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Headspace analysis of CO2 frequently has been used to quantify the concentration of CO2 in fresh water. According to basic chemical theory, not considering chemical equilibration of the carbonate system in the sample vials will result in a systematic error. By analysing the potential error for different types of water and experimental conditions, we show that the error incurred by headspace analysis of CO2 is less than 5 % for typical samples from boreal systems which have low alkalinity (< 900 µmol L−1), with pH < 7.5, and high pCO2 (> 1000 µatm). However, the simple headspace calculation can lead to high error (up to −300 %) or even impossibly negative values in highly undersaturated samples equilibrated with ambient air, unless the shift in carbonate equilibrium is explicitly considered. The precision of the method can be improved by lowering the headspace ratio and/or the equilibration temperature. We provide a convenient and direct method implemented in an R script or a JMP add-in to correct CO2 headspace results using separately measured alkalinity.

Freshwaters are important emitters of carbon dioxide (CO2) and methane (CH4), two potent greenhouse gases (GHGs). While aquatic surface GHG fluxes have been extensively measured, there is much less information about their underlying sources. In lakes and reservoirs, surface GHG can originate from horizontal riverine flow, the hypolimnion, littoral sediments, and water column metabolism. These sources are generally studied separately, leading to a fragmented assessment of their relative role in sustaining CO2 and CH4 surface fluxes. In this study, we quantified sources and sinks of CO2 and CH4 in the epilimnion along a hydrological continuum in a permanently stratified tropical reservoir (Borneo). Results showed that horizontal inputs are an important source of both CO2 and CH4 (>90 % of surface emissions) in the upstream reservoir branches. However, this contribution fades along the hydrological continuum, becoming negligible in the main basin of the reservoir, where CO2 and CH4 are uncoupled and driven by different processes. In the main basin, vertical CO2 inputs and sediment CH4 inputs contributed to on average 60 % and 23 % respectively to the surface fluxes of the corresponding gas. Water column metabolism exhibited wide amplitude and range for both gases, making it a highly variable component, but with a large potential to influence surface GHG budgets in either direction. Overall our results show that sources sustaining surface CO2 and CH4 fluxes vary spatially and between the two gases, with internal metabolism acting as a fluctuating but key modulator. However, this study also highlights challenges and knowledge gaps related to estimating ecosystem-scale CO2 and CH4 metabolism, which hinder aquatic GHG flux predictions.

Reservoirs are important sources of greenhouse gases (GHGs) to the atmosphere, and their number is rapidly increasing, especially in tropical regions. Accurately predicting their current and future emissions is essential but hindered by fragmented data on the subject, which often fail to include all emission pathways (surface diffusion, ebullition, degassing, and downstream emissions) and the high spatial and temporal flux variability. Here we conducted a comprehensive sampling of Batang Ai reservoir (Malaysia), and compared field-based versus modelled estimates of its annual carbon footprint for each emission pathway. Carbon dioxide (CO2) and methane (CH4) surface diffusion were higher in upstream reaches. Reducing spatial and temporal sampling resolution resulted in up to a 64 % and 33 % change in the flux estimate, respectively. Most GHGs present in discharged water were degassed at the turbines, and the remainder were gradually emitted along the outflow river, leaving time for CH4 to be partly oxidized to CO2. Overall, the reservoir emitted 2475 gCO2eqm-2yr-1, with 89 % occurring downstream of the dam, mostly in the form of CH4. These emissions, largely underestimated by predictions, are mitigated by CH4 oxidation upstream and downstream of the dam but could have been drastically reduced by slightly raising the water intake elevation depth. CO2 surface diffusion and CH4 ebullition were lower than predicted, whereas modelled CH4 surface diffusion was accurate. Investigating latter discrepancies, we conclude that exploring morphometry, soil type, and stratification patterns as predictors can improve modelling of reservoir GHG emissions at local and global scales.

The concentration of dissolved organic carbon (DOC) in groundwater emanating as spring discharge at several locations in Florida, USA and the net increase in DOC in the downstream receiving waters were measured as part of a larger investigation of carbon dynamics in flowing waters. Springs with high discharge (>2.8 m3 s−1) were found to be the most organic-poor natural waters yet reported (13 ± 1.6 μmol C L−1), while springs with lesser discharge exhibited somewhat higher DOC concentrations (values ranging from 30 to 77 μmol C L−1). DOC concentrations increased rapidly downstream from the point of spring discharge, with the calculated net areal input rate of DOC ranging from 0.04 to 1.64 mol C m−2 d−1 across springs. Rates of DOC increase were generally greater in those springs with high discharge rates. These input rates compare favorably with values reported for gross primary production in these macrophyte-dominated spring systems, assuming that 17% of macrophyte primary production is lost, on average, as DOC. The measures reported here are possible only because of the remarkably low DOC levels in the up-surging groundwaters and the short residency times of the water in the spring-runs themselves.

Air-sea CO2 exchange depends on the air-sea CO2 gradient and the gas transfer velocity (k), computed as a function of wind speed. Large discrepancies among relationships predicting k from wind suggest that other processes also contribute significantly to modulate CO2 exchange. Here we report, on the basis of the relationship between the measured gas transfer velocity and the organic carbon concentration at the ocean surface, a significant role of surface organic matter in suppressing air-sea gas exchange, at low and intermediate winds, in the open ocean, confirming previous observations. The potential role of total surface organic matter concentration (TOC) on gas transfer velocity (k) was evaluated by direct measurements of air-sea CO2 fluxes at different wind speeds and locations in the open ocean. According to the results obtained, high surface organic matter contents may lead to lower air-sea CO2 fluxes, for a given air-sea CO2 partial pressure gradient and wind speed below 5 m s−1, compared to that observed at low organic matter contents. We found the bias in calculated gas fluxes resulting from neglecting TOC to co-vary geographically and seasonally with marine productivity. These results support previous evidences that consideration of the role of organic matter in modulating air-sea CO2 exchange may improve flux estimates and help avoid possible bias associated to variability in surface organic concentration across the ocean.

Planktonic and benthic incubations (bare and Posidonia oceanica vegetated sediments) were performed at monthly intervals from March 2001 to October 2002 in a seagrass vegetated area of the Bay of Palma (Mallorca, Spain). Results showed a contrast between the planktonic compartment, which was on average near metabolic balance (−4.6±5.9 mmol O2 m-2 d-1) and the benthic compartment, which was autotrophic (17.6±8.5 mmol O2 m-2 d-1). During two cruises in March and June 2002, planktonic and benthic incubations were performed at several stations in the bay to estimate the whole-system metabolism and to examine its relationship with partial pressure of CO2 (pCO2) and apparent oxygen utilisation (AOU) spatial patterns. Moreover, during the second cruise, when the residence time of water was long enough, net ecosystem production (NEP) estimates based on incubations were compared, over the Posidonia oceanica meadow, to rates derived from dissolved inorganic carbon (DIC) and oxygen (O2) mass balance budgets. These budgets provided NEP estimates in fair agreement with those derived from direct metabolic estimates based on incubated samples over the Posidonia oceanica meadow. Whereas the seagrass community was autotrophic, the excess organic carbon production therein could only balance the planktonic heterotrophy in shallow waters relative to the maximum depth of the bay (55 m). This generated a horizontal gradient from autotrophic or balanced communities in the shallow seagrass-covered areas, to strongly heterotrophic communities in deeper areas of the bay. It seems therefore that, on an annual scale in the whole bay, the organic matter production by the Posidonia oceanica may not be sufficient to fully compensate the heterotrophy of the planktonic compartment, which may require external organic carbon inputs, most likely from land.

The direct CO2 released by respiration of humans and domesticated animals, as well as CO2 derived from the decomposition of their resulting wastes was calculated in order to ascertain the direct and indirect metabolic contribution of humanity to CO2 release. Human respiration was estimated to release 0.6 Gt C year−1 and that of their associated domestic animals was estimated to release 1.5 Gt C year−1, to which an indirect release of 1.0 Gt C year−1, derived from decomposition of the organic waste and garbage produced by humans and their domestic animals, must be added. These combined direct and indirect metabolic sources, estimated at 3.1 Gt C year−1, have increased 7 fold since pre-industrial times and are predicted to continue to rise over the 21st century.

Headspace analysis of CO 2 frequently has been used to quantify the concentration of CO 2 in fresh water. According to basic chemical theory, not considering chemical equilibration of the carbonate system in the sample vials will result in a systematic error. By analysing the potential error for different types of water and experimental conditions, we show that the error incurred by headspace analysis of CO 2 is less than 5 % for typical samples from boreal systems which have low alkalinity (< 900 µ mol L -1), with pH < 7.5, and high p CO 2 (> 1000 µ atm). However, the simple headspace calculation can lead to high error (up to - 300 %) or even impossibly negative values in highly undersaturated samples equilibrated with ambient air, unless the shift in carbonate equilibrium is explicitly considered. The precision of the method can be improved by lowering the headspace ratio and/or the equilibration temperature. We provide a convenient and direct method implemented in an R script or a JMP add-in to correct CO 2 headspace results using separately measured alkalinity. [ABSTRACT FROM AUTHOR]

Air-sea CO2 exchange depends on the air-sea CO2 gradient and the gas transfer velocity (k), computed as a function of wind speed. Large discrepancies among relationships predicting k from wind suggest that other processes also contribute significantly to modulate CO2 exchange. Here we report, on the basis of the relationship between the measured gas transfer velocity and the organic carbon concentration at the ocean surface, a significant role of surface organic matter in suppressing air-sea gas exchange, at low and intermediate winds, in the open ocean, confirming previous observations. The potential role of total surface organic matter concentration (TOC) on gas transfer velocity (k) was evaluated by direct measurements of air-sea CO2 fluxes at different wind speeds and locations in the open ocean. According to the results obtained, high surface organic matter contents may lead to lower air-sea CO2 fluxes, for a given air-sea CO2 partial pressure gradient and wind speed below 5 m s-1, compared to that observed at low organic matter contents. We found the bias in calculated gas fluxes resulting from neglecting TOC to co-vary geographically and seasonally with marine productivity. These results support previous evidences that consideration of the role of organic matter in modulating air-sea CO2 exchange may improve flux estimates and help avoid possible bias associated to variability in surface organic concentration across the ocean. [ABSTRACT FROM AUTHOR]