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Small headwater streams are recognized for intense outgassing to the atmosphere of climate‐relevant carbon dioxide (CO2) and methane (CH4). Though these headwaters are markedly oversaturated for both CO2 and CH4, the origins and controls over the fate of these two carbon‐gases are still poorly constrained, especially for the stronger greenhouse gas CH4. Here, by measuring stream‐based production of CO2 and CH4, concurrently with their rates of outgassing to the atmosphere, we identify distinct biophysical control mechanisms for each gas. We show that while CO2 is largely imported from the catchment in proportion to discharge, CO2 outgassing can be modulated by in‐stream metabolism to offset outgassing by up to 30% in spring and summer. In contrast, CH4 shows a non‐linear response to seasonal changes in discharge and is predominantly produced in the streambed in relation to sediment type. Further, once released from the streambed, outgassing of CH4 at the surface and flow‐driven dilution occur far more rapidly than biological methane oxidation and CH4 leaves the water largely unaltered by biology. Incorporating the intense carbon cycling of headwater streams into the global carbon cycle will require distinct parameterizations for each carbon gas in Earth system models., Plain Language Summary: There is growing interest in the global carbon cycle and how carbon is transformed in the landscape into the greenhouse gases carbon dioxide (CO2) and methane–with methane being by far the more potent than CO2. Streams and rivers are recognized hotspots of carbon cycling in the landscape, commonly harboring large amounts of CO2 and methane–yet what controls either gas in streams is not fully understood. Without that understanding, we cannot predict how carbon cycling will respond to climate change or to other human alteration of the landscape. Here we researched different components of the carbon cycle in streams to show that each gas is influenced by quite distinct “biophysical” control mechanisms. While CO2 in streams results largely from physical run‐off from the land, once in a stream it can be changed by the stream biology that ebbs and flows with the seasons. Contrastingly, methane is largely created by biology within the streambed itself but once released into the wider stream that methane is then dispersed by the physical forces of stream flow. Put more simply, CO2 is physically carried to the stream to then be altered by biology, whereas as methane is borne from biology in the stream, to then be physically carried away., Key Points: There are different controls on the outgassing of the greenhouse gases carbon dioxide and methane in streams. Carbon dioxide results largely from physical run‐off from the land and is then altered in stream by biology depending on season. In contrast, methane is created in the streambed but once released to the stream is then dispersed by the physical forces of stream flow., Natural Environment Research Council (NERC) http://dx.doi.org/10.13039/501100000270, Deutsche Forschungsgemeinschaft (DFG) http://dx.doi.org/10.13039/501100001659, EC | H2020 | H2020 Priority Excellent Science | H2020 European Research Council (ERC) http://dx.doi.org/10.13039/100010663, FNU, Danish National Research Foundation

Headwater streams are important in the carbon cycle and there is a need to better parametrize and quantify exchange of carbon-relevant gases. Thus, we characterized variability in the gas exchange coefficient (k2) and dissolved oxygen (O2) gas transfer velocity (k) in two lowland headwaters of the River Avon (UK). The traditional one-station open-water method was complemented by in situ quantification of riverine sources and sinks of O2 (i.e., groundwater inflow, photosynthesis, and respiration in both the water column and benthic compartment) enabling direct hourly estimates of k2 at the reach–scale (~ 150 m) without relying on the nighttime regression method. Obtained k2 values ranged from 0.001 h−1 to 0.600 h−1. Average daytime k2 were a factor two higher than values at night, likely due to diel changes in water temperature and wind. Temperature contributed up to 46% of the variability in k on an hourly scale, but clustering temperature incrementally strengthened the statistical relationship. Our analysis suggested that k variability is aligned with dominant temperature trends rather than with short-term changes. Similarly, wind correlation with k increased when clustering wind speeds in increments correspondent with dominant variations (1 m s−1). Time scale is thus an important consideration when resolving physical drivers of gas exchange. Mean estimates of k600 from recent parametrizations proposed for upscaling, when applied to the settings of this study, were found to be in agreement with our independent O2 budget assessment (within < 10%), adding further support to the validity of upscaling efforts aiming at quantifying large-scale riverine gas emissions.

Most applications of laser induced fluorescence (LIF) for dissolved oxygen (DO) imaging in flowing water are based on luminescence intensity measurements of a dissolved indicator. A major limitation for applying the technique in the bottom boundary layer (BBL) is the sorption of the luminescent dye to organic surfaces at the sediment. Many sediment and soil studies have used planar optodes on transparent foils as an imaging technique for observing concentration distributions across the sediment-water interface. The presence of the foil, however, is restricting the free flow and therewith the DO concentration above the sediment surface. In this study, we applied the phosphorescence lifetime LIF (tau LIF) technique in combination with nanoparticles coated with platinum complexes as DO indicators. By using a planar laser light sheet for fluorescence excitation, the three-dimensional flow field around the sampling area is not restricted. In contrast to the intensity-based LIF technique, this method extracts the lifetime of the luminescence by evaluating the exponential decrease of the phosphorescence intensity after a short excitation light pulse. The method is therefore independent of dye concentration and is not affected by spatial inhomogeneities of the excitation light intensity. We applied the technique to visualize the burrow-ventilation activity of the tube-dwelling Chironomus plumosus larvae. Sequences of the two-dimensional DO concentration distributions showed the intermittent outburst of highly-depleted plumes from the outlet of the burrows, which mixed rapidly with the ambient oxygen-rich water.

We suggest the application of a flux parameterization commonly used over terrestrial areas for calculation of CO2 fluxes over sea ice surfaces. The parameterization is based on resistance analogy. We present a concept for parameterization of the CO2 fluxes over sea ice suggesting to use properties of the atmosphere and sea ice surface that can be measured or calculated on a routine basis. Parameters, which can be used in the conceptual model, are analysed based on data sampled from a seasonal fast-ice area, and the different variables influencing the exchange of CO2 between the atmosphere and ice are discussed. We found the flux to be small during the late winter with fluxes in both directions. Not surprisingly we find that the resistance across the surface controls the fluxes and detailed knowledge of the brine volume and carbon chemistry within the brines as well as knowledge of snow cover and carbon chemistry in the ice are essential to estimate the partial pressure of pCO2 and CO2 flux. Further investigations of surface structure and snow cover and driving parameters such as heat flux, radiation, ice temperature and brine processes are required to adequately parameterize the surface resistance.

A major issue of Arctic marine science is to understand whether the Arctic Ocean is, or will be, a source or sink for air–sea CO2 exchange. This has been complicated by the recent discoveries of ikaite (a polymorph of CaCO3·6H2O) in Arctic and Antarctic sea ice, which indicate that multiple chemical transformations occur in sea ice with a possible effect on CO2 and pH conditions in surface waters. Here, we report on biogeochemical conditions, microscopic examinations and x-ray diffraction analysis of single crystals from a melting 1.7 km2 (0.5–1 m thick) drifting ice floe in the Fram Strait during summer. Our findings show that ikaite crystals are present throughout the sea ice but with larger crystals appearing in the upper ice layers. Ikaite crystals placed at elevated temperatures disintegrated into smaller crystallites and dissolved. During our field campaign in late June, melt reduced the ice floe thickness by 0.2 m per week and resulted in an estimated 3.8 ppm decrease of pCO2 in the ocean surface mixed layer. This corresponds to an air–sea CO2 uptake of 10.6 mmol m−2 sea ice d−1 or to 3.3 ton km−2 ice floe week−1. This is markedly higher than the estimated primary production within the ice floe of 0.3–1.3 mmol m−2 sea ice d−1. Finally, the presence of ikaite in sea ice and the dissolution of the mineral during melting of the sea ice and mixing of the melt water into the surface oceanic mixed layer accounted for half of the estimated pCO2 uptake.

Annual air–sea exchange of CO2 in Young Sound, NE Greenland was estimated using pCO2 surface-water measurements during summer (2006–2009) and during an ice-covered winter 2008. All surface pCO2 values were below atmospheric levels indicating an uptake of atmospheric CO2. During sea ice formation, dissolved inorganic carbon (DIC) content is reduced causing sea ice to be under saturated in CO2. Approximately 1% of the DIC forced out of growing sea ice was released into the atmosphere while the remaining 99% was exported to the underlying water column. Sea ice covered the fjord 9 months a year and thereby efficiently blocked air–sea CO2 exchange. During sea ice melt, dissolution of CaCO3 combined with primary production and strong stratification of the water column acted to lower surface-water pCO2 levels in the fjord. Also, a large input of glacial melt water containing geochemically reactive carbonate minerals may contribute to the low surface-water pCO2 levels. The average annual uptake of atmospheric CO2 was estimated at 2.7 mol CO2 m-2 yr-1 or 32 g C m-2 yr-1 for the study area, which is lower than estimates from the Greenland Sea. Variability in duration of sea ice cover caused significant year-to-year variation in annual gas exchange.DOI: 10.1111/j.1600-0889.2011.00540.x

We have compared 14 different sediment incubation chambers, most of them were used on bottom landers. Measurements of mixing time, pressure gradients at the bottom and Diffusive Boundary Layer thickness (DBL) were used to describe the hydrodynamic properties of the chambers and sediment-water solute fluxes of silicate (34 replicates) and oxygen (23 replicates) during three subsequently repeated incubation experiments on a homogenized, macrofauna-free sediment. The silicate fluxes ranged from 0.24 to 1.01 mmol m(-2) day(-1) and the oxygen fluxes from 9.3 to 22.6 mmol m(-2) day(-1). There was no statistically significant correlation between measured fluxes and the chamber design or between measured fluxes and hydrodynamic settings suggesting that type of chamber was not important in these flux measurements. For verification of sediment homogeneity, 61 samples of meiofauna were taken and identified to major taxa. In addition. 13 sediment cores were collected. sectioned into 5-10-mm slices and separated into pore water and solid phase. The pore water profiles of disolved silicale were used to calculate diffusive fluxes of silicate. These fluxes ranged from 0.63 to 0.87 mmol m(-2) day(-1). All of the collected sediment parameters indicated that the sediment homogenization process had been satisfactorily accomplished, hydrodynamic variations inside and between chambers are a reflection of the chamber design and the stirring device, In general. pump stirrers with diffusers give a more even distribution of bottom currents and DBL thicknesses than paddle wheel-type stirrers, Most chambers display no or low static differential pressures when the water is mixed at rates of normal Use, Consequently. there is a low risk of creating stirrer induced pressure effects on the measured fluxes. Centrally placed stirrers are preferable to off-center placed stirrers which are more difficult to map and do not seem to give any hydrodynamic advantages, A vertically rotating stirrer gives about five times lower static differential pressures at the same stirring, speed as the same stirrer mounted horizontally If the aim is to simulate or mimic resuspension at high flow velocities, it cannot be satisfactorily done in a chamber using it horizontal (standing) rotating impeller (as is the case for most chambers in use) due to the creation of unnatural conditions. i,e. large static differential pressures and pre-mature resuspension at certain locations in the chamber.

Benthic communities and benthic mineralization were studied in two shallow coastal regions of New Zealand: Tasman Bay, a possible future site for mussel farm development, and Beatrix Bay, which already hosts several longline mussel farms.