This version available http://nora.nerc.ac.uk/502345/ NERC has developed NORA to enable users to access research outputs wholly or partially funded by NERC. Copyright and other rights for material on this site are retained by the rights owners. Users should read the terms and conditions of use of this material at http://nora.nerc.ac.uk/policies.html#access NOTICE: this is the author's version of a work that was accepted for publication in Journal of Hydrology. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Journal of Hydrology, 492. 139-150. 10.1016Hydrology, 492. 139-150. 10. /j.jhydrol.2013 Contact CEH NORA team at noraceh@ceh.ac.ukThe NERC and CEH trademarks and logos ('the Trademarks') are registered trademarks of NERC in the UK and other countries, and may not be used without the prior written consent of the Trademark owner. increase of 6 mg C/l/day, i.e. net photo-induced production was possible. 22iii) Activation energy of the degradation was estimated as 2.6 ± 1.2 kJ/gC. 23iv)The apparent quantum yield varied from 9.6 and -1.7 mmol C/mol photons.

The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Abstract The oxidative ratio (OR) of the organic matter of the terrestrial biosphere is a key parameter in the understanding of the magnitude of the carbon sink represented both by the terrestrial biosphere and by the global oceans. However, no study has considered the oxidation state of all the organic pools and fluxes within one environment. In this study all organic matter pathways (dissolved organic matter, particulate organic matter, CO 2 , and CH 4 ) were measured within an upland peat ecosystem in northern England. The study showed the following: (1) The peat soil of ecosystem was accumulating oxygen at a rate of between À16 and À73 t O km À2 yr À1 ; (2) Although there was no significant variation in oxidation state in the peat profile, there was a significant increase in degree of unsaturation with depth; (3) The dissolved organic matter leaving the ecosystem was significantly more oxidized than the other carbon pools analyzed while the particulate organic matter was not significantly different from the peat soil profile; and (4) Assuming that all carbon flux from the site was as CO 2 , the OR of the ecosystem was 1.07; when the nature and speciation of the release pathways were considered, the ecosystem OR was 1.04. At the global scale, correcting for the speciation of carbon fluxes means that the annual global fluxes of carbon to land = 1.49 ± 0.003 Gt C/yr and to the oceans = 2.01 ± 0.004 Gt C/yr.

Few studies have quantified the role of instream processes on net dissolved and particulate organic carbon (DOC and POC, respectively) export from peatland catchments, and those that have offer conflicting evidence. In this study, we evaluated evidence for active organic matter processing under field conditions, via a coordinated campaign across four UK catchments with peatland headwaters, targeted on potential 'hotspots' and 'hot moments' of physico-chemical carbon cycling. We hypothesised that specific hotspots and hot moments would occur where waters enriched with DOC and POC sourced from headwaters are exposed to: (1) mixing with freshwaters of different pH, conductivity and metal concentrations; and (2) mixing with seawater during autumn when DOC concentrations were at their highest. We observed instances of POC removal in headwaters, and potential for rapid conversion between dissolved and particulate carbon forms and for net removal of peat-derived carbon at confluences further downstream (where observed, on the order of 52-75 % for POC, and 5-44 % for DOC). Estuary transect surveys indicated that up to 30 % of fluvial DOC can be removed under high flow conditions. However, in the majority of cases concentrations remained within the range that would be expected based on conservative transport. These findings indicate that rapid (e.g. solubility-related) processes within the river system may be important but sporadic, thus are unlikely to provide major removal pathways for peat-derived organic carbon.

This study proposes a multicomponent, multiprocess scheme to explain the turnover of organic matter (particulate and dissolved organic matter) in streams. The scheme allows for production and degradation of organic matter by both photic and aphotic processes with transformation of dissolved organic carbon (DOC) to increasingly refractory forms. The proposed scheme was compared to 10 months of experimental observations of the turnover and fate of particulate and dissolved organic matter in stream water from a peat-covered catchment. The scheme was able to explain average decline in DOC concentration of 65% over 70 h with a 13% mean average percentage error based on turnover in three types of organic matter (particulate, labile dissolved, and refractory dissolved) although the order and rate of reactions did change between sets of experimental observations. The modeling suggests that activation energies are low for all except the most refractory forms of DOC in turn, suggesting that processes are not sensitive to temperature change. Application of the modeling scheme to organic matter turnover in the River Tees, northern England, showed that annual removal of total organic carbon was equivalent to between 13 and 33 t C/km 2 /yr from an at source export of between 22 and 56 t C/km 2 /yr giving a total in-stream loss rate of between 53 and 62% over a median in-stream residence time of 35 h.

This study used thermogravimetric analysis (TGA) to study the transit of organic C through a peatland ecosystem. The biomass, litter, peat soil profile, particulate organic matter (POM), and dissolved organic matter (DOM) fluxes were sampled from the Moor House National Nature Reserve, a peat‐covered catchment in northern England where both the dry matter and carbon budget for the catchment were known. The study showed that although TGA traces showed distinct differences between organic matter reservoirs and fluxes, the traces could not readily be associated with particular functionalities or elemental properties. The TGA trace shows that polysaccharides are preferentially removed by humification and degradation with residual peat being dominated by lignin compositions. The DOM is derived from the degradation of lignin while the POM is derived from erosion of the peat profile. The carbon lost as gases (CO2 and CH4) was estimated to be composed of 92 to 95% polysaccharide carbon. The composition of the organic matter lost from the peat ecosystem means that the oxidative ratio (OR) of the ecosystem experienced by the atmosphere was between 0.96 and 0.99: currently, the Intergovernmental Panel on Climate Change uses an OR value of 1.1 for all ecosystems.