts which can easily mask the regional and seasonal gradients. Therefore, whenever local in situ measures are used to infer larger-scale budgets, one faces the challenge of identifying the mesoscale structuring effect, if not simply to filter it out. In the case of the KEOPS2 investigation of biogeochemical responses to natural iron fertilization, this problem was tackled by designing an adaptive sampling strategy based on regionally optimized multisatellite products analyzed in real time by specifically designed Lagrangian diagnostics. This strategy identified the different mesoscale and stirring structures present in the region and tracked the dynamical frontiers among them. It also enabled back trajectories for the ship-sampled stations to be estimated, providing important insights into the timing and pathways of iron supply, which were explored further using a model based on first-order iron removal. This context was essential for the interpretation of the field results. The mesoscale circulation-based strategy was also validated post-cruise by comparing the Lagrangian maps derived from satellites with the patterns of more than one hundred drifters, including some adaptively released during KEOPS2 and a subsequent research voyage. The KEOPS2 strategy was adapted to the specific biogeochemical characteristics of the region, but its principles are general and will be useful for future in situ biogeochemical surveys.

Mineralogical characteristics and transformations during long-term operation of a zero-valent iron reactive barrier

Received for publication October 31, 2002. Design and operation of Fe0 permeable reactive barriers (PRBs) can be improved by understanding the long-term mineralogical transformations that occur within PRBs. Changes in mineral precipitates, cementation, and corrosion of Fe0 filings within an in situ pilot-scale PRB were examined after the first 30 months of operation and compared with results of a previous study of the PRB conducted 15 months earlier using X-ray diffraction and scanning electron microscopy employing energy dispersive X-ray and backscatter electron analyses. Iron (oxy)hydroxides, aragonite, and maghemite and/or magnetite occurred throughout the cores collected 30 mo after installation. Goethite, lepidocrocite, mackinawite, aragonite, calcite, and siderite were associated with oxidized and cemented areas, while green rusts were detected in more reduced zones. Basic differences from our last detailed investigation include (i) mackinawite crystallized from amorphous FeS, (ii) aragonite transformed into calcite, (iii) akaganeite transformed to goethite and lepidocrocite, (iv) iron (oxy)hydroxides and calcium and iron carbonate minerals increased, (v) cementation was greater in the more recent study, and (vi) oxidation, corrosion, and disintegration of Fe0 filings were greater, especially in cemented areas, in the more recent study. If the degree of corrosion and cementation that was observed from 15 to 30 mo after installation continues, certain portions of the PRB (i.e., up-gradient entrance of the ground water to the Fe0 section of the PRB) may last less than five more years, thus reducing the effectiveness of the PRB to mitigate contaminants. Abbreviations: EDX, energy dispersive X-ray • Fe0, zerovalent iron • PRB, permeable reactive barrier • SEM, scanning electron microscopy • XRD, X-ray diffraction

Impact of sample preparation on mineralogical analysis of iron reactive barrier materials

Permeable reactive barriers (PRBs) of zero-valent iron (Fe0) are increasingly being used to remediate contaminated ground water. Corrosion of Fe0 filings and the formation of precipitates can occur when the PRB material comes in contact with ground water and may reduce the lifespan and effectiveness of the barrier. At present, there are no routine procedures for preparing and analyzing the mineral precipitates from Fe0 PRB material. These procedures are needed because mineralogical composition of corrosion products used to interpret the barrier processes can change with iron oxidation and sample preparation. The objectives of this study were (i) to investigate a method of preparing Fe0 reactive barrier material for mineralogical analysis by X-ray diffraction (XRD), and (ii) to identify Fe mineral phases and rates of transformations induced by different mineralogical preparation techniques. Materials from an in situ Fe0 PRB were collected by undisturbed coring and processed for XRD analysis after different times since sampling for three size fractions and by various drying treatments. We found that whole-sample preparation for analysis was necessary because mineral precipitates occurred within the PRB material in different size fractions of the samples. Green rusts quickly disappeared from acetone-dried samples and were not present in air-dried and oven-dried samples. Maghemite/magnetite content increased over time and in oven-dried samples, especially after heating to 105°C. We conclude that care must be taken during sample preparation of Fe0 PRB material, especially for detection of green rusts, to ensure accurate identification of minerals present within the barrier system.

Microbiological characteristics in a zero-valent iron reactive barrier

Zero-valent iron (Fe0)-based permeable reactive barriertreatment has been generating great interest for passivegroundwater remediation, yet few studies have paid particularattention to the microbial activity and characteristics withinand in the vicinity of the Fe0-barrier matrix. The presentstudy was undertaken to evaluate the microbial population andcommunity composition in the reducing zone of influence byFe0 corrosion in the barrier at the Oak Ridge Y-12 Plantsite. Both phospholipid fatty acids and DNA analyses were usedto determine the total microbial population and microbialfunctional groups, including sulfate-reducing bacteria,denitrifying bacteria, and methanogens, in groundwater andsoil/iron core samples. A diverse microbial community wasidentified in the strongly reducing Fe0 environment despitea relatively high pH condition within the Fe0 barrier (up topH 10). In comparison with those found in the backgroundsoil/groundwater samples, the enhanced microbial populationranged from 1 to 3 orders of magnitude and appeared to increase from upgradient of the barrier to downgradient soil. Inaddition, microbial community composition appeared to change overtime, and the bacterial types of microorganismsincreased consistently as the barrier aged. DNA analysisindicated the presence of sulfate-reducing and denitrifyingbacteria in the barrier and its surrounding soil. However, theactivity of methanogens was found to be relatively low,presumably as a result of the competition by sulfate/metal-reducing bacteria and denitrifying bacteria because of the unlimited availability of sulfate and nitrate in the site groundwater. Results of this study provide evidenceof a diverse microbial population within and in the vicinity ofthe iron barrier, although the important roles of microbial activity, either beneficially or detrimentally, on the longevityand enduring efficiency of the Fe0 barriers are yet to be evaluated.