Comparison of CO2 Dynamics and Air–Sea Gas Exchange in Differing Tropical Reef Environments

An array of MAPCO₂ buoys, CRIMP-2, Ala Wai, and Kilo Nalu, deployed in the coastal waters of Hawaii, have produced multi-year high temporal resolution CO₂ records in three different coral reef environments off the island of Oahu, Hawaii. This study, which includes data from June 2008 to December 2011, is part of an integrated effort to understand the factors that influence the dynamics of CO₂–carbonic acid system parameters in waters surrounding Pacific high-island coral reef ecosystems and subject to differing natural and anthropogenic stresses. The MAPCO₂ buoys are located on the Kaneohe Bay backreef, and fringing reef sites on the south shore of Oahu, Hawaii. The buoys measure CO₂ and O₂ in seawater and in the atmosphere at 3-h intervals, as well as other physical and biogeochemical parameters (conductivity, temperature, depth, chlorophyll-a, and turbidity). The buoy records, combined with data from synoptic spatial sampling, have allowed us to examine the interplay between biological cycles of productivity/respiration and calcification/dissolution and biogeochemical and physical forcings on hourly to inter-annual time scales. Air–sea CO₂ gas exchange was also calculated to determine whether the locations were sources or sinks of CO₂ over seasonal, annual, and interannual time periods. Net annualized fluxes for CRIMP-2, Ala Wai, and Kilo Nalu over the entire study period were 1.15, 0.045, and ?0.0056 mol C m^?2 year^?1, respectively, where positive values indicate a source or a CO₂ flux from the water to the atmosphere, and negative values indicate a sink or flux of CO₂ from the atmosphere into the water. These values are of similar magnitude to previous estimates in Kaneohe Bay as well as those reported from other tropical reef environments. Total alkalinity (A_T) was measured in conjunction with pCO₂, and the carbonic acid system was calculated to compare with other reef systems and open ocean values around Hawaii. These findings emphasize the need for high-resolution data of multiple parameters when attempting to characterize the carbonic acid system in locations of highly variable physical, chemical, and biological parameters (e.g., coastal systems and reefs).     

Nutrient Inputs, Phytoplankton Response, and CO2 Variations in a Semi-Enclosed Subtropical Embayment, Kaneohe Bay, Hawaii

The marine shelf areas in subtropical and tropical regions represent only 35% of the total shelf areas globally, but receive a disproportionately large amount of water (65%) and sediment (58%) discharges that enter such environments. Small rivers and/or streams that drain the mountainous areas in these climatic zones deliver the majority of the sediment and nutrient inputs to these narrow shelf environments; such inputs often occur as discrete, episodic introductions associated with storm events. To gain insight into the linked biogeochemical behavior of subtropical/tropical mountainous watershed-coastal ocean ecosystems, this work describes the use of a buoy system to monitor autonomously water quality responses to land-derived nutrient inputs and physical forcing associated with local storm events in the coastal ocean of southern Kaneohe Bay, Oahu, Hawaii, USA. The data represent 2.5 years of near-real time observations at a fixed station, collected concurrently with spatially distributed synoptic sampling over larger sections of Kaneohe Bay. Storm events cause most of the fluvial nutrient, particulate, and dissolved organic carbon inputs to Kaneohe Bay. Nutrient loadings from direct rainfall and/or terrestrial runoff produce an immediate increase in the N:P ratio of bay waters up to values of 48 and drive phytoplankton biomass growth. Rapid uptake of such nutrient subsidies by phytoplankton causes rapid declines of N levels, return to N-limited conditions, and subsequent decline of phytoplankton biomass over timescales ranging from a few days to several weeks, depending on conditions and proximity to the sources of runoff. The enhanced productivity may promote the drawing down of pCO₂ and lowering of surface water column carbonate saturation states, and in some events, a temporary shift from N to P limitation. The productivity-driven CO₂ drawdown may temporarily lead to air-to-sea transfer of atmospheric CO₂ in a system that is on an annual basis a source of CO₂ to the atmosphere due to calcification and perhaps heterotrophy. Storms may also strongly affect proximal coastal zone pCO₂ and hence carbonate saturation state due to river runoff flushing out high pCO₂ soil and ground waters. Mixing of the CO₂-charged water with seawater causes a salting out effect that releases CO₂ to the atmosphere. Many subtropical and tropical systems throughout the Pacific region are similar to Kaneohe Bay, and our work provides an important indication of the variability and range of CO₂ dynamics that are likely to exist elsewhere. Such variability must be taken into account in any analysis of the direction and magnitude of the air?Csea CO₂ exchange for the integrated coastal ocean, proximal and distal. It cannot be overemphasized that this research illustrates several examples of how high frequency sampling by a moored autonomous system can provide details about ecosystem responses to stochastic atmospheric forcing that are commonly missed by traditional synoptic observational approaches. Finally, the work exemplifies the utility of combining synoptic sampling and real-time autonomous observations to elucidate the biogeochemical and physical responses of coastal subtropical/tropical coral reef ecosystems to climatic perturbations.     

Sedimentation,dredging, and spoil disposal in a subtropical estuarine lagoon

Kaneohe Bay, Hawaii, is an estuary used as a harbor for a military installation and for recreation, fishing, and research purposes. Rapid shoaling of the bay had been reported and attributed to increased stream erosion and sedimentation from the newly suburbanized watershed. Comparison of a 1976 bathymetric survey of Kaneohe Bay with that of a 1927 survey indicates an average shoaling of the lagoonal area of 1.0 m. Average shoaling for the north and middle bay at 0.6m/49 years (1.2 cm yr⁻¹ is lower than for the south bay at 1.5m/49 years (3.1 cm yr⁻¹). The total lagoonal fill in the 49-year period is about 1.95× 10⁷ m³, assigned as follows: 64% carbonate detritus from the reefs as well as growth of living coral and unrecorded dredging spill, 9% recorded dredging spoils, and only 27% terrigenous sediment. Seismic reflection profiles distinguish spoil from natural sediment and show that the infilling sediment is trapped between, burying reef structures built during Quaternary lower stands of the sea. There had been little obvious change between 1882 and 1927 surveys. All information suggests that increased shoaling rates since 1927 are due to reported and unreported disposal of dredge spoil, mainly from 1939 to 1945 for ship and seaplane channels in the south bay, and not from increased runoff and urbanization around the south bay. Hawaii Institute of Geophysics Contribution No. 1257.     

Carbon dioxide dynamics in rivers and coastal waters of the “big island” of Hawaii,USA, during baseline and heavy rain conditions

The distributions of the partial pressure of carbon dioxide (pCO₂) and total alkalinity (TA) were examined for a 6-month period in the Wailuku and Wailoa rivers and coastal waters of Hilo Bay on the west coast of the Island of Hawaii, USA. Main results for the largest and turbulent Wailuku River show in the watershed an oversaturation in CO₂ with respect to atmospheric equilibrium and a CO₂ undersaturation in the estuary. In the Wailoa river-estuary system, extremely high pCO₂ values ranging from 1500 to 10500 ppm were measured with significant shifts in pCO₂ from drought to flood period. In the two rivers, water residence time, groundwater inputs and occasional flood events are the predominant drivers of the spatial and temporal patterns in the distribution of pCO₂. In Hilo Bay, CO₂ oversaturation dominates and the bay was a source of CO₂ to the atmosphere during the study period. TA is conservative along the salinity gradient, indicating calcification in the bay is not a significant source of CO₂ to the atmosphere.     

Impact of storm runoff from tropical watersheds on coastal water quality and productivity

Storm runoff in the steep watersheds in Hawaii leads to sediment and freshwater pulses to coastal waters that quickly affect nearshore water quality. This is particularly true in semi-enclosed embayments, such as Kaneohe Bay, Oahu, where water has a relatively long residence time compared to more open coastal areas of the islands. In this paper the authors discuss water quality and productivity in Kaneohe Bay after back-to-back rain events in late November and early December 2003, following a particularly dry summer. The short-term biogeochemical response of coastal waters and the ecosystem to runoff and physical forcing was evaluated through a combination of continuous in situ measurements and adaptive synoptic sampling carried out on a variety of temporal and spatial scales.     

Long-term pCO2 dynamics in rivers in the Chesapeake Bay watershed

Streams and rivers are major exporters of C and other dissolved materials from watersheds to coastal waters. In streams and rivers, substantial amounts of terrigenous organic C is metabolized and degassed as CO₂ to the atmosphere. A long-term evaluation of CO₂ dynamics in streams is essential for understanding factors controlling CO₂ dynamics in streams in response to changes in climate and land-use. Long-term changes in the partial pressure of CO₂ (pCO₂) were computed in the Anacostia River and the lower Potomac River in the Chesapeake Bay watershed. Long-term estimates were made using routine monitoring data of pH, total alkalinity, and dissolved nutrients from 1985 to 2006 at 14 stations. Longitudinal variability in pCO₂ dynamics was also investigated along these rivers downstream of the urban Washington D.C. metropolitan area. Both rivers were supersaturated with CO₂ with respect to atmospheric CO₂ levels (392 μatm) and the highly urbanized Anacostia waters (202–9694 μatm) were more supersaturated than the Potomac waters (557–3800 μatm). Long-term variability in pCO₂ values may be due to changes in river metabolism and organic matter and nutrient loadings. Both rivers exchange significant amounts of CO₂ with the atmosphere (i.e., Anacostia at 0.2–72 mmol m⁻² d⁻¹ and Potomac at 0.12–24 mmol m⁻² d⁻¹), implying that waterways receiving organic matter and nutrient subsidies from urbanized landscapes have the potential to increase river metabolism and atmospheric CO₂ fluxes along the freshwater–estuarine continuum.     

Nutrient Mass Flux between Florida Bay and the Florida Keys National Marine Sanctuary

There is a net discharge of water and nutrients through Long Key Channel from Florida Bay to the Florida Keys National Marine Sanctuary (FKNMS). There has been speculation that this water and its constituents may be contributing to the loss of coral cover on the Florida Keys Reef tract over the past few decades, as well as speculation that changes in freshwater flow in the upstream Everglades ecosystem associated with the Comprehensive Everglades Restoration Plan may exacerbate this phenomenon. The results of this study indicate that although there is a net export of approximately 3,850 (±404) ton N year^?1 and 63 (±7) ton P year^?1, the concentrations of these nutrients flowing out of Florida Bay are the same as those flowing in. This implies that no significant nutrient enrichment is occurring in the waters of the FKNMS in the vicinity of Long Key Channel. Because of the effect of restricted southwestward water flow through Florida Bay by shallow banks and small islands, the volume of relatively high-nutrient water from central and eastern portions of the bay exiting through the channel is small compared to the average tidal exchange. Nutrient loading of relatively enriched bay waters is mediated by tidal exchange and mixing with more ambient concentrations of the western Florida Bay and Hawk Channel. System-wide budgets indicate that the contribution of Florida Bay waters to the inorganic nitrogen pool of the Keys coral reef is small relative to offshore inputs.     

Carbonate Chemistry and Air–Sea CO2 Flux in a NW Mediterranean Bay Over a Four-Year Period: 2007–2011

The Service d’Observation de la Rade de Villefranche-sur-Mer is designed to study the temporal variability of hydrological conditions as well as the abundance and composition of holo- and meroplankton at a fixed station in this bay of the northwest Mediterranean. The weekly data collected at this site, designated as “Point B” since 1957, represent a long-term time series of hydrological conditions in a coastal environment. Since 2007, the historical measurements of hydrological and biological conditions have been complemented by measurements of the CO₂–carbonic acid system parameters. In this contribution, CO₂–carbonic acid system parameters and ancillary data are presented for the period 2007–2011. The data are evaluated in the context of the physical and biogeochemical processes that contribute to variations in CO₂ in the water column and exchange of this gas between the ocean and atmosphere. Seasonal cycles of the partial pressure of CO₂ in seawater (pCO₂) are controlled principally by variations in temperature, showing maxima in the summer and minima during the winter. Normalization of pCO₂ to the mean seawater temperature (18.5 °C), however, reveals an apparent reversal of the seasonal cycle with maxima observed in the winter and minima in the summer, consistent with a biogeochemical control of pCO₂ by primary production. Calculations of fluxes of CO₂ show this area to be a weak source of CO₂ to the atmosphere during the summer and a weak sink during the winter but near neutral overall (range ?0.3 to +0.3 mmol CO₂ m^?2 h^?1, average 0.02 mmol CO₂ m^?2 h^?1). We also provide an assessment of errors incurred from the estimation of annual fluxes of CO₂ as a function of sampling frequency (3-hourly, daily, weekly), using data obtained at the Hawaii Kilo Nalu coastal time-series station, which shows similar behavior to the Point B location despite significant differences in climate and hydrological conditions and the proximity of a coral reef ecosystem.     

Controls on nutrient and phytoplankton dynamics during normal flow and storm runoff conditions, southern Kaneohe Bay, Hawaii

Fluvial effects on nutrient and phytoplankton dynamics were evaluated in southern Kaneohe Bay, Oahu, Hawaii. Fluvial inputs occurred as small, steady baseflows interrupted by intense pulses of storm runoff. Baseflow river inputs only affected restricted areas around stream mouths, but the five storm events sampled during this study produced transient runoff plumes of much greater spatial extent. Nutrient loading via runoff generally led to an increase of the phytoplankton biomass and gross primary productivity in southern Kaneohe Bay, but the rapid depletion of nutrients resulted in a decline of the algal populations in the relatively short time of days. Under baseline conditions, water column primary productivity in southern Kaneohe Bay is normally nitrogen limited. Following storm events, the high ratio of dissolved inorganic nitrogen to dissolved inorganic phosphorus (DIN:DIP, 25–29) fluxes of runoff nutrients drove bay waters towards phosphorus limitation. A depletion of phosphate relative to DIN in surface waters was observed following all storm events. Due to high flushing rates, recovery times of bay waters from storm perturbations ranged from 3 to 8 d and appeared to be correlated with tidal range. Storm inputs have a significant effect on the water column ecosystem and biogeochemistry in southern Kaneohe Bay. The perturbations were only transient events and the system rapidly recovered to prestorm conditions.     

Air–water CO<Subscript>2</Subscript> flux in an algae bloom year for Lake Hongfeng,Southwest China: implications for the carbon cycle of global inland waters

The carbon cycle of global inland waters is quantitatively comparable to other components in the global carbon budget. Among inland waters, a significant part is man-made lakes formed by damming rivers. Man-made lakes are undergoing a rapid increase in number and size. Human impacts and frequent algae blooms lead to it necessary to make a better constraint on their carbon cycles. Here, we make a primary estimation on the air–water CO₂ transfer flux through an algae bloom year for a subtropical man-made lake—Hongfeng Lake, Southwest China. To do this a new type of glass bottles was designed for content and isotopic analysis of DIC and other environmental parameters. At the early stage of algae bloom, CO₂ was transferred from the atmosphere to the lake with a net flux of 1.770 g·C·m^?2. Later, the partial pressure (pCO₂) of the aqueous CO₂ increased rapidly and the lake outgassed to the atmosphere with a net flux of 95.727 g·C·m^?2. In the remaining days, the lake again took up CO₂ from the atmosphere with a net flux of 14.804 g·C·m^?2. As a whole, Lake Hongfeng released 4527 t C to the atmosphere, accounting for one-third of the atmosphere/soil CO₂ sequestered by chemical weathering in the whole drainage. With an empirical mode decomposition method, we found air temperature plays a major role in controlling water temperature, aqueous pCO₂ and hence CO₂ flux. This work indicates a necessity to make detailed and comprehensive carbon budgets in man-made lakes.     

Land–sea carbon and nutrient fluxes and coastal ocean CO2 exchange and acidification: Past,present, and future

Epochs of changing atmospheric CO₂ and seawater CO₂–carbonic acid system chemistry and acidification have occurred during the Phanerozoic at various time scales. On the longer geologic time scale, as sea level rose and fell and continental free board decreased and increased, respectively, the riverine fluxes of Ca, Mg, DIC, and total alkalinity to the coastal ocean varied and helped regulate the C chemistry of seawater, but nevertheless there were major epochs of ocean acidification (OA). On the shorter glacial–interglacial time scale from the Last Glacial Maximum (LGM) to late preindustrial time, riverine fluxes of DIC, total alkalinity, and N and P nutrients increased and along with rising sea level, atmospheric PCO₂ and temperature led, among other changes, to a slightly deceasing pH of coastal and open ocean waters, and to increasing net ecosystem calcification and decreasing net heterotrophy in coastal ocean waters. From late preindustrial time to the present and projected into the 21st century, human activities, such as fossil fuel and land-use emissions of CO₂ to the atmosphere, increasing application of N and P nutrient subsidies and combustion N to the landscape, and sewage discharges of C, N, P have led, and will continue to lead, to significant modifications of coastal ocean waters. The changes include a rapid decline in pH and carbonate saturation state (modern problem of ocean acidification), a shift toward dissolution of carbonate substrates exceeding production, potentially leading to the “demise” of the coral reefs, reversal of the direction of the sea-to-air flux of CO₂ and enhanced biological production and burial of organic C, a small sink of anthropogenic CO₂, accompanied by a continuous trend toward increasing autotrophy in coastal waters.     

Physiological and isotopic responses of scleractinian corals to ocean acidification

Uptake of anthropogenic CO₂ by the oceans is altering seawater chemistry with potentially serious consequences for coral reef ecosystems due to the reduction of seawater pH and aragonite saturation state (Ω_arag). The objectives of this long-term study were to investigate the viability of two ecologically important reef-building coral species, massive Porites sp. and Stylophora pistillata, exposed to high pCO₂ (or low pH) conditions and to observe possible changes in physiologically related parameters as well as skeletal isotopic composition. Fragments of Porites sp. and S. pistillata were kept for 6-14 months under controlled aquarium conditions characterized by normal and elevated pCO₂ conditions, corresponding to pH_T values of 8.09, 7.49, and 7.19, respectively. In contrast with shorter, and therefore more transient experiments, the long experimental timescale achieved in this study ensures complete equilibration and steady state with the experimental environment and guarantees that the data provide insights into viable and stably growing corals. During the experiments, all coral fragments survived and added new skeleton, even at seawater Ω_arag < 1, implying that the coral skeleton is formed by mechanisms under strong biological control. Measurements of boron (B), carbon (C), and oxygen (O) isotopic composition of skeleton, C isotopic composition of coral tissue and symbiont zooxanthellae, along with physiological data (such as skeletal growth, tissue biomass, zooxanthellae cell density, and chlorophyll concentration) allow for a direct comparison with corals living under normal conditions and sampled simultaneously. Skeletal growth and zooxanthellae density were found to decrease, whereas coral tissue biomass (measured as protein concentration) and zooxanthellae chlorophyll concentrations increased under high pCO₂ (low pH) conditions. Both species showed similar trends of δ¹¹B depletion and δ¹⁸O enrichment under reduced pH, whereas the δ¹³C results imply species-specific metabolic response to high pCO₂ conditions. The skeletal δ¹¹B values plot above seawater δ¹¹B vs. pH borate fractionation curves calculated using either the theoretically derived α_B value of 1.0194 (Kakihana et al. (1977) Bull. Chem. Soc. Jpn.50, 158) or the empirical α_B value of 1.0272 (Klochko et al. (2006) EPSL248, 261). However, the effective α_B must be greater than 1.0200 in order to yield calculated coral skeletal δ¹¹B values for pH conditions where Ω_arag ? 1. The δ¹¹B vs. pH offset from the seawater δ¹¹B vs. pH fractionation curves suggests a change in the ratio of skeletal material laid down during dark and light calcification and/or an internal pH regulation, presumably controlled by ion-transport enzymes. Finally, seawater pH significantly influences skeletal δ¹³C and δ¹⁸O. This must be taken into consideration when reconstructing paleo-environmental conditions from coral skeletons.     

Coastal Ocean Last Glacial Maximum to 2100 CO2-Carbonic Acid-Carbonate System: A Modeling Approach

Using coupled terrestrial and coastal zone models, we investigated the impacts of deglaciation and anthropogenic inputs on the CO₂–H₂O–CaCO₃ system in global coastal ocean waters from the Last Glacial Maximum (LGM: 18,000 year BP) to the year 2100. With rising sea level and atmospheric CO₂, the carbonate system of coastal ocean water changed significantly. We find that 6 × 10¹² metric tons of carbon were emitted from the coastal ocean, growing due to the sea level rise, from the LGM to late preindustrial time (1700 AD) because of net heterotrophy and calcification processes. This carbon came to reside in the atmosphere and in the growing vegetation on land and in uptake of atmospheric CO₂ through the weathering of rocks on land. It appears that carbonate accumulation, mainly, but not exclusively, in coral reefs from the LGM to late preindustrial time could account for about 24 ppmv of the 100 ppmv rise in atmospheric CO₂, lending some support to the “coral reef hypothesis”. In addition, the global coastal ocean is now, or soon will be, a sink of atmospheric CO₂. The temperature rise of 4–5°C since the LGM led to increased weathering rates of inorganic and organic materials on land and enhanced riverine fluxes of total C, N, and P to the coastal ocean of 68%, 108%, and 97%, respectively, from the LGM to late preindustrial time. During the Anthropocene, these trends have been exacerbated owing to rising atmospheric CO₂, due to fossil fuel combustion and land-use practices, other human activities, and rising global temperatures. River fluxes of total reactive C, N, and P are projected to increase from late preindustrial time to the year 2100 by 150%, 380%, and 257%, respectively, modifying significantly the behavior of these element cycles in the coastal ocean, particularly in proximal environments. Despite the fact that the global shoal water carbonate mass has grown extensively since the LGM, the pH_T (pH values on the total proton scale) of global coastal waters has decreased from ~8.35 to ~8.18 and the carbonate ion concentration declined by ~19% from the LGM to late preindustrial time. The latter represents a rate of decline of about 0.028 μmol CO₃ ^2? per decade. In comparison, the decrease in coastal water pH_T from the year 1900 to 2000 was about 8.18–8.08 and is projected to decrease further from about 8.08 to 7.85 between 2000 and 2100, according to the IS92a business-as-usual scenario of CO₂ emissions. Over these 200 years, the carbonate ion concentration will fall by ~120 μmol kg^?1 or 6 μmol kg^?1 per decade. This decadal rate of decline of the carbonate ion concentration in the Anthropocene is 214 times the average rate of decline for the entire Holocene. Hence, when viewed against the millennial to several millennial timescale of geologic change in the coastal ocean marine carbon system, one can easily appreciate why ocean acidification is the “other CO₂ problem”.     

Spatial and Temporal Variability of the CO2 Fluxes in a Tropical, Highly Urbanized Estuary

The spatial and temporal variations of the flux of CO₂ were determined during 2007 in the Recife estuarine system (RES), a tropical estuary that receives anthropogenic loads from one of the most populated and industrialized areas of the Brazilian coast. The RES acts as a source of nutrients (N and P) for coastal waters. The calculated CO₂ fluxes indicate that the upstream inputs of CO₂ from the rivers are largely responsible for the net annual CO₂ emission to the atmosphere of +30 to +48 mmol m^?2 day^?1, depending on the CO₂ exchange calculation used, which mainly occurs during the late austral winter and early summer. The observed inverse relationship between the CO₂ flux and the net ecosystem production (NEP) indicates the high heterotrophy of the system (except for the months of November and December). The NEP varies between ?33 mmol m^?2 day^?1 in summer and ?246 mmol m^?2 day^?1 in winter. The pCO₂ values were permanently high during the study period (average ~4,700 μatm) showing a gradient between the inner (12,900 μatm) and lower (389 μatm) sections on a path of approximately 30 km. This reflects a state of permanent pollution in the basin due to the upstream loading of untreated domestic effluents (N/P?=?1,367:6 μmol kg^?1 and pH?=?6.9 in the inner section), resulting in the continuous mineralization of organic material by heterotrophic organisms and thereby increasing the dissolved CO₂ in estuarine waters.     

Soil temperature and moisture controls on surface fluxes and profile concentrations of greenhouse gases in karst area in central part of Guizhou Province, southwest China

In order to better understand the spatiotemporal variations and interrelationships of greenhouse gases (GHG), monthly surface fluxes and profile concentrations of GHG (CO₂, N₂O and CH₄) in karst areas in the Guizhou Province, southwest China, were measured from June 2006 to May 2007. GHG fluxes showed high variability, with a range of 460.9?C1,281.2?mg?m^?2?h^?1 for CO₂, ?25.4 to 81.5???g?m^?2?h^?1 for N₂O and ?28.7 to ?274.9???g?m^?2?h^?1 for CH₄, but no obvious seasonal change trends of the fluxes existed. Profile concentrations of CO₂, N₂O and CH₄ varied between 0.5 and 31.5?mL?L^?1, 0.273 and 0.734, and 0.1 and 3.5???L?L^?1, respectively. In general, concentrations of CO₂ and N₂O increased with depth, while CH₄ had an inverse trend. However, in October, November and January, the reversal of depth patterns of GHG concentrations took place below 15?cm, close to the soil?Crock interface. The spatiotemporal distribution of CO₂ in soil profile was significantly positively correlated with that of N₂O (p?<?0.05?C0.01) and negatively correlated with that of CH₄ (p?<?0.01). The correlation analysis showed that soil temperature and moisture may be responsible for GHG dynamics in the soils, rather than the exchange of GHG between land and atmosphere.     

The Carbonate Chemistry of the “Fattening Line,” Willapa Bay, 2011–2014

Willapa Bay has received a great deal of attention in the context of rising atmospheric CO₂ and the concomitant effects of changes in bay carbonate chemistry, referred to as ocean acidification, and the potential effects on the bay’s naturalized Pacific oyster (Crassostrea gigas) population and iconic oyster farming industry. Competing environmental stressors, historical variability in the oyster settlement record, and the absence of adequate historical observations of bay-water carbonate chemistry all conspire to cast confusion regarding ocean acidification as the culprit for recent failures in oyster larval settlement. We present the first measurements of the aqueous CO₂ partial pressure (PCO₂) and the total dissolved carbonic acid (TCO₂) at the “fattening line,” a location in the bay that has been previously identified as optimal for both larval oyster retention and growth, and collocated with a long historical time series of larval settlement. Samples were collected from early 2011 through late 2014. These measurements allow the first rigorous characterization of Willapa Bay aragonite mineral saturation state (Ω_ar), which has been shown to be of leading importance in determining the initial shell formation and growth of larval Crassostrea gigas. Observations show that the bay is usually below Ω_ar levels that have been associated with poor oyster hatchery production and with chronic effects noted in experimental work. Bay water only briefly rises to favorable Ω_ar levels and does so out of phase with optimal thermal conditions for spawning. Thermal and carbonate conditions are thus coincidentally favorable for early larval development for only a few weeks at a time each year. The limited concurrent exceedance of thermal and Ω_ar thresholds suggests the likelihood of high variability in settlement success, as seen in the historical record; however, estimates of the impact of elevated atmospheric CO₂ suggest that pre-industrial Ω_ar conditions were more persistently favorable for larval development and more broadly coincident with thermal optima.     

Carbon dioxide emissions from the Three Gorges Reservoir,China

Carbon dioxide (CO₂) emission from the river-type reservoir is an hotspot of carbon cycle within inland waters. However, related studies on the different types of reservoirs are still inadequate. Therefore, we sampled the Three Gorges Reservoir (TGR), a typical river-type reservoir having both river and lake characteristics, using an online system (HydroCTM/CO₂) and YSI-6600v2 meter to determine the partial pressure of carbon dioxide (pCO₂) and physical chemical parameters in 2013. The results showed that the CO₂ flux from the mainstream ranged from 26.1 to 92.2 mg CO₂/m² h with average CO₂ fluxes of 50.0 mg/m² h. The CO₂ fluxes from the tributary ranged from ?10.91 to 53.95 mg CO₂/m² h with area-weighted average CO₂ fluxes of 11.4 mg/m² h. The main stream emits CO₂ to the atmosphere the whole year; however, the surface water of the tributary can sometimes act as a sink of CO₂ for the atmosphere. As the operation of the TGR, the tributary became more favorable to photosynthetic uptake of CO₂ especially in summer. The total CO₂ flux was estimated to be 0.34 and 0.03 Tg CO₂/year from the mainstream and the tributaries, respectively. Our emission rates are lower than previous estimates, but they are in agreement with the average CO₂ flux from temperate reservoirs estimated by Barros et al. (Nat Geosci 4(9):593–596, 2011).     

Effects of stormwater nutrient discharges on eutrophication processes in nearshore waters of the Florida keys

Rainfall events cause episodic discharges of groundwaters contaminated with septic tank effluent into nearshore waters of the Florida keys, enhancing eutrophication in sensitive coral reef communities. Our study characterized the effects of stormwater discharges by continuously (30-min intervals) measuring salinity, temperature, tidal stage, and dissolved oxygen (DO) along an offshore eutrophication gradient prior to and following heavy rainfall at the beginning of the 1992 rainy season. The gradient included stations at a developed canal system (PP) on Big Pine Key, a seagrass meadow in a tidal channel (PC), a nearshore patch reef (PR), a bank reef at Looe Key National Marine Sanctuary (LK), and a blue water station (BW) approximately 9 km off of Big PIne Key. Water samples were collected at weekly intervals during this period to determine concentrations of total nitrogen (TN), ammonium (NH₄ ⁺), nitrate plus nitrite NO₃ ^? plus NO₂ ^?), total phosphorus (TP), total dissolved phosphorus (TDP), soluble reactive phosphorus (SRP), and chlorophyll a (chl a). Decreased salinity immediately followed the first major rainfall at Big Pine Key, which was followed by anoxia (DO <0.1 mg I^?1), high concentrations of NH₄ ⁺ (≈24 μM), TDP (≈1.5 μM), and chl a (≈20 μg I^?1). Maximum concentration of TDP (≈0.30 μM) also followed the initial rainfall at the PC, PR, and LK stations. In contrast, NH₄ ⁺ (≈4.0 μM) and chl a (0.45 μg I^?1) lagged the rain event by 1–3 wk, depending on distance from shore. The highest and most variable concentrations of NH₄ ⁺, TDP, and chl a occurred at PP, and all nutrient parameters correlated positively with rainfall. DO at all stations was positively correlated with tide and salinity and the lowest values occurred during low tide and low salinity (high rainfall) periods. Hypoxia (DO <2.5 mg I^?1) was observed at all stations follwing the stormwater discharges, including the offshore bank reef station LK. Our study demonstrated that high frequency (daily) sampling is necessary to track the effects of episodic rainfall events on water quality and that such effects can be detected at considerable distances (12 km) from shore. The low levels of DO and high levels of nutrients and chl a in coastal waters of the Florida Keys demand that special precautions be exercised in the treatment and discharge of wastewaters and land-based runoff in order to preserve sensitive coral reef communities.     

Dissolution of Carbonate Sediments Under Rising <Emphasis Type="Italic">p</Emphasis>CO<Subscript>2</Subscript> and Ocean Acidification: Observations from Devil’s Hole,Bermuda

Rising atmospheric pCO₂ and ocean acidification originating from human activities could result in increased dissolution of metastable carbonate minerals in shallow-water marine sediments. In the present study, in situ dissolution of carbonate sedimentary particles in Devil’s Hole, Bermuda, was observed during summer when thermally driven density stratification restricted mixing between the bottom water and the surface mixed layer and microbial decomposition of organic matter in the subthermocline layer produced pCO₂ levels similar to or higher than those levels anticipated by the end of the 21st century. Trends in both seawater chemistry and the composition of sediments in Devil’s Hole indicate that Mg-calcite minerals are subject to selective dissolution under conditions of elevated pCO₂. The derived rates of dissolution based on observed changes in excess alkalinity and estimates of vertical eddy diffusion ranged from 0.2 mmol to 0.8 mmol CaCO₃ m⁻² h⁻¹. On a yearly basis, this range corresponds to 175–701 g CaCO₃ m⁻² year⁻¹; the latter rate is close to 50% of the estimate of the current average global coral reef calcification rate of about 1,500 g CaCO₃ m⁻² year⁻¹. Considering a reduction in marine calcification of 40% by the year 2100, or 90% by 2300, as a result of surface ocean acidification, the combination of high rates of carbonate dissolution and reduced rates of calcification implies that coral reefs and other carbonate sediment environments within the 21st and following centuries could be subject to a net loss in carbonate material as a result of increasing pCO₂ arising from burning of fossil fuels.     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^?1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^?1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).