Water residence time is an important predictor of dissolved organic matter composition and drinking water treatability.

Freshwater ecosystems are critical resources for drinking water. In recent decades, dissolved organic matter (DOM) inputs into aquatic systems have increased significantly, particularly in central and northern Europe, due to climatic and anthropogenic drivers. The associated increase in dissolved organic carbon (DOC) concentration can change lake ecosystem services and adversely affect drinking water treatment processes. In this study, we examined spatial and temporal patterns of DOM treatability with granular activated carbon (GAC) and biological reactivity based on 14-day bacterial respiration incubations at 11 sites across Mälaren during six-time points between July 2019 and February 2021. Mälaren is the third largest lake in Sweden and provides drinking water for over 2 million people including the capital city Stockholm. In our spatio-temporal analysis, we assessed the influence of phytoplankton abundance, water chemistry, runoff, and climate on DOM composition, GAC removal efficiency, and biological reactivity. Variations in DOM composition were characterized using optical measurements and Orbitrap mass spectrometry. Multivariate statistical analyses indicated that DOM produced during warmer months was easier to remove by GAC. Removal efficiency of GAC varied from 41 to 87 %, and the best predictor of treatability using mass spectrometry was double bond equivalents (DBE), while the best optical predictors were specific UV absorbance (SUVA), and freshness index. The oxygen consumption rate (k) from the bacterial respiration incubations ranged from 0.04 to 0.71 d-1 and higher in warmer months and at deeper basins and was associated with more aliphatic and fresh DOM. The three deepest lake basins with the longest water residence time (WRT) were temporally the most stable in terms of DOM composition and had the highest DOC removal efficiency and k rates. DOM composition in these three lake basins was optically clearer than in basins located closer to terrestrial inputs and had a signature suggesting it was derived from in-lake processes including phytoplankton production and bacterial processing of terrestrial DOM. This means that with increasing WRT, DOM derived from terrestrial sources shifts to more aquatically produced DOM and becomes easier to remove with GAC. These findings indicate WRT can be highly relevant in shaping DOM composition and thereby likely to affect its ease of treatability for drinking water purposes.

Water table depth and plant species determine the direction and magnitude of methane fluxes in floodplain meadow soils.

Methane (CH4) is a powerful greenhouse gas with ongoing efforts aiming to quantify and map emissions from natural and managed ecosystems. Wetlands play a significant role in the global CH4 budget, but uncertainties in their total emissions remain large, due to a combined lack of CH4 data and fuzzy boundaries between mapped ecosystem categories. European floodplain meadows are anthropogenic ecosystems that originated due to traditional management for hay cropping. These ecosystems are seasonally inundated by river water, and straddle the boundary between grassland and wetland ecosystems; however, an understanding of their CH4 function is lacking. Here, we established a replicated outdoor floodplain-meadow mesocosm experiment to test how water table depth (45, 30, 15 cm below the soil surface) and plant composition affect CH4 fluxes over an annual cycle. Water table was a major controller on CH4, with significantly higher fluxes (overall mean 9.3 mg m-2 d-1) from the high (15 cm) water table treatment. Fluxes from high water table mesocosms with bare soil were low (mean 0.4 mg m-2 d-1), demonstrating that vegetation drove high emissions. Larger emissions came from high water table mesocosms with aerenchymatous plant species (e.g. Alopecurus pratensis, mean 12.8 mg m-2 d-1), suggesting a role for plant-mediated transport. However, at low (45 cm) water tables A. pratensis mesocosms were net CH4 sinks, suggesting that there is plasticity in CH4 exchange if aerenchyma are present. Plant cutting to simulate a hay harvest had no effect on CH4, further supporting a role for plant-mediated transport. Upscaling our CH4 fluxes to a UK floodplain meadow using hydrological modelling showed that the meadow was a net CH4 source because oxic periods of uptake were outweighed by flooding-induced anoxic emissions. Our results show that floodplain meadows can be either small sources or sinks of CH4 over an annual cycle. Their CH4 exchange appears to respond to soil temperature, moisture status and community composition, all of which are likely to be modified by climate change, leading to uncertainty around the future net contribution of floodplain meadows to the CH4 cycle.

Wetland productivity determines trade-off between biodiversity support and greenhouse gas production.

Establishing wetlands for nutrient capture and biodiversity support may introduce trade-offs between environmentally beneficial functions and detrimental greenhouse gas emissions. Investigating the interaction of nutrient capture, primary production, greenhouse gas production and biodiversity support is imperative to understanding the overall function of wetlands and determining possible beneficial synergistic effects and trade-offs. Here, we present temporally replicated data from 17 wetlands in hemi-boreal Sweden. We explored the relationship between nutrient load, primary producing algae, production of methane and nitrous oxide, and emergence rates of chironomids to determine what factors affected each and how they related to each other. Chironomid emergence rates correlated positively with methane production and negatively with nitrous oxide production, where water temperature was the main driving factor. Increasing nutrient loads reduced methanogenesis through elevated nitrogen concentrations, while simultaneously enhancing nitrous oxide production. Nutrient loads only indirectly increased chironomid emergence rates through increased chlorophyll-a concentration, via increased phosphorus concentrations, with certain taxa and food preference functional groups benefitting from increased chlorophyll-a concentrations. However, water temperature seemed to be the main driving factor for chironomid emergence rates, community composition and diversity, as well as for greenhouse gas production. These findings increase our understanding of the governing relationships between biodiversity support and greenhouse gas production, and should inform future management when constructing wetlands.

Forest streams are important sources for nitrous oxide emissions.

Streams and river networks are increasingly recognized as significant sources for the greenhouse gas nitrous oxide (N2 O). N2 O is a transformation product of nitrogenous compounds in soil, sediment and water. Agricultural areas are considered a particular hotspot for emissions because of the large input of nitrogen (N) fertilizers applied on arable land. However, there is little information on N2 O emissions from forest streams although they constitute a major part of the total stream network globally. Here, we compiled N2 O concentration data from low-order streams (~1,000 observations from 172 stream sites) covering a large geographical gradient in Sweden from the temperate to the boreal zone and representing catchments with various degrees of agriculture and forest coverage. Our results showed that agricultural and forest streams had comparable N2 O concentrations of 1.6 ± 2.1 and 1.3 ± 1.8 µg N/L, respectively (mean ± SD) despite higher total N (TN) concentrations in agricultural streams (1,520 ± 1,640 vs. 780 ± 600 µg N/L). Although clear patterns linking N2 O concentrations and environmental variables were difficult to discern, the percent saturation of N2 O in the streams was positively correlated with stream concentration of TN and negatively correlated with pH. We speculate that the apparent contradiction between lower TN concentration but similar N2 O concentrations in forest streams than in agricultural streams is due to the low pH (<6) in forest soils and streams which affects denitrification and yields higher N2 O emissions. An estimate of the N2 O emission from low-order streams at the national scale revealed that ~1.8 × 109  g N2 O-N are emitted annually in Sweden, with forest streams contributing about 80% of the total stream emission. Hence, our results provide evidence that forest streams can act as substantial N2 O sources in the landscape with 800 × 109  g CO2 -eq emitted annually in Sweden, equivalent to 25% of the total N2 O emissions from the Swedish agricultural sector.

Characterisation of the semi-volatile component of Dissolved Organic Matter by Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry.

Proton Transfer Reaction - Mass Spectrometry (PTR-MS) is a sensitive, soft ionisation method suitable for qualitative and quantitative analysis of volatile and semi-volatile organic vapours. PTR-MS is used for various environmental applications including monitoring of volatile organic compounds (VOCs) emitted from natural and anthropogenic sources, chemical composition measurements of aerosols, etc. Here we apply thermal desorption PTR-MS for the first time to characterise the chemical composition of dissolved organic matter (DOM). We developed a clean, low-pressure evaporation/sublimation system to remove water from samples and coupled it to a custom-made thermal desorption unit to introduce the samples to the PTR-MS. Using this system, we analysed waters from intact and degraded peat swamp forest of Kalimantan, Indonesian Borneo, and an oil palm plantation and natural forest in Sarawak, Malaysian Borneo. We detected more than 200 organic ions from these samples and principal component analysis allowed clear separation of the different sample origins based on the composition of organic compounds. The method is sensitive, reproducible, and provides a new and comparatively cheap tool for a rapid characterisation of water and soil DOM.

Quantifying tropical peatland dissolved organic carbon (DOC) using UV-visible spectroscopy.

UV-visible spectroscopy has been shown to be a useful technique for determining dissolved organic carbon (DOC) concentrations. However, at present we are unaware of any studies in the literature that have investigated the suitability of this approach for tropical DOC water samples from any tropical peatlands, although some work has been performed in other tropical environments. We used water samples from two oil palm estates in Sarawak, Malaysia to: i) investigate the suitability of both single and two-wavelength proxies for tropical DOC determination; ii) develop a calibration dataset and set of parameters to calculate DOC concentrations indirectly; iii) provide tropical researchers with guidance on the best spectrophotometric approaches to use in future analyses of DOC. Both single and two-wavelength model approaches performed well with no one model significantly outperforming the other. The predictive ability of the models suggests that UV-visible spectroscopy is both a viable and low cost method for rapidly analyzing DOC in water samples immediately post-collection, which can be important when working at remote field sites with access to only basic laboratory facilities.

Management effects on greenhouse gas dynamics in fen ditches.

Globally, large areas of peatland have been drained through the digging of ditches, generally to increase agricultural production. By lowering the water table it is often assumed that drainage reduces landscape-scale emissions of methane (CH4) into the atmosphere to negligible levels. However, drainage ditches themselves are known to be sources of CH4 and other greenhouse gases (GHGs), but emissions data are scarce, particularly for carbon dioxide (CO2) and nitrous oxide (N2O), and show high spatial and temporal variability. Here, we report dissolved GHGs and diffusive fluxes of CH4 and CO2 from ditches at three UK lowland fens under different management; semi-natural fen, cropland, and cropland restored to low-intensity grassland. Ditches at all three fens emitted GHGs to the atmosphere, but both fluxes and dissolved GHGs showed extensive variation both seasonally and within-site. CH4 fluxes were particularly large, with medians peaking at all three sites in August at 120-230mgm-2d-1. Significant between site differences were detected between the cropland and the other two sites for CO2 flux and all three dissolved GHGs, suggesting that intensive agriculture has major effects on ditch biogeochemistry. Multiple regression models using environmental and water chemistry data were able to explain 29-59% of observed variation in dissolved GHGs. Annual CH4 fluxes from the ditches were 37.8, 18.3 and 27.2gCH4m-2yr-1 for the semi-natural, grassland and cropland, and annual CO2 fluxes were similar (1100 to 1440gCO2m-2yr-1) among sites. We suggest that fen ditches are important contributors to landscape-scale GHG emissions, particularly for CH4. Ditch emissions should be included in GHG budgets of human modified fens, particularly where drainage has removed the original terrestrial CH4 source, e.g. agricultural peatlands.

Influence of Water Table Depth on Pore Water Chemistry and Trihalomethane Formation Potential in Peatlands.

Drained peatland catchments are reported to produce more colored, dissolved organic carbon (DOC)-rich water, presenting problems for potable water treatment. The blocking of peatland drainage ditches to restore the water table is increasingly being considered as a strategy to address this deterioration in water quality. However, the effect of ditch blocking on the potential of DOC to form trihalomethanes (THMs) has not been assessed. In this study, the effect of peat rewetting on pore water DOC concentration and characteristics (including THM formation potential [THMFP]) was assessed over 12 months using peat cores collected from two drained peatland sites. The data show little evidence of differences in DOC concentration or characteristics between the different treatments. The absence of any difference in the THMFP of pore water between treatments suggests that, in the short term at least, ditch blocking may not have an effect on the THMFP of waters draining peatland catchments.

Investigations of freezing and cold storage for the analysis of peatland dissolved organic carbon (DOC) and absorbance properties.

Although measured rates of biological degradation of DOC are typically low under dark conditions, it is assumed that water samples must be analysed soon after collection to provide an accurate measure of DOC concentration and UV-visible absorbance. To examine the impact of storage on DOC quality and quantity, we took water samples from an ombrotrophic peatland, and stored them in the dark at 4 °C for 138-1082 days. A median of 29% of DOC was lost during storage, but losses of absorbance at 254 nm were less. DOC loss followed a first-order exponential decay function, and was dependent on storage time. DOC half-life was calculated as 1253 days. Specific absorbance at 254 nm suggested that samples containing more aromatic DOC were more resistant to degradation, although time functioned as the primary control. Samples from two fens showed that loss of absorbance was greater at 400 nm rather than 254 nm, after 192 days storage, suggesting that non-aromatic DOC is preferentially degraded. These results suggest that samples can be stored for several months before losses of DOC become detectable, and that it is possible to back-calculate initial DOC concentrations in long-term stored samples based on known decay rates. Freeze/thaw experiments using samples from a range of peatlands suggested that DOC concentration was mostly unaffected by the process, but DOC increased 37% in one sample. Freezing had unpredictable and sometimes strong effects on absorbance, SUVA and E ratios, therefore freezing is not recommended as a method of preservation for these analyses.

UV-visible absorbance spectroscopy as a proxy for peatland dissolved organic carbon (DOC) quantity and quality: considerations on wavelength and absorbance degradation.

Absorbance in the UV or visible spectrum (UV-vis) is commonly used as a proxy for DOC concentrations in waters draining upland catchments. To determine the appropriateness of different UV-vis measurements we used surface and pore water samples from two Welsh peatlands in four different experiments: (i) an assessment of single wavelength proxies (1 nm increments between 230-800 nm) for DOC concentration demonstrated that 254 nm was more accurate than 400 nm. The highest R(2) values between absorbance and DOC concentration were generated using 263 nm for one sample set (R(2) = 0.91), and 230 nm for the other three sample sets (respective R(2) values of 0.86, 0.81, and 0.93). (ii) A comparison of different DOC concentration proxies, including single wavelength proxies, a two wavelength model, a proxy using phenolic concentration, and a proxy using the area under a UV spectrum at 250-350 nm. It was found that both a single wavelength proxy (≤263 nm) and a two wavelength model performed well for both pore water and surface water. (iii) An evaluation of the E2 : E3, E2 : E4, E4 : E6 ratios, and SUVA (absorbance at 254 nm normalised to DOC concentration) as indicators of DOC quality showed that the E4 : E6 ratio was subject to extensive variation over time, and was highly correlated between surface water and pore water, suggesting that it is a useful metric to determine temporal changes in DOC quality. (iv) A repeated weekly analysis over twelve weeks showed no consistent change in UV-vis absorbance, and therefore an inferred lack of degradation of total DOC in samples that were filtered and stored in the dark at 4 °C.