Comparison of isotope pairing and N2:Ar methods for measuring sediment denitrification—Assumption, modifications, and implications

Denitrification has been measured during the last few years using two different methods in particular: isotope pairing measured on a triple-collector isotopic ratio mass spectrometer and N₂:Ar ratios measured on a membrane inlet mass spectrometer (MIMS). This study compares these two techniques in short-term batch experiments. Rates obtained using the original N₂∶Ar method were up to 3 to 4 times higher than rates obtained using the isotope pairing technique due to O₂ reacting with the N₂ during MIMS analysis. Oxygen combines with N₂ within the mass spectrometer ion source forming NO⁺ which reduces the N₂ concentration. The decrease in N₂ is least at lower O₂ concentrations and since oxygen is typically consumed during incubations of sediment cores, the result is often a pseudo-increase in N₂ concentration being interpreted as denitrification activity. The magnitude of this ocygen effect may be instrument specific. The reaction of O₂ with N₂ and the subsequent decrease in N₂ was only partly correctly using an O₂ correction curve for the relationship between N₂ and O₂ concentrations. The O₂ corrected N₂∶Ar denitrification rates were lower, but still did not match the isotope pairing rates and the variability between replicates was much higher. Using a copper reduction column heated to 600°C to remove all of the O₂ from the sample before MIMS analysis resulted in comparable rates (slightly lower), and comparable variability between replicates, to the isotope pairing technique. The N₂:Ar technique determines the net N₂ production as the difference between N₂ production by denitrification and N₂ consumption by N-fixation, while N-fixation has little effect on the isotope pairing technique which determines a rate very close to the gross N₂ production. When the two different techniques were applied on the same sediment, the small difference in rates obtained by the two methods seemed to reflect N-fixation as also supported from measurements of ethylene production in acetylene enriched sediment cores. The N₂:Ar and isotope pairing techniques may be combined to provide simultaneous measurements of denitrification and N-fixation. Both techniques have several assumptions that must be met to achieve accurate rates; a number of tests are outlined that can be applied to demonstrate that these assumptions are being meet.     

Benthic Carbon Mineralization and Nutrient Turnover in a Scottish Sea Loch: An Integrative In Situ Study

Based on in situ microprofiles, chamber incubations and eddy covariance measurements, we investigated the benthic carbon mineralization and nutrient regeneration in a ~65-m-deep sedimentation basin of Loch Etive, UK. The sediment hosted a considerable amount of infauna that was dominated by the brittle star A. filiformis. The numerous burrows were intensively irrigated enhancing the benthic in situ O₂ uptake by ~50 %, and inducing highly variable redox conditions and O₂ distribution in the surface sediment as also documented by complementary laboratory-based planar optode measurements. The average benthic O₂ exchange as derived by chamber incubations and the eddy covariance approach were similar (14.9 ± 2.5 and 13.1 ± 9.0 mmol m^?2 day^?1) providing confidence in the two measuring approaches. Moreover, the non-invasive eddy approach revealed a flow-dependent benthic O₂ flux that was partly ascribed to enhanced ventilation of infauna burrows during periods of elevated flow rates. The ratio in exchange rates of ΣCO₂ and O₂ was close to unity, confirming that the O₂ uptake was a good proxy for the benthic carbon mineralization in this setting. The infauna activity resulted in highly dynamic redox conditions that presumably facilitated an efficient degradation of both terrestrial and marine-derived organic material. The complex O₂ dynamics of the burrow environment also concurrently stimulated nitrification and coupled denitrification rates making the sediment an efficient sink for bioavailable nitrogen. Furthermore, bioturbation mediated a high efflux of dissolved phosphorus and silicate. The study documents a high spatial and temporal variation in benthic solute exchange with important implications for benthic turnover of organic carbon and nutrients. However, more long-term in situ investigations with like approaches are required to fully understand how environmental events and spatio-temporal variations interrelate to the overall biogeochemical functioning of coastal sediments.     

Estuarine modification of nutrient and sediment exports to the Great Barrier Reef Marine Park from the Daintree and Annan River catchments

Nutrient and suspended sediment concentrations were measured in the dry season and during the rising and falling stages of flood events in the Annan and Daintree rivers to estimate catchment exports. These flood events were also sampled along the salinity gradient in the estuary and nearshore shelf to quantify the modification of terrestrial sediment and nutrient loads as they pass through estuaries into the Great Barrier Reef lagoon. In the Daintree River TSS concentrations were found to increase between the catchment and the estuary plume. The source of TSS may have been scour of the estuarine channel or from land use in the catchment of the lower estuary. In the dry season nitrogen enters the Annan and Daintree estuaries predominantly in the form of PON and DON in roughly equal proportions. Nitrogen exports to the GBR are mostly in the form of DON. In the wet season the majority of nitrogen enters the estuaries as DON and leaves as PON. Nitrogen removal in the estuaries and plumes appears to be biologically mediated once suspended sediment concentrations decrease to a point where phytoplankton growth is not light limited. In the dry season phosphorus enters and leaves the estuaries primarily in organic form. PIP is the dominant form of phosphorus in river water, but leaves the estuary more evenly distributed between all forms. These estuarine processes result in less nitrogen and phosphorus being delivered to the GBR lagoon than is exported from the catchment. The differences between these estuaries highlights the need for further work to explore modifications in estuaries that drain into the Great Barrier Reef lagoon.     

The effects of two benthic chamber stirring systems on the diffusive boundary layer,oxygen flux,and passive flow through model macrofauna burrows

Diffusive boundary layers (DBL), sediment oxygen flux, and natural passive flow through model macrofauna burrows were compared in two benthic chambers: one with a conventional rotational stirrer and the other with a two-dimensional flow diffuser system. Oxygen microprobe profiles showed that at similar velocities the mean diffusive boundary layer (DBL) thickness induced by a conventional rotor stirrer (453±118 μm) was not significantly different to that produced by the diffuser system (403±53 μm). The rotor produced twice as much DBL spatial variability (coefficient of variation 27%) as the diffuser (CV 11%). Variability between the rotor system’s DBL transect replicates was also two times greater (average CV of 22%) compared to the diffuser (CV 14%). At equivalent stirring speeds over experimental sediments, mean O₂ consumption rates were also not significantly different between the two systems. The diffuser induced consistently greater (16–37%) passive Bernoullian flow through model macrofauna borrows irrespective of the position of inhalant-exhalent openings. The rotor stimulated anomalous burrow flow regimes over a greater area of the chamber floor (36%) compared to the diffuser (23%). Depending on vent orientation the rotor was shown to reverse (exhalent to inhalant) burrow flow regimes in the central 9% of the chamber floor. This artifact of radial pressure and velocity differentials may have severe implications for tube dwelling infauna that rely on unidirectional flow. The diffuser system more closely mimicked natural two-dimensional water flow over the sediment surface and structures therein and is likely to give more representative results when measuring benthic processes within incubation devices.     

On the long-term context of the 1997–2009 ‘Big Dry’ in South-Eastern Australia: insights from a 206-year multi-proxy rainfall reconstruction

This study presents the first multi-proxy reconstruction of rainfall variability from the mid-latitude region of south-eastern Australia (SEA). A skilful rainfall reconstruction for the 1783–1988 period was possible using twelve annually-resolved palaeoclimate records from the Australasian region. An innovative Monte Carlo calibration and verification technique is introduced to provide the robust uncertainty estimates needed for reliable climate reconstructions. Our ensemble median reconstruction captures 33% of inter-annual and 72% of decadal variations in instrumental SEA rainfall observations. We investigate the stability of regional SEA rainfall with large-scale circulation associated with El Niño–Southern Oscillation (ENSO) and the Inter-decadal Pacific Oscillation (IPO) over the past 206 years. We find evidence for a robust relationship with high SEA rainfall, ENSO and the IPO over the 1840–1988 period. These relationships break down in the late 18th–early 19th century, coinciding with a known period of equatorial Pacific Sea Surface Temperature (SST) cooling during one of the most severe periods of the Little Ice Age. In comparison to a markedly wetter late 18th/early 19th century containing 75% of sustained wet years, 70% of all reconstructed sustained dry years in SEA occur during the 20th century. In the context of the rainfall estimates introduced here, there is a 97.1% probability that the decadal rainfall anomaly recorded during the 1998–2008 ‘Big Dry’ is the worst experienced since the first European settlement of Australia.     

The Contribution of Groundwater Discharge to Nutrient Exports from a Coastal Catchment: Post-Flood Seepage Increases Estuarine N/P Ratios

Four months of daily nutrient and radon (a natural groundwater tracer) observations at the outlet of a heavily drained coastal wetland illustrated how episodic floods and diffuse groundwater seepage influence the biogeochemistry of a sub-tropical estuary (Richmond River, New South Wales, Australia). Our observations downstream of the Tuckean Swamp (an acid sulphate soil floodplain) covered a dry stage, a flood triggered by a 213-mm rain event and a post-flood stage when surface water chemistry was dominated by groundwater discharge. Significant correlations were found between radon and ammonium and N/P ratios and between radon and dissolved organic nitrogen (DON) during the post-flood stage. While the flood lasted for 14?% of the time of the surface water time series, it accounted for 18?% of NH₄, 32?% of NO _x , 66?% of DON, 58?% of PO₄ and 55?% of dissolved organic phosphorus (DOP) catchment exports. Over the 4-month study period, groundwater fluxes of 35.0, 3.6, 36.3, 0.5 and 0.7?mmol?m^?2?day^?1 for NH₄, NO _x , DON, PO₄ and DOP, respectively, were estimated. The groundwater contribution to the total surface water catchment exports was nearly 100?% for ammonium, and <20?% for the other nutrients. Post-flood groundwater seepage shifted the system from a DON to a dissolved inorganic N-dominated system and doubled N/P ratios in surface waters. We hypothesise that the Richmond River Estuary N/P ratios may reflect a widespread trend of tidal rivers and estuaries becoming more groundwater-dominated and phosphorus-limited as coastal wetlands are drained for agriculture, grazing and development.     

Frequency dependence of magnetic susceptibility for populations of single-domain grains

A recent paper (Dearing et al . 1996) on the use of frequency dependence of magnetic susceptibility (Xfd) in magnetic grain-size investigations of environmental materic has proposed a fundamentally new model for the magnetic susceptibility of single-domain (SD) grains measured at different frequencies, and is divergent from the no well-established theory of SD behaviour. This new model appears to be founded on a confusion about the behaviour of SD grains, as predicted by theory, and magnetic measurements of real materials, which naturally have a distribution of magnetic grain sizes. Here I try to clear up this confusion by showing how different log-normal distributions of magnetic grain sizes affect the frequency dependence of magnetic susceptibility measurement. This analysis highlights that the limiting maximum Xfd value of ˜ 15 per cent obtained for environmental materials can be explained simply as a constraint imposed by the magnetic grain-size distribution having a finite minimum width (˜1.0 on a natural log scale). There is no reason to suppose that if the grain-size dispersion was narrower higher Xfd values could not be observed. Furthermore, the Xfd value is non-unique and so cannot be used quantitatively to determine the amount or grain-size distribution of SD grains in a sample