Effects of acid sulphate on DOC release in mineral soils: the influence of SO42−retention and Al release

Dissolved organic carbon (DOC) in acid-sensitive upland waters is dominated by allochthonous inputs from organic-rich soils, yet inter-site variability in soil DOC release to changes in acidity has received scant attention in spite of the reported differences between locations in surface water DOC trends over the last few decades. In a previous paper, we demonstrated that pH-related retention of DOC in O horizon soils was influenced by acid-base status, particularly the exchangeable Al content. In the present paper, we investigate the effect of sulphate additions (0–437 μeq l−1) on DOC release in the mineral B horizon soils from the same locations. Dissolved organic carbon release decreased with declining pH in all soils, although the shape of the pH-DOC relationships differed between locations, reflecting the multiple factors controlling DOC mobility. The release of DOC decreased by 32–91% in the treatment with the largest acid input (437 μeq l−1), with the greatest decreases occurring in soils with very small % base saturation (BS, <3%) and/or large capacity for sulphate (SO42−) retention (up to 35% of added SO42−). The greatest DOC release occurred in the soil with the largest initial base status (12% BS). These results support our earlier conclusions that differences in acid-base status between soils alter the sensitivity of DOC release to similar sulphur deposition declines. However,superimposed on this is the capacity of mineral soils to sorb DOC and SO42−, and more work is needed to determine the fate of sorbed DOC under conditions of increasing pH and decreasing SO42−.

The simulation of the opposing fluxes of latent heat and CO2 over various land-use types: coupling a gas exchange model to a mesoscale atmospheric model

A mesoscale meteorological model (FOOT3DK) is coupled with a gas exchange model to simulate surface fluxes of CO2 and H2O under field conditions. The gas exchange model consists of a C3 single leaf photosynthesis sub-model and an extended big leaf (sun/shade) sub-model that divides the canopy into sunlit and shaded fractions. Simulated CO2 fluxes of the stand-alone version of the gas exchange model correspond well to eddy-covariance measurements at a test site in a rural area in the west of Germany. The coupled FOOT3DK/gas exchange model is validated for the diurnal cycle at singular grid points, and delivers realistic fluxes with respect to their order of magnitude and to the general daily course. Compared to the Jarvis-based big leaf scheme, simulations of latent heat fluxes with a photosynthesis-based scheme for stomatal conductance are more realistic. As expected, flux averages are strongly influenced by the underlying land cover. While the simulated net ecosystem exchange is highly correlated with leaf area index, this correlation is much weaker for the latent heat flux. Photosynthetic CO2 uptake is associated with transpirational water loss via the stomata, and the resulting opposing surface fluxes of CO2 and H2O are reproduced with the model approach. Over vegetated surfaces it is shown that the coupling of a photosynthesis-based gas exchange model with the land-surface scheme of a mesoscale model results in more realistic simulated latent heat fluxes.

Controlling spurious diapycnal mixing in eddy-resolving height-coordinate ocean models: insights from virtual deliberate tracer release experiments

A perceived limitation of z-coordinate models associated with spurious diapycnal mixing in eddying, frontal flow, can be readily addressed through appropriate attention to the tracer advection schemes employed. It is demonstrated that tracer advection schemes developed by Prather and collaborators for application in the stratosphere, greatly improve the fidelity of eddying flows, reducing levels of spurious diapycnal mixing to below those directly measured in field experiments, ∼1 × 10−5 m2 s−1. This approach yields a model in which geostrophic eddies are quasi-adiabatic in the ocean interior, so that the residual-mean overturning circulation aligns almost perfectly with density contours. A reentrant channel configuration of the MIT General Circulation Model, that approximates the Antarctic Circumpolar Current, is used to examine these issues. Virtual analogs of ocean deliberate tracer release field experiments reinforce our conclusion, producing passive tracer solutions that parallel field experiments remarkably well.

Identification of micro-scale anthropogenic CO2, heat and moisture sources – processing eddy covariance fluxes for a dense urban environment

Anthropogenic emissions of heat and exhaust gases play an important role in the atmospheric boundary layer, altering air quality, greenhouse gas concentrations and the transport of heat and moisture at various scales. This is particularly evident in urban areas where emission sources are integrated in the highly heterogeneous urban canopy layer and directly linked to human activities which exhibit significant temporal variability. It is common practice to use eddy covariance observations to estimate turbulent surface fluxes of latent heat, sensible heat and carbon dioxide, which can be attributed to a local scale source area. This study provides a method to assess the influence of micro-scale anthropogenic emissions on heat, moisture and carbon dioxide exchange in a highly urbanized environment for two sites in central London, UK. A new algorithm for the Identification of Micro-scale Anthropogenic Sources (IMAS) is presented, with two aims. Firstly, IMAS filters out the influence of micro-scale emissions and allows for the analysis of the turbulent fluxes representative of the local scale source area. Secondly, it is used to give a first order estimate of anthropogenic heat flux and carbon dioxide flux representative of the building scale. The algorithm is evaluated using directional and temporal analysis. The algorithm is then used at a second site which was not incorporated in its development. The spatial and temporal local scale patterns, as well as micro-scale fluxes, appear physically reasonable and can be incorporated in the analysis of long-term eddy covariance measurements at the sites in central London. In addition to the new IMAS-technique, further steps in quality control and quality assurance used for the flux processing are presented. The methods and results have implications for urban flux measurements in dense urbanised settings with significant sources of heat and greenhouse gases.

Evidence of a universal scaling relationship for leaf CO2 drawdown along an aridity gradient

The leaf carbon isotope ratio (δ13C) of C3 plants is inversely related to the drawdown of CO2 concentration during photosynthesis, which increases towards drier environments. We aimed to discriminate between the hypothesis of universal scaling, which predicts between-species responses of δ13C to aridity similar to within-species responses, and biotic homoeostasis, which predicts offsets in the δ13C of species occupying adjacent ranges. The Northeast China Transect spans 130–900 mm annual precipitation within a narrow latitude and temperature range. Leaves of 171 species were sampled at 33 sites along the transect (18 at ≥ 5 sites) for dry matter, carbon (C) and nitrogen (N) content, specific leaf area (SLA) and δ13C. The δ13C of species generally followed a common relationship with the climatic moisture index (MI). Offsets between adjacent species were not observed. Trees and forbs diverged slightly at high MI. In C3 plants, δ13C predicted N per unit leaf area (Narea) better than MI. The δ13C of C4 plants was invariant with MI. SLA declined and Narea increased towards low MI in both C3 and C4 plants. The data are consistent with optimal stomatal regulation with respect to atmospheric dryness. They provide evidence for universal scaling of CO2 drawdown with aridity in C3 plants.

Sensitivity analysis of an ocean carbon cycle model in the North Atlantic: an investigation of parameters affecting the air-sea CO2 flux, primary production and export of detritus

The sensitivity of the biological parameters in a nutrient-phytoplankton-zooplankton-detritus (NPZD) model in the calculation of the air-sea CO2 flux, primary production and detrital export is analysed. We explore the effect on these outputs of variation in the values of the twenty parameters that control ocean ecosystem growth in a 1-D formulation of the UK Met Office HadOCC NPZD model used in GCMs. We use and compare the results from one-at-a-time and all-at-a-time perturbations performed at three sites in the EuroSITES European Ocean Observatory Network: the Central Irminger Sea (60° N 40° W), the Porcupine Abyssal Plain (49° N 16° W) and the European Station for Time series in the Ocean Canary Islands (29° N 15° W). Reasonable changes to the values of key parameters are shown to have a large effect on the calculation of the air-sea CO2 flux, primary production, and export of biological detritus to the deep ocean. Changes in the values of key parameters have a greater effect in more productive regions than in less productive areas. The most sensitive parameters are generally found to be those controlling well-established ocean ecosystem parameterisations widely used in many NPZD-type models. The air-sea CO2 flux is most influenced by variation in the parameters that control phytoplankton growth, detrital sinking and carbonate production by phytoplankton (the rain ratio). Primary production is most sensitive to the parameters that define the shape of the photosynthesis-irradiance curve. Export production is most sensitive to the parameters that control the rate of detrital sinking and the remineralisation of detritus.

The impact of diurnal variability in sea surface temperature on the atlantic air-sea CO2 flux

The effect of diurnal variations in sea surface temperature (SST) on the air-sea flux of CO2 over the central Atlantic ocean and Mediterranean Sea (60 S–60 N, 60 W–45 E) is evaluated for 2005–2006. We use high spatial resolution hourly satellite ocean skin temperature data to determine the diurnal warming (ΔSST). The CO2 flux is then computed using three different temperature fields – a foundation temperature (Tf, measured at a depth where there is no diurnal variation), Tf, plus the hourly ΔSST and Tf, plus the monthly average of the ΔSSTs. This is done in conjunction with a physically-based parameterisation for the gas transfer velocity (NOAA-COARE). The differences between the fluxes evaluated for these three different temperature fields quantify the effects of both diurnal warming and diurnal covariations. We find that including diurnal warming increases the CO2 flux out of this region of the Atlantic for 2005–2006 from 9.6 Tg C a−1 to 30.4 Tg C a−1 (hourly ΔSST) and 31.2 Tg C a−1 (monthly average of ΔSST measurements). Diurnal warming in this region, therefore, has a large impact on the annual net CO2 flux but diurnal covariations are negligible. However, in this region of the Atlantic the uptake and outgassing of CO2 is approximately balanced over the annual cycle, so although we find diurnal warming has a very large effect here, the Atlantic as a whole is a very strong carbon sink (e.g. −920 Tg C a−1 Takahashi et al., 2002) making this is a small contribution to the Atlantic carbon budget.

Exploring the climatic impact of the continental vegetation on the Mezosoic atmospheric CO2 and climate history

In this contribution, we continue our exploration of the factors defining the Mesozoic climatic history. We improve the Earth system model GEOCLIM designed for long term climate and geochemical reconstructions by adding the explicit calculation of the biome dynamics using the LPJ model. The coupled GEOCLIM-LPJ model thus allows the simultaneous calculation of the climate with a 2-D spatial resolution, the coeval atmospheric CO2, and the continental biome distribution. We found that accounting for the climatic role of the continental vegetation dynamics (albedo change, water cycle and surface roughness modulations) strongly affects the reconstructed geological climate. Indeed the calculated partial pressure of atmospheric CO2 over the Mesozoic is twice the value calculated when assuming a uniform constant vegetation. This increase in CO2 is triggered by a global cooling of the continents, itself triggered by a general increase in continental albedo owing to the development of desertic surfaces. This cooling reduces the CO2 consumption through silicate weathering, and hence results in a compensating increase in the atmospheric CO2 pressure. This study demonstrates that the impact of land plants on climate and hence on atmospheric CO2 is as important as their geochemical effect through the enhancement of chemical weathering of the continental surface. Our GEOCLIM-LPJ simulations also define a climatic baseline for the Mesozoic, around which exceptionally cool and warm events can be identified.

Systematic study of the impact of fresh water fluxes on the glacial carbon cycle

During glacial periods, atmospheric CO2 concentration increases and decreases by around 15 ppm. At the same time, the climate changes gradually in Antarctica. Such climate changes can be simulated in models when the AMOC (Atlantic Meridional Oceanic Circulation) is weakened by adding fresh water to the North Atlantic. The impact on the carbon cycle is less straightforward, and previous studies give opposite results. Because the models and the fresh water fluxes were different in these studies, it prevents any direct comparison and hinders finding whether the discrepancies arise from using different models or different fresh water fluxes. In this study we use the CLIMBER-2 coupled climate carbon model to explore the impact of different fresh water fluxes. In both preindustrial and glacial states, the addition of fresh water and the resulting slow-down of the AMOC lead to an uptake of carbon by the ocean and a release by the terrestrial biosphere. The duration, shape and amplitude of the fresh water flux all have an impact on the change of atmospheric CO2 because they modulate the change of the AMOC. The maximum CO2 change linearly depends on the time integral of the AMOC change. The different duration, amplitude, and shape of the fresh water flux cannot explain the opposite evolution of ocean and vegetation carbon inventory in different models. The different CO2 evolution thus depends on the AMOC response to the addition of fresh water and the resulting climatic change, which are both model dependent. In CLIMBER-2, the rise of CO2 recorded in ice cores during abrupt events can be simulated under glacial conditions, especially when the sinking of brines in the Southern Ocean is taken into account. The addition of fresh water in the Southern Hemisphere leads to a decline of CO2, contrary to the addition of fresh water in the Northern Hemisphere.

Multi-season eddy covariance observations of energy, water and carbon fluxes over a suburban area in Swindon, UK

Eddy covariance measurements of the turbulent sensible heat, latent heat and carbon dioxide fluxes for 12 months (2011–2012) are reported for the first time for a suburban area in the UK. The results from Swindon are comparable to suburban studies of similar surface cover elsewhere but reveal large seasonal variability. Energy partitioning favours turbulent sensible heat during summer (midday Bowen ratio 1.4–1.6) and latent heat in winter (0.05–0.7). A significant proportion of energy is stored (and released) by the urban fabric and the estimated anthropogenic heat flux is small but non-negligible (0.5–0.9 MJ m−2 day−1). The sensible heat flux is negative at night and for much of winter daytimes, reflecting the suburban nature of the site (44% vegetation) and relatively low built fraction (16%). Latent heat fluxes appear to be water limited during a dry spring in both 2011 and 2012, when the response of the surface to moisture availability can be seen on a daily timescale. Energy and other factors are more relevant controls at other times; at night the wind speed is important. On average, surface conductance follows a smooth, asymmetrical diurnal course peaking at around 6–9 mm s−1, but values are larger and highly variable in wet conditions. The combination of natural (vegetative) and anthropogenic (emission) processes is most evident in the temporal variation of the carbon flux: significant photosynthetic uptake is seen during summer, whilst traffic and building emissions explain peak release in winter (9.5 g C m−2 day−1). The area is a net source of CO2 annually. Analysis by wind direction highlights the role of urban vegetation in promoting evapotranspiration and offsetting CO2 emissions, especially when contrasted against peak traffic emissions from sectors with more roads. Given the extent of suburban land use, these results have important implications for understanding urban energy, water and carbon dynamics.

Dinitrogen release from arylpentazole: A picosecond time-resolved infrared, spectroelectrochemical, and DFT computational study

p-(Dimethylamino)phenyl pentazole, DMAP-N5 (DMAP = Me2N−C6H4), was characterized by picosecond transient infrared spectroscopy and infrared spectroelectrochemistry. Femtosecond laser excitation at 310 or 330 nm produces the DMAP-N5 (S1) excited state, part of which returns to the ground state (τ = 82 ± 4 ps), while DMAP-N and DMAP-N3 (S0) are generated as double and single N2-loss photoproducts with η ≈ 0.14. The lifetime of DMAP-N5 (S1) is temperature and solvent dependent. [DMAP-N3]+ is produced from DMAP-N5 in a quasireversible, one-electron oxidation process (E1/2 = +0.67 V). Control experiments with DMAP-N3 support the findings. DFT B3LYP/6-311G** calculations were used to identify DMAP-N5 (S1), DMAP-N3 +, and DMAP-N in the infrared spectra. Both DMAP-N5 (S1) and [DMAP-N5]+ have a weakened N5 ring structure.

Assembly of an injectable noncytotoxic peptide-based hydrogelator for sustained release of drugs

A new synthetic tripeptide-based hydrogel has been discovered at physiological pH and temperature. This hydrogel has been thoroughly characterized using different techniques including field emission scanning electron microscopic (FESEM) and high-resolution transmission electron microscopic (HR-TEM) imaging, small- and wide-angle X-ray diffraction analyses, FT-IR, circular dichroism, and rheometric analyses. Moreover, this gel exhibits thixotropy and injectability. This hydrogel has been used for entrapment and sustained release of an antibiotic vancomycin and vitamin B12 at physiological pH and temperature for about 2 days. Interestingly, MTT assay of these gelator molecules shows almost 100% cell viability of this peptide gelator, indicating its noncytotoxicity.

The influence of vegetation, fire spread and fire behaviour on biomass burning and trace gas emissions: results from a process-based model

A process-based fire regime model (SPITFIRE) has been developed, coupled with ecosystem dynamics in the LPJ Dynamic Global Vegetation Model, and used to explore fire regimes and the current impact of fire on the terrestrial carbon cycle and associated emissions of trace atmospheric constituents. The model estimates an average release of 2.24 Pg C yr−1 as CO2 from biomass burning during the 1980s and 1990s. Comparison with observed active fire counts shows that the model reproduces where fire occurs and can mimic broad geographic patterns in the peak fire season, although the predicted peak is 1–2 months late in some regions. Modelled fire season length is generally overestimated by about one month, but shows a realistic pattern of differences among biomes. Comparisons with remotely sensed burnt-area products indicate that the model reproduces broad geographic patterns of annual fractional burnt area over most regions, including the boreal forest, although interannual variability in the boreal zone is underestimated.