Rene Freiberg

History of anthropogenically mediated eutrophication of Lake Peipsi as revealed by the stratigraphy of fossil pigments and molecular size fractions of pore-water dissolved organic matter

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.

Responses of metabolic pathways to polycyclic aromatic compounds in flounder following oil spill in the Baltic Sea near the Estonian coast

In January 2006 an oil spill that involved approximately 40tons of heavy fuel oil affected more than 30km 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 380/430nm, 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.

Pigment-Based Chemotaxonomy - A Quick Alternative to Determine Algal Assemblages in Large Shallow Eutrophic Lake?

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.

Biomarkers of effects of hypoxia and oil-shale contaminated sediments in laboratory-exposed gibel carp (Carassius auratus gibelio)

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.

Determination of glyphosate in surface water with high organic matter content

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.

A comparison of the palaeolimnology of Peipsi and Võrtsjärv: connected shallow lakes in north-eastern Europe for the twentieth century, especially in relation to eutrophication progression and water-level fluctuations

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 Võrtsjärv, 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 Võrtsjärv. 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 Võrtsjärv, 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.

Drastic changes in lake ecosystem development as a consequence of flax retting: a multiproxy palaeolimnological study of Lake Kooraste Linajärv, Estonia

This study demonstrates the power of multiproxy palaeolimnological analyses in investigating environmental changes in the Lake Kooraste Linajärv 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.

Parallel assessment of marine autotrophic picoplankton using flow cytometry and chemotaxonomy

Autotrophic picoplankton (0.2-2μm) 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 composition 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.

Late glacial and early Holocene climate and environmental changes in the eastern Baltic area inferred from sediment C/N ratio

Abstract 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 Svētiņu, 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 fluctuations 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, indicating 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 paleolimnological analyses for investigating past environmental changes in lakes and their watersheds.

Sedimentary carbon forms in relation to climate and phytoplankton biomass in a large, shallow, hard-water boreal lake

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 Võrtsjärv, 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 Võrtsjärv were influenced by both hydrological (most significant in colder periods) and biogeochemical processes. Increased nutrient and water input to Lake Võrtsjärv, 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.