Spatio-temporal variability and controls on methane and nitrous oxide in the Guadalquivir Estuary, Southwestern Europe

Estuaries are significant methane (CH4) and nitrous oxide (N2O) emitters, although dynamics of both greenhouse gases in these ecosystems are regulated by complex processes. In this work, we aimed at characterizing the spatio-temporal distribution of CH4 and N2O in the Guadalquivir river estuary (SW Spain), the southernmost European estuary. During eight sampling cruises conducted between 2016 and 2017, surface water CH4 and N2O concentrations were measured along the salinity gradient of the estuary by using static-head space equilibration gas chromatography. The CH4 and N2O saturation ranges over the estuarine transect were 520–30,800% (average 2285%) and 40–390% (average 183%), respectively and air–water fluxes ranged from 13 to 1000 µmol m− 2 day− 1(average 66.2 µmol m− 2 day− 1) for CH4 and from − 7 to 35 µmol m− 2 day− 1 (average 8.5 µmol m− 2 day− 1) for N2O. A slight increase in the emissions was detected upstream and no seasonal trends were observed. Mixing between freshwater and oceanic waters influenced biogeochemistry of estuarine waters, affecting CH4 and N2O fluxes. In order to identify potential sources of CH4 and N2O, biogeochemical parameters involved in the formation pathways of both gases, such as salinity, dissolved oxygen, nutrients and organic matter were analyzed. Results suggested that sulfate inhibition and microbial oxidation played a relevant role in dissolved CH4 accumulation in the water column whereas associations found between N2O, nitrate and oxygen indicated that nitrification was a major source of this gas. Therefore, the influence of the tidal-fluvial interaction on ecosystem metabolism regulates trace gas dynamics in the Guadalquivir estuary.This research was funded by the project 1539/2015 from the Spanish Ministry for Agriculture, Food and Environment.Peer reviewe

Methodology for Measuring Greenhouse Gas Emissions from Agricultural Soils Using Non-isotopic Techniques

Several approaches exist for measuring greenhouse gases (GHGs), mainly CO2, N2O, and CH4, from soil surfaces. The principle methods that are used to measure GHG from agricultural sites are chamber-based techniques. Both open and closed chamber techniques are in use ; however, the majority of field applications use closed chambers. The advantages and disadvantages of different chamber techniques and the principal steps of operation are described. An important part of determining the quality of the flux measurements is the storage and the transportation of the gas samples from the field to the laboratory where the analyses are carried out. Traditionally, analyses of GHGs are carried out via gas chromatographs (GCs). In recent years, optical analysers are becoming increasingly available ; these are user-friendly machines and they provide a cost-effective alternative to GCs. Another technique which is still under development, but provides a potentially superior method, is Raman spectroscopy. Not only the GHGs, but also N2, can potentially be analysed if the precision of these techniques is increased in future development. An important part of this chapter deals with the analyses of the gas concentrations, the calculation of fluxes, and the required safety measures. Since non-upland agricultural lands (i.e. flooded paddy soils) are steadily increasing, a section is devoted to the specificities of GHG measurements in these ecosystems. Specialised techniques are also required for GHG measurements in aquatic systems (i.e. rivers), which are often affected by the transfer of nutrients from agricultural fields and therefore are an important indirect source of emission of GHGs. A simple, robust, and more precise method of ammonia (NH3) emission measurement is also described