Climate and land use shape the water balance and water quality in selected European lakes.

This study provides insights into factors that influence the water balance of selected European lakes, mainly in Central Europe, and their implications for water quality. An analysis of isotopic, chemical and land use data using statistical and artificial intelligence models showed that climate, particularly air temperature and precipitation, played a key role in intensifying evaporation losses from the lakes. Water balance was also affected by catchment factors, notably groundwater table depth. The study shows that lakes at lower altitudes with shallow depths and catchments dominated by urban or crop cover were more sensitive to water balance changes. These lakes had higher evaporation-to-inflow ratios and increased concentrations of total nitrogen in the water. On the other hand, lakes at higher elevations with deeper depths and prevailing forest cover in the catchment were less sensitive to water balance changes. These lakes, which are often of glacial origin, were characterized by lower evaporation losses and thus better water quality in terms of total nitrogen concentrations. Understanding connections between water balance and water quality is crucial for effective lake management and the preservation of freshwater ecosystems.

Carbon and nutrient pools and fluxes in unmanaged mountain Norway spruce forests, and losses after natural tree dieback.

Forest areas infected by insects are increasing in Europe and North America due to accelerating climate change. A 2000-2020 mass budget study on major elements (C, N, P, Ca, Mg, K) in the atmosphere-plant-soil-water systems of two unmanaged catchments enabled us to evaluate changes in pools and fluxes related to tree dieback and long-term accumulation/losses during the post-glacial period. A bark-beetle outbreak killed >75 % of all trees in a mature mountain spruce forest in one catchment and all dead biomass was left on site. A similar forest in a nearby catchment was only marginally affected. We observed that: (1) the long-term (millennial) C and N accumulation in soils averaged 10-22 and 0.5-1.1 kg ha-1 yr-1, respectively, while losses of Ca, Mg, and K from soils ranged from 0.1 to 2.6 kg ha-1 yr-1. (2) Only <0.8 % and <1.5 % of the respective total C and N fluxes entering the soil annually from vegetation were permanently stored in soils. (3) The post-disturbance decomposition of dead tree biomass reduced vegetation element pools from 27 % (C) to 73 % (P) between 2004 and 2019. (4) Tree dieback decreased net atmospheric element inputs to the impacted catchment, and increased the leaching of all elements and gaseous losses of C (∼2.3 t ha-1 yr-1) and N (∼14 kg ha-1 yr-1). The disturbed catchment became a net C source, but ∼50 % of the N released from dead biomass accumulated in soils. (5) Despite the severe forest disturbance, the dissolved losses of Ca and Mg represented 52-58 % of their leaching from intact stands during the peaking atmospheric acidification from 1970 to 1990. (6) Disturbance-related net leaching of P, Ca, Mg, and K were 4, 69, 16, and 114 kg ha-1, respectively, which represented 7-38 % of the losses potentially related to sanitary logging and subsequent removal of the aboveground tree biomass.

In the right place, at the right time: the integration of bacteria into the Plankton Ecology Group model.

BACKGROUND: Planktonic microbial communities have critical impacts on the pelagic food web and water quality status in freshwater ecosystems, yet no general model of bacterial community assembly linked to higher trophic levels and hydrodynamics has been assessed. In this study, we utilized a 2-year survey of planktonic communities from bacteria to zooplankton in three freshwater reservoirs to investigate their spatiotemporal dynamics. RESULTS: We observed site-specific occurrence and microdiversification of bacteria in lacustrine and riverine environments, as well as in deep hypolimnia. Moreover, we determined recurrent bacterial seasonal patterns driven by both biotic and abiotic conditions, which could be integrated into the well-known Plankton Ecology Group (PEG) model describing primarily the seasonalities of larger plankton groups. Importantly, bacteria with different ecological potentials showed finely coordinated successions affiliated with four seasonal phases, including the spring bloom dominated by fast-growing opportunists, the clear-water phase associated with oligotrophic ultramicrobacteria, the summer phase characterized by phytoplankton bloom-associated bacteria, and the fall/winter phase driven by decay-specialists. CONCLUSIONS: Our findings elucidate the major principles driving the spatiotemporal microbial community distribution in freshwater ecosystems. We suggest an extension to the original PEG model by integrating new findings on recurrent bacterial seasonal trends. Video Abstract.

Contrasting catchment soil pH and Fe concentrations influence DOM distribution and nutrient dynamics in freshwater systems.

Organic matter (OM) quantity, quality, and nutrient dynamics within twelve shallow lakes in the Czech Republic were assessed in the context of catchment soil pH and iron (Fe) concentration. The catchments of the lakes were classified into two categories: (i) slightly acidic (soil pH = 5.1-6.3) with Fe-rich soils (H_Fe; Fe = 315-344 mg kg-1 in Mehlich 3 extract); and (ii) neutral (soil pH = 6.8-7.6) with Fe-poor soils (L_Fe; Fe = 126-259 mg kg-1 in Mehlich 3 extract). The quality of OM in the two lake types was characterized using a combination of spectroscopic techniques (UV-Vis, fluorescence, and Fourier Transform Infrared spectroscopy). We show that dissolved nutrient and dissolved organic carbon (DOC) concentrations, as well as the amount of aromatic and protein-like compounds in the water column and sediment porewater were significantly (p < 0.01) lower in the H_Fe lakes compared to the waterbodies located within L_Fe catchments. The FTIR analyses of the H_Fe sediments contained higher relative concentrations of aromatic compounds with hydroxyl-containing functional groups and carbohydrates, while more aliphatic and oxidised OM was found in the L_Fe lake sediments. These results suggest that the pH value of catchment soils and, particularly, their Fe content have profound geochemical effects on the mobility of OM and nutrients in the sediments of recipient waters. Because the OM-Fe association stabilises OM in sediments, waterbodies within L_Fe catchments are likely more vulnerable to increasing eutrophication and oxygen depletion compared to those in H_Fe catchments and this has important implications for water quality management, risk assessment, and predictions of aquatic ecosystem vulnerability under conditions of accelerating climate change.

Diversity dynamics of aerobic anoxygenic phototrophic bacteria in a freshwater lake.

Aerobic anoxygenic photoheterotrophic (AAP) bacteria represent a functional group of prokaryotic organisms that harvests light energy using bacteriochlorophyll-containing photosynthetic reaction centers. They represent an active and rapidly growing component of freshwater bacterioplankton, with the highest numbers observed usually in summer. Species diversity of freshwater AAP bacteria has been studied before in lakes, but its seasonal dynamics remain unknown. In this report, we analysed temporal changes in the composition of the phototrophic community in an oligo-mesotrophic freshwater lake using amplicon sequencing of the pufM marker gene. The AAP community was dominated by phototrophic Gammaproteobacteria and Alphaproteobacteria, with smaller contribution of phototrophic Chloroflexota and Gemmatimonadota. Phototrophic Eremiobacteriota or members of Myxococcota were not detected. Interestingly, some AAP taxa, such as Limnohabitans, Rhodoferax, Rhodobacterales or Rhizobiales, were permanently present over the sampling period, while others, such as Sphingomonadales, Rhodospirillales or Caulobacterales appeared only transiently. The environmental factors that best explain the seasonal changes in AAP community were temperature, concentrations of oxygen and dissolved organic matter.

Forest damage and subsequent recovery alter the water composition in mountain lake catchments.

Forest damage by insect infestation directly affects the trees themselves, but also indirectly affects water quality via soil processes. The changes in water composition may undergo different pathways depending on site-specific characteristics and forest components, especially the proportion of coniferous and deciduous trees. Here, we test whether changes in forest components and the intensity of disturbance can predict the chemical properties of water outflow from affected lake catchments. Information about forest regeneration (a phase dominated by deciduous trees) and the proportions of damaged and healthy coniferous trees and treeless areas were obtained from satellite data. The four study catchments of Prásilské, Laka, Plesné, and Certovo lakes are geographically close and located in the same mountain range (Sumava Mts., Czech Republic) at similar altitude, but they differ in extents of forest disturbances and recoveries. The water quality measured at the lake catchment outflows differed, and better reflected the development of forest components and health than did meteorological (temperature and precipitation) or hydrological (discharge) variables. Several of the outflow properties (concentrations of inorganic aluminium, protons, potassium, calcium, magnesium, alkalinity, dissolved organic carbon (DOC), nitrate, and total phosphorus), responded catchment-specifically and with different delays to forest disturbance. The most pronounced differences occurred in DOC concentrations, which started to increase in the most disturbed Plesné and Laka catchments 7 and 6 years, respectively, after the peak in tree dieback, but did not increase significantly in the Prásilské catchment, which was disturbed several times during the last 3-4 decades. This study demonstrates an importance of extents of forest disturbances, the following changes in forest composition, and catchment-specific characteristics on water composition.

Diverse effects of accelerating climate change on chemical recovery of alpine lakes from acidic deposition in soil-rich versus scree-rich catchments.

The current recovery of mountain lakes from atmospheric acidification is increasingly affected (both accelerated and/or delayed) by climate change. We evaluated long-term trends in the ionic composition of 30 lakes situated in the alpine zone of the Tatra Mountains, and compared the rates of their recovery with model (MAGIC) simulations done 20 years ago for the 2003-2020 period. The observed recovery was faster than the model forecast, due to greater reductions in acidic deposition than projected. Trends in water composition were further modified by climate change. Rising temperatures increased the length of the growing season and retention of inorganic N and SO42- more in soil-rich compared with soil-poor catchments. In contrast, elevated precipitation and an increase in rainfall intensity reduced water residence time in soils, and consequently reduced N retention, especially in soil-poor catchments. It is likely that increases in rainfall intensity and annual number of days without snow, along with air temperatures fluctuating around the freezing point elevated the physical erosion of rocks, especially in high-elevation, steep, and scree-rich areas where rocks are not thermally insulated and stabilized by soils. Weathering of exposed accessory calcite in the eroded granodiorite bedrock was a source of Ca2+ and HCO3-, while S-bearing minerals likely contributed to lake water SO42- and partly mitigated its deposition-related decrease in scree-rich catchments. The extent of climate effects on changes in the water composition of alpine lakes recovering from acidic deposition thus depended on elevation and cover of soil and scree in catchments. Our results highlight the need for incorporating dominant climate-related process into existing process-based models to increase their reliability in predicting the future development of lake water composition.

Recovery of freshwater microbial communities after extreme rain events is mediated by cyclic succession.

Small lakes and ponds occupy an enormous surface area of inland freshwater and represent an important terrestrial-water interface. Disturbances caused by extreme weather events can have substantial effects on these ecosystems. Here, we analysed the dynamics of nutrients and the entire plankton community in two flood events and afterwards, when quasi-stable conditions were established, to investigate the effect of such disturbances on a small forest pond. We show that floodings result in repeated washout of resident organisms and hundredfold increases in nutrient load. Despite this, the microbial community recovers to a predisturbance state within two weeks of flooding through four well-defined succession phases. Reassembly of phytoplankton and especially zooplankton takes up to two times longer and features repetitive and adaptive patterns. Release of dissolved nutrients from the pond is associated with inflow rates and community recovery, and returns to predisturbance levels before microbial compositions recover. Our findings shed light on the mechanisms underlying functional resilience of small waterbodies and are relevant to global change-induced increases in weather extremes.

Disruptions and re-establishment of the calcium-bicarbonate equilibrium in freshwaters.

During recent decades, increasing anthropogenic activities have affected natural ionic composition, including the strongest and most common relationship between ionic concentrations in the majority of natural global freshwaters, i.e., the Ca2+-ANC (acid neutralizing capacity) equilibrium. Using long-term monitoring data and MAGIC modelling, we evaluated effects of major present environmental stressors (synthetic fertilizers, liming, acidic deposition, forest disturbances, and climate change) on the Ca2+-ANC equilibrium. We evaluated the effects for three different types of terrestrial ecosystems, a circumneutral lowland agricultural catchment, two acid sensitive mountain forest catchments differing in forest health, and one acid sensitive alpine catchment. All catchments are in a region with the world-largest changes in fertilizing rates and acidic deposition in the 20th century, with increasing impacts until the late 1980s, and their subsequent abrupt, dramatic decreases. These strong changes resulted in a substantial disruption, followed by continuing re-establishment of the Ca2+-ANC relationship in all study waters. The shape of the disruption and the following re-establishment of its new value were dependent on the intensity, duration, and combination of stressors, as well as on catchment characteristics (bedrock composition, soil amount and composition, vegetation status, and hydrology). We conclude that a new equilibrium may deviate from its natural value due to the (1) legacy of fertilizing, acidic deposition and liming, affecting the soil Ca2+ pools, (2) forest disturbances and management practices, and (3) climate change.

Bacterial and Eukaryotic Small-Subunit Amplicon Data Do Not Provide a Quantitative Picture of Microbial Communities, but They Are Reliable in the Context of Ecological Interpretations.

High-throughput sequencing (HTS) of gene amplicons is a preferred method of assessing microbial community composition, because it rapidly provides information from a large number of samples at high taxonomic resolution and low costs. However, mock community studies show that HTS data poorly reflect the actual relative abundances of individual phylotypes, casting doubt on the reliability of subsequent statistical analysis and data interpretation. We investigated how accurately HTS data reflect the variability of bacterial and eukaryotic community composition and their relationship with environmental factors in natural samples. For this, we compared results of HTS from three independent aquatic time series (n = 883) with those from an established, quantitative microscopic method (catalyzed reporter deposition-fluorescence in situ hybridization [CARD-FISH]). Relative abundances obtained by CARD-FISH and HTS disagreed for most bacterial and eukaryotic phylotypes. Nevertheless, the two methods identified the same environmental drivers to shape bacterial and eukaryotic communities. Our results show that amplicon data do provide reliable information for their ecological interpretations. Yet, when studying specific phylogenetic groups, it is advisable to combine HTS with quantification using microscopy and/or the addition of internal standards.IMPORTANCE High-throughput sequencing (HTS) of amplified fragments of rRNA genes provides unprecedented insight into the diversity of prokaryotic and eukaryotic microorganisms. Unfortunately, HTS data are prone to quantitative biases, which may lead to an erroneous picture of microbial community composition and thwart efforts to advance its understanding. These concerns motivated us to investigate how accurately HTS data characterize the variability of microbial communities, the relative abundances of specific phylotypes, and their relationships with environmental factors in comparison to an established microscopy-based method. We compared results obtained by HTS and catalyzed reporter deposition-fluorescence in situ hybridization (CARD-FISH) from three independent aquatic time series for both prokaryotic and eukaryotic microorganisms (almost 900 data points, the largest obtained with both methods so far). HTS and CARD-FISH data disagree with regard to relative abundances of bacterial and eukaryotic phylotypes but identify similar environmental drivers shaping bacterial and eukaryotic communities.

Changes in microclimate and hydrology in an unmanaged mountain forest catchment after insect-induced tree dieback.

Hydrological and microclimatic changes after insect-induced tree dieback were evaluated in an unmanaged central European mountain (Plesné, PL) forest and compared to climate-related changes in a similar, but almost intact (Certovo, CT) control forest during two decades. From 2004 to 2008, 93% of Norway spruce trees were killed by a bark beetle outbreak, and the entire PL area was left to subsequent natural development. We observed that (1) climate-related increases in daily mean air temperature (2 m above ground) were 1.6 and 0.5 °C on an annual and growing season basis, respectively, and an increase in daily mean soil temperature (5 cm below ground) was 0.9 °C during growing seasons at the CT control from 2004 to 2017; (2) daily mean soil and air temperatures increased by 0.7-1.2 °C on average more at the disturbed PL plots than in the healthy forest; (3) water input to soils increased by 20% but decreased by 17% at elevations of 1122 and 1334 m, respectively, due to decreased occult deposition to, and evaporation from, canopies after tree dieback; (4) soil moisture was 5% higher on average (but up to 17% higher in dry summer months) in the upper PL soil horizons for 5-6 years following the tree dieback; (5) run-off from the PL forest ~6% (~70 mm yr-1) increased relatively to the CT forest (but without extreme peak flows and erosion events) after tree dieback due to the ceased transpiration of dead trees and elevated water input to soils; and (6) relative air humidity was 4% lower on average at disturbed plots than beneath living trees. The rapid tree regeneration during the decade following tree dieback resulted in a complete recovery in soil moisture, a slow recovery of discharge and air humidity, but a still insignificant recovery in air and soil temperatures.

Solar Radiation as the Likely Cause of Acid-Soluble Rare-Earth Elements in Sediments of Fresh Water Humic Lakes.

We studied photochemically induced precipitation of rare-earth elements (REEs) in water from a tributary to Plesné Lake and a tributary to Jirická Pond, Czech Republic. Both tributaries had high concentrations of dissolved organic matter (∼1.8 mmol C L-1). Filtered (0.2 µm) samples were exposed to artificial solar radiation of 350 W m-2 for 48 to 96 h, corresponding to 3 to 6 days of natural solar radiation in summer at the sampling locations. Experiments were performed with altered and unaltered pH ranging from 3.8 to 6.0. The formation of particulate REEs occurred in all exposed samples with the fastest formation observed at the original pH. The formation of particulate metals continued in irradiated samples after the end of irradiation, suggesting that photochemically induced reactions and/or continuing precipitation continue in darkness or in deeper water due to mixing. Results were compared with paleolimnological records in the Plesné Lake sediment. At pH 5.0, the photochemically induced sediment flux was 3509 nmol m-2 y-1 for Ce, corresponding to 42% of the REEs' annual sediment flux in recent sediment layers. Combining the formation rates obtained in the laboratory irradiation experiments and known 1 day incident solar radiation enabled the estimation of a possible REE sediment flux. For Plesné Lake, the photochemically induced formation of particulate REEs explained 10-44% of the REE concentrations in the upper sediment layers. Observed photochemically induced sequestration of REEs into sediments can explain a significant part of the REEs' history in the Holocene sediment.

Do the joint effects of size, shape and ecocorona influence the attachment and physical eco(cyto)toxicity of nanoparticles to algae?

We systematically investigated how the combinations of size, shape and the natural organic matter (NOM)-ecocorona of gold (Au) engineered nanoparticles (ENPs) influence the attachment of the particles to algae and physical toxicity to the cells. Spherical (10, 60 and 100 nm), urchin-shaped (60 nm), rod-shaped (10 × 45, 40 × 60 and 50 × 100 nm), and wire-shaped (75 × 500, 75 × 3000 and 75 × 6000 nm) citrate-coated and NOM-coated Au-ENPs were used. Among the spherical particles only the spherical 10 nm Au-ENPs caused membrane damage to algae. Only the rod-shaped 10 × 45 nm induced membrane damage among the rod-shaped Au-ENPs. Wire-shaped Au-ENPs caused no membrane damage to the algae. NOM ecocorona decreased the membrane damage effects of spherical 10 nm and rod-shaped 10 × 45 nm ENPs. The spherical Au-ENPs were mostly loosely attached to the cells compared to other shapes, whereas the wire-shaped Au-ENPs were mostly strongly attached compared to particles with other shapes. NOM ecocorona determined the strength of Au-ENPs attachment to the cell wall, leading to the formation of loose rather than strong attachment of Au-ENPs to the cells. After removal of the loosely and strongly attached Au-ENPs, some particles remained anchored to the surface of the algae. The highest concentration was detected for spherical 10 nm Au-ENPs followed by rod-shaped 10 × 45 nm Au-ENPs, while the lowest concentration was observed for the wire-shaped Au-ENPs. The combined effect of shape, size, and ecocorona controls the Au-ENPs attachment and physical toxicity to cells.

Method for Extraction and Quantification of Metal-Based Nanoparticles in Biological Media: Number-Based Biodistribution and Bioconcentration.

A multistep sample preparation method was developed to separate metal-based engineered nanoparticles (ENPs) from biological samples. The method was developed using spiked zebrafish tissues and standard titanium dioxide (TiO2) and cerium dioxide (CeO2) ENPs. Single-particle inductively coupled plasma mass spectrometry was used to quantify the separated particles in terms of number concentration. This method demonstrated mass recoveries of more than 90% and did not strikingly alter the median particles size. High number recoveries were calculated for CeO2 ENPs (>84%). Particle number recoveries were poor for TiO2 ENPs (<25%), which could be due to the interference of 48Ca with the measured isotope 48Ti. The method was verified using zebrafish exposed to CeO2 ENPs to test its applicability for nanotoxicokinetic investigations. Total mass of Ce and particle number concentration of CeO2 ENPs were measured in different tissues. Notably, the mass-based biodistribution of Ce in the tissues did not follow the number-based biodistribution of CeO2. Moreover, the calculated mass-based bioconcentration factors showed a different pattern in comparison to the number-based bioconcentration factors. Our findings suggest that considering mass as the sole dose-metric may not provide sufficient information to investigate toxicity and toxicokinetics of ENPs.

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.

Factors Affecting the Leaching of Dissolved Organic Carbon after Tree Dieback in an Unmanaged European Mountain Forest.

Forest disturbances affect ecosystem biogeochemistry, water quality, and carbon cycling. We analyzed water chemistry before, during, and after a dieback event at a headwater catchment in the Bohemian Forest (central Europe) together with an un-impacted reference catchment, focusing on drivers and responses of dissolved organic carbon (DOC) leaching. We analyzed data regarding carbon input to the forest floor via litter and throughfall, changes in soil moisture and composition, streamwater chemistry, discharge, and temperature. We observed three key points. (i) In the first 3 years following dieback, DOC production from dead biomass led to increased concentrations in soil, but DOC leaching did not increase due to chemical suppression of its solubility by elevated concentrations of protons and polyvalent cations and elevated microbial demand for DOC associated with high ammonium (NH4+) concentrations. (ii) DOC leaching remained low during the next 2 years because its availability in soils declined, which also left more NH4+ available for nitrifiers, increasing NO3- and proton production that further increased the chemical suppression of DOC mobility. (iii) After 5 years, DOC leaching started to increase as concentrations of NO3-, protons, and polyvalent cations started to decrease in soil water. Our data suggest that disturbance-induced changes in N cycling strongly influence DOC leaching via both chemical and biological mechanisms and that the magnitude of DOC leaching may vary over periods following disturbance. Our study adds insights as to why the impacts of forest disturbances are sometime observed at the local soil scale but not simultaneously on the larger catchment scale.

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.

Temperature Dependence of Photodegradation of Dissolved Organic Matter to Dissolved Inorganic Carbon and Particulate Organic Carbon.

Photochemical transformation of dissolved organic matter (DOM) has been studied for more than two decades. Usually, laboratory or "in-situ" experiments are used to determine photodegradation variables. A common problem with these experiments is that the photodegradation experiments are done at higher than ambient temperature. Five laboratory experiments were done to determine the effect of temperature on photochemical degradation of DOM. Experimental results showed strong dependence of photodegradation on temperature. Mathematical modeling of processes revealed that two different pathways engaged in photochemical transformation of DOM to dissolved inorganic carbon (DIC) strongly depend on temperature. Direct oxidation of DOM to DIC dominated at low temperatures while conversion of DOM to intermediate particulate organic carbon (POC) prior to oxidation to DIC dominated at high temperatures. It is necessary to consider this strong dependence when the results of laboratory experiments are interpreted in regard to natural processes. Photodegradation experiments done at higher than ambient temperature will necessitate correction of rate constants.

Interaction of extrinsic chemical factors affecting photodegradation of dissolved organic matter in aquatic ecosystems.

Photochemical degradation of dissolved organic matter (DOM) plays an important role in the carbon cycle. Irradiation experiments were conducted to evaluate the influence of chemical factors, specifically those expected to be altered in natural waters by atmospheric acid deposition, on photodegradation of DOM. These included pH, nitrate, iron and calcium. The experiments were carried out using stream and lake water samples with a wide range of dissolved organic carbon (DOC) concentration. Decreasing DOC concentration along with decreasing absorbance was observed during three-week exposures to natural solar radiation as well as during laboratory experiments with artificial solar radiation. The pH of the samples significantly affected degradation rates of DOM especially with elevated iron, while no influence of nitrate or calcium concentration was observed. Addition of Fe(III) did not significantly affect photodegradation and photobleaching rate constants in samples at circumneutral pH. Acid pH increased photodegradation rates. The results suggest that photodegradation rates of DOM will decrease during recovery from acidification. Hence, lower photodegradation rates may be responsible for increases in DOM observed in some regions of North America and Europe.