Catherine S. Moody

Modeling the rate of turnover of DOC and particulate organic carbon in a UK, peat‐hosted stream: Including diurnal cycling in short‐residence time systems

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/km2/yr from an at source export of between 22 and 56 t C/km2/yr giving a total in-stream loss rate of between 53 and 62% over a median in-stream residence time of 35 h.

The effective oxidation state of a peatland

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, CO2, and CH4) 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 −16 and −73 t O km−2 yr−1; (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 CO2, 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.

Modeling rates of DOC degradation using DOM composition and hydroclimatic variables

The fluvial fluxes of dissolved organic carbon (DOC) from peatlands form an important part of that ecosystems carbon cycle, contributing approximately 35% of the overall peatland carbon budget. The in-stream processes acting on the DOC, such as photodegradation and biodegradation, can lead to DOC loss and thus contribute CO2 to the atmosphere. The aim of this study was to understand what controls the rates of DOC degradation. Water samples from a headwater, peat-covered catchment, were collected over a 23 month period and analyzed for the DOC degradation rate and dissolved organic matter (DOM) composition in the context of hydroclimatic monitoring. Measures of DOM composition included 13C solid-state nuclear magnetic resonance spectroscopy, bomb calorimetry, and elemental analysis. Regression analysis showed that there was a significant role for the composition of the DOM in controlling degradation with degradation rates significantly increasing with the proportion of aldehyde and carboxylic acid functional groups but decreasing with the proportion of N-alkyl functional groups. The highest rates of DOC degradation occurred when aldehyde functionality was at its greatest and this occurred on the recession limb of storm hydrographs. Including this knowledge into models of fluvial carbon fate for an 818 km2 catchment gave an annual average DOC removal rate of 67% and 50% for total organic carbon, slightly lower than previously predicted. The compositional controls suggest that DOM is primarily being used as a ready energy source to the aquatic ecosystem rather than as a nutrient source.

The total phosphorus budget of a peat‐covered catchment

Although many studies have considered the carbon or greenhouse gas budgets of peat ecosystems, only a few have considered the nutrient budget of peat soils, and this, in turn, has limited the ability of studies to consider the impact of changes in climate and atmospheric deposition on the phosphorus budget of a peat soil. This study considered the total phosphorus (P) budget of an upland peat-covered catchment over the period 1993 to 2012. The study has shown (i) total atmospheric deposition of phosphorus varied from 62 to 175 kg P/km2/yr; (ii) the carbon:phosphorus ratio of the peat profile declines significantly from values in the litter layer (C:P = 1326) to approximately constant at 30 cm depth (C:P = 4240); (iii) the total fluvial flux of phosphorus varied from 49 to 111 kg P/km2/yr, of which between 45 and 77% was dissolved P; and (iv) the total phosphorus sink varied from −5.6 to +71.7 kg P/km2/yr with a median of +29.4 kg P/km2/yr, which is within the range of the estimated long-term accumulation rate of phosphorus in the peat profile of between 3 and 32 kg P/km2/yr. The phosphorus budget of the peat ecosystem relies on rapid recycling near the soil surface, and this means that any vegetation management may critically deprive the ecosystem of this nutrient.

A molecular budget for a peatland based upon 13C solid state nuclear magnetic resonance

Peatlands can accumulate organic matter into long‐term carbon (C) storage within the soil profile. This study used solid‐state 13C nuclear magnetic resonance (13C‐NMR) to investigate the transit of organic C through a peatland ecosystem to understand the molecular budget that accompanies the long‐term accumulation of C. Samples of biomass, litter, peat soil profile, particulate organic matter, and dissolved organic matter (DOM) were taken from the Moor House National Nature Reserve, a peat‐covered catchment in northern England where both the dry matter and C budget for the ecosystem were known. The results showed that: The interpretation of the 13C‐NMR spectra shows that polysaccharides are preferentially removed through the ecosystem, while lignin components are preferentially retained and come to dominate the organic matter accumulated at depth in the profile. The DOM is derived from the oxidation of both biomass and the degradation of lignin, while the particulate organic matter is derived from erosion of the peat profile. The DOM is differentiated by its proportion of oxidized functional groups and not by its aromatic content. The changes in functionality leading to DOM production suggest side chain oxidation resulting in C‐C cleavage/depolymerisation of lignin, a common reaction within white rot fungi. The 13C‐NMR budget shows that O‐alkyl functional groups are disproportionately lost between primary production and accumulation in the deep peat, while C‐alkyl functional groups are disproportionately preserved. The carbon lost as gases (CO2 and CH4) was estimated to be composed of 93% polysaccharide‐derived carbon and 7% lignin‐derived carbon.

The flux of organic matter through a peatland ecosystem: The role of cellulose, lignin, and their control of the ecosystem oxidation state

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.

Organic matter properties of Fennoscandian ecosystems: Potential oxidation of northern environments under future change?

The oxidative ratio (OR) of an ecosystem, which reflects the ratio of O2:CO2 associated with ecosystem gas exchanges, is an important parameter in understanding the sink of CO2 represented by the terrestrial biosphere. There is a growing body of ecosystem-based approaches to understand OR; however, there are still a number of unknowns. This study addressed two gaps in our understanding of the oxidation of the terrestrial biosphere: (1) What is the oxidation state of Arctic ecosystems, and in particular permafrost soils? (2) Will coupled climate and land use change cause the terrestrial organic matter oxidation state to change? The study considered eight locations along a transect from southern Sweden to northern Norway and sampled different organic matter types (soil, litter, trees, and herbaceous vegetation) as well as different soil orders (Inceptisols, Spodosols, Histosols, and Gelisols). The study showed that although there was no difference between soil orders, there was a significant effect due to location with OR increasing from 1.03 at the southernmost location to 1.09 in the northernmost location; this increase is independent of soil order or type of organic matter. The pattern of post hoc differences in the OR with latitude suggests that the increase in OR is correlated with the northern limit of arable agriculture. The study suggests that the combined effects of climate and land use change could lead to a decrease in terrestrial organic matter OR and an increase in its oxidation state.

Thermodynamic control of the carbon budget of a peatland.

The transformations and transitions of organic matter into, through, and out of an ecosystem must obey the second law of thermodynamics. This study considered the transition in the solid components of the organic matter flux through an entire ecosystem. Organic matter samples were taken from each organic matter reservoir and fluvial transfer pathway in a 100% peat‐covered catchment (Moor House National Nature Reserve, North Pennines, UK) and were analyzed by elemental analysis and bomb calorimetry. The samples analyzed were as follows: bulk aboveground and belowground biomass; individual plant functional types (heather, mosses, and sedges); plant litter layer; peat soil; and samples of particulate and dissolved organic matter (POM and DOM). Samples were compared to standards of lignin, cellulose, and plant protein. It was possible to calculate: enthalpy of formation ( urn:x-wiley:21698953:media:jgrg21153:jgrg21153-math-0001); entropy of formation ( urn:x-wiley:21698953:media:jgrg21153:jgrg21153-math-0002); and Gibbs free energy of formation ( urn:x-wiley:21698953:media:jgrg21153:jgrg21153-math-0003) for each of the samples and standards. The increase (decreasing negative values) in urn:x-wiley:21698953:media:jgrg21153:jgrg21153-math-0004 through the ecosystem mean that for all but litter production, the transformations through the system must be balanced by production of low (large negative values) urn:x-wiley:21698953:media:jgrg21153:jgrg21153-math-0005 products, not only CO2 or CH4 but also DOM. The change in urn:x-wiley:21698953:media:jgrg21153:jgrg21153-math-0006 down the peat profile shows that reaction of the soil organic matter decreases or even ceases at depth and the majority of the reaction has occurred above 40 cm below the surface. This approach represents a new objective way to test and trace organic matter transformations in and through an ecosystem.

Water-level dynamics in natural and artificial pools in blanket peatlands

Perennial pools are common natural features of peatlands, and their hydrological functioning and turnover may be important for carbon fluxes, aquatic ecology, and downstream water quality. Peatland restoration methods such as ditch blocking result in many new pools. However, little is known about the hydrological function of either pool type. We monitored six natural and six artificial pools on a Scottish blanket peatland. Pool water levels were more variable in all seasons in artificial pools having greater water level increases and faster recession responses to storms than natural pools. Pools overflowed by a median of 9 and 54 times pool volume per year for natural and artificial pools, respectively, but this varied widely because some large pools had small upslope catchments and vice versa. Mean peat water-table depths were similar between natural and artificial pool sites but much more variable over time at the artificial pool site, possibly due to a lower bulk specific yield across this site. Pool levels and pool-level fluctuations were not the same as those of local water tables in the adjacent peat. Pool-level time series were much smoother, with more damped rainfall or recession responses than those for peat water tables. There were strong hydraulic gradients between the peat and pools, with absolute water tables often being 20–30 cm higher or lower than water levels in pools only 1–4 m away. However, as peat hydraulic conductivity was very low (median of 1.5 × 10−5 and 1.4 × 10−6 cm s−1 at 30 and 50 cm depths at the natural pool site), there was little deep subsurface flow interaction. We conclude that (a) for peat restoration projects, a larger total pool surface area is likely to result in smaller flood peaks downstream, at least during summer months, because peatland bulk specific yield will be greater; and (b) surface and near-surface connectivity during storm events and topographic context, rather than pool size alone, must be taken into account in future peatland pool and stream chemistry studies.