Air-water CO2 Fluxes Research Articles

Decadal changes in surface CO2 concentrations and CO2 fluxes in a mountain lake

AbstractClimate warming impacts biogeochemical cycles in lakes. However, the factors controlling CO2 dynamics in mountain lakes over multidecadal scales are poorly understood. Here, we capitalized on long‐term monthly data (1995–2022) of oligotrophic mountain Lake Tovel and calculated surface CO2 concentrations and flux by applying geochemical relationships and the thin boundary layer approach. Advanced time‐series and regression modeling was used to determine temporal patterns and environmental parameters explaining surface CO2 concentrations and flux. Surface CO2 concentrations were highest from 2009 to 2017 (annual mean: 109.1 μmol CO2 L−1) but lower before and after this period. Concomitantly, the air–water CO2 flux (μmol CO2 m−2 d−1) showed a period of lowest (mean1995–2010: 6.4 ± 0.7), highest (mean2011–2017: 35.7 ± 2.1), and intermediate emissions (mean2018–2022: 19.3 ± 4.7). Temporal modeling showed that hypolimnetic and deep hypolimnetic dissolved oxygen (DO) had the same change points and trends as surface CO2 concentrations. In multiple linear regression, hypolimnetic DO, silica, and the standardized precipitation index (pseudo‐R2adj. = 0.62; p < 0.01) best predicted annual mean surface CO2 concentrations. Regression results and the overlap between temporal trend patterns indicated that surface CO2 concentrations of Lake Tovel were positively influenced by external (loading of allochthonous carbon) and internal (lake autumn mixing) factors. The recent decline in surface CO2 concentrations from the year 2018 was attributed to increased stratification that offset lake autumn mixing and thus lead to the observed decline. These results help us to better understand the carbon cycle in mountain lakes in a changing climate.

Temporal variability of air-water gas exchange of carbon dioxide in clam and fish aquaculture ponds

The growing trend of land-based aquaculture has heightened the significance of comprehensively assessing air-water carbon dioxide (CO2) gas exchange in these inland waters, given their potential impact on carbon neutral strategies. However, temporal variations of partial pressure of CO2 (pCO2) and CO2 flux in clam and fish aquaculture ponds were barely investigated. We assessed the water surface pCO2 in one to five months intervals by deploying a lab-made buoy in three clam ponds and three fishponds located in tropical and subtropical climates. Measurements were conducted over a 24 h period each time, spanning from April 2021 to June 2022, covering the stocking, middle, and harvesting stages of the culture cycle. Diurnal pCO2 variations were dominantly controlled by biologically driven changes in dissolved inorganic carbon and total alkalinity (~97 %), while temperature and salinity effects were minor (~3 %). Clam ponds acted as a sink of atmospheric CO2 during stocking stages and transitioned to a source during middle to harvesting stages. In contrast, fishponds acted as a source of atmospheric CO2 throughout culture cycles and CO2 flux strengthened when reaching harvesting stages. Overall, clam ponds acted as a weak sink for atmospheric CO2 (−2.8 ± 17.3 mmol m−2 d−1), whereas fishponds acted as a source (16.8 ± 21.7 mmol m−2 d−1). CO2 emission was stronger during daytime coinciding with higher windspeeds compared to nighttime in fishponds. We suggest incorporating high temporal resolution measurements to account for diurnal and culture-stage variations, enabling more accurate estimates of air-water CO2 flux in aquaculture ponds. Moreover, the findings of this study highlight the importance of feeding, aeration, and biological activities (photosynthesis, remineralization, and calcification) in controlling the air-water CO2 flux in aquaculture ponds and such information can be used in implementing better strategies to achieve carbon neutral goals.

Multi-annual variability of pCO2(aq) and air-water CO2 flux in the mangrove-dominated Dhamra Estuary draining into the Bay of Bengal (India).

Small estuaries often remain neglected while characterizing air-water CO2 flux dynamics. This study reports the seasonal, spatial, and multi-annual variability of carbon biogeochemistry, emphasizing air-water CO2 flux from a small tropical mangrove-dominated estuary (Dhamra Estuary) of the Bay of Bengal, based on the 9-year-long sampling survey (2013 to 2021). The sampling covered twelve pre-fixed locations of this estuary. A suite of biogeochemical parameters was kept within the purview of this study to deliniate the interrelationship between CO2 fluxes and potential factors that can regulate/govern pCO2(aq) dynamics. Air water CO2 exchange rates were calculated using five globally accepted empirical gas transfer velocity equations and varied in a range of - 832.5 to 7904 μmol m-2 h-1. The estuary was a sink for CO2 in monsoon season, having the highest average flux rates of - 380.9 ± 125.5 μmol m-2 h-1, whereas a source in pre-monsoon (38.29 ± 913.1 μmol m-2 h-1) and post-monsoon (91.81 ± 1009.8 μmol m-2 h-1). The significant factors governing pCO2 were pH, salinity, total alkalinity and dissolved inorganic carbon (DIC). This long-term seasonal study emphasizes the need to include small regional estuaries for more accurate estimates of global CO2 flux to upscale the global carbon budget and its controlling mechanism.

Interannual and seasonal variability and future forecasting of pCO2(water) using the ARIMA model and CO2 fluxes in a tropical estuary.

The seasonal and interannual variation in the partial pressure of carbon dioxide in water [pCO2(water)] and air-water CO2 exchange in the Mahanadi estuary situated on the east coast of India was studied between March 2013 and March 2021. The principal aim of the study was to analyze the spatiotemporal variability and future trend of pCO2 and air-water CO2 fluxes along with the related carbonate chemistry parameters like water temperature, pH, salinity, nutrients, and totalalkalinity, over 9 years. The seasonal CO2 flux over nine years was also calculated using five worldwide accepted equations. The seasonal map of pCO2(water) followed a general trend of being high in monsoon (2628 ± 3484 μatm) associated with high river inflow and low during pre-monsoon (445.6 ± 270.0 μatm). High pCO2 in water compared to the atmosphere (average 407.6-409.4 μatm) was observed in the estuary throughout the sampling period. The CO2 efflux computed using different gas transfer velocity formulas was also consistent with pCO2 water acquiring the peak during monsoon in the Mahanadi estuary (6033 ± 9478 μmol m-2 h-1) and trough during pre-monsoon (21.66± 187.2 μmol m-2 h-1). The estuary acted as a net source of CO2 throughout the study period, with significant seasonality in the flux magnitudes. However, CO2 sequestration via photosynthesis by phytoplankton resulted in lower emission rates toward the atmosphere in summer. This study uses the autoregressive integrated moving average (ARIMA) model to forecast pCO2(water) for the future. Using measured and predicted values, our work demonstrated that pCO2(water) has an upward trend in the Mahanadi estuary. Our results demonstrate that long-term observations from estuaries should be prioritized to upscale the global carbon budget.

Interannual variability of air-water CO2 flux in a large eutrophic estuary

Air-water CO2 fluxes in estuarine environments are characterized by high interannual variability, in part due to hydrological variability that alters estuarine carbonate chemistry through multiple physical and biogeochemical processes. To understand the relative contributions of these varied controls on interannual air-water CO2 fluxes in the mainstem Chesapeake Bay, we implemented both hindcast and scenario simulations using a coupled physical-biogeochemical model. Significant spatiotemporal variability in bay-wide fluxes was found over a 10-year period (1996-2005), where the mainstem Bay was primarily a net CO2 sink, except in drought periods. Sensitivity scenario results suggested substantial effects of riverine nutrient and organic matter (OM) inputs to CO2 flux variations. The high correlations between riverine inputs and upper-Bay fluxes were due to elevated respiration under increased OM inputs. The interannual flux variations in the lower Bay was mostly regulated by the nutrient inputs. Both nutrient and OM inputs contributed to the flux variability in the mid Bay. It is found that the interannual CO2 flux of the mainstem was most sensitive to riverine nutrient inputs associated with the hydrological changes. For each hindcast simulation we computed the ratio of organic carbon turnover time to water residence time (λ), a proxy for CO2 efflux potential, and found that the wetter periods had a relatively lower λ. The variability of mainstem CO2 fluxes can be well represented using a generic function of λ. The model results showed that higher river flows would lead to enhanced CO2 sinks into a large eutrophic estuary by promoting net autotrophy.

High‐frequency variability of carbon dioxide fluxes in tidal water over a temperate salt marsh

AbstractExisting analyses of salt marsh carbon budgets rarely quantify carbon loss as CO2 through the air–water interface in inundated marshes. This study estimates the variability of partial pressure of CO2 (pCO2) and air–water CO2 fluxes over summer and fall of 2014 and 2015 using high‐frequency measurements of tidal water pCO2 in a salt marsh of the U.S. northeast region. Monthly mean CO2 effluxes varied in the range of 5.4–25.6 mmol m−2 marsh d−1 (monthly median: 4.8–24.7 mmol m−2 marsh d−1) during July to November from the tidal creek and tidally‐inundated vegetated platform. The source of CO2 effluxes was partitioned between the marsh and estuary using a mixing model. The monthly mean marsh‐contributed CO2 effluxes accounted for a dominant portion (69%) of total CO2 effluxes in the inundated marsh, which was 3–23% (mean 13%) of the corresponding lateral flux rate of dissolved inorganic carbon (DIC) from marsh to estuary. Photosynthesis in tidal water substantially reduced the CO2 evasion, accounting for 1–86% (mean 31%) of potential CO2 evasion and 2–26% (mean 11%) of corresponding lateral transport DIC fluxes, indicating the important role of photosynthesis in controlling the air–water CO2 evasion in the inundated salt marsh. This study demonstrates that CO2 evasion from inundated salt marshes is a significant loss term for carbon that is fixed within marshes.

Effects of calcification on air-water CO2 fluxes in tropical seagrass meadows: A mesocosm experiment

Seagrass meadows deliver a range of ecosystem services, where one of the more important is the capacity to store carbon and serve as sinks for atmospheric carbon dioxide. The capacity of seagrass meadows for carbon storage might, however, be modified and complicated by several factors; one important factor is the possible effects of calcification within the meadows. In tropical areas, seagrass meadows can contain high proportions of calcareous organisms, which through their calcification may cause release of CO2. To study this aspect of the CO2 balance within tropical seagrass systems, we investigated the air-water CO2 flux in seagrass mesocosms with different plant community compositions, i.e. mixtures of seagrass and calcifying macroalgae, having similar overall photosynthetic oxygen evolution rates. The measured CO2 fluxes changed both in rate and direction over the day and were significantly related to plant community composition. Downward fluxes of CO2 were found only over vegetation with high proportion of seagrass and in the afternoon, whereas occurrence of calcifying algae appeared to reverse the flow. A partial least squares (PLS) regression model indicated that pH, pCO2 and dissolved inorganic carbon (DIC) were the primary environmental variables predicting the CO2 fluxes. Our findings show that algal calcification might partly counteract the carbon sequestration in seagrass meadows.

Interaction between seawater carbon dioxide dynamics and stratification in shallow coastal waters: A preliminary study based on a weekly validated three-dimensional ecological model

Shallow coastal waters (SCWs) have attracted wide attention in recent years due to their strong carbon sequestration capacity. However, the complex carbon dioxide (CO2) dynamics in the water column makes it difficult to estimate the air–water CO2 fluxes (FCO2) accurately. We developed a numerical model of CO2 dynamics in water based on field measurements for a typical stratified semi-enclosed shallow bay: the Yatsushiro Sea, Japan. The developed model showed an excellent ability to reproduce the stratification and CO2 dynamics of the Yatsushiro Sea. Through numerical model simulations, we analyzed the annual CO2 dynamics in the Yatsushiro Sea in 2018. The results show that the effect of stratification on the CO2 dynamics in seawater varies greatly depending on the distance from the estuary and the period. In the estuarine region, stratification manifests itself throughout the year by promoting the maintenance of a high partial pressure of CO2 (pCO2) in surface waters, resulting in surface pCO2 being higher than atmospheric pCO2 for up to 40 days during the flood period (average surface pCO2 of 539.94 µatm). In contrast, in areas farther from the estuary, stratification mainly acts to promote the maintenance of high pCO2 in surface waters during periods of high freshwater influence. Then changes to a lower surface pCO2 before the freshwater influence leads towards complete dissipation. Finally, we estimated the FCO2 of the Yatsushiro Sea in 2018, and the results showed that the Yatsushiro Sea was a sink area for atmospheric CO2 in 2018 (−1.70 mmol/m2/day).

Drivers of inorganic carbon dynamics and air–water CO2 fluxes in two large tropical estuaries: Insights from coupled radon (222Rn) and pCO2 surveys

AbstractEstuaries and coastal waters are generally significant emitters of CO2 to the atmosphere. Globally, submarine groundwater discharge (SGD) is a significant driver of inorganic carbon dynamics and the partial pressure of CO2 in water [pCO2(water)] in estuaries and coastal waters. However, there are few studies of CO2 emission and SGD in large tropical estuaries. To investigate the drivers of pCO2(water) dynamics in two large tropical estuaries in India, the Hooghly and Matla estuaries, we conducted coupled radon and pCO2(water) surveys of groundwater and surface waters. We also collected high‐temporal‐resolution (1 min) data of related biogeochemical parameters. Using radon‐222 (222Rn) as a proxy for SGD, we found significant regulation of pCO2(water) by SGD in both studied estuaries. This observation can be considered direct evidence of the influence of SGD on pCO2(water) and consequent air–water CO2 fluxes in these two previously poorly studied estuaries. Our finding that total alkalinity (TAlk) and dissolved inorganic carbon (DIC) were also significantly higher in the groundwater than in the estuarine surface waters also supports a substantial contribution of SGD to the inorganic carbon dynamics of these estuaries. However, high groundwater TAlk to DIC ratios (> 1) indicate that SGD also enhances the carbonate buffering capacity in these estuaries. By contributing to an improved understanding of the role of SGD in inorganic carbon cycling in tropical estuaries and coastal oceans, this study will contribute to efforts to upscale regional‐scale coastal carbon budgets to a global scale.

Dataset for the article entitled "Drivers of inorganic carbon dynamics and air–water CO2 fluxes in two large tropical estuaries: insights from coupled radon (222Rn) and pCO2 surveys"

Dataset for the article entitled "Drivers of inorganic carbon dynamics and air–water CO2 fluxes in two large tropical estuaries: insights from coupled radon (222Rn) and pCO2 surveys"

Reassessing riverine carbon dioxide emissions from the Indian subcontinent

Anthropogenic perturbations are increasing uncertainties in estimating CO2 emissions via air-water CO2 flux (FCO2) from large rivers of the Indian subcontinent. This study aimed to provide an improved estimate of the total FCO2 from the subcontinental rivers by combining calculations of the partial pressure of CO2 (pCO2) in eight major rivers with new measurements in the Ganges and Godavari. The average pCO2 in the two newly surveyed rivers, including tributaries, wastewater drains, and impoundments, were 3–6 times greater than the previously reported values. In some highly polluted urban tributaries and middle reaches of the Ganges that drain metropolitan areas, the measured pCO2 exceeded 20,000 μatm, ~40 times the background levels of the headwaters originating in the carbonate-rich Himalayas. The high pCO2 above 28,000 μatm in the lower reach of the Godavari was seven times the moderate levels of pCO2 in the headwaters of the volcanic Deccan Traps, indicating enhanced CO2 production in soils and anthropogenic sources under favorable conditions for organic matter degradation. Across the northern rivers, pCO2 exhibited a significant negative relationship with dissolved oxygen, but a positive relationship with inorganic N or P concentrations. The strong influence of water pollution on riverine pCO2 suggests that CO2 emissions from hypoxic, eutrophic reaches can greatly exceed phytoplanktonic CO2 uptake. Spatially resolved pCO2 data, combined with three gas transfer velocity estimates, provided a higher range of FCO2 from the subcontinental rivers (100.9–130.2 Tg CO2 yr−1) than the previous estimates (7.5–61.2 Tg CO2 yr−1). The revised estimates representing 2–5% of the global riverine FCO2 illustrate the importance of the Indian subcontinental rivers under increasing anthropogenic pressures in constraining global inland waters FCO2.

A CO2 sink in a tropical coastal lagoon impacted by cultural eutrophication and upwelling

Tropical coastal lagoons are recognized as very productive ecosystems. However, very little is known on the direction and magnitude of their CO2 exchange with the atmosphere. We report on air-water CO2 fluxes and carbon concentrations in a tropical shallow lagoon impacted by cultural eutrophication. During two contrasting field surveys, the first in Nov. 2019 during dry conditions and the second in Feb. 2020 during wet summer condition and intrusion of coastal upwelling waters inside the lagoon. At both seasons, spatial in situ monitoring of temperature, salinity and partial pressure of CO2 (pCO2) reveal the presence of undersaturated pCO2 values (between 60 and 300 ppmv), uptake of atmospheric CO2 (between 0.9 and 9.2 mmol m−2 h−1) inside the lagoon, at salinities between 10 and 32. Temporal monitoring data at the mouth of the lagoon throughout tidal cycles revealed the entrance of cold South Atlantic Central Waters (SACW) from the Cabo Frio's upwelling during flood tides in Feb. 2020 but not in Nov. 2019. The cold SACW with temperatures down to 16 °C were supersaturated in CO2 (pCO2 about 520 ppmv) and a CO2 source to the atmosphere (between 0.2 and 1.4 mmol m−2 h−1). During mixing of this SACW in the most marine compartment of the lagoon, the biological CO2 uptake and enhanced autotrophy overcame the effect of degassing SACW waters by heating. For both cruises, a consistent landward trend consisted in a decrease in pCO2 and dissolved inorganic carbon (DIC) mirrored by an increase of dissolved organic carbon (DOC) (between 4.6 and 19.8 mg L−1), particulate organic carbon (POC) (between 3.3 and 12.3 mg L−1), and chlorophyll a (Chl a) (between 7.6 and 217 μg L−1). POC, DOC and Chl a and the POC:Chl a ratio suggest that, organic carbon in the lagoon is a mixture of phytoplankton biomass produced in the lagoon, domestic wastewater loaded from multiple point sources and pulsated inputs from small rivers. Our study in the Saquarema lagoon confirms recent works in other densely populated tropical coastal ecosystems, revealing that eutrophication enhances the autotrophy of shallow tropical lagoons, making them act as efficient factories for atmospheric CO2 absorption and organic carbon storage in sediments and export to the ocean.

Outwelling of total alkalinity and dissolved inorganic carbon from the Hooghly River to the adjacent coastal Bay of Bengal.

The seasonal variability of the lateral flux of total alkalinity (TAlk) and dissolved inorganic carbon (DIC) of the tropical Hooghly estuary is analyzed in this work. In situ observations of water temperature, salinity, dissolved oxygen, TAlk, and pH were measured in four different stations of the Hooghly estuary. It was measured once every month during 2015-2016, and subsequently, DIC was estimated. A carbon budget was constructed to quantify carbon flows through the freshwater-marine continuum of the Hooghly estuary, and plausible impacts on the adjacent coastal ocean, the northern Bay of Bengal, were examined. The biogeochemical mass balance box model was used to compute the seasonal flow of carbon flux, and subsequently, the annual budgeting of lateral fluxes of TAlk and DIC to the adjacent coastal ocean was carried out. The net annual TAlk and DIC flux from the Hooghly estuary to the adjacent coastal ocean were 4.45 ± 1.90 × 1011mol and 4.59 ± 1.70 × 1011mol, respectively. The net annual DIC flux of the Hooghly estuary is about 30 to 60 times higher than surface area integrated air-water CO2 flux, which is an indication of promoting acidification in the adjacent coastal ocean. The present study indicates that the lateral DIC flux has increased substantially in the Hooghly estuary during the last two decades. The increase in inorganic carbon load in the Hooghly estuary due to the enhanced discharge of inorganic and organic matter load in the upper reaches of the estuary led to this increase in lateral DIC flux. The results strongly establish the need of having such regional studies for better understanding the estuarine carbon dynamics, and its role in controlling the adjacent coastal ocean dynamics.

Contribution of Biological Effects to Carbonate‐System Variations and the Air–Water CO2 Flux in Urbanized Bays in Japan

AbstractWe evaluated the contribution of net biological effects (photosynthesis + respiration + decomposition) to the carbonate parameters and air–water CO2 fluxes in Tokyo Bay, Ise Bay, and Osaka Bay in Japan. The carbonate parameters (fugacity of CO2, total alkalinity, and dissolved inorganic carbon) were measured mainly by cargo ships traveling between Japan and other countries. We used the measurement data from three inner bays and surrounding outer bays in Japan along with reference data from previous studies for complementary analysis. We found that (a) the inner and outer bays in this study were strong annual atmospheric CO2 sinks, (b) the annual biological effect on the air–water CO2 fluxes was about 6%–27% of the measured CO2 fluxes, and it affected the seasonal variation of the CO2 flux, and (c) the biological effect was largest in Tokyo Bay, and almost the same in Ise and Osaka Bays. The intensity of the biological effect corresponded mainly with nutrient concentrations, which seemed to be controlled by the wastewater treatment in urbanized areas around the bays. Our results suggest that labile carbon/nutrient ratio of wastewater should be a major consideration for evaluating the biological effect on the carbon cycle in urbanized bays, which will continue to expand globally.

Seasonal and spatial variability in surface pCO2 and air–water CO2 flux in the Chesapeake Bay

AbstractInteractions between riverine inputs, internal cycling, and oceanic exchange result in dynamic variations in the partial pressure of carbon dioxide (pCO2) in large estuaries. Here, we report the first bay‐wide, annual‐scale observations of surface pCO2 and air–water CO2 flux along the main stem of the Chesapeake Bay, revealing large annual variations in pCO2 (43–3408 μatm) and a spatial‐dependence of pCO2 on internal and external drivers. The low salinity upper bay was a net source of CO2 to the atmosphere (31.2 mmol m−2 d−1) supported by inputs of CO2‐rich Susquehanna River water and the respiration of allochthonous organic matter, but part of this region was also characterized by low pCO2 during spring and fall phytoplankton blooms. pCO2 decreased downstream due to CO2 ventilation supported by long water residence times, stratification, mixing with low pCO2 water masses, and carbon removal by biological uptake. The mesohaline middle bay was a net CO2 sink (−5.8 mmol m−2 d−1) and the polyhaline lower bay was nearly in equilibrium with the atmosphere (1.0 mmol m−2 d−1). Although the main stem of the bay was a weak CO2 source (3.7 ± 3.3 × 109 mol C) during the dry hydrologic (calendar) year 2016, our observations showed higher river discharge could decrease CO2 efflux. In contrast to many other estuaries worldwide that are strong sources of CO2 to the atmosphere, the Chesapeake Bay and potentially other large estuaries are very weak CO2 sources in dry years, and could even turn into a CO2 sink in wet years.

Lateral carbon fluxes and CO2 evasion from a subtropical mangrove-seagrass-coral continuum

Mangrove, seagrass, and coral habitats often lie adjacent to each other in the tropics and subtropics. Lateral carbon fluxes and their consecutive effects on CO2 dynamics and air–water fluxes along the ecosystem continuum are often overlooked. We measured the partial pressure of CO2 in water and associated biogeochemical parameters with a high temporal resolution and estimated air–water CO2 fluxes along the ecosystem continuum. Their lateral fluxes were estimated by using a biogeochemical mass-balance model. The results showed that the waters surrounding mangrove, seagrass, and coral habitats acted as a strong, moderate, and weak source of atmospheric CO2, respectively. The mangrove zone acted as a net source for TAlk, DIC, and DOC, but as a net sink for POC. The contribution of riverine and mangrove-derived OM was substantially high in mangrove sediment, indicating that net transport of POC towards the coastal sea was suppressed by the sediment trapping function of mangroves. The seagrass zone acted as a net source of all carbon forms and TAlk, whereas the coral zone acted as a net sink of TAlk, DIC, and DOC. The lateral transport of carbon from mangroves and rivers offset atmospheric CO2 uptake in the seagrass zone. DOC degradation might increase DIC, and other biogeochemical processes facilitate the functioning of the coral zone as a DOC sink. However, as a result of DIC uptake by autotrophs, mainly in the coral zone, the whole ecosystem continuum was a net sink of DIC and atmospheric CO2 evasion was lowered. We conclude that lateral transport of riverine and mangrove-derived DIC, TAlk, and DOC affect CO2 dynamics and air–water fluxes in seagrass and coral ecosystems. Thus, studies of lateral carbon fluxes at local and regional scales can improve global carbon budget estimates.

Challenges in Quantifying Air-Water Carbon Dioxide Flux Using Estuarine Water Quality Data: Case Study for Chesapeake Bay.

Estuaries play an uncertain but potentially important role in the global carbon cycle via CO2 outgassing. The uncertainty mainly stems from the paucity of studies that document the full spatial and temporal variability of estuarine surface water partial pressure of carbon dioxide ( pCO2). Here, we explore the potential of utilizing the abundance of pH data from historical water quality monitoring programs to fill the data void via a case study of the mainstem Chesapeake Bay (eastern United States). We calculate pCO2 and the air‐water CO2 flux at monthly resolution from 1998 to 2018 from tidal fresh to polyhaline waters, paying special attention to the error estimation. The biggest error is due to the pH measurement error, and errors due to the gas transfer velocity, temporal sampling, the alkalinity mixing model, and the organic alkalinity estimation are 72%, 27%, 15%, and 5%, respectively, of the error due to pH. Seasonal, interannual, and spatial variability in the air‐water flux and surface pCO2 is high, and a correlation analysis with oxygen reveals that this variability is driven largely by biological processes. Averaged over 1998–2018, the mainstem bay is a weak net source of CO2 to the atmosphere of 1.2 (1.1, 1.4) mol m−2 yr−1 (best estimate and 95% confidence interval). Our findings suggest that the abundance of historical pH measurements in estuaries around the globe should be mined in order to constrain the large spatial and temporal variability of the CO2 exchange between estuaries and the atmosphere.

CO2 effluxes from an urban tidal river flowing through two of the most populated and polluted cities of India.

Urbanized rivers flowing through polluted megacities receive substantial amount of carbon from domestic sewage and industrial effluents which can significantly alter the air-water CO2 flux rates. In this regard, we quantified the partial pressure of CO2 in the surface water (pCO2(water)), air-water CO2 fluxes, and associated biogeochemical parameters in the Hooghly River, India, flowing through two of the most polluted cities of the country, Kolkata and Howrah, over a complete annual cycle during spring tidal phase (SP) and neap tidal phase (NP). This urbanized part of Hooghly River was always supersaturated with CO2 having an annual mean pCO2(water) and air-water CO2 flux of ~ 3800 μatm and ~ 49 mol C m-2 year-1, respectively. Significant seasonal variability was observed for both pCO2(water) and air-water CO2 flux (pre-monsoon, 3038 ± 539 μatm and 5049 ± 964 μmol m-2 h-1; monsoon, 4609 ± 711 μatm and 7918 ± 1400 μmol m-2 h-1; post-monsoon, 2558 ± 258 μatm and 4048 ± 759 μmol m-2 h-1, respectively). Monthly mean pH and total alkalinity varied from 7.482 to 8.099 and from 2437 to 4136 μmol kg-1, respectively, over the annual cycle. pCO2(water) showed significant positive correlation with turbidity and negative correlation with electrical conductivity and gross primary productivity (GPP). High water discharge could have facilitated high turbidity, especially during the monsoon season, which led to depletion in GPP and enhancement in pCO2(water) which in turn led to very high CO2 effluxes. The CO2 efflux rate in this urbanized riverine stretch was substantially higher than that observed in previous studies carried out in the less urbanized estuarine stretch of Hooghly. This indicates that the presence of highly urbanized and polluted metropolis potentially enhanced the pCO2(water) and CO2 effluxes of this river. Similar observations were made recently in some Asian and Australian urban rivers.

Air–Sea CO2 dynamics from tropical estuarine system Mahanadi, India

The biogeochemical characteristics of Mahanadi estuarine system in eastern India were investigated to understand the seasonality in carbon parameters and their influence on sea–air CO2 gradient. In general, the stations close to the estuary had higher salinity and total alkalinity; and lower pCO2(water) relative to the inner most stations. In contrast, the riverine stations had low pH and high pCO2(water) and lower total alkalinity. The chlorophyll a values ranged between 0.27 to 11.22 mg m−3 during this investigation. We found that the seasonal oscillations in sea–air CO2 gradient (ΔpCO2 = pCO2(water)–pCO2(air)) were negative during winter and positive during summer, wherein the estuary acted as a weak source. The average air–water CO2 flux density values varied between −5.65 to 13.11 μmol m−2 h−1 throughout the study period. Two-way ANOVA showed strong seasonal control on environmental variables. The relationships observed between pH and salinity with pCO2 suggest that fluvial inputs of nutrients and the accompanying heterotrophic processes may possibly control the sea–air CO2 gradient in the surface waters of the Mahanadi estuary.

The net GHG emissions of the China Three Gorges Reservoir: I. Pre-impoundment GHG inventories and carbon balance

One of the paramount questions related to environmental and climate change impacts from hydropower and reservoirs, is how to quantify the greenhouse gas (GHG) emissions of dam construction and reservoir creation, mostly in terms of reservoir net GHG emissions. Net emissions are described as the emissions after impoundment subtracting the emissions before the reservoir was built (pre-impoundment). The evaluation of pre-impoundment GHG emissions is essential to answer the above questions, yet there are few related case studies. Herein, we proposed a conceptual framework to evaluate the pre-impoundment GHG emissions of China’s Three Gorges Reservoir (TGR). Reservoir flooded areas prior to impoundment were divided into two categories: 1) flooded land, where pre-impoundment CO2 and CH4 fluxes from different historical land uses were estimated following tier 1 methodology of IPCC national inventories, and 2) river surface, where pre-impoundment CO2 fluxes were estimated by a calibrated two dimensional modified biogeochemical model with an air-water gas transfer module. An empirical regression model between measured air-water CO2 and CH4 fluxes in unflooded river reaches was used to estimate pre-impoundment river surface CH4 flux. The pre-impoundment GHG emissions of the TGR were 5.1 × 105 tCO2eq·yr−1, with 95% confidence intervals of 4.7–6.1 × 105 tCO2eq·yr−1. Approximately 46% of the pre-impoundment GHG emissions were from flooded land, while the rest 54% were from river surfaces. Mass balance indicated that approximately 72% of the downstream riverine C export was from the upstream river basin of the Yangtze River. Pre-impoundment C emissions were only ∼6.58% of the total riverine C export downstream. Most of the C in the system was mainly from the upstream river basin of the Yangtze River; thus, an increase in anthropogenic loads of C and nutrients in the Three Gorges Reservoir Area did not result in an apparent increase in pre-impoundment river surface GHG emissions.