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We tested the feasibility of using sedimentary algal pigment analyses by spectral deconvolution to infer past lake-water total phosphorus concentrations. We established equations that link lake-water nutrient concentrations and sediment pigment concentrations, using a combination of calibration in both space and time, with a training set of 31 Swedish lakes. The calibration dataset yielded a significant positive relationship between total carotenoid concentrations and lake-water total phosphorus concentrations. We also compared sediment-pigment-based nutrient inferences with time series of water column monitoring data to evaluate whether temporal changes in total phosphorus concentrations are well captured by analysis of sedimentary pigments. We found that changes in pigment preservation through time can alter the relationship between concentrations of lake-water nutrients and sedimentary pigments, thus limiting the reliability of historical ecological conditions inferred from pigments in the sediment. Our data suggested that ratios of Chlorophyll derivatives to total carotenoids (CD/TC ratio) and Chlorophyll a to Chlorophyll derivatives (CPI) can be used as proxies for pigment preservation. Using our approach, inferred temporal changes in water-column total phosphorus concentrations in lakes are promising, but require further development, specifically with respect to the influence of pigment degradation in both the water column and sediments, as well as the factors that control such degradation.

1. Most studies aiming to explore the response of algae and zooplankton trophic interactions to climate variability have only been focused on unidirectional and very shortterm trends in temperature changes. As a result, the non-stationary aspect of climate change (warming and cooling periods, frequencies) remains completely unstudied. 2. We studied elemental and stable isotope composition of sedimentary organic matter, photosynthetic pigments, and carbon stable isotope composition of Cladocera resting eggs in a sediment record covering the last c. 2,600 years. We examined how past climate change acting at different timescales affected algal biomass and community composition, and carbon assimilation by zooplankton in a boreal lake. 3. Our study revealed major effects of both long-term climate trends and shorter term fluctuations on algae–zooplankton interactions in a boreal lake. We found the main climate trends, in particular the Little Ice Age, induced algal biomass and community composition changes and drastic changes in carbon assimilation by zooplankton. Interestingly, we found that temperature fluctuations could also contribute to regulating algae–zooplankton interactions. Specifically, we observed drastic changes in sedimentary markers and stable isotope composition of zooplankton remains during the most recent period, suggesting a strong influence of ongoing anthropogenic change on algae–zooplankton interactions. 4. Our study confirms previous findings showing close long-term linkage between the temporal dynamics of zooplankton diet and planktonic algae, and that both climate trends and short-term fluctuations are key in regulating consumer– resource trophic interactions. 5. Novel approaches that combine high temporal resolution paleolimnological reconstructions and contemporary monitoring studies are needed to better understand climate change effects on algae–zooplankton interactions and lake food webs. Eesti Teadusagentuur, Grant/Award Number: PRG709 and PRG1167; Svenska Forskningsrådet Formas, Grant/Award Number: 2016-861; Oscar and Lilli Lamm Foundation. Eesti Teadusagentuur, Grant/Award Number: PRG709 and PRG1167; Svenska Forskningsrådet Formas, Grant/Award Number: 2016-861; Oscar and Lilli Lamm Foundation.

Photoautotrophic picoplankton (0.2–2 μm) can be a major contributor to primary production and play a significant part in the ecosystem carbon flow. However, the understanding about the dynamics of both eukaryotic and prokaryotic components of picoplankton in shallow eutrophic freshwater environments is still poor. Very few studies in these ecosystems reveal the taxonomic composition of picoeukaryotes. The main objective of this study was to investigate the seasonal dynamics of phototrophic picoplankton with the emphasis on the eukaryote community composition in a large shallow, eutrophic lake of the northern temperate zone (Lake Võrtsjärv). Phytoplankton pigments were employed to determine the taxonomic composition of photoautotrophic picoplankton. We found out that photoautotrophic picoplankton constitutes an important part of the phytoplankton community in Lake Võrtsjärv and its contribution can be highly variable (from ~9.3% to ~39%) in different years. The eukaryotic photoautotrophic picoplankton was dominated by diatoms followed by chrysophytes and other minor groups. Picoeukaryotes were prevailing in low-light conditions and low temperatures as their predominance in the picoplankton community was tightly linked to the presence or absence of ice cover. Ice cover strongly suppressed the growth of picocyanobacteria. Total phosphorus, turbidity and metazooplankton abundance had a clear relationship with photoautotrophic picoplankton chlorophyll a.

Research about the occurrence and extent of the cyanobacterial blooms in the Baltic Sea is critical due to their increased magnitude and frequency. Monitoring of the blooms is complicated due to their spatially and tem- porally heterogeneous nature. For adequate assessment of the water quality, phytoplankton dynamics needs to be tracked in large areas with high monitoring frequency. The main objectives of this study were (1) to describe phytoplankton community composition by pigment-based chemotaxonomy and validate the results with mi- croscopy; (2) to improve the retrieval of information about phytoplankton community by combining remote sensing with laboratory based approaches (3) to develop a region-specific algorithm to calculate cyanobacteria biomass from reflectance spectra; (4) to detect and quantify potentially toxic bloom-forming cyanobacteria with molecular methods. In our study the reflectance-based chlorophyll a (Chl a) values overestimated the High- performance Liquid Chromatography (HPLC) values although the correlations with HPLC Chl a measurements were very strong (rp ∼ 0.8, p < 0.001). We found that 709 nm/620 nm reflectance ratio correlated strongly (rp = 0.75, p < 0.01) to cyanobacteria wet biomass in CDOM-rich Väinameri even at low cyanobacterial bio- mass levels. Correlations between pigment-based chemotaxonomy and microscopy were significant in case of cyanobacteria (rp = 0.73, p < 0.01), cryptophytes (rp = 0.71, p < 0.05) and dinoflagellates (rp = 0.64, p < 0.05). This work was supported by Estonian Ministry of Education and Research (IUT 21-02), Estonian Science Foundation (ETF9102, ETF8576), Estonian Research Council (PUTJD719), base-financed pro- ject P180023PKKH of Estonian University of Life Sciences and by Estonian Doctoral School of Earth Sciences and Ecology. We thank Dr Teele Ligi (University of Tartu) for valuable help, Simon Wright and other developers of CHEMTAX program (Australian Antarctic Division, CSIRO). The authors acknowledge CYANOCOST-COST ES 1105 for networking and sharing knowledge. This work was supported by Estonian Ministry of Education and Research (IUT 21-02), Estonian Science Foundation (ETF9102, ETF8576), Estonian Research Council (PUTJD719), base-financed pro- ject P180023PKKH of Estonian University of Life Sciences and by Estonian Doctoral School of Earth Sciences and Ecology. We thank Dr Teele Ligi (University of Tartu) for valuable help, Simon Wright and other developers of CHEMTAX program (Australian Antarctic Division, CSIRO). The authors acknowledge CYANOCOST-COST ES 1105 for networking and sharing knowledge.

Understanding the long-term dynamics of ecological communities on the centuries-to-millennia scale is important for explaining present-day biodiversity patterns. Placing these patterns in a historical context could yield reliable tools for predicting possible future scenarios. Paleoarchives of macro+ and micro-fossil remains, and most importantly biomarkers such as fossil pigments and ancient DNA present in various sedimentary deposits, allow long term changes in ecological communities to be analysed. We use recent compilations of data including fossil pigments, metabarcoding of sedimentary ancient DNA and microfossils together with data analysis to understand the impact of gradual versus abrupt climate changes on a lake`s ecosystem status over the last 14.5 kyr. We give examples of hypotheses that need long-term data, which can be addressed using well-established paleoproxy variables. These variables describe the climate, together with vegetation change and the appearance of anthropogenic forcing, either as a gradual change or an abrupt event. We were able to detect abrupt changes in the lake ecosystem during the stable period of the Holocene Thermal Maximum and we highlight the increased frequency and degree of perturbation in lakes due to non-immediate human activity over a larger region. Both observations demonstrate an impaired relationship between a gradual external driver and ecosystem response and apply to future scenarios of climate warming and increased human impact in north-eastern Europe.

Autotrophic picoplankton (0.2–2 μm) can be a significant contributor to primary production and hence play an important role in carbon flow. The phytoplankton community structure in the Baltic Sea is very region specific and the understanding of the composition and dynamics of pico-size phytoplankton is generally poor. The main objective of this study was to determine the contribution of picoeukaryotic algae and their taxonomic com- position in late summer phytoplankton community of the West-Estonian Archipelago Sea. We found that about 20% of total chlorophyll a (Chl a) in this area belongs to autotrophic picoplankton. With increasing total Chl a, the Chl a of autotrophic picoplankton increased while its contribution in total Chl a decreased. Picoeukaryotes play an important role in the coastal area of the Baltic Sea where they constituted around 50% of the total autotrophic picoplankton biomass. The most abundant groups of picoeukaryotic algae were cryptophytes (16%), chlorophytes (13%) and diatoms (9%). Picocyanobacteria were clearly dominated by phycoerythrin containing Synechococcus. The parallel use of different assessment methods (CHEMTAX and flow cytometry) revealed the share of eukaryotic and prokaryotic part of autotrophic picoplankton. We gratefully thank Dr. Tiit Kutser (Estonian Marine Institute, Uni- versity of Tartu) for organizing the cruises and helping with the sample collection and Karolin Teeveer for providing microscopy counts. This work was supported by Estonian Ministry of Education and Research (IUT 21-02); Estonian Science Foundation (ETF9102, ETF8576); Swiss Grant for Programme “Enhancing public environmental monitoring ca- pacities” and Estonian Doctoral School of Earth Sciences and Ecology. We are thankful for the two reviewers who provided excellent advice to improve this manscript. We gratefully thank Dr. Tiit Kutser (Estonian Marine Institute, Uni- versity of Tartu) for organizing the cruises and helping with the sample collection and Karolin Teeveer for providing microscopy counts. This work was supported by Estonian Ministry of Education and Research (IUT 21-02); Estonian Science Foundation (ETF9102, ETF8576); Swiss Grant for Programme “Enhancing public environmental monitoring ca- pacities” and Estonian Doctoral School of Earth Sciences and Ecology. We are thankful for the two reviewers who provided excellent advice to improve this manscript.

Understanding the long-term dynamics of ecological communities on the centuries-to-millennia scale is important for explaining the emergence of present-day biodiversity patterns and for predicting possible future scenarios. Fossil pigments and ancient DNA present in various sedimentary deposits can be analysed to study long-term changes in ecological communities. We analysed recent compilations of data, including fossil pigments, microfossils, and molecular inventories from the sedimentary archives, to understand the impact of gradual versus abrupt climate changes on the ecosystem status of a regional model lake over the last ~14.5 kyr. Such long and complete paleo-archives are scarce in North-Eastern Europe. The study site lies in a sensitive area, both climatically and in respect to vegetation. Namely the maritime-continentality line runs west to east in the central Baltic area to NE Europe and its south- north transect lies within the gradual decay of the nemoral forest into a boreal environment. Therefore, the selected location is an ideal sampling point to decipher long term environmental changes in the temperate climate zone. The main objective of the present study was to find out external factors influencing phototroph dynamics at temperate Lake Lielais Sv etin ̧ u over the post-glacial period (~14.5 kyr). We were able to model climate change together with vegetation change and the appearance of anthropogenic forcing, either as a gradual change or as abrupt events that influenced the phototrophs, which are keystone groups within the lacustrine ecosystem. Most interestingly, the gradual increase of species richness of phototrophs was linked to similar increase in fungal parasites of the same group e phototrophs. Abrupt climate change in the Late Glacial period caused abrupt events in the ecosystem but equally abrupt events were caused by gradual changes during the stable period of the Holocene Thermal Maximum (HTM). In addition, we highlight the increased frequency and degree of perturbation in pristine lakes due to low impact human activity over a larger region. Both observations demonstrate an impaired relationship between gradual external drivers and ecosystem response and apply to future scenarios of climate warming and increased human impact in north-eastern Europe. lmar Tõnno and Rene Freiberg were supported by the Estonian Research Council (ETAg) IUT21-2, PRG705, PRG709 and PRG1167. Veljo Kisand was supported by grants PUT134 and PUT1389 (ETAg) and Institute of Technology, University of Tartu basic funding grant. Siim Veski was supported by IUT1-8 and PRG323 (ETAg). Normunds Stivrins was additionally financially supported by the Latvian Council of Science project No. LZP-2020/2e0060. lmar Tõnno and Rene Freiberg were supported by the Estonian Research Council (ETAg) IUT21-2, PRG705, PRG709 and PRG1167. Veljo Kisand was supported by grants PUT134 and PUT1389 (ETAg) and Institute of Technology, University of Tartu basic funding grant. Siim Veski was supported by IUT1-8 and PRG323 (ETAg). Normunds Stivrins was additionally financially supported by the Latvian Council of Science project No. LZP-2020/2e0060.

Reconstructions of past food web dynamics are necessary for better understanding long-term impacts of climate change on subarctic lakes. We studied elemental and stable isotopic composition of sedimentary organic matter, photosynthetic pigments and carbon stable isotopic composition of Daphnia (cladocera; crustacea) resting eggs (δ13cclado) in a sediment record from a small subarctic lake. We examined how regional climate and landscape changes over the last 5800 years affected the relative importance of allochthonous and autochthonous carbon transfer to zooplankton. Overall, δ13cclado values were well in line with the range of theoretical values of aquatic primary producers, confirming that zooplankton consumers in subarctic lakes, even in the long-term perspective, are mainly fuelled by autochthonous primary production. Results also revealed greater incorporations of benthic algae into zooplankton biomass in periods that had a warmer and drier climate and clearer water, whereas a colder and wetter climate and lower water transparency induced higher contributions of planktonic algae to Daphnia biomass. This study thus emphasizes long-term influence of terrestrial-aquatic linkages and in- lake processes on the functioning of subarctic lake food webs. This study was funded by the Oscar and Lilli Lamm foundation, FORMAS (Grant Number: 2016-861) and by institutional research grant IUT 21-2. We acknowledge Jenny Ekman and Jonas Lundholm (SLU Umeå, Sweden) and Christian Hossann (INRA PTEF Nancy, France) for assistance in stable isotope analysis, and Malin Kylander (University of Stockholm, Sweden) for XRF core scanning. The PTEF facility is supported by the French National Research Agency through the Laboratory of Excellence ARBRE (ANR-11-LABX-0002-01). Open access funding provided by Swedish University of Agricultural Sciences. This study was funded by the Oscar and Lilli Lamm foundation, FORMAS (Grant Number: 2016-861) and by institutional research grant IUT 21-2. We acknowledge Jenny Ekman and Jonas Lundholm (SLU Umeå, Sweden) and Christian Hossann (INRA PTEF Nancy, France) for assistance in stable isotope analysis, and Malin Kylander (University of Stockholm, Sweden) for XRF core scanning. The PTEF facility is supported by the French National Research Agency through the Laboratory of Excellence ARBRE (ANR-11-LABX-0002-01). Open access funding provided by Swedish University of Agricultural Sciences.

We used HPLC to identify and quantify pigments in a Holocene sediment record from large, shallow Lake Peipsi, Estonia. The aim of our study was to track the influence of long-term climate change (i.e. temperature fluctuations) on past dynamics of aquatic primary producers. Sedimentary pigments were separated and quantified in 182 samples that span the last ca. 10,000 years. There was an increasing trend in sedimentary pigment concentrations from basal to upper sediment layers, suggesting a gradual increase in lake trophic status through time. Using additive models, our results suggested that primary producer dynamics in Lake Peipsi were closely related to temperature fluctuations. We, however, identified two periods (early Holocene and after ca. 2.5 cal ka BP) when the relationship between primary producer composition and temperature was weak, suggesting the influence of additional drivers on the primary producer community. We postulate that: (a) the increase of primary producer biomass in the early Holocene could have been caused by input of allochthonous organic matter and nutrients from the flooded areas when water level in Lake Peipsi was increasing, and (b) changes in the abundance and structure of primary producer assemblages since ca. 2.5 cal ka BP was related to widespread agricultural activities in the Lake Peipsi catchment. These results suggest that human activities can disrupt the relationship between the primary producer community and temperature in large, shallow lakes. This research was supported by institutional research grants IUT21-2, IUT1-8 and PRG323 and Estonian Science Foundation Grants Nos. 6741, 7888 and 9102. We acknowledge colleagues S. Veski, A. Heinsalu and J. Vassiljev for sediment coring and establishing the chronology, and A. Leeben for participating in the early stage of manuscript development. We are grateful for the comments and corrections made by two anonymous reviewers of the manuscript. This research was supported by institutional research grants IUT21-2, IUT1-8 and PRG323 and Estonian Science Foundation Grants Nos. 6741, 7888 and 9102. We acknowledge colleagues S. Veski, A. Heinsalu and J. Vassiljev for sediment coring and establishing the chronology, and A. Leeben for participating in the early stage of manuscript development. We are grateful for the comments and corrections made by two anonymous reviewers of the manuscript.

The coexistence of potentially toxic bloom-forming cyanobacteria (CY) and generally smaller-sized grazer communities has raised the question of zooplankton (ZP) ability to control harmful cyanobacterial blooms and highlighted the need for species-specific research on ZP-CY trophic interactions in naturally occurring communities. A combination of HPLC, molecular and stable isotope analyses was used to assess in situ the importance of CY as a food source for dominant crustacean ZP species and to quantify the grazing on potentially toxic strains of Microcystis during bloom formation in large eutrophic Lake Peipsi (Estonia). Aphanizomenon, Dolichospermum, Gloeotrichia and Microcystis dominated bloom-forming CY, while Microcystis was the major genus producing cyanotoxins all over the lake. Grazing studies showed that CY, and especially colonial CY, formed a significant, and also preferred component of algae ingested by the cladocerans Bosmina spp. and Daphnia spp. while this was not the case for the more selective calanoid copepod Eudiaptomus gracilis. Molecular analyses confirmed the presence of CY, including Microcystis, in ZP guts. Further analyses using qPCR targeting cyanobacterial genusspecific mcyE synthase genes indicated that potentially toxic strains of Microcystis can be ingested directly or indirectly by all the dominant crustacean grazers. However, stable isotope analyses indicated that little, if any, assimilation from ingested bloom-forming CY occurred. The study suggests that CY, and particularly Microcystis with both potentially toxic and non-toxic strains, can be widely ingested by cladoceran grazers during a bloom event with implications for control of CY abundance and for transfer of CY toxins through the food web. Funding for this research was provided by institutional research funding IUT 21-2 of the Estonian Ministry of Education and Research and by base-financed project P180023PKKH of Estonian University of Life Sciences. The authors are grateful to Tuula Sinisalo and Mikko Kiljunen for assistance with the stable isotope analyses at Jyväskylä University. COST Action ES 1105 “CYANOCOST – Cyanobacterial blooms and toxins in water resources: Occurrence, impacts and management” is acknowledged for networking and sharing of knowledge. [CG] Funding for this research was provided by institutional research funding IUT 21-2 of the Estonian Ministry of Education and Research and by base-financed project P180023PKKH of Estonian University of Life Sciences. The authors are grateful to Tuula Sinisalo and Mikko Kiljunen for assistance with the stable isotope analyses at Jyväskylä University. COST Action ES 1105 “CYANOCOST – Cyanobacterial blooms and toxins in water resources: Occurrence, impacts and management” is acknowledged for networking and sharing of knowledge. [CG]

Carbon storage in lakes can have huge implications for the global carbon cycle, as lakes annually accumulate up to one half the amount of organic carbon buried in marine sediments. Yet little is known of the effect of recent climate change on carbon storage in lakes. We analyzed century-scale time series of climate variables (precipitation, temperature, NAO winter index) and profiles of sediment characteristics in a dated sediment core from shallow, eutrophic Lake Vortsjarv, south Estonia. We used path analysis to evaluate the effect of climate conditions on phytoplankton biomass in the lake and accumulation of organic and inorganic carbon in the sediment. Changes in winter and spring climate influenced the lake’s phytoplankton growth significantly. Carbon pathways in hard-water Lake Vortsjarv were influenced by both hydrological (most significant in colder periods) and biogeochemical processes. Increased nutrient and water input to Lake Vortsjarv, anticipated with projected climate warming, favours greater in-lake productivity, larger accumulation of inorganic carbon in sediments, and an increase in organic carbon mineralisation, which fuels atmospheric greenhouse gas emissions from the lake.

The study of lake sediments and archived biological remains is a promising approach to better under- stand the impacts of climate change on aquatic ecosystems. Small lakes have been shown to be strongly sensitive to past climate change, but similar information is lacking for large lakes. By identifying re- sponses to climate change of carbon flows through benthic food web in two different sized lakes, we aimed to understand how lake morphometry can mediate the effects of climate change. We recon- structed the dynamics of phytoplankton community composition and carbon resources sustaining chironomid biomass during the Holocene from the combined analysis of sedimentary pigment quanti- fication and carbon stable isotopic composition of subfossil chironomid head capsules (d13 C HC) in a large lake in the Baltic area (Estonia). Our results showed that chironomid biomass in the large lake was mainly sustained by phytoplankton, with no significant relationship between d13 C HC values and tem- perature fluctuations. We suggest that lake morphometry (including distance of the sampling zone to the shoreline, and lake volume for primary producers) mediates the effects of climate change, making large lakes less sensitive to climate change. Complementary studies are needed to better understand differ- ences in organic matter dynamics in different sized lakes and to characterize the response of the aquatic carbon cycle to past climate change. Financial support was provided by institutional research grants IUT1-8 and IUT21-2 from the Estonian Science Agency and by Estonian University of Life Sciences, project No. 8M160101PKLJ. We are grateful to Christian Hossann (INRA Nancy, Champenoux) for assistance in carbon stable isotope analysis. The PTEF facility is supported by the French National Research Agency through the Laboratory of Excellence ARBRE (ANR-11-LABX-0002-01). We acknowledge the contributions of Atko Heinsalu, Siim Veski and Jüri Vassiljev for coring and sediment dating. We also thank G. L. Simpson for valuable comments on statistical analyses. Editing services were provided by Sea Pen Scientific Writing. Financial support was provided by institutional research grants IUT1-8 and IUT21-2 from the Estonian Science Agency and by Estonian University of Life Sciences, project No. 8M160101PKLJ. We are grateful to Christian Hossann (INRA Nancy, Champenoux) for assistance in carbon stable isotope analysis. The PTEF facility is supported by the French National Research Agency through the Laboratory of Excellence ARBRE (ANR-11-LABX-0002-01). We acknowledge the contributions of Atko Heinsalu, Siim Veski and Jüri Vassiljev for coring and sediment dating. We also thank G. L. Simpson for valuable comments on statistical analyses. Editing services were provided by Sea Pen Scientific Writing.

Given the increased interest in non-pollen palynomorphs (microscopic objects other than pollen identified from pollen slides) in palaeoecological studies, it is necessary to seek a deeper understanding of the reliability of these results. We combined quantitative information of algal pigments and sedimentary ancient DNA (sedaDNA) of phylotaxonomical resolution to validate the richness and abundance of fossil algae in the sediment of a small temperate lake. For the first time, fossil and sedaDNA algae data were combined in a composite data-set and used to reconstruct algae turnover rates over the last 14,500 years. This comparison serves as both an example of howfossil algae can be used to answer various research questions and as a method of revealing towhat extent we can rely on palaeoecological interpretations based solely on the fossil algae record from pollen slides. We wish to thank EBOR, Institutional Research Funding IUT1-8 and IUT21-2, and Personal Research Funding granted to V.K. (PUT-134 and PUT-1389) for support. We would also like to thank B. van Geel and the second anonymous reviewer for their constructive comments and suggestions. We wish to thank EBOR, Institutional Research Funding IUT1-8 and IUT21-2, and Personal Research Funding granted to V.K. (PUT-134 and PUT-1389) for support. We would also like to thank B. van Geel and the second anonymous reviewer for their constructive comments and suggestions.

This study demonstrates the power of multiproxy palaeolimnological analyses in investigating environmental changes in the Lake Kooraste Linajarv ecosystem through historical time in response to flax retting. Flax retting history was proven by applying pollen and macrofossil evidence and by using several biotic and geochemical proxies on a sediment core. Continuous findings of flax pollen and macrofossil remains in lake sediments were considered as strong evidence for the occurrence of retting. Analyses of the well-dated sediment core show the consequences of flax retting in the lake. As a result, the once clear soft water oligotrophic endorheic lake with limited sedimentation has turned into a hypertrophic high-sedimentation lake with anoxic bottom water, strong stratification and intense water blooms. Despite the fact that flax retting was forbidden in Estonia around ad 1950s and retting has not occurred over the last six decades, anthropogenic alterations were so pervasive in the past, that they have prevented any lake water improvements until the present-day.

In North-East Estonia, considerable amounts of toxicants (e.g. polycyclic aromatic hydrocarbons (PAHs), phenols, heavy metals) leach into water bodies through discharges from the oil-shale industry. In addition, natural and anthropogenic hypoxic events in water bodies affect the health of aquatic organisms. Here we report a study on the combined effects of contaminated sediment and hypoxia on the physiology of gibel carp (Carssius auratus gibelio). We conducted a laboratory exposure study that involved exposure to polluted sediments from oil-shale industries (River Purtse) and sediments from a relatively clean environment (River Selja), together with sediments spiked with PAHs. The oxygen content (saturation vs. hypoxia (< 2 mg/L)) was changed to reflect hypoxia. A multi-biomarker approach was chosen to enable the combined effects to be assessed comprehensively and integratively. We used HPLC to measure the PAH concentration in sediment and fish muscle, fixed wavelength fluorescence (FF) analyses to indicate the presence of PAH metabolites in fish bile, and nuclear abnormalities in erythrocytes as markers of geno- and cyto-toxicity; and we monitored the change in body condition and measured EROD activity to indicate CYP1A induction. High levels of PAH conjugates in fish bile were found in the group exposed to the Purtse River sediment under hypoxia. The results suggested that induction of the CYP1A gene was modulated by hypoxia as well as by heavy metals. We found a correlation between several erythrocyte abnormalities (8-shaped nuclei and blebbed nuclei) and PAH metabolite content in fish. In conclusion, a measurable effect of pollution from the oil-shale industry on fish health parameters was clear under different oxygen levels.

In this paper, we investigate the sample preparation and analysis process in order to achieve adequate results for surface water collected from rivers that flow through swamps and are consequently rich in organic matter. We show that matrix effects in glyphosate determination can be reduced by optimizing sample volume, liquid chromatography (LC) mobile phase buffer concentration and pH as well as gradient speed. Also, aspects of derivatization procedure (borate buffer concentration, fluorenylmethyloxycarbonyl chloride concentration) and their influence on accuracy are considered in detail. We encountered a cross-talk effect in the mass spectra, interfering with quantization during analysis, which was removed by optimizing MS parameters. As a result it was demonstrated that isotope-labelled internal standard with just one 13C atom is sufficient for the analysis.All these aspects were found to strongly impact the accuracy of the glyphosate determination but have received little or no attention in earlier works. We propose a reliable solid phase extraction and LC/ESI/MS/MS method for determination of glyphosate in organic-rich waters and demonstrate that LoD can be decreased by about two times using an ESI nebulizer with a modified design.

We applied a multi-proxy palaeolimnological approach to provide insights into the natural variability and human-mediated trends of two interconnected temperate large shallow lakes, Peipsi and Vortsjarv, during the twentieth century. The history of the lakes was assessed on the basis of age-related changes in the sediment main constituents (water, organic matter and carbonate), sub-fossil pigments, diatom assemblages and organic matter dissolved in pore water. The temporal changes in the palaeodata indicate an increase of the in-lake biological production in both lakes from about the 1960s, suggesting enhanced nutrient inputs. In subsequent decades, the gradual increase of autochthonous organic matter becomes more obvious, indicating progressive eutrophication of the lakes. Palaeolimnological indicators from the sediment record of Lake Peipsi indicate a slight recession of the lake’s eutrophication in the 1990s but not for Lake Vortsjarv. The results of the study also suggest that after the lakes became eutrophied, the climatically induced water-level fluctuations ceased to be the main driver determining the abundance of phytoplankton. Responses of the lakes to human-induced impacts are better recorded in the sediments of Lake Peipsi than in those of Lake Vortsjarv, which is shallower of the two and where the wave-induced resuspension of deposits markedly smooths or erases the signals of environmental changes. The results of the investigation expand the knowledge on how large shallow lakes respond to human-mediated and natural perturbations, including those in the lake catchment areas and the capability of the lakes to store the chronology and sequence of these changes.

We investigated stratigraphic changes in fossil pigments and the molecular structure of the UV-absorbing fraction of pore-water dissolved organic matter in a sedimentary record from Lake Peipsi (Estonia/Russia) temporally covering the 20th century. The aims of the study were to define the onset of eutrophication in the lake and to track its course. An attempt was also made to reconstruct lake conditions before the intensive nutrient loading began. Fossil pigment analysis indicated that the eutrophication of the lake started in the 1960s and accelerated in the 1970s. Sedimentary pigments also indicate a continuing tendency of the lake ecosystem towards eutrophy in the 1980s and 1990s. However, changes in the molecular size structure of pore-water dissolved organic matter indicated that the contribution of autochthonous matter to the organic pool of the lake ecosystem had already started to increase around the end of the 1930s. We conclude that this rise was generated by a coincidence of several anthropogenic and natural factors. The pore-water data also show that a slight relative reduction in the autochthonous organic matter took place in the 1990s. A discordance in the paleodata obtained for the beginning of the 20th century complicates clear conclusions about earlier conditions in the lake. On the one hand, the qualitative characteristics of pore-water dissolved organic matter and the low concentration of chlorophyll a indicate that the phytoplankton biomass was low in Lake Peipsi during that period. On the other hand, the concentrations of marker pigments of specific phytoplankton groups are high, comparable with the values in the recent sediments. Possible reasons for the high levels of these pigments in the early 1900s sediments, such as a shift in the preservation conditions of organic substances and their transport from the lake’s catchment, are discussed.

Pigment-based chemotaxonomy and CHEMTAX software have proven to be a valuable phytoplankton monitoring tool in marine environments, but are yet underdeveloped to determine algal assemblages in freshwater ecosystems. The main objectives of this study were (1) to compare the results of direct microscopy and CHEMTAX in describing phytoplankton community composition dynamics in a large, shallow and eutrophic lake; (2) to analyze the efficiency of the pigment-based method to detect changes in phytoplankton seasonal dynamics and during rapid bloom periods; (3) to assess the suitability of specific marker pigments and available marker pigment:chlorophyll a ratios to follow seasonal changes in eutrophic freshwater environment. A 5-year (2009-2013) parallel phytoplankton assessment by direct microscopy and by CHEMTAX was conducted using published marker pigment:chlorophyll a ratios. Despite displaying some differences from microscopy results, the pigment-based method successfully described the overall pattern of phytoplankton community dynamics during seasonal cycle in a eutrophic lake. Good agreement between the methods was achieved for most phytoplankton groups - cyanobacteria, chlorophytes, diatoms and cryptophytes. The agreement was poor in case of chrysophytes and dinoflagellates. Our study shows clearly that published marker pigment:chlorophyll a ratios can be used to describe algal class abundances, but they need to be calibrated for specific freshwater environment. Broader use of this method would enable to expand monitoring networks and increase measurement frequencies of freshwater ecosystems to meet the goals of the Water Framework Directive.

Small-bodied cladocerans and cyclopoid copepods are becoming increasingly dominant over large crustacean zooplankton in eutrophic waters where they often coexist with cyanobacterial blooms. However, relatively little is known about their algal diet preferences. We studied grazing selectivity of small crustaceans (the cyclopoid copepods Mesocyclops leuckarti, Thermocyclops oithonoides, Cyclops kolensis, and the cladocerans Daphnia cucullata, Chydorus sphaericus, Bosmina spp.) by liquid chromatographic analyses of phytoplankton marker pigments in the shallow, highly eutrophic Lake Võrtsjärv (Estonia) during a seasonal cycle. Copepods (mainly C. kolensis) preferably consumed cryptophytes (identified by the marker pigment alloxanthin in gut contents) during colder periods, while they preferred small non-filamentous diatoms and green algae (identified mainly by diatoxanthin and lutein, respectively) from May to September. All studied cladoceran species showed highest selectivity towards colonial cyanobacteria (identified by canthaxanthin). For small C. sphaericus, commonly occuring in the pelagic zone of eutrophic lakes, colonial cyanobacteria can be their major food source, supporting their coexistence with cyanobacterial blooms. Pigments characteristic of filamentous cyanobacteria and diatoms (zeaxanthin and fucoxanthin, respectively), algae dominating in Võrtsjärv, were also found in the grazers' diet but were generally avoided by the crustaceans commonly dominating the zooplankton assemblage. Together these results suggest that the co-occurring small-bodied cyclopoid and cladoceran species have markedly different algal diets and that the cladocera represent the main trophic link transferring cyanobacterial carbon to the food web in a highly eutrophic lake.

In January 2006 an oil spill that involved approximately 40 tons of heavy fuel oil affected more than 30 km of the north-west coast of Estonia. The aquatic pollution of the coastal area of the Baltic Sea was monitored by measuring the content of selected polycyclic aromatic hydrocarbons (PAHs and PAH metabolites) in flounder (Platichthys flesus trachurus Duncker). One hundred and thirty-one fish were collected: muscle and liver tissues were analyzed by high-performance liquid chromatography (HPLC); bile and urine samples were analyzed using fixed wavelengths fluorescence. Fifteen different types of PAHs were analyzed in liver and muscle, and four types of PAH metabolites were analyzed in bile and urine (2-, 3-, 4- and 5-ringed PAH metabolites represented by naphthalene, phenanthrene, pyrene and benzo(a)pyrene). Fluorescence analyses were carried out using excitation/emission wavelength pairs: 290/380, 256/380, 341/383 and 380/430 nm, respectively. There was a time-dependent decrease of PAH concentrations in liver (83%), bile (82%) and urine (113%). HPLC analysis of muscle tissues demonstrated low concentrations of single PAHs, but a decrease of concentrations during the study period was not observed. During the analyses concentrations of PAH metabolites in bile and urine were compared. Liver metabolic transformation activity is believed to exceed that of the kidney but the analyses demonstrated high metabolite concentration in fish urine, particularly of 4- and 5-ring PAH metabolites. The results indicate remarkable buffer capacity of hydrodynamically active sea as well as considerable importance of kidney-urine metabolic pathways in flounder physiology.

Our aim was to find out to which extent fossil phytoplankton pigments in the large shallow and turbid Lake Võrtsjärv carry information on the history of phytoplankton communities. For this purpose we examined how the changes in the pigment composition of surface sediments follow their changes in the water column. Depth-integrated lake water and surface sediment samples were collected weekly in May–October 2007. Considering cyanobacterial and diatom dominance in phytoplankton, we analysed fucoxanthin, diadinoxanthin and diatoxanthin as marker pigments for diatoms, zeaxanthin as a marker pigment for total cyanobacteria and canthaxanthin as a marker pigment for colonial cyanobacteria. Chlorophyll a and its derivative pheophytin a were applied as indicators for total phytoplankton. The dynamics of phytoplankton pigments in surface sediments generally did not follow their dynamics in the water column, possibly due to intensive resuspension and a high sedimentation rate in a large and shallow lake. It was noticed that the surface sediment carries information on pigment degradation intensity and on weight and size characteristics of phytoplankton cells, which affect their sinking and floating velocities. Higher pigment contents of sediment in spring were presumably caused by lower resuspension due to high water level and slower degradation in cold water. Pheophytin a and the marker pigments of cyanobacteria were found to be persistent against degradation in upper sediment layers, which makes them useful indicators for tracking the historical changes in phytoplankton communities also in a shallow lake. Sharp decrease in chemically unstable pigment contents between the sediment surface and deeper layers indicates that only the uppermost sediment surface is resuspended in Lake Võrtsjärv. The transformation of the diatom marker carotenoid diadinoxanthin to diatoxanthin was found to occur mainly in sediments and not in the water column, and the process is not induced by excess light.

We assessed the utility of using the sediment total organic carbon/total nitrogen (C/N) ratio as an indicator of paleoclimate changes in the eastern Baltic area during the late glacial and early Holocene. The C/N ratio in sediments from Lake Lielais Sve ̄tin ̧ u, eastern Latvia, was compared with other sediment variables that are used as proxies of past climate and environment. Analysis revealed that although the organic matter (OM) content in late glacial sediments was extremely low, the C/N ratio captured information about OM origin, and fluctua- tions in the ratio tracked climate oscillations. The C/N ratio was significantly positively correlated with pollen-inferred mean summer temperature. Therefore, C/N ratio was lower under colder conditions, indicat- ing a predominantly phytoplankton origin of OM, and was higher during warmer conditions, when there was more vegetation around the lake. A strong positive correlation between C/N ratio and the paleopigment beta carotene suggested that elevated phytoplankton production resulted from higher nutrient availability that was controlled largely by the input of terrestrial OM to the lake during warmer climate episodes. Thus, C/N ratio was a good indicator of paleoclimate changes, at least for the late glacial period, when generally cold conditions prevailed. This study also demonstrates the power of multi-proxy paleolimno- logical analyses for investigating past environmental changes in lakes and their watersheds. This study was supported by the Estonian Ministry of Education and Research through institutional research funding (IUT1–8, IUT21–2, PUT1173), the Estonian Science Foundation (ETF9031) EBOR project and national basic funding for science project Y5-AZ03-ZF-N-110 ‘‘Dabas resursu ilgtspe ̄jı ̄ga izmantosˇana klimata pa ̄rmain ̧ u konteksta ̄’’ Nr. ZD2010/AZ03. This paper was revised by Elsevier Language Editing Services. Two anonymous referees and Co-Editor in Chief Mark Brenner provided helpful comments on the manuscript. This study was supported by the Estonian Ministry of Education and Research through institutional research funding (IUT1–8, IUT21–2, PUT1173), the Estonian Science Foundation (ETF9031) EBOR project and national basic funding for science project Y5-AZ03-ZF-N-110 ‘‘Dabas resursu ilgtspe ̄jı ̄ga izmantosˇana klimata pa ̄rmain ̧ u konteksta ̄’’ Nr. ZD2010/AZ03. This paper was revised by Elsevier Language Editing Services. Two anonymous referees and Co-Editor in Chief Mark Brenner provided helpful comments on the manuscript.