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Excess nitrogen (N) losses from intensive agricultural production are a world-wide problem causing eutrophication in vulnerable aquatic ecosystems such as estuaries. Therefore, Denmark as one of the most intensively farmed countries in the world has enforced mandatory regulations on agricultural production since the late 1980s. We demonstrate the outcome of the regulations imposed on agriculture by analyzing decadal trends in nitrate (NO3-) concentrations and loads in streams using 29 years of detailed monitoring data and survey information on agricultural practices at field level from five intensively cultivated headwater catchments. The analysis includes the importance of four main drivers (climate, land use, agricultural practices, and biogeophysical properties of catchments), each divided into different factors that may influence stream NO3- loads during three subperiods defined by the time of introduction of different mitigation measures: i) 1990-1998, ii) 1999-2007, and iii) 2008-2018. Significant correlations with annual flow-weighted stream NO3- concentrations and/or loads were found for factors representing all of the four main drivers including precipitation, large scale climate fluctuations, runoff, previous year's runoff, baseflow index, number of annual frost days, agricultural area, livestock density, field N surplus, catch crop cover, manure storage capacity, method and time of manure spreading, and time of soil tillage. Changes in the four drivers were reflected by the load-runoff (L-Q) relationships for each of the three subperiods within each of the five headwater catchments. The five catchments experienced large but catchment-specific downward shifts in the L-Q relationship attributable to changes in land use and agricultural management within the catchments. The documented large downward shifts in NO3- loads demonstrated for the five catchments (30-52%) as a consequence of mandatory regulation over a period of nearly three decades are a unique example of how agriculture can reduce its environmental impact.

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Integrated buffer zones (IBZ) are novel mitigation measures designed to decrease the loading of nitrogen (N) transported by subsurface drainage systems from agricultural fields to streams. In IBZ, drainage water flows into a pond with free water surface followed by an inundated, vegetated filterbed. This design provides an environment favorable for denitrification and thus a decrease in nitrate concentration is expected as water flow through the IBZ. However, due to the establishment of anaerobic conditions, there is a risk for increasing emissions of the greenhouse gases nitrous oxide (N2O) and methane (CH4). In this year-long study, we evaluated the N removal efficiency along with the risk of N2O and CH4 emissions from two pilot-scale IBZs (IBZ1 and 2). The two IBZs had very different yearly removal efficiencies, amounting to 29% and 71% of the total N load at IBZ1 and 2, respectively. This was probably due to differences in infiltration rates to the filterbed, which was 22% and 81% of the incoming water at IBZ1 and 2, respectively. The site (IBZ2) with the highest removal efficiency was a net N2O sink, while 0.9% of the removed nitrate was emitted as N2O at IBZ1. Both IBZs were net sources of CH4 but with different pathways of emission. In IBZ1 CH4 was mainly lost directly to the atmosphere, while waterborne losses dominated in IBZ2. In conclusion, the IBZs were effective in removing N three years after establishment, and although the IBZs acted as greenhouse gas sources, especially due to CH4, the emissions were comparable to those of natural wetlands and other drainage transport mitigation measures.

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In the future, the world is expected to rely increasingly on renewable biomass resources for food, fodder, fibre and fuel. The sustainability of this transition to bioeconomy for our water systems depends to a large extent on how we manage our land resources. Changes in land use together with climate change will affect water quantity and quality, which again will have implications for the ecosystem services provided by water resources. These are the main topics of this Ambio special issue on "Environmental effects of a green bio-economy". This paper offers a summary of the eleven papers included in this issue and, at the same time, outlines an approach to quantify and mitigate the impacts of bioeconomy on water resources and their ecosystem services, with indications of useful tools and knowledge needs.

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Reference conditions of water bodies are defined as the natural or minimal anthropogenically disturbed state. We compared the methods for determining total phosphorus and total nitrogen concentrations in rivers in Finland, Norway and Sweden as well as the established reference conditions and evaluated the possibility for transfer and harmonisation of methods. We found that both methods and values differed, especially for lowland rivers with a high proportion of agriculture in the catchment. Since Denmark has not yet set reference conditions for rivers, two of the Nordic methods were tested for Danish conditions. We conclude that some of the established methods are promising but that further development is required. We moreover argue that harmonisation of reference conditions is needed to obtain common benchmarks for assessing the impacts of current and future land use changes on water quality.

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In this study, we explored how a targeted land use change in a Danish catchment (River Odense) may provide multi-functional benefits through nitrogen (N)-load reductions to obtain good ecological quality in Odense estuary, protection of N-vulnerable groundwater aquifers, protection of Natura2000 sites and carbon sequestration. An N-load model linked to GIS thematic layers of known protected areas (Natura2000 sites and N-vulnerable groundwater aquifers) was utilised targeting high N-load areas to locate set-aside land. The achieved multi-functional benefits within the catchment and estuary were assessed and cost-benefit assessment was performed by dividing the total welfare costs of the set-aside by the total multi-functional benefits gained from each strategy. The results show that obtaining multi-functional benefits at the lowest cost requires a targeted shift of set-aside from the traditional hot-spot N-load areas to designated protected areas.

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Nordic water bodies face multiple stressors due to human activities, generating diffuse loading and climate change. The 'green shift' towards a bio-based economy poses new demands and increased pressure on the environment. Bioeconomy-related pressures consist primarily of more intensive land management to maximise production of biomass. These activities can add considerable nutrient and sediment loads to receiving waters, posing a threat to ecosystem services and good ecological status of surface waters. The potential threats of climate change and the 'green shift' highlight the need for improved understanding of catchment-scale water and element fluxes. Here, we assess possible bioeconomy-induced pressures on Nordic catchments and associated impacts on water quality. We suggest measures to protect water quality under the 'green shift' and propose 'road maps' towards sustainable catchment management. We also identify knowledge gaps and highlight the importance of long-term monitoring data and good models to evaluate changes in water quality, improve understanding of bioeconomy-related impacts, support mitigation measures and maintain ecosystem services.

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Diffusive losses of nitrogen and phosphorus from agricultural areas have detrimental effects on freshwater and marine ecosystems. Mitigation measures treating drainage water before it enters streams hold a high potential for reducing nitrogen and phosphorus losses from agricultural areas. To achieve a better understanding of the opportunities and challenges characterising current and new drainage mitigation measures in oceanic and continental climates, we reviewed the nitrate and total phosphorus removal efficiency of: (i) free water surface constructed wetlands, (ii) denitrifying bioreactors, (iii) controlled drainage, (iv) saturated buffer zones and (v) integrated buffer zones. Our data analysis showed that the load of nitrate was substantially reduced by all five drainage mitigation measures, while they mainly acted as sinks of total phosphorus, but occasionally, also as sources. The various factors influencing performance, such as design, runoff characteristics and hydrology, differed in the studies, resulting in large variation in the reported removal efficiencies.

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Drainage systems provide a more or less direct conduit for excess water and nutrients from fields to surface water. High nutrient loads to streams and lakes are known to adversely affect water quality and may potentially cause algae blooms. Therefore, in-field as well as edge-of-field mitigation measures that can assist in reducing the loss of nutrients are needed. The aim of this study was to investigate the effectiveness and possibility of using controlled drainage during the drainage season to reduce nutrient losses while growing a winter crop in a temperate climate. The 3-yr-long (2012-2015) study was conducted on four experimental field plots on loamy soil. The impacts of controlled drainage on groundwater levels, drain flow, and water quality at regulation levels of 50 and 70 cm above the conventional drain pipe level were determined by using a before-after control-impact study design. A regulation level of 70 cm was required to significantly elevate groundwater levels and reduce the drain outflow and N and P loss, which decreased by 37 to 54%, 38 to 51%, and 43 to 46%, respectively, relative to conventional drainage levels. Denitrification in the root zone, as measured with stable isotopes, was not markedly enhanced at the plots with controlled drainage, except on a few occasions. Resetting the groundwater level to conventional levels in early spring only had a marginal influence on water and nutrient losses. Thus, potential water quality tradeoffs (e.g., increased N loss to groundwater) need to be more thoroughly investigated before implementing controlled drainage as a mitigation measure in Denmark.

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Vegetated buffer strips (VBS) between agricultural areas and surface waters are important retention areas for eroded particulate P through which they may obtain critically high degrees of P saturation imposing high risk of soluble P leaching. We tested topsoil removal and three harvesting frequencies (once, twice, or four times per year) of natural buffer vegetation to reduce P leaching with the aim to offset erosional P accumulation and high degrees of P saturation. We used a simple numerical time-step model to estimate changes in VBS soil P levels with and without harvest. Harvesting offset erosional deposition as it resulted in an annual ammonium oxalate-extractable P reduction of 0.3 to 2.8% (25-cm topsoil content) in soils of the VBS and thus, with time, reduced potential P leaching below a baseline of 50 µg L. Topsoil removal only marginally reduced potential leaching at two sites and not anywhere near this baseline. The harvest frequency only marginally affected the annual P removal, making single annual harvests the most economical. We estimate 50 to 300 yr to reach the P leaching baseline, due to substantial amounts of P accumulated in the soils. Even in high-erosion-risk situations in our study, harvesting reduced soil P content and the P leaching risk. We suggest harvesting as a practical and efficient management to combat P leaching from agricultural VBS, not just for short-term reductions of dissolved P, but also for reductions of the total soil P pool and for possible multiple benefits for VBS.

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Buffer strips between land and waters are widely applied measures in diffuse pollution management, with desired outcomes across other factors. There remains a need for evidence of pollution mitigation and wider habitat and societal benefits across scales. This paper synthesizes a collection of 16 new primary studies and review papers to provide the latest insights into riparian management. We focus on the following areas: (i) diffuse pollution removal efficiency of conventional and saturated buffer strips, (ii) enhancing biodiversity of buffers, (iii) edge-of-field technologies for improving nutrient retention, and (iv) potential reuse of nutrients and biomass from buffers. Although some topics represent emerging areas, for other well-studied topics (e.g., diffuse pollution), it remains that effectiveness of conventional vegetated buffer strips for water quality improvement varies. The collective findings highlight the merits of targeted, designed buffers that support multiple benefits, more efficiently interrupting surface and subsurface contaminant flows while enhancing diversity in surface topography, soil moisture and C, vegetation, and habitat. This synthesis also highlights that despite the significant number of studies on the functioning of riparian buffers, research gaps remain, particularly in relation to (i) the capture and retention of soluble P and N in subsurface flows through buffers, (ii) the utilization of captured nutrients, (iii) the impact of buffer design and management on terrestrial and aquatic habitats and species, and (iv) the effect of buffers (saturated) on greenhouse gas emissions and the potential for pollution swapping.

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Integrated buffer zones (IBZs) have recently been introduced in the Northwestern Europe temperate zone to improve delivery of ecosystem services compared with the services associated with long-established vegetated buffer zones. A common feature of all the studied IBZ sites is that tile drainage, which previously discharged directly into the streams, is now intercepted within the IBZ. Specifically, the design of IBZs combines a pond, where soil particles present in drain water or surface runoff can be deposited, and a planted subsurface flow infiltration zone. Together, these two components should provide an optimum environment for microbial processes and plant uptake of nutrients. Nutrient reduction capacities, biodiversity enhancement, and biomass production functions were assessed with different emphasis across 11 IBZ sites located in Denmark, Great Britain, and Sweden. Despite the small size of the buffer zones (250-800 m) and thus the small proportion of the drained catchment (mostly <1%), these studies cumulatively suggest that IBZs are effective enhancements to traditional buffer zones, as they (i) reduce total N and P loads to small streams and rivers, (ii) act as valuable improved habitats for aquatic and amphibian species, and (iii) offer economic benefits by producing fast-growing wetland plant biomass. Based on our assessment of the pilot sites, guidance is provided on the implementation and management of IBZs within agricultural landscapes.

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Integrated buffer zones (IBZs) represent a novel form of edge-of-field technology in Northwest Europe. Contrary to the common riparian buffer strips, IBZs collect tile drainage water from agricultural fields by combining a ditch-like pond (POND), where soil particles can settle, and a flow-through filter bed (FILTERBED) planted with Alnus glutinosa (L.), a European alder (black alder). The first experimental IBZ facility was constructed and thoroughly tested in Denmark for its capability to retain various nitrogen (N) and phosphorus (P) species within the first three years after construction. We calculated the water and nutrient budget for the total IBZ and for the two compartments, POND and FILTERBED, separately. Furthermore, a tracer experiment using sodium bromide was conducted in order to trace the water flow and estimate the hydraulic residence time in the FILTERBEDs. The monthly average removal efficiency amounted to 10-67% for total N and 31-69% for total P, with performance being highest during the warm season. Accordingly, we suggest that IBZs may be a valuable modification of dry buffer strips in order to mitigate the adverse impacts of high nutrient loading from agricultural fields on the aquatic environment.

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Vegetated buffer strips constitute a transition zone between terrestrial and aquatic ecosystems and provide several ecosystem services. Buffer strips are often applied as a mitigation measure against diffuse pollution in agricultural areas, primarily because they may retain nutrients and in this way help protect the aquatic environment. Additionally, they can improve biodiversity in an otherwise homogenous landscape and may therefore have a value in their own right. In the present study, we characterized the structural and functional features of the vegetation in Danish buffer strips using a nationwide dataset to explore: i) their floristic quality in terms of species diversity and conservation value and ii) based on their functional characteristics, their potential to retain nutrients. Moreover, we analyzed how the structural and functional characteristics varied along gradients in the environmental features of the catchment. We found that the floristic quality of the buffer vegetation was generally low, exhibiting an average of only 3.3% of the number of species of conservation interest. Instead, Danish buffer strips were dominated by widespread and productive species that are tolerant of anthropogenic impacts in the catchment. The abundance of highly productive plant species was positively related to high intensity land use, whereas the abundance of stress-tolerant plant species was positively related to low intensity land use. The high productivity of the buffer strips implies a large bio-storage potential, and these areas might therefore offer an opportunity to remove nutrients by harvesting the plant biomass. We discuss how Danish buffer strips could be exploited via appropriate management (e.g. harvesting) to maximize nutrient retention and at the same time improve floristic quality.

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A large part of the organic carbon in streams is transported by pulses of terrestrial dissolved organic carbon (tDOC) during hydrological events, which is more pronounced in agricultural catchments due to their hydrological flashiness. The majority of the literature considers stationary benthic biofilms and hyporheic biofilms to dominate uptake and processing of tDOC. Here, we argue for expanding this viewpoint to planktonic bacteria, which are transported downstream together with tDOC pulses, and thus perceive them as a less variable resource relative to stationary benthic bacteria. We show that pulse DOC can contribute significantly to the annual DOC export of streams and that planktonic bacteria take up considerable labile tDOC from such pulses in a short time frame, with the DOC uptake being as high as that of benthic biofilm bacteria. Furthermore, we show that planktonic bacteria efficiently take up labile tDOC which strongly increases planktonic bacterial production and abundance. We found that the response of planktonic bacteria to tDOC pulses was stronger in smaller streams than in larger streams, which may be related to bacterial metacommunity dynamics. Furthermore, the response of planktonic bacterial abundance was influenced by soluble reactive phosphorus concentration, pointing to phosphorus limitation. Our data suggest that planktonic bacteria can efficiently utilize tDOC pulses and likely determine tDOC fate during downstream transport, influencing aquatic food webs and related biochemical cycles.

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New scientific understanding is catalyzed by novel technologies that enhance measurement precision, resolution or type, and that provide new tools to test and develop theory. Over the last 50 years, technology has transformed the hydrologic sciences by enabling direct measurements of watershed fluxes (evapotranspiration, streamflow) at time scales and spatial extents aligned with variation in physical drivers. High frequency water quality measurements, increasingly obtained by in situ water quality sensors, are extending that transformation. Widely available sensors for some physical (temperature) and chemical (conductivity, dissolved oxygen) attributes have become integral to aquatic science, and emerging sensors for nutrients, dissolved CO2, turbidity, algal pigments, and dissolved organic matter are now enabling observations of watersheds and streams at time scales commensurate with their fundamental hydrological, energetic, elemental, and biological drivers. Here we synthesize insights from emerging technologies across a suite of applications, and envision future advances, enabled by sensors, in our ability to understand, predict, and restore watershed and stream systems.

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Current ecotoxicological research on particle-associated pyrethroids in freshwater systems focuses almost exclusively on sediment-exposure scenarios and sediment-dwelling macroinvertebrates. We studied how suspended particles influence acute effects of lambda-cyhalothrin and bifenthrin on the epibenthic freshwater amphipod Gammarus pulex (L.) using brief pulse exposures followed by a 144 h post exposure recovery phase. Humic acid (HA) and the clay mineral montmorillonite (MM) were used as model sorbents in environmentally realistic concentrations (5, 25 and 125 mg L(-1)). Mortality of G. pulex was recorded during the post exposure recovery phase and locomotor behavior was measured during exposure to lambda-cyhalothrin. We found that HA in concentrations ≥25 mg L(-1) adsorbed the majority of pyrethroids but only reduced mortality of G. pulex up to a factor of four compared to pyrethroid-only treatments. MM suspensions adsorbed a variable fraction of pyrethroids (10% for bifenthrin and 70% for lambda-cyhalothrin) but did not significantly change the concentration-response relationship compared to pure pyrethroid treatments. Behavioral responses and immobilisation rate of G. pulex were reduced in the presence of HA, whereas behavioral responses and immobilisation rate were increased in the presence of MM. This indicates that G. pulex was capable of sensing the bioavailable fraction of lambda-cyhalothrin. Our results imply that suspended particles reduce to only a limited extent the toxicity of pyrethroids to G. pulex and that passive uptake of pyrethroids can be significant even when pyrethroids are adsorbed to suspended particles.

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Agricultural land covers approximately 40% of Earth's land surface and affects hydromorphological, biogeochemical and ecological characteristics of fluvial networks. In the northern temperate region, agriculture also strongly affects the amount and molecular composition of dissolved organic matter (DOM), which constitutes the main vector of carbon transport from soils to fluvial networks and to the sea, and is involved in a large variety of biogeochemical processes. Here, we provide first evidence about the wider occurrence of agricultural impacts on the concentration and composition of fluvial DOM across climate zones of the northern and southern hemispheres. Both extensive and intensive farming altered fluvial DOM towards a more microbial and less plant-derived composition. Moreover, intensive farming significantly increased dissolved organic nitrogen (DON) concentrations. The DOM composition change and DON concentration increase differed among climate zones and could be related to the intensity of current and historical nitrogen fertilizer use. As a result of agriculture intensification, increased DON concentrations and a more microbial-like DOM composition likely will enhance the reactivity of catchment DOM emissions, thereby fuelling the biogeochemical processing in fluvial networks, and resulting in higher ecosystem productivity and CO2 outgassing.

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We couple current findings of pesticides in surface and groundwater to the history of pesticide usage, focusing on the potential contribution of legacy pesticides to the predicted ecotoxicological impact on benthic macroinvertebrates in headwater streams. Results suggest that groundwater, in addition to precipitation and surface runoff, is an important source of pesticides (particularly legacy herbicides) entering surface water. In addition to current-use active ingredients, legacy pesticides, metabolites and impurities are important for explaining the estimated total toxicity attributable to pesticides. Sediment-bound insecticides were identified as the primary source for predicted ecotoxicity. Our results support recent studies indicating that highly sorbing chemicals contribute and even drive impacts on aquatic ecosystems. They further indicate that groundwater contaminated by legacy and contemporary pesticides may impact adjoining streams. Stream observations of soluble and sediment-bound pesticides are valuable for understanding the long-term fate of pesticides in aquifers, and should be included in stream monitoring programs.

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Mitigation activities to improve water quality and quantity in streams as well as stream management and restoration efforts are conducted in the European Union aiming to improve the chemical, physical and ecological status of streams. Headwater streams are often characterised by impairment of hydromorphological, chemical, and ecological conditions due to multiple anthropogenic impacts. However, they are generally disregarded as water bodies for mitigation activities in the European Water Framework Directive despite their importance for supporting a higher ecological quality in higher order streams. We studied 11 headwater streams in the Hove catchment in the Copenhagen region. All sites had substantial physical habitat and water quality impairments due to anthropogenic influence (intensive agriculture, urban settlements, contaminated sites and low base-flow due to water abstraction activities in the catchment). We aimed to identify the dominating anthropogenic stressors at the catchment scale causing ecological impairment of benthic macroinvertebrate communities and provide a rank-order of importance that could help in prioritising mitigation activities. We identified numerous chemical and hydromorphological impacts of which several were probably causing major ecological impairments, but we were unable to provide a robust rank-ordering of importance suggesting that targeted mitigation efforts on single anthropogenic stressors in the catchment are unlikely to have substantial effects on the ecological quality in these streams. The SPEcies At Risk (SPEAR) index explained most of the variability in the macroinvertebrate community structure, and notably, SPEAR index scores were often very low (<10% SPEAR abundance). An extensive re-sampling of a subset of the streams provided evidence that especially insecticides were probably essential contributors to the overall ecological impairment of these streams. Our results suggest that headwater streams should be considered in future management and mitigation plans. Catchment-based management is necessary because several anthropogenic stressors exceeded problematic thresholds, suggesting that more holistic approaches should be preferred.

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The release of chemicals such as chlorinated solvents, pesticides and other xenobiotic organic compounds to streams, either from contaminated sites, accidental or direct application/release, is a significant threat to water resources. In this paper, different methods for evaluating the impacts of chemical stressors on stream ecosystems are evaluated for a stream in Denmark where the effects of major physical habitat degradation can be disregarded. The methods are: (i) the Danish Stream Fauna Index, (ii) Toxic Units (TU), (iii) SPEAR indices, (iv) Hazard Quotient (HQ) index and (v) AQUATOX, an ecological model. The results showed that the hydromorphology, nutrients, biological oxygen demand and contaminants (pesticides and trichloroethylene from a contaminated site) originating from groundwater do not affect the good ecological status in the stream. In contrast, the evaluation by the novel SPEAR(pesticides) index and TU indicated that the site is far from obtaining good ecological status - a direct contradiction to the ecological index currently in use in Denmark today - most likely due to stream sediment-bound pesticides arising from the spring spraying season. In order to generalise the findings of this case study, the HQ index and AQUATOX were extended for additional compounds, not only partly to identify potential compounds of concern, but also to determine thresholds where ecological impacts could be expected to occur. The results demonstrate that some commonly used methods for the assessment of ecological impact are not sufficient for capturing - and ideally separating - the effects of all anthropogenic stressors affecting ecosystems. Predictive modelling techniques can be especially useful in supporting early decisions on prioritising hot spots, serving to identify knowledge gaps and thereby direct future data collection. This case study presents a strong argument for combining bioassessment and modelling techniques to multi-stressor field sites, especially before cost-intensive studies are conducted.

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