Water pCO2 Research Articles

Integrating High-Resolution Coastal Acidification Monitoring Data Across Seven United States Estuaries.

Beginning in 2015, the United States Environmental Protection Agency’s (EPA’s) National Estuary Program (NEP) started a collaboration with partners in seven estuaries along the East Coast (Barnegat Bay; Casco Bay), West Coast (Santa Monica Bay; San Francisco Bay; Tillamook Bay), and the Gulf of Mexico (GOM) Coast (Tampa Bay; Mission-Aransas Estuary) of the United States to expand the use of autonomous monitoring of partial pressure of carbon dioxide (pCO2) and pH. Analysis of high-frequency (hourly to sub-hourly) coastal acidification data including pCO2, pH, temperature, salinity, and dissolved oxygen (DO) indicate that the sensors effectively captured key parameter measurements under challenging environmental conditions, allowing for an initial characterization of daily to seasonal trends in carbonate chemistry across a range of estuarine settings. Multi-year monitoring showed that across all water bodies temperature and pCO2 covaried, suggesting that pCO2 variability was governed, in part, by seasonal temperature changes with average pCO2 being lower in cooler, winter months and higher in warmer, summer months. Furthermore, the timing of seasonal shifts towards increasing (or decreasing) pCO2 varied by location and appears to be related to regional climate conditions. Specifically, pCO2 increases began earlier in the year in warmer water, lower latitude water bodies in the GOM (Tampa Bay; Mission-Aransas Estuary) as compared with cooler water, higher latitude water bodies in the northeast (Barnegat Bay; Casco Bay), and upwelling-influenced West Coast water bodies (Tillamook Bay; Santa Monica Bay; San Francisco Bay). Results suggest that both thermal and non-thermal influences are important drivers of pCO2 in Tampa Bay oxygen, National Estuary Program and Mission-Aransas Estuary. Conversely, non-thermal processes, most notably the biogeochemical structure of coastal upwelling, appear to be largely responsible for the observed pCO2 values in West Coast water bodies. The co-occurrence of high salinity, high pCO2, low DO, and low temperature water in Santa Monica Bay and San Francisco Bay characterize the coastal upwelling paradigm that is also evident in Tillamook Bay when upwelling dominates freshwater runoff and local processes. These data demonstrate that high-quality carbonate chemistry observations can be recorded from estuarine environments using autonomous sensors originally designed for open-ocean settings.

Spatial and temporal distribution of carbon dioxide flux in Amagasaki Canal, Japan

ABSTRACT Recently, blue carbon – carbon captured by coastal ecosystems – has been gaining increased research attention for its potential to sequester anthropogenic CO2. The Amagasaki Canal, in the inner part of Osaka Bay, Japan, has high nutrient concentrations and phytoplankton abundance; primary production by phytoplankton is high in such hypertrophic environments. This could lead to the enhanced absorption of atmospheric CO2. This study investigated the temporal changes and spatial variability in water quality and CO2 flux in the Amagasaki Canal, and it analyzed factors affecting the partial pressure of CO2 (pCO2) in canal water using covariance structure analysis. The CO2 flux in the canal varied between −24.9 and 66.8 mmol-C/m2/d. There were seasonal changes in water quality, with a tendency of CO2 release during autumn and winter. In spring and summer, when phytoplankton were active and chlorophyll-a concentrations were high, concentrations of dissolved inorganic carbon were low and atmospheric CO2 was absorbed into the water. Covariance structure analysis indicated that biological processes indirectly influenced pCO2 via pH and dissolved oxygen concentrations, pointing to the contribution of the primary production rate as part of the biological processes.

Controlling factors of seasonal and spatial variation of riverine CO2 partial pressure and its implication for riverine carbon flux

Global carbon cycle is closely related to the earth's energy budget, because CO2 plays an active role in the global climate change. The higher CO2 partial pressure (pCO2) in inland water in comparison with atmosphere, causing a CO2 evasion from water to the air. However, the relationship between CO2 evasion, riverine carbon export, and hydrochemistry in watershed has remained largely unknown. This study collected 84 river water samples in Jiulongjiang River, to further address this subject on a small watershed scale. Water temperature fluctuation, riverine photosynthesis, and acidic matter input could not account for the seasonal variation of pCO2 in Jiulongjiang River. The spatial shifts of pCO2 were derived from the mixing process between headwater and soil influx. The soil influx with high pCO2 compensated the CO2 lost from evasion and caused pCO2 in Jiulongjiang River higher than the atmospheric level. The seasonal variation of pCO2 was caused by the precipitation difference between the wet season and dry season. The addition of rainwater significantly decreased the riverine pCO2 and HCO3− concentration in the wet season. The CO2 evasion rate in Jiulongjiang River was clearly higher than that in most worldwide large rivers. The annual CO2 evasion flux in Jiulongjiang River Basin was estimated about 2.48 × 105 T C/year, which was higher than the riverine total carbon export. The CO2 evasion rate exhibited significantly positive relationship with water surface area, indicating that the global CO2 evasion flux may be roughly estimated based on the observed regression relationship. Overall, our study indicated that it still requires collaborative effects to investigate the carbon dynamics in river water, more estimations of CO2 outgassing flux from river water under different hydrologic and geologic conditions are necessary.

Carbon dioxide dynamics of Bhalswa Lake: a human-impacted urban wetland of Delhi, India

Urban lakes in developing economies face tremendous anthropogenic pressure which tends to modify their role in the regional carbon cycle. This makes it imperative to quantify their carbon budget and identify the underlying factors and processes. Present study aims to understand the seasonal carbon dioxide (CO2) dynamics of an urban lake in a semi-arid subtropical region and identify major controls operating on it. Systematic sampling of Bhalswa lake waters was undertaken in winter and summer of 2017–2018. The hydrochemical data generated were used to determine partial pressure and evasion flux of CO2 using pH and total alkalinity couple. The lake waters show CO2 supersaturation with respect to atmospheric equilibrium and act as a source of CO2 to the atmosphere in both seasons. The average partial pressure of carbon dioxide (pCO2) and CO2 evasion flux observed is 1033.73 ± 229.07 µatm and 6.33 ± 2.23 mmol m−2 d−1, and 1034.99 ± 187.37 µatm and 11.65 ± 3.42 mmol m−2 d−1 during winter and summer, respectively. Neither pCO2 nor CO2 evasion flux shows any significant seasonal difference. For yearly dynamics, dissolved organic carbon, dissolved inorganic carbon and dissolved oxygen act as strong controls on lake water pCO2. While for individual seasons, pH and water temperature act as significant controls. Among various pollution sources, untreated sewage and dairy waste, seepage of polluted groundwater and atmospheric dust impact the lake's carbon dynamics. The present study will help better understand the role of freshwater wetlands of ever-expanding urban areas in the regional carbon cycle of developing economies.

Correlation between the carbon isotopic composition of planktonic foraminifera-bound organic matter and surface water pCO2 across the equatorial Pacific

For times prior to those represented by the air trapped in Antarctic ice core records, the concentration of CO2 in the atmosphere must be reconstructed using geochemical proxies. The δ13C of particulate organic carbon (POC) produced in ocean surface waters has previously been observed to covary with the concentration of CO2 in the water. Relative to bulk sedimentary organic carbon, the minute quantity of organic matter trapped within the shell walls of planktonic foraminifera, “foraminifera-bound organic matter” (FBOM), has the potential advantage of being protected from diagenetic alteration and contamination by allochthonous organic matter. Here, with new protocols and instrumentation, FBOM-δ13C is investigated as a potential proxy for the aqueous CO2 concentration ([CO2(aq)]) and thus the partial pressure of CO2 (pCO2) in past surface waters. We achieve a full method precision for FBOM-δ13C of 0.4‰ (1SD) on sample sizes of 20 nanomole C by adding a cryofocus step, a helium sheath flow to the oxidation and reduction reactors, and other modifications to an elemental analyzer and by introducing new approaches to reduce contamination during sample preparation. FBOM-δ13C was analyzed in core-top sediments from the eastern tropical Pacific that span the equatorial maximum in surface water [CO2(aq)]. FBOM-δ13C is lower than predicted for marine phytoplankton, consistent with a substantial lipid component in FBOM. Anticorrelation is observed between FBOM-δ13C and climatological [CO2(aq)]; the relationship is statistically significant (P <0.05) in mixed-species samples and in 4 out of 5 picked species. The slope of the FBOM-δ13C:[CO2(aq)] anticorrelation is equivalent to or greater than has been measured for the δ13C of suspended POC in the surface ocean. Based on the few species analyzed in this study, endosymbiont-bearing and -barren species do not clearly differ from each other either in terms of their average value of FBOM-δ13C or the strength of the FBOM-δ13C:[CO2(aq)] anticorrelation, despite the recognized importance of the photosynthetic endosymbionts as a source of organic carbon for the symbiotic species. Correcting for variations in the δ13C of CO2(aq) and phytoplankton growth rate did not improve the significance of the FBOM-δ13C:[CO2(aq)] anticorrelation. The findings support the possibility that FBOM-δ13C can be used as a paleoceanographic proxy for surface water [CO2(aq)] and thus atmospheric pCO2.

Searles Lake evaporite sequences: Indicators of late Pleistocene/Holocene lake temperatures, brine evolution, and pCO2

Abstract Searles Lake, California, was a saline-alkaline lake that deposited &amp;gt;25 non-clastic minerals that record the history of lake chemistry and regional climate. Here, the mineralogy and petrography from the late Pleistocene/Holocene (32–6 ka) portion of a new Searles Lake sediment core, SLAPP-SRLS17, is combined with thermodynamic models to determine the geochemical and paleoclimate conditions required to produce the observed mineral phases, sequences, and abundances. The models reveal that the primary precipitates formed by open system (i.e., fractional crystallization), whereas the early diagenetic salts formed by salinity-driven closed system back-reactions (i.e., equilibrium crystallization). For core SLAPP-SRLS17, the defining evaporite sequence trona → burkeite → halite indicates brine temperatures within a 20–29 °C range, implying thermally insulating lake depths &amp;gt;10 m during salt deposition. Evaporite phases reflect lake water pCO2 consistent with contemporaneous atmospheric values of ∼190–270 ppmv. However, anomalous layers of nahcolite and thenardite indicate pulses of pCO2 &amp;gt; 700–800 ppm, likely due to variable CO2 injection along faults. Core sedimentology indicates that Searles Lake was continuously perennial between 32 ka and 6 ka such that evaporite units reflect periods of net evaporation but never complete desiccation. Model simulations indicate that cycles of partial evaporation and dilution strongly influence long-term brine evolution by amassing certain species, particularly Cl–, that only occur in late-stage soluble salts. A model incorporating long-term brine dynamics corrects previous mass-balance anomalies and shows that the late Pleistocene/Holocene (32–6 ka) salts are partially inherited from the solutes introduced into earlier lakes going back at least 150 ka.

Summertime Evolution of Net Community Production and CO2 Flux in the Western Arctic Ocean

AbstractTo examine seasonal and regional variabilities in metabolic status and the coupling of net community production (NCP) and air‐sea CO2 fluxes in the western Arctic Ocean, we collected underway measurements of surface O2/Ar and partial pressure of CO2 (pCO2) in the summers of 2016 and 2018. With a box‐model, we demonstrate that accounting for local sea ice history (in addition to wind history) is important in estimating NCP from biological oxygen saturation (Δ(O2/Ar)) in polar regions. Incorporating this sea ice history correction, we found that most of the western Arctic exhibited positive Δ(O2/Ar) and negative pCO2 saturation, Δ(pCO2), indicative of net autotrophy but with the relationship between the two parameters varying regionally. In the heavy ice‐covered areas, where air‐sea gas exchange was suppressed, even minor NCP resulted in relatively high Δ(O2/Ar) and low pCO2 in water due to limited gas exchange. Within the marginal ice zone, NCP and CO2 flux magnitudes were strongly inversely correlated, suggesting an air to sea CO2 flux induced primarily by biological CO2 removal from surface waters. Within ice‐free waters, the coupling of NCP and CO2 flux varied according to nutrient supply. In the oligotrophic Canada Basin, NCP and CO2 flux were both small, controlled mainly by air‐sea gas exchange. On the nutrient‐rich Chukchi Shelf, NCP was strong, resulting in great O2 release and CO2 uptake. This regional overview of NCP and CO2 flux in the western Arctic Ocean, in its various stages of ice‐melt and nutrient status, provides useful insight into the possible biogeochemical evolution of rapidly changing polar oceans.

Ocean acidification compromises energy management in Sparus aurata (Pisces: Teleostei)

The effects of ocean acidification mediated by an increase in water pCO2 levels on marine organisms are currently under debate. Elevated CO2 concentrations in the seawater induce several physiological responses in teleost fish, including acid-base imbalances and osmoregulatory changes. However, the consequences of CO2 levels enhancement on energy metabolism are mostly unknown. Here we show that 5 weeks of exposure to hypercapnia (950 and 1800 μatm CO2) altered intermediary metabolism of gilthead seabream (Sparus aurata) compared to fish acclimated to current ocean values (440 μatm CO2). We found that seabream compromises its physiological acid-base balance with increasing water CO2 levels and the subsequent acidification. Intestinal regions (anterior, mid, and rectum) engaged in maintaining this balance are thus altered, as seen for Na+/K+-ATPase and the vacuolar-type H+-ATPase activities. Moreover, liver and muscle counteracted these effects by increasing catabolic routes e.g., glycogenolysis, glycolysis, amino acid turnover, and lipid catabolism, and plasma energy metabolites were altered. Our results demonstrate how a relatively short period of 5 weeks of water hypercapnia is likely to disrupt the acid-base balance, osmoregulatory capacity and intermediary metabolism in S. aurata. However, long-term studies are necessary to fully understand the consequences of ocean acidification on growth and other energy-demanding activities, such as reproduction.

Rainfall-driven and hydrologically-controlled variations in cave CO2 sources and dynamics: Evidence from monitoring soil CO2, stream flow and cave CO2

Speleothems are used as a promising proxy for high-resolution paleoclimate reconstruction. Partial pressures of CO2 (pCO2) is one of the most important factors in the processes of speleothem formation in caves. The objective of our study was to monitor the CO2 variations in the overlying soil, the cave air and the stream, and distinguish its sources and processes based on stable carbon isotopes in the Xueyu Cave system from October 2014 to February 2017. Overlying soil CO2 was influenced by soil temperature and soil moisture. The cave air pCO2 and equilibrium pCO2 in the stream water during two years showed very similar seasonal variations, fluctuating with high values in wet seasons and low values in dry seasons. The average δ13Csoil air value was −19.3 ± 0.8‰ and δ13Ccave air value was −18.8 ± 0.4‰ in November; while the average δ13Csoil air value was −23.9 ± 1.4‰ and δ13Ccave air value was −23.3 ± 0.3‰ in June. Moreover, the contribution from soil during the transitional ventilation (in November) was calculated based on the two end-members model of stable carbon isotopes. On the contrary, in wet season, cave air CO2 were mainly controlled by soil CO2 inputs. The total amount of C from stream degassing was calculated, which was higher in June than in November. High-resolution monitoring of cave air CO2 and its sources reveals the highly sensitive nature of CO2 dynamics within cave environments, and highlights its sensitivity to hydrological conditions in the cave system.

A system for the determination of surface water pCO2 in a highly variable environment, exemplified in the southern Baltic Sea

Measurement of pCO2 in highly dynamic coastal zones such as the southern Baltic Sea presents many challenges. In this study, we designed a system to measure pCO2 and then validated it in a series of laboratory and seagoing tests. The fast response time of the system was shown to provide a better resolution of CO2 system gradients. In the open waters of the Baltic Sea, the accuracy of the pCO2 measurements (±1.3 µatm) met the requirements of the ICOS (±2.0 µatm). In the coastal zone, there was less consistency between pCO2, DIC and pH measurements, suggesting the need to redefine the quality assurance and control requirements for the measurement of pCO2 in dynamic regions.

The Variability of Partial Pressure of Carbon Dioxide (pCO2) in a River-Influenced Coastal Upwelling System: A Case of the Northeast Pacific Coast

The Northeast Pacific coastal ocean, as a typical river-influenced coastal upwelling system, is characterized by significant variability of sea surface partial pressure of carbon dioxide (pCO2, 1000 μatm). This study reviewed the pCO2 variability and its underlying controlling mechanism in this highly dynamic region by bringing together previous scientific findings and historical data. The large pCO2 variability reflects the complex interactions between physical processes (riverine input and coastal upwelling) and the biological responses to the nutrient transportation associated with these physical processes, while temperature and air-sea gas exchange play a minor role in affecting pCO2. Both the river water and upwelled subsurface water are characterized by higher concentrations of pCO2 and nutrients when compared to the coastal surface water. The presence of high chlorophyll-a and low pCO2 in river plumes and areas adjacent to upwelling locations showed the intense biological CO2 uptake. The influences of riverine input and coastal upwelling thus mainly depend on the competing effect of high background pCO2 of river water and upwelled subsurface water vs. the biological dropdown of pCO2 resulting from the riverine- and upwelling-associated nutrient supplies. The strength of upwelling-favorable wind plays an important role in the pCO2 variability by affecting the intensity of coastal upwelling, with stronger wind speed causing more intense upwelling. The long-term pCO2 increasing rate in the Northeast Pacific coast is observed to be lower than that in the North Pacific open ocean.

High‐frequency time‐series autonomous observations of sea surface pCO2 and pH

AbstractCarbon dioxide partial pressure (pCO2) in surface water was continuously measured every 3 h from July 2012 to June 2013 using an autonomous pCO2 system (MAPCO2) deployed on a moored buoy on the East China Sea shelf (31°N, 124.5°E). Sea surface pCO2 and pH had the largest variations in summer, ranging from 215 to 470 μatm, and 7.941 to 8.263 (averagely 8.084 ± 0.080), respectively. They varied little in winter, ranging from 328 to 395 μatm, and 8.003 to 8.074 (averagely 8.052 ± 0.010), respectively. The seasonal average sea surface pCO2 was respectively 335 ± 70 μatm, 422 ± 43 μatm, 362 ± 11 μatm, and 311 ± 59 μatm in summer, autumn, winter, and spring, and was overall undersaturated with respect to atmosphere on a yearly basis. Although the average sea surface pCO2 in summer was below the atmospheric level, the net CO2 flux has suggested a CO2 source status due to the influence of typhoon. Our observation thus demonstrated the significant, even dominant impact of episodic typhoon events on surface ocean CO2 chemistry and air–sea CO2 gas exchange, which would be impossible to capture by shipboard observation. The high wind stress and curl associated with the northward movement of typhoon induced complex sea surface water movement, vertical mixing, and subsequent biological drawdown, which differed in pre‐, onset, and post‐typhoon stages. Based on our estimates, the degassing fluxes during typhoon reached as high as 82 mmol m−2 CO2 and 242 mmol m−2 CO2 in summer and autumn, respectively, accounting for twice as large as the summer CO2 sink during non‐typhoon period, and 28% of the total CO2 source in autumn.

High‐resolution distribution pattern of surface water nitrous oxide along a cruise track from the Okhotsk Sea to the western Arctic Ocean

AbstractNitrous oxide in the surface water was measured using an automatic underway system, along with measurements of surface water pCO2, dissolved oxygen, salinity, temperature, and sea ice coverage, along a cruise track through the Bering Sea and Chukchi Sea to the Canadian Basin during the 7th Chinese National Arctic Research Expedition. The results show that, overall, the regions along the cruise track are net sources of N2O to the atmosphere. Several N2O oversaturation maxima were observed along the cruise track, with an absolute maximum of approximately 60%. According to the hydrographic setting and the distribution patterns of pCO2, dissolved oxygen, and sea ice coverage in the study area, it was concluded that the N2O oversaturation maxima may result from hydrographic processes, such as mixing of different water masses, upwelling or convection, and possible production beneath the sea ice. Additionally, the lowest value of approximately 90% may result from dilution related to the melting of sea ice. An evaluation of the air–sea flux along the cruise track shows that the continental shelf and upwelling region are N2O sources, whereas the study area in the open Arctic Ocean does not show obvious source or sink characteristics.

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.

In situ Photosynthetic Activities and Associated Biogeochemical Changes in Three Tropical Seagrass Species

Tropical seagrasses, experience considerable spatio-temporal changes in light and other biogeochemical conditions and adopt species-specific acclimatization strategies. Variation in photo-acclimatory responses of three tropical seagrass species (Cymodocea serrulata, Thalassia hemprichii and Enhalus acoroides) were studied by measuring photosynthetic electron transport rates (ETR) using Pulse Amplitude Modulated (PAM) fluorometry technique. Quantitative values of ETR and rates of photosynthetic O2 evolution (net O2 exchange corrected for dark respiration) were compared to establish species-specific relationships in these shallow water conditions. The apparent average molar ratio of O2 evolution to ETR for Cymodocea serrulata, Thalassia hemprichii and Enhalus acoroides were estimated as 0.23, 0.19 and 0.20, respectively. The highest photosynthetic activity (ETRmax) varied significantly among the three studied species in the decreasing order as: E. acoroides (59.27); T. hemprichii (54.06) and C. serrulata (46.72). The effective quantum yield (Y) of PS II (Photosystem II), one of the most useful indicators of stress conditions for seagrass, was observed to be significantly higher for E. acoroides compared to the other two species. Variability of Y in the ambient conditions are explained by the difference in water temperature and pCO2 for the three seagrass species. This study is useful in predicting the photo-acclimation strategies to any change in light availability and subsequent biogeochemical changes at the bottom surface, by these shallow water tropical seagrass species.

Surface Water CO2 variability in the Gulf of Mexico (1996\u20132017)

Approximately 380,000 underway measurements of sea surface salinity, temperature, and carbon dioxide (CO2) in the Gulf of Mexico (GoM) were compiled from the Surface Ocean CO2 Atlas (SOCAT) to provide a comprehensive observational analysis of spatiotemporal CO2 dynamics from 1996 to 2017. An empirical orthogonal function (EOF) was used to derive the main drivers of spatial and temporal variability in the dataset. In open and coastal waters, drivers were identified as a biological component linked to riverine water, and temperature seasonality. Air-sea flux estimates indicate the GoM open (− 0.06 ± 0.45 mol C m−2 year−1) and coastal (− 0.03 ± 1.83 mol C m−2 year−1) ocean are approximately neutral in terms of an annual source or sink for atmospheric CO2. Surface water pCO2 in the northwest and southeast GoM open ocean is increasing (1.63 ± 0.63 µatm year−1 and 1.70 ± 0.14 µatm year−1, respectively) at rates comparable to those measured at long-term ocean time-series stations. The average annual increase in coastal CO2 was 3.20 ± 1.47 µatm year-1 for the northwestern GoM and 2.35 ± 0.82 µatm year−1 for the west Florida Shelf. However, surface CO2 in the central (coastal and open) GoM, which is influenced by Mississippi and Atchafalaya River outflow, remained fairly stable over this time period.

Effects of chemical weathering and CO2 outgassing on δ13CDIC signals in a karst watershed

As the important part of carbon cycle research, riverine dissolved inorganic carbon (DIC) has attracted continuous attentions for its close relationship with global climate change. In order to investigate the dominant factors of dissolved inorganic carbon species and its stable carbon isotopic signals in large watershed under base flow condition, 81 river water samples were collected in the Xijiang River during the dry season in 2015. The elemental ratios in river water revealed the hydro-chemistry in Xijiang River were mainly controlled by the carbonate weathering. The characteristics of the most samples were the high DIC concentrations and narrow range of δ13CDIC, which can be interpreted as the result of chemical weathering under open system based on the simulated calculation of soil respiration and mineral dissolution. The relatively lower DIC concentrations and δ13CDIC values have been observed in tributaries draining silicate terrains, this result may be controlled both by the mineral dissolution and CO2 outgassing. Most samples had the over-saturated pCO2 levels compared to the atmosphere, the respiratory quotient (RQ) demonstrated that high pCO2 values were not from the biologic respiration, instead, the groundwater influx with the high soil pCO2 increased pCO2 level in river waters. The CO2 concentration gradient between river water and atmosphere caused a violent CO2 outgassing accompanied isotope fractionation. The outgassing significantly dropped the pCO2 in river water and caused an enrichment of C13 in DIC. Based on the theoretical calculation and previous observation, the negative correlation between the δ13CDIC and pCO2 in river water was caused by the CO2 outgassing. Additionally, the isotope exchange between the DIC and atmosphere CO2 can also partially increase the riverine CO2. This study examined the impacts of soil respiration, minerals dissolution and CO2 outgassing on DIC and δ13CDIC, and found that the riverine δ13CDIC is probably not reflect the mixing of source signals such as soil CO2 and carbonate, instead, it is mainly controlled by the fractionation in minerals dissolution and CO2 outgassing.

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.

A Forty-Year Karstic Critical Zone Survey (Baget Catchment, Pyrenees-France): Lithologic and Hydroclimatic Controls on Seasonal and Inter-Annual Variations of Stream Water Chemical Composition, pCO2, and Carbonate Equilibrium

The long-term trends and seasonal patterns of stream water chemical composition in a small remote forested karst catchment, were investigated from 1978 to 2018. Calcium, magnesium, and bicarbonates, the dominant ions, increased over the period together with temperature, while sulfates decreased. Carbonate and sulfate mineral dissolution was the main source of these elements. These trends and the seasonal opposite patterns of discharge vs. temperature, calcite saturation index vs. pCO2 and bicarbonate vs. sulfates, suggested the influence of discharge, of reduced long-range atmospheric pollution, and of increasing air temperature on biological activity and carbonate dissolution. Furthermore, the hydrological regime controlled the seasonal stream water chemical composition and fluxes by: (i) a dilution during the high discharge period, (ii) a change in the contribution rate of the waters draining different lithological areas in the catchment, e.g., the increased sulfates to bicarbonates ratio during summer low flows, with a maximum alkalinity decrease of 24%, and (iii) a “piston” and a “flushing” effects of dissolved elements stored in soils and epikarst with the first autumn heavy rains. Long-term stream water hydrochemical surveys of karst system have proved to be powerful indicators of biogeochemical processes, water sources and pathways under variable natural and anthropogenic environmental pressure conditions.

Temporal variability of the carbonate system and air-sea CO2 exchanges in a Mediterranean human-impacted coastal site

The temporal evolution of the carbonate system and air-sea CO2 fluxes are investigated for the first time in the Bay of Marseille (BoM – North Western Mediterranean Sea), a coastal system affected by anthropogenic forcing from the Marseille metropolis. This study presents a two-year time-series (between 2016 and 2018) of fortnightly measurements of AT, CT, pH and derived seawater carbonate parameters at the SOLEMIO station. On this land-ocean boundary area, no linear relationship between AT and salinity in surface water is observed due to sporadic intrusions of freshwater coming from the Rhone River. On an annual scale, the BoM acts as a sink of atmospheric CO2. This result is consistent with previous studies in the Mediterranean Sea. Mean daily air-sea CO2 fluxes range between −0.8 mmolC.m−2.d−1 and -2.2 mmolC.m−2.d−1 during the study period, depending on the atmospheric CO2 sampling site used for the estimates. This study shows that the pCO2 in the surface water is predominantly driven by temperature changes, even if partially counterbalanced by biological activity. Therefore, temperature is the main contributor to the air-sea CO2 exchange variability. Mean daily Net Ecosystem Production (NEP) estimates from CT budget shows an ecosystem in which autotrophic processes are associated with a sink of CO2. Despite some negative NEP values, the observed air-sea CO2 fluxes in the BoM are negative, suggesting that thermodynamic processes are the predominant drivers for these fluxes.