Dissolved organic matter (DOM) plays an important role in freshwater biogeochemistry. To investigate the influence of catchment character on the quality and quantity of DOM in freshwaters, 45 sampling sites draining subcatchments of contrasting soil type, hydrology, and land cover within one large upland‐dominated and one large lowland‐dominated catchment were sampled over a 1‐yr period. Dominant land cover in each subcatchment included: arable and horticultural, blanket peatland, coniferous woodland, and improved, unimproved, acid, and calcareous grasslands. The composition of the C, N, and P pool was determined as a function of the inorganic nutrient species (NO3−, NO2−, NH4+, and PO43−) and dissolved organic nutrient (dissolved organic carbon [DOC], dissolved organic nitrogen [DON], and dissolved organic phosphorus [DOP]) concentrations. DOM quality was assessed by calculation of the molar DOC : DON and DOC : DOP ratios and specific ultraviolet absorbance (SUVA254). In catchments with little anthropogenic nutrient inputs, DON and DOP typically composed > 80% of the total dissolved nitrogen (TDN) and total dissolved phosphorus (TDP) concentrations. By contrast, in heavily impacted agricultural catchments DON and DOP typically comprised 5–15% of TDN and 10–25% of TDP concentrations. Significant differences in DOC : DON and DOC : DOP ratios were observed between land cover class with significant correlations observed between both the DOC : DON and DOC : DOP molar ratios and SUVA254 (rs = 0.88 and 0.84, respectively). Analysis also demonstrated a significant correlation between soil C : N ratio and instream DOC : DON/DOP (rs = 0.79 and 0.71, respectively). We infer from this that soil properties, specifically the C : N ratio of the soil organic matter pool, has a significant influence on the composition of DOM in streams draining through these landscapes.

A comprehensive cross-biome assessment of major nitrogen (N) species that includes dissolved organic N (DON) is central to understanding interactions between inorganic nutrients and organic matter in running waters. Here, we synthesize stream water N chemistry across biomes and find that the composition of the dissolved N pool shifts from highly heterogeneous to primarily comprised of inorganic N, in tandem with dissolved organic matter (DOM) becoming more N-rich, in response to nutrient enrichment from human disturbances. We identify two critical thresholds of total dissolved N (TDN) concentrations where the proportions of organic and inorganic N shift. With low TDN concentrations (0-1.3 mg/L N), the dominant form of N is highly variable, and DON ranges from 0% to 100% of TDN. At TDN concentrations above 2.8 mg/L, inorganic N dominates the N pool and DON rarely exceeds 25% of TDN. This transition to inorganic N dominance coincides with a shift in the stoichiometry of the DOM pool, where DOM becomes progressively enriched in N and DON concentrations are less tightly associated with concentrations of dissolved organic carbon (DOC). This shift in DOM stoichiometry (defined as DOC:DON ratios) suggests that fundamental changes in the biogeochemical cycles of C and N in freshwater ecosystems are occurring across the globe as human activity alters inorganic N and DOM sources and availability. Alterations to DOM stoichiometry are likely to have important implications for both the fate of DOM and its role as a source of N as it is transported downstream to the coastal ocean.Plain Language Summary Ammonium and nitrate in freshwaters have received considerable attention due to their clear ecological and health effects. A comprehensive assessment of N in freshwaters that includes DON is lacking. Including DON in studies of surface water chemistry is important because it can cause eutrophication and certain forms can be rapidly removed by microbial communities. Here, we document how elevated levels of TDN impact the concentrations and relative proportions of all three forms of dissolved N and the stoichiometry of DOM. Our results suggest that human activities fundamentally alter the composition of the dissolved nitrogen pool and the WYMORE ET AL.

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Two lowland catchments in the U.K. were sampled throughout 2010-11 to investigate the dominant controls on dissolved organic matter quantity and composition. The catchments had marked differences in terms of nutrient status, land cover and contrasting lithologies resulting in differences in the dominant flow pathways (groundwater vs. surface water dominated). The Upper Wylye is a chalk stream with a baseflow index of 0.98, draining a catchment dominated by intensive agricultural production. Millersford Brook is a lowland peat catchment with a baseflow index of 0.43, draining a semi-natural catchment with heather moorland and coniferous forest. Samples were collected weekly between October 2010 and September 2011 from eleven sampling locations. Samples were analysed to determine dissolved organic carbon, nitrogen and phosphorus fractions with DOM composition evaluated via the DOC:DON ratio, DOC:DOP ratio, specific UV absorption at 254nm, absorbance ratio (a250:a365) and the spectral slope parameter between 350 and 400nm (S350-400). Significant differences were observed in all determinands between the catchments, over time, and spatially along nutrient enrichment and geoclimatic gradients. Seasonal variation in preferential flow pathways mobilising groundwater-derived DOM were identified as likely controls on the delivery of DOM in the permeable chalk dominated catchment. Steeper S350-400 values and elevated a250:a365 ratios in this catchment suggest material of a lower bulk aromatic C content and molecular weight delivered during the winter months when compared to the summer. DOC:DON ratios were markedly lower in the chalk catchment than the peatland catchment, reflecting the paucity of organic matter within the mineral soils of the chalk landscape, and higher fertiliser application rates. This manuscript highlights that DOM composition varies according to catchment landscape character and hydrological function.

Dissolved organic matter (DOM) represents a key component of carbon (C) cycling in freshwater ecosystems. While the behaviour of bulk dissolved organic carbon (DOC) in aquatic ecosystems is well studied, comparatively little is known about the turnover of specific DOC compounds. The aim of this study was to investigate the persistence of 14 C-labelled low molecular weight (LMW) DOC at a wide range of concentrations (0.1 µM to 10 mM), in sediments and waters from oligotrophic and mesotrophic rivers within the same catchment. Overall, rates of DOC loss varied between compound groups (amino acids > sugars = organic acids > phenolics). Sediment-based microbial communities contributed to higher DOC loss from river waters, which was attributed, in part, to its greater microbial biomass. At higher DOC compound concentrations, DOC loss was greater in mesotrophic rivers in comparison to oligotrophic headwaters. A lag-phase in substrate use within sediments provided evidence of microbial growth and adaptation, ascribed here to the lack of inorganic nutrient limitation on microbial C processing in mesotrophic communities. We conclude that the higher microbial biomass and available inorganic nutrients in sediments enables the rapid processing of LMW DOC, particularly during high C enrichment events and in N and P-rich mesotrophic environments.

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Sewage treatment systems are a common feature across the landscape of the United Kingdom, serving an estimated 96% of the population and discharging approximately eleven billion litres of treated wastewater daily. While large treatment facilities are ubiquitous across the landscape, they are not the only method employed in domestic wastewater treatment. This study investigates whether differences in nutrient export (carbon, nitrogen and phosphorus) and organic matter composition (determined by optical indices, SUVA254, S350-400 and E2:E3) from treated effluent could be detected between four of the most common facilities employed in the treatment of wastewater across the U.K. Set in the context of the River Wylye, a small headwater catchment, treatment facilities studied included; a septic tank system, small packet treatment works, and two large sewage treatment works, one of which employed phosphorus stripping for phosphorus removal. Inorganic N and P concentrations ranging between 7.51 and 42.4 mg N l-1 and 0.22 and 8.9 mg P l-1 respectively, with DOC concentrations ranging between 1.63 and 11.8 mg C l-1. Optical indices were comparable to those observed in microbially dominated endmember aquatic systems suggesting the dominance of low molecular weight material when compared to values observed across temperate aquatic systems. Combining data from both the Environment Agency and Ordinance Survey we estimate that only 25% of domestic properties in the study catchment have a corresponding Environment Agency consent/exemption permit meaning the numbers of small discharges are significantly underestimated, thus undermining efforts under current legislation to improve stream ecosystem health.

Dissolved organic matter (DOM) plays a central role in regulating productivity and nutrient cycling in freshwaters. It is therefore vital that we can representatively sample and preserve DOM in freshwaters for subsequent analysis. Here we investigated the effect of filtration, temperature (5 and 25°C) and acidification (HCl) on the persistence of low molecular weight (MW) dissolved organic carbon (DOC), nitrogen (DON) and orthophosphate in oligotrophic and eutrophic freshwater environments. Our results showed the rapid loss of isotopically-labelled glucose and amino acids from both filtered (0.22 and 0.45μm) and unfiltered waters. We ascribe this substrate depletion in filtered samples to the activity of ultra-small (<0.45μm) microorganisms (bacteria and archaea) present in the water. As expected, the rate of C, N and P loss was much greater at higher temperatures and was repressed by the addition of HCl. Based on our results and an evaluation of the protocols used in recently published studies, we conclude that current techniques used to sample water for low MW DOM characterisation are frequently inadequate and lack proper validation. In contrast to the high degree of analytical precision and rigorous statistical analysis of most studies, we argue that insufficient consideration is still given to the presence of ultra-small microorganisms and potential changes that can occur in the low MW fraction of DOM prior to analysis.