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Estuaries play an important role in connecting the global carbon cycle across the land-to-ocean continuum, but little is known about Australia's contribution to global CO 2 emissions. Here we present an Australia-wide assessment, based on CO 2 concentrations for 47 estuaries upscaled to 971 assessed Australian estuaries. We estimate total mean (±SE) estuary CO 2 emissions of 8.67 ± 0.54 Tg CO 2 -C yr -1 , with tidal systems, lagoons, and small deltas contributing 94.4%, 3.1%, and 2.5%, respectively. Although higher disturbance increased water-air CO 2 fluxes, its effect on total Australian estuarine CO 2 emissions was small due to the large surface areas of low and moderately disturbed tidal systems. Mean water-air CO 2 fluxes from Australian small deltas and tidal systems were higher than from global estuaries because of the dominance of macrotidal subtropical and tropical systems in Australia, which have higher emissions due to lateral inputs. We suggest that global estuarine CO 2 emissions should be upscaled based on geomorphology, but should also consider land-use disturbance, and climate., (© 2024. The Author(s).)

Fungi are key players in terrestrial organic matter (OM) degradation, but little is known about their role in marine environments. Here we compared the degradation of kelp (Ecklonia radiata) in mesocosms with and without fungicides over 45 days. The aim was to improve our understanding of the vital role of fungal OM degradation and remineralisation and its relevance to marine biogeochemical cycles (e.g., carbon, nitrogen, sulfur, or volatile sulfur). In the presence of fungi, 68 % of the kelp detritus degraded over 45 days, resulting in the production of 0.6 mol of dissolved organic carbon (DOC), 0.16 mol of dissolved inorganic carbon (DIC), 0.23 mol of total alkalinity (TA), and 0.076 mol of CO 2 , which was subsequently emitted to the atmosphere. Conversely, when fungi were inhibited, the bacterial community diversity was reduced, and only 25 % of the kelp detritus degraded over 45 days. The application of fungicides resulted in the generation of an excess amount of 1.5 mol of DOC, but we observed only 0.02 mol of DIC, and 0.04 mol of TA per one mole of kelp detritus, accompanied by a CO 2 emission of 0.081 mol. In contrast, without fungi, remineralisation of kelp detritus to DIC, TA, dimethyl sulfide (DMS), dimethylsulfoniopropionate (DMSP) and methanethiol (MeSH) was significantly reduced. Fungal kelp remineralisation led to a remarkable 100,000 % increase in DMSP production. The observed substantial changes in sediment chemistry when fungi are inhibited highlight the important biogeochemical role of fungal remineralisation, which likely plays a crucial role in defining coastal biogeochemical cycling, blue carbon sequestration, and thus climate regulation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Accurately tracing the sources and fate of excess PO 4 3- in waterways is necessary for sustainable catchment management. The natural abundance isotopic composition of O in PO 4 3- (δ 18 O P ) is a promising tracer of point source pollution, but its ability to track diffuse agricultural pollution is unclear. We tested the hypothesis that δ 18 O P could distinguish between agricultural PO 4 3- sources by measuring the integrated δ 18 O P composition and P speciation of contrasting inorganic fertilisers (compound vs rock) and soil textures (sand, loam, clay) in southwestern Australia. δ 18 O P composition differed between the three soil textures sampled across six livestock farms: sandy soils had lower overall δ 18 O P values (21 ± 1‰) than the loams (23 ± 1‰), which corresponded with a smaller, but more readily leachable, PO 4 3- pool. Fertilisers had greater δ 18 O P variability (∼8‰), with fluctuations due to type and manufacturing year. Consequently, catchment 'agricultural soil leaching' δ 18 O P signatures could span from 18 to 25‰ depending on both fertiliser type and timing (lag between application and leaching). These findings emphasise the potential of δ 18 O P to untangle soil-fertiliser P dynamics under controlled conditions, but that its use to trace catchment-scale agricultural PO 4 3- losses is limited by uncertainties in soil biological P cycling and its associated isotopic fractionation., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Sediment microbial communities are an important sink for both organic and inorganic nitrogen (N), with microphytobenthos (MPB) biomass making the largest contribution to short-term N-assimilation and retention. Coastal waters are increasingly subject to anthropogenic nutrient enrichment, but the effect of nutrient enrichment on microbial assimilation, processing, and fate of MPB-derived N (MPB-N) remains poorly characterised. In this study, an MPB-dominated microbial community was labeled in situ with a pulse of 15 NH 4 + -N. Laboratory core incubations of this labeled sediment under increasing nutrient concentrations (NH 4 + and PO 4 3- : ambient, 2 × ambient, 5 × ambient, and 10 × ambient) were used to investigate changes in the processing and flux pathways of the 15 N-labeled MPB-N across 10.5 d under nutrient enrichment. Short-term retention of MPB-N by MPB was stimulated by nutrient addition, with higher 15 N in MPB in the nutrient amended treatments (71-93%) than in the ambient treatment (38%) at 0.5 d After 10.5 d, the nutrient amended treatments had increased turnover of MPB-N out of MPB biomass into an uncharacterised pool of sediment ON (45-75%). Increased turnover of MPB-N likely resulted from decreased recycling of MPB-N between MPB and heterotrophic bacteria as inorganic nutrients were preferentially used as an N source and remineralisation of sediment ON decreased. Decreased breakdown of sediment ON reduced the efflux of MPB-N via DON in the amended (3.9-5.2%) versus the ambient treatment (10.9%). Exports of MPB-N to the water column were relatively small, accounting for a maximum of 14% of 15 N exported from the sediment, and were predominantly exported DON and N 2 (denitrification). Overall, there was considerable retention of MPB-N over 10.5 d, but increased nutrient loading shifted N from MPB biomass into other sediment ON., Competing Interests: Declaration of Competing Interest None., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Nitrous oxide (N 2 O), like carbon dioxide, is a long-lived greenhouse gas that accumulates in the atmosphere. Over the past 150 years, increasing atmospheric N 2 O concentrations have contributed to stratospheric ozone depletion 1 and climate change 2 , with the current rate of increase estimated at 2 per cent per decade. Existing national inventories do not provide a full picture of N 2 O emissions, owing to their omission of natural sources and limitations in methodology for attributing anthropogenic sources. Here we present a global N 2 O inventory that incorporates both natural and anthropogenic sources and accounts for the interaction between nitrogen additions and the biochemical processes that control N 2 O emissions. We use bottom-up (inventory, statistical extrapolation of flux measurements, process-based land and ocean modelling) and top-down (atmospheric inversion) approaches to provide a comprehensive quantification of global N 2 O sources and sinks resulting from 21 natural and human sectors between 1980 and 2016. Global N 2 O emissions were 17.0 (minimum-maximum estimates: 12.2-23.5) teragrams of nitrogen per year (bottom-up) and 16.9 (15.9-17.7) teragrams of nitrogen per year (top-down) between 2007 and 2016. Global human-induced emissions, which are dominated by nitrogen additions to croplands, increased by 30% over the past four decades to 7.3 (4.2-11.4) teragrams of nitrogen per year. This increase was mainly responsible for the growth in the atmospheric burden. Our findings point to growing N 2 O emissions in emerging economies-particularly Brazil, China and India. Analysis of process-based model estimates reveals an emerging N 2 O-climate feedback resulting from interactions between nitrogen additions and climate change. The recent growth in N 2 O emissions exceeds some of the highest projected emission scenarios 3,4 , underscoring the urgency to mitigate N 2 O emissions.

Estuarine sediments are important sites for the interception, processing, and retention of organic matter, prior to its export to the coastal oceans. Stimulated microbial co-metabolism (priming) potentially increases export of refractory organic matter through increased production of hydrolytic enzymes. Using the microphytobenthos community to directly introduce a pulse of labile carbon into sediment, we traced a priming effect and assessed the decomposition and export of preexisting organic matter. We show enhanced efflux of preexisting carbon from intertidal sediments enriched with water column nutrients. Nutrient enrichment increased production of labile microphytobenthos carbon, which stimulated degradation of previously unavailable organic matter and led to increased liberation of "old" (6855 ± 120 years BP) refractory carbon as dissolved organic carbon (DOC). These enhanced DOC effluxes occurred at a scale that decreases estimates for global organic carbon burial in coastal systems and should be considered as an impact of eutrophication on estuarine carbon budgets.

Large rivers, including the Murray River system in southeast Australia, are disturbed by many activities. The arrival of European settlers to Australia by the mid-1800s transformed many floodplain wetlands of the lower Murray River system. River impoundment and flow regulation in the late 1800s and, from the 1930s, resulted in species invasion, and elevated nutrient concentrations causing widespread eutrophication. An integrated palaeoecology, and palaeo-and-modern food web approach, incorporating mixing models, was undertaken to reveal changes in a regulated wetland (i.e. Kings Billabong). The lack of preserved sediment suggests the wetland was naturally intermittent before 1890. After this time, when used as a water retention basin, the wetland experienced net sediment accumulation. Subfossil cladocerans, and δ 13 C of Daphnia, chironomid, and bulk sediment, all reflected an early productive, likely clear water state and shifts in trophic state following river regulation in the 1930s. Food web mixing models, based on δ 13 C and δ 15 N in subfossil and modern Daphnia, fish, and submerged and emergent macrophytes, also indicated a shift in the trophic relationships between fish and Daphnia. By the 1970s, a new state was established but a further significant alteration of nitrogen and carbon sources, and trophic interactions, continued through to the early 2000s. A possible switch from Daphnia as a prey of Australian Smelt could have modified the food web of the wetland by c. 2006. The timing of this change corresponded to the expansion of emergent macrophytes possibly due to landscape level disruptions. The evidence of these changes suggests a need for a broader understanding of the evolution of wetlands for the management of floodplains in the region.

Policies aiming to preserve vegetated coastal ecosystems (VCE; tidal marshes, mangroves and seagrasses) to mitigate greenhouse gas emissions require national assessments of blue carbon resources. Here, we present organic carbon (C) storage in VCE across Australian climate regions and estimate potential annual CO 2 emission benefits of VCE conservation and restoration. Australia contributes 5-11% of the C stored in VCE globally (70-185 Tg C in aboveground biomass, and 1,055-1,540 Tg C in the upper 1 m of soils). Potential CO 2 emissions from current VCE losses are estimated at 2.1-3.1 Tg CO 2 -e yr -1 , increasing annual CO 2 emissions from land use change in Australia by 12-21%. This assessment, the most comprehensive for any nation to-date, demonstrates the potential of conservation and restoration of VCE to underpin national policy development for reducing greenhouse gas emissions.

The term Blue Carbon (BC) was first coined a decade ago to describe the disproportionately large contribution of coastal vegetated ecosystems to global carbon sequestration. The role of BC in climate change mitigation and adaptation has now reached international prominence. To help prioritise future research, we assembled leading experts in the field to agree upon the top-ten pending questions in BC science. Understanding how climate change affects carbon accumulation in mature BC ecosystems and during their restoration was a high priority. Controversial questions included the role of carbonate and macroalgae in BC cycling, and the degree to which greenhouse gases are released following disturbance of BC ecosystems. Scientists seek improved precision of the extent of BC ecosystems; techniques to determine BC provenance; understanding of the factors that influence sequestration in BC ecosystems, with the corresponding value of BC; and the management actions that are effective in enhancing this value. Overall this overview provides a comprehensive road map for the coming decades on future research in BC science.

A dimethyl sulfide (DMS) vertical concentration profile and DMS surface emission flux were quantified in undisturbed acid sulfate soils (ASS) at Cudgen Lake on the north coast of New South Wales, Australia. A deuterated internal standard was used to account for soil adsorption characteristics. The DMS vertical concentration profile increased exponentially from 0.6 m depth to the surface layer. This profile reflected the adsorption properties of the ASS horizons present and the experimentally determined octanol/water partition coefficient for DMS of 1.36, suggesting that DMS would be mobilised in the soil water medium for upward translocation in time due to surface evaporation. The organic material in the oxidised ASS crustal layer had a chemically strong adsorption affinity for DMS, which appeared to restrain its emission from surface soil particles to the atmosphere. The seasonally averaged DMS surface flux estimate from the Cudgen Lake ASS was 9 ng S m -2 min -1 , which is relatively low by comparison to DMS fluxes reported from other wetland soils such as salt-marshes and acidic peat bogs. The worldwide annual average DMS emission from ASS was estimated to be 1.14 × 10 -3  Tg S, which is globally insignificant by comparison to DMS emission from the world's oceans., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The enrichment of sediments with nutrients and organic matter (eutrophication) is a key anthropogenic stressor of estuaries worldwide, impacting their sediment condition, ecology and ecosystem service provision. A key challenge for estuary managers and scientists is how to effectively quantify and monitor these changes in ecological condition in a timely and cost-effective manner. We developed a Rapid Assessment Protocol (RAP) for characterizing sediment condition based on the qualitative characteristics of sediment colour, odour and texture. We evaluated its utility for assessing sediment condition, and particularly the degree and effects of sediment enrichment (as quantified by complementary measurements of total C, organic C and total N) across 97 sites throughout a eutrophic microtidal estuary. RAP results were strongly and significantly correlated with the degree of sediment enrichment, with RAP scores correctly identifying the assigned enrichment class (low, medium, high) of 83.5% of sites. More enriched sediments exhibited poorer condition, manifested as significantly lower RAP scores for sediment colour, texture and odour, particularly (but not only) where enrichment coincided with elevated mud content. The RAP was particularly successful (<12% misclassification) at identifying sites with low levels of enrichment, indicating its promise as a first-pass survey approach for identifying potential reference or control sites to support impact assessments. RAP approaches based on qualitative sediment characteristics can provide a useful proxy for the degree and impacts of inorganic and organic enrichment, with potentially broad applicability for supporting timely, cost-effective assessment and monitoring of sediment condition in estuaries worldwide.

Calcium carbonates (CaCO 3 ) often accumulate in mangrove and seagrass sediments. As CaCO 3 production emits CO 2 , there is concern that this may partially offset the role of Blue Carbon ecosystems as CO 2 sinks through the burial of organic carbon (C org ). A global collection of data on inorganic carbon burial rates (C inorg , 12% of CaCO 3 mass) revealed global rates of 0.8 TgC inorg  yr -1 and 15-62 TgC inorg  yr -1 in mangrove and seagrass ecosystems, respectively. In seagrass, CaCO 3 burial may correspond to an offset of 30% of the net CO 2 sequestration. However, a mass balance assessment highlights that the C inorg burial is mainly supported by inputs from adjacent ecosystems rather than by local calcification, and that Blue Carbon ecosystems are sites of net CaCO 3 dissolution. Hence, CaCO 3 burial in Blue Carbon ecosystems contribute to seabed elevation and therefore buffers sea-level rise, without undermining their role as CO 2 sinks.

Coccolithophores are unicellular marine phytoplankton and important contributors to global carbon cycling. Most work on coccolithophore sensitivity to climate change has been on the small, abundant bloom-forming species Emiliania huxleyi and Gephyrocapsa oceanica. However, large coccolithophore species can be major contributors to coccolithophore community production even in low abundances. Here we fit an analytical equation, accounting for simultaneous changes in CO 2 and light intensity, to rates of photosynthesis, calcification and growth in Scyphosphaera apsteinii. Comparison of responses to G. oceanica and E. huxleyi revealed S. apsteinii is a low-light adapted species and, in contrast, becomes more sensitive to changing environmental conditions when exposed to unfavourable CO 2 or light. Additionally, all three species decreased their light requirement for optimal growth as CO 2 levels increased. Our analysis suggests that this is driven by a drop in maximum rates and, in G. oceanica, increased substrate uptake efficiency. Increasing light intensity resulted in a higher proportion of muroliths (plate-shaped) to lopadoliths (vase shaped) and liths became richer in calcium carbonate as calcification rates increased. Light and CO 2 driven changes in response sensitivity and maximum rates are likely to considerably alter coccolithophore community structure and productivity under future climate conditions.

Organic matter burial in mangrove forests results in the removal and long-term storage of atmospheric CO 2 , so-called "blue carbon." However, some of this organic matter is metabolized and returned to the atmosphere as CH 4 . Because CH 4 has a higher global warming potential than the CO 2 fixed in the organic matter, it can offset the CO 2 removed via carbon burial. We provide the first estimate of the global magnitude of this offset. Our results show that high CH 4 evasion rates have the potential to partially offset blue carbon burial rates in mangrove sediments on average by 20% (sensitivity analysis offset range, 18 to 22%) using the 20-year global warming potential. Hence, mangrove sediment and water CH 4 emissions should be accounted for in future blue carbon assessments.

Ocean acidification refers to the lowering of the ocean's pH due to the uptake of anthropogenic CO 2 from the atmosphere. Coral reef calcification is expected to decrease as the oceans become more acidic. Dissolving calcium carbonate (CaCO 3 ) sands could greatly exacerbate reef loss associated with reduced calcification but is presently poorly constrained. Here we show that CaCO 3 dissolution in reef sediments across five globally distributed sites is negatively correlated with the aragonite saturation state (Ω ar ) of overlying seawater and that CaCO 3 sediment dissolution is 10-fold more sensitive to ocean acidification than coral calcification. Consequently, reef sediments globally will transition from net precipitation to net dissolution when seawater Ω ar reaches 2.92 ± 0.16 (expected circa 2050 CE). Notably, some reefs are already experiencing net sediment dissolution., (Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Supplementing ruminants with nitrate (NO3-) reduces their enteric methane (CH 4 ) emissions; however, the greenhouse gas (GHG) mitigation achieved can be partially offset by small emissions of nitrous oxide (N 2 O), a more potent GHG. Sheep were dosed intraruminally with 15 NO3- to investigate whether dietary NO3- is a precursor of N 2 O and/or di-nitrogen gas (N 2 ), and to quantify the amounts of NO3- recovered as N 2 O and N 2 in gas emissions from sheep adapted or not adapted to dietary NO3-. Ruminally cannulated sheep were adapted to a hay diet supplemented with NO3- (n = 3; 10 g NO3-/kg DM) or urea (n = 3; 5.3 g urea/kg DM). On the day of the experiment all sheep were dosed intraruminally with 15 NO3- and quickly moved into gas-tight chambers to enable recovery of 15 N in N 2 O and N 2 to be measured. Measurements of gases accumulating in the chambers were made over 10 successive 50 min periods; this enabled the amount of N 2 O produced, and the recovery of 15 NO3--N in N 2 O and N 2 to be determined over a total of 10 hr. Only 0.04% of labelled NO3--N was recovered as N 2 O, and this was not dependent (p > .05) on whether or not the animals had been adapted to dietary NO3-. Approximatively 3% of 15 NO3--N was recovered as 15 N 2 , which was also not dependent (p > .05) on whether sheep had been adapted to NO3-. Because the kinetics of rumen ammonia (NH 3 ) were uncertain, the recovery of 15 N from NO3- in rumen NH 3 could not accurately be quantified, but our results suggest that approximately 76% of dietary NO3- was converted to NH 3 in the rumen. We conclude that the small amount of NO3- recovered in N 2 was evidence of denitrification, previously thought not to occur in the rumen., (© 2017 Blackwell Verlag GmbH.)

Worldwide, coral reef ecosystems are experiencing increasing pressure from a variety of anthropogenic perturbations including ocean warming and acidification, increased sedimentation, eutrophication, and overfishing, which could shift reefs to a condition of net calcium carbonate (CaCO3) dissolution and erosion. Herein, we determine the net calcification potential and the relative balance of net organic carbon metabolism (net community production; NCP) and net inorganic carbon metabolism (net community calcification; NCC) within 23 coral reef locations across the globe. In light of these results, we consider the suitability of using these two metrics developed from total alkalinity (TA) and dissolved inorganic carbon (DIC) measurements collected on different spatiotemporal scales to monitor coral reef biogeochemistry under anthropogenic change. All reefs in this study were net calcifying for the majority of observations as inferred from alkalinity depletion relative to offshore, although occasional observations of net dissolution occurred at most locations. However, reefs with lower net calcification potential (i.e., lower TA depletion) could shift towards net dissolution sooner than reefs with a higher potential. The percent influence of organic carbon fluxes on total changes in dissolved inorganic carbon (DIC) (i.e., NCP compared to the sum of NCP and NCC) ranged from 32% to 88% and reflected inherent biogeochemical differences between reefs. Reefs with the largest relative percentage of NCP experienced the largest variability in seawater pH for a given change in DIC, which is directly related to the reefs ability to elevate or suppress local pH relative to the open ocean. This work highlights the value of measuring coral reef carbonate chemistry when evaluating their susceptibility to ongoing global environmental change and offers a baseline from which to guide future conservation efforts aimed at preserving these valuable ecosystems.

Little is known about the bulk hydrogen stable isotope composition (δ 2 H) of seaweeds. This study investigated the bulk δ 2 H in several different seaweed species collected from three different beaches in Brazil, Australia, and Argentina. Here, we show that Ulvophyceae (a group of green algae) had lower δ 2 H values (between -94‰ and -130‰) than red algae (Florideophyceae), brown algae (Phaeophyceae), and species from the class Bryopsidophyceae (another group of green algae). Overall the latter three groups of seaweeds had δ 2 H values between -50‰ and -90‰. These findings were similar at the three different geographic locations. Observed differences in δ 2 H values were probably related to differences in hydrogen (H) metabolism among algal groups, also observed in the δ 2 H values of their lipids. The marked difference between the δ 2 H values of Ulvophyecae and those of the other groups could be useful to trace the food source of food webs in coastal rocky shores, to assess the impacts of green tides on coastal ecosystems, and to help clarify aspects of their phylogeny. However, reference materials for seaweed δ 2 H are required before the full potential of using the δ 2 H of seaweeds for ecological studies can be exploited., (© 2017 Phycological Society of America.)

Dimethylsulfoniopropionate (DMSP) and eleven other target zwitterions were quantified in the branch tips of six Acropora species and Stylophora pistillata hard coral growing on the reef flat surrounding Heron Island in the southern Great Barrier Reef (GBR), Australia. Hydrophilic interaction liquid chromatography mass spectrometry (HILIC-MS) was used for sample analysis with isotope dilution MS applied to quantify DMSP. The concentration of DMSP was ten times greater in A. aspera than A. valida, with this difference being maintained throughout the spring, summer and winter seasons. In contrast, glycine betaine was present in significantly higher concentrations in these species during the summer than the winter. Exposure of branch tips of A. aspera to air and hypo-saline seawater for up to 1 h did not alter the concentrations of DMSP present in the coral when compared with control samples. DMSP was the most abundant target zwitterion in the six Acropora species examined, ranging from 44-78% of all target zwitterions in A. millepora and A. aspera, respectively. In contrast, DMSP only accounted for 7% in S. pistillata, with glycine betaine and stachydrine collectively accounting for 88% of all target zwitterions in this species. The abundance of DMSP in the six Acropora species examined points to Acropora coral being an important source for the biogeochemical cycling of sulfur throughout the GBR, since this reef-building branching coral dominates the coral cover of the GBR. Graphical Abstract HILIC-MS extracted ion chromatogram showing zwitterionic metabolites from the branching coral Acropora isopora.

Here, we report the first-ever measurements of light CO 2 respiration rate (CRR) by seaweeds. We measured the influence of temperature (15-25°C) and light (irradiance from 60 to 670 μmol · m -2  · s -1 ) on the light CCR of two subtropical seaweed species, and measured the CRR of seven different seaweed species under the same light (150 μmol · m -2  · s -1 ) and temperature (25°C). There was little effect of irradiance on light CRR, but there was an effect of temperature. Across the seven species light CRR was similar to OCR (oxygen consumption rate in the dark), with the exception of a single species. The outlier species was a coralline alga, and the higher light CRR was probably driven by calcification. CRR could be estimated from OCR, as well as carbon photosynthetic rates from oxygen photosynthetic rates, which suggests that previous studies have probably provided good estimations of gross photosynthesis for seaweeds., (© 2017 Phycological Society of America.)

Dimethylsulfoniopropionate (DMSP) in scleractinian coral is usually analysed indirectly as dimethylsulfide (DMS) using gas chromatography (GC) with a sulfur-specific detector. We developed a headspace GC method for mass spectral analysis of DMSP in branching coral where hexa-deuterated DMSP (d 6 -DMSP) was added to samples and standards to optimise the analytical precision and quantitative accuracy. Using this indirect HS-GC-MS method, we show that common coral sample handling techniques did not alter DMSP concentrations in Acropora aspera and that endogenous DMS was insignificant compared to the store of DMSP in A. aspera. Field application of the indirect HS-GC-MS method in all seasons over a 5-year period at Heron Island in the southern Great Barrier Reef indicated that healthy colonies of A. aspera ordinarily seasonally conserve their branch tip store of DMSP; however, this store increased to a higher concentration under extended thermal stress conditions driven by a strong El Niño Southern Oscillation event. A liquid chromatography mass spectral method (LC-MS) was subsequently developed for direct analysis of DMSP in branching coral, also utilising the d 6 -DMSP internal standard. The quantitative comparison of DMSP in four species of Acropora coral by indirect HS-GC-MS and direct LC-MS analyses gave equivalent concentrations in A. aspera only; in the other three species, HS-GC-MS gave consistently higher concentrations, indicating that indirect analysis of DMSP may lead to artificially high values for some coral species. Graphical Abstract Dimethylsulfoniopropionate (DMSP) was quantified in Acropora spp. of branching coral using deuterated stable isotope dilution mass spectrometry.

The transfer of organic material from one coastal environment to another can increase production in recipient habitats in a process known as spatial subsidy. Microorganisms drive the generation, transformation, and uptake of organic material in shallow coastal environments, but their significance in connecting coastal habitats through spatial subsidies has received limited attention. We address this by presenting a conceptual model of coastal connectivity that focuses on the flow of microbially mediated organic material in key coastal habitats. Our model suggests that it is not the difference in generation rates of organic material between coastal habitats but the amount of organic material assimilated into microbial biomass and respiration that determines the amount of material that can be exported from one coastal environment to another. Further, the flow of organic material across coastal habitats is sensitive to environmental change as this can alter microbial remineralization and respiration rates. Our model highlights microorganisms as an integral part of coastal connectivity and emphasizes the importance of including a microbial perspective in coastal connectivity studies.

The abundant and diverse microorganisms that inhabit aquatic systems are both determinants and indicators of aquatic health, providing essential ecosystem services such as nutrient cycling but also causing harmful blooms and disease in impacted habitats. Estuaries are among the most urbanized coastal ecosystems and as a consequence experience substantial environmental pressures, providing ideal systems to study the influence of anthropogenic inputs on microbial ecology. Here we use the highly urbanized Sydney Harbor, Australia, as a model system to investigate shifts in microbial community composition and function along natural and anthopogenic physicochemical gradients, driven by stormwater inflows, tidal flushing and the input of contaminants and both naturally and anthropogenically derived nutrients. Using a combination of amplicon sequencing of the 16S rRNA gene and shotgun metagenomics, we observed strong patterns in microbial biogeography across the estuary during two periods: one of high and another of low rainfall. These patterns were driven by shifts in nutrient concentration and dissolved oxygen leading to a partitioning of microbial community composition in different areas of the harbor with different nutrient regimes. Patterns in bacterial composition were related to shifts in the abundance of Rhodobacteraceae, Flavobacteriaceae, Microbacteriaceae, Halomonadaceae, Acidomicrobiales, and Synechococcus, coupled to an enrichment of total microbial metabolic pathways including phosphorus and nitrogen metabolism, sulfate reduction, virulence, and the degradation of hydrocarbons. Additionally, community beta-diversity was partitioned between the two sampling periods. This potentially reflected the influence of shifting allochtonous nutrient inputs on microbial communities and highlighted the temporally dynamic nature of the system. Combined, our results provide insights into the simultaneous influence of natural and anthropogenic drivers on the structure and function of microbial communities within a highly urbanized aquatic ecosystem.

Two sediment cores were collected in a mangrove forest to construct geochronologies for the previous century using natural and anthropogenic radionuclide tracers. Both sediment cores were dated using (239+240)Pu global fallout signatures as well as (210)Pb, applying both the Constant Initial Concentration (CIC) and the Constant Rate of Supply (CRS) models. The (239+240)Pu and CIC model are interpreted as having comparable sediment accretion rates (SAR) below an apparent mixed region in the upper ∼5 to 10 cm. In contrast, the CRS dating method shows high sediment accretion rates in the uppermost intervals, which is substantially reduced over the lower intervals of the 100-year record. A local anthropogenic nutrient signal is reflected in the high total phosphorus (TP) concentration in younger sediments. The carbon/nitrogen molar ratios and δ(15)N values further support a local anthropogenic nutrient enrichment signal. The origin of these signals is likely the treated sewage discharge to Moreton Bay which began in the early 1970s. While the (239+240)Pu and CIC models can only produce rates averaged over the intervals of interest within the profile, the (210)Pb CRS model identifies elevated rates of sediment accretion, organic carbon (OC), nitrogen (N), and TP burial from 2000 to 2013. From 1920 to 2000, the three dating methods provide similar OC, N and TP burial rates, ∼150, 10 and 2 g m(-2) year(-1), respectively, which are comparable to global averages., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

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 O 2 uptake by ~50 %, and inducing highly variable redox conditions and O 2 distribution in the surface sediment as also documented by complementary laboratory-based planar optode measurements. The average benthic O 2 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 O 2 flux that was partly ascribed to enhanced ventilation of infauna burrows during periods of elevated flow rates. The ratio in exchange rates of Σ CO 2 and O 2 was close to unity, confirming that the O 2 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 O 2 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., (© The Author(s) 2016.)

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., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Nitrous oxide is a powerful, long-lived greenhouse gas, but we know little about the role of estuarine areas in the global N2 O budget. This review summarizes 56 studies of N2 O fluxes and associated biogeochemical controlling factors in estuarine open waters, salt marshes, mangroves, and intertidal sediments. The majority of in situ N2 O production occurs as a result of sediment denitrification, although the water column contributes N2 O through nitrification in suspended particles. The most important factors controlling N2 O fluxes seem to be dissolved inorganic nitrogen (DIN) and oxygen availability, which in turn are affected by tidal cycles, groundwater inputs, and macrophyte density. The heterogeneity of coastal environments leads to a high variability in observations, but on average estuarine open water, intertidal and vegetated environments are sites of a small positive N2 O flux to the atmosphere (range 0.15-0.91; median 0.31; Tg N2 O-N yr(-1) ). Global changes in macrophyte distribution and anthropogenic nitrogen loading are expected to increase N2 O emissions from estuaries. We estimate that a doubling of current median NO3 (-) concentrations would increase the global estuary water-air N2 O flux by about 0.45 Tg N2 O-N yr(-1) or about 190%. A loss of 50% of mangrove habitat, being converted to unvegetated intertidal area, would result in a net decrease in N2 O emissions of 0.002 Tg N2 O-N yr(-1) . In contrast, conversion of 50% of salt marsh to unvegetated area would result in a net increase of 0.001 Tg N2 O-N yr(-1) . Decreased oxygen concentrations may inhibit production of N2 O by nitrification; however, sediment denitrification and the associated ratio of N2 O:N2 is expected to increase., (© 2015 John Wiley & Sons Ltd.)

The remediation of four estrogenic endocrine-disrupting compounds (EDCs), estrone (E1), estradiol (E2), ethinylestradiol (EE2) and estriol (E3), was measured in saturated and unsaturated carbonate sand-filled columns dosed with wastewater from a sewage treatment plant. The estrogen equivalency (EEQ) of inlet wastewater was 1.2 ng L(-1) and was remediated to an EEQ of 0.5 ng L(-1) through the unsaturated carbonate sand-filled columns. The high surface area of carbonate sand and associated high microbial activity may have assisted the degradation of these estrogens. The fully saturated sand columns showed an increase in total estrogenic potency with an EEQ of 2.4 ng L(-1), which was double that of the inlet wastewater. There was a significant difference (P < 0.05) in total estrogenic potency between aerobic and anaerobic columns. The breakdown of conjugated estrogens to estrogenic EDCs formed under long residence time and reducing conditions may have been responsible for the increase in the fully saturated columns. This may also be explained by the desorption of previously sorbed estrogenic EDCs. The effect of additional filter materials, such as basalt sediment and coconut fibre, on estrogenic EDC reduction was also tested. None of these amendments provided improvements in estrogen remediation relative to the unamended unsaturated carbonate sand columns. Aerobic carbonate sand filters have good potential to be used as on-site wastewater treatment systems for the reduction of estrogenic EDCs. However, the use of fully saturated sand filters, which are used to promote denitrification, and the loss of nitrogen as N2 were shown to cause an increase in EEQ. The potential for the accumulation of estrogenic EDCs under anaerobic conditions needs to be considered when designing on-site sand filtration systems required to reduce nitrogen. Furthermore, the accumulation of estrogens under anaerobic conditions such as under soil absorption systems or leachate fields has the potential to contaminate groundwater especially when the water table levels fluctuate.

Optimizing the utility of constructed waterways as residential development with water-frontage, along with a productive and functional habitat for wildlife is of considerable interest to managers. This study examines Lake Hugh Muntz, a large (17 ha) freshwater lake built in Gold Coast City, Australia. A ten year water quality monitoring programme shows that the lake has increasing nutrient concentrations, and together with summer algal blooms, the lake amenity as a popular recreational swimming and triathlon training location is at risk. A survey of fish and aquatic plant communities showed that the lake supports a sub-set of species found in adjacent natural wetlands. Sediment contaminants were below the lower Australian trigger values, except As, Hg, Pb and Zn, probably a function of untreated and uncontrolled stormwater runoff from nearby urban roads. Sediment biogeochemistry showed early signs of oxygen depletion, and an increase in benthic organic matter decomposition and oxygen consumption will result in more nitrogen recycled to the water column as NH4(+) (increasing the intensity of summer algal blooms) and less nitrogen lost to the atmosphere as N2 gas via denitrification. A series of catchment restoration initiatives were modeled and the optimal stormwater runoff restoration effort needed for lake protection will be costly, particularly retrospective, as is the case here. Overall, balancing the lifestyles and livelihoods of residents along with ecosystem protection are possible, but require considerable trade-offs between ecosystem services and human use.

Sediment organic loading has been shown to affect estuarine nitrification and denitrification, resulting in changes to sediment biogeochemistry and nutrient fluxes detrimental to estuarine health. This study examined the effects of organic loading on nutrient fluxes and microbial communities in sediments receiving effluent from a paper and pulp mill (PPM) by applying microcosm studies and molecular microbial ecology techniques. Three sites near the PPM outfall were compared to three control sites, one upstream and two downstream of the outfall. The control sites showed coupled nitrification-denitrification with minimal ammonia release from the sediment. In contrast, the impacted sites were characterised by nitrate uptake and substantial ammonia efflux from the sediments, consistent with a decoupling of nitrification and denitrification. Analysis of gene diversity demonstrated that the composition of nitrifier communities was not significantly different at the impacted sites compared to the control sites; however, analysis of gene abundance indicated that whilst there was no difference in total bacteria, total archaea or ammonia-oxidising archaea (AOA) abundance between the control and impacted sites, there was a significant reduction in ammonia-oxidising bacteria (AOB) at the impacted sites. The results of this study demonstrate an effect of organic loading on estuarine sediment biogeochemistry and highlight an apparent niche differentiation between AOA and AOB.

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.

We investigated the effects of the burrowing cirratulid polychaete Cirriformia filigera (Delle Chiaje, 1828) on benthic respiration and nitrogen regeneration in metal-contaminated estuarine sediments using laboratory mesocosms. C. filigera is a dominant component of assemblages in the most severely contaminated sediments within the Derwent estuary, southern Australia. In the presence of C. filigera sediment O2 consumption doubled, with approximately 55% of this increase due to their respiration and the remaining 45% attributable to oxidation reactions and increased microbial respiration associated with burrow walls. Combined NO3 and NO2 fluxes were unaffected. The addition of labile organic matter did not affect benthic fluxes, in the presence or absence of C. filigera, presumably due to the short timeframe of the experiment and naturally enriched test sediments. The results suggest that a combination of tolerance and burrowing activity enables this species to provide an ecosystem service in the removal of N from contaminated sites., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

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.

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 inputs to estuarine and coastal waters worldwide are increasing and this in turn is increasing the prevalence of eutrophication and hypoxic and anoxic episodes in these systems. Many urbanised estuaries are also subject to high levels of anthropogenic metal contamination. Environmental O(2) levels may influence whether sediments act as sinks or sources of metals. In this study we investigated the effect of an extended O(2) depletion event (40 days) on fluxes of trace metals (and the metalloid As) across the sediment-water interface in sediments from a highly metal contaminated estuary in S.E. Tasmania, Australia. We collected sediments from three sites that spanned a range of contamination and measured total metal concentration in the overlying water using sealed core incubations. Manganese and iron, which are known to regulate the release of other divalent cations from sub-oxic sediments, were released from sediments at all sites as hypoxia developed. In contrast, the release of arsenic, cadmium, copper and zinc was comparatively low, most likely due to inherent stability of these elements within the sediments, perhaps as a result of their refractory origin, their association with fine-grained sediments or their being bound in stable sulphide complexes. Metal release was not sustained due to the powerful effect of metal-sulphide precipitation of dissolved metals back into sediments. The limited mobilisation of sediment bound metals during hypoxia is encouraging, nevertheless the results highlight particular problems for management in areas where hypoxia might occur, such as the release of metals exacerbating already high loads or resulting in localised toxicity., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Settlement ponds are used to treat aquaculture discharge water by removing nutrients through physical (settling) and biological (microbial transformation) processes. Nutrient removal through settling has been quantified, however, the occurrence of, and potential for microbial nitrogen (N) removal is largely unknown in these systems. Therefore, isotope tracer techniques were used to measure potential rates of denitrification and anaerobic ammonium oxidation (anammox) in the sediment of settlement ponds in tropical aquaculture systems. Dinitrogen gas (N(2)) was produced in all ponds, although potential rates were low (0-7.07 nmol N cm(-3) h(-1)) relative to other aquatic systems. Denitrification was the main driver of N(2) production, with anammox only detected in two of the four ponds. No correlations were detected between the measured sediment variables (total organic carbon, total nitrogen, iron, manganese, sulphur and phosphorous) and denitrification or anammox. Furthermore, denitrification was not carbon limited as the addition of particulate organic matter (paired t-Test; P = 0.350, n = 3) or methanol (paired t-Test; P = 0.744, n = 3) did not stimulate production of N(2). A simple mass balance model showed that only 2.5% of added fixed N was removed in the studied settlement ponds through the denitrification and anammox processes. It is recommended that settlement ponds be used in conjunction with additional technologies (i.e. constructed wetlands or biological reactors) to enhance N(2) production and N removal from aquaculture wastewater.

Free surface water constructed wetlands (CWs) provide a buffer between domestic wastewater treatment plants and natural waterways. Understanding the biogeochemical processes in CWs is crucial to improve their performance. In this study we measured a range of water and sediment parameters, and biogeochemical processes, in an effort to describe the processing of nutrients within two wetland cells in series. As a whole the studied CW effectively absorbed both nitrogen (N) and phosphorus (P) emanating from the waste treatment plant. However the two individual cells showed marked differences related to the availability of oxygen within the water column and the sediments. In one cell we speculated that the prevalence of surface plant species reduced its ability to function as a net nutrient sink. Here we observed a build-up of sediment organic matter, sediment anoxia, a decoupling of nitrification-denitrification, and a flux of N and P out of the sediments to the overlying water. The availability of DO in the surface sediments of the second studied cell led to improved coupling between nitrification-denitrification and a net uptake of both NH4+ and PO4(3-). We hypothesise that the dominance of deeply rooted macrophytes in the second cell was responsible for the improved sediment quality., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Daily observations of dissolved aluminum, iron, and manganese in an estuary downstream of a coastal acid sulfate soil (CASS) catchment provided insights into how floods and submarine groundwater discharge drive wetland metal exports. Extremely high Al, Fe, and Mn concentrations (up to 40, 374, and 8 mg L(-1), respectively) were found in shallow acidic groundwaters from the Tuckean Swamp, Australia. Significant correlations between radon (a natural groundwater tracer) and metals in surface waters revealed that metal loads were driven primarily by groundwater discharge. Dissolved Fe, Mn, and Al loads during a 16-day flood triggered by a 213 mm rain event were respectively 80, 35, and 14% of the total surface water exports during the four months of observations. Counter clockwise hysteresis was observed for Fe and Mn in surface waters during the flood due to delayed groundwater inputs. Groundwater-derived Fe fluxes into artificial drains were 1 order of magnitude higher than total surface water exports, which is consistent with the known accumulation of monosulfidic black ooze within the wetland drains. Upscaling the Tuckean catchment export estimates yielded dissolved Fe fluxes from global acid sulfate soil catchments on the same order of magnitude of global river inputs into estuaries.

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.

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.

This study describes the spatial variability in nitrogen (N) transformation within a constructed wetland (CW) treating domestic effluent. Nitrogen cycling within the CW was driven by settlement and mineralization of particulate organic nitrogen and uptake of NO3-. The concentration of NO3- was found to decrease, as the delta15N-NO3- signature increased, as water flowed through the CW, allowing denitrification rates to be estimated on the basis of the degree of fractionation of delta15N-NO3-. Estimates of denitrification hinged on the determination of a net isotope effect (eta), which was influenced byprocesses that enrich or deplete 15NO3- (e.g., nitrification), as well as the rate constants associated with the different processes involved in denitrification (i.e., diffusion and enzyme activity). The influence of nitrification on eta was quantified; however, it remained unclear how eta varied due to variability in denitrification rate constants. A series of stable isotope amendment experiments was used to further constrain the value of eta and calculate rates of denitrification, and nitrification, within the wetland. The maximum calculated rate of denitrification was 956 +/- 187 micromol N m(-2) h(-1), and the maximum rate of nitrification was 182 +/- 28.9 micromol N m(-2) h(-1). Uptake of NO3- was quantitatively more important than denitrification throughoutthe wetland. Rates of N cycling varied spatially within thewetland, with denitrification dominating in the downstream deoxygenated region of the wetland. Studies that use fractionation of N to derive rate estimates must exercise caution when interpreting the net isotope effect. We suggest a sampling procedure for future natural abundance studies that may help improve the accuracy of N cycling rate estimates.

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.

This study used anaerobic slurry assays and intact core incubations to quantify potential rates of anammox (anaerobic ammonia oxidation) in sediments along the flow path of a surface flow constructed wetland receiving secondary treated sewage effluent. Anammox occurred at two of the four sites assayed with a maximum rate of 199.4 +/- 18.7 micromol N x m(-2) x hr(-1) (24% of total N2 production) at the discharge end of the wetland. Denitrification was the major producer of N2, with a maximum rate of 965.3 +/- 122.8 micromol N x m(-2) x hr(-1) at site 2. Oxygen was probably the key regulator of anammox activity within the studied CW. In addition to anammox, we found evidence that nitrifier-denitrification was potentially responsible for the production of N2O. Total production of N2O was 15.1% of the total gaseous N produced. Limitations to the methodology for quantifying anammox in CW's are outlined. This study demonstrated that denitrification is not the only pathway for gaseous production in constructed wetlands and that wetlands may be significant sources of greenhouse gases such as N2O.

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.