Sabine Lengger

University of Bristol, Organic Geochemistry Unit, Post-Doc

Followers

Following

Co-author

Public Views

Address: Organic Geochemistry Unit
School of Chemistry
University of Bristol
Cantock's Close
BS8 1TS

less

InterestsView All (16)

Uploads

Papers by Sabine Lengger

Mudstones and embedded concretions show differences in lithology-related, but not source-related biomarker distributions

Organic Geochemistry

Production and preservation of archaeal glycerol dibiphytanyl glycerol tetraethers as intact polar lipids in marine sediments: Implications for their use in microbial ecology and TEX86 paleothermometry

A new method for the rapid analysis of 1H-Pyrrole-2,5-diones (maleimides) in environmental samples by two-dimensional gas chromatography time-of-flight mass spectrometry

Journal of chromatography. A, Jan 26, 2016

Maleimides (1H-Pyrrole-2,5-diones) are monopyrrolic pigment derivatives with specific alkyl side ... more Maleimides (1H-Pyrrole-2,5-diones) are monopyrrolic pigment derivatives with specific alkyl side chains that can be directly linked to their tetrapyrrole precursors, most notably chlorophylls and bacteriochlorophylls. These compounds can be used as palaeoenvironmental indicators such as algal productivity and redox conditions in ancient and modern aquatic systems. Here, we present a new method using two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC-ToF-MS), which enables the rapid analysis of maleimides in complex mixtures and different matrices (e.g. sediments and soils), therefore largely simplifying the previous intricate maleimide purification protocol. This method also reduces the potential for bias associated with partial losses due to low recovery and the high volatility of maleimides. The maleimide distributions and concentrations obtained by GC×GC-ToF-MS were reproducible and in agreement with the previously used purification procedure followed by a...

Characterization of Leucetta prolifera, a calcarean cyanosponge from south-western Australia, and its symbionts

Journal of the Marine Biological Association of the United Kingdom, 2015

The biology and ecology of calcarean sponges are not as well understood as they are for demospong... more The biology and ecology of calcarean sponges are not as well understood as they are for demosponges. Here, in order to gain new insights, particularly about symbiotic relationships, the calcarean spongeLeucetta proliferawas sampled from south-western Australia and examined for its assumed photosymbionts. Pulse amplitude modulated fluorometry and extraction of photopigments established that the sponge was photosynthetic. Molecular analysis of the bacterial symbionts via sequencing of the V1–V3 region of the 16S rDNA gene confirmed that between 5 and 22% of all sequences belonged to the phylum Cyanobacteria, depending on the individual sample, with the most dominant strain aligning withHormoscilla spongeliae, a widely distributed sponge symbiont. Analysis of fatty acids suggested that the sponge obtains nutrition through photosynthates from its symbionts. The relationship is assumed to be mutualistic, with the sponge receiving dietary support and the cyanobacteria sheltering in the sp...

Use of the distributions of adamantane acids to profile short-term temporal and pond-scale spatial variations in the composition of oil sands process-affected waters

Environmental science. Processes & impacts, Jan 5, 2015

Oil industry produced waters, such as the oils sands process-affected waters (OSPW) of Alberta, C... more Oil industry produced waters, such as the oils sands process-affected waters (OSPW) of Alberta, Canada, represent a challenge in terms of risk assessment and reclamation due to their extreme complexity, particularly of the organic chemical constituents, including the naphthenic acids (NA). The identification of numerous NA in single samples has raised promise for the use of NA distributions for profiling OSPW. However, monitoring of the success of containment is still difficult, due to the lack of knowledge of the homogeneity (or otherwise) of OSPW composition within, and between, different industry containments. Here we used GC×GC-MS to compare the NA of five OSPW samples from each of two different industries. Short-term temporal and pond-scale spatial variations in the distributions of known adamantane acids and diacids and other unknown tricyclic acids were examined and a statistical appraisal of the replicate data made. The presence/absence of individual acids easily distinguish...

$Research paper thumbnail of Mass spectral characterisation of a polar, esterified fraction of an organic extract of an oil sands process water$

Mass spectral characterisation of a polar, esterified fraction of an organic extract of an oil sands process water

by Alan Scarlett and Sabine Lengger

Rapid Communications in Mass Spectrometry, 2014

RATIONALE: Characterising complex mixtures of organic compounds in polar fractions of heavy petro... more RATIONALE: Characterising complex mixtures of organic compounds in polar fractions of heavy petroleum is challenging, but is important for pollution studies and for exploration and production geochemistry. Oil sands process-affected water (OSPW) stored in large tailings ponds by Canadian oil sands industries contains such mixtures. METHODS: A polar OSPW fraction was obtained by silver ion solid-phase extraction with methanol elution. This was examined by numerous methods, including electrospray ionisation (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) and ultra-high-pressure liquid chromatography (uHPLC)/Orbitrap MS, in multiple ionisation and MS/MS modes. Compounds were also synthesised for comparison. RESULTS: The major ESI ionisable compounds detected (+ion mode) were C 15-28 SO 3 species with 3-7 double bond equivalents (DBE) and C 27-28 SO 5 species with 5 DBE. ESI-MS/MS collision-induced losses were due to water, methanol, water plus methanol and water plus methyl formate, typical of methyl esters of hydroxy acids. Once the fraction was re-saponified, species originally detected by positive ion MS, could be detected only by negative ion MS, consistent with their assignment as sulphur-containing hydroxy carboxylic acids. The free acid of a keto dibenzothiophene alkanoic acid was added to an unesterified acid extract of OSPW in known concentrations as a putative internal standard, but attempted quantification in this way proved unreliable. CONCLUSIONS: The results suggest the more polar acidic organic SO 3 constituents of OSPW include C 15-28 S-containing, alicyclic and aromatic hydroxy carboxylic acids. SO 5 species are possibly sulphone analogues of these. The origin of such compounds is probably via further biotransformation (hydroxylation) of the related S-containing carboxylic acids identified previously in a less polar OSPW fraction. The environmental risks, corrosivity and oil flow assurance effects should be easier to assess, given that partial structures are now known, although further identification is still needed.

Download

Two New Beggiatoa Species Inhabiting Marine Mangrove Sediments in the Caribbean

PLOS ONE, 2015

Beggiatoaceae, giant sulphur-oxidizing bacteria, are well known to occur in cold and temperate wa... more Beggiatoaceae, giant sulphur-oxidizing bacteria, are well known to occur in cold and temperate waters, as well as hydrothermal vents, where they form dense mats on the floor. However, they have never been described in tropical marine mangroves. Here, we describe two new species of benthic Beggiatoaceae colonizing a marine mangrove adjacent to mangrove roots. We combined phylogenetic and lipid analysis with electron microscopy in order to describe these organisms. Furthermore, oxygen and sulphide measurements in and ex situ were performed in a mesocosm to characterize their environment. Based on this, two new species, Candidatus Maribeggiatoa sp. and Candidatus Isobeggiatoa sp. inhabiting tropical marine mangroves in Guadeloupe were identified. The species identified as Candidatus Maribeggiatoa group suggests that this genus could harbour a third cluster with organisms ranging from 60 to 120 μm in diameter. This is also the first description of an Isobeggiatoa species outside of Arctic and temperate waters. The multiphasic approach also gives information about the environment and indications for the metabolism of these bacteria. Our study shows the widespread occurrence of members of Beggiatoaceae family and provides new insight in their potential role in shallow-water marine sulphide-rich environments such as mangroves.

A new twist to a traditional approach to environmental monitoring: differentiation of oil sands process-affected waters and natural systems by comparison of individual organic acids

by Alan Scarlett and Sabine Lengger

Impact of sedimentary degradation and deep water column production on GDGT abundance and distribution in surface sediments in the Arabian Sea

The TEX 86 is a widely used paleotemperature proxy based on isoprenoid glycerol dibiphytanyl 16 g... more The TEX 86 is a widely used paleotemperature proxy based on isoprenoid glycerol dibiphytanyl 16 glycerol tetraethers (GDGTs) produced by Thaumarchaeota. Archaeal membranes are composed of 17 GDGTs with polar head groups (IPL-GDGTs), most of which are expected to be degraded completely 18 or transformed into more recalcitrant core lipid (CL)-GDGTs upon cell lysis. Here, we examined the 19 differences in concentration and distribution of core lipid (CL)-and intact polar lipid (IPL)-GDGTs in 20 surface sediments at different deposition depths, and different oxygen bottom water concentrations (<3 21 to 83 mol · L -1 ). Surface sediments were sampled from 900 to 3000 m depth on a seamount (Murray 22

Download

$Research paper thumbnail of Can two-dimensional gas chromatography/mass spectrometric identification of bicyclic aromatic acids in petroleum fractions help to reveal further details of aromatic hydrocarbon biotransformation pathways?$

Can two-dimensional gas chromatography/mass spectrometric identification of bicyclic aromatic acids in petroleum fractions help to reveal further details of aromatic hydrocarbon biotransformation pathways?

Rapid Communications in Mass Spectrometry, 2014

The identification of key acid metabolites ('signature' metabolites) has allowed significant impr... more The identification of key acid metabolites ('signature' metabolites) has allowed significant improvements to be made in our understanding of the biodegradation of petroleum hydrocarbons, in reservoir and in contaminated natural systems, such as aquifers and seawater. On this basis, anaerobic oxidation is now more widely accepted as one viable mechanism, for instance. However, identification of metabolites in the complex acid mixtures from petroleum degradation is challenging and would benefit from use of more highly resolving analytical methods. METHODS: Comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GCxGC/TOFMS) with both nominal mass and accurate mass measurement was used to study the complex mixtures of aromatic acids (as methyl esters) in petroleum fractions. RESULTS: Numerous mono-and di-aromatic acid isomers were identified in a commercial naphthenic acids fraction from petroleum and in an acids fraction from a biodegraded petroleum. In many instances, compounds were identified by comparison of mass spectral and retention time data with those of authentic compounds. CONCLUSIONS: The identification of a variety of alkyl naphthalene carboxylic and alkanoic and alkyl tetralin carboxylic and alkanoic acids, plus identifications of a range of alkyl indane acids, provides further evidence for 'signature' metabolites of biodegradation of aromatic petroleum hydrocarbons. Identifications such as these now offer the prospect of better differentiation of metabolites of bacterial processes (e.g. aerobic, methanogenic, sulphate-reducing) in polar petroleum fractions. Colours indicate the intensities of the responses (green > yellow > pink). (C)

Download

Fossilization and degradation of archaeal intact polar tetraether lipids in deeply buried marine sediments (Peru Margin)

Geobiology, 2014

Glycerol dibiphytanyl glycerol tetraether (GDGT) lipids are part of the cellular membranes of Tha... more Glycerol dibiphytanyl glycerol tetraether (GDGT) lipids are part of the cellular membranes of Thaumarchaeota, an archaeal phylum composed of aerobic ammonia oxidizers, and are used in the paleotemperature proxy TEX86. GDGTs in live cells possess polar head groups and are called intact polar lipids (IPL-GDGTs). Their transformation to core lipids (CL) by cleavage of the head group was assumed to proceed rapidly after cell death, but it has been suggested that some of these IPL-GDGTs can, just like the CL-GDGTs, be preserved over geological timescales. Here, we examined IPL-GDGTs in deeply buried (0.2–186 mbsf, ~2.5 Myr) sediments from the Peru Margin. Direct measurements of the most abundant IPL-GDGT, IPL-crenarchaeol, specific for Thaumarchaeota, revealed depth profiles, which differed per head group. Shallow sediments (<1 mbsf) contained IPL-crenarchaeol with both glycosidic and phosphate head groups, as also observed in thaumarchaeal enrichment cultures, marine suspended particulate matter and marine surface sediments. However, hexose, phosphohexose-crenarchaeol is not detected anymore below 6 mbsf (~7 kyr), suggesting a high lability. In contrast, IPL-crenarchaeol with glycosidic head groups is preserved over timescales of Myr. This agrees with previous analyses of deeply buried (>1 m) marine sediments, which only reported glycosidic and no phosphate-containing IPL-GDGTs. TEX86 values of CL-GDGTs did not markedly change with depth, and the TEX86 of IPL-derived GDGTs decreased only when the proportions of monohexose- to dihexose-GDGTs changed, likely due to the enhanced preservation of the monohexose GDGTs. Our results support the hypothesis that in situ GDGT production and differential IPL degradation in sediments is not substantially affecting TEX86 paleotemperature estimations based on CL–GDGTs and indicates that likely only a small amount of IPL-GDGTs present in deeply buried sediments is part of cell membranes of active archaea. The amount of archaeal biomass in the deep biosphere based on these IPLs may have been substantially overestimated.

Download

Lack of 13C-label incorporation suggests low turnover rates of thaumarchaeal intact polar tetraether lipids in sediments from the Iceland shelf

Biogeosciences, 2014

Thaumarchaeota are amongst the most abundant microorganisms in aquatic environments, however, th... more Thaumarchaeota are amongst the most abundant
microorganisms in aquatic environments, however, their
metabolism in marine sediments is still debated. Labeling
studies in marine sediments have previously been undertaken,
but focused on complex organic carbon substrates
which Thaumarchaeota have not yet been shown to take up.
In this study, we investigated the activity of Thaumarchaeota
in sediments by supplying different 13C-labeled substrates
which have previously been shown to be incorporated into archaeal
cells in water incubations and/or enrichment cultures.
We determined the incorporation of 13C-label from bicarbonate,
pyruvate, glucose and amino acids into thaumarchaeal
intact polar lipid-glycerol dibiphytanyl glycerol tetraethers
(IPL-GDGTs) during 4–6 day incubations of marine sediment
cores from three sites on the Iceland shelf. Thaumarchaeal
intact polar lipids, in particular crenarchaeol, were detected
at all stations and concentrations remained constant or
decreased slightly upon incubation. No 13C incorporation in
any IPL-GDGT was observed at stations 2 (clay-rich sediment)
and 3 (organic-rich sediment). In bacterial/eukaryotic
IPL-derived fatty acids at station 3, contrastingly, a large
uptake of 13C label (up to + 80‰ ) was found. 13C was
also respired during the experiment as shown by a substantial
increase in the 13C content of the dissolved inorganic
carbon. In IPL-GDGTs recovered from the sandy sediments
at station 1, however, some enrichment in 13C (1–4‰ )
was detected after incubation with bicarbonate and pyruvate.
The low incorporation rates suggest a low activity of Thaumarchaeota
in marine sediments and/or a low turnover rate
of thaumarchaeal IPL-GDGTs due to their low degradation
rates. Cell numbers and activity of sedimentary Thaumarchaeota
based on IPL-GDGT measurements may thus have
previously been overestimated.

Diamondoid diacids ('O4' species) in oil sands process-affected water

Rapid Communications in Mass Spectrometry, 2013

RATIONALE: As a by-product of oil sands extraction, large volumes of oil sands process water (OSP... more RATIONALE: As a by-product of oil sands extraction, large volumes of oil sands process water (OSPW) are generated, which are contaminated with a large range of water-soluble organic compounds. The acids are thought to be derived from hydrocarbons via natural biodegradation pathways such as α- and β-oxidation of alkyl substituents, which could produce mono- and diacids, for example. However, while several monoacids (‘O2’ species) have been identified, the presence of diacids (i.e. ’O4’ species) has only been deduced from results obtained via Fourier transform infrared (FTIR) spectroscopy, Fourier transform ion cyclotron resonance high-resolution mass spectrometry (FTICR-HRMS) and nuclear magnetic resonance (1H-NMR) spectroscopy and the structures have never been confirmed. METHODS: An extract of an OSPW from a Canadian tailings pond was analysed and the retention times and the electron ionization mass spectra of some analytes were compared with those of bis-methyl esters of authentic diacids by gas chromatography × gas chromatography/time-of-flight mass spectrometry (GCxGC/TOFMS) in nominal and accurate mass configurations. RESULTS: Two diamondoid diacids (3-carboxymethyladamantane-1-carboxylic acid and adamantane-1,3-dicarboxylic acid) were firmly identified as their bis-methyl esters by retention time and mass spectral matching and several other structural isomers were more tentatively assigned. Diacids have substantially increased polarity over the hydrocarbon and monoacid species from which they probably derive: as late members of biodegradation processes they may be useful indicators of weathering and ageing, not only of OSPW, but potentially of crude oil residues more generally.
CONCLUSIONS: Structures of O4 species in OSPW have been identified. This confirms pathways of microbial biodegradation, which were only postulated previously, and may be a further indication that remediation of OSPW toxicity can occur by natural microbial action. The presence and abundance of these diacids might therefore be useful as a measure of biodegradation and weathering.

Download

Differential degradation of intact polar and core glycerol dialkyl glycerol tetraether lipids upon post-depositional oxidation

Organic Geochemistry, 2013

Archaeal and bacterial glycerol dialkyl glycerol tetraether lipids (GDGTs) are used in various pr... more Archaeal and bacterial glycerol dialkyl glycerol tetraether lipids (GDGTs) are used in various proxies, such as TEX86 and the BIT index. In living organism, they contain polar head groups (intact polar lipids – IPLs). IPL GDGTs have also been detected in ancient marine sediments and it is unclear whether or not they are fossil entities or are part of living cells. In order to determine the extent of degradation of IPL GDGTs over geological timescales, we analyzed turbidite deposits, which had been partly reoxidized for several kyr after deposition on the Madeira Abyssal Plain. Analysis of core lipid (CL) and IPL-derived GDGTs showed a reduction in concentration by two orders of magnitude upon post-depositional oxidation, while IPL GDGTs with a mono- or dihexose head group decreased by 2–3 orders of magnitude. The BIT index for CL- and IPL-derived GDGTs increased substantially upon oxidation from 0.1 to up to 0.5. Together with changing MBT/CBT values, this indicates preferential preservation of soil-derived branched GDGTs over marine isoprenoid GDGTs, combined with in situ production of branched GDGTs in the sediment. The TEX86 value for IPL-derived GDGTs decreased by 0.07 upon oxidation, while that of CL GDGTs showed no significant change. Isolation of IPLs revealed that the TEX86 value for monohexose GDGTs was 0.55, while the that for dihexose GDGTs was substantially higher, 0.70. Thus, the decrease in TEX86 for IPL-derived GDGTs was in agreement with the dominance of monohexose GDGTs in the oxidized turbidite, probably caused by a combination of in situ production as well as selective preservation of terrestrial isoprenoid GDGTs. Due to the low amount of IPL GDGTs vs. CL GDGTs, the impact of IPL degradation on CL-based TEX86 paleotemperature estimates was negligible.

Download

Intact polar and core glycerol dibiphytanyl glycerol tetraether lipids in the Arabian Sea oxygen minimum zone: II. Selective preservation and degradation in sediments.

… et Cosmochimica Acta, Jan 1, 2012

The TEX86 is a proxy based on a ratio of pelagic archaeal glycerol dibiphytanyl glycerol tetraeth... more The TEX86 is a proxy based on a ratio of pelagic archaeal glycerol dibiphytanyl glycerol tetraether lipids (GDGTs), and used for estimating past sea water temperatures. Concerns exist that in situ production of GDGTs lipids by sedimentary Archaea may affect its validity. In this study, we investigated the influence of benthic GDGT production on the TEX86 by analyzing the concentrations and distributions of GDGTs present as intact polar lipids (IPLs) and as core lipids (CLs) in three sediment cores deposited under contrasting redox conditions across a depth range from 900 to 3000 m below sea level in and below the Arabian Sea oxygen minimum zone (OMZ). Direct analysis of IPLs with crenarchaeol as CL via HPLC/ESI-MS2 revealed that surface sediments in the OMZ were relatively depleted in the phospholipid hexose, phosphohexose (HPH)-crenarchaeol compared to suspended particulate matter from the water column, suggesting preferential and rapid degradation of this IPL. In sediment cores recovered from deeper, more oxic environments, concentrations of HPH-crenarchaeol peaked at the surface, probably due to in situ production by ammonia-oxidizing Archaea, followed by a rapid decrease with increasing depth. No surface maximum was observed in the sediment core from within the OMZ. In contrast, the glycolipids, monohexose-crenarchaeol and dihexose-crenarchaeol, did not change in concentration with depth in the sediment, indicating that they were relatively well preserved and likely mostly derived from fossil pelagic GDGTs. These results suggest that phospholipids are more sensitive to degradation, while glycolipids might be preserved over longer time scales, in line with previous incubation and modeling studies. Furthermore, in situ produced IPL-GDGTs did not accumulate as IPLs, and did not influence the CL-TEX86. This suggests that in-situ produced GDGT lipids were more susceptible to degradation than fossil CL and IPL and did not accumulate as CL. In agreement, no significant changes of TEX86 with sediment depth in the core lipids were observed. However, consistent differences between IPL-derived TEX86 and CL-TEX86 were found. These could be explained by a different composition of CL-GDGT of the glyco- and phospholipids, in combination with dissimilar degradation rates of phospholipids vs. glycolipids. We also observed consistent differences in both IPL-derived and CL-TEX86 between the different cores, equivalent to 3 °C when converted to temperature, despite the proximity of the core locations. These differences may potentially be due to a larger addition of GDGTs produced in deeper, colder waters to the (sub)surface-derived GDGTs for the deeper core sites.

Download

Comparison of extraction and work up techniques for analysis of core and intact polar tetraether lipids from sedimentary environments

Organic …, Jan 1, 2012

Glycerol dibiphytanyl glycerol tetraether-based intact polar lipids (IPL GDGTs) are used as bioma... more Glycerol dibiphytanyl glycerol tetraether-based intact polar lipids (IPL GDGTs) are used as biomarkers for living Archaea and are analyzed utilizing a variety of extraction and quantification techniques. Most IPL GDGT studies have used a modified Bligh–Dyer extraction method, but it has been suggested that Soxhlet extraction may be more efficient for environmental samples and biomass. We investigated the impact of three different extractions (Soxhlet, Bligh–Dyer and accelerated solvent extraction, ASE), two IPL quantification methods and two work up techniques (Na2SO4 and SiO2 column) on the amount and distribution of CL (core lipid)- and IPL-derived GDGTs and crenarchaeol-based IPLs in marine sediments from the Arabian Sea and Icelandic shelf, as well as a microbial mat from a Dutch beach. The different extraction procedures gave a similar yield of CL- and IPL-derived GDGTs. Direct analysis of crenarchaeol IPLs showed, however, that, while GDGTs with a monohexose head group were not affected by the extraction method, there was a large effect on IPL GDGTs containing dihexose or hexose, phosphohexose head groups. Quantification of IPL-derived GDGTs by way of either separation over a silica column or by subtraction of CL GDGTs in the total lipid extract before and after hydrolysis gave similar results, but the ‘subtraction-method’ had a relatively large quantification error. However, the silica column, as well as drying over a Na2SO4 column, resulted in a loss of the hexose, phosphohexose IPLs by up to 80%. Based on the results, a modified Bligh–Dyer extraction with as little further treatment as possible is recommended to allow measurement of the full range of IPL GDGTs in sediments.

Download

Sabine Lengger

Uploads

Papers by Sabine Lengger

Log In