Joanne Margaret Oakes

Novel use of cavity ring-down spectroscopy to investigate aquatic carbon cycling from microbial to ecosystem scales

Development of cavity ring-down spectroscopy (CRDS) has enabled real-time monitoring of carbon stable isotope ratios of carbon dioxide and methane in air. Here we demonstrate that CRDS can be adapted to assess aquatic carbon cycling processes from microbial to ecosystem scales. We first measured in situ isotopologue concentrations of dissolved CO2 ((12)CO2 and (13)CO2) and CH4 ((12)CH4 and (13)CH4) with CRDS via a closed loop gas equilibration device during a survey along an estuary and during a 40 h time series in a mangrove creek (ecosystem scale). A similar system was also connected to an in situ benthic chamber in a seagrass bed (community scale). Finally, a pulse-chase isotope enrichment experiment was conducted by measuring real-time release of (13)CO2 after addition of (13)C enriched phytoplankton to exposed intertidal sediments (microbial scale). Miller-Tans plots revealed complex transformation pathways and distinct isotopic source values of CO2 and CH4. Calculations of δ(13)C-DIC based on CRDS measured δ(13)C-CO2 and published fractionation factors were in excellent agreement with measured δ(13)C-DIC using isotope ratio mass spectroscopy (IRMS). The portable CRDS instrumentation used here can obtain real-time, high precision, continuous greenhouse gas data in lakes, rivers, estuaries and marine waters with less effort than conventional laboratory-based techniques.

Stable isotopes trace estuarine transformations of carbon and nitrogen from primary-and secondary-treated paper and pulp mill effluent

Stable isotope analysis of a novel combination of carbon and nitrogen pools traced inputs and processing of primary-treated (PE) and secondary-treated effluent (SE) from a paper and pulp mill (PPM) in a temperate Australian estuary. Distinct carbon stable isotope ratios of dissolved organic carbon (DOC) near the PPM outfall indicated large PE and reduced SE inputs of DOC. DOC was remineralized to dissolved inorganic carbon regardless of season, but rates were lower in winter. PE discharge in winter elevated DOC concentrations along much of the estuary. Distinct stable isotope ratios confirmed particulate organic matter (POM) input from PE and SE to the water column and into the sediment. This was relatively localized, indicating rapid POM settlement regardless of season. SE discharge increased nutrient inputs and enhanced algal productivity, particularly in summer when chlorophyll-a concentrations were elevated throughout the estuary. SE discharge reduced pCO(2) from levels associated with PE discharge. However, the estuary remained heterotrophic as subsequent respiration or decomposition of algal material offset reductions in PPM organic matter input. The influence of the PPM was apparent throughout the estuary, demonstrating the ability of anthropogenic inputs, and changes to these, to affect ecosystem functioning.

Short-term enhancement and long-term suppression of denitrification in estuarine sediments receiving primary- and secondary- treated paper and pulp mill discharge

To determine the role of sediment denitrification in removing inputs of primary- (PE) and secondary-treated effluent (SE) from a pulp and paper mill (PPM), organic matter (OM) associated with PE (residual wood fiber) and SE (activated sludge biomass and phytoplankton) was added to estuarine intertidal sediments and denitrification rates were measured over 27 days. Labile sludge biomass and phytoplankton initially stimulated denitrification, including for pre-existing sediment N. After 2.5 d, however, denitrification was suppressed apparently due to microbial competition for N to process the refractory (high C:N) material remaining. Wood fiber suppressed denitrification throughout the experiment due to competition for N to process the refractory OM. Ultimate long-term denitrification suppression by phytoplankton is offset by initial enhanced denitrification rates. Although nutrient release during degradation of sludge biomass and wood fiber may stimulate phytoplankton production, N equivalent to 127% of the expected daily phytoplankton load was denitrified within 24 h, allowing for permanent removal of PPM-derived N. Compared to primary treatment, secondary treatment of PPM effluent has greater potential for N removal.

Wastewater nitrogen and trace metal uptake by biota on a high-energy rocky shore detected using stable isotopes

On high-energy rocky shores receiving treated wastewater, impacts are difficult to distinguish against a highly variable background and are localised due to rapid dilution. We demonstrate that nitrogen stable isotope values (δ(15)N) of rocky shore biota are highly sensitive to wastewater inputs. For macroalgae (Ulva lactuca and Endarachne binghamiae), grazing snails (Bembicium nanum and Nerita atramentosa), and predatory snails (Morula marginalba), δ(15)N was enriched near a wastewater outfall and declined with distance, returning to background levels within 290m. Any of these species therefore indicates the extent of influence of wastewater, allowing identification of an appropriate scale for studies of ecosystem impacts. For M. marginalba, significant regressions between δ(15)N and tissue copper, manganese, and zinc concentrations indicate a possible wastewater source for these metals. This suggests that δ(15)N is a proxy for exposure to wastewater contaminants, and may help to attribute variations in rocky shore communities to wastewater impacts.

Processing of particulate organic carbon associated with secondary-treated pulp and paper mill effluent in intertidal sediments: a 13C pulse-chase experiment

To determine the benthic transformation pathways and fate of carbon associated with secondary-treated pulp and paper mill (PPM) effluent, (13)C-labeled activated sludge biomass (ASB) and phytoplankton (PHY) were added, separately, to estuarine intertidal sediments. Over 28 days, (13)C was traced into sediment organic carbon, fauna, seagrass, bacteria, and microphytobenthos and into fluxes of dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) from inundated sediments, and carbon dioxide (CO2(g)) from exposed sediments. There was greater removal of PHY carbon from sediments (~85% over 28 days) compared to ASB (~75%). Although there was similar (13)C loss from PHY and ASB plots via DIC (58% and 56%, respectively) and CO2(g) fluxes (<1%), DOC fluxes were more important for PHY (41%) than ASB (12%). Faster downward transport and loss suggest that fauna prefer PHY, due to its lability and/or toxins associated with ASB; this may account for different carbon pathways. Secondary-treated PPM effluent has lower oxygen demand than primary-treated effluent, but ASB accumulation may contribute to sediment anoxia, and respiration of ASB and PHY-derived DOC may make the water column more heterotrophic. This highlights the need to optimize secondary-treatment processes to control the quality and quantity of organic carbon associated with PPM effluent.

Impact of peatlands on carbon dioxide (CO 2 ) emissions from the Rajang River and Estuary, Malaysia

1 Institute of Environmental Physics, University of Bremen, Otto-Hahn-Allee 1, 28359 Bremen, Germany 5 2 Leibniz Center for Tropical Marine Research, Fahrenheitstr. 6, 28359 Bremen, Germany 3 Institute of Geology, University of Hamburg, Bundesstr. 55, 20146 Hamburg, Germany 4 Swinburne University of Technology, Faculty of Engineering, Computing and Science, Jalan Simpang Tiga, 93350 Kuching, Sarawak, Malaysia 5 Centre for Coastal Biogeochemistry, School of Environment, Science and Engineering, Southern Cross University, Lismore 10 NSW 2480, Australia