Continuous fluorescence assessment of organic matter variability on the Bournbrook River,Birmingham, UK

Continuous monitoring of dissolved organic matter (DOM) character and concentration at hourly resolution is rare, despite the importance of analysing organic matter variability at high‐temporal resolution to evaluate river carbon budgeting, river water health by detecting episodic pollution and to determine short‐term variations in chemical and ecological function. The authors report a 2‐week experiment performed on DOM sampled from Bournbrook, Birmingham, UK, an urban river for which spectrophotometric (fluorescence, absorbance), physiochemical (dissolved organic carbon [DOC], electrical conductivity, pH) and isotopic (D/H) parameters have been measured at hourly frequency. Our results show that the river had sub‐daily variations in both organic matter concentration and characteristics. In particular, after relatively high‐magnitude precipitation events, organic carbon concentration increased, with an associated increase in intensity of both humic‐like and tryptophan‐like fluorescence. D/H isotopic ratio demonstrates different hydrological responses to different rainfall events, and organic matter character reflects this difference. Events with precipitation < 2 mm typically yielded isotopically heavy water with relatively hydrophilic DOM and relatively low specific absorbance. Events with precipitation > 2 mm had isotopically lighter water with higher specific absorbance and a decrease in the proportion of microbially derived to humic‐like fluorescence. In our heavily urbanized catchment, we interpret these signals as one where riverine DOM is dominated by storm sewer‐derived ‘old’ organic matter at low‐rainfall amounts and a mixed signal at high‐precipitation amounts where ‘event’ surface runoff‐derived organic matter dominate during storm sewer and combined sewer overflow routed DOM. Copyright © 2009 John Wiley & Sons, Ltd.     

Sources and biodegradability of dissolved organic matter in two headwater peatland catchments at the Marcell Experimental Forest,northern Minnesota,USA

Where they are present in catchments, peatlands are a dominant source of dissolved organic matter (DOM) to surrounding waterways due, in part, to high production rates. Despite the preponderance of peatlands in northern latitudes and expected peatland vulnerability to climate change, little is known about peatland DOM degradation relative to a more comprehensive understanding of degradation when DOM is sourced from upland-dominated catchments. We compared DOM biodegradability of various sources of stream water in two catchments having peatlands (22%–33% of the area) surrounded by upland forests (70%–90% of the area, either deciduous or coniferous). We measured total organic carbon (TOC), and biodegradable dissolved organic carbon concentrations; bacterial respiration rates; streamflow; and upland runoff during and after snowmelt (March to June, 2009–2011). We also explored if DOM in upland runoff stimulated biodegradation of peatland-derived DOM (i.e., a priming effect), and if forest cover type affected DOM biodegradability. As expected, the peatlands were the largest sources of both water (72%–80%) and TOC (92%–96%) to the streams although more area in each catchment was in uplands (70%–90%). Several results were unexpected, yet revealing: (1) DOM from peatlands sometimes had the same biodegradability as DOM from uplands, (2) upland sources of DOM had negligible effects on biodegradability in the peatland and downstream, and (3) upland deciduous cover did not yield more degradable DOM than conifer cover. The most pronounced effect of upland runoff was dilution of downstream TOC concentrations when there was upland runoff. Overall, the effects of upland DOM may have been negligible due to the overriding effect of the large amount of biodegradable DOM that originated in bogs. This research highlights that peatland-sourced DOM has important effects on downstream DOM biodegradability even in catchments where upland area is substantially larger than peatland area.     

Changes in dissolved organic matter (DOM) amount and composition along nested headwater stream locations during baseflow and stormflow

Amount and composition of dissolved organic matter (DOM) were evaluated for multiple, nested stream locations in a forested watershed to investigate the role of hydrologic flow paths, wetlands and drainage scale. Sampling was performed over a 4‐year period (2008–2011) for five locations with drainage areas of 0.62, 3.5, 4.5, 12 and 79 ha. Hydrologic flow paths were characterized using an end‐member mixing model. DOM composition was determined using a suite of spectrofluorometric indices and a site‐specific parallel factor analysis model. Dissolved organic carbon (DOC), humic‐like DOM and fluorescence index were most sensitive to changes with drainage scale, whereas dissolved organic nitrogen, specific UV absorbance, Sr and protein‐like DOM were least sensitive. DOM concentrations and humic‐like DOM constituents were highest during both baseflow and stormflow for a 3.5‐ha catchment with a wetland near the catchment outlet. Whereas storm‐event concentrations of DOC and humic DOM constituents declined, the mass exports of DOC increased with increasing catchment scale. A pronounced dilution in storm‐event DOC concentration was observed at peak stream discharge for the 12‐ha drainage location, which was not as apparent at the 79‐ha scale, suggesting key differences in supply and transport of DOM. Our observations indicate that hydrologic flow paths, especially during storms, and the location and extent of wetlands in the catchment are key determinants of DOM concentration and composition. This study furthers our understanding of changes in DOM with drainage scale and the controls on DOM in headwater, forested catchments. Copyright © 2014 John Wiley & Sons, Ltd.     

The impact of ditch blocking on fluvial carbon export from a UK blanket bog

We investigated the effects of ditch blocking on fluvial carbon concentrations and fluxes at a 5‐year, replicated, control‐intervention field experiment on a blanket peatland in North Wales, UK. The site was hydrologically instrumented, and run‐off via open and blocked ditches was analysed for dissolved organic carbon (DOC), particulate organic carbon, dissolved carbon dioxide, and dissolved methane. DOC was also analysed in peat porewater and overland flow. The hillslope experiment was embedded within a paired control‐intervention catchment study, with 3 years of preblocking and 6 years of postblocking data. Results from the hillslope showed large reductions in discharge via blocked ditches, with water partly redirected into hillslope surface and subsurface flows, and partly into remaining open ditches. We observed no impacts of ditch blocking on DOC, particulate organic carbon, dissolved carbon dioxide or methane in ditch waters, DOC in porewaters or overland flow, or stream water DOC at the paired catchment scale. Similar DOC concentrations in ditch water, overland flow, and porewater suggest that diverting flow from the ditch network to surface or subsurface flow had a limited impact on concentrations or fluxes of DOC entering the stream network. The subdued response of fluvial carbon to ditch blocking in our study may be attributable to the relatively low susceptibility of blanket peatlands to drainage, or to physical alterations of the peat since drainage. We conclude that ditch blocking cannot be always be expected to deliver reductions in fluvial carbon loss, or improvements in the quality of drinking water supplies.     

Release of dissolved organic carbon from upland peat

This study examines the release of dissolved organic carbon (DOC) from upland peat during the period of the autumn flushing. Hydroclimatic conditions were monitored in conjunction with measurements of absorbance and the E4/E6 ratio of the stream draining an 11·4 km² upland peat catchment in northern England. During two months of monitoring the effects of 67 separate rainfall events were examined showing that:

• The peat behaves hydrologically as if it were a two end‐member system consisting of old, interevent, and new, event, water. Runoff is initiated by percolation excess of new water at the acrotelm–catotelm interface.
• The discharge of dissolved organic matter behaves like a three end‐member system with the between‐event water being low in DOC and storm events being characterized by two types of water. Initial runoff being characterized by new water rich in DOC that gives way to new water depleted in DOC. This transition can be ascribed to the runoff progressing from throughflow within the acrotelm progressing to saturation‐excess overland flow.
• Depletion of DOC during storm events is accompanied by a change in the character of the DOC as the E4/E6 ratio changes. This suggests that the decrease in DOC during events is the result of exhaustion of reserves rather than changes in the flowpaths being utilized by runoff.
• The amount of carbon released in any event is critically dependent upon the time between events during which oxidation processes generate a reservoir of available carbon. Production of available carbon in the catchment is as high as 4·5 g C per day per m³ of peat, suggesting a turnover rate of peat of the order of 42 years. Copyright © 2002 John Wiley & Sons, Ltd.

     

Short term fluctuations in dissolved organic matter concentrations in streamflow draining a forested watershed and their relation to the catchment budget

Dissolved organic matter (DOM) concentrations in throughfall, throughflow, and runoff were recorded in a small (95 ha) woodland catchment in North Warwickshire for a period of eight weeks following a prolonged dry spell. DOM is shown to be positively related to stream discharge over the sampling period, although distinctive flushing effects were identified. The net contribution of DOM to total dissolved solids load carried in the river was only 2.4 per cent, and represented significantly less than published carbon losses by mineralization of soil organic matter. Throughfall inputs were some 100 times higher than streamflow outputs from the catchment.     

Studying solute and particulate sediment transfer in a small Mediterranean mountainous catchment subject to land abandonment

The sediment budget of the small research catchment of Cal Parisa (Vallcebre, Eastern Pyrenees) was studied by hydrological monitoring and assessment of the erosion rates in the major sediment sources. This area is characterized by clayey mudrock prone to landsliding and badland erosion, but the catchment was selected in an area free of major badland features, as a representative of middle mountain regions where a system of terraces and drainage ditches had been built for agricultural use but is now abandoned. Streamwater chemistry is dominated by Ca²⁺ and HCO₃⁻ at concentrations close to calcite saturation. Total dissolved solids show dilution during runoff peaks and positive hysteresis loops that support a slow contribution of subsurface water. Relative dissolved ion concentrations are different for each event analysed. Particulate sediment yield is very low and represents only about 1 per cent of gross erosion in the catchment. Mineralogical analysis of suspended sediments shows an enrichment in calcite because of precipitation. Chemical analysis of suspended sediments, using common one-litre water samples, shows higher contents of Ca, P and Mn in transported sediment than in sediment source areas, attributed to the precipitation of calcite, and enrichment in organic particulate matter during events respectively for the two first elements, whereas enrichment in Mn remains uncertain. Solid matter yield is therefore clearly dominated by dissolved transport as a result of both high calcium bicarbonate concentrations in runoff waters and strong suspended sediment conveyance discontinuities. Land conservation structures are very effective because they are in good condition whereas the soil is covered by dense permanent vegetation. Nevertheless, this state is unstable because the network of drainage ditches needs maintenance; its spontaneous breakdown after abandonment may result in the rearrangement of the elementary stream network and gullying of old fields in hollows. © 1997 John Wiley & Sons, Ltd.     

Bioavailability and radiocarbon age of fluvial dissolved organic matter (DOM) from a northern peatland-dominated catchment: effect of land-use change

The radiocarbon age and biodegradability of dissolved organic matter (DOM) from a northern peat-dominated river system was studied and the effects of land-use were compared. Samples were obtained from streams and ditches comprising sub-catchments of the Kiiminki River, Northern Finland. Sample sites included areas of natural mire, areas subjected to moderate disturbance (ditching to enhance forestry), and areas subjected to serious land use change (agriculture and peat excavation). The study employed a 55 day bioassay that measured the biodegradation potential of surface-water DOM. We identified release of modern (mean 6–13 year old) DOM from natural sites, and material aged up to 1,553 years from disturbed sites. The proportion of biodegradable DOC ranged from 4.1 to 17.9 %, and bacterial DOC removal was modelled using twin-pool and reactivity-continuum (beta distribution) approaches. Bacterial growth efficiency ranged from 0.11 to 0.26 between areas of different land use, and these relatively low values reflect the humic-rich DOM released from boreal peatland. Despite the range of land-use types studied, including intensive peatland excavation areas, there was no detectable relationship between the biological lability of DOM and its radiocarbon age.     

The freshwater dissolved organic matter fluorescence–total organic carbon relationship

The fluorescent properties of dissolved organic matter (DOM) enable comparisons of humic‐like (H‐L) and fulvic‐like (F‐L) fluorescence intensities with dissolved organic carbon (DOC) in aquatic systems. The fluorescence‐DOC relationship differed in gradient, i.e. the fluorescence per gram of carbon, and in the strength of the correlation coefficient. We compare the fluorescence intensity of the F‐L and H‐L fractions and DOC of freshwater DOM in north Shropshire, England, featuring a river, wetland, spring, pond and sewage DOM sources. Correlations between fluorescence and DOC varied between sample sites. Wetland water samples for the F‐L peak gave the best correlation, r = 0·756; the lowest correlation was from final treated sewage effluent, r = 0·167. The relationship between fluorescence and DOC of commercially available International Humic Substances Society standards were also examined and they generally showed a lower fluorescence per gram of carbon for the F‐L peak than the natural samples, whereas peat wetland DOM gave a greater fluorescence per gram of carbon than river DOM. Here, we propose the strength of the fluorescence–DOC correlation to be a useful tool when discriminating sources of DOM in fresh water. Copyright © 2007 John Wiley & Sons, Ltd.     

Using synchronous fluorescence spectroscopy and principal components analysis to monitor dissolved organic matter dynamics in a glacier system

The molecular characteristics of dissolved organic matter (DOM) reflect both its source material and its biogeochemical history. In glacial systems, DOM characteristics might be expected to change over the course of a melt season as changes in the glacier drainage system cause the mobilization of DOM from different OM pools. To test this hypothesis we used Principal Components Analysis (PCA) of synchronous fluorescence spectra to detect and describe changes in the DOM in meltwater from a glacier system in the Coast Mountains of northern British Columbia, Canada. For most of the melt season, the dominant component of subglacially routed meltwater DOM is characterized by a tyrosine‐like fluorophore. This DOM component is most likely derived from supraglacial snowmelt. During periods of high discharge, a second component of DOM is present which is humic in character and similar to DOM sampled from a nearby non‐glacial stream. This DOM component is inferred to be derived from a moss‐covered soil environment that has been glacially overrun. It is probably entrained into glacial melt waters when the supraglacial meltwater flux exceeds the capacity of the principal subglacial drainage channels and water floods areas of the glacier bed that are normally isolated from the subglacial drainage system. Another source of DOM also appears to be mobilized during periods of high air temperatures. It is characterized by both humic and proteinaceous fluorophores and may be derived from the drainage of supraglacial cryoconite holes. Copyright © 2009 John Wiley & Sons, Ltd.     

Spectrophotometric discrimination of river dissolved organic matter

There is a need to be able to differentiate the dissolved organic matter (DOM) fraction in river waters. Research in the 1970s and 1980s has attempted to utilize both absorbance and fluorescence to distinguish between DOM fractions in river waters, but both were limited by the available technology. Total organic carbon content has, therefore, been widely used as a standard method of measuring DOM concentration, although it has little power to differentiate DOM fractions. Recent advances in fluorescence spectrophotometry enable rapid and optically precise analysis of DOM. Here, we show how a combination of both fluorescence and absorbance can be used to discriminate statistically between spatial variations of DOM in tributaries in a small catchment of the Ouseburn, NE England. The results of the discriminant analysis suggest that about 70% of the samples can be correctly classified to its tributary. Discriminant function 1 explains 60·8% of the variance in the data and the fulvic‐like fluorescence intensity has the largest absolute correlation within this function; discriminant function 2 explains a further 21·5% of the variance and the fulvic‐like fluorescence emission wavelength has the largest absolute correlation within this function. The discriminant analysis does not correctly classify all tributaries every time, and successfully discriminates between the different tributaries 70% of the time. Occasions when the tributary waters are less well discriminated are due to either episodic pollution events (at two sites) or due to tributaries that have strong seasonal trends in spectrophotometric parameters, which allows the sites to be misclassified. Results suggest that spectrophotometric techniques have considerable potential in the discrimination of DOM in rivers. Copyright © 2002 John Wiley & Sons, Ltd.     

DOC budgets of drained peat catchments: implications for DOC production in peat soils

The blocking of drainage ditches in peat has been proposed as a possible mitigation strategy for the widely observed increases in dissolved organic carbon (DOC) concentrations from northern peatlands. This study tested the hypothesis that drain‐blocking could lead to lower DOC concentrations by measuring the DOC export from a series of small peat‐covered catchments over a period of 2 years. Six catchments were chosen: two were pristine that had never been drained; three where drains had been blocked (one in 1995, and two in 2003); and a control peat drain catchment where the drain was left unblocked throughout the study. In the case where drains were blocked as part of thus study, the drains were observed for 2 months before blocking and 2 years after blocking. The results show that: (i) high concentrations of DOC can come from water ponded in the drain; (ii) the DOC export (flux of DOC per area of catchment) from the six study catchments shows a high degree of positive correlation with both catchment size and water yield; (iii) distinctly lower DOC export with water yield was observed for the catchments containing higher‐order channels (>27 500 m²) as opposed to single drain catchments (>7500 m²); (iv) drain‐blocking resulted in a statistically significant decrease in DOC export (average was 39%) but the effect upon DOC concentration explained only 1% of the variance in the data. The results suggest that drain blocking works by decreasing the flow from the drain, not by changing the production of DOC in the peat. The change in export with catchment size implies a considerable removal of DOC from large catchments. Copyright © 2009 John Wiley & Sons, Ltd.     

Continuous measurement of spectrophotometric absorbance in peatland streamwater in northern England: implications for understanding fluvial carbon fluxes

Bog systems tend to have a flashy hydrological regime with low baseflows and rapid and high storm peaks. Water derived from peatlands often contains significant amounts of organic humic and fulvic materials which form the largest fraction of the dissolved organic carbon component of the fluvial carbon flux. However, most estimates of dissolved organic carbon flux from peatlands are based on sampling that is infrequent and which may miss the periods of high flux during storm events. In order to better characterize the behaviour and fluxes of fluvial carbon it is necessary to operate more frequent sampling. This paper presents data from a continuously operating field‐based spectrophotometer simultaneously measuring absorbance across 200–730 nm at 2·5 nm intervals in runoff from an upland peatland stream. It is shown that absorbance at different wavelengths that have previously been used to characterize dissolved organic carbon varies rapidly during storm events. The probe is shown to even detect changes in absorbance characteristics in response to rainfall events before the stream discharge starts to rise. The high‐resolution behaviour of absorbance characteristics during storm events is different depending on the wavelength studied. Thus, the choice of wavelength used as a proxy for dissolved organic carbon needs careful attention and it may be that automated spectrophotometric methods which provide rich time‐series data from across the spectrum can tell us more about fluxes, processes and sources of aquatic carbon in peatland systems in the future than traditional practices have hitherto allowed. Copyright © 2011 John Wiley & Sons, Ltd.     

The impact of ditch blocking on the hydrological functioning of blanket peatlands

Ditch blocking in blanket peatlands is common as part of peatland restoration. The effects of ditch blocking on flow regimes and nearby water tables were examined in a field trial. After an initial 6‐month monitoring period, eight ditches had peat dams installed 10 m apart along their entire length (dammed), four of these ditches were also partially infilled through bank reprofiling (reprofiled). Four ditches were left open with no dams or reprofiling (open). These 12 ditches and the surrounding peat were monitored for 4 more years. An initial five‐fold reduction in discharge occurred in the dammed and the reprofiled ditches with the displaced water being diverted to overland flow and pathways away from the ditches. However, there was a gradual change over time in ditch flow regime in subsequent years, with the overall volume of water leaving the dammed and the reprofiled ditches increasing per unit of rainfall to around twice that which occurred in the first year after blocking. Hence, monitoring for greater than one year is important for understanding hydrological impacts of peatland restoration. Overland flow and flow in the upper ~4 cm of peat was common and occurred in the inter‐ditch areas for over half of the time after ditch blocking. There was strong evidence that topographic boundaries of small ditch catchments, despite being defined using a high‐resolution Light Detection And Ranging‐based terrain model, were not always equivalent to actual catchment areas. Hence, caution is needed when upscaling area‐based fluxes, such as aquatic carbon fluxes, from smaller scale studies including those using ditches and small streams. The effect of ditch blocking on local water tables was spatially highly variable but small overall (time‐weighted mean effect <2 cm). Practitioners seeking to raise water tables through peatland restoration should first be informed either by prior measurement of water tables or by spatial modelling to show whether the peatland already has shallow water tables or whether there are locations that could potentially undergo large water‐table recoveries.     

Spatial and temporal dynamics of stream water particulate and dissolved N, P and C forms along a catchment transect, NE Scotland

The dynamics of dissolved and particulate N, P and organic C were examined for field drains, through a headwater (4 km²), into a mesoscale stream (51 km²) and river (1844 km²) catchment. Distributions of N and P forms were similar in the agricultural headwater and field drains; annual P fluxes of particulate and dissolved forms were of equal magnitude, whilst N was dominated by NO₃–N. Across all scales organic P was an important, often dominant, component of the dissolved P. Temporal variation in nutrient concentrations and proportions was greatest in the headwater, where storms resulted in the generation of large concentrations of suspended particulate matter, particulate and dissolved P, particularly following dry periods. The data suggest that groundwater and minor point source inputs to the mesoscale catchment buffered the temporal variability in hydrochemistry relative to the headwater. Summer low flows were associated with large PO₄–P concentrations in the mesoscale catchment at a critical time of biological sensitivity. At the largest river catchment scale, organic forms of C, N and P dominated. Inorganic nutrient concentrations were kept small through dilution by runoff from upland areas and biological processes converted dissolved N and P to particulate forms. The different processes operating between the drain/headwater to the large river scale have implications for river basin management. Given the prevalence of organic and particulate P forms in our catchment transect, the bioavailability of these fractions needs to be better understood.     

Fluvial organic carbon composition and concentration variability within a peatland catchment—Implications for carbon cycling and water treatment

Fluvial organic carbon (OC) transformations are an important component of carbon cycling and greenhouse gas production in inland waters resulting in considerable recent interest in the fate of fluvial OC exported from carbon rich soils such as peatlands. Additionally, peatland catchments are important drinking water collection areas, where high OC concentrations in runoff have water treatment implications. This analysis presents the results from a year‐round intensive study within a water treatment catchment draining an area of peatland, considering carbon transformations along a continuum from headwater river, through a storage reservoir and pipe, to a water treatment works. The study uses a unique combination of methods (colourmetric, ultrafiltration, and ¹⁴C radiocarbon dating) to assess catchment wide changes in fluvial carbon composition (colour, size, and age) alongside concentration measures. The results indicate clear patterns of carbon transformations in the river and reservoir and dissolved low molecular weight coloured carbon to be most subject to change, with both loss and replacement within the catchment residence time. Although the evidence suggests dissolved OC (DOC) gains are from particulate OC breakdown, the mechanisms of DOC loss are less certain and may represent greenhouse gas losses or conversions to particulate OC. The transformations presented here appear to have minimal impact on the amount of harder to treat (<10 kDa) dissolved carbon, although they do have implications for total DOC loading to water treatment works. This paper shows that peatland fluvial systems are not passive receptors of particulate and dissolved organic carbon but locations where carbon is actively cycled, with implications for the understanding of carbon cycling and water treatment in peatland catchments.     

Dissolved organic matter variations in coastal plain wetland watersheds: The integrated role of hydrological connectivity,land use,and seasonality

Dissolved organic matter (DOM) is integral to fluvial biogeochemical functions, and wetlands are broadly recognized as substantial sources of aromatic DOM to fluvial networks. Yet how land use change alters biogeochemical connectivity of upland wetlands to streams remains unclear. We studied depressional geographically isolated wetlands on the Delmarva Peninsula (USA) that are seasonally connected to downstream perennial waters via temporary channels. Composition and quantity of DOM from 4 forested, 4 agricultural, and 4 restored wetlands were assessed. Twenty perennial streams with watersheds containing wetlands were also sampled for DOM during times when surface connections were present versus absent. Perennial watersheds had varying amounts of forested wetland (0.4–82%) and agricultural (1–89%) cover. DOM was analysed with ultraviolet–visible spectroscopy, fluorescence spectroscopy, dissolved organic carbon (DOC) concentration, and bioassays. Forested wetlands exported more DOM that was more aromatic‐rich compared with agricultural and restored wetlands. DOM from the latter two could not be distinguished suggesting limited recovery of restored wetlands; DOM from both was more protein‐like than forested wetland DOM. Perennial streams with the highest wetland watershed cover had the highest DOC levels during all seasons; however, in fall and winter when temporary streams connect forested wetlands to perennial channels, perennial DOC concentrations peaked, and composition was linked to forested wetlands. In summer, when temporary stream connections were dry, perennial DOC concentrations were the lowest and protein‐like DOM levels the highest. Overall, DOC levels in perennial streams were linked to total wetland land cover, but the timing of peak fluxes of DOM was driven by wetland connectivity to perennial streams. Bioassays showed that DOM linked to wetlands was less available for microbial use than protein‐like DOM linked to agricultural land use. Together, this evidence indicates that geographically isolated wetlands have a significant impact on downstream water quality and ecosystem function mediated by temporary stream surface connections.     

The potential role of freshwater luminescence measurements in exploring runoff pathways in upland catchments

The forested Coalburn catchment (1·5 km²) in northern England experiences episodic stream acidification. To plan for sustainable management of the plantation forest cycle, an understanding is required of the flow pathways and hydrochemical routing signatures of the organic and mineral soils that make up the source areas for runoff. A tentative mixing model, based on simple water chemistry exists for the major (terrestrial) sources and buffers of acidification; it is being expanded and consolidated by a detailed approach to the organic components of runoff, via sampling and analysis of the luminescence of surface waters at the catchment outlet and in two distinctive feeder streams. Luminescence measurements are presented that permit a simple apportionment of source areas. However, the technique also appears to have potential for identifying differential flow sourcing between the acrotelm and catotelm of intact peat deposits and for clarifying the influence of forest root systems in altering the organic chemistry of infiltrating waters. Applications may include the monitoring and prediction of coloured water events for the water supply industry. Copyright © 2001 John Wiley & Sons, Ltd.     

Impacts of upland open drains upon runoff generation: a numerical assessment of catchment‐scale impacts

Shallow upland drains, grips, have been hypothesized as responsible for increased downstream flow magnitudes. Observations provide counterfactual evidence, often relating to the difficulty of inferring conclusions from statistical correlation and paired catchment comparisons, and the complexity of designing field experiments to test grip impacts at the catchment scale. Drainage should provide drier antecedent moisture conditions, providing more storage at the start of an event; however, grips have higher flow velocities than overland flow, thus potentially delivering flow more rapidly to the drainage network. We develop and apply a model for assessing the impacts of grips on flow hydrographs. The model was calibrated on the gripped case, and then the gripped case was compared with the intact case by removing all grips. This comparison showed that even given parameter uncertainty, the intact case had significantly higher flood peaks and lower baseflows, mirroring field observations of the hydrological response of intact peat. The simulations suggest that this is because delivery effects may not translate into catchment‐scale impacts for three reasons. First, in our case, the proportions of flow path lengths that were hillslope were not changed significantly by gripping. Second, the structure of the grip network as compared with the structure of the drainage basin mitigated against grip‐related increases in the concentration of runoff in the drainage network, although it did marginally reduce the mean timing of that concentration at the catchment outlet. Third, the effect of the latter upon downstream flow magnitudes can only be assessed by reference to the peak timing of other tributary basins, emphasizing that drain effects are both relative and scale dependent. However, given the importance of hillslope flow paths, we show that if upland drainage causes significant changes in surface roughness on hillslopes, then critical and important feedbacks may impact upon the speed of hydrological response. Copyright © 2012 John Wiley & Sons, Ltd.     

Fluvial carbon flux from headwater peatland streams: significance of particulate carbon flux

The extensive blanket peatlands of the UK uplands account for almost half of total national terrestrial carbon storage. However, much of the blanket peat is severely eroded so that the contemporary role of the peatland system in carbon sequestration is compromised by losses of organic carbon in dissolved (DOC) and particulate (POC) form in the fluvial system. This paper presents the first detailed assessment of dissolved and organic carbon losses from a severely eroded headwater peatland (River Ashop, South Pennines, UK). Total annual fluvial organic carbon losses range from 29–106 Mg C km,^‐2 decreasing from the headwaters to the main catchment outlet. In contrast to less eroded systems fluvial organic carbon flux is dominated by POC. POC:DOC ratios decrease from values of 4 in the headwaters to close to unity at the catchment outlet. These results demonstrate the importance of eroding headwater sites as sources of POC to the fluvial system. Comparison with a range of catchment characteristics reveals that drainage density is the best predictor of POC:DOC but there is scatter in the relation in the headwaters. Steep declines in specific POC yield from headwater catchments are consistent with storage of POC within the fluvial system. Key to the significance of fluvial carbon flux in greenhouse gas budgets is understanding the fate of fluvial carbon. Further work on the fate of POC and the role of floodplains in fluvial carbon cycling is urgently required. Copyright © 2012 John Wiley & Sons, Ltd.