Sergey Oleynik

Isotopic evidence for a marine ammonium source in rainwater at Bermuda

Emissions of anthropogenic nitrogen (N) to the atmosphere have increased tenfold since preindustrial times, resulting in increased N deposition to terrestrial and coastal ecosystems. The sources of N deposition to the ocean, however, are poorly understood. Two years of event-based rainwater samples were collected on the island of Bermuda in the western North Atlantic, which experiences both continent- and ocean-influenced air masses. The rainwater ammonium concentration ranged from 0.36 to 24.6 μM, and the ammonium δ15N from −12.5 to 0.7‰; and neither has a strong relationship with air mass history (6.0 ± 4.2 μM, −4.1 ± 2.6‰ in marine air masses and 5.9 ± 3.2 μM, −5.8 ± 2.5‰ in continental air masses; numerical average ± standard deviation). A simple box model suggests that the ocean can account for the concentration and isotopic composition of ammonium in marine rainwater, consistent with the lack of correlation between ammonium δ15N and air mass history. If so, ammonium deposition reflects the cycling of N between the ocean and the atmosphere, rather than representing a net input to the ocean. The δ15N data appear to require that most of the ammonium/a flux to the ocean is by dissolution in surface waters rather than atmospheric deposition. This suggests that the atmosphere and surface ocean are near equilibrium with respect to air/sea gas exchange, implying that anthropogenic ammonia will equilibrate near the coast and not reach the open marine atmosphere. Whereas ~90% of the ammonium deposition to the global ocean has previously been attributed to anthropogenic sources, the evidence at Bermuda suggests that the anthropogenic contribution could be much smaller.

Ammonia and nitrite oxidation in the Eastern Tropical North Pacific

Nitrification plays a key role in the marine nitrogen (N) cycle, including in oceanic oxygen minimum zones (OMZs), which are hot spots for denitrification and anaerobic ammonia oxidation (anammox). Recent evidence suggests that nitrification links the source (remineralized organic matter) and sink (denitrification and anammox) of fixed N directly in the steep oxycline in the OMZs. We performed shipboard incubations with 15N tracers to characterize the depth distribution of nitrification in the Eastern Tropical North Pacific (ETNP). Additional experiments were conducted to investigate photoinhibition. Allylthiourea (ATU) was used to distinguish the contribution of archaeal and bacterial ammonia oxidation. The abundance of archaeal and β-proteobacterial ammonia monooxygenase gene subunit A (amoA) was determined by quantitative polymerase chain reaction. The rates of ammonia and nitrite oxidation showed distinct subsurface maxima, with the latter slightly deeper than the former. The ammonia oxidation maximum coincided with the primary nitrite concentration maximum, archaeal amoA gene maximum, and the subsurface nitrous oxide maximum. Negligible rates of ammonia oxidation were found at anoxic depths, where high rates of nitrite oxidation were measured. Archaeal amoA gene abundance was generally 1 to 2 orders of magnitude higher than bacterial amoA gene abundance, and inhibition of ammonia-oxidizing bacteria with 10 μM ATU did not affect ammonia oxidation rates, indicating the dominance of archaea in ammonia oxidation. These results depict highly dynamic activities of ammonia and nitrite oxidation in the oxycline of the ETNP OMZ.

Nitrous oxide production by nitrification and denitrification in the Eastern Tropical South Pacific oxygen minimum zone

The Eastern Tropical South Pacific oxygen minimum zone (ETSP-OMZ) is a site of intense nitrous oxide (N2O) flux to the atmosphere. This flux results from production of N2O by nitrification and denitrification, but the contribution of the two processes is unknown. The rates of these pathways and their distributions were measured directly using 15N tracers. The highest N2O production rates occurred at the depth of peak N2O concentrations at the oxic-anoxic interface above the oxygen deficient zone (ODZ) because slightly oxygenated waters allowed (1) N2O production from both nitrification and denitrification and (2) higher nitrous oxide production yields from nitrification. Within the ODZ proper (i.e., anoxia), the only source of N2O was denitrification (i.e., nitrite and nitrate reduction), the rates of which were reflected in the abundance of nirS genes (encoding nitrite reductase). Overall, denitrification was the dominant pathway contributing the N2O production in the ETSP-OMZ.

Antarctic Zone nutrient conditions during the last two glacial cycles

In a sediment core from the Pacific sector of the Antarctic Zone (AZ) of the Southern Ocean, we report diatom-bound N isotope (δ15Ndb) records for total recoverable diatoms and two distinct diatom assemblages (pennate and centric rich). These data indicate tight coupling between the degree of nitrate consumption and Antarctic climate across the last two glacial cycles, with δ15Ndb (and thus the degree of nitrate consumption) increasing at each major Antarctic cooling event. Coupled with evidence from opal- and barium-based proxies for reduced export production during ice ages, the δ15Ndb increases point to ice age reductions in the supply of deep ocean-sourced nitrate to the AZ surface. The two diatom assemblages and species abundance data indicate that the δ15Ndb changes are not the result of changing species composition. The pennate and centric assemblage δ15Ndb records indicate similar changes but with a significant decline in their difference during peak ice ages. A tentative seasonality-based interpretation of the centric-to-pennate δ15Ndb difference suggests that late summer surface waters became nitrate free during the peak glacials.

Glacial‐to‐interglacial changes in nitrate supply and consumption in the subarctic North Pacific from microfossil‐bound N isotopes at two trophic levels

Reduced nitrate supply to the subarctic North Pacific (SNP) surface during the last ice age has been inferred from coupled changes in diatom-bound δ15N (DB-δ15N), bulk sedimentary δ15N, and biogenic fluxes. However, the reliability of bulk sedimentary and DB-δ15N has been questioned, and a previously reported δ15N minimum during Heinrich Stadial 1 (HS1) has proven difficult to explain. In a core from the western SNP, we report the foraminifera-bound δ15N (FB-δ15N) in Neogloboquadrina pachyderma and Globigerina bulloides, comparing them with DB-δ15N in the same core over the past 25 kyr. The δ15N of all recorders is higher during the Last Glacial Maximum (LGM) than in the Holocene, indicating more complete nitrate consumption. N. pachyderma FB-δ15N is similar to DB-δ15N in the Holocene but 2.2‰ higher during the LGM. This difference suggests a greater sensitivity of FB-δ15N to changes in summertime nitrate drawdown and δ15N rise, consistent with a lag of the foraminifera relative to diatoms in reaching their summertime production peak in this highly seasonal environment. Unlike DB-δ15N, FB-δ15N does not decrease from the LGM into HS1, which supports a previous suggestion that the HS1 DB-δ15N minimum is due to contamination by sponge spicules. FB-δ15N drops in the latter half of the Bolling/Allerod warm period and rises briefly in the Younger Dryas cold period, followed by a decline into the mid-Holocene. The FB-δ15N records suggest that the coupling among cold climate, reduced nitrate supply, and more complete nitrate consumption that characterized the LGM also applied to the deglacial cold events.

Constraining the Timing and Amplitude of Early Serpukhovian Glacioeustasy With a Continuous Carbonate Record in Northern Spain

During the Late Paleozoic Ice Age (LPIA, 345–260 Ma), an expansion of ice house conditions at 330 Ma caused a nearly synchronous, global unconformity. Subaerially exposed paleotropical carbonates were dissolved by meteoric waters, mixed with the light terrestrial carbon, and recrystallized with overprinted, diagenetic dC values. In Northern Spain, development of a rapidly subsiding foreland basin kept local sea level relatively high, allowing continuous carbonate deposition to record dC without meteoric overprint. The Spanish sections show a 2& increase in dC that can be modeled as the ocean’s response to the creation of a significant light carbon sink through widespread meteoric diagenesis of marine carbonates during the near-global hiatus. About 15–35 m of sea level fall would have exposed a large enough volume of carbonate to account for the positive excursion in dC of oceanic DIC. Combining the dC data with high resolution biostratigraphy and new ID-TIMS U-Pb zircon ages from interbedded tuffs, we calculate that the depositional hiatus and glacioeustatic fall caused by the early Serpukhovian phase of ice growth lasted for approximately 3.5 My.