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.     

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.     

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”.     

Is Ocean Acidification an Open-Ocean Syndrome? Understanding Anthropogenic Impacts on Seawater pH

Ocean acidification due to anthropogenic CO₂ emissions is a dominant driver of long-term changes in pH in the open ocean, raising concern for the future of calcifying organisms, many of which are present in coastal habitats. However, changes in pH in coastal ecosystems result from a multitude of drivers, including impacts from watershed processes, nutrient inputs, and changes in ecosystem structure and metabolism. Interaction between ocean acidification due to anthropogenic CO₂ emissions and the dynamic regional to local drivers of coastal ecosystems have resulted in complex regulation of pH in coastal waters. Changes in the watershed can, for example, lead to changes in alkalinity and CO₂ fluxes that, together with metabolic processes and oceanic dynamics, yield high-magnitude decadal changes of up to 0.5 units in coastal pH. Metabolism results in strong diel to seasonal fluctuations in pH, with characteristic ranges of 0.3 pH units, with metabolically intense habitats exceeding this range on a daily basis. The intense variability and multiple, complex controls on pH implies that the concept of ocean acidification due to anthropogenic CO₂ emissions cannot be transposed to coastal ecosystems directly. Furthermore, in coastal ecosystems, the detection of trends towards acidification is not trivial and the attribution of these changes to anthropogenic CO₂ emissions is even more problematic. Coastal ecosystems may show acidification or basification, depending on the balance between the invasion of coastal waters by anthropogenic CO₂, watershed export of alkalinity, organic matter and CO₂, and changes in the balance between primary production, respiration and calcification rates in response to changes in nutrient inputs and losses of ecosystem components. Hence, we contend that ocean acidification from anthropogenic CO₂ is largely an open-ocean syndrome and that a concept of anthropogenic impacts on marine pH, which is applicable across the entire ocean, from coastal to open-ocean environments, provides a superior framework to consider the multiple components of the anthropogenic perturbation of marine pH trajectories. The concept of anthropogenic impacts on seawater pH acknowledges that a regional focus is necessary to predict future trajectories in the pH of coastal waters and points at opportunities to manage these trajectories locally to conserve coastal organisms vulnerable to ocean acidification.     

Human perturbations on the global biogeochemical cycles of coupled Si–C and responses of terrestrial processes and the coastal ocean

We present a model of the global biogeochemical cycle of silicon (Si) that emphasizes its linkages to the carbon cycle and temperature. The Si cycle is a crucial part of global nutrient biogeochemistry regulating long-term atmospheric CO₂ concentrations due to silicate mineral weathering reactions involving the uptake of atmospheric CO₂ and production of riverine dissolved silica, cations and bicarbonate. In addition and importantly, the Si cycle is strongly coupled to the other nutrient cycles of N, P, and Fe; hence siliceous organisms represent a significant fraction of global primary productivity and biomass. Human perturbations involving land-use changes, burning of fossil fuel, and inorganic N and P fertilization have greatly altered the terrestrial Si cycle, changing the river discharge of Si and consequently impacting marine primary productivity primarily in coastal ocean waters.     

Initial responses of carbonate-rich shelf sediments to rising atmospheric pCO2 and “ocean acidification”: Role of high Mg-calcites

Carbonate-rich sediments at shoal to shelf depths (<200 m) represent a major CaCO₃ reservoir that can rapidly react to the decreasing saturation state of seawater with respect to carbonate minerals, produced by the increasing partial pressure of atmospheric carbon dioxide (pCO₂) and “acidification” of ocean waters. Aragonite is usually the most abundant carbonate mineral in these sediments. However, the second most abundant (typically ∼24 wt%) carbonate mineral is high Mg-calcite (Mg-calcite) whose solubility can exceed that of aragonite making it the “first responder” to the decreasing saturation state of seawater. For the naturally occurring biogenic Mg-calcites, dissolution experiments have been used to predict their “stoichiometric solubilities” as a function of mol% MgCO₃. The only valid relationship that one can provisionally use for the metastable stabilities for Mg-calcite based on composition is that for the synthetically produced phases where metastable equilibrium has been achieved from both under- and over-saturation. Biogenic Mg-calcites exhibit a large offset in solubility from that of abiotic Mg-calcite and can also exhibit a wide range of solubilities for biogenic Mg-calcites of similar Mg content. This indicates that factors other than the Mg content can influence the solubility of these mineral phases. Thus, it is necessary to turn to observations of natural sediments where changes in the saturation state of surrounding waters occur in order to determine their likely responses to the changing saturation state in upper oceanic waters brought on by increasing pCO₂. In the present study, we investigate the responses of Mg-calcites to rising pCO₂ and “ocean acidification” by means of a simple numerical model based on the experimental range of biogenic Mg-calcite solubilities as a function of Mg content in order to bracket the behavior of the most abundant Mg-calcite phases in the natural environment. In addition, observational data from Bermuda and the Great Bahama Bank are also presented in order to project future responses of these minerals. The numerical simulations suggest that Mg-calcite minerals will respond to rising pCO₂ by sequential dissolution according to mineral stability, progressively leading to removal of the more soluble phases until the least soluble phases remain. These results are confirmed by laboratory experiments and observations from Bermuda. As a consequence of continuous increases in atmospheric CO₂ from burning of fossil fuels, the average composition of contemporary carbonate sediments could change, i.e., the average Mg content in the sediments may slowly decrease. Furthermore, evidence from the Great Bahama Bank indicates that the amount of abiotic carbonate production is likely to decline as pCO₂ continues to rise.     

Ocean acidification and photic‐zone anoxia at the Toarcian Oceanic Anoxic Event: Insights from the Adriatic Carbonate Platform

Severe global climate change led to the deterioration of environmental conditions in the oceans during the Toarcian Stage of the Jurassic. Carbonate platforms of the Western Tethys Ocean exposed in Alpine Tethyan mountain ranges today offer insight into this period of environmental upheaval. In addition to informing understanding of climate change in deep time, the effect of ancient carbon cycle perturbations on carbonate platforms has important implications for anthropogenic climate change; the patterns of early Toarcian environmental deterioration are similar to those occurring in modern oceans. This study focuses on the record of the early Toarcian Oceanic Anoxic Event (ca 183.1 Ma) in outcrops of the north‐west Adriatic Carbonate Platform in Slovenia. Amidst environmental deterioration, the north‐west Adriatic Platform abruptly transitioned from a healthy, shallow‐water environment with diverse metazoan ecosystems to a partially drowned setting with low diversity biota and diminished sedimentation. An organic carbon‐isotope excursion of ?2.2‰ reflects the massive injection of CO₂ into the ocean‐atmosphere system and marks the stratigraphic position of the Toarcian Oceanic Anoxic Event. A prominent dissolution horizon and suppressed carbonate deposition on the platform are interpreted to reflect transient shoaling of the carbonate compensation depth to unprecedentedly shallow levels as the dramatic influx of CO₂ overwhelmed the ocean’s buffering capacity, causing ocean acidification. Trace metal geochemistry and palaeoecology highlight water column deoxygenation, including the development of photic‐zone anoxia, preceding and during the Toarcian Oceanic Anoxic Event. Ocean acidification and reduced oxygen levels likely had a profoundly negative effect on carbonate‐producing biota and growth of the Adriatic Platform. These effects are consistent with the approximate doubling of the concentration of CO₂ in the ocean‐atmosphere system from pre‐event levels, which has previously been linked to a volcanic triggering mechanism. Mercury enrichments discovered in this study support a temporal and genetic link between volcanism, the Toarcian Oceanic Anoxic Event and the carbonate crisis.     

Multiple Factors driving Variability of CO2 Exchange Between the Ocean and Atmosphere in a Tropical Coral Reef Environment

In this paper, we present the results of the first automated continuous multi-year high temporal frequency study of CO₂ dynamics in a coastal coral reef ecosystem. The data cover 2.5?years of nearly continuous operation of the CRIMP-CO₂ buoy spanning particularly wet and dry seasons in southern Kaneohe Bay, a semi-enclosed tropical coral reef ecosystem in Hawaii. We interpret our observational results in the context of how rapidly changing physical and biogeochemical conditions affect the pCO₂ of surface waters and the magnitude and direction of air–sea exchange of CO₂. Local climatic forcing strongly affects the biogeochemistry, water column properties, and gas exchange between the ocean and atmosphere in Kaneohe Bay. Rainfall driven by trade winds and other localized storms generates pulses of nutrient-rich water, which exert a strong control on primary productivity and impact carbon cycling in the water column of the bay. The “La Ni?a” winter of 2005–2006 was one of the wettest winters in Hawaii in 30?years and contrasted sharply with preceding and subsequent drier winter seasons. In addition, short-term variability in physical forcing adds complexity and helps drive the response of the CO₂–carbonic acid system of the bay. Freshwater pulses to Kaneohe Bay provide nutrient subsidies to bay waters, relieving the normal nitrogen limitation of this system and driving phytoplankton productivity. Seawater pCO₂ responds to the blooms as well as to physical forcing mechanisms, leading to a relatively wide range of pCO₂ in seawater from about 250 to 650?μatm, depending on conditions. Large drawdowns in pCO₂ following storms occasionally cause bay waters to switch from being a source of CO₂ to the atmosphere to being a sink. Yet, during our study period, the southern sector of Kaneohe Bay remained a net source of CO₂ to the atmosphere on an annualized basis. The integrated net annual flux of CO₂ from the bay to the atmosphere varied between years by a factor of more than two and was lower during the wet “La Ni?a” year, than during the following year. Over the study period, the net annualized flux was 1.80?mol?C?m^?2?year^?1. Our CO₂ flux estimates are consistent with prior synoptic work in Kaneohe Bay and with estimates in other tropical coral reef ecosystems studied to date. The high degree of climatological, physical, and biogeochemical variability observed in this study suggests that automated high-frequency observations are needed to capture the short-, intermediate-, and long-term variability of CO₂ and other properties of these highly dynamic coastal coral reef ecosystems.     

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).     

Rapid Alkalization in Lake Inawashiro, Fukushima, Japan: Implications for Future Changes in the Carbonate System of Terrestrial Waters

The global carbon cycle, one of the important biogeochemical cycles controlling the surface environment of the Earth, has been greatly affected by human activity. Anthropogenic nutrient loading from urban sewage and agricultural runoff has caused eutrophication of aquatic systems. The impact of this eutrophication and consequent photosynthetic activity on CO₂ exchange between freshwater systems and the atmosphere is unclear. In this study, we focused on how nutrient loading to lakes affects their carbonate system. Here, we report results of surveys of lakes in Japan at different stages of eutrophication. Alkalization due to photosynthetic activity and decreases in PCO₂ had occurred in eutrophic lakes (e.g., Lake Kasumigaura), whereas in an acidotrophic lake (Lake Inawashiro) that was impacted by volcanic hot springs, nutrient loading was changing the pH and carbon cycling. When the influence of volcanic activity was stronger in the past in Lake Inawashiro, precipitation of volcanic-derived iron and aluminum had removed nutrients by co-precipitation. During the last three decades, volcanic activity has weakened and the lake water has become alkalized. We inferred that this rapid alkalization did not result just from the reduction in acid inputs but was also strongly affected by increased photosynthetic activity during this period. Human activities affect many lakes in the world. These lakes may play an important part in the global carbon cycle through their influence on CO₂ exchange between freshwater and the atmosphere. Biogeochemical changes and processes in these systems have important implications for future changes in aquatic carbonate systems on land.     

Globally increased pelagic carbonate production during the Mid-Brunhes dissolution interval and the CO2 paradox of MIS 11

The Mid-Brunhes dissolution interval (MBDI) represents a period of global carbonate dissolution, lasting several hundred thousand years, centred around Marine Isotope Stage (MIS) 11. Here we report the effects of dissolution in ODP core 982, taken from 1134 m in the North Atlantic. Paradoxically, records of atmospheric CO₂ from Antarctic ice-cores reveal no long term trend over the last 400 kyr and suggest that CO₂ during MIS 11 was no higher than during the present interglacial. We suggest that a global increase in pelagic carbonate production during this period, possibly related to the proliferation of the Gephyrocapsa coccolithophore, could have altered marine carbonate chemistry in such a way as to drive increased dissolution under the constraints of steady state. An increase in the production of carbonate in surface waters would cause a drawdown of global carbonate saturation and increase dissolution at the seafloor. In order to reconcile the record of atmospheric CO₂ variability we suggest that an increase in the flux of organic matter from the surface to deep ocean, associated with either a net increase in primary production or the enhanced ballasting effect provided by an increased flux of CaCO₃, could have countered the effect of increased calcification on CO₂.     

Tidal pumping drives nutrient and dissolved organic matter dynamics in a Gulf of Mexico subterranean estuary

We hypothesize that nutrient cycling in a Gulf of Mexico subterranean estuary (STE) is fueled by oxygen and labile organic matter supplied by tidal pumping of seawater into the coastal aquifer. We estimate nutrient production rates using the standard estuarine model and a non-steady-state box model, separate nutrient fluxes associated with fresh and saline submarine groundwater discharge (SGD), and estimate offshore fluxes from radium isotope distributions. The results indicate a large variability in nutrient concentrations over tidal and seasonal time scales. At high tide, nutrient concentrations in shallow beach groundwater were low as a result of dilution caused by seawater recirculation. During ebb tide, the concentrations increased until they reached a maximum just before the next high tide. The dominant form of nitrogen was dissolved organic nitrogen (DON) in freshwater, nitrate in brackish waters, and ammonium in saline waters. Dissolved organic carbon (DOC) production was two-fold higher in the summer than in the winter, while nitrate and DON production were one order of magnitude higher. Oxic remineralization and denitrification most likely explain these patterns. Even though fresh SGD accounted for only ∼5% of total volumetric additions, it was an important pathway of nutrients as a result of biogeochemical inputs in the mixing zone. Fresh SGD transported ∼25% of DOC and ∼50% of total dissolved nitrogen inputs into the coastal ocean, with the remainder associated with a one-dimensional vertical seawater exchange process. While SGD volumetric inputs are similar seasonally, changes in the biogeochemical conditions of this coastal plain STE led to higher summertime SGD nutrient fluxes (40% higher for DOC and 60% higher for nitrogen in the summer compared to the winter). We suggest that coastal primary production and nutrient dynamics in the STE are linked.     

Nearshore Carbonate Dissolution in the Hawaiian Archipelago?

Inorganic carbon measurements made in the late 1980s suggest that alkalinity in the waters surrounding the Hawaiian Archipelago is elevated relative to the oligotrophic waters of the North Pacific. These observations have been interpreted as evidence for a “halo” of elevated carbonate saturation state produced by the dissolution of highly soluble magnesium calcites and aragonite on the island platform or in the water column surrounding the islands. If present, this “halo” has implications for air–sea carbon dioxide exchange in Hawaiian waters and may impact the response of coral reef communities to the acidification of the surface waters of the global ocean. The purpose of this study was to assess the magnitude and extent of the elevated calcium carbonate saturation state observed on previous expeditions to this region. Transects were conducted near several atolls in the Northwestern Hawaiian Islands from shallow water adjacent to the forereef to the open ocean 15 km from the island. Hydrographic profiles were collected at each station, and discrete water samples were collected for the measurement of carbon system parameters necessary to compute calcium carbonate saturation state. Our data were compared with observations made at the Hawaii Ocean Time-series site at Station ALOHA and with hydrographic data collected on the WOCE lines in the North Pacific around the archipelago. We did not detect a carbonate dissolution halo around the islands. We conclude that the previously observed halo was probably an analytical artifact, or possibly a result of extreme variability in carbon chemistry surrounding the islands.     

Changes in Surface Morphology of Calcite Exposed to the Oceanic Water Column

Reactions occurring on the surfaces of biogenic carbonate minerals can have important consequences for the biogeochemical cycle of carbon. In this study, carbonate mineral surface reactions with ambient seawater were investigated by atomic force microscopy (AFM). A sampling method was developed in which calcite surfaces were hung at discrete depths on a sediment trap array line for a three-day deployment period in subtropical North Pacific waters. Changes in surface morphologies were examined at nanometer resolution and evaluated using as a constraint the depth profile of calcite saturation in these waters. Evidence suggests that: (1) organic films which develop on carbonate surfaces exposed to shallow seawater may be responsible for the oversaturated state of the upper oceanic water column, (2) dissolution of carbonate minerals within the shallow warm layer of the ocean could be responsible for part of the alkalinity anomaly observed in the North Pacific.     

海洋水色卫星遥感研究与进展

系统介绍了目前海洋水色卫星遥感在海洋碳通量、生物海洋学及上层海洋过程研究,以及海岸带环境监测与管理中的主要应用方向;分析了上述应用对水色卫星传感器在时空分辨率、光谱波段设置和空间覆盖范围等方面的具体设计要求;概括了新一代水色卫星传感器的特点;指出了水色卫星遥感资料应用中的定标、大气校正及定量反演技术等关键问题;介绍了各国海洋水色卫星遥感的发展计划,提出了我国海洋水色卫星遥感研究的对策。     

Do we have enough pieces of the jigsaw to integrate CO2 fluxes in the coastal ocean?

Annually integrated air-water CO₂ flux data in 44 coastal environments were compiled from literature. Data were gathered in 8 major ecosystems (inner estuaries, outer estuaries, whole estuarine systems, mangroves, salt marshes, coral reefs, upwelling systems, and open continental shelves), and up-scaled in the first attempt to integrate air-water CO₂ fluxes over the coastal ocean (26×10⁶ km²), taking into account its geographical and ecological diversity. Air-water CO₂ fluxes were then up-scaled in global ocean (362×10⁶ km²) using the present estimates for the coastal ocean and those from Takahashi et al. (2002) for the open ocean (336×10⁶ km²). If estuaries and salt marshes are not taken into consideration in the up-scaling, the coastal ocean behaves as a sink for atmospheric CO₂(−1.17 mol C m⁻² yr⁻¹) and the uptake of atmospheric CO₂ by the global ocean increases by 24% (−1.93 versus −1.56 Pg C yr⁻¹). The inclusion of the coastal ocean increases the estimates of CO₂ uptake by the global ocean by 57% for high latitude areas (−0.44 versus −0.28 Pg C yr⁻¹) and by 15% for temperate latitude areas (−2.36 versus −2.06 Pg C yr⁻¹) At subtropical and tropical latitudes, the contribution from the coastal ocean increases the CO₂ emission to the atmosphere from the global oceam by 13% (0.87 versus 0.77 Pg C yr⁻¹). If estuaries and salt marshes are taken into consideration in the upscaling, the coastal ocean behaves as a source for atmospheric CO₂ (0.38 mol C m⁻² yr⁻¹) and the uptake of atmospheric CO₂ from the global ocean decreases by 12% (−1.44 versus −1.56 Pg C yr⁻¹) At high and subtropical and tropical latitudes, the coastal ocean behaves as a source for atmospheric CO₂ but at temperate latitudes, it still behaves as a moderate CO₂ sink. A rigorous up-scaling of air-water CO₂ fluxes in the coastal ocean is hampered by the poorly constrained estimate of the surface area of inner estuaries. The present estimates clearly indicate the significance of this biogeochemically, highly active region of the biosphere in the global CO₂ cycle.     

Assessment of the CO<Subscript>2</Subscript> fluxes between the ocean and the atmosphere in the eastern part of the Laptev Sea in the ice-free period

The carbonate system of waters of the inner, middle, and outer shelves was studied for a long period in the eastern part of the Laptev Sea. It is shown that the inner and middle shelves is a heterotrophic province and is a source of CO₂ to the atmosphere during August–September. The average CO₂ flux is 7.9 mmol m^–2 day^–1 and during one month waters of inner and middle shelves release into the atmosphere up to 0.7 Tg of carbon (C). The outer part of the shelf absorbs up to ~0.1 Tg C at an average rate of 3.9 mmol m^–2 day^–1 during the month. Generally, the ice-free zone of the eastern shelf of the Laptev Sea is a source of CO₂ in the studied season: the amount of C released into the atmosphere within a month is ~0.6 Tg.     

Bio-volatilization of polonium: Results from laboratory analyses

Polonium, like other elements in the Group VI Oxygen series (S, Se, Te), has the potential to form volatile alkyl derivatives. This may be evident in its pervasive radioactive excesses in the atmosphere and coastal waters, and its deficiency in surface open ocean waters. We present evidence for the formation of volatile polonium species. The first evidence comes from duplicating experiments that proved the existence of volatile tellurium, its Group VI congener. Cultures of bread mold at room temperature spiked with polonium tracers showed a significant and reproducible loss of about 0.5% per day of volatile polonium species. In another set of experiments, between 30–50% loss of²¹⁰Po was observed from Floridan groundwater when nitrogen was bubbled through it over durations of 5–30 minutes. Polonium volatility is highly relevant for biogeochemical studies because it may provide a natural radiochemical tracer for recycling of similar volatile sulfur and other Group VI metal species between the geosphere, atmosphere, and hydrosphere.     

Carbonate Chemistry Dynamics of Surface Waters in the Northern Gulf of Mexico

This paper presents the results of two cruises in the Northern Gulf of Mexico in 2008 that investigated local and short-term factors influencing the carbonate chemistry dynamics and saturation state with respect to aragonite (Ω_aragonite) of surface seawater in this region. One cruise covered much of the northern half of the Gulf, and the other focused on the coastal zone west of the Atchafalaya Bay outlet of the Mississippi River—the region where the hypoxic “dead zone” occurs on the Louisiana shelf. Offshore waters (>100 m depth) exhibited only small variations in CO₂ fugacity (fCO₂), total alkalinity (TA) and Ω_aragonite. Values were close to those typically observed in subtropical Atlantic Ocean and Caribbean Sea waters of similar salinity. However, inner shelf waters (<50 m depth) exhibited large variations in fCO₂, TA, and Ω_aragonite that were not directly related to salinity or distance from the Mississippi River plume. Changes in TA values were not the result of simple mixing of end-member freshwater and seawater TA concentrations but exhibited a minimum in values near salinity of 25. This minimum could be the result of microbial recycling across salinity gradients, biological removal of alkalinity by formation of calcium carbonate or mixing of a third end-member with a low alkalinity such as Terrebonne Bay. All waters were supersaturated with respect to aragonite. Offshore waters had an average Ω_aragonite of 3.86 with a standard deviation of only ±0.06 and inner shelf waters had a range in Ω_aragonite values from 3.9 to 9.7 with a median of 4.3. Shelf water Ω_aragonite values were elevated relative to the offshore as a consequence of both high TA input from Mississippi River and biological drawdown of CO₂. A dominant factor controlling Ω_aragonite distribution in offshore waters with relatively constant temperatures was fCO₂, with higher supersaturation occurring in areas with low fCO₂.