Influence of palaeoweathering on trace metal concentrations and environmental proxies in black shales

The mineralogical and chemical compositions of Lower Carboniferous (Tournaisian) marine black shale from the Kowala quarry, the Holy Cross Mountains, Poland, were investigated. This study focuses on disturbances in palaeoenvironmental proxies caused by palaeoweathering, which progressively changed the major and trace element abundances. Palaeomagnetic investigations reveal that the Devonian – Carboniferous succession was weathered during the Permian-Triassic by the infiltration of oxidizing fluids related to karstification following post-Variscan exhumation. The weathering process led to vermiculitization of chlorite, partial dissolution of calcite and replacement of pyrite by hematite and goethite. Moreover, the concentrations of some trace metals, including Co, Cu, Pb, Mo, Ni, As and U, significantly decreased. Consequently, some elemental abundance ratios that are used as environmental proxies, including U/Th, Ni/Co and V/Cr, were altered. Elements that are bound to iron sulphides (e.g., Mo) appear to be especially prone to mobilization by even a lightly weathered black shale. The documented weathering, including changes in elemental concentrations, can potentially create misinterpretations of the original palaeoenvironmental conditions. In addition, the palaeoweathering of the studied samples appears to have substantially changed the carbon, oxygen, nitrogen and molybdenum stable isotope values. The nitrogen and molybdenum stable isotope ratios, in particular, appear to be most sensitive to the effects of weathering and therefore are good indicators of (palaeo)weathering processes. The major cause of these changes is the decay of organic matter and pyrite. For the organic carbon stable isotopes ratios, the main factor that controlls this process appears to be the preferential degradation of labile organic matter. A combination of the total organic carbon (TOC), total sulphur (TS) content, Mo concentration and stable isotope compositions seems to be the most useful for identify (palaeo)weathering. Our results suggest that reductions in TS and Mo in tandem with diminished Mo stable isotope values in the absence of obvious changes to the TOC content provide the most compelling evidence of (palaeo)weathering

Investigating the effect of El Niño on nitrous oxide distribution in the Eastern Tropical South Pacific

The open ocean is a major source of nitrous oxide (N2O), an atmospheric trace gas attributable to global warming and ozone depletion. Intense sea-to-air N2O fluxes occur in major oceanic upwelling regions such as the eastern tropical South Pacific (ETSP). The ETSP is influenced by the El Niño–Southern Oscillation that leads to inter-annual variations in physical, chemical, and biological properties in the water column. In October 2015, a strong El Niño event was developing in the ETSP; we conduct field observations to investigate (1) the N2O production pathways and associated biogeochemical properties and (2) the effects of El Niño on water column N2O distributions and fluxes using data from previous non-El Niño years. Analysis of N2O natural abundance isotopomers suggested that nitrification and partial denitrification (nitrate and nitrite reduction to N2O) were occurring in the near-surface waters; indicating that both pathways contributed to N2O effluxes. Higher-than-normal sea surface temperatures were associated with a deepening of the oxycline and the oxygen minimum layer. Within the shelf region, surface N2O supersaturation was nearly an order of magnitude lower than that of non-El Niño years. Therefore, a significant reduction of N2O efflux (75 %–95 %) in the ETSP occurred during the 2015 El Niño. At both offshore and coastal stations, the N2O concentration profiles during El Niño showed moderate N2O concentration gradients, and the peak N2O concentrations occurred at deeper depths during El Niño years; this was likely the result of suppressed upwelling retaining N2O in subsurface waters. At multiple stations, water-column inventories of N2O within the top 1000 m were up to 160 % higher than those measured in non-El Niño years, indicating that subsurface N2O during El Niño could be a reservoir for intense N2O effluxes when normal upwelling is resumed after El Niño

Seasonal variations in the nitrogen isotopic composition of settling particles at station K2 in the western subarctic North Pacific

Intensive observations using hydrographical cruises and moored sediment trap deployments during 2010 and 2012 at station K2 in the North Pacific western subarctic gyre (WSG) revealed seasonal changes in δ15N of both suspended and settling particles. Suspended particles (SUS) were collected from depths between the surface and 200 m; settling particles by drifting traps (DST; 100-200 m) and moored traps (MST; 200 and 500 m). All particles showed higher δ15N values in winter and lower in summer, contrary to the expected by isotopic fractionation during phytoplankton nitrate consumption. We suggest that these observed isotopic patterns are due to ammonium consumption via light-controlled nitrification, which could induce variations in δ15N(SUS) of 0.4-3.1 ‰ in the euphotic zone (EZ). The δ15N(SUS) signature was reflected by δ15 N(DST) despite modifications during biogenic transformation from suspended particles in the EZ. δ15 N enrichment (average: 3.6 ‰) and the increase in C:N ratio (by 1.6) in settling particles suggests year-round contributions of metabolites from herbivorous zooplankton as well as TEPs produced by diatoms. Accordingly, seasonal δ15 N(DST) variations of 2.4-7.0 ‰ showed a significant correlation with primary productivity (PP) at K2. By applying the observed δ15 N(DST) vs. PP regression to δ15 N(MST) of 1.9-8.0 ‰, we constructed the first annual time-series of PP changes in the WSG. Moreover, the monthly export ratio at 500 m was calculated using both estimated PP and measured organic carbon fluxes. Results suggest a 1.6 to 1.8 times more efficient transport of photosynthetically-fixed carbon to the intermediate layers occurs in summer/autumn rather than winter/spring

Endangered right whales enhance primary productivity in the bay of fundy

This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. Marine mammals have recently been documented as important facilitators of rapid and efficient nutrient recycling in coastal and offshore waters. Whales enhance phytoplankton nutrition by releasing fecal plumes near the surface after feeding and by migrating from highly productive, high-latitude feeding areas to low-latitude nutrient-poor calving areas. In this study, we measured NH4 + and PO4 3- release rates from the feces of North Atlantic right whales (Eubalaena glacialis), a highly endangered baleen whale. Samples for this species were primarily collected by locating aggregations of whales in surface- Active groups (SAGs), which typically consist of a central female surrounded by males competing for sexual activity. When freshly collected feces were incubated in seawater, high initial rates of N release were generally observed, which decreased to near zero within 24 hours of sampling, a pattern that is consistent with the active role of gut microflora on fecal particles. We estimate that at least 10% of particulate N in whale feces becomes available as NH4 + within 24 hours of defecation. Phosphorous was also abundant in fecal samples: Initial release rates of PO4 3- were higher than for NH4 +, yielding low N/P nutrient ratios over the course of our experiments. The rate of PO4 3- release was thus more than sufficient to preclude the possibility that nitrogenous nutrients supplied by whales would lead to phytoplankton production limited by P availability. Phytoplankton growth experiments indicated that NH4 + released from whale feces enhance productivity, as would be expected, with no evidence that fecal metabolites suppress growth. Although North Atlantic right whales are currently rare (approximately 450 individuals), they once numbered about 14,000 and likely played a substantial role in recycling nutrients in areas where they gathered to feed and mate. Even though the NH4 + released from fresh whale fecal material is a small fraction of total whale fecal nitrogen, and recognizing the fact that the additional nitrogen released in whale urine would be difficult to measure in a field study, the results of this study support the idea that the distinctive isotopic signature of the released NH4 + could be used to provide a conservative estimate of the contribution of the whale pump to primary productivity in coastal regions where whales congregate

No iron fertilization in the equatorial Pacific Ocean during the last ice age

The equatorial Pacific Ocean is one of the major high-nutrient, low-chlorophyll regions in the global ocean. In such regions, the consumption of the available macro-nutrients such as nitrate and phosphate is thought to be limited in part by the low abundance of the critical micro-nutrient iron1. Greater atmospheric dust deposition2 could have fertilized the equatorial Pacific with iron during the last ice age—the Last Glacial Period (LGP) but the effect of increased ice-age dust fluxes on primary productivity in the equatorial Pacific remains uncertain. Here we present meridional transects of dust (derived from the 232Th proxy), phytoplankton productivity (using opal, 231Pa/230Th and excess Ba), and the degree of nitrate consumption (using foraminifera-bound δ15N) from six cores in the central equatorial Pacific for the Holocene (0–10,000 years ago) and the LGP (17,000–27,000 years ago). We find that, although dust deposition in the central equatorial Pacific was two to three times greater in the LGP than in the Holocene, productivity was the same or lower, and the degree of nitrate consumption was the same. These biogeochemical findings suggest that the relatively greater ice-age dust fluxes were not large enough to provide substantial iron fertilization to the central equatorial Pacific. This may have been because the absolute rate of dust deposition in the LGP (although greater than the Holocene rate) was very low. The lower productivity coupled with unchanged nitrate consumption suggests that the subsurface major nutrient concentrations were lower in the central equatorial Pacific during the LGP. As these nutrients are today dominantly sourced from the Subantarctic Zone of the Southern Ocean, we propose that the central equatorial Pacific data are consistent with more nutrient consumption in the Subantarctic Zone, possibly owing to iron fertilization as a result of higher absolute dust fluxes in this region7,8. Thus, ice-age iron fertilization in the Subantarctic Zone would have ultimately worked to lower, not raise, equatorial Pacific productivity

Doubling of marine dinitrogen-fixation rates based on direct measurements

Biological dinitrogen fixation provides the largest input of nitrogen to the oceans, therefore exerting important control on the ocean’s nitrogen inventory and primary productivity. Nitrogen-isotope data fromocean sediments suggest that the marine-nitrogen inventory has been balanced for the past 3,000 years (ref. 4). Producing a balanced marine-nitrogenbudget based on direct measurements has proved difficult, however, with nitrogen loss exceeding the gain from dinitrogen fixation by approximately 200 TgNyr-1 (refs 5, 6). Here we present data from the Atlantic Ocean and show that the most widely used method of measuring oceanic N2-fixation rates underestimates the contribution of N2-fixing microorganisms (diazotrophs) relative to a newly developed method. Using molecular techniques to quantify the abundance of specific clades of diazotrophs in parallel with rates of 15N2 incorporation into particulate organic matter, we suggest that the difference between N2-fixation rates measured with the established method and those measured with the new method8 can be related to the composition of the diazotrophic community. Our data show that in areas dominated by Trichodesmium, the established method underestimatesN2-fixation rates by an averageof 62%. We also find that the newly developed method yields N2-fixation rates more than six times higher than those from the established method when unicellular, symbiotic cyanobacteria and c-proteobacteria dominate the diazotrophic community. On the basis of average areal rates measured over the Atlantic Ocean, we calculated basin-wide N2-fixation rates of 14+/-1TgNyr-1 and 24+/-1TgNyr-1 for the established and new methods, respectively. If our findings can be extrapolated to other ocean basins, this suggests that the global marine N2-fixation rate derived from direct measurements may increase from 103+/-8TgNyr-1 to 177+/-8TgNyr-1, and that the contribution of N2 fixers other than Trichodesmium is much more significant than was previously thought

Pre-Whaling Genetic Diversity and Population Ecology in Eastern Pacific Gray Whales: Insights from Ancient DNA and Stable Isotopes

Commercial whaling decimated many whale populations, including the eastern Pacific gray whale, but little is known about how population dynamics or ecology differed prior to these removals. Of particular interest is the possibility of a large population decline prior to whaling, as such a decline could explain the ∼5-fold difference between genetic estimates of prior abundance and estimates based on historical records. We analyzed genetic (mitochondrial control region) and isotopic information from modern and prehistoric gray whales using serial coalescent simulations and Bayesian skyline analyses to test for a pre-whaling decline and to examine prehistoric genetic diversity, population dynamics and ecology. Simulations demonstrate that significant genetic differences observed between ancient and modern samples could be caused by a large, recent population bottleneck, roughly concurrent with commercial whaling. Stable isotopes show minimal differences between modern and ancient gray whale foraging ecology. Using rejection-based Approximate Bayesian Computation, we estimate the size of the population bottleneck at its minimum abundance and the pre-bottleneck abundance. Our results agree with previous genetic studies suggesting the historical size of the eastern gray whale population was roughly three to five times its current size

Carbon sequestration in the deep Atlantic enhanced by Saharan dust

Enhanced atmospheric input of dust-borne nutrients and minerals to the remote surface ocean can potentially increase carbon uptake and sequestration at depth. Nutrients can enhance primary productivity, and mineral particles act as ballast, increasing sinking rates of particulate organic matter. Here we present a two-year time series of sediment trap observations of particulate organic carbon flux to 3,000 m depth, measured directly in two locations: the dust-rich central North Atlantic gyre and the dust-poor South Atlantic gyre. We find that carbon fluxes are twice as high and a higher proportion of primary production is exported to depth in the dust-rich North Atlantic gyre. Low stable nitrogen isotope ratios suggest that high fluxes result from the stimulation of nitrogen fixation and productivity following the deposition of dust-borne nutrients. Sediment traps in the northern gyre also collected intact colonies of nitrogen-fixing Trichodesmium species. Whereas ballast in the southern gyre is predominantly biogenic, dust-derived mineral particles constitute the dominant ballast element during the enhanced carbon fluxes in the northern gyre. We conclude that dust deposition increases carbon sequestration in the North Atlantic gyre through the fertilization of the nitrogen-fixing community in surface waters and mineral ballasting of sinking particles

Modeling denitrification in aquatic sediments

Author Posting. © The Author(s), 2008. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Biogeochemistry 93 (2009): 159-178, doi:10.1007/s10533-008-9270-z.Sediment denitrification is a major pathway of fixed nitrogen loss from aquatic systems. Due to technical difficulties in measuring this process and its spatial and temporal variability, estimates of local, regional and global denitrification have to rely on a combination of measurements and models. Here we review approaches to describing denitrification in aquatic sediments, ranging from mechanistic diagenetic models to empirical parameterizations of nitrogen fluxes across the sediment-water interface. We also present a compilation of denitrification measurements and ancillary data for different aquatic systems, ranging from freshwater to marine. Based on this data compilation we reevaluate published parameterizations of denitrification. We recommend that future models of denitrification use (1) a combination of mechanistic diagenetic models and measurements where bottom waters are temporally hypoxic or anoxic, and (2) the much simpler correlations between denitrification and sediment oxygen consumption for oxic bottom waters. For our data set, inclusion of bottom water oxygen and nitrate concentrations in a multivariate regression did not improve the statistical fit.Financial support for AEG to work on the manuscript came from NSF NSF-DEB-0423565. KF, DB and DDT acknowledge support from NOAA CHRP grant NA07NOS4780191

Global rates of water-column denitrification derived from nitrogen gas measurements

Biologically available nitrogen (N) limits phytoplankton growth over much of the ocean. The rate at which N is removed from the contemporary ocean by denitrifying bacteria is highly uncertain 1-3. Some studies suggest that N losses exceed inputs 2,4-6; others argue for a balanced budget 3,7,8. Here, we use a global ocean circulation model to simulate the distribution of N 2 gas produced by denitrifying bacteria in the three main suboxic zones in the open ocean. By fitting the model to measured N 2 gas concentrations, we infer a globally integrated rate of water-column denitrification of 66 ±6 Tg N yr -1. Taking into account isotopic constraints on the fraction of denitrification occurring in the water column versus marine sediments, we estimate that the global rate of N loss from marine sediments and the oceanic water column combined amounts to around 230 ±60 Tg N yr -1. Given present estimates of N input rates, our findings imply a net loss of around 20 ± 70 Tg of N from the global ocean each year, indistinguishable from a balanced budget. A balanced N budget, in turn, implies that the marine N cycle is governed by strong regulatory feedbacks. © 2012 Macmillan Publishers Limited. All rights reserved