Anoxic nitrification: Evidence from Humber Estuary sediments (UK)

Conventional understanding of the nitrogen cycle in marine sediments has changed in recent years with the discovery of an alternative pathway for ammonia oxidation via the reduction of manganese oxides (during anoxic nitrification). In anoxic sediments, the potential for manganese oxides to serve as oxidant for nitrification may be considerable yet previous work on manganese-rich sediments has suggested anoxic nitrification may not be significant. In this study, the potential for anoxic nitrification in a range of sediment types was investigated. Laboratory incubation of sediment from three sites on the Humber Estuary, a microbially diverse environment, showed anoxic accumulation of nitrate, nitrite and dinitrogen gas, with and without the addition of synthetic manganese oxides. Incubation experiments confirmed anoxic nitrification as microbially mediated, with heat-killed controls yielding negative results. The anoxic nitrification reaction significantly depleted ammonia concentrations, and occurred simultaneously with manganese-, iron- and sulphate reduction, and methanogenesis. Taken in conjunction with other studies, results suggest anoxic nitrification may not only be dependent on total manganese concentrations but on manganese dynamics. Anoxic nitrification may be explained as a non-steady state reaction, dependent on the recent stability of a sediment system. Physical perturbation of sediments may cause the redistribution and/or introduction of manganese oxides and promote anoxic nitrification. The significance and persistence of anoxic nitrification is likely to depend on the frequency and magnitude of sediment perturbation, which explains why the reaction varies so widely across studied sites, and why it may not occur in some manganese-rich sediment.     

Clinoform nucleation and growth in coarse-grained deltas, Loreto basin, Baja California Sur, Mexico: a response to episodic accelerations in fault displacement

We investigate the controls on the architecture of coarse‐grained delta progradational units (PUs) in the Pliocene Loreto basin (Baja California Sur, Mexico), a half‐graben located on the western margin of the Gulf of California. Dorsey et al. (1997b) argued that delta progradation and transgression cycles in the basin were driven by episodic fault‐controlled subsidence along the basin‐bounding Loreto fault. Here we test this hypothesis by a detailed analysis of the sedimentary architecture of 11 exceptionally well‐exposed, vertically arranged fluvio‐deltaic PUs, each of which shows lateral facies transition from proximal alluvial facies palaeo‐seaward into distal pro‐delta facies. Of these 11 PUs, seven exhibit a lateral transition from a shoal water to Gilbert‐delta facies associations as they are traced palaeo‐seaward. This transition is characterised by down‐transport development of foresets, which grow in height up to 35 m. Foreset units thicken in a basinward direction, with initially an oblique topset–foreset geometry that becomes increasingly sigmoidal. Each delta is capped by a shell bed that records drowning of the delta top. This systematic transition in delta architecture records increasing water depth through time during individual episodes of progradation. A mechanism that explains this transition is an accelerating rate of fault‐controlled subsidence during each PU. During episodes of low slip rate, shoal‐water deltas prograde across the submerged topography of the underlying delta unit. As displacement rate accelerates, increasing bathymetry at the delta front leads to steepening of foresets and initiation of Gilbert deltas. Subsequent delta drowning results from sediment starvation at the shoreline at high slip rates because of sediment trapping upstream. The observed delta architecture suggests that the long‐term (>100 kyr) history of slip on the Loreto fault was characterised by repetitive episodes of accelerating displacement accumulation. Such episodic fault behaviour is most likely to be because of variations in temporal and spatial strain partitioning between the Loreto fault and other faults in the Gulf of California. A physical explanation for the acceleration phenomenon involves evolving frictional properties on the episodically active Loreto fault.     

The effects of stock size and environmental variability on Cape hake recruitment in Namibia: an unsolved puzzle (a comment on Kainge et al. 2013)

Measuring and forecasting recruitment are central to the understanding and management of fish stocks. Kainge et al. (2013) studied the effect of spawning stock size and environmental fluctuations on the recruitment levels of the Cape hake Merluccius capensis in Namibia. However, their study contains some flaws that undermine the conclusion that Cape hake recruitment is under the influence of upwelling in summer. Until those flaws are properly addressed, this conclusion, in our view, should be treated with caution.     

Temporal and geochemical evolution of the Cenozoic intraplate volcanism of Zealandia

In order to constrain better the distribution, age, geochemistry and origin of widespread Cenozoic intraplate volcanism on Zealandia, the New Zealand micro-continent, we report new ⁴⁰Ar/³⁹Ar and geochemical (major and trace element and Sr–Nd–Hf–Pb isotope) data from offshore (Chatham Rise, Campbell and Challenger Plateaus) and onland (North, South, Auckland, Campbell, Chatham and Antipodes Islands of New Zealand) volcanism on Zealandia. The samples include nephelinite, basanite through phonolite, alkali basalt through trachyte/rhyolite, and minor tholeiite and basaltic andesite, all of which have ocean island basalt (OIB)-type trace element signatures and which range in age from 64.8 to 0.17 Ma. Isotope ratios show a wide range in composition (⁸⁷Sr/⁸⁶Sr = 0.7027–0.7050, ¹⁴³Nd/¹⁴⁴Nd = 0.5128–0.5131, ¹⁷⁷Hf/¹⁷⁶Hf = 0.2829–0.2831, ²⁰⁶Pb/²⁰⁴Pb = 18.62–20.67, ²⁰⁷Pb/²⁰⁴Pb = 15.54–15.72 and ²⁰⁸Pb/²⁰⁴Pb = 38.27–40.34) with samples plotting between mid-ocean-ridge basalts (MORB) and Cretaceous New Zealand intraplate volcanic rocks.Major characteristics of Zealandia's Cenozoic volcanism include longevity, irregular distribution and lack of age progressions in the direction of plate motion, or indeed any systematic temporal or spatial geochemical variations. We believe that these characteristics can be best explained in the context of lithospheric detachment, which causes upwelling and melting of the upper asthenospheric mantle and portions of the removed lithosphere. We propose that a large-scale seismic low-velocity anomaly, that stretches from beneath West Antarctica to Zealandia at a depth of > 600 km may represent a geochemical reservoir that has been in existence since the Cretaceous, and has been supplying the upper mantle beneath Zealandia with HIMU-type plume material throughout the Cenozoic. In addition, the sources of the Cenozoic intraplate volcanism may be at least partially derived through melting of locally detached Zealandia lower lithosphere.     

Evidence for ocean acidification in the Great Barrier Reef of Australia

Geochemical records preserved in the long-lived carbonate skeleton of corals provide one of the few means to reconstruct changes in seawater pH since the commencement of the industrial era. This information is important in not only determining the response of the surface oceans to ocean acidification from enhanced uptake of CO₂, but also to better understand the effects of ocean acidification on carbonate secreting organisms such as corals, whose ability to calcify is highly pH dependent. Here we report an ∼200 year δ¹¹B isotopic record, extracted from a long-lived Porites coral from the central Great Barrier Reef of Australia. This record covering the period from 1800 to 2004 was sampled at yearly increments from 1940 to the present and 5-year increments prior to 1940. The δ¹¹B isotopic compositions reflect variations in seawater pH, and the δ¹³C changes in the carbon composition of surface water due to fossil fuel burning over this period. In addition complementary Ba/Ca, δ¹⁸O and Mg/Ca data was obtained providing proxies for terrestrial runoff, salinity and temperature changes over the past 200 years in this region. Positive thermal ionization mass spectrometry (PTIMS) method was utilized in order to enable the highest precision and most accurate measurements of δ¹¹B values. The internal precision and reproducibility for δ¹¹B of our measurements are better than ±0.2‰ (2σ), which translates to a precision of better than ±0.02 pH units. Our results indicate that the long-term pre-industrial variation of seawater pH in this region is partially related to the decadal-interdecadal variability of atmospheric and oceanic anomalies in the Pacific. In the periods around 1940 and 1998 there are also rapid oscillations in δ¹¹B compositions equivalent changes in pH of almost 0.5 U. The 1998 oscillation is co-incident with a major coral bleaching event indicating the sensitivity of skeletal δ¹¹B compositions to loss of zooxanthellate symbionts. Importantly, from the 1940s to the present-day, there is a general overall trend of ocean acidification with pH decreasing by about 0.2-0.3 U, the range being dependent on the value assumed for the fractionation factor α_(B3-B4) of the boric acid and borate species in seawater. Correlations of δ¹¹B with δ¹³C during this interval indicate that the increasing trend towards ocean acidification over the past 60 years in this region is the result of enhanced dissolution of CO₂ in surface waters from the rapidly increasing levels of atmospheric CO₂, mainly from fossil fuel burning. This suggests that the increased levels of anthropogenic CO₂ in atmosphere has already caused a significant trend towards acidification in the oceans during the past decades. Observations of surprisingly large decreases in pH across important carbonate producing regions, such as the Great Barrier Reef of Australia, raise serious concerns about the impact of Greenhouse gas emissions on coral calcification.     

The Effect of Macrofauna on Porewater Profiles and Nutrient Fluxes in the Intertidal Zone of the Humber Estuary

Macrofauna, nutrient fluxes, porewater chemistry and sediment characteristics were measured at six intertidal mudflat sites in the Humber Estuary, U.K., during the different seasons. Nereis diversicolor , Macoma balthica and Corophium volutator were found to be the dominant macrofauna. Salinity was the baseline control on macrofauna distribution but this was overprinted by periodic impoverishment due to sediment mobilization. High resolution gel probe porewater samplers provided direct evidence for the impact of burrows on porewater chemistry. The macrofauna modified nutrient fluxes during periods of mud flat stability. Nereis caused a decrease in silicate and phosphate effluxes but enhanced ammonia release and nitrate uptake. Macoma enhanced ammonia and nitrite release. The impact of Corophium was not possible to discern. The Humber is a large, highly dynamic macrotidal estuary in which sediment resuspension has a large impact on porewater profiles, nutrient fluxes and macrofaunal communities. Simple patterns and inter-relationships which are seen in small sheltered estuaries are not observed in the Humber.     

Palaeogeographical changes in response to glacial–interglacial cycles,as recorded in Middle and Late Pleistocene seismic stratigraphy,southern North Sea

Offshore stratigraphic records from the North Sea contain information to reconstruct palaeo-ice-sheet extent and understand sedimentary processes and landscape response to Pleistocene glacial–interglacial cycles. We document three major Middle to Late Pleistocene stratigraphic packages over a 401-km² area (Norfolk Vanguard/Boreas Offshore Wind Farm), offshore East Anglia, UK, through the integration of 2D seismic, borehole and cone penetration test data. The lowermost unit is predominantly fluviatile [Yarmouth Roads Formation, Marine Isotope Stage (MIS) 19–13], including three northward-draining valleys. The middle unit (Swarte Bank Formation) records the southernmost extent of tunnel valley-fills in this area of the North Sea, providing evidence for subglacial conditions most likely during the Anglian stage (MIS 12) glaciation. The Yarmouth Roads and Swarte Bank deposits are truncated and overlain by low-energy estuarine silts and clays (Brown Bank Formation; MIS 5d–4). Smaller scale features, including dune-scale bedforms, and abrupt changes in cone penetration test parameters, provide evidence for episodic changes in relative sea level within MIS 5. The landscape evolution recorded in deposits of ~MIS 19–5 are strongly related to glacial–interglacial cycles, although a distinctive aspect of this low-relief ice-marginal setting are opposing sediment transport directions under contrasting sedimentary process regimes.     

Measurement of soluble reactive phosphorus concentration profiles and fluxes in river-bed sediments using DET gel probes

DET (diffusive equilibrium in thin films) gel probes were used for sampling river-bed sediment porewaters, to characterise in situ soluble reactive phosphorus (SRP) concentration profiles and fluxes. DET probes were deployed in three contrasting rural streams: (1) a headwater ‘pristine’ stream, with minimal P inputs from low intensity grassland and no point sources, (2) an intensively cultivated arable catchment, and (3) a stream subject to high P loadings from sewage effluent and intensive arable farming. The DET results showed highly enriched porewater SRP concentrations of between ca. 400 and 5000 μg-P l⁻¹ in the sewage-impacted stream. In contrast, the arable and pristine streams had porewater SRP concentrations <70 μg-P l⁻¹ and <20 μg-P l⁻¹, respectively. Porewater SRP concentration profiles in both the sewage-impacted and arable-impacted streams showed well-defined vertical structure, indicating internal sources and sinks of SRP within the sediment. However, there was little variability in porewater SRP concentrations in the pristine stream. The DET porewater profiles indicated net diffusion of SRP (a) from the overlying river water into the surface sediment and (b) from subsurface sediment upwards towards the sediment–water interface. A mass balance for the sewage-impacted site showed that the influx of SRP into the surface sediments from the overlying river water was small (ca. 1% of the daily river SRP load). The DET results indicated that, in the arable and sewage-impacted streams, the surface ‘cap’ of fine sediment may play an important role in inhibiting upward movement of SRP from subsurface porewaters into the overlying river water, under steady-state, low-flow conditions.     

Using an unbaited stationary video system to investigate the behaviour and interactions of bull sharks Carcharhinus leucas under an aquaculture farm

Bull sharks Carcharhinus leucas are common along the coast of Reunion Island (South-West Indian Ocean) and were suspected to aggregate in the vicinity of an aquaculture farm in Saint-Paul Bay on the west coast. In order to understand the behaviour and interaction of bull sharks near aquaculture cages at Saint-Paul Bay, we deployed an experimental unbaited stationary video camera. From 175 hours of recording during daylight hours from March to April 2012, eight individual female bull sharks (seven adults and one immature) were identified based on their natural markings. These sharks were resighted between 3 and 45 times. Residency analysis revealed site attachment under the aquaculture cages for at least three individuals over the course of the study. Recorded behaviours included intraspecific social interactions such as synchronised swimming. Social interactions and relatively strong paired associations for two pairs of females suggest some level of sociality among bull sharks around Reunion Island. Overall, our results demonstrate the utility of unbaited video systems to monitor the behaviour of adult coastal sharks.     

Ion migration in nepheline: a dielectric spectroscopy and computer modelling study

 Using a combination of dielectric spectroscopy and atomistic computer simulation techniques, the dynamical behaviour of the loosely bound (Na⁺ and K⁺) channel ions in nepheline has been investigated. The low-frequency dielectric properties of a natural Bancroft nepheline have been studied from room temperature to 1100 K. At each temperature, the dielectric constant, conductivity and dielectric loss were determined over a range of frequencies from 100 Hz to 10 MHz. At high temperatures a distinct Debye-type relaxation in the dielectric loss spectrum was observed; the activation energy for this process was determined to be 1.38 ± 0.02 eV. Atomistic simulation techniques were used to elucidate the mechanism and energetics of cation migration. A mechanism involving the hopping of Na⁺ ions between oval sites and partially occupied hexagonal (K⁺) sites, via a bottleneck consisting of a distorted sixfold ring of (Al,Si)O₄ tetrahedra, was found to give a calculated energy barrier in very good agreement with the experimentally determined activation energy. These results confirm the nature of the process responsible for the observed dielectric behaviour. Overall, this study demonstrates the intrinsic, microscopic control of cation diffusion processes in rock-forming minerals. Identifying specific energy barriers and preferred diffusion pathways is fundamental to the prediction of diffusion energetics. Received: 8 May 2000 / Accepted: 21 July 2000