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Nearly 40% of the Earth’s ice-free surface area is cropland or pasture. Measurements of dissolved organic matter along a gradient of agricultural land use suggest that agricultural watersheds contain less complex, more microbially derived dissolved organic matter than natural wetlands. Nearly 40% of the Earth’s ice-free surface area is cropland or pasture 1 . Agricultural land use can increase the delivery of nutrients such as nitrogen and phosphorus to fluvial ecosystems 2 , but the impact of farming on riverine dissolved organic carbon is still largely unknown, despite increasing recognition that rivers act as important modifiers in the global carbon cycle 3 , 4 . Here, we examine the character of riverine dissolved organic matter in 34 watersheds along a gradient of agricultural land use. We show that changes in the character of dissolved organic matter are related to agricultural land use, nitrogen loading and wetland loss. Specifically, we find that the structural complexity of dissolved organic matter decreases as the ratio of continuous croplands to wetlands increases. At the same time, the amount of microbially derived dissolved organic matter increases with greater agricultural land use. Furthermore, we find that periods of soil dryness are associated with a decrease in the structural complexity of dissolved organic matter. We suggest that these effects of land use and climate on the character of riverine dissolved organic matter have important implications for global carbon cycling, owing to their potential to control rates of microbial carbon processing (for example, uptake, retention and outgassing) in agricultural systems.

Dissolved organic matter (DOM) is recognized for its importance in freshwater ecosystems, but historical reliance on DOM quantity rather than indicators of DOM composition has led to an incomplete understanding of DOM and an underestimation of its role and importance in biogeochemical processes. A single sample of DOM can be composed of tens of thousands of distinct molecules. Each of these unique DOM molecules has their own chemical properties and reactivity or role in the environment. Human activities can modify DOM composition and recent research has uncovered distinct DOM pools laced with human markers and footprints. Here we review how land use change, climate change, nutrient pollution, browning, wildfires, and dams can change DOM composition which in turn will affect internal processing of freshwater DOM. We then describe how human-modified DOM can affect biogeochemical processes. Drought, wildfires, cultivated land use, eutrophication, climate change driven permafrost thaw, and other human stressors can shift the composition of DOM in freshwater ecosystems increasing the relative contribution of microbial-like and aliphatic components. In contrast, increases in precipitation may shift DOM towards more relatively humic-rich, allochthonous forms of DOM. These shifts in DOM pools will likely have highly contrasting effects on carbon outgassing and burial, nutrient cycles, ecosystem metabolism, metal toxicity, and the treatments needed to produce clean drinking water. A deeper understanding of the links between the chemical properties of DOM and biogeochemical dynamics can help to address important future environmental issues, such as the transfer of organic contaminants through food webs, alterations to nitrogen cycling, impacts on drinking water quality, and biogeochemical effects of global climate change.

Surface water samples were collected from 43 streams distributed throughout watersheds of mixed land use in southern Ontario, Canada. Absorbance and fluorescence spectroscopy with parallel factor analysis (PARAFAC) was used to characterize dissolved organic matter (DOM). DOM characteristics were related to environmental variables, microbial activity indicators (bacterial production and extracellular leucine aminopeptidase activity), and riparian land use to understand better how these factors influence DOM in streams. PARAFAC produced a six-component model (C1 to C6). Temperature correlated with each PARAFAC component, suggesting that water source, drainage area, and light penetration broadly affected DOM characteristics. C1 and C2 represented terrestrial, humic-like DOM fluorophore groups and comprised 41-65% of stream DOM fluorescence. C5, a tryptophan-like component, related negatively to a humiflcation index but positively to leucine-aminopeptidase activity and recently produced DOM, suggesting that C5 consisted of autochthonous, microbially produced DOM. C3, C4, and C6 showed signs of quinone-like, humic-like, and microbial transformable fluorophores. The distribution of these potentially redox-active PARAFAC components indicated that DOM was in a more reduced state in streams with higher bacterial production and agricultural land use than in streams with increased wetlands area, which had greater relative abundance of the oxidized quinone-like component. Anthropogenic land use and microbial activity altered the quantity and quality of DOM exported from human-affected streams from that observed in forest- and wetland-dominated streams. DOM in agriculturally affected streams was likely more labile and accessible to the microbial community than DOM in wetland streams, which supported low rates of microbial activity.

Most dissolved organic carbon in rivers originates from young carbon in soils and vegetation. A global radiocarbon data set suggests that human disturbance is also introducing aged carbon to rivers and to active carbon cycling. Approximately 8% of anthropogenic carbon dioxide emissions are estimated to come from land-use change 1 , but this estimate excludes fluxes of terrestrial carbon to aquatic ecosystems from human disturbance. Carbon fluxes from land to rivers have probably increased by 0.1 to 0.2 petagrams of carbon per year as a result of disturbances such as deforestation, agricultural intensification and the injection of human wastewater 2 . Most dissolved organic carbon in rivers originates from young organic carbon from soils and vegetation 3 , but aged carbon removed from the modern carbon cycle is also exported in many systems. Here we analyse a global data set of radiocarbon ages of riverine dissolved organic carbon and spatial data on land cover, population and environmental variables. We find that the age of dissolved organic carbon in rivers increases with population density and the proportion of human-dominated landscapes within a watershed, and decreases with annual precipitation. We reason that disturbance reintroduces aged soil organic matter into the modern carbon cycle, although fossil carbon in fertilizer or petroleum products may also be a source of aged carbon in disturbed watersheds. The total export from the terrestrial environment to freshwater systems remains unknown; nevertheless, our results suggest that 3–9% of dissolved organic carbon in rivers is aged carbon mobilized by human disturbance.

We present the results of a full year of high-resolution monitoring of hydrologic event-driven export of stream dissolved organic matter (DOM) from the forested Bigelow Brook watershed in Harvard Forest, Massachusetts, USA. A combination of in situ fluorescent dissolved organic matter (FDOM) measurement, grab samples, and bioassays was utilized. FDOM was identified as a strong indicator of concentration for dissolved organic carbon (DOC, r 2 = 0.96), dissolved organic nitrogen (DON, r 2 = 0.81), and bioavailable DOC (BDOC, r 2 = 0.81). Relationships between FDOM and concentration were utilized to improve characterization of patterns of hydrological event-driven export and the quantification of annual export. This characterization was possible because DOM composition remained relatively consistent seasonally; however, a subtle shift to increased fluorescence per unit absorbance was observed for summer and fall seasons and percent BDOC did increase slightly with increasing concentrations. The majority of export occurred during pulsed hydrological events, so the greatest impact of bioavailable exports may be on downstream aquatic ecosystems. Export from individual events was highly seasonal in nature with the highest flow weighted mean concentrations (DOC FW ) being observed in late summer and fall months, but the highest total export being observed for larger winter storms. Seasonal trends in DOC export coincide with weather driven changes in surface and subsurface flow paths, potential for depletion and rebuilding of a flushable soil organic matter pool, and the availability of terrestrial carbon sources such as leaf litter. Our approach and findings demonstrate the utility of high frequency FDOM measurement to improve estimates of intra-annual temporal trends of DOM export.

Water‐extractable organic matter (WEOM) in soil affects contaminant mobility and toxicity, heterotrophic production, and nutrient cycling in terrestrial and aquatic ecosystems. This study focuses on the influences of land use history and agricultural management practices on the water extractability of organic matter and nutrients from soils. Water‐extractable organic matter was extracted from soils under different crop rotations (an annual rotation of wheat–pea/bean–wheat–flax or a perennial‐based rotation of wheat–alfalfa–alfalfa–flax) and management systems (organic or conventional) and examined for its concentration, composition, and biodegradability. The results show that crop rotations including perennial legumes increased the concentration of water‐extractable organic carbon (WEOC) and water‐extractable organic nitrogen (WEON) and the biodegradability of WEOC in soil but depleted the quantity of water‐extractable organic phosphorus (WEOP) and water‐extractable reactive phosphorus. The 30‐d incubation experiments showed that bioavailable WEOC varied from 12.5% in annual systems to 22% for perennial systems. The value of bioavailable WEOC was found to positively correlate with WEON concentrations and to negatively correlate with C:N ratio and the specific ultraviolet absorbance of WEOM. No significant treatment effect was present with the conventional and organic management practices, which suggested that WEOM, as the relatively labile pool in soil organic matter, is more responsive to the change in crop rotation than to mineral fertilizer application. Our results indicated that agricultural landscapes with contrasting crop rotations are likely to differentially affect rates of microbial cycling of organic matter leached to soil waters.

Concentration-discharge (C-Q) relationships have been widely used to assess the hydrochemical processes that control solute fluxes from streams. Here, using a large regional dataset we assessed long-term C-Q relationships for total phosphorus (TP), soluble reactive phosphorus (SRP), total Kjeldahl nitrogen (TKN), and nitrate (NO₃) for 63 streams in Ontario, Canada, to better understand seasonal regional behavior of nutrients. We used C-Q plots, Kruskal-Wallis tests, and breakpoint analysis to characterize overall regional nutrient C-Q relationships and assess seasonal effects, anthropogenic impacts, and differences between “rising” and “falling” hydrograph limbs to gain an understanding of the dominant processes controlling overall C-Q relationships. We found that all nutrient concentrations were higher on average in catchments with greater levels of anthropogenic disturbance (agricultural and urban land use). TP, SRP, and TKN showed similar C-Q dynamics, with nearly flat or gently sloping C-Q relationships up to a discharge threshold after which C-Q slopes substantially increased during the rising limb. These thresholds were seasonally variable, with summer and winter thresholds occurring at lower flows compared with autumn and greater variability during snowmelt. These patterns suggest that seasonal strategies to reduce high flows, such as creating riparian wetlands or reservoirs, in conjunction with reducing related nutrient transport during high flows would be the most effective way to mitigate elevated in-stream concentrations and event export. Elevated rising limb concentrations suggest that nutrients accumulate in upland parts of the catchment during drier periods and that these are released during rain events. NO₃ C-Q patterns tended to be different from the other nutrients and were further complicated by anthropogenic land use, with greater reductions on the falling limb in more disturbed catchments during certain seasons. There were few significant NO₃ hydrograph limb differences, indicating that there was likely to be no dominant hysteretic pattern across our study region due to variability in hysteresis from catchment to catchment. This suggests that this nutrient may be difficult to successfully manage at the regional scale.

A shift in natural hydrologic patterns, such as increases in the frequency, and changes in the magnitude of flood events are expected with climate change. A better understanding of how land use and hydrological patterns interact to affect solute levels in aquatic systems is needed so we can better navigate expected climatic changes. Here we analyzed spatiotemporal event-based data from 21 predominantly agricultural catchments with varying contributions of natural land cover. We studied the effect of hydrological events on stream dissolved phosphorus and nitrogen concentrations and dissolved organic matter (DOM) composition and bioavailability over 4 years. Our results suggest that flow regime and flood condition control stream DOM composition, nitrogen and phosphorus dynamics, modulated by seasonal processes and land use properties, like soil organic carbon content. Although higher flows generally increased solute concentrations as well as the fraction of terrestrial, humic-like DOM, this pattern was highly dependent on the catchment land use and event timing. General additive models indicated a threshold of about 30–40% natural land cover, below which DOC and nutrients showed a positive relationship with discharge, but when more than 30–40% natural features (for example, wetlands, woodlots and grasslands) were present in the catchments, this shifted to a negative relationship. This suggests that in agricultural landscapes, the presence of natural land cover is important as it can decrease solute concentrations in streams and may act as a buffer, mitigating the effect of floods on DOM and nutrient export rates.

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Struvite (NH4MgPO4·6H2O) may be an appropriate fertilizer to address phosphorus (P) deficiencies in organic cropping systems, but field studies assessing crop response to struvite are lacking. Field experiments were conducted over 3 yr on a low‐P, alkaline soil in Manitoba to assess the effect of struvite application rate on the yield and P accumulation of organically managed grain and forage crops. Struvite was applied to spring wheat (Triticum aestivum L.) and flax (Linum usitatissimum L.) at 0, 20, 30, and 40 kg P ha–1 in separate experiments each year and to alfalfa (Medicago sativa L.)–grass forage at 0, 30, 60, and 90 kg P ha–1 in a single application in a 3‐yr experiment. Wheat grain yield, P concentration, and P accumulation increased linearly with increasing struvite rate, whereas flax showed little to no response. Forage yield, P concentration, and P accumulation also increased with struvite rate. Benefits to forage yield and P accumulation were greatest in the second year, demonstrating important residual effects of struvite application. Struvite application shifted forage composition to become dominated by alfalfa whereas the unfertilized treatment was dominated by grasses. Annual P recovery efficiency was 4–7% for wheat, 1–2% for flax, and 7–12% for forage and did not vary significantly with struvite application rate. Our findings demonstrate that struvite applied at a relatively high rate is an effective P source for wheat and alfalfa‐based forage under organic management, but not for flax. Core Ideas Wheat and alfalfa–grass yield and P concentration increased with struvite application rate. Alfalfa–grass yield increased in the second and third years after struvite application. Struvite application increased flax grain P concentration but not yield. Phosphorus recovery efficiency from struvite by crops did not vary with application rate.