Sources of sedimentary biomarkers and proxies with potential paleoenvironmental significance for the Baltic Sea

Author’s Accepted Manuscript Sources of sedimentary biomarkers and proxies with potential paleoenvironmental significance for the Baltic Sea Jérôme Kaiser, Helge W. Arz www.elsevier.com/locate/csr

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S0278-4343(16)30144-3 http://dx.doi.org/10.1016/j.csr.2016.03.020 CSR3399

To appear in: Continental Shelf Research Received date: 4 September 2015 Revised date: 29 January 2016 Accepted date: 17 March 2016 Cite this article as: Jérôme Kaiser and Helge W. Arz, Sources of sedimentary biomarkers and proxies with potential paleoenvironmental significance for the Baltic Sea, Continental Shelf Research, http://dx.doi.org/10.1016/j.csr.2016.03.020 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Sources of sedimentary biomarkers and proxies with potential paleoenvironmental significance for the Baltic Sea Jérôme Kaiser*, Helge W. Arz Leibniz Institute for Baltic Sea Research (IOW), Seestrasse 15, 18119 Rostock-Warnemünde, Germany *Corresponding author. [email protected]

Abstract The Baltic Sea is a shallow, semi-enclosed and intra-continental shelf sea characterized by anoxic bottom waters in the deepest basins, allowing for the preservation of sedimentary organic matter. In the present study, the most abundant, naturally-occurring lipids in surface sediments from the entire Baltic Sea and the Skagerrak area were identified and their potential sources were assigned. Together with long-chain n-alkanes derived from land plant leaf waxes, diploptene and branched glycerol dialkyl glycerol tetraethers (GDGTs) are of allochthonous origin, while isoprenoid GDGTs, hydroxylated isoprenoid GDGTs (OHGDGTs), n-C25:1, n-C27:1 and n-C29:1 alkenes are autochthonous lipids. The isoprenoid and OH-GDGTs are probably derived from Thaumarchaeota and the long-chain n-alkenes from phototrophic organisms. Significant correlations were found between indexes based on isoprenoid and OH-GDGTs and Baltic Sea surface and bottom temperatures. The calibrations obtained for surface temperature have statistically similar slopes, but different intercepts than calibrations established for the Nordic Seas. The branched and isoprenoid tetraether index can be used to estimate the percentage of soil (terrestrial) organic matter in the sediments of the Baltic Sea. High values of the Paq’ ratio (defined here as the ratio of odd numbered n-C23 and n-C25 over n-C23 to n-C29 alkanes) in the northern Baltic Sea originate from the presence of both Sphagnum mosses in the drainage basin and submerged macrophytes, such as Potamogeton sp. and Myriophyllum sp., in the freshwater to brackish water of the coastal areas. The Paq’ ratio may thus reflect fluctuations in the regional expansion of freshwater to brackish coastal environments in the Baltic Sea.

Keywords

Biomarkers; hydrocarbons; n-alkenes; (OH-) GDGTs; crenarchaeol; Baltic Sea

1. Introduction

Organic matter (OM) deposited in aquatic environments includes both autochthonous material derived from organisms living in the water column and/or in the sediment, and allochthonous material consisting of OM from terrestrial organisms reaching the depositional centre by fluvial and/or aeolian transport (Peters et al., 2005; Bianchi and Canuel, 2011). Potential other OM sources are weathering of ancient sediments and anthropogenic inputs arising from combustion, oils and coals, as well as synthetic products. Organic molecular proxies are based on the abundance of specific organic compounds (biological lipids) derived from marine and terrestrial organisms that can be extracted from sedimentary OM and applied for paleoenvironmental reconstructions (Eglinton and Eglinton, 2008). Multiple factors controlling the input, transportation, sedimentation, and preservation of these compounds complicate the application of these proxies. Because microorganisms consume and degrade the primary planktonic products within the water column and at the sediment/water interface, only a small portion of the lipids added to or generated within the aquatic environment are incorporated into the sediments as molecular fossils (Peters et al., 2005; Bianchi and Canuel, 2011). While OM is poorly preserved in oxic environments due to high predation and bacterial degradation, oxygen deficiency within the water column and the sediment/water interface preserves the more labile lipids, and a greater amount of OM reaching the sediment is preserved (Cranwell, 1982). Therefore, the higher preservation of OM and the absence of sediment bioturbation from benthic organisms make anoxic environments such as the deep basins of the Baltic Sea ideal for the application of biomarkers. So far only few studies have focused on naturally-occurring, sedimentary biomarkers with potential applications for paleoenvironmental reconstructions in the Baltic Sea. Pigments produced by photosynthetic organisms such as chlorophyll (chlorophyll a, b, c) and carotenoids (e.g. fucoxanthin, zeaxanthin, peridinin, alloxanthin, lutein, ββ-carotene) have been studied thoroughly in the Baltic Sea. Studies on phytoplankton species (Ston et al., 2002) and macroalgae (Bianchi et al., 1997a) of the Baltic Sea suggested that pigments can be useful for elucidating the composition of phytoplankton populations in natural samples and for distinguishing between macroalgal and planktonic inputs to the benthic communities of

the Baltic Sea. In the surface sediments, pigments were used as biomarkers of the taxonomic composition of phytoplankton and to characterize the source of OM (Lotocka, 1998; Bianchi et al., 2002a,b; Kowalewska, 2005). However, carotenoids and especially chlorophyll are relatively labile and susceptible to oxidative degradation in the water column and the surface sediments, resulting in preferential degradation of some pigments, while other pigments are well preserved (Abele-Oeschger, 1991; Lotocka, 1998; Bianchi et al., 2000, 2002a). Next to carotenoids, lignin-phenols (e.g. syringyl, vanillyl), which are biosynthesized by vascular land plants and used as markers for terrestrial plant derived OM, have been studied in water samples (Bianchi et al., 1997b) and surface sediments (Miltner and Emeis, 2000, 2001) of the Baltic Sea. These studies showed that the northern and southern Baltic Sea sediments are rich in terrestrial plant derived OM, while the central Baltic Sea is dominated by phytoplankton derived OM. Pigments have been further applied as biomarkers to sediment cores from different basins of the Baltic Sea in order to reconstruct changes in cyanobacterial blooms (Poutanen and Nikkilä, 2001; Borgendahl and Westman, 2007; Funkey et al., 2014) and inputs of terrigenous OM (Miltner et al., 2005) during the post-glacial development of the Baltic Sea. In comparison, only a few studies have focussed on lipids in the Baltic Sea, even though they are less labile than pigments (Wakeham et al., 1997). Pazdro et al. (2001) and Vonk et al. (2008) used different lipids to assess the origin and diagenetic fate of the OM exported into the northern Bothnian Bay and the Pomeranian Bay, respectively. Both studies showed that despite degradational processes the variations in biological activity and hydrological conditions are the main factors responsible for the variability of lipids contents in the surface sediments. Two studies focused on the potential of C37 to C39 alkenones (ketones biosynthesized by coccolithophorids) as temperature and/or salinity proxies for the Baltic Sea and conclude that none of these two proxies can be applied for paleoenvironmental reconstructions in the Baltic Sea (Schulz et al., 2000; Blanz et al., 2005). Recently, proxies based on lipids derived from specific bacterial and archaeal groups were analysed in the water column and sediments of the Baltic Sea. Kabel et al. (2012) provided a local calibration for the TEX86, a temperature proxy based on thaumarchaeotal membrane lipids (Schouten et al., 2013), and applied it to a sediment core covering the last millennium. Blumenberg et al. (2013), Berndmeyer et al. (2013, 2014), and Schmale et al. (2012) studied the vertical distribution of different lipid biomarkers, and especially biomarkers for aerobic methanotrophy, in the stratified water columns and underlying sediments of the Gotland Basin and the Landsort Deep. Most recently, Kaiser et al. (2016) identified certain C25 highly

branched isoprenoid alkenes produced by the marine planktonic diatom Pseudosolenia calcar-avis isolated from southern Baltic Sea water and further discussed their potential as sedimentary biomarker. The present study focuses on certain naturally-occurring, specific lipids found in 57 surface sediments from the Baltic Sea, from the Skagerrak to the Bothnian Bay. Apolar (hydrocarbons) and polar (GDGTs) lipids were identified, quantified, their potential sources were assigned, and they were evaluated as potential paleoenvironmental proxies for the Baltic Sea.

2. Study area

The Baltic Sea is a shallow, semi-enclosed and intra-continental shelf sea. It is one of the largest brackish water bodies by area with 422000 km2, a volume of 20000 km³ and a catchment area of 1745000 km2. While the average water depth is 55 m, the Baltic Sea has several deep basins, such as the Bornholm Basin (105 m), Gotland Basin (250 m), Landsort Deep (460 m) and Faro Deep (205 m), separated from each other by sills (Fig. 1). The Baltic Sea can be divided into some main geographical regions such as the northern Baltic Sea (Bothnian Sea and Bothnian Bay), the Gulf of Finland, the central Baltic Sea (including the Gotland Basin and Landsort and Faro Deeps), the Gulf of Riga and the southern Baltic Sea (with the Bornholm and Arkona Basins, as well as the Belt Sea). The Baltic Sea is further connected with the North Sea through the Kattegat and the Skagerrak. Based on satellite data (Acker and Leptoukh, 2007), mean annual sea surface temperature ranges between 5 °C in the Bothnian Bay and 10 °C in the Skagerrak strait. The seasonal amplitude is highest in the Bothnian Bay (17 °C) and lowest in the Skagerrak (14 °C). The mean annual concentration of chlorophyll-a pigments, used as an index of algal biomass, is ca. two times higher in the Baltic Sea (6 mg m-3) than in the Skagerrak (3 mg m-3). In the northern Baltic Sea, phytoplankton blooms occur mainly in April/May and are dominated by diatoms and dinoflagellates (Andersson et al., 1996). In the central Baltic Sea, the annual development of the phytoplankton is characterized by blooms in April, July and September, the summer bloom having the highest biomass. The spring and autumn blooms consist mainly

of diatoms and dinoflagellates, while in summer blue-green algae (cyanobacteria) bloom predominantly in the central area of the Baltic Sea (Wasmund et al., 2012). The yearly volume of precipitation in the catchment area of the Baltic Sea amounts to 450 km3. In the northern basins runoff is highest in spring due to snowmelt, while in the southern basin it is highest in winter. Surface salinity is < 4 psu in the Bothnian Bay and the Gulf of Finland and increases to 8 psu in the Bornholm basin. A sharp salinity gradient from 10 to 32 psu characterizes the Kattegat and Skagerrak straits. The large freshwater input from rivers drives the large-scale circulation in the Baltic Sea. On its way to the North Sea the fresh water mixes with Baltic Sea water creating a brackish surface layer. This outflowing water is compensated by a restricted inflow of saline water from the North Sea through the shallow Kattegat strait. This estuarine circulation creates two water masses separated by a permanent and stable halocline at 50-80 mwd, which restricts the vertical transport of oxygen. While minor water inflows from the North Sea are relatively frequent, the deep water is ventilated mainly by large perturbations, so called major Baltic inflows. During the past two decades, significant inflows have occurred only four times: in 1983, 1993, 2003 and 2014 (Lass and Matthäus, 1996; Mohrholz et al., 2015). The lack of salty water inflows caused stagnation periods, during which the ventilation of the Baltic Sea deep water ceased, the oxygen concentrations decreased and the hydrogen sulfide concentrations increased, resulting in hypoxic (≤ 2 ml of oxygen per litre; Diaz and Rosenberg, 2008) to suboxic (≤ 0.1 ml l-1 O2; Schnetger and Dellwig, 2012) or even anoxic to euxinic conditions below ca. 80-100 mwd in the deep basins (Meier et al., 2006). Today, about 15 % of the bottom area of the central Baltic is anoxic, and about 28 % is hypoxic (Hansson et al., 2011). Such hypoxic to anoxic environments allow for the accumulation of well-preserved, organic rich sediments.

3. Material and methods

Surface sediments from the entire Baltic Sea and including the Skagerrak and Kattegat areas (n = 57; Fig. 1 and Table 1) were sampled during expeditions M86/1 (R/V Meteor; November 2011), P435 (R/V Poseidon; June 2012), 06EZ1215 and EMB046 (R/V Elisabeth Mann Borgese; July 2012 and May 2013, respectively). A multi-corer was used in order to keep the water-sediment interface undisturbed. Short sediment cores and CTD (Conductivity, Temperature, Depth) profiles were taken at stations with water depths ranging from ca. 20 m

in the Arkona Basin to 660 m in the Skagerrak. The core-tops (0-1 cm) were sampled on board, kept refrigerated in aluminium foil and further freeze-dried and homogenized in the laboratory. Two samples of submerged macrophytes from the southern Baltic Sea (Potamogeton pectinatus and Myriophyllum spicatum) were also analysed. All analyses on the surface sediments and macrophytes have been performed at the IOW.

3.1. Elemental analysis

Total carbon (TC), total sulfur (TS) and total nitrogen (TN) were analyzed by means of an EA 1110 CHN (CE-instruments) and Multi EA 2000 CS (Analytik, Jena) elemental analyzer. Total inorganic carbon (TIC) was determined by means of a TIC module connected with the elemental analyzer, involving the acidic removal of carbonates from sediment samples and analysis of the CO2 released in a carrier gas stream. Total organic carbon (TOC) was calculated by the subtraction of TIC from TC values. The C/N ratio was defined as the molar ratio between TOC and TN: C/N = (TOC/12) / (TN/14).

3.2. Gas chromatography and mass spectrometry (GC/MS)

Sediments (0.3 to 1.5 g dry weight), as well as two macrophytes (0.4 to 1.5 g dry weight), were extracted by accelerated solvent extraction (Dionex ASE 350) at high pressure (100 bar) and high temperature (100 °C) with a mixture of dichloromethane and methanol (DCM: MeOH, 9:1). The total extracts were separated by silica gel column chromatography into four fractions by elution with n-hexane (apolar), n-hexane/DCM, DCM and DCM:MeOH (polar). The polar fractions were further filtered through a 4 mm diameter PTFE syringe filter (0.45µm). Internal (squalane, nonadecan-2-one, 5α-androstan-3β-ol, C46-GTGT; added after the extraction) and external (n-hexatriacontane; added before injection) standards were used for quantification. As TOC can vary due to the degree of preservation of OM (which is high in the suboxic to euxinic basins of the Baltic Sea) and/or due to the supply of inorganic material to the sediment (dilution effect), the concentrations of the different compounds were normalized to TOC (µg g-1 TOC or mg g-1 TOC).

The apolar fractions were measured on a multichannel TraceUltra Gas Chromatograph (ThermoScientific) equipped with a split/splitless inlet, a DB-5 MS (30 m x 0.32 mm x 0.25 µm) capillary column and a FID detector. The temperature program was from 40 °C to 290 °C at 4° C/min followed by a 20 min plateau. Hydrogen was used as carrier gas. The ChromCard software was used to visualize the chromatograms. Peak identification was based on comparison of peak retention times with external standards (n-C8 to n-C40 alkanes) and on GC/MS analyses, GC/MS was performed with an Agilent HP6890 Series GC system coupled to a HP5973 Mass Selective Detector equipped with a split/splitless injector and a DB-5 MS 60 m x 0.25 mm x 0.25 µm capillary column. The oven temperature was programmed from 40 °C to 290 °C at 4° C/min followed by a 20 min plateau. Helium was used as carrier gas. The electron impact ionization mode conditions were as follows: ion energy 70eV; ion source temperature 230°C; mass range 50-550 m/z; electron multiplier voltage 1600V. The ChemStation software was used for the visualization of mass spectra. Structural identification was determined by mass spectral interpretation of the ion fragmentation and comparison with published mass spectra.

3.3. High performance liquid chromatography atmospheric pressure chemical ionization mass spectrometry (HPLC APCI-MS)

The polar fractions were analyzed by HPLC APCI-MS. Analyses were performed on a ThermoScientific Dionex Ultimate 3000 UHPLC system coupled to a ThermoScientific MSQ Plus. Separation of the individual GDGTs was achieved on a Prevail Cyano column (Grace, 3 µm, 150 mm x 2.1 mm) maintained at 35 °C. Using a flow rate of 0.25 ml min-1, the gradient of the mobile phase was first held isocratic for 5 min with 100 % solvent A (nhexane/isopropanol, 99:1), followed by a linear gradient to 90% solvent A and 10% solvent B (n-hexane/isopropanol, 90:10) within 20 min, followed by a linear gradient to 100% solvent B at 40 min (method modified after Liu et al., 2012a). Cleaning the column was achieved by back flushing with 100% solvent B for 5 min at 0.6 ml min-1. Finally, the column was equilibrated with 100% solvent A for 10 min. GDGTs were detected using positive-ion APCIMS and selective ion monitoring (SIM) of their [M+H]+ ions (Schouten et al., 2007) with APCI source conditions as follows: nebulizer gas 45 psi, corona current +5 µA, probe heater temperature 600 °C and cone voltage 130 V. Compound concentrations were estimated using

the relative response factor (0.7 for the period of analysis) between the C46-GDGT standard (obtained from David H. Thompson, Purdue University) and pure crenarchaeol (obtained from Ann Pearson, Harvard University). Hydroxylated isoprenoid GDGTs (OH-GDGTs) were detected in the respective SIM range of the isoprenoidal GDGTs: OH-GDGT-01318 in the m/z 1300 SIM scan, OH-GDGT-11316 and 2OH-GDGT-01334 in the m/z 1298 SIM scan, and OH-GDGT-21314 in the m/z 1296 SIM scan (Liu et al., 2012b). Appendix 1 shows a typical total ion monitoring chromatogram from Baltic Sea surface sediments, as well as the molecular structures of the GDGTs.

4. Results

4.1. TOC, TS, dissolved O2 concentrations and the C/N ratio TOC values in the surface sediments are ranging between 0 % and 4 % in oxic bottom waters, between 4 % and 6 % in suboxic bottom waters (≤ 2 ml l-1 O2) and between 7 % and 15 % in the sub- to anoxic bottom waters (< 0.3 ml l-1 O2) of the Gotland Basin and the Landsort Deep (Table 1; Fig. 2). TOC values are in close agreement with those published previously in Leipe et al. (2011). The highly variable, spatial distribution of TOC in the surface sediments of the Baltic Sea is related to the origin and transport pathways of TOC, as well as the environmental conditions prevailing at the seafloor, including morphology, currents and redox conditions (see for details Leipe et al., 2011). The concentration of TS in the sediment, which comprises mainly iron monosulfides (pyrite) resulting from the biological reduction of dissolved sulphate (Berner, 1984; Böttcher and Lepland, 2000), is lowest (< 0.4 %) in oxic bottom waters and highest (> 1.2 %) in sub- to anoxic bottom waters (Table 1; Fig. 2). Accordingly, TOC and TS are significantly correlated (r = 0.86; Table 2). C/N values range between 7 and 13 with a mean value of 9.4 (Table 1).

4.2. Apolar lipid fraction: n-alkanes, n-alkenes and diploptene The distribution of the long-chain n-alkanes (n-C17 to n-C33) is unimodal and centred on the nC27 alkane, which has a mean concentration of 300 µg g-1 TOC (Fig. 3A). n-C17 alkane has the lowest mean concentration with ca. 6 µg g-1 TOC. The odd- over even-number preference of

n-alkanes and a mean carbon preference index (CPI, based on n-C27 to n-C33 alkanes; Table 1) value of 2 are typical for sedimentary land plant derived n-alkanes (Bray and Evans, 1961; Eglinton and Hamilton, 1967; Simoneit and Mazurek, 1982). The hydrocarbon fraction is characterized by the presence of a series of n-C19:1 to n-C29:1 alk-1-enes with the most abundant being n-C25:1 and n-C27:1 alkenes (with a mean concentration of ca. 6 µg g-1 TOC). Diploptene [hop-22(29)-ene] is abundant with a mean concentration > 90 µg g-1 TOC. While n-C23, n-C25, n-C27 and n-C29 alkanes are positively inter-correlated, they are not correlated with n-C25:1, n-C27:1 and n-C29:1 alkenes, suggesting distinct source organisms (Table 2). The n-C31 alkane is co-eluting with a so far unidentified compound, what may explain slightly lower correlation coefficients with the other land plant derived n-alkanes (Table 1), and was therefore not considered further in this study. The distribution of n-C23 to n-C35 alkanes in the submerged macrophytes Potamogeton pectinatus and Myriophyllum spicatum is characterized by the dominance of the n-C23 and n-C25 alkanes (Fig. 4). The concentrations of the n-C25 alkane are ca. 8 and 35 µg g-1 dw in Potamogeton pectinatus and Myriophyllum spicatum, respectively.

4.3. Polar lipid fraction: isoprenoid, branched and hydroxylated GDGTs Isoprenoid GDGTs (Appendix 1) are dominated by GDGT-0 and crenarchaeol (mean concentrations between 100 and 200 µg g-1 TOC; Fig. 3B), while GDGT-3 and the crenarchaeol regioisomer have the lowest mean concentrations (ca. 1.5 µg g-1 TOC). The mean crenarchaeol/(crenarchaeol + GDGT-0) ratio in the surface sediments is 0.57 (Table 1), and is slightly lower in the Skagerrak (0.53) than in the Baltic Sea (0.63). The mean concentrations of branched GDGTs are between 1.5 µg g-1 TOC (GDGT-IIIa) and 4.5 µg g-1 TOC (GDGT-Ia). OH-GDGTs’ mean concentrations are increasing from 1.5 µg g-1 TOC for OH-GDGT-21314, 5 µg g-1 TOC for OH-GDGT-11316 to 35 µg g-1 TOC for OH-GDGT-01318, which is the third most abundant GDGT (Fig. 3B).The mean concentration of the dihydroxylated 2OH-GDGT-01334 is 8 µg g-1 TOC. The branched and isoprenoid tetraether (BIT) index is ranging between 0 and 0.6 with a mean value of 0.1 (Table 1). Both isoprenoid GDGTs and OH-GDGTs are highly positively correlated (r ≥ 0.92; Table 2). However, both are uncorrelated to branched GDGTs. The BIT index is positively correlated to the concentrations of branched GDGTs, but negatively to the concentrations of isoprenoid and hydroxylated GDGTs. Note here that the TEX86 water temperature proxy (Schouten et al.,

2002), which has been calibrated for the Baltic Sea (Kabel et al., 2012), is not included in the present study.

5. Discussion In order to classify the different organic compounds as having an allochtonous (terrestrial) or autochtonous (aquatic) source, next to a Pearson coefficient correlation matrix (Table 2), a principal component analysis (PCA; Meglen, 1992), also based on a correlation matrix, has been applied to the different lipid compounds using the software PAST (PAleontological STatistics) version 3.03 © (Hammer et al., 2001) (Fig. 5).

5.1. Compounds with an allochthonous source In a first order, the origin of sedimentary OM can be distinguished by the characteristic C/N ratio of algae and vascular plants. Terrestrial vegetation has a typical C/N ratio of > 12, as it is composed mainly by nitrogen-poor lignin and cellulose. C3 vascular plants and C4 grasses have values of ca. 12 and above 30, respectively. Algae and phytoplankton, which are nitrogen rich, typically have C/N ratios between 4 and 7, resulting in marine organic C/N values < 8 (Meyers, 1994; Müller and Voss, 1999; Lamb, 2006). In the surface sediments of the Baltic Sea, the mean C/N value of 9.4 (standard deviation of 1.1) resembles published data from the central Baltic Sea (Szczepanska et al., 2012) and the coastal region of the southern Baltic Sea (Müller and Voss, 1999), and is within the range of brackish to marine-brackish sediments (Yu et al., 2010). Such a value lies between marine OM (C/N < 8) and terrestrial OM (C/N >12) values obtained from the southern Baltic Sea (Müller and Voss, 1999; Müller, 2001). The increasing mean C/N values from the Arkona Basin (8.3) to the Bothnian Bay (11.4) very likely reflect an increasing amount of terrestrial OM in the surface sediments. Furthermore, the C/N ratio is correlated with (r = 0.5) and plots near to n-C23, n-C25, n-C27 and n-C29 alkanes (Table 2; Fig. 5), which originate from higher plant leaf waxes (Eglinton and Hamilton, 1967; Eglinton and Eglinton, 2008). Diploptene occurs in bacteria, such as cyanobacteria (Wakeham, 1990; Elvert et al., 2001), as well as in some terrestrial ferns (Ageta and Arai, 1983), in mosses (Toyota et al., 1998; Huang et al., 2010) and possibly in soil microorganisms (Prahl et al., 1992). Diploptene concentrations are comparable to plant wax long-chain n-alkanes (Fig. 2A) and plot near to the n-alkanes and the C/N ratio in the PCA

(Fig. 5). Therefore, long-chain, odd-numbered n-alkanes and diploptene have most likely a dominant allochthonous source in the surface sediments of the Baltic Sea. Branched GDGTs are probably produced by bacteria thriving in soils and are thought to belong to the phylum Acidobacteria (Oppermann et al., 2010; Weijers et al., 2010; Sinninghe Damsté et al., 2011). However, a number of studies from lake (Tierney and Russell, 2009; Sinninghe Damsté and et al., 2009; Loomis et al., 2011, 2014) and marine (Peterse et al., 2009; Liu et al., 2014) environments suggest that branched GDGTs may also be produced in situ within the water column and/or at the water/surface sediment interface. In the surface sediments of the Baltic Sea, branched GDGTs correlate positively with the C/N ratio and long-chain odd-numbered n-alkanes, and are therefore most likely of terrestrial origin (Fig. 5; Table 2). The BIT index, a proxy based on the relative abundance of soil-derived branched GDGTs and crenarchaeol (a specific lipid for aquatic Thaumarchaeota; see Table 1 and Section 5.2), allows for an estimation of the relative amount of soil-derived OM in sediments. Low BIT index values (< 0.15) are typical for open marine environments receiving a small quantity of soil-derived OM, while high values (> 0.9) are characteristic for soils (Schouten et al., 2013 and references therein). As the BIT index is also correlated to terrestrial n-alkanes and branched GDGTs, it can be thus used as proxy to estimate the relative input of terrestrial (soil) OM in the sediments of the Baltic Sea (Table 2; see Section 5.3). Finally, the positive correlations between the BIT index, branched GDGTs and the C/N ratio (Table 2) further indicates that the C/N ratio is reflecting changes in the source of TOC in Baltic Sea sediments. Odd-numbered n-C23 to n-C29 alkanes, diploptene, and branched GDGTs form a pool of terrestrially-derived biomarkers in the surface sediment of the Baltic Sea (Fig. 5). The spatial distribution of allochthonous compounds is illustrated in Fig. 6A and 6B by the n-C29 alkane and the sum of branched GDGTs. The concentrations are highest in the northern Baltic Sea, where the greatest freshwater inputs to the Baltic Sea occur (Elmgren, 1984), and decrease southward and westward. A similar pattern has been observed in the distribution of ligninphenols derived from terrestrial vascular plant (e.g. syringyl, vanillyl, cinnamyl) in particulate organic material from the northern Baltic Sea and the Gotland Sea (Bianchi et al., 1997b) and in surface sediments from the southern Baltic Sea (Miltner and Emeis, 2000, 2001) It should be considered that long-chain n-alkanes may also have a petrogenic source (Simoneit and Mazurek, 1982). However, elevated concentrations of petroleum hydrocarbons are observed only in coastal areas of the Baltic Sea and sediment from the open waters seem

to be devoid of petroleum hydrocarbons (Belyayeva and Bobyleva, 1981; Osterrhot and Petrick, 1982; HELCOLM, 1996; Vonk et al., 2008). A dominant fraction of naturallyoccurring, long-chain n-alkanes in the surface sediments of the Baltic Sea is also indicated by sedimentary CPI values ≥ 2, as the random cleavage of alkyl chains in kerogen produces nalkanes with no odd or even predominance resulting in CPI values ≤ 1 (Mazurek and Simoneit, 1984).

5.2. Compounds with an autochthonous source

Crenarchaeol, isoprenoid GDGTs, OH-GDGTs and n-C25:1, n-C27:1 and n-C29:1 alkenes are all positively correlated and are grouped distinctly into compounds with an autochthonous source (Fig. 5; Table 2). Isoprenoid GDGTs have been found in cultures of Thaumarchaeota (see review by Schouten et al., 2013, and Pearson and Ingalls, 2013). Thaumarchaeota are the dominant group of archaea in marine systems (Auguet et al., 2009) and most likely form a major source of isoprenoid GDGTs. Crenarchaeol is considered as specific to the phylum Thaumarchaeota, and may be a biomarker for ammonium-oxidizing Thaumarchaeota (Pitcher et al., 2011). A cluster of Thaumarchaeota nearly specific to the Baltic Sea is abundant in the suboxic to anoxic part of the water column (> 80 mwd) in the deep basins of the central and western Baltic Sea, where they contribute to ammonia oxidation (Labrenz et al., 2007, 2010; Brettar et al., 2012; Thureborn et al., 2013; Berg et al., 2015a, 2015b). The slightly different values of the crenarchaeol/(crenarchaeol + GDGT-0) ratio (Table 1) of the Skagerrak (0.53) and the Baltic Sea (0.63) may thus reflect different thaumarchaeotal clusters (Pearson and Ingalls, 2012; Schouten et al., 2013). A very recent study suggests that Marine Group II Euryarchaeota may also produce isoprenoid GDGTs in significant amounts (Lincoln et al., 2014). However, while Euryarchaeota are also present in the water column of the Baltic Sea, they are much less abundant than Thaumarchaeota (Thureborn et al., 2013). Unfortunately, no data on archaeal distribution in the water column of oxic areas of the Baltic Sea are available yet. Although isoprenoid GDGTs were also found in worldwide soils (Weijers et al., 2006; Coffinet et al., 2014), the absence of correlation between isoprenoid GDGTs and branched GDGTs suggests they have distinct sources. Mono- (OH-GDGT-0, -1 and -2) and dihydroxylated (2OH-GDGT-0; Appendix 1) analogues of known isoprenoid GDGTs have been identified in worldwide marine and lake sediments (Liu et al., 2012b,

2012c; Fietz et al., 2013; Huguet et al., 2013), and now for the first time in the Baltic Sea. OH-GDGTs were found in an extremophile Euryarchaeota culture (Methanothermococcus thermolithotrophicus) and are present in different strains of planktonic Thaumarchaeota (Liu et al., 2012c; Elling et al., 2014, 2015). The high positive correlations between isoprenoid GDGTs and OH-GDGTs (r ≥ 0.9) in the Baltic Sea surface sediments strongly suggest a common autochthonous source organism (Fig. 5 and Table 2). A series of n-C19:1 to n-C29:1 alkenes with maximum concentrations at n-C25:1 and n-C27:1 is found in the surface sediment of the Baltic Sea (Fig. 3A), as well as in the surface water of the central Baltic Sea (Landsort Deep; Berndmeyer et al., 2014). n-C25:1 and n-C27:1 alkenes may have multiple natural sources. Higher plants and some insects produce n-alkenes, but their distributions differ from the one found in the Baltic Sea surface sediments and include broader ranges from n-C18:1 to n-C32:1 alkenes (Cardoso et al., 1983) and from n-C24:1 to nC45:1 alkenes (Blomquist and Jackson, 1979; Chikaraishi et al., 2012), respectively. Furthermore, n-C25:1 and n-C27:1 alkenes are not correlated to terrestrial compounds in the surface sediment of the Baltic Sea, but are strongly correlated to isoprenoid GDGTs and OHGDGTs, suggesting an autochthonous origin as well (Fig. 5; Table 2). Cyanobacteria are potential producers of n-C21:1 to n-C27:1 alkenes. These compounds have been reported for Anacystis (Gelpi et al., 1970) and Oscillatoria (Matsumoto et al., 1990), but other studies found only trace amounts or even an absence of n-alkenes in cyanobacteria (Paoletti et al., 1967; Murray and Thomson, 1977; Cardoso et al., 1983). Although Oscillatoria vaucher is known to occur in the Baltic Sea, it is found only in minor abundance (Kononen et al., 1996; Vahtera et al., 2007). Therefore, cyanobacteria are probably not a major source of n-alkenes in the surface sediments of the Baltic Sea. Some green algae also produce n-alkenes. Botryococcus braunii and Scenedesmus spp. contain predominantly n-C23:1 to n-C33:1 alkenes (Gelpi et al., 1970) and n-C21:1 to n-C27:1 alkenes (Gelpi et al., 1970; Paoletti et al., 1976; Cranwell et al., 1990), respectively. Chlorella sp. produces also n-C23:1 and n-C27:1 alkenes, but in very small amounts (Paoletti et al., 1976). All the aforementioned green algae species inhabit the Baltic Sea: Chlorella sp. is present in the Bothnian Bay, Scenedesmus spp. is present in the central and southern Baltic Sea and Botryococcus braunii is present in the whole Baltic Sea (Hällfors, 2004). Therefore, the most abundant n-alkenes found in the surface sediment of the Baltic Sea can be considered as autochthonous lipids produced by phototrophic organisms.

The spatial distribution of lipids with an autochthonous origin, as represented by the concentrations of crenarchaeol and the sum of n-C25:1 and n-C27:1 alkenes, is highest in the central Baltic Sea (Figs. 6C and 6D) in agreement with a previous study based on pigments from water column samples (Bianchi et al., 1997b). On the one hand, high concentrations of crenarchaeol in the central and southern Baltic Sea reflect probably the predominant occurrence of Thaumarchaeota within deep hypoxic to anoxic basins (Landsort Deep, Gotland and Bornholm basins; Labrenz et al., 2010; Berg et al., 2015b). On the other hand, high concentrations of n-C25:1 and n-C27:1 alkenes may reflect the high summer primary productivity occurring in the central Baltic Sea (Wasmund et al., 2012).

5.3. BIT index and estimation of the percentage of soil OM

The BIT index represents a tool for estimating the relative input of soil (terrestrial) OM (OMsoil) in the sediment, assuming a BIT value of 1 in soils and of 0 in the open ocean (Hopmans et al., 2000; Smith et al., 2012). While the BIT index can also be controlled by changing crenarchaeol rather than branched GDGTs concentrations, the positive correlations between the BIT values and the concentrations of both branched GDGTs and leaf-wax nalkanes (Table 2; Fig. 5) strongly suggest that the BIT index indeed reflects the relative contribution of OMsoil in the sediments. Converting BIT index values into percentages of OMsoil (%OMsoil = BIT * 100) results in a low mean value (2%) in the central Baltic Sea, intermediate mean values (8-13%) in the Skagerrak, Arkona Basin and Bothnian Sea, and a high mean value (29%) in the Bothnian Bay (Fig. 6E). However, Smith et al. (2012) demonstrated that the mixing between soil and marine end-members of the BIT index may not be linear, resulting in overestimated %OMsoil values. The authors offered an alternative method using branched GDGT concentrations in a binary model between marine and soil endmembers, such as %OMsoil = (branched GDGTsample * 100)/branched GDGTsoil. Using a mean concentration of 96.6 % branched GDGTs in soils from the drainage basin of the Baltic Sea (Fig. 1; Table 3), %OMsoil based on branched GDGTs only was estimated and the obtained values are the same as the estimations based on the BIT index (Table 1). The %OMsoil results obtained here are in agreement with previous estimations of the percentage of terrestrial OM (OMterr) in surface sediments of certain regions of the Baltic Sea. Using lignin-phenols, Bianchi et al. (1997) estimated the contribution of OMterr to suspended OM in the northern

Baltic Sea to be about 30%. Voss and Struck (1997) analyzed the carbon isotopic composition of sediment from the Arkona basin and could estimate an OMterr of ca. 15%. Miltner and Emeis (2001) estimated the contribution of land-derived OM to be between 10 and 30% in the southern and central Baltic Sea using lignin oxidation products. Therefore, the BIT index is a valuable proxy for at least qualitative or even quantitative estimation of the input of OMsoil in the sediments of the Baltic Sea. The pattern of OMsoil probably results from high inputs of OMsoil by rivers in the northern and southern Baltic Sea, as well as in the Skagerrak straits, and low amounts of OMsoil reaching the more pelagic central Baltic Sea (Fig. 6E).

5.4. Paq proxy

Paq is a proxy for the input to the sediment of n-alkanes derived from submerged/floating aquatic plants versus emergent and terrestrial plants, and was defined by Ficken et al. (2000) as: Paq = (n-C23 + n-C25)/(n-C23 + n-C25 + n-C29 + n-C31 alkanes) (a) Terrestrial plants have Paq values around 0.1, while submerged/floating plants, whose distribution is dominated by n-C23 and n-C25 alkanes, have Paq values around 0.7 (Ficken et al., 2000). In the Baltic Sea surface sediments, n-C31 alkane is co-eluting with a so far unidentified compound (Fig. 3A). Therefore, a new Paq ratio (Paq’) was defined disregarding the n-C31 alkane: Paq’ = (n-C23 + n-C25)/(n-C23 + n-C25 + n-C29 alkanes) (b) Furthermore, Bush and McInerney (2013) suggested a different ratio defined as n-C23/(n-C23 + n-C27 alkanes). In the surface sediments of the Baltic Sea, all three different ratios are strongly positively correlated (r ≥ 0.9; Table 2), and Paq’ was chosen as representative. Paq’ values are lowest in the Skagerrak and the central Baltic Sea, higher in the southern Baltic Sea and highest in the Bothnian Sea and Bothnian Bay (Fig. 6F). In the semi-enclosed, sheltered and soft bottom coastal bays of the southern and northern Baltic Sea, the vegetation is mainly made up of salt tolerant or freshwater submerged plants, the most common being Potamogeton spp. and Myriophyllum spp., two freshwater angiosperms (Munsterhjelm, 1997; Schubert and Schories, 2008; Paulomäki et al., 2011). Indeed, the hydrocarbon fractions of

Potamogeton pectinatus and Myriophyllum spicatum specimens from the Baltic Sea are dominated by the n-C25 alkane and have high Paq’ values of 0.6 and 0.9, respectively (Fig. 4). A similar n-alkane distribution in these macrophytes has already been reported (Aischner et al., 2010; Ficken et al., 2000; Tuo et al., 2011). Therefore, high abundances of submerged/floating plants such as Potamogeton spp. and Myriophyllum spp. in sheltered areas may represent a potential source for the relatively high Paq’ ratios found in the surface sediments of the southern and northern Baltic Sea (Fig. 6F). However, as suggested by Vonk et al. (2008), high Paq values in surface sediments from the Bothnian Bay may reflect also a high contribution of OM derived from Sphagnum mosses, which are present abundantly in the peatlands characterizing the drainage basin of the northern Baltic Sea (Vonk et al., 2008; Montanarella et al., 2006). Indeed, Vonk and Gustafsson (2009) have compared Paq and nC23/(n-C23 + n-C27 alkanes) ratios of 12 Sphagnum species from sub-Arctic Scandinavia to surface sediments from the Bothnian Bay. The ratios are very similar with mean Paq values of 0.61 and 0.62 in the Sphagnum species and the sediments, respectively, and mean n-C23/(nC23 + n-C27 alkanes) values of 0.54 and 0.60. High Paq’ (or Paq) values in the sediments of the Baltic Sea probably reflect the presence of both submerged/floating plants thriving in brackish water of sheltered areas and Sphagnum mosses from the drainage basin of the Baltic Sea. An increasing Paq’ ratio may thus reflect a regional expansion of coastal brackish to freshwater environments (peatlands) in the Baltic Sea.

5.5. OH-GDGT indices as temperature proxy

Based on the observation that the relative abundance of OH-GDGTs is increasing in cold regions, Huguet et al. (2013) found a significant correlation between the relative abundance of OH-GDGTs and SST in worldwide surface sediments. Fietz et al. (2013) have tested further the distribution of OH-GDGTs and their application as a temperature proxy using water samples and sediments from the Nordic Seas. They conclude that OH-GDGTs could be used as indicators of polar water masses and as temperature proxy in the cold waters of polar regions. The temperature gradient from the Baltic Sea represents a unique opportunity for testing the potential of OH-GDGTs as a temperature proxy in a transitional environment from marine to brackish waters. Two indices proposed by Fietz et al. (2013) based on the relative

abundance of isoprenoid and OH-GDGTs were applied to the surface sediments of the Baltic Sea. One index is the OH-GDGT% defined as: OH-GDGT% = ΣOH-GDGTs / (ΣOH-GDGTs + ΣisoGDGTs) * 100 (c) , where ΣOH-GDGTs includes OH-GDGT1318 and OH-GDGT1316, and ΣisoGDGTs includes GDGT-1 to -3, crenarchaeol and its regioisomer (Appendix 1). The other index is the ratio OH-GDGT1318/crenarchaeol. Both indexes correlate relatively well with mean annual SST in the Baltic Sea (SSTBS) and the following regression lines were obtained (Fig. 7): SSTBS = (OH-GDGT% - 18.38) / -0.93 (r2 = 0.7; SEE = 0.8 °C; n = 56) (d) SSTBS = (OH-GDGT1318/crenarchaeol - 0.33) / -0.02 (r2 = 0.7; SEE = 0.8 °C; n = 56) (e) The linear correlations obtained by Fietz et al. (2013) for the Nordic Seas (SSTNS) are as follows: SSTNS = (OH-GDGT% - 8.68) / -0.67 (r2 = 0.6; SEE = 1.2 °C; n = 11) (f) SSTNS = (OH-GDGT1318/crenarchaeol - 0.25) / -0.03 (r2 = 0.6; SEE = 1.2 °C; n = 11) (g) To determine whether the slopes and intercepts of the regression lines are significantly different from each other, t-tests can be performed given the mean, slope, intercept, standard errors, sum of squared error and sample size for each dataset (Cohen et al., 2003; Wuensch, 2014). The results (Table 4) reveal that for both indices the calibration curves have statistically identical slopes, but different intercepts resulting in large differences in estimated temperature (ca. 2 °C for OH-GDGT1318/crenarchaeol calibrations and ca. 11 °C for OHGDGT% calibrations; not shown). While similar slopes indicate that the physiological factors exert a relatively small effect on the relationship between OH-GDGT production and temperature, other factors such as seasonality, depth of production and/or different OHGDGT producers may cause differences in the intercepts. However, such data on OH-GDGTs are available neither for the Baltic Sea, nor for the Nordic Seas. Furthermore, given that Thaumarchaeota thrive at depth in the anoxic basins of the Baltic Sea (Labrenz et al., 2007, 2010; Brettar et al., 2012; Thureborn et al., 2013; Berg et al., 2015a, 2015b), OHGDGT1318/crenarchaeol and OH-GDGT% indices were also plotted against bottom temperature (Tbottom; obtained during the different sampling expeditions; see Section 3) for the sediments from the Baltic Sea only (excluding Skagerrak). The following significant regression lines were obtained (Fig. 7):

Tbottom = (OH-GDGT% - 13.55) / -0.48 (r2 = 0.5; SEE = 1.4 °C; n = 42) (h) Tbottom = (OH-GDGT1318/crenarchaeol - 0.25) / -0.01 (r2 = 0.6; SEE = 1.2 °C; n = 42) (i) The correlation coefficients are lower and the SEE larger in comparison to the calibrations with SST. These calibrations are statistically different from the Fietz et al. (2013) calibrations, as well as from the SST calibrations (Table 4). Based on the available data on Thaumarchaeota and OH-GDGTs in the Baltic Sea, we suggest that the Tbottom may be more realistic than the SSTBS calibrations. However, the present study represents a first attempt of developing OH-GDGT-based temperature calibrations for the Baltic Sea, and further studies based on e.g. water-column particulate matter are necessary to gauge the potential of this temperature proxy.

6. Conclusions

TOC in surface sediments from the entire Baltic Sea and the Skagerrak is below 6 % under oxic to suboxic conditions and ranges between 7 and 15 % in the deep anoxic basins. The main lipids of the apolar and polar fractions were identified and the concentrations of individual lipids range between ca. 1.5 and 300 µg g-1 TOC. Branched GDGTs, diploptene and n-C25 to n-C29 odd-numbered alkanes have a terrestrial origin and can therefore be used as proxy for the input of OMterr in the sediment. The BIT index may represent a tool to estimate the percentage of OMsoil. The amount of allochthonous lipids is highest in the northern Baltic Sea, where runoff and the input of fresh water are dominant. Highest Paq (or Paq’) values in the northern Baltic Sea reflects the elevated abundance of Sphagnum mosses in the drainage basins and the presence of submerged macrophytes in the brackish coastal areas. The Paq’ ratio may thus reflect fluctuations in the regional expansion of freshwater to brackish coastal environments in the Baltic Sea. Autochthonous lipids, including isoprenoid GDGTs, OHGDGTs, n-C25:1 and n-C27:1 alkenes, are most abundant in the central Baltic Sea, where summer primary productivity is high and bottom water anoxic conditions prevail. The relative amount of OH-GDGTs to isoprenoid GDGTs, as expressed in the OH-GDGT% and OHGDGT1318/crenarchaeol indices, is temperature dependant in the Baltic Sea surface sediments. Both indices are significantly correlated with both SST and bottom temperature. These local

calibrations based on OH-GDGTs represent a new tool for reconstructing past SST in the Baltic Sea.

Acknowledgments

Ellen Hopmans, Julius Lipp and Jens Hefter are thanked for advice on HPLC-MS analytical methods. We are grateful to Christiane Volkmann for providing the macrophytes and to Nadine Hollmann for lab work. Hendrik Shubert gave very useful information on the flora of the Baltic Sea. We thank Francien Peterse for making the BIT index and branched GDGTs data from soils samples available. James Collins kindly improved English language. Two anonymous reviewers are thanked for their useful comments on an earlier version of the manuscript. We also thank the crews of the expeditions M86/1 onboard R/V Meteor (November 2011), P435 onboard R/V Poseidon (June 2012), and 06EZ1215 and EMB046 onboard R/V Elisabeth Mann Borgese (July 2012 and May 2013, respectively).

Figure captions

Figure 1. Location of the surface sediments (n = 57) from the Baltic Sea. Lakes and rivers are shown, as well as the location of five soil samples (a-f; Peterse et al., 2012). Numbers refer to Table 1. Elevation and bathymetry are given in meters above/below sea level. Figure 2. (A) Percentage (dry weight) of total organic carbon (TOC) in the surface sediment of the Baltic Sea, and (B-C) oxygen (O2) concentration (ml l-1) in the bottom water plotted against TOC and total sulphur (TS) percentages. The vertical dotted lines at 2 ml l-1 and 0.3 ml l-1 O2 represent the limits between oxic, suboxic and anoxic conditions, respectively. Figure 3. Mean concentrations (normalized to TOC) of n-C17 to n-C33 alkanes, n-C19:1 to n-C29:1 alkenes and diploptene (A) and of isoprenoid, branched and hydroxylated isoprenoid GDGTs (B) in the surface sediments of the Baltic Sea. See Appendix 1 for

the molecular structure of GDGTs. The asterisk in (A) denotes the co-elution of n-C31 alkane with an unidentified compound. Note the breaks in the ordinates. Figure 4. Concentrations (µg/g dry weight) of n-C23 to n-C35 alkanes in Potamogeton pectinatus and Myriophyllum spicatum isolated from the southern Baltic Sea. Paq and Paq’ values are given. Note the breaks in the ordinates. Figure 5. Principal component analysis (PCA; based on a correlation matrix) of the biomarker concentrations, C/N and Paq’ values in the surface sediments of the Baltic Sea. The 95 % ellipse is shown. Numbers refer to Table 1 and Fig. 1.Figure 6. Spatial distribution of the concentrations (µg/g TOC) of (A) n-C29 alkane, (B) the branched GDGTs (sum of GDGT-Ia, -IIa and IIIa), (C) crenarchaeol and (D) the sum of n-C25:1 and n-C27:1 alkenes, (E) the estimated percentage of soil OM (%OMsoil) based on the BIT index and (F) Paq’ in the surface sediments of the Baltic Sea. The data were plotted with the Ocean Data View software (Schlitzer, 2010). Figure 6. Spatial distribution of the concentrations (µg/g TOC) of (A) n-C29 alkane, (B) the branched GDGTs (sum of GDGT-Ia, -IIa and IIIa), (C) crenarchaeol and (D) the sum of n-C25:1 and n-C27:1 alkenes, (E) the estimated percentage of soil OM (%OMsoil) based on the BIT index, and (F) Paq’ in the surface sediments of the Baltic Sea. The data were plotted with the Ocean Data View software (Schlitzer, 2010). Figure 7. Linear regressions between (A) OH-GDGT% and (B) OH-GDGT1318/cren and mean annual (2005-2010) sea surface temperature (SST; °C) (A, B) and bottom temperature (Tbottom) (C, D). SEE = standard error of estimates. SST data are from MODIS Aqua satellite (11 micron night; 4 km spatial resolution; Giovanni - Ocean Color Radiometry Online Visualization and Analysis - GES DISC: Goddard Earth Sciences, Data and Information Services Center; Acker and Leptoukh, 2007). Tbottom were measured by CTD during the different sampling expeditions.

Table captions

Appendix

Appendix 1. Upper panel: A typical HPLC APCI-MS total ion chromatogram showing the distribution of glycerol ether lipids in the surface sediment of the Baltic Sea. Lower panel: molecular structures and m/z diagnostic values [M+H]+ of the detected lipids. See Liu et al. (2012b) for a detailed approach on the molecular structures of glycerol ether lipids.

References Acker, J.G., Leptoukh, G., 2007. Online analysis enhances use of NASA Earth science data. Eos Trans. AGU 88, 14-17. Ageta, H., Arai, Y., 1983. Fern constituents: pentacyclic triterpenoids isolated from Polypodium niponicum and P. Formosanum. Phytochemistry 22, 1801-1808. Aichner, B., Herzschuh, U., Wilkes, H., 2010. Influence of aquatic macrophytes on stable carbon isotope signatures of sedimentary organic matter in lakes on the Tibetan Plateau. Organic Geochemistry 41, 706–718. Andersson, A., Hajdu, S., Haecky, P., Kuparinen, J., Wikner, J., 1996. Succession and growth limitation of phytoplankton in the Gulf of Bothnia (Baltic Sea). Marine Biology 126, 791-801. Auguet, J.C., Montanie, H., Hartmann, H.J., Lebaron, P., Casamayor, E.O., Catala, P., Delmas, D., 2009. Potential Effect of Freshwater Virus on the Structure and Activity of Bacterial Communities in the Marennes-Oleron Bay (France). Microbial Ecology 57, 295306. Belyayeva, A.N., Bobyleva, N.V., 1981. Alkanes of plankton and bottom sediments from the Baltic Sea. Oceanology 21, 712-716. Berg, C., Listmann, L., Vandieken, V., Vogts, A., Juergens, K., 2015a. Chemoautotrophic growth of ammonia-oxidizing Thaumarchaeota enriched from a pelagic redox gradient in the Baltic Sea. Frontiers in Microbiology 5, 786. Berg, C., Vandieken, V., Thamdrup, B., Juergens, K., 2015b. Significance of archaeal nitrification in hypoxic waters of the Baltic Sea. Isme Journal 9, 1319-1332. Berndmeyer, C., Thiel, V., Schmale, O., Blumenberg, M., 2013. Biomarkers for aerobic methanotrophy in the water column of the stratified Gotland Deep (Baltic Sea). Organic Geochemistry 55, 103-111. Berndmeyer, C., Thiel, V., Schmale, O., Wasmund, N., Blumenberg, M., 2014. Biomarkers in the stratified water column of the Landsort Deep (Baltic Sea). Biogeosciences 11, 7009-7023.

Berner, R.A., 1984. Sedimentary pyrite formation: an update. Geochimica et Cosmochimica Acta 48, 605-615. Bianchi, T.S., Kautsky, L., Argyrou, M., 1997a. Dominant chlorophylls and carotenoids in macroalgae of the Baltic Sea (Baltic Proper): their use as potential biomarkers. Sarsia 82, 5562. Bianchi, T.S., Rolff, C., Lambert, C.D., 1997b. Sources and composition of particulate organic carbon in the Baltic Sea: the use of plant pigments and lignin-phenols as biomarkers. Marine Ecology Progress Series 156, 25-31.Bianchi, T.S., Johansson, B., Elmgren, R., 2000. Breakdown of phytoplankton pigments in Baltic sediments: effects of anoxia and loss of deposit-feeding macrofauna. Journal of Experimental Marine Biology and Ecology 251, 161183. Bianchi, T.S., Rolff, C., Widbom, B., Elmgren, R., 2002a. Phytoplankton Pigments in Baltic Sea Seston and Sediments: Seasonal Variability, Fluxes, and Transformations. Estuarine, Coastal and Shelf Science 55, 369-383. Bianchi, T.S., Engelhaupt, E., McKee, B.A., Miles, S., Elmgren, R., Hajdu, S., Savage, C., Baskaran, M., 2002b. Do sediments from coastal sites accurately reflect time trends in water column phytoplankton? A test from Himmerfjarden Bay (Baltic Sea proper). Limnology and Oceanography 47, 1537-1544. Bianchi, T.S., Canuel, E.A., 2011. Chemical Biomarkers in Aquatic Ecosystems. Princeton University Press, 396 pp. Retrieved from http://www.jstor.org/stable/j.ctt7sn38. Blanz, T., Emeis, K.C., Siegel, H., 2005. Controls on alkenone unsaturation ratios along the salinity gradient between the open ocean and the Baltic Sea. Geochimica et Cosmochimica Acta 69, 3589-3600. Blomquist, G.J., Jackson, L.L., 1979. Chemistry and biochemistry of insect waxes. Progress in Lipid Research 17, 319-345. Blumenberg, M., Berndmeyer, C., Moros, M., Muschalla, M., Schmale, O., Thiel, V., 2013. Bacteriohopanepolyols record stratification, nitrogen fixation and other biogeochemical perturbations in Holocene sediments of the central Baltic Sea. Biogeosciences 10, 2725-2735. Borgendahl, J., Westman, P., 2007. Cyanobacteria as a trigger for increased primary productivity during sapropel formation in the Baltic Sea - A study of the Ancylus/Litorina transition. Journal of Paleolimnology 38, 1-12. Böttcher, M.E., Lepland, A., 2000. Biogeochemistry of sulfur in a sediment core from the west-central Baltic Sea: Evidence from stable isotopes and pyrite textures. Journal of Marine Systems 25, 299-312. Bray, E.E., Evans, E.D., 1961. Distribution of n-paraffins as a clue to recognition of source beds. Geochimica et Cosmochimica Acta 22, 2-15. Brettar, I., Christen, R., Hoefle, M.G., 2012. Analysis of bacterial core communities in the central Baltic by comparative RNA-DNA-based fingerprinting provides links to structurefunction relationships. Isme Journal 6, 195-212.

Bush, R.T., McInerney, F.A., 2013. Leaf wax n-alkane distributions in and across modern plants: Implications for paleoecology and chemotaxonomy. Geochimica et Cosmochimica Acta 117, 161-179. Cardoso, J.N., Gaskell, S.J., Quirk, M.M., G. Eglinton, G., 1983. Hydrocarbon and fatty acid distributions in Rostherne lake sediment (England). Chemical Geology 38, 107-128. Chikaraishi, Y., Kaneko, M., Ohkouchi, N., 2012. Stable hydrogen and carbon isotopic compositions of long-chain (C21–C33) n-alkanes and n-alkenes in insects. Geochimica et Cosmochimica Acta 95, 53-62. Coffinet, S., Huguet, A., Williamson, D., Fosse, C., Derenne, S., 2014. Potential of GDGTs as a temperature proxy along an altitudinal transect at Mount Rungwe (Tanzania). Organic Geochemistry 68, 82-89. Cohen, J., Cohen, P., Stephen, G.W., Leona, S.A., 2003. Applied multiple regression/correlation analysis for the behavioral sciences, third ed. L. Erlbaum Associates, Mahwah, New Jersey. Cranwell, P.A., 1982. Lipids of aquatic sediments and sedimenting particles. Progress in Lipid Research 21, 271-308. Cranwell, P.A., Jaworski, G.H.M., Bickley, H.M., 1990. Hydrocarbons, sterols, esters and fatty acids in six freshwater chlorophytes. Phytochemistry 29, 145-151. Diaz, R.J., Rosenberg, R., 2008. Spreading dead zones and consequences for marine ecosystems. Science 321, 926-929. Eglinton, G., Hamilton, R.J., 1967. Leaf Epicuticular Waxes, Science 156, 1322-1335. Eglinton, T.I., Eglinton, G., 2008. Molecular proxies for paleoclimatology. Earth and Planetary Science Letters 275, 1-16. Elling, F.J., Könneke, M., Lipp, J.S., Becker, K.W., Gagen, E.J., Hinrichs, K.-U., 2014. Effects of growth phase on the membrane lipid composition of the thaumarchaeon Nitrosopumilus maritimus and their implications for archaeal lipid distributions in the marine environment. Geochimica et Cosmochimica Acta 141, 579-597. Elling, F.J., Könneke, M., Mußmann, M., Greve, A., Hinrichs, K.-U., 2015. Influence of temperature, pH, and salinity on membrane lipid composition and TEX86 of marine planktonic thaumarchaeal isolates. Geochimica et Cosmochimica Acta 171, 238-255. Elmgren, R., 1984. Trophic dynamics in the enclosed, brackish Baltic Sea. Rapports et procès-verbaux des réunions / Conseil permanent international pour l'exploration de la mer 183, 152-169. Elvert, M., Whiticar, M.J., Suess, E., 2001. Diploptene in varved sediments of Saanich Inlet: indicator of increasing bacterial activity under anaerobic conditions during the Holocene. Marine Geology 174, 371-383.

Ficken, K.J., Li, B., Swain, D.L., Eglinton, G., 2000. An n-alkane proxy for the sedimentary input of submerged/floating freshwater aquatic macrophytes. Organic Geochemistry 31, 745749. Fietz, S., Huguet, C., Rueda, G., Hambach, B., Rosell-Mele, A., 2013. Hydroxylated isoprenoidal GDGTs in the Nordic Seas. Marine Chemistry 152, 1-10. Funkey, C.P., Conley, D.J., Reuss, N.S., Humborg, C., Jilbert, T., Slomp, C.P., 2014. Hypoxia Sustains Cyanobacteria Blooms in the Baltic Sea. Environmental Science & Technology 48, 2598-2602. Gelpi, E., Schneider, H.J., Mann, J., Oró, J., 1970. Hydrocarbons of geochemical significance in microscopic algae. Phytochemistry 9, 603-612. Hällfors, G., 2004. Checklist of Baltic Sea Phytoplankton Species (including some heterotrophic protistan groups). Baltic Sea Environment Proceedings 95, pp. 208. Hammer, Ø., Harper, D.A.T., Ryan, P.D., 2001. PAST: Paleontological statistics software package for education and data analysis. Palaeontologia Electronica 4, 1-9. Hansson, M., Andersson, L., Axe, P., 2011. Areal Extent and Volume of Anoxia and Hypoxia in the Baltic Sea, 1960-2011. Swedish Meteorological and Hydrological Institute (SMHI) Report Oceanography 42, pp. 76. HELCOLM, 1996. Third periodic assessment of the state of the marine environment of the Baltic Sea, 1989-1993: Executive summary. Baltic Sea Environment Proceedings 64a, pp. 28. Hinkle, D., Wiersman, W., Jurs, S., 2003. Applied statistics for the behavioral sciences. Houghton Mifflin Co., Boston, 756 pp. Hopmans, E.C., Weijers, J.W.H., Schefuss, E., Herfort, L., Sinninghe Damsté, J.S., Schouten, S., 2004. A novel proxy for terrestrial organic matter in sediments based on branched and isoprenoid tetraether lipids. Earth and Planetary Science Letters 24, 107–116. Huang, X., Wang, C., Xue, J., Meyers, P.A., Zhang, Z., Tan, K., Zhang, Z., Xie, S., 2010. Occurrence of diploptene in moss species from the Dajiuhu Peat land in southern China. Organic Geochemistry 41, 321-324. Huguet, C., Fietz, S., Rosell-Mele, A., 2013. Global distribution patterns of hydroxy glycerol dialkyl glycerol tetraethers. Organic Geochemistry 57, 107-118. Kaiser, J., Belt, S., Tomczak, M., Wasmund, N., Arz, H.W., 2015. C25 highly branched isoprenoid alkenes in the Baltic Sea produced by the marine planktonic diatom Pseudosolenia calcar-avis. Organic Geochemistry, http://dx.doi.org/10.1016/j.orggeochem.2016.01.002 Kabel, K., Moros, M., Porsche, C., Neumann, T., Adolphi, F., Andersen, T.J., , Siegel, H., Gerth, M., Leipe, T., Jansen, E., Sinninghe Damsté, J.S., 2012. Impact of climate change on the Baltic Sea ecosystem over the past 1,000 years. Nature Climate Change 2, 871–874.

Kononen, K., Kuparinen, J., Mäkelä, K., Laanemets, J., Pavelson, J., Nõmman, S., 1996. Initiation of cyanobacterial blooms in a frontal region at the entrance to the Gulf of Finland, Baltic Sea. Limnology and Oceanography 41, 98-112. Kowalewska, G., 2005. Algal pigments in sediments as a measure of eutrophication in the Baltic environment. Quaternary International 130, 141-151. Labrenz, M., Jost, G., Juergens, K., 2007. Distribution of abundant prokaryotic organisms in the water column of the central Baltic Sea with an oxic-anoxic interface. Aquatic Microbial Ecology 46, 177-190. Labrenz, M., Sintes, E., Toetzke, F., Zumsteg, A., Herndl, G.J., Seidler, M., Juergens, K., 2010. Relevance of a crenarchaeotal subcluster related to Candidatus Nitrosopumilus maritimus to ammonia oxidation in the suboxic zone of the central Baltic Sea. Isme Journal 4, 1496-1508. Lamb, A.L., Wilson, G.P., Leng, M.J., 2006. A review of coastal palaeoclimate and relative sea-level reconstructions using δ13C and C/N ratios in organic material. Earth Science Reviews 75, 29-57. Lass, H.U., Matthaus, W., 1996. On temporal wind variations forcing salt water inflows into the Baltic Sea. Tellus Series a-Dynamic Meteorology and Oceanography 48, 663-671. Leipe, T., Tauber, F., Vallius, H., Virtasalo, J., Uscinowicz, S., Kowalski, N., Hille, S., Lindgren, S., Myllyvirta, T., 2011. Particulate organic carbon (POC) in surface sediments of the Baltic Sea. Geo-Marine Letters 31, 175-188. Lincoln, S.A., Wai, B., Eppley, J.M., Church, M.J., Summons, R.E., DeLong, E.F., 2014. Planktonic Euryarchaeota are a significant source of archaeal tetraether lipids in the ocean. Proceedings of the National Academy of Sciences of the United States of America 111, 98589863.Liu, X.-L., Lipp, J.S., Schroeder, J.M., Summons, R.E., Hinrichs, K.-U., 2012a. Isoprenoid glycerol dialkanol diethers: A series of novel archaeal lipids in marine sediments. Organic Geochemistry 43, 50-55. Liu, X.-L., Lipp, J.S., Simpson, J.H., Lin, Y.-S., Summons, R.E., Hinrichs, K.-U., 2012c. Mono- and dihydroxyl glycerol dibiphytanyl glycerol tetraethers in marine sediments: Identification of both core and intact polar lipid forms. Geochimica et Cosmochimica Acta 89, 102-115. Liu, X.-L., Summons, R.E., Hinrichs, K.-U., 2012b. Extending the known range of glycerol ether lipids in the environment: structural assignments based on tandem mass spectral fragmentation patterns. Rapid Communications in Mass Spectrometry 26, 2295-2302. Liu, X.-L., Zhu, C., Wakeham, S.G., Hinrichs, K.-U., 2014. In situ production of branched glycerol dialkyl glycerol tetraethers in anoxic marine water columns. Marine Chemistry 166, 1-8.

Loomis, S.E, Russell, J.M., Ladd, B., Street-Perrott, F.A., Sinninghe Damsté, J.S., 2012. Calibration and application of the br GDGT temperature proxy on East African lake sediments. Earth and Planetary Science Letters 357-358, 277-288. Loomis, S.E., Russell, J.M., Eggermont, H., Verschuren, D., Sinninghe Damsté, J.S., 2014. Effects of temperature, pH and nutrient concentration on br GDGT distributions in East African lakes: Implications for paleoenvironmental reconstruction. Organic Geochemistry 66, 25-37. Lotocka, M. 1998. Carotenoid pigments in Baltic Sea sediments. Oceanologia 40, 27-38. Matsumoto, G.I., Akiyama, M., Watanuki, K., Torii, T., 1990. Unusual distributions of longchain n-alkanes and n-alkenes in Antarctic soil. Organic Geochemistry 15, 403-412. Meglen, R.R., 1992. Examining large databases: A chemometric approach using principal component analysis. Marine Chemistry 39, 217-237. Meier, H.E.M., Feistel, R., Piechura, J., Arneborg, L., Burchard, H., Fiekas, V., Golenko, N., Kuzmina, N., Mohrholz, V., Nohr, C., Paka, V.T., Sellschopp, J., Stips, A., Zhurbas, V., 2006. Ventilation of the Baltic Sea deep water: A brief review of present knowledge from observations and models. Oceanologia 48, 133-164. Meyers, P.A., 1994. Preservation of elemental and isotopic source identification of sedimentary organic matter. Chemical Geology 114, 289-302. Miltner, A., Emeis, K.C., 2000. Origin and transport of terrestrial organic matter from the Oder lagoon to the Arkona Basin, Southern Baltic Sea. Organic Geochemistry 31, 57-66. Miltner, A., Emeis, K.C., 2001. Terrestrial organic matter in surface sediments of the Baltic Sea, Northwest Europe, as determined by CuO oxidation. Geochimica et Cosmochimica Acta 65, 1285-1299. Mohrholz, V., Naumann, M., Nausch, G., Krüger, S., Gräwe, U., 2015. Fresh oxygen for the Baltic Sea - An exceptional saline inflow after a decade of stagnation. Journal of Marine Systems 148, 152-166. Montanarella, L., Jones, R.J.A., Hiederer, R., 2005. The distribution of peatland in Europe. Mires and Peat Volume 1, Article 01, http://www.mires-and-peatland.net. Müller, A., 2001. Late- and Postglacial Sea-Level Change and Paleoenvironments in the Oder Estuary, Southern Baltic Sea. Quaternary Research 55, 86-96. Müller, A., Voss, M., 1999. The palaeoenvironments of coastal lagoons in the southern Baltic Sea, II. δ13C and δ15N ratios of organic matter — sources and sediments. Palaeogeography, Palaeoclimatology, Palaeoecology 145, 17-32. Munsterhjelm, R., 1997. The aquatic macrophyte vegetation of flads and gloes, S coast of Finland. Acta Botanica Fennica 157, 1-68.

Murray, J., Thomson, A., 1977. Hydrocarbon production in Anacystis montana and Botryococcus braunii. Phytochemistry 16, 465-468. Oppermann, B.I., Michaelis, W., Blumenberg, M., Frerichs, J., Schulz, H.M., Schippers, A., Beaubien, S.E., Krueger, M., 2010. Soil microbial community changes as a result of longterm exposure to a natural CO2 vent. Geochimica et Cosmochimica Acta 74, 2697-2716. Paoletti, C., Pushparaj, B., Florenzano, G., Capella, P., Lercker, G., 1976. Unsaponifiable matter of green and blue-green algal lipids as a factor of biochemical differentiation of their biomasses: I. Total unsaponifiable and hydrocarbon fraction. Lipids 11, 258-265. Paulomäki, H., Abel, C., Aguilar, R. 2011. Conservation proposals for ecologically important areas in the Baltic Sea. Imprenta Roal, S.L., 127 pp. Pazdro, K., Staniszewski, A., Bełdowski, J., Emeis, K.-Ch., Leipe, Th., Pempkowiak, J., 2001. Variations in organic matter bound in fluffy layer suspended matter from the Pomeranian Bay (Baltic Sea). Oceanologija 43, 405–20. Pearson, A., Ingalls, A.E., 2013. Assessing the Use of Archaeal Lipids as Marine Environmental Proxies. Annual Review of Earth and Planetary Sciences 41, 359-384. Peters, K.E., Walters, C.C., Moldowan, J.M., 2005. The biomarker guide I: Biomarkers and isotopes in the environment and human history. 2nd edition, Cambridge University Press, New York, 471 pp. Peterse, F., Kim, J.-H., Schouten, S., Kristensen, D.K., Koç, N., Sinninghe Damsté, J.S., 2009. Constraints on the application of the MBT/CBT palaeothermometer at high latitude environments (Svalbard, Norway). Organic Geochemistry 40, 692-699. Pitcher, A., Hopmans, E.C., Mosier, A.C., Park, S.J., Rhee, S-.K., Francis, C.A., Schouten, S., Sinninghe Damsté, J.S., 2011. Core and intact polar glycerol dibiphytanyl glycerol tetraether lipids of ammonia-oxidizing Archaea enriched from marine and estuarine sediments. Applied Environmental Microbiology 77, 3468-3477. Poutanen, E.L., Nikkila, K., 2001. Carotenoid pigments as tracers of cyanobacterial blooms in recent and post-glacial sediments of the Baltic Sea. Ambio 30, 179-183. Prahl, F.G., Hayes, J.M., Xie, T.-M., 1992. Diploptene: an indicator of terrigenous organic carbon in Washington coastal sediments. Limnology and Oceanography 37, 1290-1300. Schlitzer, R., 2010. Ocean Data View. http://odw.awi.de (version 4.3.2). Schmale, O., Blumenberg, M., Kiesslich, K., Jakobs, G., Berndmeyer, C., Labrenz, M., Thiel, V., Rehder, G., 2012. Aerobic methanotrophy within the pelagic redox-zone of the Gotland Deep (central Baltic Sea). Biogeosciences 9, 4969-4977. Schnetger, B., Dellwig, O., 2012. Dissolved reactive manganese at pelagic redoxclines (part I): A method for determination based on field experiments. Journal of Marine Systems 90, 2330.

Schouten, S., Hopmans, E.C., Schefuss, E., Sinninghe Damsté, J.S., 2002. Distributional variations in marine crenarchaeotal membrane lipids: A new tool for reconstructing ancient sea water temperatures?. Earth and Planetary Science Letters 204, 265-274. Schouten, S., Forster, A., Panoto, F.E., Sinninghe Damsté, J.S., 2007. Towards calibration of the TEX86 palaeothermometer for tropical sea surface temperatures in ancient greenhouse worlds. Organic Geochemistry 38, 1537-1546. Schouten, S., Hopmans, H.E., Sinninghe Damsté, J.S., 2013. The organic geochemistry of glycerol dialkyl glycerol tetraether lipids: A review. Organic Geochemistry 54, 19–61. Schubert, H., Schories, D., 2008. Macrophytobenthos; in State and Evolution of the Baltic Sea, 1952-2005: A Detailed 50-Year Survey of Meteorology and Climate, Physics, Chemistry, Biology, and Marine Environment (eds R. Feistel, G. Nausch and N. Wasmund), John Wiley & Sons, Inc., Hoboken, NJ, USA. Schulz, H.M., Schoner, A., Emeis, K.C., 2000. Long-chain alkenone patterns in the Baltic Sea - an ocean-freshwater transition. Geochimica et Cosmochimica Acta 64, 469-477. Szczepańska, A., Zaborska, A., Maciejewska, A., Kuliński, K., Pempkowiak, J., 2012. Distribution and origin of organic matter in the Baltic Sea sediments dated with 210Pb and 137 Cs. Geochronometria 39, 1-9.Simoneit, B.R.T., Mazurek, M.A., 1982. Organic matter in the troposphere - II. Natural background of biogenic lipid matter in aerosols over the rural western United States. Atmospheric Environment 16, 2139-2159. Sinninghe Damsté, J.S., Ossebaar, J., Abbas, B., Schouten, S., Verschuren, D., 2009. Fluxes and distribution of tetraether lipids in an equatorial African lake: Constraints on the application of the TEX86 palaeothermometer and BIT index in lacustrine settings. Geochimica et Cosmochimica Acta 73, 4232-4249. Sinninghe Damsté, J.S., Rijpstra, W.I.C., Hopmans, E.C., Weijers, J.W.H., Foesel, B.U., Overmann, J., Dedysh, S.N., 2011. 13,16-Dimethyl octacosanedioic acid (iso-diabolic acid): a common membrane-spanning lipid of Acidobacteria subdivisions 1 and 3. Applied and Environmental Microbiology 77, 4147-4154. Smith, R.W., Bianchi, T.S., Li, X., 2012. A re-evaluation of the use of branched GDGTs as terrestrial biomarkers: Implications for the BIT Index. Geochimica et Cosmochimica Acta 80, 14-29. Ston, J., Kosakowska, A., Lotocka, M., Lysiak-Pastuszak, E., 2002. Pigment composition in relation to phytoplankton community structure and nutrient content in the Baltic Sea. Oceanologia 44, 419-437. Thureborn, P., Lundin, D., Plathan, J., Poole, A.M., Sjoberg, B.-M., Sjoling, S., 2013. A Metagenomics Transect into the Deepest Point of the Baltic Sea Reveals Clear Stratification of Microbial Functional Capacities. Plos One 8, e74983.

Tierney, J.E., Russell, J.M., 2009. Distributions of branched GDGTs in a tropical lake system: Implications for lacustrine application of the MBT/CBT paleoproxy. Organic Geochemistry 40, 1032-1036. Toyota, M., Masuda, K., Asakawa, Y., 1998. Triterpenoid constituents of the moss Floribundaria aurea subsp. nipponica. Phytochemistry 48, 297-299. Tuo, J., Wu, C., Zhang, M., Chen, R., 2011. Distribution and carbon isotope composition of lipid biomarkers in Lake Erhai and Lake Gahai sediments on the Tibetan Plateau. Journal of Great Lakes Research 37, 447-455. Vahtera, E., Conley, D.J., Gustafsson, B.G., Kuosa, H., Pitkänen, H., Savchuk, O.P., Tamminen, T., Viitasalo, M., Voss, M., Wasmund, N., Wulff , F., 2007. Internal ecosystem feedbacks enhance nitrogen-fixing cyanobacteria blooms and complicate management in the Baltic Sea. Ambio 36, 186-194. Vonk, J.E., Gustafsson, O., 2009. Calibrating n-alkane Sphagnum proxies in sub-Arctic Scandinavia. Organic Geochemistry 40, 1085-1090. Vonk, J.E., van Dongen, B.E., Gustafsson, O., 2008. Lipid biomarker investigation of the origin and diagenetic state of sub-arctic terrestrial organic matter presently exported into the northern Bothnian Bay. Marine Chemistry 112, 1-10. Voss, M., Struck, U., 1997. Stable nitrogen and carbon isotopes as indicator of eutrophication of the Oder river (Baltic sea). Marine Chemistry 59, 35-49. Wakeham, S.G., 1990. Algal and bacterial hydrocarbons in particulate organic matter and interfacial sediments of the Cariaco Trench. Geochimica et Cosmochimica Acta 54, 13251336. Wakeham, S.G., Lee, C., Hedges, J.I., Hernes, P.J., Peterson, M.J., 1997. Molecular indicators of diagenetic status in marine organic matter. Geochimica et Cosmochimica Acta 61, 53635369. Wasmund, N., Lehtinen, S., Ameryk, A., Nausch, G. and Johansen, M., 2012. Phytoplankton and microbial plankton in the Baltic Sea. In O’Brien, T. D., Li, W. K. W., and Morán, X. A. G. (eds)., ICES Phytoplankton and Microbial Plankton Status Report 2009/2010, ICES Cooperative Research Report No. 313, 38-69. Wasmund, N., Nausch, G., Matthaus, W., 1998. Phytoplankton spring blooms in the southern Baltic Sea - spatio-temporal development and long-term trends. Journal of Plankton Research 20, 1099-1117. Weijers, J.W.H., Schouten, S., Geenevasen, J.A.J., David, O.R.P., Coleman, J., Pancost, R.D., Sinninghe Damsté, J.S., 2006. Membrane lipids of mesophilic anaerobic bacteria thriving in peats have typical archaeal traits. Environmental Microbiology 8, 648–657.

Weijers, J.W.H., Wiesenberg, G.L.B., Bol, R., Hopmans, E.C., Pancost, R.D., 2010. Carbon isotopic composition of branched tetraether membrane lipids in soils suggests a rapid turnover and a heterotrophic life style of their source organism(s). Biogeosciences 7, 2959-2973. Wuensch, K.L., 2014. Comparing Correlation Coefficients, Slopes, and Intercepts. Retrieved from http://core.ecu.edu/psyc/wuenschk/StatsLessons.htm. Yu, F., Zong, Y., Lloyd, J.M., Huang, G., Leng, M.J., Kendrick, C., Lamb, A.L., Yim, W.W.S., 2010. Bulk organic δ13C and C/N as indicators for sediment sources in the Pearl River delta and estuary, southern China. Estuarine, Coastal and Shelf Science 87, 618-630.

Table 1. Main parameters and indices determined in the surface sediments of the Baltic Sea (n = 57).

R e g i o n

A r k o n a B a s i n A r k o n

S a m p l e

L a t i t u d e

L o n g i t u d e

( ° I N D )

( ° E )

5 4 . 8 3 8 5 4 . 2 8

1 3 . 5 3 3 1 1 . 5 6

4 6

4 7

n w a b C t o 2 e t T 9 r t b a d o l o e m k t p T C S t a t O O T / S o n h 2 C S N T m e ( µ g / ( g m l ( ( T ( / ( ( ° ° O m l %% C C C ) ) ) ) ) ) )

d i p l o p t e n e ( µ g / g

nC 25 :1 + nC 27 :1 al ke n es

nC2 3/( nC2 3+ nC2 P 5 C P a al P a q ka I q ' ne a b c s)

(µ g/ T g O T C O ) C)

c r e n a r c h a e o l ( µ g / g

cre nar cha eol/ (cr ena rch aeo l+ GD GT0)

T O C )

is o p r e n o i d G D G T s

b r a n c h e d G D G T s

( µ g / g T O C )

( µ g / g T O C )

d

e

0 0

4 1

1 5 0 8 9 2 . . . . . 1 7 6 6 3 4 8 4

1 . . . 4 3 0. 4 1 21 8 0 8 33

1 9

4 3 0 8 9 9 1 . . . . . . 2 3 8 8 6 6 2 0

1 . . . 3 3 0. 2 2 13 9 7 7 33

3 9

0.6 4

6 3

0.6 4

5 4

O H G D G T s i

O H G D G T % j

O H G D G T 1 3 1 8/ c r e n

( µ g / g T O C )

4

0 . 0 9

1 5 . 7

5

0 . 1 3

1 3 . 1

0 0

3 3

% O M % so O il M (b s ra o nc il he ( d B G B I D I T G T ) Ts f g )h

9. 1

12 .7

6

8 . 9 6

0. 1 4

6

9 . 2 2

0. 1 5

a B a s i n A r k o n a B a s i n A r k o n a B a s i n B o r n h o l m

4 7

5 4 . 8 6 3 5 8

1 3 . 5 3 4 4 1

5 4 . 8 6 5 6 2

1 3 . 4 3 4 3 1

5 B 4 a . s 9 i 2 1 n 9 7 B o r n h o l m 5 B 5 a . s 3 i 3 7 n 7 8 B 5 o 5 r . n 4 h 4 1 o 5 1

1 5 . 5 8 8 4 3

1 5 . 3 6 3 1 5 . 4 6 8

1 5 0 8 9 2 . . . . . 0 7 5 6 2 5 8 8

1 5 0 8 9 1 . . . . . 7 7 5 8 4 4 8 3

2 4 0 8 9 . . . . . 6 6 9 9 9 4 5 1

4 0

2 7

8

19

0 1 . . 4 6 0

0 . 3 0. 8 33

17

0 1 . . 3 7 8

0 . 3 0. 7 32

17

0 2 . . 5 8 1

0 . 4 0. 4 43

5

2 . . . 3 3 0. 9 6 8 30

11

0 2 . . 4 6 1

1 1 2

1 0 8

1 0 0

0.6 0

0.6 3

9 0

9 5

5 1 8 9 7 1 . . . . . 0 2 2 1 6 3 2 7

2 0

2 1

0 . 4 0. 1 36

6 2 0

1 9 1

1 7 7

0.6 3

1 6 5

0.5 7

1 1 3 6

0 0

5 1 8 9 7 1 . . . . . 2 2 8 2 0 3 2 4

1 9 4

0.6 0

3 3 6

1 4

0 . 1 1

1 1 . 9

1 2

0 . 1 0

1 0 . 7

1 1

0 . 1 0

1 0 . 1

2 7

0 . 4 0 . 4 3

1 0

0 . 5 0 . 5 4

2 3

1 0 . 2 3

0. 1 7

2 1

1 0 . 1 7

0. 1 6

9. 8

2 1

1 0 . 9 7

0. 1 8

4. 1

1 2 4

9 . 5 3

0. 1 7

4 5

1 1 . 4 8

0. 2 0

11 .5

10 .3

5. 2

l m B a s i n B o r n h o l m 5 B 5 a . s 2 i 5 9 n 0 0 B o r n h o l m 5 B 5 a . s 2 i 6 8 n 4 2 B o t h n i 6 a 5 n . B 0 a 3 0 y 5 0 B o t h n i 6 a 4 n . B 2 a 4 0 y 3 4 B 6 o 5 t 4 . h 4 4

1 5 . 0 6 7 3 0

5 1 7 9 7 . . . . . 9 2 0 1 8 3 2 0

1 5 . 0 4 6 7 8

5 0 8 9 7 2 . . . . . 0 2 1 7 1 3 2 7

2 3 . 1 3 7 2 5

1 6 3 0 1 5 5 . . . . . 4 7 7 1 8 9 4 9

2 2 . 0 2 9 2 3 . 2

1 0 9

6 4 0 . . . 8 8 2

7 9

6 2 0 . . . 7 7 1

1 1 . 3 1 1 . 5

5 2 3 . . 6 8 5 9 6 3 5 . . 6 2 2 4

1 9

6 2

5 0

5 0

3 7

7

0 2 . . 4 6 1

0 . 4 0. 0 34

15

0 2 . . 4 0 2

0 . 4 0. 2 38

6

0 2 . . 6 9 0

0 . 4 0. 9 54

6

2 . 4

5

3 . 1

0 . 5 4 0 . 6 3

0 . 4 7 0 . 5 1

1 1 8

1 6 0

8 2

0.6 1

0.6 1

0.6 1

2 0 2

2 7 5

1 4 4

1 1

0 . 8 0 . 9 9

1 2

0 . 7 0 . 7 3

3 8

0 . 3 2

3 3 . 1

0 . 2 3 0 . 3 5

2 4 . 2 3 5 . 8

0. 47

1 0 6

0.6 0

1 8 9

3 2

0. 57

7 0

0.5 9

1 2 5

3 7

8. 6

7. 0

32 .0

2 7

1 1 . 4 4

0. 1 9

3 5

1 0 . 8 6

0. 1 8

2 3

1 3 . 0 7

0. 2 3

23 .4

3 0

34 .6

2 1

1 3 . 0 1 1 3 . 6

0. 2 3 0. 2 4

n i a n B a y B o t h n i a n B a y B o t h n i a n S e a B o t h n i a n S e a B o t h n i a n S e a B o t h n i a n S e a

4 9 5 8

0

6 3 . 8 5 3 5 3

2 1 . 5 8 5 3 9

6 1 . 0 2 6 4 6

1 9 . 7 1 1 4 8 2

4 2 0 9 6 3 . . . . . 1 6 9 1 3 9 3 6

6 2 . 8 2 4 5 5

1 8 . 8 2 8 0 9 6

1 5 3 0 0 6 3 4 . . . . . . 7 2 0 1 3 5 2 1

6 2 . 7 2 7 6 8

1 8 . 0 4 9 9 1

1 6 3 0 1 5 3 5 . . . . . . 0 7 3 1 5 8 3 3

6 1 . 0 2 8 8 5

1 9 . 5 1 7 2 9 7

1 6 3 0 1 5 2 2 . . . . . . 8 8 7 1 1 9 2 9

4 2 0 9 3 3 . . . . . 6 6 8 1 2 7 4 2

2 5

4 9

6 4

7 2

5 2

6

0 3 . . 5 0 1

0 . 4 0. 4 41

5

0 2 . . 5 6 1

0 . 4 0. 5 45

6

0 2 . . 5 8 0

0 . 4 0. 4 42

8

0 2 . . 4 9 8

0 . 4 0. 1 40

5

0 2 . . 5 7 0

0 . 4 0. 3 44

3 7

6 6

8 6

4 7

6 6

0.5 9

0.6 1

0.6 0

0.5 7

0.5 9

6 7

1 1 4

1 4 9

8 7

1 1 9

1 4

0 . 2 7

2 8 . 1

8

0 . 1 0

1 0 . 7

1 1

0 . 1 2

1 2 . 0

2 8

0 . 3 7

3 8 . 2

8

0 . 1 1

1 0 . 9

27 .2

10 .4

11 .6

36 .9

10 .6

1 2

1 4 . 2 3

0. 2 6

1 4

1 0 . 8 4

0. 1 9

2 0

1 1 . 4 4

0. 2 0

1 2

1 1 . 4 7

0. 2 1

1 6

1 1 . 7 9

0. 2 1

B o t h n i a n S e a B o t h n i a n S e a B o t h n i a n S e a B o t h n i a n S e a B o t h n i a n S e a B o t h n i a

6 2 . 8 3 8 0 0

1 8 . 9 1 2 7 2 9

5 2 0 9 6 4 . . . . . 1 3 9 1 9 7 3 3

6 2 . 8 3 7 1 0

1 9 . 0 2 4 1 3 3

1 4 3 0 0 6 5 . . . . . 1 9 0 1 3 7 3 5

6 1 . 0 4 0 1 0

1 8 . 9 9 8 9 5

5 2 0 9 6 2 2 . . . . . . 2 1 5 1 4 7 3 7

6 3 . 1 5 3 1 3

1 9 . 9 1 0 1 0 1

1 5 1 0 0 6 2 2 . . . . . . 3 6 8 1 8 6 2 1

6 1 . 7 5 8 6 3

1 9 . 2 9 5 3 4

6 2 . 4 6 1 3 6

2 0 . 0 8 8 2 9

4 0 0 7 6 2 2 . . . . . . 1 8 5 0 8 5 4 7

4 1 0 9 6 2 4 . . . . . . 2 6 2 1 0 7 9 6

1 7

6 7

2 4

3 1

2 9

1 9

8

0 3 . . 5 0 2

0 . 4 0. 4 43

6

0 2 . . 5 8 1

0 . 4 0. 4 43

3

0 3 . . 5 1 4

0 . 4 0. 5 45

2

0 2 . . 5 9 2

0 . 4 0. 5 45

2

0 3 . . 5 3 0

0 . 4 0. 5 42

3

0 3 . . 5 5 2

0 . 4 0. 5 44

7 5

8 3

1 2 6

5 9

5 5

8 2

0.6 0

0.5 9

0.5 8

0.5 9

0.5 8

0.6 0

1 3 1

1 4 7

2 2 6

1 0 5

1 0 0

1 4 3

1 2

0 . 1 4

1 4 . 2

9

0 . 1 0

1 0 . 6

9

0 . 6 0 . 7 8

6

0 . 9 1 . 0 9

5

0 . 8 0 . 8 0

1 1

0 . 1 2

1 2 . 6

13 .7

10 .2

6. 5

9. 6

7. 7

12 .2

1 9

1 2 . 3 5

0. 2 2

2 0

1 1 . 4 2

0. 2 0

3 3

1 2 . 6 2

0. 2 3

1 5

1 2 . 0 1

0. 2 2

1 4

1 2 . 0 3

0. 2 2

1 8

1 0 . 9 9

0. 1 9

n S e a G o tl a n d B a s i n G o tl a n d B a s i n G o tl a n d B a s i n G o tl a n d B a s i n G o tl a n d B a s i n G o tl

5 7 . 3 1 1 3 7

2 0 . 1 2 3 4 4 1

1 0 1 1 9 6 1 . . . . . 7 3 8 7 1 9 4 0

2 . . . 3 4 0. 3 1 48 1 8 0 32

5 8 . 0 1 0 7 0

1 9 . 8 1 8 9 1 8

1 1 0 2 1 0 8 6 1 . . . . . . 8 3 7 6 0 6 4 1

1 . . . 3 4 0. 3 9 40 7 9 0 32

5 7 . 3 1 8 8 4

2 0 . 2 2 5 3 1 1

1 0 3 1 8 9 . . . . . 5 3 0 1 1 2 6 7

6

0 3 . . 3 4 2

5 7 . 0 1 8 9 3

1 9 . 9 1 8 8 5 9

1 0 1 2 9 1 . . . . 4 3 5 0 3 9 6 7

1 . . . 3 4 0. 2 3 43 8 7 0 32

1 9 . 7 1 8 1 9 .

0 . 3 0 . 1

2 0 2 2

5 8 . 1 0 2 5 7 .

1 6 5 2 2 3

1 2 . 4 1 4 .

0 0

4 0 5

0.5 8

7 3 2

0.5 6

6 7 2

7

0 . 1 0 . 2 9

5

0 . 1 0 . 1 6

6

0 . 1 0 . 2 6

8

0 . 1 0 . 2 1

0 0

3

0 . 3 0. 4 23

3 7 2

4 0 3

0.5 9

7 5 0

0.5 4

8 7 8

0 0

4 9 2

0 0

1 . 6 1 . 4

9 . 0 8 . 5

8 . 6 9 . 1

5 1 . 9 9 0 2 3 6 4

2 . . . 3 3 0. 2 8 31 2 8 8 28 2 0

24

0 0 3 . . 0. . 3 3 25

3 5 2 4 8 7

0.5 7 0.5 4

6 8 6 9 5 3

4

9

0 . 0 1 0 . 0

1 . 8 1 . 9

1. 8

1. 5

1. 6

1. 1

1. 7 1. 9

7 3

8 . 7 8

0. 1 5

6 8

8 . 8 3

0. 1 5

8 9

1 0 . 1 6

0. 1 8

9 6

9 . 5 3

0. 1 6

7 7 1 0 6

9 . 7 4 9 . 6

0. 1 8 0. 1 8

a n d B a s i n G o tl a n d B a s i n G o tl a n d B a s i n G o tl a n d B a s i n L a n d s o rt B a s i n L a n d s o rt B a

1 8 0 4 6 6

2

1 2 4

5 6 . 9 2 6 7 6

1 9 . 3 1 7 7 1 8

1 0 5 1 9 8 6 2 . . . . . . 7 1 2 5 3 9 4 4

2 . . . 3 3 0. 3 5 49 3 6 7 27

5 7 . 3 3 4 3 6

2 0 . 2 2 2 4 0 2

1 0 4 1 8 9 6 3 . . . . . . 5 1 3 1 2 2 4 2

3 . . . 3 3 0. 4 3 13 1 1 3 24

5 7 . 3 5 0 9 5

2 0 . 0 2 6 3 3 6

1 1 0 5 1 0 6 2 . . . . . 3 1 1 6 4 9 4 9

27

0 3 . . 2 3 9

0 . 3 0. 4 23

5 8 . 5 1 8 2 3

1 8 . 2 4 3 4 4 1

0 7 1 9 8 5 . . . . . . 6 3 9 2 2 4 7 4

1 0

2

0 2 . . 3 2 8

0 . 3 0. 9 31

5 8 . 6 1 0 4 3

1 8 . 7 2 1 1 1 4

0 8 1 9 8 5 1 . . . . . . 0 3 0 6 1 5 6 9

2 . . . 3 3 0. 8 14 3 9 8 30

2

0 0

5 6 1

0.5 4

1 0 8 7

0.5 0

9 6 5

8

0 . 1 0 . 1 4

7

0 . 1 0 . 2 6

6

0 . 2 0 . 2 0

1

0 . 1 0 . 1 5

1 1

0 . 2 0 . 2 0

0 0

2 6

4 6 2

2 8 1

8 6

0.5 9

0.6 1

1 4 7

0.5 6

1 0 6 1

0 0

5 6 8

4 9 9

5

1. 4

1 1 7

9 . 2 8

0. 1 7

1. 6

1 1 2

9 . 9 9

0. 2 0

6 3

1 0 . 7 2

0. 1 7

1. 5

2 0

1 1 . 4 4

0. 1 9

1. 9

1 2 2

9 . 9 4

0. 1 8

1. 9

s i n L a n d s o rt B a s i n L a n d s o rt B a s i n L a n d s o rt B a s i n L a n d s o rt B a s i n L a n d s o rt B a s i

5 8 . 0 1 1 5 6

1 7 . 9 2 8 0 1 1

5 8 . 3 1 5 6 2

1 7 . 8 1 1 0 8 3

0 8 1 9 8 5 . . . . . . 5 3 9 4 1 5 4 7

5 8 . 6 3 7 4 3

1 8 . 5 2 1 5 8 0

1 0 1 1 9 8 5 3 . . . . . . 5 2 1 1 6 4 9 8

5 8 . 5 4 9 0 7

1 8 . 4 1 6 9 8 0

5 8 . 6 4 7 9 3

1 8 . 5 2 1 5 8 0

0 7 1 8 8 5 1 . . . . . . 4 3 9 6 9 8 1 2

0 9 1 9 8 5 1 . . . . . . 8 2 4 6 7 4 8 5

0 9 1 9 8 5 1 . . . . . . 5 2 8 5 9 4 9 4

2 1

6

2 9

2 4

2 1

16

0 2 . . 3 0 9

0 . 3 0. 8 30

5

0 2 . . 4 8 4

0 . 4 0. 0 32

24

0 2 . . 3 4 5

0 . 3 0. 5 24

31

0 2 . . 3 4 5

0 . 3 0. 6 27

25

0 2 . . 3 3 5

0 . 3 0. 9 31

6 3 9

1 3 8

2 8 6

3 0 5

3 0 3

0.5 6

0.5 6

0.5 7

0.6 0

0.6 0

1 1 7 8

2 5 4

5 2 5

5 2 4

5 2 7

1 4

0 . 2 0 . 2 2

3

0 . 2 0 . 2 1

5

0 . 1 0 . 2 9

7

0 . 2 0 . 2 4

7

0 . 2 0 . 2 2

2. 1

2. 1

1. 8

2. 3

2. 1

1 4 2

1 0 . 4 2

0. 1 9

3 6

1 2 . 1 6

0. 2 2

7 1

1 1 . 5 9

0. 2 1

6 8

1 1 . 1 0

0. 1 8

6 9

1 1 . 2 3

0. 1 9

n L a n d s o rt B a s i n L a n d s o rt B a s i n L a n d s o rt B a s i n L a n d s o rt B a s i n S k a g e rr a k S e a S

5 8 . 9 5 7 2 4

1 9 . 2 1 4 0 1 3

5 9 . 3 5 5 4 8

2 0 . 1 0 4 0 3

0 0 7 8 5 1 . . . . . 4 5 4 0 1 1 5 0

5 8 . 3 5 6 7 5

1 7 . 8 1 3 0 4 4

1 1 0 0 1 0 8 5 1 . . . . . . 7 3 9 7 2 5 4 1

5 8 . 6 6 3 1 9

1 8 . 2 4 6 3 7 5

1 0 1 1 9 8 5 2 . . . . . . 5 2 6 1 3 2 9 2

5 7 . 8 2 2 9 3 5

7 . 3 9 7 9

5 . 5 5

4 6 0 5

1 0 7 1 0 8 5 1 . . . . . . 1 2 3 8 0 4 5 2

1 6

20

0 2 . . 3 3 6

0 . 3 0. 7 29

3 0 7

0.5 9

5 3 5

6

0 0

2 . 5 2

0 . 3 0

1 1 . 1 9

9 1 . 6 9 6 1 9 6 1

1 0

2 7

3 2

4 2 4

2

2 . . . 5 4 0. 7 1 7 46

32

0 2 . . 3 6 7

0 . 3 0. 9 30

28

0 2 . . 3 3 7

0 . 3 0. 7 27

3 3 9

7 5

1 . 9 1

0 . 3 1 0

0 . 3 0. 2 27 0 0.

1 2 1 9

8 3

2 8 5

0.5 6

0.5 8

1 5 4

5 0 9

0.5 6

6 3 3

0.5 1 0.5

2 4 7 1

0 . 2 0 . 2 1

6

0 . 7 0 . 7 3

5

0 . 1 0 . 2 8

6

0 . 1 0 . 2 9

1 0 8

0 . 0 8 0

8 . 1 7

2. 0

7. 0

1. 8

1. 9

7. 8 7.

7 5

1 1 . 9 2

0. 2 1

2 6

1 4 . 1 3 *

0. 2 7 *

6 8

1 1 . 5 1

0. 2 0

8 2

1 1 . 0 3

0. 1 9

2 3 1

8 . 3 3 8

0. 1 6 0.

k a g e rr a k S e a S k a g e rr a k S e a S k a g e rr a k S e a S k a g e rr a k S e a S k a g e rr a k S e a S k a g e rr a k

8 . 5 2 9

. 3 4 2 8 6

. . . . . 5 7 3 6 8

5 9

2

. . . 28 9 3 3

8

2

9 7

. . 0 8 7

1 3

5 8 . 4 1 4 2

9 . 8 5 0 4 1 3

5 2 0 9 9 1 . . . . . 8 5 5 3 6 9 6 3

5 7 . 9 1 5 1

7 . 2 2 9 9 4 7

1 5 2 0 2 9 1 . . . . . 8 5 8 3 8 8 6 6

5 7 . 8 2 6 9

7 . 2 4 9 5 4 7

5 2 0 9 9 1 . . . . . 7 5 3 3 4 9 6 1

5 7 . 5 5 7 7

7 . 2 2 9 5 6 9

1 5 2 0 9 0 1 . . . . . 8 5 6 2 4 2 6 4

5 7 . 6 3 8 5

7 . 2 3 9 0 9 1

5 2 0 9 1 . . . . 1 6 5 2 3 6 0 6 2

0 0

4 4

5

2 . . . 2 3 0. 0 9 1 26

5

2 . . . 3 3 0. 0 0 1 26

8

1 . . . 3 3 0. 9 4 4 32

5

2 . . . 2 3 0. 0 7 0 25

5

2 . . . 3 3 0. 2 0 2 27

7 8

0.5 3

1 5 5

0.5 1

2 1 6

0.5 1

2 6 0

0.5 2

2 4 0

0.5 2

1 8 9

8

0 . 9 0 . 9 3

1 1

0 . 1 0

1 2

0 . 9 0 . 9 1

8

0 . 6 0 . 7 8

1 0

0 . 1 0

0 0

4 5

1 0 5

0 0

4 0

1 2 5

0 0

5 8

1 1 8

0 0

4 1

9 3

1 0 . 0

1 0 . 1

5

8. 9

9. 7

8. 8

6. 6

9. 8

8

. 0 7

1 5

1 4

8 . 0 7

0. 1 5

2 4

9 . 7 3

0. 1 9

2 5

8 . 2 9

0. 1 6

2 5

9 . 1 3

0. 1 7

2 0

9 . 3 2

0. 1 7

S e a S k a g e rr a k S e a S k a g e rr a k S e a S k a g e rr a k S e a S k a g e rr a k S e a S k a g e rr a k S e a S k a g

5 7 . 7 1 9 0

7 . 2 3 9 5 4 3

5 2 0 9 1 . . . . 1 4 5 4 3 1 0 6 3

5 7 . 7 1 5 0 2

7 . 2 3 9 9 4 0

5 2 0 9 1 . . . . 1 7 5 4 3 4 0 6 5

5 7 . 8 1 9 1 5

7 . 2 3 9 4 4 8

5 2 0 9 9 1 . . . . . 8 5 4 3 7 8 6 8

5 8 . 4 4 2 2 9

9 . 4 5 7 0 7 9

5 2 0 8 9 1 . . . . . 5 5 1 2 4 8 6 6

4 8

5 8

5 8 . 4 4 0 5 8 . 4

9 . 7 2 7 9 . 5 9

0 0

3 4

6

2 . . . 2 3 0. 0 9 2 25

6

1 . . . 3 3 0. 8 0 1 25

7

2 . . . 3 3 0. 0 1 1 26

5

1 . . . 3 3 0. 7 3 3 28

5

1 . . . 3 3 0. 7 2 3 29

8 2

0.5 5

1 5 5

5

0 1 . . 3 7 1

1 0 2

0.5 6

1 9 1

1 1 1

0.5 0

2 3 3

0.5 1

2 0 9

0.5 1

2 6 8

0.5 6

1 4 4

9

0 . 7 0 . 8 9

9

0 . 8 0 . 8 6

1 2

0 . 8 0 . 8 5

8

0 . 1 0

0 0

4 6

1 0 0

0 0

4 6

1 2 9

0 0

4 0

7 8

0 0

6 6 5 5 3 7

5 2 0 8 9 1 . . . . . 2 4 2 3 3 8 6 3 5 2 0 8 9 1 . . . . . 2 5 3 3 0 7 6 2

3 1

3 0

0 . 3 0. 2 27

8

8

0 . 0 9 0 . 0 7

1 0 . 2

7. 7

8. 4

8. 2

9. 9

2 2

8 . 2 6

0. 1 6

2 0

8 . 3 2

0. 1 6

2 5

8 . 2 6

0. 1 6

1 6

9 . 7 2

0. 1 7

9 . 4

9. 1

1 6

7 . 2

6. 9

2 0

9 . 2 5 9 . 0 4

0. 1 7 0. 1 6

e 9 8 rr 6 a k S e a S k a g e rr 5 a 8 9 k . . 0 0 0 8 1 . . S 4 5 5 5 2 0 8 9 1 1 . 7 . 0. . 3 3 0. 7 0.5 4 e 6 9 8 5 . . . . . 4 4 0 . 7. 1 6 1 a 2 2 0 3 5 3 3 4 7 6 5 2 5 6 2 3 28 9 7 6 6 7 7 4 4 5 5 a CPI (n-alkanes) = 0.5*(([n-C27]+[n-C29]+[n-C31]+[n-C33])/([n-C26]+[n-C28]+[n-C30]+[n-C32])) + 0.5*([n-C27]+[n-C29]+[n-C31]+[n-C33])/([n-C28]+[n-C30]+[n-C32]+[n-C34])) b

Paq = (n-C23 + n-C25 alkanes)/(n-C23 + n-C25 + n-C29 + n-C31 alkanes)

Table 2. Correlation coefficients (r) and p values (in italic) between different parameters measured on the surface sediments. The concentrations of the biomarkers were normalized to TOC before analysis. Bold values indicate r ≥ 0.5 and p < 0.001.

n = T 5 O O 7 2 C 0 . O 0 2 0 T O 0 C .

T S 0 . 0 0 0 . 0

C / N 0 . 0 1 0 . 5

n C 1 7 0 . 1 9 0 . 5

n C 2 3 0 . 0 0 0 . 0

n C 2 5 0 . 0 1 0 . 3

n C 2 7 0 . 0 1 0 . 3

n C 2 9 0 . 0 0 0 . 2

n C 3 1 0 . 9 5 0 . 0

P a q 0 . 0 2 0 . 0

P a q ' 0 . 3 0 0 . 2

n C 2 3 / ( n C 2 3 + n C 2 5 ) 0 . 0 0 0 . 0

d i p l o p t e n e 0 . 0 0 0 . 0

n C 2 5 : 1 0 . 0 0 0 . 0

n C 2 7 : 1 0 . 0 0 0 . 0

n C 2 9 : 1 0 . 0 0 0 . 0

G D G T 0 0 . 0 0 0 . 0

G D G T 1 0 . 0 0 0 . 0

G D G T 2 0 . 0 0 0 . 0

G D G T 3 0 . 0 0 0 . 0

c r e n 0 . 0 0 0 . 0

c r e n ' 0 . 0 0 0 . 0

G D G T I a 0 . 0 0 0 . 0

G D G T I I a 0 . 0 0 0 . 0

G D G T I I I a 0 . 9 6 0 . 7

O H G D G T 0

O H G D G T 1

O H G D G T 2

1 3 1 8 0 . 0 0 0 . 0

1 3 1 6 0 . 0 0 0 . 0

1 3 1 4 0 . 0 0 0 . 0

2 O H G D G T 0 n 1 3 = 3 B 4 I 5 T 7 0 0 . . 0 0 O 0 0 2 0 0 T . . O 0 0 C

8 7 0 . T 9 S 2

C / N n C 1 7 n C 2 3 n C 2 5 n C 2 7 n C 2 9 n C 3 1

0 . 3 4 0 . 1 7 0 . 4 7 0 . 3 3 0 . 3 6 0 . 3 8 0 . 0 1

0 P . a 3 q 1 P a q ' n

0 . 1 4 0

0 6 1 3 4 4 8 3 2 3 0 2 0 0 0 0 0 0 0 0 0 1 5 2 0 0 0 0 0

0 . 8 6 0 . 0 8 0 . 0 9 0 . 2 9 0 . 1 3 0 . 1 3 0 . 1 4 0 . 2 9 0 . 3 0 0 . 1 6 -

0 . 1 9 0 . 1 8 0 . 2 3 0 . 4 7 0 . 3 6 0 . 3 8 0 . 4 3 0 . 0 5 0 . 3 6 0 . 1 9 -

0 . 0 9

0 . 0 0

0 . 0 1

0 . 0 0

0 . 0 0

0 . 7 1

0 . 0 1

0 . 1 7

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 1

0 . 6 9

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 T 0 S

0 . 1 1

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 6

0 . 1 9

0 . 0 5

0 . 0 0

0 . 8 7

0 . 9 1

0 . 8 4

0 . 1 6

0 . 2 2

0 . 1 8

0 . 2 8

0 . 1 6

0 . 1 7

0 . 0 0

0 . 0 0

0 . 5 5

0 . 2 1

0 . 2 1

0 . 3 7

0 . 2 9

0 . 9 3

0 . 8 3

0 . 5 0

0 . 1 0

0 . 0 5

0 . 1 2

0 . 0 6

0 . 2 2

0 . 0 0

0 . 8 6

0 . 9 0

0 . 7 0

0 . 4 5

0 . 4 7

0 . 4 6

0 . 5 6

0 . 2 6

0 . 2 8

0 . 4 7

0 . 9 1

0 . 1 0

0 . 1 7

0 . 2 7

0 . 3 0

0 . 1 3

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 9

0 . 0 6

0 . 0 3

0 . 0 1

0 . 0 4

0 . 0 2

0 . 0 0

0 . 0 2

0 . 0 4

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 3

0 . 0 2

0 . 0 8

0 . 1 2

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 5 5

0 . 4 1

0 . 2 3

0 . 1 5

0 . 3 2

0 . 1 8

0 . 0 5

0 . 1 6

0 . 2 7

0 . 0 0

0 . 0 0

0 . 0 0

0 . 2 8

0 . 2 2

0 . 4 6

0 . 6 5

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 4 9

0 . 3 6

0 . 2 2

0 . 1 6

0 . 3 5

0 . 1 9

0 . 0 6

0 . 1 5

0 . 2 6

0 . 0 0

0 . 0 0

0 . 0 0

0 . 2 6

0 . 2 3

0 . 4 5

0 . 6 1

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 5 0

0 . 3 7

0 . 2 8

0 . 1 2

0 . 3 0

0 . 1 4

0 . 0 4

0 . 0 9

0 . 1 7

0 . 0 0

0 . 0 0

0 . 0 3

0 . 1 6

0 . 1 7

0 . 3 5

0 . 3 9

0 . 0 4

0 . 0 4

0 . 0 8

0 . 0 0

0 . 0 3

0 . 0 5

0 . 1 0

0 . 1 8

0 . 0 5

0 . 1 9

0 . 2 7

0 . 2 6

0 . 2 2

0 . 0 3

0 . 0 2

0 . 2 1

0 . 1 9

0 . 1 0

0 . 0 5

0 . 0 6

0 . C 0 / 0 N n 0 . C 4 1 2 7 n 0 . C 0 2 0 3 n 0 . C 0 2 0 5 n 0 . C 0 2 0 7 n 0 . C 0 2 0 9 n 0 . C 0 3 5 1

0 . 2 1 0 . 5 0

0 . 0 1

0 . 5 0

0 . 0 3

0 . 9 7

0 . 5 2

0 . 0 9

0 . 9 5

0 . 9 9

0 . 5 1

0 . 2 2

0 . 8 9

0 . 9 4

0 . 9 7

0 . 4 3

0 . 2 6 0 . 2 1 0 . 2 5 -

0 . 6 1

0 . 7 5

0 . 8 0

0 . 8 4

0 . 7 8

0 . 7 7

0 . 7 1

0 . 6 0

0 . 2 8

0 . 0 0

0 . 0 0

0 . 7 3

0 . 1 3

0 . 0 7

0 . 0 2

0 . 0 1

0 . 0 1

0 . 0 1

0 . 0 0

0 . 0 2

0 . 0 4

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 5

0 . 0 1

0 . 0 3

0 . 1 9

0 . P 0 a 0 q

0 . 7 1 0

0 . 7 1 0

0 . 6 4 0

0 . 5 1 0

0 . 2 7 0

0 . 9 7 0 0

0 . 0 0

0 . 7 4 0

0 . 6 9 0

0 . 4 8 0

0 . 1 5 0

0 . 0 6 0

0 . 1 0 0

0 . 0 9 0

0 . 0 1 0

0 . 1 7 0

0 . 2 6 0

0 . 0 2 0

0 . 0 0 0

0 . 0 0 0

0 . 3 0 0

0 . 1 0 0

0 . 2 1 0

0 . 7 3 0

0 . 0 0 0

0 . 2 5 0 . 1 8 0

P a q ' n

C 2 3 / ( n C 2 3 + n C 2 5 ) d i p l o p t e n e n C 2 5 : 1 n C 2 7 : 1 n C 2 9 : 1 G D G T

. 0 0 . 4 . . 2 5 4 4 6 5 8

0 . . . . . . . . 8 7 7 5 2 9 9 1 1 5 0 9 4 7 3 7

0 . 5 0

0 . 3 2

0 . 5 1

0 . 3 8

0 . 6 0

0 . 4 0

0 . 3 8

0 . 4 4

0 . 5 7

0 . 4 8

0 . 7 2

0 . 7 9

0 . 7 7

0 . 0 2

0 . 0 2

0 . 2 3

0 . 0 8

0 . 0 9

0 . 0 9

0 . 0 2

0 . 2 5

0 . 1 1

0 . 1 2

0 . 0 5 0 . 1

0 . 2 9 0 . 3

0 . 1 6 0 . 2

0 . 1 6 0 . 1

0 . 6 9

0 . 7 7

0 . 7 6

0 . 0 2

0 . 6 3 0 . 6

0 . 7 1 0 . 7 6

0 . 7 1 0 . 7 4

0 . 0 3 0 . 1

0 . 0 5

0 . 0 5

0 . 1 5

0 . 2 9

0 . 2 0

0 . 0 5

0 . 2 9

0 . 1 2

0 . 2 6

0 . 2 4

0 . 0 9

0 . 3 2

0 . 1 5 0 . 2

0 . 2 2 0 . 1 8

0 . 3 2 0 . 3

0 . 1 9 0 . 2

0 . 3 8 0 . 4

. . . . . . . . . . . . . . . . . . 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 C 8 3 2 0 0 0 0 0 0 0 0 0 1 0 0 0 2 0 2 3 / ( n C 2 3 + n C 2 5 ) d i p l o p 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 t . . . . . . . . . . . . . . . . . e 2 2 4 0 0 0 0 0 0 0 0 6 0 0 0 0 0 n 9 9 7 2 6 3 2 1 1 0 2 1 0 1 2 0 0 e n C 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 . . . . . . . . . . . . . . . . . 5 1 0 0 0 0 0 0 0 0 0 0 6 0 0 0 0 0 : 4 0 0 0 0 0 0 0 0 4 8 3 0 0 0 0 0 1 n C 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 . . . . . . . . . . . . . . . . . 7 1 9 0 0 0 0 0 0 0 0 0 5 0 0 0 0 0 : 4 9 0 0 0 0 0 0 0 5 7 2 0 0 0 0 0 1 n C 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 . . . . . . . . . . . . . . . . . 9 1 9 9 0 0 0 0 0 0 0 0 3 0 0 0 0 0 : 0 6 7 0 0 0 0 0 0 7 5 7 0 0 0 0 0 1 - 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 G 0 . . . . . . . . . . . . . . . . D . 5 5 5 0 0 0 0 0 1 2 0 0 0 0 0 0 G 3 8 6 6 0 0 0 0 0 9 7 1 0 0 0 0 0 T

0 G D G T 1 G D G T 2 G D G T 3 c r e n c r e n ' G D G T I a G D G T I I a G D G T I I I

9

0 . 6 5 0 . 6 7 0 . 7 0 0 . 7 4 0 . 6 7

9 0 3 0 9 1

0 . 7 6

0 . 7 5

0 . 6 9

0 . 1 7

0 . 1 0

0 . 2 7

0 . 1 3

0 . 1 3

0 . 1 4

0 . 7 3

0 . 1 8

0 . 1 0

0 . 3 0

0 . 1 8

0 . 1 8

0 . 2 0

0 . 1 5 0 . 1 9 0 . 1 9

0 . 0 8 0 . 1 5 0 . 1 4

0 . 3 8 0 . 3 2 0 . 2 8

0 . 2 6 0 . 1 9 0 . 1 5

0 . 2 5 0 . 1 9 0 . 1 5

0 . 2 7 0 . 2 3 0 . 1 9

0 . 7 7

0 . 7 6

0 . 7 7

0 . 7 9

0 . 7 3

0 . 7 2

0 . 5 3

0 . 3 2

0 . 3 9

0 . 4 3

0 . 2 6

0 . 0 1

0 . 0 5

0 . 6 8

0 . 5 8

0 . 5 8

0 . 5 6

6 5 7 1

0 . 2 6

0 . 3 4

0 . 2 2

0 . 4 3

0 . 2 5

0 . 5 8

0 . 5 7

0 . 5 6

0 . 9 8

0 . 1 8

0 . 3 5

0 . 2 3

0 . 4 4

0 . 2 9

0 . 5 7

0 . 5 6

0 . 5 5

0 . 9 8

0 . 9 8

0 . 4 5 0 . 3 2 0 . 2 7

0 . 3 2 0 . 1 8 0 . 1 5

0 . 5 4 0 . 4 3 0 . 3 9

0 . 3 0 0 . 3 5 0 . 3 3

0 . 6 0

0 . 6 0

0 . 5 9

0 . 9 4

0 . 9 4

0 . 9 5

0 . 6 2

0 . 6 1

0 . 5 9

0 . 9 9

0 . 9 6

0 . 9 8

0 . 9 4

0 . 5 8

0 . 5 6

0 . 5 5

0 . 9 5

0 . 9 4

0 . 9 5

0 . 9 1

0 . 9 5

0 . 4 1

0 . 2 7

0 . 2 6

0 . 2 4

0 . 1 7

0 . 1 0

0 . 1 1

0 . 1 7

0 . 1 7

0 . 1 5

0 . 2 4

0 . 2 6

0 . 1 5

0 . 0 8

0 . 0 9

0 . 1 5

0 . 1 3

0 . 1 2

0 . 9 6

0 . 0 9

0 . 1 2

0 . 3 5

0 . 3 8

0 . 4 0

0 . 3 4

0 . 3 8

0 . 3 8

0 . 6 3

0 . 1 5 0 . 1 5 0 . 1 7

0 . 5 1

0 . 1 0

0 . 2 9

0 . 4 0

0 . 3 2

0 . 4 8

0 . 3 2

0 . 4 6

0 . 0 2

0 . 7 6

0 . 6 7

0 . 6 5

0 . 6 0

0 . 3 2

0 . 5 5

0 . 4 8

0 . 5 9

0 . 3 0

0 . 2 3

0 . 0 5

0 . 0 8

0 . 2 2

0 . 4 3

0 . 4 0

0 . 3 7

0 . 2 9

0 . 1 7

0 . 3 9

0 . 4 0

0 . 3 6

0 . 0 7

0 . 0 7

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 4 6

0 . 5 5

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 4 0

0 . 5 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 2 0

0 . 2 6

0 . 0 1

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 2 0

0 . 3 2

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 2 5

0 . 3 6

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

0 . 2 0

0 . 1 9

0 . 4 1

0 . 1 8

0 . 0 0

0 . 0 0

0 . 4 0

0 . 3 4

0 . 6 6

0 . 4 4

0 . 0 0

0 . 0 0

0 . 0 1

0 . 0 0

0 . 0 1

0 . 0 1

0 . 7 3

0 G D G T 1 G D G T 2 G D G T 3 c r e n c r e n ' G D G T I a G D G T I I a G D G T I I I

a O H G D G T 0 1 3 1 8 O H G D G T 1 1 3 1 6 O H G D G T 2 1 3 1 4 2 O H G D G T 0

a O H G D G T 0 0 . 7 5

0 . 7 7

0 . 7 8

0 . 1 7

0 . 1 9

0 . 2 8

0 . 1 5

0 . 1 5

0 . 1 9

0 . 1 8

0 . 2 7

0 . 1 4

0 . 3 9

0 . 3 7

0 . 5 9

0 . 5 7

0 . 5 4

0 . 9 8

0 . 9 4

0 . 9 5

0 . 9 2

0 . 9 9

0 . 9 4

0 . 1 7

0 . 1 1

0 . 3 9

0 . 7 5

0 . 8 2

0 . 7 7

0 . 1 7

0 . 1 5

0 . 3 0

0 . 1 6

0 . 1 6

0 . 1 9

0 . 2 2

0 . 3 4

0 . 2 2

0 . 4 6

0 . 3 5

0 . 5 9

0 . 5 7

0 . 5 4

0 . 9 7

0 . 9 7

0 . 9 6

0 . 9 5

0 . 9 8

0 . 9 3

0 . 1 8

0 . 1 3

0 . 3 6

0 . 9 8

0 . 7 2

0 . 8 2

0 . 7 5

0 . 1 2

0 . 1 4

0 . 2 4

0 . 1 0

0 . 1 0

0 . 1 3

0 . 2 6

0 . 2 9

0 . 1 7

0 . 4 1

0 . 3 2

0 . 6 1

0 . 5 9

0 . 5 7

0 . 9 7

0 . 9 7

0 . 9 6

0 . 9 4

0 . 9 7

0 . 9 3

0 . 1 1

0 . 0 6

0 . 4 0

0 . 9 7

0 . 9 9

0 . 7 9

0 . 1 4

0 . 2 0

0 . 2 1

0 . 0 6

0 . 0 7

0 . 1 2

0 . 2 5

0 . 1 8

0 . 0 5

0 . 3 1

0 . 3 8

0 . 9 2

0 . 1 8

0 . 1 0

0 . 3 6

0 . 9 8

0 . 9 6

0 . 7 6

0 . 8 1

0 . 6 3

0 . 6 0

0 . 5 7

0 . 9 6

0 . 9 3

0 . 9 3

0 . 8 8

0 . 9 7

0 . 0 0

0 . 0 0

0 . 0 0

0 . 0 0

1 3 1 8 O H G D G T 1

0 . 0 0

0 . 0 0

0 . 0 0

1 3 1 6 O H G D G T 2

0 . 0 0

0 . 0 0

1 3 1 4 2 O H G D G T 0

0 . 9 7

0 . 0 0

1 3 3 4

1 3 3 4

0 B . I 7 T 1

0 . 5 2

0 . 6 3

0 . 5 1

0 . 1 1

0 . 7 7

0 . 6 6

0 . 6 7

0 . 6 5

0 . 2 6

0 . 6 0

0 . 4 7

n n = T C C 5 O O T / 1 7 2 C S N 7

n T C C O O T / 1 2 C S N 7

n C 2 3

n C 2 3

n C 2 5

n C 2 5

n C 2 7

n C 2 7

n C 2 9

n C 2 9

n P C P a 3 a q 1 q '

n C 3 1

0 . 6 6 n C 2 3 / ( n C 2 3 + n C 2 5 )

0 . 4 3

d i p l o p t e n e

0 . 4 2

n C 2 5 : 1

P P a a q q '

0 . 4 3

n C 2 7 : 1

d i p l o p t e n e

0 . 4 1

n C 2 9 : 1

n C 2 5 : 1

0 . 5 5

G D G T 0

n C 2 7 : 1

0 . 5 0

G D G T 1

n C 2 9 : 1

0 . 5 1

G D G T 2

G D G T 0

0 . 5 8

G D G T 3

G D G T 1

0 . 5 6

c r e n

G D G T 2

0 . 5 1

c r e n '

G D G T 3

0 . 8 2

G D G T I a

c r e n

0 . 8 0

G D G T I I a

c r e n '

0 . 3 5

G D G T I I I a

G D G T I a

0 . 5 4

O H G D G T 0

0 . 5 5

O H G D G T 1

0 . 4 8

O H G D G T 2

0 . 4 9

B I T

2 O H G D G T 0

n 1 1 1 1 3 = 3 3 3 3 B 1 1 1 4 I 5 8 6 4 T 7

G D G T I I a

G D G T I I I a

O H G D G T 0

O H G D G T 1

O H G D G T 2

2 O H G D G T 0

1 3 1 8

1 3 1 6

1 3 1 4

1 3 B 3 I 4 T

1 . 8 0 E 1 8

O 2 0 . 8 6 T 9 O 3 C 2

0 . 9 2 3 T 7 S 3

0 . 3 C 4 / 4 N 2

n C 1 7 n C 2 3

0 . 1 7 4 7 6 0 . 4 6 7

1 . 3 9 E 2 4 1 . 2 3 E 1 7

0 . 8 5 9 1 7 0 . 0 7 7 9 7 4 0 . 0 8 9 0 0 3 0 . 2 8

0 . 0 0 8 7 4 9 3

0 . 1 9 3 5 3

0 . 5 6 4 2 6

0 . 5 1 0 2 9

0 . 1 8 5 3 1

0 . 1 7 7 9 8

0 . 2 2 6 5 0 . 4 7

0 . 2 1 1 7 7 0 . 4 9 8

0 . 0 9 0 2 2

0 . 0 0 0 2 4 6 9 0 . 0 2 8 6 9 2 0 . 0 0 0 2 1 6 0 9

0 . 1 1 3 7 8

7 . 8 1 E 0 5

0 . 9 2 5 9 0 . 0 1 2

0 . 0 1 1 0 1 8

0 . 0 0 6 7 0 9 7

0 . 0 0 3 3 7 3 5

0 . 3 4 1 8 2

0 . 3 4 1 4

0 . 0 0 6 1 4 6 7

0 . 0 0 3 3 1 0 7

0 . 2 8 4 9 2 0 . 0 0 0 7 5 7 7 4

8 . 3 2 E 0 5

3 . 7 3 E 0 5

4 . 8 1 E 0 5

0 . 7 1 4 8 2 0 . 0 0 0 9 1 2 2 2

0 . 8 3 1 8 8 . 1 3 E

0 . 4 9 5 6 5 1 . 2 2 E

0 . 0 9 6 6 7 5 8 . 6 7 E

0 . 0 5 3 9 6 2 4 . 2 8 E

0 . 9 4 6 0 9 0 . 0 2 7 7 5 6

0 . 0 2 0 1 8 6 0 . 0 2 2 3 8 5

0 . 2 9 7 7 1

6 . 6 2 E 0 5

0 . 2 3 3 3 4

0 . 0 1 5 3

4 . 0 7 E 1 0 3 . 3 9 E 1 3

0 . 1 6 6 2 7

5 . 2 9 E 0 5

2 . 1 7 E 1 2

0 . 0 6 1 8 7 1

0 . 1 8 9 4 2

0 . 0 0 3 4 3 9 8

0 . 8 6 8 5 4

0 . 9 0 9 0 2

0 . 8 3 9 6 4

0 . 1 5 7 9 9

0 . 2 1 9 7 6

0 . 1 7 7 1 8

0 . 2 7 7 8 7

0 . 1 6 4 8 3

0 . 1 6 5 5 2

6 . 0 0 E 0 5

0 . 1 2 3 7 8 5 . 8 6 E

0 . 0 5 5 6 4 8 . 6 6 E

6 . 5 5 E 0 7 0 . 0 0 2

0 . 8 6 0 5 3 0 . 0 8 8

0 . 8 9 8 9 8 0 . 0 5 9

0 . 7 0 3 3 4 0 . 0 2 8

0 . 4 5 3 8 9 0 . 0 1 3

0 . 4 7 4 5 7 0 . 0 4 3

0 . 4 5 8 3 1 0 . 0 2 4

0 . 5 6 4 2 5 0 . 0 0 3

0 . 2 6 2 3 7 0 . 0 1 5

0 . 2 8 4 9 1 0 . 0 3 5

0 . 4 7 2 8 8 7 . 1 7 E

0 . 0 0 5 6 4 3 8

2 . 3 0 E 0 9 4 . 2 3 E 1 2

1 . 7 6 E 0 7 8 . 8 4 E 1 0

2 . 0 1 E 0 9 1 . 1 6 E 1 1

4 . 1 8 E 0 8 5 . 3 6 E 1 2

1 . 3 7 E 0 8 2 . 0 1 E 1 1

1 . 5 4 E 0 9 2 . 9 3 E 1 2

4 . 8 8 E 1 1 2 . 8 8 E 1 2

9 . 2 9 E 0 9 9 . 9 0 E 1 1

1 . 9 7 E 0 5 0 . 0 1 3 7 6 7

5 . 3 9 E 1 2

5 . 0 2 E 1 0

6 . 3 3 E 1 1

2 . 6 0 E 0 9

1 . 8 0 E 1 0

9 . 6 2 E 1 2

2 . 1 6 E 1 3

2 . 4 4 E 1 0

0 . 0 0 2 9 8 5

0 . 0 0 0 9 0 3 5 7 0 . 0 5 3 8 3 4

0 . 0 1 4 1 0 . 0 0 0 3 0 7 9 2

0 . 9 0 5 2 5 . 8 9 E

0 . 7 1 6 0 5

2 . 7 1 E 1 1 3 . 2 9 E 1 2

2 . 1 5 E 1 1 1 . 0 6 E 1 4

4 . 0 2 E 1 0 1 . 1 6 E 1 4

6 . 2 7 E 1 2 1 . 7 6 E 1 4

4 . 9 1 E 1 0 3 . 1 7 E 0 5

0 . 6 8 5 0 2

5 . 0 5 E 1 3

2 . 4 5 E 1 2

2 . 0 4 E 1 1

3 . 0 2 E 1 3

1 . 2 9 E 0 7

0 . 9 6 3 1 7

0 . 5 4 6 6 9

0 . 2 0 8 8 2

0 . 2 1 4 2 1

0 . 3 7 0 3

0 . 2 8 5 1 7

5 . 0 6 E 0 5

0 . 0 9 7 0 1 6 0 . 0 0 0

0 . 1 6 7 5 4 0 . 0 3 3

0 . 2 7 1 0 4 0 . 0 2 1

0 . 3 0 4 2 0 . 0 7 7

0 . 1 3 4 5 7 0 . 1 2 0

0 . 4 2 3 6 5 3 . 0 3 E

3 9 1 9 5 8 9 1 9 4 9 8

n C 2 5

0 . 3 3 4 3 7

n C 2 7

0 . 3 5 5 1 5

n C 2 9

0 . 3 8 1 9 1

n C 3 1

0 . 0 0 9 1 5 9 7

P a q P

0 . 3 0 7 0

0 . 1 2 8 2 3

0 . 3 5 8 6 9

0 . 1 2 8 3 4 0 . 1 4 4 0 9

0 . 3 8 2 6 1 0 . 4 3 3 4 1

0 . 2 9 1 5 9

0 . 0 4 9 4 6 4

0 . 3 0 2 0 8 -

0 . 3 6 2 0 9 -

- - - 3 3 2 0 6 0 1 7

0 . 4 9 7 2 7

0 . 0 2 8 7 6 4

0 . 9 7 0 8 8

0 . 5 1 7 6 7

0 . 0 9 2 0 9 5

0 . 9 5 4 7 5

0 . 9 9 1 9 2

0 . 5 1 1 3

0 . 2 2 2 1 9

0 . 8 9 3 6 5

0 . 9 4 1 3 1

0 . 4 2 7 4 4

0 . 2 5 6 6 5

0 . 6 1 1 7 8

0 . 7 5 2 3 7

0 . 2 4 8 9 3 0

0 . 2 0 6 2 3 -

0 . 7 8 3 4 6 0

5 . 1 7 E 5 1

0 . 7 6 8 2 1 0

1 . 3 0 E 2 7

1 . 5 0 E 1 1

1 . 6 2 E 3 4

1 . 3 9 E 1 3 2 . 7 6 E 1 6

0 . 9 6 7 4 8

0 . 7 9 5 8

0 . 7 1 4 1 1 0

0 . 8 4 0 8 4

0 . 6 0 3 1 8 0

0 . 2 7 5 1 9 0

- - 2 4 6 6 3 8 4 3 7 9 - - 9 1 1 7 7 9 1 1 7 5 1 2 1 0 1 3 3 0 9 8 3 7 9 1 9 9 3 9 2 5 2 5 8 0 0 3 6 . 0 2 9 . . . 0 0 0 0 0 0 . 0 0 . . 0 0 1 0 . . . . . 0 . . 2 2 0 6 3 3 0 4 2 1 3 1 4 1 2 3 4 2 E E 6 . 0 2 4 2 8 9 5 6 E E 0 - - 7 5 6 7 6 0 4 3 9 7 - - 0 1 1 9 5 9 2 0 4 6 5 0 0 0 0 1 2 0 7 2 1 8 5 8 3 9 8 2 6 9 9 0 . 4 8 0 0 1 3 0 . . 0 0 0 0 0 0 0 . 0 0 . . . 4 0 0 . . . . . . 0 . . 9 3 0 7 2 6 4 3 2 1 3 1 5 1 2 9 5 0 E E 7 9 5 2 6 5 9 6 4 5 E E 4 - - 1 2 9 2 2 4 1 8 9 9 - - 5 1 0 2 0 6 9 5 1 3 8 7 3 0 0 6 0 8 3 5 1 6 6 1 9 6 7 4 6 8 2 6 4 4 0 5 9 0 . . . 0 0 0 0 0 . 0 0 . . . 8 3 0 . . . . 0 . 0 . . 8 5 0 4 1 9 4 3 2 1 . 1 4 0 1 7 9 2 E E E 9 7 7 2 2 3 2 9 6 E E 6 - - - 9 1 6 2 9 7 2 1 5 - - 5 0 0 0 0 2 3 8 5 6 1 2 5 0 0 2 7 5 6 8 5 7 3 9 7 8 5 5 6 7 3 0 . 0 0 0 0 0 0 0 . 0 0 . . 0 0 . 0 0 0 0 . . 0 0 . 0 0 0 . . 0 . . . . 0 0 . 3 0 1 2 5 1 1 5 1 2 2 2 2 1 2 8 4 6 9 0 0 8 3 8 7 6 1 9 6 1 2 3 9 7 0 2 0 8 6 0 2 5 4 9 0 8 5 7 9 1 7 4 1 6 9 8 8 0 3 8 6 4 5 6 7 2 3 1 6 4 9 2 1 4 9 0 0 0 . 0 0 4 0 0 . 0 . 0 0 0 . 1 . . 0 0 . . 0 . 0 0 . . 0 . 0 9 . . 0 0 0 0 0 0 0 0 0 1 0 0 7 1 6 1 5 1 7 4 1 4 1 7 3 E 2 2 8 6 7 0 3 3 6 2 9 E 1 - 6 6 3 7 9 4 6 1 3 0 1 - 0 3 8 2 5 4 5 5 2 8 5 6 7 0 4 4 4 8 3 9 2 2 1 4 9 7 2 5 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0

3 2 1 7 7 4 7 1 9 9 2

0 . 2 7 6 9 6

1 . 9 4 E 0 8

0 . 2 2 0 9 9

0 . 4 5 5 1 5

0 . 6 5 2 0 2

0 . 2 6 3 4 8

0 . 2 3 3 7

0 . 4 5 4 5 7

0 . 6 0 9 7 9

0 . 1 5 7 4

0 . 1 6 5 4 7

0 . 3 5 1 2 4

0 . 3 8 5 9 9

1 . 5 4 E 0 8 4 . 0 3 E 0 8

0 . 1 8 5 7 5

0 . 1 0 1 9 3

0 . 0 5 2 2 9 8

0 . 0 6 3 3 7 1

0 . 0 5 4 7 8 4

0 . 0 4 5 8 1 9 0

0 . 0 0 8 8 7 0 5 0

0 . 0 2 9 1 2 8 0

0 . 1 9 0 0 5 0

9 . 8 8 E 0 7 0

a . 0 0 q 1 . . ' 4 1 1 0 6 8 3 0 5 6 3 8 9 7

d i p l o p t e n e

n C 2 5 : 1

0 . 5 0 3 2

0 . 3 1 9 8 2

0 . 5 0 8 9 4

0 . 7 1 5 2 6

0 . 7 8 8 2 4

0 . 7 7 1 5 1

n C 2 7 : 1

0 . 6 9 3 1 2

n C 2 9 : 1 G D G T 0

0 . 6 2 7 4 7 0 . 6 9 4

0 . 7 6 5 1

0 . 7 6 2 7 3

0 . 7 0 5 6 0 . 7 5 5 0

0 . 7 1 2 6 8 0 . 7 3 6 9

. 1 7 6 3 6

0 . 3 8 1 1 8 0 . 0 2 2 4 1 6 0 . 0 1 5 4 7 8 0 . 0 2 7 4 0 4 0 . 1 8 9

0 . 2 5 4 9 4

. 7 0 5 8 5

0 . 6 0 3 9 9

0 . 3 9 6 3 8

0 . 0 2 3 7 9 6

0 . 2 2 7 7

. 7 1 0 2

0 . 3 7 8 6 5 0 . 0 8 0 4 3 2

. 6 4 0 5 8

0 . 4 3 7 2 6 0 . 0 9 2 8 6 2

. 5 1 4 0 8

0 . 5 6 7 8 6 0 . 0 9 1 3 6 7

. 2 6 8 3 8

. 9 6 6 1 2

. 7 3 8 0 5

0 . 4 7 7 9 8

0 . 0 4 7 2 9 2

0 . 2 8 8 0 4

0 . 2 0 4 9

0 . 0 4 5 2 7 8 0 . 0 5 4 3 2 7

0 . 0 1 7 1 9 5

0 . 2 5 0 9 6

0 . 1 1 1 9 8

0 . 1 2 3 6 1

0 . 1 2 0 6 7

0 . 2 6 0 8 5

0 . 2 4 3 1 7

0 . 0 9 4 5 0 2

0 . 0 5 1 5 4 8 0 . 1 0 1

0 . 2 9 0 0 7 0 . 3 2 6

0 . 1 6 2 4 6 0 . 1 9 5

0 . 1 6 3 9 6 0 . 1 8 7

0 . 1 4 6 6 4 0 . 2 0 6

0 . 2 1 8 3 6 0 . 1 7 9 9

0 . 3 1 5 7 0 . 3 6 1

0 . 1 9 3 0 8 0 . 2 4 9

. 6 8 8 1 5

0 . 2 9 3 9 6 0 . 1 4 1 4 4

0 . 1 4 3 1 9 0 . 0 9 7 9 2 8 0 . 3 0 6

. 4 8 4 4

. 0 6 0 9 3 9

. 0 9 5 5 0 1

. 0 8 5 7 4 4

. 0 1 4 7 0 8

. 1 6 9 4 4

. 2 5 7 4 3

0 . 0 5 8 1 6 2

0 . 0 2 9 1 4 6

. 0 1 5 5 1 2

. 0 0 0 1 3 6 3 1

0 . 0 2 4 0 7 1

0 . 0 0 7 2 8 6 6

0 . 0 1 1 1 1 9

0 . 0 0 1 3 7 8 5

0 . 0 2 2 6 1 2

. 0 0 2 1 1 9 3

. 3 0 4 9 2

. 1 0 0 1

. 2 1 0 3 5

. 7 3 4 4 4

0 . 6 0 9 4 9

0 . 0 0 4 2 0 3 8

0 . 0 0 6 8 7 3 3

0 . 0 1 6 7 5 1

0 . 0 0 4 0 0 9

0 . 2 8 7 9 5

0 . 4 6 8 6 3

0 . 0 2 0 2 4 3

7 . 6 4 E 5 1

1 . 6 1 E 3 3

2 . 5 6 E 0 6

2 . 1 7 E 0 6

3 . 7 9 E 0 6

6 . 3 4 E 0 7

2 . 2 8 E 0 7

2 . 1 4 E 0 6

0 . 0 4 4 8 0 3

0 . 0 8 1 0 3 2

0 . 6 3 0 8 3

1 . 4 5 E 0 6

1 . 5 3 E 0 6

4 . 8 4 E 0 7

1 . 6 0 E 0 7

1 . 9 7 E 3 4

5 . 0 1 E 0 6

3 . 4 0 E 0 6

5 . 5 6 E 0 6

6 . 5 4 E 0 7

4 . 4 3 E 0 7

5 . 5 9 E 0 6

0 . 0 4 7 5 6 9

0 . 0 6 9 6 1 1

0 . 5 2 3 4 5

3 . 3 7 E 0 6

3 . 0 9 E 0 6

1 . 2 3 E 0 6

6 . 5 6 E 0 7

4 . 9 6 E 0 6

5 . 4 9 E 0 6 2 . 5 3 E -

9 . 0 6 E 0 6 1 . 7 2 E -

1 . 6 9 E 0 6 4 . 7 4 E -

1 . 2 5 E 0 6 5 . 9 8 E -

1 . 0 0 E 0 5 3 . 5 4 E -

0 . 0 6 7 6 8 2 0 . 1 9 4 4

0 . 0 5 3 7 5 2 0 . 2 6 6 2

0 . 3 6 7 9 1 0 . 0 0 8 0

1 . 2 8 E 0 5 2 . 3 9 E -

1 . 3 7 E 0 5 4 . 0 2 E -

4 . 1 3 E 0 6 3 . 8 2 E -

4 . 2 1 E 0 6 1 . 6 7 E -

0 . 9 9 1 8 1

0 . 9 6 4 6 0 . 5 7 7 5

. 1 5 0 1 5

0 . 9 6 7 2 4 0 . 5 6 3 5

0 . 5 6 3 7

. 0 0 0 2 4 1 9 2 0 . 0 0 0 8 9 1 6 2 0 . 0 0 1 1 2 5 0 . 0 0 0 9 3 8 3 9 0 . 0 0 1 4 9 7 9 9 . 8 0 E -

9 8 6 5 1 0 3 1 9 5 0 . 0 9 6 6 3 2

G D G T 1

0 . 6 5 1 0 5

0 . 7 6 2 7 7

0 . 6 9 1 4 9

0 . 1 6 5 0 8

G D G T 2

0 . 6 6 8 0 2

0 . 7 4 9 3 2

0 . 7 2 5 0 4

0 . 1 8 1 2 7

G D G T 3

0 . 6 9 8 4 4

0 . 7 6 8 6 6

0 . 7 5 6 9 4

0 . 1 4 6 1 9

0 . 1 0 0 2 0 . 0 7 7 9 7 5

0 . 7 9 2 1

0 . 1 8 6 4 9

0 . 7 2 1 4 2 0 . 3 8

0 . 1 8 6 1 9 0 . 5 0 5

0 . 7 c 3 r 9 e 8 n 1

c r e n ' G D G T -

0 . 6 7 3 7 1 0 . 5 3 2

0 . 7 6 8 8

0 . 7 3 1 9 3 0 . 3 2

4 7 5 8 4

0 7 8 4 5 7 4 9 7

0 . 2 2 2 9 6

0 . 2 5 2 4 4

0 . 5 8 0 8 2

0 . 5 7 1 7

0 . 2 6 7 9 6

0 . 1 3 3 9 6

0 . 1 2 5 0 3

0 . 1 4 0 8 8

0 . 2 5 6 8

0 . 3 3 6 6 4

0 . 2 9 7 8 2

0 . 1 7 8 2 5

0 . 1 7 5 5 9

0 . 1 9 9 0 7

0 . 1 7 7 4 5

0 . 3 5 1 3 6

0 . 2 2 9 6 3

0 . 2 8 9 1 5

0 . 5 6 9 4 6

0 . 5 6 1 3 3

0 . 5 5 0 7

0 . 9 8 0 4

0 . 3 8 2 5 2

0 . 2 6 1 5 8

0 . 2 5 3 6 9

0 . 2 7 0 0 2

0 . 1 4 8 2 9

0 . 4 5 0 8 9

0 . 3 2 1 6 1

0 . 2 9 8 5 8

0 . 6 0 4 6 1

0 . 6 0 4 0 2

0 . 5 8 5 8 1

0 . 9 4 3 4 8

0 . 1 5 0 9 5

0 . 3 1 8 5 7

0 . 1 8 9 0 2

0 . 1 9 3 2 6

0 . 2 2 5 8

0 . 1 5 0 7 8

0 . 3 1 6 7 8

0 . 1 8 4 5 1

0 . 3 5 1 7 9

0 . 6 2 2 9 6

0 . 6 1 1 1 6

0 . 5 9 1 7 9

0 . 9 8 6 5 5

0 . 1 4 4 0 9 0 . 0 9 6

0 . 2 7 8 5 2 0 . 6 7 7

0 . 1 5 1 9 0 . 5 8 2

0 . 1 8 6 1 8 0 . 5 6 0

0 . 1 6 6 4 8 0 . 2 8 8

0 . 2 7 0 2 1 0 . 4 0 2

0 . 1 5 2 5 0 . 3 1 9

0 . 3 3 3 9 7 0 . 4 1 3

0 . 1 4 9 5 0 . 5 8 0

0 . 5 8 1 1 7 0 . 2 6

0 . 5 6 1 2 1 0 . 2 6

0 . 5 6 1 6 2

0 . 5 4 8 4 1 0 . 2 4

0 . 9 7 6 4 6

0 . 9 4 8 6 9 0 . 1 7

3 4 2 4 2 7 6 8 8 0 8 5 9 8 3 0 5 2 1 5 . . . . . 0 0 0 9 3 9 0 . . 0 1 6 3 2 4 5 3 E E E E 6 4 1 - - - - 3 9 3 4 2 3 2 6 3 4 1 8 2 8 7 5 8 0 2 1 4 . 0 . . . 0 0 . 2 6 9 . 0 0 9 7 9 1 3 . 2 8 E E E 9 4 0 1 - - - 9 9 4 1 2 3 3 6 5 1 5 8 8 0 8 7 9 0 1 2 . 0 0 . . 0 0 0 . . 1 6 . . 0 9 9 0 1 1 2 9 4 4 E E 9 5 0 4 5 - - 5 7 9 9 0 2 2 3 9 5 3 2 7 2 3 4 7 0 4 . 0 0 . 0 0 0 . 0 . 0 . . 0 9 . 9 0 1 3 3 6 9 4 E 9 2 6 1 7 1 - 5 2 6 1 6 6 3 6 1 2 9 8 7 0 4 7 1 0 . 0 0 0 0 0 0 . . . 0 . . 0 9 9 9 . 2 3 3 4 5 0 9 5 6 1 3 2 6 5 0 2 9 3 3 9 2 6 8 4 6 3 7 7 2 3 1 - - - - 4 1 0 0 0 0 0 . . . . . . . 5 1 0 1 1 1 1 6 3 9 1 7 7 5 E E

3 3 3 3 0 9 7 6 1 6

3 . 1 4 E 2 8

6 . 2 6 E 3 4

6 . 3 7 E 3 5

5 . 7 9 E 2 5

8 . 1 3 E 0 5

2 . 3 2 E 3 0

3 . 5 7 E 3 2

2 . 6 3 E 3 3

1 . 6 6 E 2 5

4 . 7 9 E 0 5

5 . 8 2 E 2 4

7 . 6 9 E 2 9

1 . 9 2 E 2 6

1 . 9 3 E 1 9

2 . 6 4 E 0 6

5 . 7 4 E 4 8

3 . 9 8 E 3 8

6 . 5 5 E 3 6

7 . 2 1 E 3 5

7 . 3 1 E 0 6

1 . 3 2 E 2 6 0 . 2 0 2

8 . 8 1 E 2 6 0 . 1 8 8

5 . 0 6 E 2 6 0 . 4 1 4

1 . 7 2 E 2 4 0 . 1 8 4

4 . 4 6 E 0 5 9 . 8 0 E

I 9 4 6 7 9 4 3 6 1 7 a 9 5 4 2 9 2 4 2 9 1 7 5 9

G D G T I I a

0 . 4 2 7 7 5 0 . 0 0 6 2 5 4 8

0 . 2 5 6 7 8

0 . 3 2 3 5 1

G D 0 0 G . . T 0 0 4 5 I 9 4 I 2 9 I 4 0 a 1 2 O H G D G T - 0 0 0 0 . . . 7 7 7 1 4 6 8 3 6 7 4 1 1 5 7 8 8 3 8 O H G D G T - 0 0 0 1 . . . 7 8 7 1 4 1 7 3 8 5 0 1 6 9 3 6 4 7 6 O - 0 0 H 0 . .

0 . 4 6 0 9 6

0 . 0 1 6 1 3 1

0 . 0 8 1 5 0 5

0 . 2 2 1 9 7

0 . 1 6 9 0 1

0 . 1 6 7 0 6 0

0 . 7 6 1 8 5

0 . 6 7 3 7 9

0 . 4 2 6 6 2

0 . 4 0 0 8 4

0 . 1 8 5 3 2

0 . 1 4 8 2 6 0

0 . 6 5 4 5

0 . 5 9 6 8 2

0 . 3 7 0 4 4

0 . 2 9 3 8 3

0 . 2 8 2 3

0 . 1 4 6 4 7

0 . 1 5 0 6

0 . 1 8 9 7 7

0 . 3 0 4 5 7 0

0 . 1 6 4 6 5 0

0 . 1 6 0 2 7 0

0 . 1 8 6 2 1 0

0 . 3 1 5 1 9

3 2 7 6 3 3 4 9 6 4 8 5 7 4 0 4 9 4 1 9 - - 0 0 0 0 - 0 0 . . . 0 . 0 . . 0 5 4 . 2 . 2 1 8 4 8 3 3 2 5 4 0 5 4 0 3 4 6 9 9 0 0 1 0 2 8 7 6 3 4 6 6 1 7 3 7

0 . 1 6 8 2 6

0 . 3 8 5

0 . 1 7 7 8 1

0 . 2 6 5 6 3

0 . 2 1 8 8 5 0 .

0 . 3 4 3 6 2 0

0 . 3 9 8 8 3

0 . 0 6 9 1 0 7

0 . 1 3 8 3

0 . 3 7 3 5 8

0 . 2 2 0

0 . 3 5 4 1 7 0

0 . 0 6 5 0 2 4

0 . 5 8 8 8 8

0 . 5 8 7 8 2 0 .

0 . 0 8 6 2 6 2

0 . 5 7 1 8 6

0 . 5 7 3 6 6 0 .

0 . 1 2 1 5 1

0 . 5 4 2 9 7

0 . 5 4 1 4 0 .

0 . 3 4 7 4 8

0 . 9 7 8 4 1

0 . 9 7 3 9 3 0 .

0 . 3 8 4 6 4

0 . 9 4 4 3 4

0 . 9 6 5 8 2 0 .

3 4 3 4 7 0 9 6 1 7 5 8 0 . 0 9 2 0 8 5

0 . 4 0 0 1 5

0 . 9 5 3 6 5

0 . 9 6 0 3 0 .

0 . 1 5 2 3 4

0 . 3 4 2 5 6

0 . 9 1 9 4 8

0 . 9 4 7 1 9 0 .

0 . 1 3 3 5

0 . 3 7 8 8 3

0 . 9 8 9 5 6

0 . 9 7 6 0 6 0 .

0 . 1 2 2 7 9

- - 0 6 3 6 3 0 3 5 7 5 1 2 7 5

1 . 1 1 E 1 0

0 . 9 5 9 9 4

0 . 3 8 3 9 5

0 . 6 3 4 9 7

0 . 7 3 0 6

0 . 9 3 5 9 9

0 . 1 7 1 5 3

0 . 1 1 4 6 5

0 . 9 3 1 2 5 0 .

0 . 1 7 6 6 6 0

0 . 1 2 8 4 5 0

0 . 3 8 9 2 4

0 . 3 6 0 9 9 0 .

0 . 3 9 5 7 7

0 . 3 4 0 9 8

0 . 6 5 6 6 5

0 . 4 3 9 0 1

6 . 1 0 E 1 4

0 . 0 0 2 7 6 6 3

0 . 0 0 5 8 0 2 4

0 . 0 0 2 2 9 7 8

0 . 0 0 5 3 3 3 5

0 . 0 0 6 7 8 2 4

6 . 4 3 E 4 0

4 . 7 2 E 3 5

1 . 5 3 E 4 3

1 . 5 6 E 0 5

9 . 5 9 E 4 5

6 . 4 8 E 3 3 5 .

1 . 1 1 E 0 5 0 .

0 . 9 7 9 4 3 0 0 . .

G D G T 2

. 7 1 5 4

8 1 5 2 8

1 3 1 4 2 O H G D G T - 0 0 0 . . 1 7 8 3 6 1 3 1 2 4 2 1 3 5 0 0 . . 7 5 1 2 B 2 1 I 9 6 T 6 1

7 4 9 2 1

0 . 7 8 9 2 4 0 . 6 3 2 7 6

. 1 2 0 9 1

. 1 3 8 5

. 2 3 5 9 9

. 1 0 0 9 1

. 1 0 1 0 4

. 1 2 5 7 7

0 . 1 4 4 0 1

0 . 2 0 0 6 2

0 . 2 0 7 9

0 . 0 6 1 0 2 7

0 . 0 6 9 0 5

0 . 1 1 7 0 2

0 . 5 1 0 0 2

0 . 1 0 8 0 6

0 . 7 6 8 3 3

0 . 6 6 2 8 7

0 . 6 6 6 2 9

0 . 6 5 1 6 2

2 5 8 3 9

. 2 8 9 1 8

. 1 6 8 4 6

. 3 1 5 6 9

6 0 9 5 6

5 9 1 9 8

5 6 7 6 4

9 7 1 6 8

0 . 2 4 7 5 5

0 . 1 7 6 1 1

0 . 0 4 5 9 2 6

0 . 3 7 5 4

0 . 2 5 5 8 1

0 . 5 9 6 2 5

0 . 4 6 7 9 6

0 . 4 2 8 1 8

0 . 6 2 9 0 4 0 . 4 2 0 5 5

0 . 6 0 3 9 5 0 . 4 2 6 5 2

0 . 5 6 7 2 4 0 . 4 1 0 9 1

0 . 9 5 7 9 6 0 . 5 4 8 9 5

9 6 8 5 8

9 6 3 9 5

9 3 5 0 8

9 7 1 1 1

0 . 9 2 6 2 0 . 4 9 7 8 8

0 . 9 2 9 5 9 0 . 5 1 1 4 2

0 . 8 8 0 1 6 0 . 5 7 6 8 5

0 . 9 6 8 4 4 0 . 5 5 5 4 2

9 3 2 6 7

0 . 9 2 3 1 0 . 5 1 3 2 1

. 1 1 0 2 2

. 0 6 0 1 6 1

3 9 5 9 5

9 6 8 9 3

9 8 6 3 1

0 . 1 7 8 2 5

0 . 1 0 4 5 4

0 . 3 6 4 3 3

0 . 8 0 2 5 1

0 . 3 5 4 7 1

0 . 9 8 4 8 5 0 . 5 3 8 3 4

0 . 9 6 2 7 3 0 . 5 4 6 1 8

0 . 8 1 6 5 3

1 4 E 3 4

0 . 9 6 6 0 6 0 . 4 7 8 2 5

Table 3. Percentages of crenarchaeol and branched GDGTs in soil samples from the drainage basin of the Baltic Sea (see for location Fig. 1). The values of the BIT index are shown as well. Sample

Abundance (%) GDGT IIa

BIT

Reference

crenarchaeol

GDGT Ia

GDGT IIIa

a

8.7

65.7

23.6

1.9

0.91

Peterse et al., 2012; unpublished data

b

6.3

60.8

29.4

3.5

0.94

Peterse et al., 2012; unpublished data

c

2.6

53.7

39.1

4.6

0.97

Peterse et al., 2012; unpublished data

d

1.6

68.2

27.9

2.3

0.98

Peterse et al., 2012; unpublished data

e

0.4

73.1

25.1

1.4

1.00

Peterse et al., 2012; unpublished data

0 0 0 1 6 8 1 4

9 . 7 1 E 0 5 0 . 4 9 3 1 8

f

0.8

66.8

29.7

2.7

0.99

Peterse et al., 2012; unpublished data

Table 4. Similarity of slopes and intercepts between the calibration curves (OH-GDGT% and OH-GDGT1318/crenarchaeol indices versus annual mean SST or bottom temperature) from Fietz et al. (2013) and this study (Fig. 7). A t-test probability value < 0.05 (in italics) indicates that the slopes/intercepts are significantly different from each other (Cohen et al., 2003; Wuensch, 2013). Tests for the intercepts were not performed when the homogeneity of slope tests were not fulfilled (i.e. no parallel linear relationship between the covariate and the dependant variable) as an invalid analysis of the intercepts may result in inaccurate data interpretation (Hinkle et al., 2003). Annual mean SST Similarity of slopes degree of freedom

tvalue

probability

Similarity of intercepts

Dependant variable

Equations

t-value

probability

OH-GDGT% OHGDGT1318/crenarchaeol

d and f

65

1.416

0.162

-62.527

0.000

e and g

65

1.252

0.215

2.849

0.006

Bottom temperature Similarity of slopes degree of freedom

Dependant variable

Equations

OH-GDGT% OHGDGT1318/crenarchaeol

d and h

50

e and i

50

tvalue 1.146 2.239

probability

Similarity of intercepts t-value

probability

0.257

-44.477

0.000

0.030

-

-

Highlights 

Identification of biomarkers in sediments of the Baltic Sea and the Skagerrak region



Development of OH-GDGT-based water temperature calibrations for the Baltic Sea



n-C27:1 and n-C29:1 alkenes as potential biomarkers for phototrophic organisms



Paq’ ratio as potential proxy for freshwater to brackish coastal environments

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