Browning from headwaters to coastal areas in the boreal region: Trends and drivers.

Browning of freshwaters, mainly caused by increased terrestrial organic carbon loading, has been widely studied during the last decades. However, there are still uncertainties regarding both the extent of browning in different aquatic ecosystems and the actual importance of different driving forces and mechanisms. To refine understanding of the extent and causes of browning and its temporal variation, we gathered a comprehensive dataset including 746 Finnish water quality monitoring stations representing various waterbody types: streams, rivers, lakes, and coastal waters. Monotonic trend analyses revealed that TOC concentrations increased in all waterbody types during the study period from 1990 to 2020, whereas non-linear trends indicated that upward trends in TOC concentrations have substantially decreased since the mid-2000s. However, despite the upward trends levelling off, non-linear analyses also indicated decreases in TOC concentrations at only a few stations. As a result, the TOC contents of the majority of Finnish waterbody types in 2020 were at a higher level than in 1990. To examine the driving forces of increasing TOC concentrations, we selected 100 riverine catchments and linked the detected trends to 24 different drivers, including both hydrometeorological and catchment characteristics. The increased TOC concentrations in surface waters could be connected to diverse human impacts: hydrometeorological variables impacted by climate change, decreased acidic deposition, and land use in terms of peatland drainage. The importance of increased temperatures was emphasized, and its role as a driver of increased leaching of organic carbon in the forthcoming years is expected to grow with climate change.

Gypsum amendment of agricultural fields to decrease phosphorus losses - Evidence on a catchment scale.

Amending agricultural fields with gypsum has been proposed as a cost-effective measure to reduce P load on coastal waters. We treated 1490 ha of clayey fields with phosphogypsum (4 t ha-1) in Southwest Finland and monitored the recipient river with online sensors and water sampling for the preceding spring and 5 years after the amendment. Gypsum immediately decreased the riverine fluxes, the effect lasting at least 5 years for particulate P (PP), total suspended solids (TSS), and dissolved organic C (DOC) and 1-2 years for dissolved reactive P (DRP). Compared with an upstream control area, the fluxes of PP, TSS, and DOC decreased by 15%, 25%, and 8.9%, respectively, as a 5-year average. Assuming the change in the fluxes occurred only due to gypsum, the amended fields showed 35%, 59%, and 64% lower losses for PP, TSS, and DOC than the unamended ones. More than half of the gypsum remained in the soil even after 5 years; thus, although the efficiency of gypsum lessened over time, its residual effect may be present. However, the difference in the erodibility between the control and treatment areas impacted the validity of the results, especially as the pre-gypsum period was short. In addition, the performance of gypsum showed spatial variation.

Catchment and lake network modify export of anaerobic oxidation capacity in boreal freshwaters.

Anaerobic terminal electron acceptors (aTEAs, i.e. NO3, Fe, SO4) enable anaerobic respiration, and each has a specific ability to oxidize reduced compounds. However, little is known about how seasonal and lake-specific aTEA fluxes form anaerobic oxidation capacity (AOC) to oxidize organic carbon in boreal systems. We compiled 26 years of data from two interconnected semi-pristine boreal lakes and defined mean daily imports, pools, and exports of aTEAs. In both lakes, the export of NO3 formed 2 %-3 % of the total AOC in summer and autumn, and up to 11 % in winter and spring. In a predominantly monomictic humic lake surrounded by peatlands, Fe was responsible for 15 %-31 % of the seasonal export of AOC, with a large proportion of Fe originating from the lake bottom. A dimictic clear-water lake downstream retained Fe and exported 87 %-95 % of AOC as SO4. In the humic lake, the annual SO4:Fe:NO3 export ratio for AOC was 10:3:1 and in the clear-water lake 15:0.4:1. In the monomictic lake, exports were specifically regulated by stratification; in the dimictic lake, exports were more regulated by spring flooding and the ascending and descending side of the peak flood. These events modified lake dynamics and caused lake-specific NO3, Fe, and SO4 exports which continued for months. We conclude that a catchment and lake network can cause spatial and temporal variation in exports of NO3, Fe, and SO4 affecting AOC export. Such natural variations in exports have significant potential to modify the system's capacity to oxidize C and resist changes in oxidation-reduction reactions coupled to nutrient cycling and the formation of greenhouse gases in downstream water bodies.

Risk Assessment of Gypsum Amendment on Agricultural Fields: Effects of Sulfate on Riverine Biota.

Gypsum (CaSO4 ∙2H2 O) amendment is a promising way of decreasing the phosphorus loading of arable lands, and thus preventing aquatic eutrophication. However, in freshwaters with low sulfate concentrations, gypsum-released sulfate may pose a threat to the biota. To assess such risks, we performed a series of sulfate toxicity tests in the laboratory and conducted field surveys. These field surveys were associated with a large-scale pilot exercise involving spreading gypsum on agricultural fields covering 18% of the Savijoki River (Finland) catchment area. The gypsum amendment in such fields resulted in approximately a four-fold increase in the mean sulfate concentration for a 2-month period, and a transient, early peak reaching approximately 220 mg/L. The sulfate concentration gradually decreased almost to the pregypsum level after 3 years. Laboratory experiments with Unio crassus mussels and gypsum-spiked river water showed significant effects on foot movement activity, which was more intense with the highest sulfate concentration (1100 mg/L) than with the control. Survival of the glochidia after 24 and 48 h of exposure was not significantly affected by sulfate concentrations up to 1000 mg/L, nor was the length growth of the moss Fontinalis antipyretica affected. The field studies on benthic algal biomass accrual, mussel and fish density, and Salmo trutta embryo survival did not show gypsum amendment effects. Gypsum treatment did not raise the sulfate concentrations even to a level just close to critical for the biota studied. However, because the effects of sulfate are dependent on both the spatial and the temporal contexts, we advocate water quality and biota monitoring with proper temporal and spatial control in rivers within gypsum treatment areas. Environ Toxicol Chem 2022;41:108-121. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Nutrient export from Finnish rivers into the Baltic Sea has not decreased despite water protection measures.

To tackle the symptoms of eutrophication in the open Baltic Sea and Finnish coastal waters, Finland has agreed to reduce both total nitrogen (TN) and total phosphorus (TP) inputs. Due to large investments in treatment of municipal and industrial wastewaters, TP loads started to decrease already in the mid-1970s and the respective TN loads in the mid-1990s. During the last two decades, much effort has been spent in decreasing the load originating from diffuse sources. Trend analyses in 1995-2016 showed that, despite various mitigation measures, riverine nutrient export has not substantially decreased, and especially the export from rivers draining agricultural lands remains high. In some areas TN concentrations and export were increasing and we found evidence that it was linked to ditching of peatlands. Several factors connected to climate/weather (e.g. temperature and precipitation) have counteracted the mitigation measures, and therefore Finland will not achieve the nutrient reduction targets by 2021.

Probabilistic Evaluation of Ecological and Economic Objectives of River Basin Management Reveals a Potential Flaw in the Goal Setting of the EU Water Framework Directive.

The biological status of European lakes has not improved as expected despite up-to-date legislation and ecological standards. As a result, the realism of objectives and the attainment of related ecological standards are under doubt. This paper gets to the bottom of a river basin management plan of a eutrophic lake in Finland and presents the ecological and economic impacts of environmental and societal drivers and planned management measures. For these purposes, we performed a Monte Carlo simulation of a diffuse nutrient load, lake water quality and cost-benefit models. Simulations were integrated into a Bayesian influence diagram that revealed the basic uncertainties. It turned out that the attainment of good ecological status as qualified in the Water Framework Directive of the European Union is unlikely within given socio-economic constraints. Therefore, management objectives and ecological and economic standards need to be reassessed and reset to provide a realistic goal setting for management. More effort should be put into the evaluation of the total monetary benefits and on the monitoring of lake phosphorus balances to reduce the uncertainties, and the resulting margin of safety and costs and risks of planned management measures.

Participatory operations model for cost-efficient monitoring and modeling of river basins--A systematic approach.

The worldwide economic downturn and the climate change in the beginning of 21st century have stressed the need for cost efficient and systematic operations model for the monitoring and management of surface waters. However, these processes are still all too fragmented and incapable to respond these challenges. For example in Finland, the estimation of the costs and benefits of planned management measures is insufficient. On this account, we present a new operations model to streamline these processes and to ensure the lucid decision making and the coherent implementation which facilitate the participation of public and all the involved stakeholders. The model was demonstrated in the real world management of a lake. The benefits, pitfalls and development needs were identified. After the demonstration, the operations model was put into operation and has been actively used in several other management projects throughout Finland.

Statistical Dimensioning of Nutrient Loading Reduction: LLR Assessment Tool for Lake Managers.

Implementation of the EU Water Framework Directive (WFD) has set a great challenge on river basin management planning. Assessing the water quality of lakes and coastal waters as well as setting the accepted nutrient loading levels requires appropriate decision supporting tools and models. Uncertainty that is inevitably related to the assessment results and rises from several sources calls for more precise quantification and consideration. In this study, we present a modeling tool, called lake load response (LLR), which can be used for statistical dimensioning of the nutrient loading reduction. LLR calculates the reduction that is needed to achieve good ecological status in a lake in terms of total nutrients and chlorophyll a (chl-a) concentration. We show that by combining an empirical nutrient retention model with a hierarchical chl-a model, the national lake monitoring data can be used more efficiently for predictions to a single lake. To estimate the uncertainties, we separate the residual variability and the parameter uncertainty of the modeling results with the probabilistic Bayesian modeling framework. LLR has been developed to answer the urgent need for fast and simple assessment methods, especially when implementing WFD at such an extensive scale as in Finland. With a case study for an eutrophic Finnish lake, we demonstrate how the model can be utilized to set the target loadings and to see how the uncertainties are quantified and how they are accumulating within the modeling chain.

Assimilation of satellite data to 3D hydrodynamic model of Lake Säkylän Pyhäjärvi.

To analyze the applicability of direct insertion of total suspended matter (TSM) concentration field based on turbidity derived from satellite data to numerical simulation, dispersion studies of suspended matter in Lake Säkylän Pyhäjärvi (lake area 154 km²; mean depth 5.4 m) were conducted using the 3D COHERENS simulation model. To evaluate the practicality of direct insertion, five cases with different initialization frequencies were conducted: (1) every time, when satellite data were available; (2) every 10 days; (3) 20 days; (4) 30 days; and (5) control run without repeated initialization. To determine the effectiveness of initialization frequency, three methods of comparison were used: simple spatial differences of TSM concentration without biomass in the lake surface layer; averaged spatial differences between initialization data and the forecasts; and time series of TSM concentration and observation data at 1 m depth at the deepest point of the lake. Results showed that direct insertion improves the forecast significantly, even if it is applied less often.

Phosphorus and nitrogen fluxes carried by 21 Finnish agricultural rivers in 1985-2006.

The Finnish Agri-Environmental Programme aims to reduce nutrient load to waters. Using national monitoring data, we estimated the agricultural load (incl. natural background) of total phosphorus (TP) and total nitrogen (TN) transported by 21 Finnish rivers to the northern Baltic Sea and analysed the flow-adjusted trends in the loads and concentrations from 1985 to 2006. We also related the loads to spatial and temporal patterns in catchment and agricultural characteristics. Agricultural load of TN increased, especially in the rivers discharging into the Bothnian Bay, while the load of TP decreased in most of the rivers, except those discharging into the Archipelago Sea. The trends may partly be related to a decrease in grassed area (TP, TN) and increased mineralisation (TN), but the available data on catchment and agricultural characteristics did not fully explain the observed pattern. Our study showed that data arising from relatively infrequent monitoring may prove useful for analysing long-term trend. The mutual correlation among the explaining variables hampered the analysis of the load generating factors.

Experimental and theoretical analysis of asymmetric induction in heterogeneous catalysis: diastereoselective hydrogenation of chiral alpha-hydroxyketones over Pt catalyst.

Assessing the origin of asymmetric induction in heterogeneously catalyzed hydrogenation is a challenging task. In this work, hydrogenation of a chiral compound, (R)-1-hydroxy-1-phenyl-2-propanone [(R)-PAC], in toluene over cinchonidine modified and unmodified Pt/Al(2)O(3) was studied. To reveal the detailed reaction mechanism and the origin of stereoselectivity in the Pt-catalyzed hydrogenation of the CO double bond, the structures and energies of several adsorption modes of (R)-PAC as well as whole reaction paths for hydrogenation were investigated on Pt(111) by density functional theory (DFT). In agreement with experimental results, the theoretically obtained potential energy profiles for the studied hydrogenation mechanisms implied that (1R,2S)-1-phenyl-1,2-propanediol is formed in excess with respect to the other diastereomeric product diol, (1R,2R)-1-phenyl-1,2-propanediol. Generally, if the elementary hydrogen addition step was thermodynamically more favorable on one of the two diastereotopic faces, it was also kinetically preferred on the same face, and vice versa. Pairwise addition of hydrogen was the most energetically favorable mechanism. Adsorption and hydrogenation of other structurally similar chiral alpha-hydroxyketones, (R)-3-hydroxy-2-butanone and (R)-2-hydroxy-1-cyclohexanone, were also studied computationally on Pt(111). The results showed that cluster model DFT calculations can be used to assess (dia)stereoselectivity in metal-catalyzed hydrogenation of even such complex organic molecules as studied here.

A combined NMR, DFT, and X-ray investigation of some cinchona alkaloid O-ethers.

Structures and conformational behavior of several cinchona alkaloid O-ethers in the solid state (X-ray), in solution (NMR and DFT), and in the gas phase (DFT) were investigated. In the crystal, O-phenylcinchonidine adopts the Open(3) conformation similar to cinchonidine, whereas the O-methyl ether derivatives of both cinchonidine and cinchonine are packed in the Closed(1) conformation. Dynamic equilibria in solutions of the alkaloids were revealed by combined experimental-theoretical spin simulation/iteration techniques for the first time. In the (1)H NMR spectra in CDCl3 and toluene-d8 at room temperature, Closed(1) conformation was observed for the O-silyl ethers as a separate set of signals. For O-methyl ether derivatives Closed(1) could be separated only at -30 degrees C in CDCl3 or toluene-d8 and for O-phenylcinchonidine at -70 degrees C in CDCl3/CD2Cl2. The ratio between the Closed(2) and Open(3) conformers was estimated by analyzing the vicinal coupling constant (3)J(H9,H8) at ambient and low temperatures. The observed conformational equilibria of O-(tert-butyldimethylsilyl)cinchonidine in CDCl 3 and toluene-d8 are in good agreement with the theoretically estimated equilibrium populations of the conformations according to Boltzmann statistics. The conformational equilibria of four cinchona alkaloid O-ether solutes in CDCl3 and toluene-d8 are discussed in the light of their relevance to the mechanism of 1-phenyl-1,2-propanedione (PPD) hydrogenation over cinchona alkaloid modified heterogeneous platinum catalysts. It was demonstrated that the conformation found to be abundant in the liquid phase has no direct correlation with the enantioselectivity of the PPD hydrogenation reaction.