pCO2 Variability Research Articles

Using CDOM optical properties for estimating DOC concentrations and pCO2 in the Lower Amazon River.

Coloured dissolved organic matter (CDOM) is one of the major contributors to the absorption budget of most freshwaters and can be used as a proxy to assess non-optical carbon fractions such as dissolved organic carbon (DOC) and the partial pressure of carbon dioxide (pCO2). Nevertheless, riverine studies that explore the former relationships are still relatively scarce, especially within tropical regions. Here we document the spatial-seasonal variability of CDOM, DOC and pCO2, and assess the potential of CDOM absorption coefficient (aCDOM(412)) for estimating DOC concentration and pCO2 along the Lower Amazon River. Our results revealed differences in the dissolved organic matter (DOM) quality between clearwater (CW) tributaries and the Amazon River mainstream. A linear relationship between DOC and CDOM was observed when tributaries and mainstream are evaluated separately (Amazon River: N = 42, R2 = 0.74, p<0.05; CW: N = 13, R2 = 0.57, p<0.05). However, this linear relationship was not observed during periods of higher rainfall and river discharge, requiring a specific model for these time periods to be developed (N = 25, R2 = 0.58, p<0.05). A strong linear positive relation was found between aCDOM(412) and pCO2(N = 69, R2 = 0.65, p<0.05) along the lower river. pCO2 was less affected by the optical difference between tributaries and mainstream waters or by the discharge conditions when compared to CDOM to DOC relationships. Including the river water temperature in the model improves our ability to estimate pCO2 (N = 69; R2 = 0.80, p<0.05). The ability to assess both DOC and pCO2 from CDOM optical properties opens further perspectives on the use of ocean colour remote sensing data for monitoring carbon dynamics in large running water systems worldwide.

A simple role of coral-algal symbiosis in coral calcification based on multiple geochemical tracers

Light-enhanced calcification of reef-building corals, which eventually create vast coral reefs, is well known and based on coral-algal symbiosis. Several controversial hypotheses have been proposed as possible mechanisms for connecting symbiont photosynthesis and coral calcification, including pH rise in the internal pool, role of organic matrix secretion, and enzyme activities. Here, based on the skeletal chemical and isotopic compositions of symbiotic and asymbiotic primary polyps of Acropora digitifera corals, we show a simple pH increase in the calcification medium as the predominant contribution of symbionts to calcification of host corals. We used the symbiotic and asymbiotic primary polyps reared for 10 days at four temperatures (27, 29, 31, and 33 °C), five salinities (34, 32, 30, 28, and 26), and four pCO2 levels (<300, 400, 800, and 1000 µatm). As a result of analyzing multiple geochemical tracers (U/Ca, Mg/Ca, Sr/Ca, δ18O, δ13C, and δ44Ca), a clear and systematic decrease in skeletal U/Ca ratio (used as a proxy for calcification fluid pH) was observed, indicating a higher pH of the fluid in symbiotic compared to asymbiotic polyps. In contrast, Mg/Ca ratios (used as a tentative proxy for organic matrix secretion) and δ44Ca (used as an indicator of Ca2+ pathway to the fluid) did not differ between symbiotic and asymbiotic polyps. This suggests that organic matrix secretion related to coral calcification is controlled mainly by the coral host itself, and a transmembrane transport of Ca2+ does not vary according to symbiosis relationship. Skeletal δ18O values of both symbiotic and asymbiotic polyps showed offsets between them with identical temperature dependence. Based on a newly proposed model, behavior of δ18O in the present study seems to reflect the rate of CO2 hydration in the calcifying fluid. Since CO2 hydration is promoted by enzyme carbonic anhydrase, the offset of δ18O values between symbiotic and asymbiotic polyps is attributed to the differences of enzyme activity, although the enzyme is functional even in the asymbiotic polyp. Symbiotic δ13C values in the temperature and salinity experiments were higher compared to those in the asymbiotic polyps due to photosynthesis, although photosynthetic δ13C signals in the pCO2 experiment were masked by the dominant δ13C gradient in dissolved inorganic carbon in seawater caused by 13C-depletd CO2 gas addition in the higher pCO2 treatments. Sr/Ca ratios showed a negligible relationship according to variation of temperature, salinity, and pCO2, although it might be attributed to relatively large deviations of replicates of Sr/Ca ratios in the present study. Overall, only the U/Ca ratio showed a significant difference between symbiotic and asymbiotic polyps throughout all experiments, indicating that the critical effect on coral calcification caused by symbiotic algae is the increase of pH of the calcifying fluid by photosynthesis.

Interannual drivers of the seasonal cycle of CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; in the Southern Ocean

Abstract. Resolving and understanding the drivers of variability of CO2 in the Southern Ocean and its potential climate feedback is one of the major scientific challenges of the ocean-climate community. Here we use a regional approach on empirical estimates of pCO2 to understand the role that seasonal variability has in long-term CO2 changes in the Southern Ocean. Machine learning has become the preferred empirical modelling tool to interpolate time- and location-restricted ship measurements of pCO2. In this study we use an ensemble of three machine-learning products: support vector regression (SVR) and random forest regression (RFR) from Gregor et al. (2017), and the self-organising-map feed-forward neural network (SOM-FFN) method from Landschützer et al. (2016). The interpolated estimates of ΔpCO2 are separated into nine regions in the Southern Ocean defined by basin (Indian, Pacific, and Atlantic) and biomes (as defined by Fay and McKinley, 2014a). The regional approach shows that, while there is good agreement in the overall trend of the products, there are periods and regions where the confidence in estimated ΔpCO2 is low due to disagreement between the products. The regional breakdown of the data highlighted the seasonal decoupling of the modes for summer and winter interannual variability. Winter interannual variability had a longer mode of variability compared to summer, which varied on a 4–6-year timescale. We separate the analysis of the ΔpCO2 and its drivers into summer and winter. We find that understanding the variability of ΔpCO2 and its drivers on shorter timescales is critical to resolving the long-term variability of ΔpCO2. Results show that ΔpCO2 is rarely driven by thermodynamics during winter, but rather by mixing and stratification due to the stronger correlation of ΔpCO2 variability with mixed layer depth. Summer pCO2 variability is consistent with chlorophyll a variability, where higher concentrations of chlorophyll a correspond with lower pCO2 concentrations. In regions of low chlorophyll a concentrations, wind stress and sea surface temperature emerged as stronger drivers of ΔpCO2. In summary we propose that sub-decadal variability is explained by summer drivers, while winter variability contributes to the long-term changes associated with the SAM. This approach is a useful framework to assess the drivers of ΔpCO2 but would greatly benefit from improved estimates of ΔpCO2 and a longer time series.

Distinguishing between physical and biological controls on the spatial variability of pCO2: A novel approach using OMP water mass analysis (St. Lawrence, Canada)

Present-day air-sea CO2 flux estimates in the coastal ocean are subject to large uncertainties due to its heterogeneous nature and concomitant lack of data. Factors controlling the dissolved inorganic carbon (DIC) and CO2 fluxes vary within and between coastal subsystems, hampering the development of robust upscaling and modeling techniques. By applying a multi-tracer, quantitative water mass analysis, physical and biogeochemical factors can be differentiated. This study adopts an expanded version of optimum multiparameter (OMP) water mass analysis, an inverse modeling technique, to estimate the mixing fractions of predefined source water masses as well as the contribution of biological activity (photosynthesis, respiration) at a given observation point in the surface mixed layer that exchanges CO2 gas with the atmosphere. We apply the method to hydrographic, nutrient, and inorganic carbon data collected in the Estuary and Gulf of St. Lawrence, the world's largest estuarine system and an excellent analogue of the more general coastal environment. Biological activity is identified as the dominant control on mixed-layer CO2 partial pressure (pCO2) dynamics along the St. Lawrence land—ocean continuum, explaining the upstream to downstream shift from pCO2 supersaturation (net heterotrophy) to pCO2 undersaturation (net autotrophy). Although mixing of freshwater and seawater along the Estuary is the major contributor to the DIC pool, it contributes little (or negligibly) to the spatial variability of surface-water pCO2.

An Assessment of Direct Dissolved Inorganic Carbon Injection to the Coastal Region: A Model Result

The amount of carbon dioxide (CO2) in the atmosphere has increased in the past 60 years and the technology of carbon capture and storage (CCS) has recently been extensively studied. One of the strategies of CCS is to directly inject a high dissolved inorganic carbon (DIC) concentration (or high partial pressure of carbon dioxide, pCO2) solution into the ocean. However, the carbonate dynamics and air-sea gas exchange are usually neglected in a CCS strategy. This study assesses the effect of a DIC-solution injection by using a simple two end-member model to simulate the variation of pH, DIC, total alkalinity (TA) and pCO2 between the river and sea mixing process for the Danshuei River estuary and Hoping River in Taiwan. We observed that the DIC-solution injection can contribute to ocean acidification and can also lead the pCO2 value to change from being undersaturated to oversaturated (with respect to the atmospheric CO2 level). Our model result also showed that the maximum Revelle factors (Δ[CO2]/[CO2])/(Δ[DIC]/[DIC]) among varied pH values (6–9) and DIC concentrations (0.5–3.5 mmol kg−1) were between pH 8.3 and 8.5 in fresh water and were between 7.3 and 7.5 in waters with a salinity of 35, reflecting the changing efficiency of dissolving CO2 gas into the DIC solution and the varying stability of this desired DIC solution. Finally, we suggest this uncoupled Revelle factor between fresh and salty water should be considered in the (anthropogenic) carbonate chemical weathering on a decade to century scale.

Detecting CO2 leakage at offshore storage sites using the covariance between the partial pressure of CO2 and the saturation of dissolved oxygen in seawater

An option to detect CO2 leakage from deep geological storage under the seabed is monitoring the partial pressure of CO2 (pCO2) in the sea. One of the challenges of this technique is to differentiate pCO2 elevations caused by CO2 leakage from variations in the natural baseline (which varies due to seasonal and other factors). This paper compares a covariance threshold for anomalous pCO2 (a threshold based on pCO2 and dissolved oxygen), with annual and seasonal constant thresholds, using data observed in two hydrologically contrasting areas in Osaka Bay, Japan. In one of these locations the water column is typically stratified throughout the year, whereas at the other it is vertically mixed. The covariance threshold often but not consistently outperforms the constant thresholds, but is effective in all the cases analyzed in the present study. In any season in the mixed area, and in winter in the stratified area, the possibility of false-negatives in the seasonal threshold method is smaller than or comparable with that in the covariance threshold one. In areas with large natural pCO2 variations, such as during summer in the stratified area, the covariance threshold method is efficient in detecting CO2 leakage whereas the seasonal threshold method is of little use. With a good understanding of local conditions, monitoring pCO2 with the covariance threshold method is a potentially useful but not sufficient option for leakage detection in the marine environment.

The effects of environmental history and thermal stress on coral physiology and immunity

Rising ocean temperatures can induce the breakdown of the symbiosis between reef building corals and Symbiodinium in the phenomenon known as coral bleaching. Environmental history may, however, influence the response of corals to stress and affect bleaching outcomes. A suite of physiological and immunological traits was evaluated to test the effect of environmental history (low vs. high variable pCO2) on the response of the reef coral Montipora capitata to elevated temperature (24.5 °C vs. thermal ramping to 30.5 °C). Heating reduced maximum photochemical efficiency (Fv/Fm) and chlorophyll a but increased tissue melanin in corals relative to the ambient treatment, indicating a role of the melanin synthesis pathway in the early stages of thermal stress. However, interactions of environmental history and temperature treatment were not observed. Rather, parallel reaction norms were the primary response pattern documented across the two temperature treatments with respect to reef environmental history. Corals with a history of greater pCO2 variability had higher constitutive antioxidative and immune activity (i.e., catalase, superoxide dismutase, prophenoloxidase) and Fv/Fm, but lower melanin and chlorophyll a, relative to corals with a history of lower pCO2 variability. This suggests that reef environments with high magnitude pCO2 variability promote greater antioxidant and immune activity in resident corals. These results demonstrate coral physiology and immunity reflect environmental attributes that vary over short distances, and that these differences may buffer the magnitude of thermal stress effects on coral phenotypes.

Carbon dynamics and CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; and CH&amp;lt;sub&amp;gt;4&amp;lt;/sub&amp;gt; outgassing in the Mekong delta

Abstract. We report a data set of biogeochemical variables related to carbon cycling obtained in the three branches (Mỹ Tho, Hàm Luông, Co^´ Chiên) of the Mekong delta (Be^´n Tre province, Vietnam) in December 2003, April 2004, and October 2004. Both the inner estuary (upstream of the mouth) and the outer estuary (river plume) were sampled, as well as side channels. The values of the partial pressure of CO2 (pCO2) ranged between 232 and 4085 ppm, O2 saturation level (%O2) between 63 and 114 %, and CH4 between 2 and 2217 nmol L−1, within the ranges of values previously reported in temperate and tropical meso- and macro-tidal estuaries. Strong seasonal variations were observed. In the upper oligohaline estuary, low pCO2 (479–753 ppm) and high %O2 (98–106 %) values were observed in April 2004 most probably related to freshwater phytoplankton growth owing to low freshwater discharge (1400 m3 s−1) and increase in water residence time; during the two other sampling periods with a higher freshwater discharge (9300–17 900 m3 s−1), higher pCO2 (1895–2664 ppm) and lower %O2 (69–84 %) values were observed in the oligohaline part of the estuary. In October 2004, important phytoplankton growth occurred in the offshore part of the river plume as attested by changes in the contribution of particulate organic carbon (POC) to total suspended matter (TSM) (%POC) and the stable isotope composition of POC (δ13C-POC), possibly related to low TSM values (improvement of light conditions for phytoplankton development), leading to low pCO2 (232 ppm) and high %O2 (114 %) values. Water in the side channels in the Mekong delta was strongly impacted by inputs from the extensive shrimp farming ponds. The values of pCO2, CH4, %O2, and the stable isotope composition of dissolved inorganic carbon (δ13C-DIC) indicated intense organic matter degradation that was partly mediated by sulfate reduction in sediments, as revealed by the slope of total alkalinity (TA) and DIC covariations. The δ13C-POC variations also indicated intense phytoplankton growth in the side channels, presumably due to nutrient enrichment related to the shrimp farming ponds. A data set in the mangrove creeks of the Ca Mau province (part of the Mekong delta) was also acquired in April and October 2004. These data extended the range of variability in pCO2 and %O2 with more extreme values than in the Mekong delta (Be^´n Tre), with maxima and minima of 6912 ppm and 37 %, respectively. Similarly, the maximum CH4 concentration (686 nmol L−1) was higher in the Ca Mau province mangrove creeks than in the Mekong delta (Be^´n Tre, maximum 222 nmol L−1) during the October 2004 cruise (rainy season and high freshwater discharge period). In April 2004 (dry season and low freshwater discharge period), the CH4 values were much lower than in October 2004 (average 19 ± 13 and 210 ± 158 nmol L−1, respectively) in the Ca Mau province mangrove creeks, owing to the higher salinity (average 33.2 ± 0.6 and 14.1 ± 1.2, respectively) that probably led to higher sediment sulfate reduction, leading to inhibition of sediment methanogenesis and higher anaerobic CH4 oxidation. In the inner estuarine region (three branches of the Mekong delta), CO2 emissions to the atmosphere averaged 121 mmol m−2 d−1, and the CH4 emissions averaged 118 µmol m−2 d−1. The CO2 emission to the atmosphere from the Mekong inner estuary was higher than reported in the Yangtze and Pearl river inner estuaries. This was probably due to the lower salinity in the Mekong delta branches, possibly due to different morphology: relatively linear channels in the Mekong delta versus funnel-shaped estuaries for the Yangtze and Pearl river inner estuaries.

The response of mesophyll conductance to short-term variation in CO2 in the C4 plants Setaria viridis and Zea mays.

Mesophyll conductance (gm) limits rates of C3 photosynthesis but little is known about its role in C4 photosynthesis. If gm were to limit C4 photosynthesis, it would likely be at low CO2 concentrations (pCO2). However, data on C4-gm across ranges of pCO2 are scarce. We describe the response of C4-gm to short-term variation in pCO2, at three temperatures in Setaria viridis, and at 25 °C in Zea mays. Additionally, we quantified the effect of finite gm calculations of leakiness (ϕ) and the potential limitations to photosynthesis imposed by stomata, mesophyll, and carbonic anhydrase (CA) across pCO2. In both species, gm increased with decreasing pCO2. Including a finite gm resulted in either no change or increased ϕ compared with values calculated with infinite gm depending on whether the observed 13C discrimination was high (Setaria) or low (Zea). Post-transitional regulation of the maximal PEP carboxylation rate and PEP regeneration limitation could influence estimates of gm and ϕ. At pCO2 below ambient, the photosynthetic rate was limited by CO2 availability. In this case, the limitation imposed by the mesophyll was similar or slightly lower than stomata limitation. At very low pCO2, CA further constrained photosynthesis. High gm could increase CO2 assimilation at low pCO2 and improve photosynthetic efficiency under situations when CO2 is limited, such as drought.

Sulphate partitioning into calcite: Experimental verification of pH control and application to seasonality in speleothems

Carbonate-associated sulphate (CAS) is a useful carrier of palaeoenvironmental information throughout the geologic record, particularly through its stable isotope composition. However, a paucity of experimental data restricts quantitative understanding of sulphate incorporation into carbonates, and consequently CAS concentrations and their diagenetic modifications are rarely interpreted. However, in the case of calcite speleothems, the remarkably high-resolution CAS records which are obtainable via modern microanalytical techniques represent a potentially invaluable source of palaeoenvironmental information. Here, we describe the results of controlled experiments of sulphate co-precipitation with calcite in freshwater solutions where pH, saturation state, and sulphate concentration were varied independently of each other. Solution pH is confirmed as the principal control on sulphate incorporation into calcite. The relative efficiency of incorporation was calculated as a partition coefficient DSO4 = (mSO4/mCO3)solid/(mSO4/mCO3)solution. High crystal growth rates (driven by either pH or saturation state) encouraged higher values of DSO4 because of an increasing concentration of defect sites on crystal surfaces. At low growth rates, DSO4 was reduced due to an inferred competition between sulphate and bicarbonate at the calcite surface. These experimental results are applied to understand the incorporation of sulphate into speleothem calcite. The experimentally determined pH-dependence suggests that strong seasonal variations in cave air PCO2 could account for annual cycles in sulphate concentration observed in stalagmites. Our new experimentally determined values of DSO4 were compared with DSO4 values calculated from speleothem-drip water monitoring from two caves within the Austrian and Italian Alps. At Obir cave, Austria, DSO4 (×105) varies between 11.1 (winter) and 9.0 (summer) and the corresponding figures for Ernesto cave, Italy, are 15.4 (winter) and 14.9 (summer). These values approximate predicted DSO4 values based on our chamber experiments containing both low (2 ppm) and high (20 ppm) sulphate concentrations. Our experimental values of DSO4 obtained at crystal growth rates typical of stalagmites, closely match those observed in other cave sites from around the world. This validates the universality of the controls behind DSO4 and will enhance the use of speleothem CAS as a palaeoenvironmental proxy.

Ecosystem controlled soil-rock pCO2 and carbonate weathering – Constraints by temperature and soil water content

Carbonate dissolution in soil-groundwater systems depends dominantly on pH, temperature and the saturation state of the solution with respect to abundant minerals. The pH of the solution is, in general, controlled by partial pressure of CO2 (pCO2) produced by ecosystem respiration, which is controlled by temperature and water availability. In order to better understand the control of land temperature on carbonate weathering, a database of published spring water hydrogeochemistry was built and analysed. Assuming that spring water is in equilibrium with the soil-water-rock-atmosphere, the soil pCO2 can be back-calculated. Based on a database of spring water chemistry, the average soil-rock CO2 was calculated by an inverse model framework and a strong relationship with temperature was observed. The identified relationship suggests a temperature control on carbonate weathering as a result of variations in soil-rock pCO2, which is itself controlled by ecosystem respiration processes. The findings are relevant for global scale analysis of carbonate weathering and carbon fluxes to the ocean, because concentration of weathering products from the soil-rock-system into the river system in humid, high temperature regions, are suggested to be larger than in low temperature regions. Furthermore, results suggest that, in specific spring samples, the hydrochemical evolution of rain water percolating through the soil-rock complex can best be described by an open system with pCO2 controlled by the ecosystem. Abundance of evaporites and pyrite sources influence significantly the chemistry of spring water and corrections must be taken into account in order to implement the inverse model framework presented in this study. Annual surface temperature and soil water content were identified as suitable variables to develop the parameterization of soil-rock pCO2, mechanistically consistent with soil respiration rate findings.

Spatial and temporal variability of seawater pCO2 within the Canadian Arctic Archipelago and Baffin Bay during the summer and autumn 2011

The partial pressure of CO2 in surface water (pCO2sw) measured within the Canadian Arctic Archipelago (CAA) and Baffin Bay was highly variable with values ranging from strongly undersaturated (118 µatm) to slightly supersaturated (419 µatm) with respect to the atmospheric levels (~386 μatm) during summer and autumn 2011. During summer, melting sea ice contributed to cold and fresh surface water and enhanced the ice-edge bloom, resulting in strong pCO2sw undersaturation. Coronation Gulf was the only area with supersaturated pCO2sw, likely due to warm CO2-enriched freshwater input from the Coppermine River. During autumn, the entire CAA (including Coronation Gulf) was undersaturated, despite generally increasing pCO2sw. Coronation Gulf was the one place where pCO2sw decreased, likely due to seasonal reduction in discharge from the Coppermine River and the decreasing sea surface temperature. The seasonal summer-to-autumn increase in pCO2sw across the archipelago is attributed in part to the continuous uptake of atmospheric CO2 through both summer and autumn and to the seasonal deepening of the surface mixed layer, bringing CO2-rich waters to the surface. These observations demonstrate how freshwater from sea ice melt and rivers affect pCO2sw differently. The general pCO2sw undersaturation during summer-autumn 2011 throughout the CAA and Baffin Bay give an estimated net oceanic sink for atmospheric CO2 over the study period of 11.4mmol CO2 m−2 d−1, assuming no sea-air CO2 flux exchange across the sea-ice covered areas.

Seasonal variation in aragonite saturation in surface waters of Puget Sound – a pilot study

A pilot study of sampling, using monthly marine flights over spatially distributed stations, was conducted with the aim to characterize the carbonate system in Puget Sound over a full year-long period. Surface waters of Puget Sound were found to be under-saturated with respect to aragonite during October–March, and super-saturated during April–September. Highest pCO2 and lowest pH occurred during the corrosive October–March period. Lowest pCO2 and highest pH occurred during the super-saturated April–September period. The monthly variations in pCO2, pH, and aragonite saturation state closely followed the variations in monthly average chlorophyll a. Super-saturated conditions during April–September are likely strongly influenced by photosynthetic uptake of CO2 during the phytoplankton growing season. The relationship between phytoplankton production, the carbonate system, and aragonite saturation state suggests that long-term trends in eutrophication processes may contribute to trends in ocean acidification in Puget Sound.

Watershed‐Scale Drivers of Air‐Water CO2 Exchanges in Two Lagoonal North Carolina (USA) Estuaries

AbstractRiverine loading of nutrients and organic matter act in concert to modulate CO2 fluxes in estuaries, yet quantitative relationships between these factors remain poorly defined. This study explored watershed‐scale mechanisms responsible for the relatively low CO2 fluxes observed in two microtidal, lagoonal estuaries. Air‐water CO2 fluxes were quantified with 74 high‐resolution spatial surveys in the neighboring New River Estuary (NewRE) and Neuse River Estuary (NeuseRE), North Carolina, which experience a common climatology but differ in marine versus riverine influence. Annually, both estuaries were relatively small sources of CO2 to the atmosphere, 12.5 and 16.3 mmol C m−2 d−1 in the NeuseRE and NewRE, respectively. Large‐scale pCO2 variations were driven by changes in freshwater age, which modulates nutrient and organic carbon supply and phytoplankton flushing. Greatest pCO2 undersaturation was observed at intermediate freshwater ages, between 2 and 3 weeks. Biological controls on CO2 fluxes were obscured by variable inputs of river‐borne CO2, which drove CO2 degassing in the river‐dominated NeuseRE. Internally produced CO2 exceeded river‐borne CO2 in the marine‐dominated NewRE, suggesting that net ecosystem heterotrophy, rather than riverine inputs, drove CO2 fluxes in this system. Variations in riverine alkalinity and inorganic carbon loading caused zones of minimum buffering capacity to occur at different locations in each estuary, enhancing the sensitivity of estuarine inorganic C chemistry to acidification. Although annual CO2 fluxes were similar between systems, watershed‐specific hydrologic factors led to disparate controls on internal carbonate chemistry, which can influence ecosystem biogeochemical cycling, trophic state, and response to future perturbations.

Reproducibility of hypercapnic ventilatory response measurements with steady-state and rebreathing methods

In this study, the hypercapnic ventilatory response (HCVR) was measured, defined as the ventilation response to carbon dioxide tension (PCO2). We investigated which method, rebreathing or steady-state, is most suitable for measurement of the HCVR in healthy subjects, primarily based on reproducibility. Secondary outcome parameters were subject experience and duration.20 healthy adults performed a rebreathing and steady-state HCVR measurement on two separate days. Subject experience was assessed using numeric rating scales (NRS). The intraclass correlation coefficient (ICCs) of the sensitivity to carbon dioxide above the ventilatory recruitment threshold and the projected apnoea threshold were calculated to determine the reproducibility of both methods.The ICCs of sensitivity were 0.89 (rebreathing) and 0.56 (steady-state). The ICCs of the projected apnoea threshold were 0.84 (rebreathing) and 0.25 (steady-state). The steady-state measurement was preferred by 16 out of 20 subjects; the differences in NRS scores were small.The hypercapnic ventilatory response measured using the rebreathing setup provided reproducible results, while the steady-state method did not. This may be explained by high variability in end-tidal PCO2. Differences in subject experience between the methods are small.

Variability of pCO2 in surface waters and development of prediction model

Inland waters are substantial sources of atmospheric carbon, but relevant data are rare in Asian monsoon regions including Korea. Emissions of CO2 to the atmosphere depend largely on the partial pressure of CO2 (pCO2) in water; however, measured pCO2 data are scarce and calculated pCO2 can show large uncertainty. This study had three objectives: 1) to examine the spatial variability of pCO2 in diverse surface water systems in Korea; 2) to compare pCO2 calculated using pH-total alkalinity (Alk) and pH-dissolved inorganic carbon (DIC) with pCO2 measured by an in situ submersible nondispersive infrared detector; and 3) to characterize the major environmental variables determining the variation of pCO2 based on physical, chemical, and biological data collected concomitantly. Of 30 samples, 80% were found supersaturated in CO2 with respect to the overlying atmosphere. Calculated pCO2 using pH-Alk and pH-DIC showed weak prediction capability and large variations with respect to measured pCO2. Error analysis indicated that calculated pCO2 is highly sensitive to the accuracy of pH measurements, particularly at low pH. Stepwise multiple linear regression (MLR) and random forest (RF) techniques were implemented to develop the most parsimonious model based on 10 potential predictor variables (pH, Alk, DIC, Uw, Cond, Turb, COD, DOC, TOC, Chla) by optimizing model performance. The RF model showed better performance than the MLR model, and the most parsimonious RF model (pH, Turb, Uw, Chla) improved pCO2 prediction capability considerably compared with the simple calculation approach, reducing the RMSE from 527–544 to 105μatm at the study sites.

The potential of using remote sensing data to estimate air–sea CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; exchange in the Baltic Sea

Abstract. In this article, we present the first climatological map of air–sea CO2 flux over the Baltic Sea based on remote sensing data: estimates of pCO2 derived from satellite imaging using self-organizing map classifications along with class-specific linear regressions (SOMLO methodology) and remotely sensed wind estimates. The estimates have a spatial resolution of 4 km both in latitude and longitude and a monthly temporal resolution from 1998 to 2011. The CO2 fluxes are estimated using two types of wind products, i.e. reanalysis winds and satellite wind products, the higher-resolution wind product generally leading to higher-amplitude flux estimations. Furthermore, the CO2 fluxes were also estimated using two methods: the method of Wanninkhof et al. (2013) and the method of Rutgersson and Smedman (2009). The seasonal variation in fluxes reflects the seasonal variation in pCO2 unvaryingly over the whole Baltic Sea, with high winter CO2 emissions and high pCO2 uptakes. All basins act as a source for the atmosphere, with a higher degree of emission in the southern regions (mean source of 1.6 mmol m−2 d−1 for the South Basin and 0.9 for the Central Basin) than in the northern regions (mean source of 0.1 mmol m−2 d−1) and the coastal areas act as a larger sink (annual uptake of −4.2 mmol m−2 d−1) than does the open sea (−4 mmol m−2 d−1). In its entirety, the Baltic Sea acts as a small source of 1.2 mmol m−2 d−1 on average and this annual uptake has increased from 1998 to 2012.

Comparison of air-sea CO2 flux and biological productivity in the South China Sea, East China Sea, and Yellow Sea: a three-dimensional physical-biogeochemical modeling study

Marginal seas play important roles in regulating the global carbon budget, but there are great uncertainties in estimating carbon sources and sinks in the continental margins. A Pacific basin-wide physical-biogeochemical model is used to estimate primary productivity and air-sea CO2 flux in the South China Sea (SCS), the East China Sea (ECS), and the Yellow Sea (YS). The model is forced with daily air-sea fluxes which are derived from the NCEP2 reanalysis from 1982 to 2005. During the period of time, the modeled monthly-mean air-sea CO2 fluxes in these three marginal seas altered from an atmospheric carbon sink in winter to a source in summer. On annualmean basis, the SCS acts as a source of carbon to the atmosphere (16 Tg/a, calculated by carbon, released to the atmosphere), and the ECS and the YS are sinks for atmospheric carbon (–6.73 Tg/a and–5.23 Tg/a, respectively, absorbed by the ocean). The model results suggest that the sea surface temperature (SST) controls the spatial and temporal variations of the oceanic pCO2 in the SCS and ECS, and biological removal of carbon plays a compensating role in modulating the variability of the oceanic pCO2 and determining its strength in each sea, especially in the ECS and the SCS. However, the biological activity is the dominating factor for controlling the oceanic pCO2 in the YS. The modeled depth-integrated primary production (IPP) over the euphotic zone shows seasonal variation features with annual-mean values of 293, 297, and 315 mg/(m2·d) in the SCS, the ECS, and the YS, respectively. The model-integrated annual-mean new production (uptake of nitrate) values, as in carbon units, are 103, 109, and 139 mg/(m2·d), which yield the f-ratios of 0.35, 0.37, and 0.45 for the SCS, the ECS, and the YS, respectively. Compared to the productivity in the ECS and the YS, the seasonal variation of biological productivity in the SCS is rather weak. The atmospheric pCO2 increases from 1982 to 2005, which is consistent with the anthropogenic CO2 input to the atmosphere. The oceanic pCO2 increases in responses to the atmospheric pCO2 that drives air-sea CO2 flux in the model. The modeled increase rate of oceanic pCO2 is 0.91 μatm/a in the YS, 1.04 μatm/a in the ECS, and 1.66 μatm/a in the SCS, respectively.

Variation of Lichen Diversity along an Elevation Gradient in the Hantana Mountain Range in Sri Lanka

Lichens are composite organisms formed by symbiotic relationships between algae or cyanobacteria and fungi. Apart from their morphological diversity, lichens hold a major significance in ecology because of their role as biological indicators. Lichens are highly sensitive to environmental stresses, such as air pollution and climate change. Accordingly, the objective of this study was to determine the variation of lichen diversity in the Hantana mountain range along an elevation gradient. Five elevations ranging from 512 to 773m above mean sea level (amsl) were selected in the Hantana mountain range, Peradeniya. The tree species selected for surveying lichens was Alstonia macrophylla because of its availability at all elevations. Two trees were selected randomly from each elevation. In each tree, a monitoring quadrate containing five independent 5x5 cm quadrate segments was hung at 1m from ground level. Lichens in quadrate segments were surveyed using a hand lens, and taxonomically identified using standard pictorial keys. The area of each lichen was measured using ImageJ software (Version 1:51k). In each tree trunk, four sides facing the four directions (North, East, West, and South) were surveyed independently. The Lichen Diversity Values (LDV) and the Indices of Atmospheric Purity (IAP) were calculated for each elevation. With the exception of one site at 583m amsl, the LDV showed a positive exponential relationship (LDV=25.161*e0.0024*E, R2=0.76) with increasing elevation (E). Reduction of air temperature and partial pressure of CO2 (pCO2) with increasing altitude could have contributed to the increasing lichen diversity. The lowermost site (L1) at 512m showed the lowest LDV (95) while the uppermost site (L5) at 773m showed the highest LDV (191). In addition to the natural variation of pCO2, proximity to roads with frequent vehicular traffic could have influenced the observed variation of LDV with elevation. The site at 583m, which did not fit in to the positive exponential relationship, had a higher LDV value (187) than that predicted from the relationship (102) probably because it was the least exposed to vehicular traffic. At all elevations, IAP values were greater than 50, which indicated that they have very low air pollution, indicating the importance of conservation programs. However, the presence of highly sensitive lichen genera such as Physica and Leptotrema being limited only to sites at upper elevations indicate that those sites are less polluted. On the other hand, lichen genera Megalospora, Graphis and Wirthiotrema were observed at all elevations. Keywords: Lichen diversity, Elevation gradient, Hantana range, Air pollution, pCO2

Estimating surface pCO2 in the northern Gulf of Mexico: Which remote sensing model to use?

Various approaches and models have been proposed to remotely estimate surface pCO2 in the ocean, with variable performance as they were designed for different environments. Among these, a recently developed mechanistic semi-analytical approach (MeSAA) has shown its advantage for its explicit inclusion of physical and biological forcing in the model, yet its general applicability is unknown. Here, with extensive in situ measurements of surface pCO2, the MeSAA, originally developed for the summertime East China Sea, was tested in the northern Gulf of Mexico (GOM) where river plumes dominate water's biogeochemical properties during summer. Specifically, the MeSAA-predicted surface pCO2 was estimated by combining the dominating effects of thermodynamics, river-ocean mixing and biological activities on surface pCO2. Firstly, effects of thermodynamics and river-ocean mixing (pCO2@Hmixing) were estimated with a two-endmember mixing model, assuming conservative mixing. Secondly, pCO2 variations caused by biological activities (ΔpCO2@bio) was determined through an empirical relationship between sea surface temperature (SST)-normalized pCO2 and MODIS (Moderate Resolution Imaging Spectroradiometer) 8-day composite chlorophyll concentration (CHL). The MeSAA-modeled pCO2 (sum of pCO2@Hmixing and ΔpCO2@bio) was compared with the field-measured pCO2. The Root Mean Square Error (RMSE) was 22.94µatm (5.91%), with coefficient of determination (R2) of 0.25, mean bias (MB) of − 0.23µatm and mean ratio (MR) of 1.001, for pCO2 ranging between 316 and 452µatm. To improve the model performance, a locally tuned MeSAA was developed through the use of a locally tuned ΔpCO2@bio term. A multi-variate empirical regression model was also developed using the same dataset. Both the locally tuned MeSAA and the regression models showed improved performance comparing to the original MeSAA, with R2 of 0.78 and 0.84, RMSE of 12.36µatm (3.14%) and 10.66µatm (2.68%), MB of 0.00µatm and − 0.10µatm, MR of 1.001 and 1.000, respectively. A sensitivity analysis was conducted to study the uncertainties in the predicted pCO2 as a result of the uncertainties in the input variables of each model. Although the MeSAA was more sensitive to variations in SST and CHL than in sea surface salinity (SSS), and the locally tuned MeSAA and the empirical regression models were more sensitive to changes in SST and SSS than in CHL, generally for these three models the bias induced by the uncertainties in the empirically derived parameters (river endmember total alkalinity (TA) and dissolved inorganic carbon (DIC), biological coefficient of the MeSAA and locally tuned MeSAA models) and environmental variables (SST, SSS, CHL) was within or close to the uncertainty of each model. While all these three models showed that surface pCO2 was positively correlated to SST, the MeSAA showed negative correlation between surface pCO2 and SSS and CHL but the locally tuned MeSAA and the empirical regression showed the opposite. These results suggest that the locally tuned MeSAA worked better in the river-dominated northern GOM than the original MeSAA, with slightly worse statistics but more meaningful physical and biogeochemical interpretations than the empirical regression model. Because data from abnormal upwelling were not used to train the models, they are not applicable for waters with strong upwelling, yet the empirical regression approach showed ability to be further tuned to adapt to such cases.