Air-water Gas Exchange Research Articles

Rainfall as a driver for near-surface turbulence and air-water gas exchange in freshwater aquatic systems.

Gas fluxes from aquatic ecosystems are a significant component of the carbon cycle. Gas exchange across the air-water interface is regulated by near-surface turbulence and can be controlled by different atmospheric forcing conditions, with wind speed and surface buoyancy flux being the most recognized drivers in empirical studies and modeling approaches. The effect of rainfall on near-surface turbulence has rarely been studied and a consistent relationship between rain rate and near-surface turbulence has not yet been established. In this study, we addressed some limitations still present in the quantitative understanding of the effect of rain rate on near-surface turbulence and on the resulting gas transfer velocity in freshwater. We performed controlled laboratory experiments over a wide range of rain rates (7 to 90 mm h-1) and estimated gas transfer velocities from high-resolution measurements of O2 concentration, while rain-induced turbulence was characterized based on particle image velocimetry. We found that the rain-induced dissipation rates of turbulent kinetic energy declined with depth following a consistent power-law relationship. Both energy dissipation rates and gas transfer velocity increased systematically with the rain rate. The results confirm a causal relationship between rainfall, turbulence, and gas exchange. We propose a power-law relationship between near-surface turbulent dissipation rates and rain rate. In combination with surface renewal theory, we derived a direct relationship between gas transfer velocity and rain rate, which can be used to assess the importance of short-term drivers, such as rain events, on gas dynamics and biogeochemical cycling in aquatic ecosystems.

Metabolism Regimes in Regulated Rivers of the Illinois River Basin, USA

Metabolism estimates organic carbon accumulation by primary productivity and removal by respiration. In rivers it is relevant to assessing trophic status and threats to river health such as hypoxia as well as greenhouse gas fluxes. We estimated metabolism in 17 rivers of the Illinois River basin (IRB) for a total of 15,176 days, or an average of 2.5 years per site. Daily estimates of gross primary productivity (GPP), ecosystem respiration (ER), net ecosystem productivity (NEP), and the air-water gas exchange rate constant (K600) are reported, along with ancillary data such as river temperature and saturated dissolved oxygen concentration, barometric pressure, and river depth and discharge. Workflows for metabolism estimation and quality assurance are described including a new method for estimating river depth. IRB rivers are dominantly heterotrophic; however, autotrophy was common in river locations coinciding with reported harmful algal blooms (HABs) events. Metabolism of these regulated Midwestern U.S. rivers can help assess the causes and consequences of excessive algal blooms in rivers and their role in river ecological health.

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.

Estimation of gas exchange coefficients from observations on the Yenisei River, Russia

AbstractThe gas exchange between water bodies and air is difficult to measure, thus the approximations of air–water gas exchange coefficient based solely on wind speed has been widely used. However, such approaches may not work well in river environments. In rivers, water currents may govern gas exchange. Thus, a new approximation for calculating the gas exchange coefficient (k) based on the near‐surface velocity scale (us) is suggested and compared to wind‐based estimates. Our velocity scale estimates are based on field observations during summer 2016 on the Yenisei River using an Acoustic Doppler Current Profiler, high‐frequency temperature profilers and a vessel‐mounted meteorological sensors‐suite. The results demonstrate that us‐derived gas exchange coefficients are higher than those based solely on wind speed. The results demonstrate that the wind approximation underestimates gas exchange coefficients during low‐wind conditions.

Unraveling the Contribution of Turbulence and Bubbles to Air-Water Gas Exchange in Running Waters.

Quantifying air‐water gas exchange is critical for estimating greenhouse gas fluxes and metabolism in aquatic ecosystems. In high‐energy streams, the gas exchange rate k is poorly constrained, due to an incomplete understanding of turbulence and bubble contributions to k. We performed a flume experiment with air bubble additions to evaluate the combined effects of turbulence and bubbles on k for helium, argon, xenon, and methane. We created contrasting hydraulic conditions by varying channel slope, bed roughness, water discharge, and bubble flux. We found that k increased from 1–4 to 17–66 m d−1 with increases in turbulence and bubble flux metrics. Mechanistic models that explicitly account for these metrics, as well as gas diffusivity and solubility, agreed well with the data and indicated that bubble‐mediated gas exchange accounted for 64–93% of k. Bubble contributions increased with bubble flux but were independent of gas type, as bubbles did not equilibrate with the water. This was evident through modeled bubble life and equilibration times inferred from bubble size distributions obtained from underwater sound spectra. Sound spectral properties correlated well with turbulence and bubble flux metrics. Our results demonstrate that (a) mechanistic models can be applied to separate free surface‐ and bubble‐mediated gas exchange in running waters, (b) bubble life and equilibration times are critical for accurate scaling of k between different gases, and (c) ambient sound spectra can be used to approximate contributions of turbulence and bubbles.

Exploring source footprint of Organophosphate esters in the Bohai Sea, China: Insight from temporal and spatial variabilities in the atmosphere from June 2014 to May 2019.

Organophosphate esters (OPEs) are still produced and used in large quantities in the world-wide, and the environmental burden and behavior have generated widespread concern, especially in some large-scale waterbodies. This study conducted a comprehensive assessment on the temporal and spatial variabilities and budget of OPEs to trace the source for the Bohai Sea (BS), based on a 5-year seasonal monitoring campaign (June 2014 to May 2019) of 12 atmospheric sites around the BS and our previous studies. The average concentration of Σ10OPEs in atmosphere during the sampling period was 7.65±6.42ngm-3, and chlorinated OPEs were the major compounds. The Seasonal-Trend decomposition procedure based on Loess (STL) analyzed that during the 5-year sampling period, the atmospheric concentrations of Σ10OPEs had a slightly increasing trend with a rate of+0.092ngm-3 yr-1, and the seasonal concentrations had a distinct seasonal distribution. The highest concentration of Σ10OPEs was observed at the sampling site of Dalian, followed by Tianjin, Yantai, and Beihuangcheng. The estimation of the fugacity ratios and air-water gas exchange fluxes established that the concentration levels of two major components of chlorinated OPEs (tris-(2-chloroethyl) phosphate (TCEP) and tris-(1-chloro-2-propyl) phosphate (TCPP)) in the atmosphere were dominated by their volatilization from BS's seawater (1.24±0.46tyr-1 for TCEP and 5.15±2.15tyr-1 for TCPP), with 73% deriving from the coastal seawater. The budget assessment suggested that the volatile fluxes of TCEP and TCPP accounted for 8% and 29% of their storages (15.6±5.32t for TCEP and 17.6±6.70t for TCPP) in the BS seawater, which were mainly contributed by continental river input (20% for TCEP and 42% for TCPP). The efforts indicated that river inputs of TCEP and TCPP needed to be paid more attention for the improvement of environmental quality of the BS.

A Review of Quantifying pCO2 in Inland Waters with a Global Perspective: Challenges and Prospects of Implementing Remote Sensing Technology

The traditional field-based measurements of carbon dioxide (pCO2) for inland waters are a snapshot of the conditions on a particular site, which might not adequately represent the pCO2 variation of the entire lake. However, these field measurements can be used in the pCO2 remote sensing modeling and verification. By focusing on inland waters (including lakes, reservoirs, rivers, and streams), this paper reviews the temporal and spatial variability of pCO2 based on published data. The results indicate the significant daily and seasonal variations in pCO2 in lakes. Rivers and streams contain higher pCO2 than lakes and reservoirs in the same climatic zone, and tropical waters typically exhibit higher pCO2 than temperate, boreal, and arctic waters. Due to the temporal and spatial variations of pCO2, it can differ in different inland water types in the same space-time. The estimation of CO2 fluxes in global inland waters showed large uncertainties with a range of 1.40–3.28 Pg C y−1. This paper also reviews existing remote sensing models/algorithms used for estimating pCO2 in sea and coastal waters and presents some perspectives and challenges of pCO2 estimation in inland waters using remote sensing for future studies. To overcome the uncertainties of pCO2 and CO2 emissions from inland waters at the global scale, more reliable and universal pCO2 remote sensing models/algorithms will be needed for mapping the long-term and large-scale pCO2 variations for inland waters. The development of inverse models based on dissolved biogeochemical processes and the machine learning algorithm based on measurement data might be more applicable over longer periods and across larger spatial scales. In addition, it should be noted that the remote sensing-retrieved pCO2/the CO2 concentration values are the instantaneous values at the satellite transit time. A major technical challenge is in the methodology to transform the retrieved pCO2 values on time scales from instant to days/months, which will need further investigations. Understanding the interrelated control and influence processes closely related to pCO2 in the inland waters (including the biological activities, physical mixing, a thermodynamic process, and the air–water gas exchange) is the key to achieving remote sensing models/algorithms of pCO2 in inland waters. This review should be useful for a general understanding of the role of inland waters in the global carbon cycle.

Aquatic Eddy Covariance: The Method and Its Contributions to Defining Oxygen and Carbon Fluxes in Marine Environments

Aquatic eddy covariance (AEC) is increasingly being used to study benthic oxygen (O2) flux dynamics, organic carbon cycling, and ecosystem health in marine and freshwater environments. Because it is a noninvasive technique, has a high temporal resolution (∼15 min), and integrates over a large area of the seafloor (typically 10-100 m2), it has provided new insights on the functioning of aquatic ecosystems under naturally varying in situ conditions and has given us more accurate assessments of their metabolism. In this review, we summarize biogeochemical, ecological, and biological insightsgained from AEC studies of marine ecosystems. A general finding for all substrates is that benthic O2 exchange is far more dynamic than earlier recognized, and thus accurate mean values can only be obtained from measurements that integrate over all timescales that affect the local O2 exchange. Finally, we highlight new developments of the technique, including measurements of air-water gas exchange and long-term deployments.

Spatial distribution and air−water exchange of organophosphate esters in the lower Great Lakes

Organophosphate esters (OPEs) have been detected at elevated concentrations in the Great Lakes region, dwarfing other flame retardants, such as polybrominated diphenylethers (PBDEs), as chemicals of emerging concern (CECs). This prompted us to deploy polyethylene (PE) passive samplers in air and water column of the lower Great Lake region (Lake Erie and Lake Ontario) to detect gaseous and dissolved OPEs, evaluate their occurrence and spatial distribution, and estimate their air-water gas exchange fluxes. The median concentration of the total dissolved and gaseous phase OPEs detected (Σ9OPEs) were 95 ng L−1 and 404 pg m−3, respectively, during April–November 2014. Gaseous and dissolved concentrations were dominated by chlorinated compounds, in particular (tris(2-chloroethyl) phosphate (TCEP) and tris(2-chloroisopropyl) phosphate (TCPP), while tri-n-butyl phosphate (TnBP) was the dominant non-chlorinated OPEs in both media. Decreasing concentration gradients from shoreline/nearshore to offshore sites for both gaseous and aqueous OPEs reflect anthropogenic influence from the adjacent rural and urban regions. The partial dependence of gaseous OPEs on temperature indicate the importance of volatilization from local sources, fresh emissions as well as advection from distant sources to air. Almost all OPEs underwent net gas-phase deposition to the lakes, dominated by TCEP and TCPPs with median fluxes of −3980 ng/m2/day and −1320 ng/m2/day; the exception was TnBP, which underwent volatilization with the median fluxes of 1980 ng/m2/day. For all air-water pairs, the gaseous diffusive fluxes were 2–4 orders of magnitude greater than the estimated particle dry deposition fluxes.

Occurrence, distribution, and fate of polychlorinated biphenyls (PCBs) in multiple coral reef regions from the South China Sea: A case study in spring-summer

Concentrations of 24 PCBs were simultaneously determined in air, seawater, and corals from the South China Sea (SCS) in spring-summer for understanding their distribution and fate in multiple coral reef regions. The ∑24PCBs (6.8–294 pg m−3) were mainly influenced by air mass origins in air samples. Southeast monsoon caused higher ∑24PCBs (mean: 61 pg m−3) than the southwest (mean: 19 pg m−3). ∑24PCBs in seawater (2.8–7.7 pg L−1) was equally distributed from the nearshore to offshore regions under low flow velocity and swirling state of the ocean current. Significantly higher air-water gas exchange deposition fluxes (3.5–29 ng m−2 d−1) than dry deposition (0.14–2.0 ng m−2 d−1) indicated that diffusion of PCBs from the atmosphere into seawater was the governing process in the SCS. PCBs in corals are strong bioaccumulative (Log BAFs: 2.49–7.86). The distribution of ∑24PCBs in coral tissues (nd – 42.9 ng g−1 dw) was significantly correlated with that in air samples, suggesting PCBs may have a migration pattern of atmosphere-ocean-corals in the SCS. Compared to a previous risk assessment study, the ∑24PCBs in corals from the SCS may cause potential risks to corals by reducing zooxanthellae density, chlorophyll-a (Chl-a) and chlorophyll-C2 (ChlC2) in corals.

Turbulence in a small boreal lake: Consequences for air-water gas exchange.

The hydrodynamics within small boreal lakes have rarely been studied, yet knowing whether turbulence at the air–water interface and in the water column scales with metrics developed elsewhere is essential for computing metabolism and fluxes of climate‐forcing trace gases. We instrumented a humic, 4.7 ha, boreal lake with two meteorological stations, three thermistor arrays, an infrared (IR) camera to quantify surface divergence, obtained turbulence as dissipation rate of turbulent kinetic energy (ε) using an acoustic Doppler velocimeter and a temperature‐gradient microstructure profiler, and conducted chamber measurements for short periods to obtain fluxes and gas transfer velocities (k). Near‐surface ε varied from 10−8 to 10−6 m2 s−3 for the 0–4 m s−1 winds and followed predictions from Monin–Obukhov similarity theory. The coefficient of eddy diffusivity in the mixed layer was up to 10−3 m2 s−1 on the windiest afternoons, an order of magnitude less other afternoons, and near molecular at deeper depths. The upper thermocline upwelled when Lake numbers (L N) dropped below four facilitating vertical and horizontal exchange. k computed from a surface renewal model using ε agreed with values from chambers and surface divergence and increased linearly with wind speed. Diurnal thermoclines formed on sunny days when winds were < 3 m s−1, a condition that can lead to elevated near‐surface ε and k. Results extend scaling approaches developed in the laboratory and for larger water bodies, illustrate turbulence and k are greater than expected in small wind‐sheltered lakes, and provide new equations to quantify fluxes.

Natural and Anthropogenic Drivers of Acidification in Large Estuaries.

Oceanic uptake of anthropogenic carbon dioxide (CO2) from the atmosphere has changed ocean biogeochemistry and threatened the health of organisms through a process known as ocean acidification (OA). Such large-scale changes affect ecosystem functions and can have impacts on societal uses, fisheries resources, and economies. In many large estuaries, anthropogenic CO2-induced acidification is enhanced by strong stratification, long water residence times, eutrophication, and a weak acid-base buffer capacity. In this article, we review how a variety of processes influence aquatic acid-base properties in estuarine waters, including coastal upwelling, river-ocean mixing, air-water gas exchange, biological production and subsequent aerobic and anaerobic respiration, calcium carbonate (CaCO3) dissolution, and benthic inputs. We emphasize the spatial and temporal dynamics of partial pressure of CO2 (pCO2), pH, and calcium carbonate mineral saturation states. Examples from three large estuaries-Chesapeake Bay, the Salish Sea, and Prince William Sound-are used to illustrate how natural and anthropogenic processes and climate change may manifest differently across estuaries, as well as the biological implications of OA on coastal calcifiers.

Air–water gas exchange in lakes and reservoirs measured from a moving platform by underwater eddy covariance

AbstractAir–water exchange rates of gasses, such as O2, CO2, and CH4, are widely used in ecosystem studies of lakes and reservoirs, but their magnitudes are often difficult to assess. In this proof‐of‐concept study, we measured gas exchange by underwater eddy covariance in such lentic systems from a moving platform. We used an Acoustic Doppler Velocimeter and a fast‐responding O2‐temperature sensor mounted in the bow of a boat to measure water velocity, O2 concentration, and temperature below the air–water interface (~ 10 cm) while the boat was propelled at constant speed (~ 25 cm s−1) by an electric trolling motor. Fluxes of O2 and heat across the air–water interface and standard gas exchange coefficients, k600, were calculated for every 3 min of traveled distance (~ 45 m). All deployments were done under calm low‐wind conditions where empirical relationships for k600 are most uncertain. Deployment averages of k600 ranged from 0.070 to 0.39 m d−1 and were strongly correlated with both the heat flux and the water temperature. In one deployment, a &gt; 20% variation in mean water column O2 concentration was measured along a 1 km long transect of a reservoir. Given the typical size of O2 concentration differences over the air–water interface that drive gas exchange, such lateral variations can, even at a near‐constant exchange coefficient, result in highly biased whole‐ecosystem fluxes if based on stationary single‐point O2 measurements. “Mobile” aquatic eddy covariance measurements enable quantification of gas exchange in lakes and reservoirs under true in situ conditions and with high temporal and spatial resolution.

Carbon Dioxide Fluxes to the Atmosphere From Waters Within Flooded Forests in the Amazon Basin

AbstractInundated tropical forests are underrepresented in analyses of the global carbon cycle and constitute 80% of the surface area of aquatic environments in the lowland Amazon basin. Diel variations in CO2 concentrations and exchanges with the atmosphere were investigated from August 2014 to September 2016 in two flooded forests sites with different wind exposure within the central Amazon floodplain (3°23′S, 60°18′W). CO2 profiles and estimates of air–water gas exchange were combined with ancillary environmental measurements. Surface CO2 concentrations ranged from 19 to 329 μM, CO2 fluxes ranged from −0.8 to 55 mmol m−2 hr−1 and gas transfer velocities ranged from 0.2 to 17 cm hr−1. CO2 concentrations and fluxes were highest during the high water period. CO2 fluxes were three times higher at a site with more wind exposure (WE) compared to one with less exposure (WP). Emissions were higher at the WP site during the day, whereas they were higher at night at the WE site due to vertical mixing. CO2 concentrations and fluxes were lower at the W P site following an extended period of exceptionally low water. The CO2 flux from the water in the flooded forest was about half of the net primary production of the forest estimated from the literature. Mean daily fluxes measured in our study (182 ± 247 mmol m−2d−1) are higher than or similar to the few other measurements in waters within tropical and subtropical flooded forests and highlight the importance of flooded forests in carbon budgets.

Considering atmospheric N2O dynamic in SWAT model avoids the overestimation of N2O emissions in river networks

Modeling studies have focused on N2O emissions in temperate rivers under static atmospheric N2O (N2Oairc), with cold temperate river networks under dynamic N2Oairc receiving less attention. To address this knowledge and methodological gap, the dissolved N2O concentration (N2Odisc) and N2Oairc algorithms were integrated with an air-water gas exchange model (FN2O) into the SWAT (Soil and Water Assessment Tool). This new model (SWAT-FN2O) allows users to simulate daily riverine N2O emissions under dynamic atmospheric N2O. The spatiotemporal fluctuations in the riverine N2O emissions was simulated and its response to the static and dynamic atmospheric N2O were analyzed in a middle-high latitude agricultural watershed in northeastern China. The results show that the SWAT-FN2O model is a useful method for capturing the hotspots in riverine N2O emissions. The model showed strong riverine N2O absorption and weak N2O emissions from September to February, which acted as a sink for atmospheric N2O in this cold temperate area. High N2O emissions occurred from April to July, which accounted for 83.34% of the yearly emissions. Spatial analysis indicated that the main stream and its tributary could contribute 302.3–1043.7 and 41.5–163.4 μg N2O/(m2·d) to the total riverine N2O emissions (15.02 t/a), respectively. The riverine N2O emissions rates in the subbasins dominated by forests and paddy fields were lower than those in the subbasins dominated by arable and residential land. Riverine N2O emissions can be overestimated under the static atmospheric N2O rather than under the increasing atmospheric N2O. This overestimation has increased from 1.52% to 23.97% from 1990 to 2016 under the static atmospheric N2O. The results of this study are valuable for water quality and future climate change assessments that aim to protect aquatic and atmospheric environments.

Net heterotrophy and carbonate dissolution in two subtropical seagrass meadows

Abstract. The net ecosystem productivity (NEP) of two seagrass meadows within one of the largest seagrass ecosystems in the world, Florida Bay, was assessed using direct measurements over consecutive diel cycles during a short study in the fall of 2018. We report significant differences between NEP determined by dissolved inorganic carbon (NEPDIC) and by dissolved oxygen (NEPDO), likely driven by differences in air–water gas exchange and contrasting responses to variations in light intensity. We also acknowledge the impact of advective exchange on metabolic calculations of NEP and net ecosystem calcification (NEC) using the “open-water” approach and attempt to quantify this effect. In this first direct determination of NEPDIC in seagrass, we found that both seagrass ecosystems were net heterotrophic, on average, despite large differences in seagrass net above-ground primary productivity. NEC was also negative, indicating that both sites were net dissolving carbonate minerals. We suggest that a combination of carbonate dissolution and respiration in sediments exceeded seagrass primary production and calcification, supporting our negative NEP and NEC measurements. However, given the limited spatial (two sites) and temporal (8 d) extent of this study, our results may not be representative of Florida Bay as a whole and may be season-specific. The results of this study highlight the need for better temporal resolution, accurate carbonate chemistry accounting, and an improved understanding of physical mixing processes in future seagrass metabolism studies.

Changes in gross oxygen production, net oxygen production, and air-water gas exchange during seasonal ice melt in Whycocomagh Bay, a Canadian estuary in the Bras d'Or Lake system

Abstract. Sea ice is an important control on gas exchange and primary production in polar regions. We measured net oxygen production (NOP) and gross oxygen production (GOP) using near-continuous measurements of the O2∕Ar gas ratio and discrete measurements of the triple isotopic composition of O2, during the transition from ice-covered to ice-free conditions, in Whycocomagh Bay, an estuary in the Bras d'Or Lake system in Nova Scotia, Canada. The volumetric gross oxygen production was 5.4+2.8-1.6 mmol O2 m−3 d−1, similar at the beginning and end of the time series, and likely peaked at the end of the ice melt period. Net oxygen production displayed more temporal variability and the system was on average net autotrophic during ice melt and net heterotrophic following the ice melt. We performed the first field-based dual tracer release experiment in ice-covered water to quantify air–water gas exchange. The gas transfer velocity at &gt;90 % ice cover was 6 % of the rate for nearly ice-free conditions. Published studies have shown a wide range of results for gas transfer velocity in the presence of ice, and this study indicates that gas transfer through ice is much slower than the rate of gas transfer through open water. The results also indicate that both primary producers and heterotrophs are active in Whycocomagh Bay during spring while it is covered in ice.

Listening to air–water gas exchange in running waters

AbstractAir–water gas exchange velocities (k) are critical components of many biogeochemical and ecological process studies in aquatic systems. However, their high spatiotemporal variability is difficult to capture with traditional methods, especially in turbulent flow. Here, we investigate the potential of sound spectral analysis to infer k in running waters, based on the rationale that both turbulence and entrained bubbles drive gas exchange and cause a characteristic sound. We explored the relationship between k and sound spectral properties using laboratory experiments and field observations under a wide range of turbulence and bubble conditions. We estimated k using flux chamber measurements of CO2 exchange and recorded sound above and below the water surface by microphones and hydrophones, respectively. We found a strong influence of turbulence and bubbles on sound pressure levels (SPLs) at octave bands of 31.5 Hz and 1000 Hz, respectively. The difference in SPLs at these bands and background noise bands showed a linear correlation with k both in the laboratory (R2 = 0.93–0.99) and in the field (median R2 = 0.42–0.90). Underwater sound indices outperformed aerial sound indices in general, and indices based on hydraulic parameters in particular, in turbulent and bubbly surface flow. The results highlight the unique potential of acoustic techniques to predict k, isolate mechanisms, and improve the spatiotemporal coverage of k estimates in bubbly flow.

Methane and nitrous oxide temporal and spatial variability in two midwestern USA streams containing high nitrate concentrations

Concentrations and emissions of greenhouse gases CO2, CH4, and N2O commonly are examined individually in aquatic environments in which each is expected to be relatively important; however, their co-occurrence and dynamic interactions in fluvial settings could provide important information about their controlling biogeochemical processes and potential contributions to global climate change. Spatial and temporal variability of CH4, N2O, and CO2 concentrations were measured from June 1999 to September 2003 in two nitrate-rich (40–1200 μM) streams draining agricultural land in the midwestern USA that differed ~13-fold in flow. Seasonal (biweekly), diel (hourly), and transport-oriented (reach-scale) sampling approaches were compared. Dissolved gas concentrations exceeded atmospheric equilibrium values up to 700- and 16-fold, for CH4 and N2O, respectively. Mean concentrations were higher in the larger stream than in the smaller stream. In both streams, CH4 emissions were generally higher in summer-fall and negatively correlated with flow and NO3− concentration while N2O emissions were generally higher in winter/spring and positively correlated with flow and NO3−. In the small stream, diel variations in the concentrations, emissions, and isotopic compositions of CH4, N2O, and NO2− resulted from diel variations in sources, sinks, and air-water gas exchange velocities. Seasonal mean total (CH4 + N2O) area-normalized emission rates, expressed as CO2 warming potential equivalents, were similar for the two streams, but the total reach-scale emission rate for the larger stream, including CO2, was about 2.9 times that of the smaller stream (131.6 vs 46.0 kg CO2 equivalents km−1 day−1, respectively). The CH4 contribution to this flux was 9–28%, despite the relatively high NO3− and O2 concentrations in the streams, indicating contributions from upwelling groundwater or reactions in streambed sediment.

Precise determination of Ar, Kr and Xe isotopic fractionation due to diffusion and dissolution in fresh water

Dissolved noble gases are ideal conservative tracers of physical processes in the Earth system due to their chemical and biological inertness. Although bulk concentrations of dissolved Ar, Kr, and Xe are commonly measured to constrain physical models of atmosphere, ocean, and terrestrial hydrosphere processes, stable isotope ratios of these gases (e.g. 136Xe/129Xe) are seldom used because of low signal-to-noise ratios. Here we present the first results from a new method of dissolved gas sampling, extraction and analysis that permits measurement of stable Ar, Kr, and Xe isotope ratios at or below ∼5 per meg amu−1 precision (1σ), two orders-of-magnitude below conventional Kr and Xe isotopic measurements. This gain in precision was achieved by quantitative extraction and subsequent purification of dissolved noble gases from 2-L water samples via helium sparging and viscous dual-inlet isotope ratio mass spectrometry. We have determined the solubility fractionation factors (αsol) for stable Ar, Kr, and Xe isotope ratios between ∼2 and 20°C via laboratory equilibration experiments. We have also conducted temperature-controlled air-water gas exchange experiments to estimate the kinetic fractionation factors (αkin) of these isotope ratios. We find that both αsol and αkin, normalized by isotopic mass difference (Δm), decrease in magnitude with atomic number but are proportional to Δm for isotope ratios of the same element. With the new ability for high precision isotopic measurements, we suggest that dissolved Kr and Xe isotope ratios in groundwater represent a promising, novel geochemical tool with important applications for groundwater modeling, water resource management, and paleoclimate.