Visualising Fe speciation diversity in ocean particulate samples by micro X-ray absorption near-edge spectroscopy

This paper is not subject to U.S. copyright. The definitive version was published in Environmental Chemistry 11 (2014): 10-17, doi:10.1071/EN13075.It is a well known truism that natural materials are inhomogeneous, so analysing them on a point-by-point basis can generate a large volume of data, from which it becomes challenging to extract understanding. In this paper, we show an example in which particles taken from the ocean in two different regions (the Western Subarctic Pacific and the Australian sector of the Southern Ocean, south of Tasmania) are studied by Fe K-edge micro X-ray absorption near-edge spectroscopy (μXANES). The resulting set of data consists of 209 spectra from the Western Subarctic Pacific and 126 from the Southern Ocean. We show the use of principal components analysis with an interactive projection visualisation tool to reduce the complexity of the data to something manageable. The Western Subarctic Pacific particles were grouped into four main populations, each of which was characterised by spectra consistent with mixtures of 1–3 minerals: (1) Fe3+ oxyhydroxides + Fe3+ clays + Fe2+ phyllosilicates, (2) Fe3+ clays, (3) mixed-valence phyllosilicates and (4) magnetite + Fe3+ clays + Fe2+ silicates, listed in order of abundance. The Southern Ocean particles break into three clusters: (1) Fe3+-bearing clays + Fe3+ oxyhydroxides, (2) Fe2+ silicates + Fe3+ oxyhydroxides and (3) Fe3+ oxides + Fe3+-bearing clays + Fe2+ silicates, in abundance order. Although there was some overlap between the two regions, this analysis shows that the particulate Fe mineral assemblage is distinct between the Western Subarctic Pacific and the Southern Ocean, with potential implications for the bioavailability of particulate Fe in these two iron-limited regions. We then discuss possible advances in the methods, including automatic methods for characterising the structure of the data.The operations of the Advanced Light Source at Lawrence Berkeley National Laboratory are supported by the Director, Office of Science, Office of Basic Energy Sciences, US Department of Energy under contract number DE-AC02-05CH11231. Collection of samples for the VERTIGO project was supported by the US National Science Foundation Program in Chemical Oceanography to Ken Buesseler and the US Department of Energy, Office of Science, Biological and Environmental Research Program to Jim Bishop. The SAZ-SENSE project was supported by the Australian Government Cooperative Research Centres Programme. Collection of spectroscopic data by PJL was supported through the WHOI Postdoctoral Scholar Program, WHOI Independent Study Award and NSF Chemical Oceanography

Dynamics of particulate organic carbon flux in a global ocean model

© The Author(s), 2014. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 11 (2014): 1177-1198, doi:10.5194/bg-11-1177-2014.The sinking of particulate organic carbon (POC) is a key component of the ocean carbon cycle and plays an important role in the global climate system. However, the processes controlling the fraction of primary production that is exported from the euphotic zone (export ratio) and how much of it survives respiration in the mesopelagic to be sequestered in the deep ocean (transfer efficiency) are not well understood. In this study, we use a three-dimensional, coupled physical–biogeochemical model (CCSM–BEC; Community Climate System Model–ocean Biogeochemical Elemental Cycle) to investigate the processes controlling the export of particulate organic matter from the euphotic zone and its flux to depth. We also compare model results with sediment trap data and other parameterizations of POC flux to depth to evaluate model skill and gain further insight into the causes of error and uncertainty in POC flux estimates. In the model, export ratios are mainly a function of diatom relative abundance and temperature while absolute fluxes and transfer efficiency are driven by mineral ballast composition of sinking material. The temperature dependence of the POC remineralization length scale is modulated by denitrification under low O2 concentrations and lithogenic (dust) fluxes. Lithogenic material is an important control of transfer efficiency in the model, but its effect is restricted to regions of strong atmospheric dust deposition. In the remaining regions, CaCO3 content of exported material is the main factor affecting transfer efficiency. The fact that mineral ballast composition is inextricably linked to plankton community structure results in correlations between export ratios and ballast minerals fluxes (opal and CaCO3), and transfer efficiency and diatom relative abundance that do not necessarily reflect ballast or direct ecosystem effects, respectively. This suggests that it might be difficult to differentiate between ecosystem and ballast effects in observations. The model's skill in reproducing sediment trap observations is equal to or better than that of other parameterizations. However, the sparseness and relatively large uncertainties of sediment trap data makes it difficult to accurately evaluate the skill of the model and other parameterizations. More POC flux observations, over a wider range of ecological regimes, are necessary to thoroughly evaluate and test model results and better understand the processes controlling POC flux to depth in the ocean.Support for this work was provided by WHOI Ocean and Climate Change Institute and NSF grants OCE-0960880 and AGS-1048827

Effects of particle composition on thorium scavenging in the North Atlantic

Author Posting. © The Author(s), 2018. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 233 (2018): 115-134, doi:10.1016/j.gca.2018.04.035.The dependence of thorium scavenging by particles on particle composition is examined at selected stations of the U.S. GEOTRACES North Atlantic Section (GA03). Scavenging is here described by the apparent, first-order rate constant of Th adsorption onto particles (k1), as estimated from an inversion of Th radioisotope and radioactive parent data. Our k1 estimates are regressed against particle phase data using two different models. Model I considers biogenic particles (POC+PIC+bSi), lithogenic particles, Mn (oxyhydr)oxides, and Fe (oxyhydr)oxides as regressors, and k1 as the regressand. Model II considers ln(POC+PIC+bSi), ln(lithogenic particles), ln(Mn (oxyhydr)oxides), and ln(Fe (oxyhydr)oxides) as regressors, and ln(k1) as the regressand, where ln() denotes the natural logarithm. Thus, models I and II posit that the effects of particle phases on k1 are, respectively, additive and multiplicative. These models are applied to three groups of stations: (i) all selected stations, (ii) stations west of theMauritanian upwelling region (“western stations”), and (iii) stations within that region (“eastern stations”). We find that model II appears to better describe the effect of particle composition on k1 than model I. Particle composition explains a larger fraction of the variance of k1 for the eastern stations (R2 = 0.60 for model I and 0.67 for model II) than for the western stations (R2 = 0.26 for model I and 0.39 for model II). When considering all stations, the variance of k1 explained by particle composition is intermediate (R2 = 0.50 for model I and 0.51 for model II). According to model II, the variance of k1 explained by particle composition is predominantly due to biogenic particles at the eastern stations and to Mn (oxyhydr)oxides at the western stations. Additionally, we find that particle composition does not explain a significantly different proportion of variance of k1 than particle concentration. It is thus concluded that, at our selected stations, (i) biogenic particles andMn (oxyhydr)oxides more strongly influence Th scavenging than any other phases considered, and (ii) particle composition and particle concentration have comparable effects on this process.We acknowledge the U.S. National Science Foundation for supporting this study (grant OCE-1232578) and the U.S. GEOTRACES North Atlantic section ship time, sampling, and data analysis

Insights from the U-238-th-234 method into the coupling of biological export and the cycling of cadmium, cobalt, and manganese in the southeast Pacific Ocean

Author Posting. © American Geophysical Union, 2019. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 33(1), (2019): 15-36, doi:10.1029/2018GB005985.Better constraints on the magnitude of particulate export and the residence times of trace elements are required to understand marine food web dynamics, track the transport of anthropogenic trace metals in the ocean, and improve global climate models. While prior studies have been successful in constructing basin‐scale budgets of elements like carbon in the upper ocean, the cycling of particulate trace metals is poorly understood. The 238U‐234Th method is used here with data from the GP‐16 GEOTRACES transect to investigate the upper ocean processes controlling the particulate export of cadmium, cobalt, and manganese in the southeastern Pacific. Patterns in the flux data indicated that particulate cadmium and cobalt behave similarly to particulate phosphorus and organic carbon, with the highest export in the productive coastal region and decreasing flux with depth due to remineralization. The export of manganese was influenced by redox conditions at the low oxygen coastal stations and by precipitation and/or scavenging elsewhere. Residence times with respect to export (total inventory divided by particulate flux) for phosphorus, cadmium, cobalt, and manganese in the upper 100 and 200 m were determined to be on the order of months to years. These GEOTRACES‐based synthesis efforts, combining a host of concentration and tracer data with unprecedented resolution, will help to close the oceanic budgets of trace metals.This work was supported by the National Science Foundation (OCE‐1232669 and OCE‐1518110), and Erin Black was also funded by a NASA Earth and Space Science Graduate Fellowship (NNX13AP31H). The authors would like to thank the captain, crew, and scientists aboard the R/V Thomas G. Thompson. A special thanks to two anonymous reviewers and Virginie Sanial for providing the additional 228Ra‐based estimates for Cd. All original data have been made available in either the supporting information or through BCO‐DMO (see Website and Database References).2019-06-1

Kinetics of thorium and particle cycling along the U.S. GEOTRACES North Atlantic Transect

© The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Deep Sea Research Part I: Oceanographic Research Papers 125 (2017): 106-128, doi:10.1016/j.dsr.2017.05.003.The high particle reactivity of thorium has resulted in its widespread use in tracing processes impacting marine particles and their chemical constituents. The use of thorium isotopes as tracers of particle dynamics, however, largely relies on our understanding of how the element scavenges onto particles. Here, we estimate apparent rate constants of Th adsorption (k1), Th desorption (k−1), bulk particle degradation (β-1), and bulk particle sinking speed (w) along the water column at 11 open-ocean stations occupied during the GEOTRACES North Atlantic Section (GA03). First, we provide evidence that the budgets of Th isotopes and particles at these stations appear to be generally dominated by radioactive production and decay sorption reactions, particle degradation, and particle sinking. Rate parameters are then estimated by fitting a Th and particle cycling model to data of dissolved and particulate 228,230,234Th, 228Ra, particle concentrations, and 234,238U estimates based on salinity, using a nonlinear programming technique. We find that the adsorption rate constant (k1) generally decreases with depth across the section: broadly, the time scale 1/k1 averages 1.0 yr in the upper 1000 m and (1.4–1.5) yr below. A positive relationship between k1 and particle concentration (P) is found, i.e., , k1 ∝ Pb where b ≥ 1, consistent with the notion that k1 increases with the number of surface sites available for adsorption. The rate constant ratio, K = k1/(k-1 + β-1), which measures the collective influence of rate parameters on Th scavenging, averages 0.2 for most stations and most depths. We clarify the conditions under which K/P is equivalent to the distribution coefficient, KD, test that the conditions are met at the stations, and find that decreases with P, in line with a particle concentration effect (dKD/dP < 0). In contrast to the influence of colloids as envisioned by the Brownian pumping hypothesis, we provide evidence that the particle concentration effect arises from the joint effect of P on the rate constants for thorium attachment to, and detachment from, particles.We acknowledge the U.S. National Science Foundation for providing funding for this study (grant OCE-1232578) and for U.S. GEOTRACES North Atlantic section ship time, sampling, and data analysis. The U.S. NSF also supported the generation of 230Th data (OCE-0927064 to LDEO, OCE-O092860 to WHOI, and OCE-0927754 to UMN) and 228,234Th data (OCE-0925158 to WHOI)

Development of coronary dysfunction in adult progeny after maternal engineered nanomaterial inhalation during gestation

Maternal exposure to environmental contaminants during pregnancy can profoundly influence the risk of developing cardiovascular disease in adult offspring. Our previous studies have demonstrated impaired cardiovascular health, microvascular reactivity, and cardiac function in fetal and young adult progeny after maternal inhalation of nano-sized titanium dioxide (nano-TiO2) aerosols during gestation. The present study was designed to evaluate the development of cardiovascular and metabolic diseases later in adulthood. Pregnant Sprague-Dawley rats were exposed to nano-TiO2 aerosols (similar to 10 mg/m(3), 134 nm median diameter) for 4 h per day, 5 days per week, beginning on gestational day (GD) 4 and ending on GD 19. Progeny were delivered in-house. Body weight was recorded weekly after birth. After 47 weeks, the body weight of exposed progeny was 9.4% greater compared with controls. Heart weight, mean arterial pressure, and plasma biomarkers of inflammation, dyslipidemia, and glycemic control were recorded at 3, 9 and 12 months of age, with no significant adaptations. While no clinical risk factors (i.e., hypertension, dyslipidemia, or systemic inflammation) emerged pertaining to the development of cardiovascular disease, we identified impaired endothelium-dependent and -independent arteriolar dysfunction and cardiac morphological alterations consistent with myocardial inflammation, degeneration, and necrosis in exposed progeny at 12 months. In conclusion, maternal inhalation of nano-TiO2 aerosols during gestation may promote the development of coronary disease in adult offspring

Coastal sources, sinks and strong organic complexation of dissolved cobalt within the US North Atlantic GEOTRACES transect GA03

© The Author(s), 2017. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 14 (2017): 2715-2739, doi:10.5194/bg-14-2715-2017.Cobalt is the scarcest of metallic micronutrients and displays a complex biogeochemical cycle. This study examines the distribution, chemical speciation, and biogeochemistry of dissolved cobalt during the US North Atlantic GEOTRACES transect expeditions (GA03/3_e), which took place in the fall of 2010 and 2011. Two major subsurface sources of cobalt to the North Atlantic were identified. The more prominent of the two was a large plume of cobalt emanating from the African coast off the eastern tropical North Atlantic coincident with the oxygen minimum zone (OMZ) likely due to reductive dissolution, biouptake and remineralization, and aeolian dust deposition. The occurrence of this plume in an OMZ with oxygen above suboxic levels implies a high threshold for persistence of dissolved cobalt plumes. The other major subsurface source came from Upper Labrador Seawater, which may carry high cobalt concentrations due to the interaction of this water mass with resuspended sediment at the western margin or from transport further upstream. Minor sources of cobalt came from dust, coastal surface waters and hydrothermal systems along the Mid-Atlantic Ridge. The full depth section of cobalt chemical speciation revealed near-complete complexation in surface waters, even within regions of high dust deposition. However, labile cobalt observed below the euphotic zone demonstrated that strong cobalt-binding ligands were not present in excess of the total cobalt concentration there, implying that mesopelagic labile cobalt was sourced from the remineralization of sinking organic matter. In the upper water column, correlations were observed between total cobalt and phosphate, and between labile cobalt and phosphate, demonstrating a strong biological influence on cobalt cycling. Along the western margin off the North American coast, this correlation with phosphate was no longer observed and instead a relationship between cobalt and salinity was observed, reflecting the importance of coastal input processes on cobalt distributions. In deep waters, both total and labile cobalt concentrations were lower than in intermediate depth waters, demonstrating that scavenging may remove labile cobalt from the water column. Total and labile cobalt distributions were also compared to a previously published South Atlantic GEOTRACES-compliant zonal transect (CoFeMUG, GAc01) to discern regional biogeochemical differences. Together, these Atlantic sectional studies highlight the dynamic ecological stoichiometry of total and labile cobalt. As increasing anthropogenic use and subsequent release of cobalt poses the potential to overpower natural cobalt signals in the oceans, it is more important than ever to establish a baseline understanding of cobalt distributions in the ocean.We also gratefully acknowledge support of funding agencies on the following grants: the US National Science Foundation (NSF-OCE 0928414, 1233261, 1435056) and the Gordon and Betty Moore Foundation (grant 3738)

Comparison of particulate trace element concentrations in the North Atlantic Ocean as determined with discrete bottle sampling and in situ pumping

Author Posting. © The Author(s), 2014. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Deep Sea Research Part II: Topical Studies in Oceanography 116 (2015): 272-282, doi:10.1016/j.dsr2.2014.11.005.The oceanic geochemical cycles of many metals are controlled, at least in part, by interactions with particulate matter, and measurements of particulate trace metals are a core component of the international GEOTRACES program. Particles can be collected by several methods, including in-line filtration from sample bottles and in situ pumping. Both approaches were used to collect particles from the water column on the U.S. GEOTRACES North Atlantic Zonal Transect cruises. Statistical comparison of 91 paired samples collected at matching stations and depths indicate mean concentrations within 5% for Fe and Ti, within 10% for Cd, Mn and Co, and within 15% for Al. Particulate concentrations were higher in bottle samples for Cd, Mn and Co but lower in bottle samples for Fe, Al and Ti, suggesting that large lithogenic particles may be undersampled by bottles in near-shelf environments. In contrast, P was 58% higher on average in bottle samples. This is likely due to a combination of analytical offsets between lab groups, differences in filter pore size, and potential loss of labile P from pump samples following misting with deionized water. Comparable depth profiles were produced by the methods across a range of conditions in the North Atlantic.This work was funded by grants from the US National Science Foundation to BST (OCE-0928289) and PJL (OCE-0963026) as part of the US GEOTRACES North Atlantic Zonal Transect program

The effect of sample drying temperature on marine particulate organic carbon composition

Author Posting. © The Author(s), 2018. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography Methods 16 (2018): 286-298, doi:10.1002/lom3.10245.Compositional changes in marine particulate organic carbon (POC) throughout the water column trace important processes that underlie the biological pump’s efficiency. While labor-intensive, particle sampling efforts offer potential to expand the empirical POC archive at different stages in the water column, provided that organic composition is sufficiently preserved between sampling and analysis. The standard procedure for preserving organic matter composition in marine samples is to immediately store particles at -80°C to -20°C until they can be freeze-dried for analysis. This report investigates the effect of warmer drying and storage temperatures on POC composition, which applies to the majority of POC samples collected in the field without intention for organic analysis. Particle samples collected off Woods Hole, MA were immediately dried at 56°C, at room temperature, or stored at -80°C until being freeze-dried. Results show that oven- and air-drying did not shift the bulk composition (i.e., carbon and nitrogen content and stable isotope composition) of POC in the samples relative to freeze-drying. Similarly, warmer drying temperatures did not affect POC thermal stability, as inferred by ramped pyrolysis/oxidation (RPO), a growing technique that uses a continuous temperature ramp to differentiate components of organic carbon by their decomposition temperature. Oven- and air-drying did depress lipid abundances relative to freeze-drying, the extent of which depended on compound size and structure. The data suggest that field samples dried at room temperatures and 56°C are appropriate for assessing bulk POC composition and thermal stability, but physical mechanisms such as molecular volatilization bias their lipid composition.This research was funded by the National Science Foundation (NSF) Graduate Research Fellowship program and the NSF Cooperative Agreement for the Operation of a National Ocean Sciences Accelerator Mass Spectrometry Facility (OCE-0753487)

Size-fractionated major particle composition and concentrations from the US GEOTRACES North Atlantic Zonal Transect

AbstractThe concentration and the major phase composition (particulate organic matter, CaCO3, opal, lithogenic matter, and iron and manganese oxyhydroxides) of marine particles is thought to determine the scavenging removal of particle-reactive TEIs. Particles are also the vector for transferring carbon from the atmosphere to the deep ocean via the biological carbon pump, and their composition may determine the efficiency and strength of this transfer. Here, we present the first full ocean depth section of size-fractionated (1–51µm, >51µm) suspended particulate matter (SPM) concentration and major phase composition from the US GEOTRACES North Atlantic Zonal Transect between Woods Hole, MA and Lisbon, Portugal conducted in 2010 and 2011. Several major particle features are notable in the section: intense benthic nepheloid layers were observed in the western North American margin with concentrations of SPM of up to 1648µg/L, two to three orders of magnitude higher than surrounding waters, that were dominated by lithogenic material. A more moderate benthic nepheloid layer was also observed in the eastern Mauritanian margin (44µg/L) that had a lower lithogenic content and, notably, significant concentrations of iron and manganese oxyhydroxides (2.5% each). An intermediate nepheloid layer reaching 102µg/L, an order of magnitude above surrounding waters, was observed associated with the Mediterranean Outflow. Finally, there was a factor of two enhancement in SPM at the TAG hydrothermal plume due almost entirely to the addition of iron oxyhydroxides from the hydrothermal vent. We observe correlations between POC and CaCO3 in large (>51µm) particles in the upper 2000m, but not deeper than 2000m, and no correlations between POC and CaCO3 at any depth in small (<51µm) particles. There were also no correlations between POC and lithogenic material in large particles. Overall, there were very large uncertainties associated with all regression coefficients for mineral ballast (“carrying coefficients”), suggesting that mineral ballast was not a strong predictor for POC in this section