High carbon dioxide emissions from Australian estuaries driven by geomorphology and climate.

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 CO2 emissions. Here we present an Australia-wide assessment, based on CO2 concentrations for 47 estuaries upscaled to 971 assessed Australian estuaries. We estimate total mean (±SE) estuary CO2 emissions of 8.67 ± 0.54 Tg CO2-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 CO2 fluxes, its effect on total Australian estuarine CO2 emissions was small due to the large surface areas of low and moderately disturbed tidal systems. Mean water-air CO2 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 CO2 emissions should be upscaled based on geomorphology, but should also consider land-use disturbance, and climate.

Fungi increases kelp (Ecklonia radiata) remineralisation and dissolved organic carbon, alkalinity, and dimethylsulfoniopropionate (DMSP) production.

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 CO2, 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 CO2 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.

Bioaccumulation of estuarine pollutants in leaf oysters (Isognomon ephippium) on the mid-north coast, New South Wales, Australia.

Filter feeding bivalves are useful bioindicators for the detection of biologically available pollutants. We investigated trace metals, metalloids, and pesticides in leaf oyster (Isognomon ephippium) soft tissue and shells and compared them to sediment in five estuaries in northern New South Wales, Australia. Concentrations of Pb, Cr, Mn, Ni, Fe and Al were higher in sediments, whereas Zn, Cd, Ag, Hg, Se and As bioaccumulated in the soft tissue. The amount of Cu, Hg and Ni in the sediment from Tweed and Richmond River estuaries exceeded the Australian national sediment quality guideline values. Only one pesticide, atrazine, was detected in leaf oyster soft tissue. Combinations of six elements in the soft tissue were the best predictors of oyster condition index and shell size, whereas sediment contaminants showed weak relationships. Overall, the bioaccumulation of metals and metalloids increases with leaf oyster size and reduces leaf oyster condition, suggesting these large bivalves are useful bioindicators for pollution in estuarine environments.

Calcium Carbonate Prenucleation Cluster Pathway Observed via In Situ Small-Angle X-ray Scattering.

For more than 150 years, our understanding of solid-phase mineral formation from dissolved constituent ions in aqueous environments has been dominated by classical nucleation theory (CNT). However, an alternative paradigm known as non-classical nucleation theory (NCNT), characterized by the existence of thermodynamically stable and highly hydrated ionic "prenucleation clusters" (PNCs), is increasingly invoked to explain mineral nucleation, including the formation of calcium carbonate (CaCO3) minerals in aqueous conditions, which is important in a wide range of geological and biological systems. While the existence and role of PNCs in aqueous nucleation processes remain hotly debated, we show, using in situ small-angle X-ray scattering (SAXS), that nanometer-sized clusters are present in aqueous CaCO3 solutions ranging from thermodynamically under- to supersaturated conditions regarding all known mineral phases, thus demonstrating that CaCO3 mineral formation cannot be explained solely by CNT under the conditions examined.

Disposable surgical masks affect the decomposition of Zostera muelleri.

The coronavirus pandemic has caused a surge in the use of both disposable and re-usable mask pollution globally. It is important to understand the potential impact this influx of novel pollution has on key ecological processes, such as detrital dynamics. We aimed to understand the impact mask pollution has on the decomposition of a common coastal seagrass, Zostera muelleri. Using an outdoor mesocosm system with heater chiller units and a gas mixer, we were able to test the impact of both re-usable single-ply homemade cotton masks and disposable surgical masks on samples of Z. muelleri detritus under different environmental conditions. We found that disposable masks, but not re-usable masks, significantly increased decomposition of Z. muelleri detritus. This may be due to the increased surface area available for detritivorous microorganism colonisation, driving further decomposition. This could have negative ramifications for seagrass communities and adjacent ecosystems.

Water quality and the health of remnant leaf oyster (Isognomon ephippium) populations in four Australian estuaries.

Leaf oysters (Isognomon ephippium) are large intertidal bivalves that form shellfish reefs. They have a patchy and restricted distribution in estuaries in northern New South Wales, Australia, where the water quality is impacted by a range of anthropogenic stressors from coastal agriculture, urbanisation, industry and recreational activities, along with natural stochastic events such as flooding. Little, however, is currently known about the tolerance of leaf oysters to poor water quality. This study investigated the condition of leaf oyster populations in four estuaries, by assessing the density, size-frequency and condition index. These biological parameters were modelled against habitat water quality parameters including nutrient loads, organic and inorganic carbon, algal biomass, sedimentation and total alkalinity. The water quality assessments were replicated during dry conditions and after rain in two estuaries. Leaf oyster density, size, and body condition significantly differed among the four estuaries. Density ranged from as few as 0.04 oysters per m2 in the heavily impacted Richmond River, up to 267 oysters per m2 in the Tweed River. Overall water quality was also significantly different among the four estuaries, and significant declines in water quality were observed after rain. Distance based linear models revealed significant correlations between biological indicators of leaf oyster reef health and a range of water quality parameters. Leaf oysters with higher condition occur in locations with high dissolved oxygen and salinity levels, whereas low pH and high nutrient run-off were associated with low density and poorer oyster condition. Nevertheless, dense populations were found to persist in areas with pH below 7.9, in high turbidity (over 27 NTU) and areas dominated by fine silt. Their ability to form dense reefs on estuarine soft muddy bottom habitats with low water flow, suggests that leaf oysters could be used to complement rock oysters in future intertidal shellfish reef restoration programs.

Ocean acidification alters the nutritional value of Antarctic diatoms.

Primary production in the Southern Ocean is dominated by diatom-rich phytoplankton assemblages, whose individual physiological characteristics and community composition are strongly shaped by the environment, yet knowledge on how diatoms allocate cellular energy in response to ocean acidification (OA) is limited. Understanding such changes in allocation is integral to determining the nutritional quality of diatoms and the subsequent impacts on the trophic transfer of energy and nutrients. Using synchrotron-based Fourier transform infrared microspectroscopy, we analysed the macromolecular content of selected individual diatom taxa from a natural Antarctic phytoplankton community exposed to a gradient of fCO2 levels (288-1263 µatm). Strong species-specific differences in macromolecular partitioning were observed under OA. Large taxa showed preferential energy allocation towards proteins, while smaller taxa increased both lipid and protein stores at high fCO2 . If these changes are representative of future Antarctic diatom physiology, we may expect a shift away from lipid-rich large diatoms towards a community dominated by smaller taxa, but with higher lipid and protein stores than their present-day contemporaries, a response that could have cascading effects on food web dynamics in the Antarctic marine ecosystem.

The influence of plastic pollution and ocean change on detrital decomposition.

Plastic pollution and ocean change have mostly been assessed separately, missing potential interactions that either enhance or reduce future impacts on ecosystem processes. Here, we used manipulative experiments with outdoor mesocosms to test hypotheses about the interactive effects of plastic pollution, ocean warming and acidification on macrophyte detrital decomposition. These experiments focused on detritus from kelp, Ecklonia radiata, and eelgrass, Zostera muelleri, and included crossed treatments of (i) no, low and high plastic pollution, (ii) current/future ocean temperatures, and (iii) ambient/future ocean partial pressure of carbon dioxide (pCO2). High levels of plastic pollution significantly reduced the decomposition rate of kelp and eelgrass by approximately 27% and 36% in comparison to controls respectively. Plastic pollution also significantly slowed the nitrogen liberation from seagrass and kelp detritus. Higher seawater temperatures significantly increased the decomposition rate of kelp and eelgrass by 12% and 5% over current conditions, respectively. Higher seawater temperatures were also found to reduce the nitrogen liberation in eelgrass. In contrast, ocean acidification did not significantly influence the rate of macrophyte decomposition or nutrient liberation. Overall, our results show how detrital processes might respond to increasing plastic pollution and ocean temperatures, which has implications for detrital-driven secondary productivity, nutrient dynamics and carbon cycling.

A comparison of species specific sensitivities to changing light and carbonate chemistry in calcifying marine phytoplankton.

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 CO2 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 CO2 or light. Additionally, all three species decreased their light requirement for optimal growth as CO2 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 CO2 driven changes in response sensitivity and maximum rates are likely to considerably alter coccolithophore community structure and productivity under future climate conditions.

Shift towards larger diatoms in a natural phytoplankton assemblage under combined high-CO2 and warming conditions.

An indoor mesocosm experiment was carried out to investigate the combined effects of ocean acidification and warming on the species composition and biogeochemical element cycling during a winter/spring bloom with a natural phytoplankton assemblage from the Kiel fjord, Germany. The experimental setup consisted of a "Control" (ambient temperature of ~4.8 °C and ~535 ± 25 µatm pCO2), a "High-CO2" treatment (ambient temperature and initially 1020 ± 45 µatm pCO2) and a "Greenhouse" treatment (~8.5 °C and initially 990 ± 60 µatm pCO2). Nutrient replete conditions prevailed at the beginning of the experiment and light was provided at in situ levels upon reaching pCO2 target levels. A diatom-dominated bloom developed in all treatments with Skeletonema costatum as the dominant species but with an increased abundance and biomass contribution of larger diatom species in the Greenhouse treatment. Conditions in the Greenhouse treatment accelerated bloom development with faster utilization of inorganic nutrients and an earlier peak in phytoplankton biomass compared to the Control and High CO2 but no difference in maximum concentration of particulate organic matter (POM) between treatments. Loss of POM in the Greenhouse treatment, however, was twice as high as in the Control and High CO2 treatment at the end of the experiment, most likely due to an increased proportion of larger diatom species in that treatment. We hypothesize that the combination of warming and acidification can induce shifts in diatom species composition with potential feedbacks on biogeochemical element cycling.

Taking the metabolic pulse of the world's coral reefs.

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.

Temperature modulates coccolithophorid sensitivity of growth, photosynthesis and calcification to increasing seawater pCO2.

Increasing atmospheric CO2 concentrations are expected to impact pelagic ecosystem functioning in the near future by driving ocean warming and acidification. While numerous studies have investigated impacts of rising temperature and seawater acidification on planktonic organisms separately, little is presently known on their combined effects. To test for possible synergistic effects we exposed two coccolithophore species, Emiliania huxleyi and Gephyrocapsa oceanica, to a CO2 gradient ranging from ∼0.5-250 µmol kg⁻¹ (i.e. ∼20-6000 µatm pCO2) at three different temperatures (i.e. 10, 15, 20°C for E. huxleyi and 15, 20, 25°C for G. oceanica). Both species showed CO2-dependent optimum-curve responses for growth, photosynthesis and calcification rates at all temperatures. Increased temperature generally enhanced growth and production rates and modified sensitivities of metabolic processes to increasing CO2. CO2 optimum concentrations for growth, calcification, and organic carbon fixation rates were only marginally influenced from low to intermediate temperatures. However, there was a clear optimum shift towards higher CO2 concentrations from intermediate to high temperatures in both species. Our results demonstrate that the CO2 concentration where optimum growth, calcification and carbon fixation rates occur is modulated by temperature. Thus, the response of a coccolithophore strain to ocean acidification at a given temperature can be negative, neutral or positive depending on that strain's temperature optimum. This emphasizes that the cellular responses of coccolithophores to ocean acidification can only be judged accurately when interpreted in the proper eco-physiological context of a given strain or species. Addressing the synergistic effects of changing carbonate chemistry and temperature is an essential step when assessing the success of coccolithophores in the future ocean.

Dissecting the impact of CO2 and pH on the mechanisms of photosynthesis and calcification in the coccolithophore Emiliania huxleyi.

Coccolithophores are important calcifying phytoplankton predicted to be impacted by changes in ocean carbonate chemistry caused by the absorption of anthropogenic CO2 . However, it is difficult to disentangle the effects of the simultaneously changing carbonate system parameters (CO2 , bicarbonate, carbonate and protons) on the physiological responses to elevated CO2 . Here, we adopted a multifactorial approach at constant pH or CO2 whilst varying dissolved inorganic carbon (DIC) to determine physiological and transcriptional responses to individual carbonate system parameters. We show that Emiliania huxleyi is sensitive to low CO2 (growth and photosynthesis) and low bicarbonate (calcification) as well as low pH beyond a limited tolerance range, but is much less sensitive to elevated CO2 and bicarbonate. Multiple up-regulated genes at low DIC bear the hallmarks of a carbon-concentrating mechanism (CCM) that is responsive to CO2 and bicarbonate but not to pH. Emiliania huxleyi appears to have evolved mechanisms to respond to limiting rather than elevated CO2 . Calcification does not function as a CCM, but is inhibited at low DIC to allow the redistribution of DIC from calcification to photosynthesis. The presented data provides a significant step in understanding how E. huxleyi will respond to changing carbonate chemistry at a cellular level.

Ocean acidification-induced food quality deterioration constrains trophic transfer.

Our present understanding of ocean acidification (OA) impacts on marine organisms caused by rapidly rising atmospheric carbon dioxide (CO(2)) concentration is almost entirely limited to single species responses. OA consequences for food web interactions are, however, still unknown. Indirect OA effects can be expected for consumers by changing the nutritional quality of their prey. We used a laboratory experiment to test potential OA effects on algal fatty acid (FA) composition and resulting copepod growth. We show that elevated CO(2) significantly changed the FA concentration and composition of the diatom Thalassiosira pseudonana, which constrained growth and reproduction of the copepod Acartia tonsa. A significant decline in both total FAs (28.1 to 17.4 fg cell(-1)) and the ratio of long-chain polyunsaturated to saturated fatty acids (PUFA:SFA) of food algae cultured under elevated (750 µatm) compared to present day (380 µatm) pCO(2) was directly translated to copepods. The proportion of total essential FAs declined almost tenfold in copepods and the contribution of saturated fatty acids (SFAs) tripled at high CO(2). This rapid and reversible CO(2)-dependent shift in FA concentration and composition caused a decrease in both copepod somatic growth and egg production from 34 to 5 eggs female(-1) day(-1). Because the diatom-copepod link supports some of the most productive ecosystems in the world, our study demonstrates that OA can have far-reaching consequences for ocean food webs by changing the nutritional quality of essential macromolecules in primary producers that cascade up the food web.

Comment on "Phytoplankton calcification in a high-CO2 world".

Iglesias-Rodriguez et al. (Research Articles, 18 April 2008, p. 336) reported that the coccolithophore Emiliania huxleyi doubles its organic matter production and calcification in response to high carbon dioxide partial pressures, contrary to previous laboratory and field studies. We argue that shortcomings in their experimental protocol compromise the interpretation of their data and the resulting conclusions.