Bradley D. Eyre

Comparison of isotope pairing and N 2 /Ar methods for measuring sediment dentrification - assumptions, 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.

Transport, retention and transformation of material in Australian estuaries

Australian estuaries can be classified into five groups on the basis of their hydrology: Mediterranean, Temperate, Transitional, Arid Tropical and Subtropical, and Wet and Dry Tropical and Subtropical. Most Australian estuaries (68%) are wet and dry tropical and subtropical systems. The five groups of estuaries found in Australia are similar to those found in other parts of the world, but within each individual category the estuaries are more variable. This variability reflects a combination of the extreme hydrology of Australian rivers and the geomorphology of Australian estuaries, which are shallow due to tectonic stability and low coastal relief. Episodic freshwater flows control the transport, retention, and transformation of material in most Australian estuaries, and for only a small part of the year during high flow events do most Australian rivers and estuaries contribute a significant amount of material to the continental shelf. Research and monitoring efforts need to be directed toward evaluating the role episodic freshwater discharges play in the functioning of Australia’s estuaries.

Diel coral reef acidification driven by porewater advection in permeable carbonate sands, Heron Island, Great Barrier Reef

can play a major role in proton (H + ) cycling in a coral reef lagoon. The diel pH range (up to 0.75 units) in the Heron Island lagoon was the broadest ever reported for reef waters, and the night‐time pH (7.69) was comparable to worst‐case scenario predictions for seawater pH in 2100. The net contribution of coarse carbonate sands to the whole system H + fluxes was only 9% during the day, but approached 100% at night when small scale (i.e., flow and topography‐induced pressure gradients) and large scale (i.e., tidal pumping as traced by radon) seawater recirculation processes were synergistic. Reef lagoon sands were a net sink for H + ,a nd the sink strength was a function of porewater flushing rate. Our observations suggest that the metabolism of advection‐ dominatedcarbonatesandsmayprovideacurrently unknown feedbackto ocean acidification. Citation: Santos, I. R., R. N. Glud, D. Maher, D. Erler, and B. D. Eyre (2011), Diel coral reef acidification driven by porewater advection in permeable carbonate sands, Heron Island, Great Barrier Reef, Geophys. Res. Lett., 38, L03604, doi:10.1029/2010GL046053.

A comparative study of nutrient behavior along the salinity Gradient of tropical and temperate estuaries

The differences and similarities between near-pristine estuaries of different latitudinal regions were examined by selecting three tropical systems from North Queensland, Australia (Jardine, Annan, Daintree) and three temperate systems from Scotland, United Kingdom (Inverness, Cromarty, Dornoch Firths) for comparison. Although estuaries from the different regions have a number of unifying features, such as salinity gradients, tidal variations and terrestrial inputs they also have a number of important differences. The most distinct of these is the timing and variability of the major physical forcings on the estuary (e.g., river flow, insolation). The three tropical estuaries were much more episodic than their temperate counterparts, with a much more dynamic salinity structure and more variable riverwater concentrations, so that delivery of material to the estuary is dominated by short-lived flood events. In contrast, seawater concentrations were more stable in the tropical estuaries due to a more constant input of insolation, resulting in year round biological activity. There was biological removal of dissolved inorganic phosphorus in the low salinity region of the tropical Jardine and Daintree estuaries and a low salinity input of nitrate in the tropical Annan estuary most likely due to nitrification in the bottom sediments, and the biological reaction zone in the tropical Annan Estuary was flushed out of the estuarine basin to the edge of the offshore plume during a flood. Similar effects were not seen in the temperate Inverness, Cromarty, and Dornoch Firths. Similarities between estuaries include mid-estuary inputs of ammonium which were seen in both the temperate and tropical estuaries, although they occur under vastly contrasting conditions of low river discharge and periods of flood, respectively. Five of the estuaries show a general increase in dissolved inorganic phosphorus concentrations towards the sea during low flows, reflecting their pristine condition, and all six estuaries had low salinity silicate maxima probably sourced from the dissolution of freshwater biogenic silicate that has been carried seaward, except in the tropical estuaries during the dry season when a benthic source is proposed.

Transport and retention of nitrogen and phosphorus in the sub-tropical Richmond River estuary, Australia - a budget approach.

Nitrogen and phosphorus loads in the sub-tropicalRichmond River estuary were quantified and materialbudgets were developed over two years of contrastingfreshwater discharge. During both years >74% of thenitrogen and >84% of the phosphorus load enteredthe estuary during one month when flooding occurred inthe catchment. Due to larger flood magnitude, loadsduring the 1995/96 year were 3.3 and 2.5 times greaterthan during the 1994/95 year for nitrogen andphosphorus respectively. During floods the estuarinebasin was completely flushed of brackish water and themajority of the nutrient loads passed directly throughthe estuary. The nutrient load retained in the estuaryduring floods was inversely proportional to floodmagnitude. Annual budgets show that >97% of thenutrient load entering the estuary was from diffusecatchment sources; precipitation, urban runoff, andsewage were negligible. Less than 2.5% of thenitrogen and <5.4% of the phosphorus loads enteringthe estuary were retained in sediments. During dryseasons the estuary became a net sink for nitrogeninput from the ocean and the estuarine sedimentsremained a net source of phosphorus to the watercolumn and ocean. The process of flood scouring islikely to be the cleansing mechanism responsible formaintaining water quality both on an annual basis andover the last 50 years and may also be responsible forpotential nitrogen limitation. The sub-tropicalRichmond River estuary contrasts with the majority oftemperate systems of North America and Europe whichtypically have lower inter- and intra-annual nutrientload variability, longer and less variable flushingtimes, and greater nutrient retention.

Coupling Automated Radon and Carbon Dioxide Measurements in Coastal Waters

Groundwater discharge could be a major, but as yet poorly constrained, source of carbon dioxide to lakes, wetlands, rivers, estuaries, and coastal waters. We demonstrate how coupled radon ((222)Rn, a natural groundwater tracer) and pCO(2) measurements in water can be easily performed using commercially available gas analysers. Portable, automated radon and pCO(2) gas analysers were connected in series and a closed air loop was established with gas equilibration devices (GED). We experimentally assessed the advantages and disadvantages of six GED. Response times shorter than 30 min for (222)Rn and 5 min for pCO(2) were achieved. Field trials revealed significant positive correlations between (222)Rn and pCO(2) in estuarine waterways and in a mangrove tidal creek, implying that submarine groundwater discharge was a source of CO(2) to surface water. The described system can provide high resolution, high precision concentrations of both radon and pCO(2) with nearly no additional effort compared to measuring only one of these gases. Coupling automated (222)Rn and pCO(2) measurements can provide new insights into how groundwater seepage contributes to aquatic carbon budgets.

Nutrient Cycling in the Sub-tropical Brunswick Estuary, Australia

A combination of mixing plots, one-dimensional salt balance modelling, nutrient loading budgets, and benthic flux measurements were used to assess nutrient cycling pathways in the enriched sub-tropical Brunswick estuary during different freshwater flows. A simple model accounting for freshwater residence times and nutrient availability was found to be a good predictor of phytoplankton biomass along the estuary, and suggested that biomass accumulation may become nutrient-limited during low flows and that recycling within the water column is important during blooms. Dissolved inorganic nitrogen (DIN) cycling budgets were constructed for the estuary during different freshwater flows accounting for all major inputs (catchment, sewage, and urban) to the estuary. Internal cycling due to phytoplankton uptake (based on measured biomass) and sediment-water fluxes (based on measured rates in each estuarine reach) was considered. Four different nutrient cycling states were identified during the study. In high flow, freshwater residence times are less than 1 d, internal cycling processes are bypassed and virtually all dissolved, and most particulate, nutrients are delivered to the continental shelf. During the growth phase of a phytoplankton bloom enhanced recycling occurs as residence times increase sufficiently to allow biomass accumulation. Remineralization of phytoplankton detritus during this phase can supply up to 50% of phytoplankton DIN demands. In post-bloom conditions, DIN uptake by phytoplankton decreases in the autumn wet season when biomass doubling times begin to exceed residence times. OM supply to the sediments diminishes and the benthos becomes nutrient-limited, resulting in DIN uptake by the sediments. As flows decrease further in the dry season, there is tight recycling and phytoplankton blooms, and uptake by the sediments can account for the entire DIN loading to the estuary resulting in complete removal of DIN from the water column. The ocean is a potentially important source of DIN to the estuary at this time. The results of the DIN cycling budgets compared favorably with mixing plots of DIN at each time. The results suggest that a combination of different approaches may be useful in developing a more comprehensive understanding of nutrient cycling behavior and the effects of nutrient enrichment in estuaries.

Water quality changes in an episodically flushed sub-tropical Australian estuary: a 50 year perspective

Abstract Recent and historical data sets from the Richmond River estuary (New South Wales, Australia) were examined for possible impacts of changing land use patterns in the catchment and estuary floodplain on water quality over the last 50 years. Floodplain management practices, including further draining and disturbance of acid sulphate soils appear to have had no appreciable effect on the processes that control the degree of oxygen saturation in the estuary. Following runoff events phosphate and nitrate concentrations at a given salinity are respectively 2.5 and 3.0 times higher than 50 years ago, due to leaching from agricultural areas where fertilisers are applied. However, these concentrations quickly decrease after the runoff event due to rapid flushing of the system. Land use changes in the last 50 years appear to have had no impact on dry or low-flow phosphate and nitrate concentrations in the estuary, which are dominantly controlled by internal processes due to long water residence times. Particulate and bottom sediment phosphorus buffering apparently maintain dry season phosphate concentrations in the estuarine water column between about 0.30 and 0.80 μM. Nitrate levels are quite low (

Linking groundwater discharge to severe estuarine acidification during a flood in a modified wetland

Periodic acidification of waterways adjacent to coastal acid sulfate soils (CASS) is a significant land and water management issue in the subtropics. In this study, we use 5-months of continuous radon ((222)Rn, a natural groundwater tracer) observations to link estuarine acidification to groundwater discharge in an Australian CASS catchment (Tuckean Swamp). The radon time series began in the dry season, when radon activities were low (2-3 dpm L(-1)), and the pH of surface water was 6.4. We captured a major rain event (213 mm on 2 March 2010) that flooded the catchment. An immediate drop in pH during the flood may be attributed to surface water interactions with soil products. During the post-flood stage, increased radon activities (up to 19.3 dpm L(-1)) and floodplain groundwater discharge rates (up to 2.01 m(3) s(-1), equivalent to 19% of total runoff) coincided with low pH (3.77). Another spike in radon activities (13.2 dpm L(-1)) coincided with the lowest recorded surface water pH (3.62) after 72 mm of rain between 17 and 20 April 2010. About 80% of catchment acid exports occurred when the estuary was dominated by groundwater discharging from highly permeable CASS during the flood recession.

Intra- and interannual export of nitrogen and phosphorus in the subtropical Richmond River catchment, Australia

Nitrogen and phosphorus concentrations were measured and exports were calculated in the subtropical Richmond River catchment between July 1994 and June 1996. A stratified sampling approach was adopted owing to the extreme and rapid changes in riverine discharge, which varied by up to 10 000 times over the study period. Nutrient concentrations were lowest during baseflow. During storm discharge, dissolve inorganic and organic and particulate nitrogen and phosphorus concentrations increased two- to five fold, and followed hysteresis patterns that were attributed to the integration and/or depletion of catchment nutrient sources during an event. Dissolved organic nitrogen and particulate phosphorus were the dominant nutrient forms. Land use and antecedent conditions had a large influence on nutrient concentrations and exports. During the 1995–96 year (slightly above the mean annual discharge) 96% of nitrogen and 98% of phosphorus loads were transported in less than 6% of the time. When averaged across the catchment, monthly riverine nutrient loads varied by up to 1061-fold during the study and exports were approximately four-fold greater during the second year relative to the first. The subtropical Richmond River catchment has greater intra- and potential interannual variability in nutrient loads and exports when compared with temperate catchments from other parts of the world. It is suggested that in tropical and subtropical Australian catchments with large intra- and interannual variation in discharge, the need for parameterizing the antecedent conditions, such as the degree of nutrient storage, may make it difficult to model spatial and temporal (short time-scale) nutrient exports. Copyright