Biomarker distributions and calculated sea surface temperatures from the North Pacific Ocean

In order to study the modern sea surface characteristics of the sub-polar North Pacific and the Bering Sea, i.e. sea surface temperature (SST) and sea ice cover, surface sediments recovered during the RV Sonne Expedition 202 in 2009 were analysed. To distinguish between marine and terrestrial organic carbon, hydrogen index values, long chain n-alkanes and specific sterols have been determined. The results show that in the Bering Sea, especially on the sea slope, the organic carbon source is mainly caused by high primary production. In the North Pacific, on the other hand, the organic material originates predominantly from terrestrial higher plants, probably related to dust input from Asia. SST has been reconstructed using the modified alkenone unsaturation index. Calibration from Müller et al. (1998, doi:10.1016/S0016-7037(98)00097-0) offers the most reliable estimate of mean annual temperature in the central North Pacific but does not correlate with mean annual temperature throughout the study area. In the eastern North Pacific and the Bering Sea, the Sikes et al. (1997, doi:10.1016/S0016-7037(97)00017-3) calibration seems to be more accurate and matches summer SST. The distribution of the novel sea ice proxy IP25 (highly branched C25 isoprenoid alkene) in surface sediments is in accord with the modern spring sea ice edge and shows the potential of this proxy to track past variation in sea ice cover in the study area.

Geochemical biomarker analyses on sediment cores PS51/154-11 and PS51/159-10 from the western Laptev Sea (Arctic Ocean)

Multi-proxy biomarker measurements were applied on two sediment cores (PS51/154, PS51/159) to reconstruct sea ice cover (IP25), biological production (brassicasterol, dinosterol) and river run-off (campesterol, beta-sitosterol) in the western Laptev Sea over the last ~17 ka with unprecedented temporal resolution. The absence of IP25 from 17.2 to 15.5 ka, in combination with minimum concentration of phytoplankton biomarkers, suggests that the western Laptev Sea shelf was mostly covered with permanent sea ice. Very minor river run-off and restricted biological production occurred during this cold interval. From ~16 ka until 7.5 ka, a long-term decrease of terrigenous (riverine) organic matter and a coeval increase of marine organic matter reflect the gradual establishment of fully marine conditions in the western Laptev Sea, caused by the onset of the post-glacial transgression. Intensified river run-off and reduced sea ice cover characterized the time interval between 15.2 and 12.9 ka, including the Bølling/Allerød warm period (14.7-12.9 ka). Prominent peaks of the DIP25 Index coinciding with maximum abundances of subpolar foraminifers, are interpreted as pulses of Atlantic water inflow on the western Laptev Sea shelf. After the warm period, a sudden return to severe sea ice conditions with strongest ice-coverage between 11.9 and 11 ka coincided with the Younger Dryas (12.9-11.6 ka). At the onset of the Younger Dryas, a distinct alteration of the ecosystem (reflected in a distinct drop in terrigenous and phytoplankton biomarkers) was detected. During the last 7 ka, the sea ice proxies reflect a cooling of the Laptev Sea spring/summer season. This cooling trend was superimposed by a short-term variability in sea ice coverage, probably representing Bond cycles (1500 ± 500 ka) that are related to solar activity changes. Hence, atmospheric circulation changes were apparently able to affect the sea ice conditions on the Laptev Sea shelf under modern sea level conditions.

Lipid biomarkers in the Enol Lake (Asturias, Northern Spain): coupled natural and human induced environmental history

The lipid content of three cores from Lake Enol (Picos de Europa National Park, Asturias, Northern Spain) was studied. The n-alkane profiles indicated a major input from terrigenous plants [predominance of high molecular weight (HMW) alkanes] since ca. 1695 AD to the water body, although the uppermost cm revealed a predominance of organic matter (OM) derived from algae, as the most abundant alkane was C17. Three units revealing different environmental conditions were defined. Unit A (ca. 1695–1860 AD) in the lowermost parts of ENO13-10 (< 12 cm) and ENO13-15 (< 28 cm) was identified and was characterized by higher OM input and evidence of minimal degradation (high CPI values, predominance of HMW n-alkanoic acids and good correspondence between the predominant n-alkane and n-alkanoic acid chains). These findings could be linked to the Little Ice Age, when cold and humid conditions may have favored an increase in total organic carbon (TOC) and n-alkane and n-alkanoic acid content (greater terrigenous OM in-wash), and may have also reduced bacterial activity. In Unit B (ca. 1860–1980 AD) the lack of correspondence between the n-alkane and n-alkanoic acid profiles of ENO13-10 (12–4 cm) and ENO13-15 (28–8 cm) suggested a certain preferential microbial synthesis of long chain saturated fatty acids from primary OM and/or bacterial activity, coinciding with a decrease in OM input, which could be linked to the global warming that started in the second half of the 19th century. In ENO13-7 the low OM input (low TOC) was accompanied by some bacterial degradation (predominance ofHMWn-alkanoic acids but with a bimodal distribution) in the lowermost 16–5 cm. Evidence of considerable phytoplankton productivity and microbial activity was especially significant in Unit C (ca. 1980–2013 AD) identified in the uppermost part of all three cores (5 cm in ENO13-7, 4 cm in ENO13-10 and 8 cm in ENO13-15), coinciding with higher concentrations of n-alkanes and n-alkanoic acids, which were considered to be linked to warmer and drier conditions, as well as to greater anthropogenic influence in modern times. Plant sterols, such as b-sitosterol, campesterol and stigmasterol, were significantly present in the cores. In addition, fecal stanols, such as 24-ethylcoprostanol from herbivores, were present, thereby indicating a continuous and significant pollution input derived from these animals since the 17th century, being more important in the last 20 years.

Terpenoid biosynthesis from 1-deoxy-d-xylulose in higher plants by intramolecular skeletal rearrangement

The incorporation of [1-13C]- and [2,3,4,5-13C4]1-deoxy-d-xylulose into β-carotene, lutein, phytol, and sitosterol in a cell culture of Catharanthus roseus was analyzed by NMR spectroscopy. The labeling patterns of the isoprene precursors, isopentenyl pyrophosphate and dimethylallyl pyrophosphate, were obtained from the terpenes by a retrobiosynthetic approach. 13C Enrichment and 13C13C coupling patterns showed conclusively that 1-deoxy-d-xylulose and not mevalonate is the predominant isoprenoid precursor of phytol, β-carotene, and lutein. Label from 1-deoxyxylulose was also diverted to phytosterols to a minor extent (6% relative to carotene and phytol formation). The data demonstrate that the formation of isopentenyl pyrophosphate from pentulose occurs strictly by an intramolecular rearrangement process.

Brassinosteroid/Sterol Synthesis and Plant Growth as Affected by lka and lkb Mutations of Pea1

The dwarf pea (Pisum sativum) mutants lka and lkb are brassinosteroid (BR) insensitive and deficient, respectively. The dwarf phenotype of the lkb mutant was rescued to wild type by exogenous application of brassinolide and its biosynthetic precursors. Gas chromatography-mass spectrometry analysis of the endogenous sterols in this mutant revealed that it accumulates 24-methylenecholesterol and isofucosterol but is deficient in their hydrogenated products, campesterol and sitosterol. Feeding experiments using 2H-labeled 24-methylenecholesterol indicated that the lkb mutant is unable to isomerize and/or reduce the Δ24(28) double bond. Dwarfism of the lkb mutant is, therefore, due to BR deficiency caused by blocked synthesis of campesterol from 24-methylenecholesterol. The lkb mutation also disrupted sterol composition of the membranes, which, in contrast to those of the wild type, contained isofucosterol as the major sterol and lacked stigmasterol. The lka mutant was not BR deficient, because it accumulated castasterone. Like some gibberellin-insensitive dwarf mutants, overproduction of castasterone in the lka mutant may be ascribed to the lack of a feedback control mechanism due to impaired perception/signal transduction of BRs. The possibility that castasterone is a biologically active BR is discussed.

Biomarker distributions in surface sediments from the Kara and Laptev Seas (Arctic Ocean)

Studies of spatial and temporal changes in modern and past sea-ice occurrence may help to understand the processes controlling the recent decrease in Arctic sea-ice cover. Here, we determined concentrations of IP25, a novel biomarker proxy for sea ice developed in recent years, phytoplankton-derived biomarkers (brassicasterol and dinosterol) and terrigenous biomarkers (campesterol and ß-sitosterol) in the surface sediments from the Kara and Laptev seas to estimate modern spatial (seasonal) sea-ice variability and organic-matter sources. C25-HBI dienes and trienes were determined as additional paleoenvironmental proxies in the study area. Furthermore, a combined phytoplankton-IP25 biomarker approach (PIP25 index) is used to reconstruct the modern sea-ice distribution more quantitatively. The terrigenous biomarkers reach maximum concentrations in the coastal zones and estuaries, reflecting the huge discharge by the major rivers Ob, Yenisei and Lena. Maxima in phytoplankton biomarkers indicating increased primary productivity were found in the seasonally ice-free central part of the Kara and Laptev seas. Neither IP25 nor PIP25, however, show a clear and simple correlation with satellite sea-ice distribution in our study area due to the complex environmental conditions in our study area and the transportation process of sea-ice diatom in the water column. Differences in the diene/IP25 and triene/IP25 ratios point to different sources of these HBIs and different environmental conditions. The diene/IP25 ratio seems to correlate positively with sea-surface temperature, while negatively with salinity distributions.

Biogenic particle and biomarker flux from a mooring time-series at AWI HAUSGARTEN

Since 2000 long-term measurements of vertical particle flux have been performed with moored sediment traps at the long-term observatory HAUSGARTEN in the eastern Fram Strait (79°N/4°E). The study area, which is seasonally covered with ice, is located in the confluence zone of the northward flowing warm saline Atlantic water with cold, low salinity water masses of Arctic origin. Current projections suggest that this area is particularly vulnerable to global warming. Total matter fluxes and components thereof (carbonate, particulate organic carbon and nitrogen, biogenic silica, biomarkers) revealed a bimodal seasonal pattern showing elevated sedimentation rates during May/June and August/September. Annual total matter flux (dry weight, DW) at ~ 300 m depth varied between 13 and 32 g/m**2/a during 2000 and 2005. Of this total flux 6-13 % was due to CaCO3, 4-21 % to refractory particulate organic carbon (POC), and 3-8 % to biogenic particulate silica (bPSi). The annual flux of all biogenic components together was almost constant during the period studied (8.5-8.8 g/m**2/a), although this varied from 27 to 67 % of the total annual flux. The fraction was lowest in a year characterized by the longest duration of ice coverage (91 and 70 days for the calendar year and summer season, May-September, respectively). Biomarker analyses revealed that organic matter originating from marine sources was present in excess of terrigenious material in the sedimented matter throughout most of the study period. Fluxes of recognizable phyto- and protozooplankton cells amounted up to 60x106 m**2/d. Diatoms and coccolithophorids were the most abundant organisms. Diatoms, mainly pennate species, dominated during the first years of the investigation. A shift in the composition occurred during the last year when numbers of diatoms declined considerably, leading to a dominance of coccolithoporids. This was also reflected in a decrease in the sedimentation of bPSi. The sedimentation of biogenic matter, however, did not differ from the amount observed during the previous years. Among the larger organisms, pteropods at times contributed significantly to both the total matter and CaCO3, fluxes.

Flux of biomarkers and organisms at AWI HAUSGARTEN from two moorings

Time-series sediment traps were deployed at 4 depths in the eastern Fram Strait from July 2007 to June 2008 to investigate variations in the magnitude and composition of the sinking particulate matter from upper waters to the seafloor. Sediment traps were deployed at 196 m in the Atlantic Water layer, at 1296 and 2364 m in the intermediate and deep waters, and at 2430 m on a benthic lander in the near-bottom layer. Fluxes of total particulate matter, particulate organic carbon, particulate organic nitrogen, biogenic matter, lithogenic matter, biogenic particulate silica, calcium carbonate, dominant phytoplankton cells, and zooplankton fecal pellets increased with depth, indicating the importance of lateral advection on fluxes in the deep Fram Strait. The lateral supply of particulate matter was further supported by the constant fluxes of biomarkers such as brassicasterol, alkenones, campesterol, beta-sitosterol, and IP25 at all depths sampled. However, enhanced fluxes of diatoms and appendicularian fecal pellets from the upper waters to the seafloor in the presence of ice during spring indicated the rapid export (15-35 days) of locally-produced large particles that likely contributed most of the food supply to the benthic communities. These results show that lateral supply and downward fluxes are both important processes influencing the transport of particulate matter to the seafloor in the deep eastern Fram Strait, and that particulate matter size dictates the prevailing sinking process.

Organic geochemical parameters (biomarker) in sedimentary sequences and sediment traps

For the reconstruction of sea-ice variability, a biomarker approach which is based on (1) the determination of sea-ice diatom-specific highly-branched isoprenoid (IP25) and (2) the coupling of phytoplankton biomarkers and IP25 has been used. For the first time, such a data set was obtained from an array of two sediment traps deployed at the southern Lomonosov Ridge in the central Arctic Ocean at water depth of 150 m and 1550 m and recording the seasonal variability of sea ice cover in 1995/1996. These data indicate a predominantly permanent sea ice cover at the trap location between November 1995 and June 1996, an ice-edge situation with increased phytoplankton productivity and sea-ice algae input in July/August 1996, and the start of new-ice formation in late September. The record of modern sea-ice variability is then used to better interpret data from sediment core PS2458-4 recovered at the Laptev Sea continental slope close to the interception with Lomonosov Ridge and recording the post-glacial to Holocene change in sea-ice cover. Based on IP25 and phytoplankton biomarker data from Core PS2458-4, minimum sea-ice cover was reconstructed for the Bølling/Allerød warm interval between about 14.5 and 13 calendar kyr BP, followed by a rapid and distinct increase in sea-ice cover at about 12.8 calendar kyr BP. This sea-ice event was directly preceded by a dramatic freshwater event and a collapse of phytoplankton productivity, having started about 100 years earlier. These data are the first direct evidence that enhanced freshwater flux caused enhanced sea-ice formation in the Arctic at the beginning of the Younger Dryas. In combination with a contemporaneous, abrupt and very prominent freshwater/meltwater pulse in the Yermak Plateau/Fram Strait area these data may furthermore support the hypothesis that strongly enhanced freshwater (and ice) export from the Arctic into the North Atlantic could have played an important trigger role for the onset of the Younger Dryas cold reversal. During the Early Holocene, sea-ice cover steadily increased again (ice-edge situation), reaching modern sea-ice conditions (more or less permanent sea-ice cover) probably at about 7-8 calendar kyr BP.

Determinação de marcadores orgânicos no perfil sedimentar do complexo estuarino de Paranaguá (PR) por CG-EM

A avaliação do aporte de matéria orgânica no ambiente aquático por atividades antrópicas pode ser realizada através da identificação e quantificação de marcadores moleculares. Diversos estudos apontam à aplicação dos marcadores moleculares com esta finalidade, no entanto, poucos avaliam a variação das concentrações desses compostos ao longo do tempo, registrada nas camadas sedimentares. O presente trabalho realiza um estudo a partir de três classes de marcadores moleculares presentes em perfis sedimentares da região do Complexo Estuarino de Paranaguá (CEP) no Paraná (PR), que nos últimos anos vêm sofrendo com o crescente desenvolvimento de atividades antrópicas. Como objetivo, tem-se identificar as principais fontes de matéria orgânica e estudar o histórico destes aportes em colunas sedimentares do CEP, relacionando as taxas de sedimentação com a deposição de origem natural e antrópica. A legislação vigente para o monitoramento ambiental, no que diz respeito à contaminação por esgoto fecal, sugere a avaliação por indicadores microbiológicos, porém, indicadores químicos como os esteróides fecais são uma alternativa bastante promissora, pois estes são persistentes, sendo menos sensíveis a variações ambientais. Outros dois marcadores moleculares de aportes antrópicos ao ambiente que foram determinados neste estudo são os alquilbenzenos lineares (LABs), presente em detergentes, que indicam aportes antrópicos oriundos de esgoto doméstico e a determinação de cafeína, tendo em vista que os esteróides fecais podem ser originários de fezes de animais de sangue quente, podendo indicar outras fontes. Para o presente trabalho foram coletados 12 testemunhos de até 1 m de profundidade em maio de 2006, totalizando 12 pontos de coleta e um montante de 121 amostras. As análises foram realizadas por cromatografia em fase gasosa com detecção por espectrometria de massas (CG-EM). Os esteróides encontrados em maior concentração foram o β- sitosterol (71,4 µg g-1), estigmasterol (8,7 µg g-1), colestanol (3,6 µg g-1) e o estigmastanol (2,8 µg g-1), todos oriundos de fonte natural, indicando que a maior contribuição para o CEP é por aporte biogênico. O coprostanol, que é um esterol fecal, foi encontrado entre as concentrações de 0,001 e 4,10 µg g-1, outros dois esteróides de origem fecal também foram detectados, coprostanona e epicoprostanol, onde as maiores concentrações foram 3,6 e 0,2 µg g-1, respectivamente, sendo encontrados em regiões próximas a centros urbanos, indicando origem antrópica. As maiores concentrações para o ∑LABs também foram encontradas em regiões próximas às cidades de Antonina e Paranaguá, sendo a maior encontrada no testemunho #3 Gererês (208 ng g-1). Para o último marcador molecular analisado, a cafeína, foi encontrada a maior concentração de 18,41 ng g-1, sendo este ponto localizado longe dos centros urbanos, porém este contaminante é bastante solúvel em água podendo ser transportado na coluna d’água e percorrer grandes distâncias. Através dos compostos analisados, pode-se perceber que a intervenção antropogênica foi mais marcante nos testemunhos coletados no eixo leste-oeste do CEP, ficando registrado nas camadas sedimentares.

Triterpene benzoates from the bark of Picramnia teapensis (Simaroubaceae)

Two new benzoic acid esters of triterpene alcohols [lup-20 (29)-en-28-oic acid 3 alpha, 7 beta -dibenzoate and 3 alpha -hydroxy-lup-20(29)-en-28-ic acid 7 beta -benzoate] were isolated from the stem bark of Picramnia teapensis Tul. The structures of these compounds were established on the basis of spectral analyses. Other known compounds, beta -sitosterol, estigmasterol, lupeol and epilupeol, were identified in mixture by GC-MS. The triterpene esters have not shown in-vitro inhibitory effect on the growth of Leucoagaricus gongylophorus (Fisher), referred also as Leucocoprinus gongylophorus (Heim), syn Rozites gongylophora (Moller), the symbiotic fungus cultivated by the leaf-cutting ant Atta sexdens L.