Undeveloped till soils in scree areas are an overlooked important phosphorus source for waters in alpine catchments.

Scree deposits in alpine catchments contain undeveloped till soils that are "hidden" between and under stones. These scree areas have no vegetation except for sparse lichen patches on stone surfaces, but the soils exhibit biological activity and active cycling of nitrogen (N), phosphorus (P), and organic carbon (C). We compared the chemical and biochemical properties of till soils in the scree areas (scree soils) with developed soils in alpine meadows (meadow soils) of 14 catchments in the alpine zone of the Tatra Mountains. The data showed that scree soils served as an important source of mobile P forms for waters in high elevation catchments. We then conducted a detailed soil survey focused on four selected alpine catchments with scree cover proportions > 30%. This study confirmed that scree soils have significantly higher concentrations of mobile P forms compared to meadow soils, and a high specific microbial activity directed towards the extraction of P with rapid turnover in the microbial biomass. The combination of these properties and the amounts of scree soils in high-elevation areas highlight their importance in overall biogeochemical P cycling in alpine catchments, and the terrestrial P export to receiving waters.

Photochemical degradation of dissolved organic matter reduces the availability of phosphorus for aquatic primary producers.

In situ experiments were done to determine the effects of the photochemical degradation of dissolved organic matter (DOM) and subsequent formation of particulate matter on dissolved phosphorus (P) concentrations in surface waters. Filtered (1.2 or 0.4 µm) headwaters (DOM of 8.1-26 mg L-1; P of 22-43 µg L-1) were exposed to solar radiation in quartz bottles located 5 cm below the water surface for 7-10 days. Dark controls were wrapped in aluminum foil. After incubation, particulate organic carbon (POC) and particulate phosphorus (PP) were determined in both the filtrate and newly formed particles. The results revealed increasing concentrations of PP and POC in exposed samples with increasing exposure time (cumulative irradiation energy). At the end of experiments, PP concentrations were from 5 to 20 µg L-1 in the exposed samples. Based on an enumeration of bacteria in the samples, we estimated the contribution of biotic and abiotic processes to the PP production. The abiotic PP formation ranged from 56 to 83% and 50-95% of the total PP in the exposed and control samples, respectively. The remainder was assumed to be bacterial P uptake. Despite the overlapping intervals, biotic and abiotic PP productions were usually higher in exposed samples than in controls. The PP and POC production was affected by the properties of DOM, such as its humic content and freshness index. We hypothesize that the observed immobilization of dissolved P in bacteria and on photochemically-formed particles can contribute to a P limitation of primary production in headwater environments that receive waters rich in soil DOM.

Long-term trends of phosphorus concentrations in an artificial lake: Socio-economic and climate drivers.

European freshwater ecosystems have undergone significant human-induced and environmentally-driven variations in nutrient export from catchments throughout the past five decades, mainly in connection with changes in land-use, agricultural practice, waste water production and treatment, and climatic conditions. We analysed the relations among concentration of total phosphorus (TP) in the Slapy Reservoir (a middle reservoir of the Vltava River Cascade, Czechia), and socio-economic and climatic factors from 1963 to 2015. The study was based on a time series analysis, using conventional statistical tools, and the identification of breaking points, using a segmented regression. Results indicated clear long-term trends and seasonal patterns of TP, with annual average TP increasing up until 1991 and decreasing from 1992 to 2015. Trends in annual, winter and spring average TP concentrations reflected a shift in development of sewerage and sanitary infrastructure, agricultural application of fertilizers, and livestock production in the early 1990s that was associated with changes from the planned to the market economy. No trends were observed for average TP in autumn. The summer average TP has fluctuated with increased amplitude since 1991 in connection with recent climate warming, changes in thermal stratification stability, increased water flow irregularities, and short-circuiting of TP-rich inflow during high flow events. The climate-change-induced processes confound the generally declining trend in lake-water TP concentration and can result in eutrophication despite decreased phosphorus loads from the catchment. Our findings indicate the need of further reduction of phosphorus sources to meet ecological quality standards of the EU Water Framework Directive because the climate change may lead to a greater susceptibility of the aquatic ecosystem to the supply of nutrients.

Trends in riverine element fluxes: A chronicle of regional socio-economic changes.

We show how concentrations of water solutes in the Vltava River (Czech Republic) and their riverine outputs from the catchment were modified by socio-economic changes, land use, and hydrology between 1960 and 2015. In the early 1960s, HCO3 and Ca were the dominant ions. During 1960-1989 (a period of planned economy with an over-use of synthetic fertilizers, excessive draining of agricultural land and little environmental protection), the riverine concentrations of strong acid anions (SAAs: SO4, NO3, and Cl) increased 2-4-fold and their leaching was accompanied for by a 1.4-1.8-fold increase in concentrations of Ca, Mg, K, and Na. SAAs mostly originated from diffuse agricultural sources (synthetic fertilizers and mineralization of organic matter in freshly drained and deeply tilled agricultural land) and their annual average concentrations (as well as those of Ca, Mg, and K) were positively correlated with discharge. During 1990-2015 (a period of a re-established market economy, reduced fertilization, ceased drainage, partial conversion of arable land to pastures, and increasing environmental protection), concentrations of SO4 and NO3 significantly decreased due to reduced agricultural production and atmospheric pollution, and their positive correlations with discharge disappeared. In contrast, Na and Cl concentrations increased due to more intensive road de-icing, and their concentrations became negatively correlated with discharge. Trends in phosphorus concentrations reflected changes in its input by both diffuse (fertilizers) and point (wastewater) sources and were discharge independent.

Photochemical cleaving of allochthonous organic-metal complexes contributes to phosphorus immobilization in surface waters.

The photochemical transformation of terrestrial dissolved organic carbon (DOC) in surface waters exposed to UV radiation causes the precipitation of metal (Al and Fe) bearing complexes with high phosphorus sorption capacities. To better elucidate this process, a series of laboratory experiments was performed with stream and river waters with pH range from 3.5 to 8.2 and concentrations of dissolved reactive phosphorus from 2 to 142 µg L-1. Samples were filtered (0.4 µm) and UV (350 nm) irradiated for 24 h at 68 W m-2, i.e. under conditions equivalent to ∼2 summer days of natural solar radiation. Irradiated samples and dark controls were then spiked with 33P-phosphate and the kinetics of P adsorption on freshly formed particles was determined after separation by ultracentrifugation. Up to 68% of the added P was removed from the solution within 48 h of the spike. The P sorption was pH dependent, with the maximum sorption ability at pHs of 6-7. We hypothesize that this process can importantly contribute to the immobilization and lower bioavailability of P in the inlet areas of (especially circum-neutral) lakes due to the intensive photochemical degradation of allochthonous DOC-metal complexes.

Effects of acidic deposition on in-lake phosphorus availability: a lesson from lakes recovering from acidification.

Lake water concentrations of phosphorus (P) recently increased in some mountain areas due to elevated atmospheric input of P rich dust. We show that increasing P concentrations also occur during stable atmospheric P inputs in central European alpine lakes recovering from atmospheric acidification. The elevated P availability in the lakes results from (1) increasing terrestrial export of P accompanying elevated leaching of dissolved organic carbon and decreasing phosphate-adsorption ability of soils due to their increasing pH, and (2) decreasing in-lake P immobilization by aluminum (Al) hydroxide due to decreasing leaching of ionic Al from the recovering soils. The P availability in the recovering lakes is modified by the extent of soil acidification, soil composition, and proportion of till and meadow soils in the catchment. These mechanisms explain several conflicting observations of the acid rain effects on surface water P concentrations.

What do results of common sequential fractionation and single-step extractions tell us about P binding with Fe and Al compounds in non-calcareous sediments?

Correct identification of P forms together with their main Fe and Al binding partners in non-calcareous sediments is of crucial importance for evaluation of P cycling in water bodies. In this paper, we assess extraction methods frequently used for this purpose, i.e., a sequential five-step fractionation (water, bicarbonate buffered dithionite solution (BD), NaOH, HCl, nitric-perchloric acid), ascorbate extraction (pH ~7.5), and oxalate extraction (pH ~3), directly on a range of laboratory prepared Fe and Al minerals enriched with adsorbed P. Extraction selectivity and efficiency for particular P, Fe and Al forms were also verified by specific combinations of these extraction methods applied on freshwater sediment samples. In the sequential fractionation, BD was highly effective in dissolving both amorphous and crystalline Fe (hydr)oxides and the associated P, while neither FeS nor Al (hydr)oxides were dissolved. The following NaOH extraction effectively dissolved both amorphous and crystalline Al (hydr)oxides. The high solubilizing power of BD and NaOH to dissolve crystalline Fe and Al oxides that have only a small P-sorption ability prevents the use of resulting Fe/P and Al/P ratios as simple predictors of total P sorption capacity of sediments and soils. Ascorbate non-selectively extracted small proportions of FeS and amorphous Fe and Al (hydr)oxides, but significant amounts of adsorbed P, which hinders its use for the characterization of P forms in non-calcareous sediments. Similar nonselective characteristics were found for oxalate extractions. As oxalate extracts most of the adsorbed phosphate, it is not possible to use it unambiguously to determine specific Fe/P and Al/P ratios of active complexes. However, this method is convenient (and more selective than NaOH step in the sequential fractionation) for the determination of amorphous Al (hydr)oxides.

Speciation of Al, Fe, and P in recent sediment from three lakes in Maine, USA.

Sequential extraction of sediments [Psenner R, Pucsko R. Die Fraktionierung organischer und anorganischer Phosphorverbindungen von Sedimenten. Arch Hydrobiol/Suppl 1988. 70(1): 111-155.] from short, (210)Pb-dated cores from three lakes in Maine USA demonstrates that sediment P is dominantly associated with the NaOH-extractable fraction (P-NaOH(25)) and less with the bicarbonate-dithionite extractable fraction (P-BD). The ratios (Al-NaOH(25))/(Fe-BD) and (Al-NaOH(25))/(P-NH(4)Cl+P-BD) for upper sediment for two oligo-mesotrophic lakes exceeded 3 and 25, the thresholds for preventing substantial release of P from sediments during hypolimnetic anoxia [Kopácek J, Borovec J, Hejzlar J, Ulrich K-U, Norton SA, Amirbahman A. Aluminum control of phosphorus sorption by lake sediments. Environ Sci Technol 2005a;39:8784-8789.]. Hypolimnetic water chemistry verifies this effect. The third lake, currently eutrophic, has values for the ratios that are below the thresholds and this lake has substantial release of P from recent sediment. The sediment characteristics remain relatively constant over the last 150+ years, indicating that the processes responsible for P retention have operated long before atmospheric acidification of watersheds might have influenced the flux of Al and Fe to the lake. In 2002, the pH of inlets and the lakes was generally between 6 and 8. Input to the lakes had high concentrations of acid-soluble particulate and dissolved Al, Fe, and P, and dissolved Al and Fe complexed with dissolved organic carbon (DOC). Lake water column and outlet Al, Fe, and P were typically 90-95% lower than inlet concentrations over a 12 month period. Photo-oxidation of Al-DOC and Fe-DOC in the lake, liberation of inorganic Al and Fe, precipitation of Al(OH)(3) and Fe(OH)(3), adsorption of P by the hydroxides, and sedimentation are responsible for the changes in water quality and long-term sediment characteristics.

Aluminum control of phosphorus sorption by lake sediments.

Release of reactive (phosphate-like) phosphorus (P) from freshwater sediments represents a significant internal P source for many lakes. Hypolimnetic P release occurs under reducing conditions that cause reductive dissolution of ferric hydroxide [Fe(OH)3]. This hypolimnetic P release may be naturally low or artificially reduced by sediment with naturally high or artificially elevated concentrations of aluminum hydroxide [Al(OH)3]. We presentfield and laboratory data for a common extraction analysis of sediments from 43 lakes differing in trophic status, pH regime, climate, and P loading. The results indicate that a simple sequential extraction of sediment may be a useful predictor of sediment's ability to release P. Sequential extractions of sediment P, Al, and Fe by water (H2O), bicarbonate-dithionite (BD), and NaOH (at 25 degrees C) showed that negligible amounts of P would be released from lake sediments during hypolimnetic anoxia if either (1) the molar Al(NaOH-25):Fe(BD) ratio is > 3 or (2) the molar Al(NaOH-25):P(H2O+BD) ratio is > 25. These ratios can be used as operational targets for estimation of sediment P release potential and Al dosing of P-rich sediment to prevent hypolimnetic P release under anoxic conditions.