First-Order Chemistry in the Surface-Flux Layer

We have discussed the behavior of a non-conserved scalar in the stationary, horizontally homogeneous, neutral surface-flux layer and, on the basis of conventional second-order closure, derived analytic expressions for flux and for mean concentration of a gas, subjected to a first-order removal process. The analytic flux solution showed a clear deviation from the constant flux, characterizing a conserved scalar in the surface-flux layer. It decreases with height and is reduced by an order of magnitude of the surface flux at a height equal to about the typical mean distance a molecule can travel before destruction. The predicted mean concentration profile, however, shows only a small deviation from the logarithmic behavior of a conserved scalar. The solution is consistent with assuming a flux-gradient relationship with a turbulent diffusivity corrected by the Damköhler ratio, the ratio of a characteristic turbulent time scale and the scalar mean lifetime. We show that if we use only first-order closure and neglect the effect of the Damköhler ratio on the turbulent diffusivity we obtain another analytic solution for the profiles of the flux and the mean concentration which, from an experimental point of view, is indistinguishable from the first analytic solution. We have discussed two cases where the model should apply, namely NO which, by night, is irreversibly destroyed by interaction with mainly O₃ and the radioactive ²²⁰Rn. Only in the last case was it possible to find data to shed light on the validity of our predictions. The agreement seemed such that a falsification of our model was impossible. It is shown how the model can be used to predict the surface flux of ²²⁰Rn from measured concentration profiles.     

Spatial and temporal dynamics of nitrogen exchange in an upwelling reach of a groundwater-fed river and potential response to perturbations changing rainfall patterns under UK climate change scenarios

We report the complex spatial and temporal dynamics of hyporheic exchange flows (HEFs) and nitrogen exchange in an upwelling reach of a 200 m groundwater-fed river. We show how research combining hydrological measurement, geophysics and isotopes, together with nutrient speciation techniques provides insight on nitrogen pathways and transformations that could not have been captured otherwise, including a zone of vertical preferential discharge of nitrate from deeper groundwater, and a zone of rapid denitrification linking the floodplain with the riverbed. Nitrate attenuation in the reach is dominated by denitrification but is spatially highly variable. This variability is driven by groundwater flow pathways and landscape setting, which influences hyporheic flow, residence time and nitrate removal. We observed the spatial connectivity of the river to the riparian zone is important because zones of horizontal preferential discharge supply organic matter from the floodplain and create anoxic riverbed conditions with overlapping zones of nitrification potential and denitrification activity that peaked 10–20 cm below the riverbed. Our data also show that temporal variability in water pathways in the reach is driven by changes in stage of the order of tens of centimetres and by strength of water flux, which may influence the depth of delivery of dissolved organic carbon. The temporal variability is sensitive to changes to river flows under UK climate projections that anticipate a 14%–15% increase in regional median winter rainfall and a 14%–19% reduction in summer rainfall. Superimposed on seasonal projections is more intensive storm activity that will likely lead to a more dynamic and inherently complex (hydrologically and biogeochemically) hyporheic zone. We recorded direct evidence of suppression of upwelling groundwater (flow reversal) during rainfall events. Such flow reversal may fuel riverbed sediments whereby delivery of organic carbon to depth, and higher denitrification rates in HEFs might act in concert to make nitrate removal in the riverbed more efficient.     

Chemical perturbations in the planetary boundary layer and their relevance for chemistry transport modelling

The role of perturbations of reactive trace gas concentration distributions in turbulent flows in the planetary boundary layer (PBL) is discussed. The paper focuses on disturbances with larger spatial scales. Sequential nesting of a chemical transport model is applied to assess the effect of neglecting subgrid chemical perturbations on the formation and loss of ozone, NO _x , peroxyacetyl nitrate (PAN) and HNO₃ calculated with a highly complex chemical mechanism. The results point to characteristic differences regarding the process of mixing of chemically reactive species in the PBL and lower troposphere.     

Seasonal and short-term controls of riparian oxygen dynamics and the implications for redox processes

Riparian zones are highly-dynamic transition zones between surface water (SW) and groundwater (GW) and function as key biogeochemical-reactors for solutes transitioning between both compartments. Infiltration of SW rich in dissolved oxygen (DO) into the riparian aquifer can supress removal processes of redox sensitive compounds like NO₃⁻, a nutrient harmful for the aquatic ecosystem at high concentrations. Seasonal and short-term variations of temperature and hydrologic conditions can influence biogeochemical reaction rates and thus the prevailing redox conditions in the riparian zone. We combined GW tracer-tests and a 1-year high-frequency dataset of DO with data-driven simulations of DO consumption to assess the effects of seasonal and event-scale variations in temperature and transit-times on the reactive transport of DO. Damköhler numbers for DO consumption (DA_DO) were used to characterize the system in terms of DO turnover potential. Our results suggest that seasonal and short-term variations in temperature are major controls for DO turnover and the resulting concentrations at our field site, while transit-times are of minor importance. Seasonal variations of temperature in GW lead to shifts from transport-limited (DA_DO > 1) to reaction-limited conditions (DA_DO < 1), while short-term events were found to have minor impacts on the state of the system, only resulting in slightly less transport-limited conditions due to decreasing temperature and transit-times. The data-driven analyses show that assuming constant water temperature along a flowpath can lead to an over- or underestimation of reaction rates by a factor of 2–3 due to different infiltrating water temperature at the SW–GW interface, whereas the assumption of constant transit-times results in incorrect estimates of NO₃⁻ removal potential based on DA_DO approach (40%–50% difference).