Rapid encapsulation of true ferns and arborane/fernane compounds fossilised in siderite concretions supports analytical distinction of plant fossils.

Fossilised true ferns (Pecopteris sp.) preserved in siderite concretions from the Mazon Creek Lagerstätte (Illinois) presented a unique opportunity to characterise the organic signatures of these late Carboniferous plants. Localised analyses of true fern fossils showed several highly abundant phytohopanoids and fernane/arborane derived aromatic products, which were present only negligibly within their siderite matrix, as well as from other types of fossilised plants. These terpenoids had been recognised in some extant ferns, but scarcely in sedimentary organic matter and their exact source remained ambiguous. The present fossil biomarker data confirms an ancient true fern origin. Furthermore, the excellent concretion preservation of a series of related terpenoid products provided a rare insight into their diagenetic formation. The benign properties of carbonate concretions could be exploited further for biomarker evidence of other fossilised organisms, with one important caveat being that biomarker signals attributed to isolated fossils be significantly distinct from background organic matter pervading the concretion matrix. For instance, hydrocarbon profiles of seed ferns (pteridosperms) and articulates (horsetails) also preserved in Mazon Creek concretions were indistinguishable from separate analysis of their concretion matrix, preventing biomarker recognition.

Plastiglomerates from uncontrolled burning of plastic waste on Indonesian beaches contain high contents of organic pollutants.

This study reports on plastiglomerate and other new forms of plastic pollution in the tropical marine continent of Indonesia. Twenty-five samples were collected from an island beach in the Java Sea where plastiglomerate, plasticrusts, and pyroplastic were formed by the uncontrolled burning of plastic waste. The most common plastic types were polyethylene and polypropylene (PE/PP), as shown by ATR-FTIR spectroscopy. However, acrylates/polyurethane/varnish (PU) and a copolymer of styrene and acrylonitrile were found as well. This suggests that plastiglomerates can form from a wider variety of plastic polymers than previously reported. FTIR analysis also indicates thermo-oxidative weathering, making the charred plastic more brittle and susceptible to microplastic formation. A subset of the samples was analyzed for associated chemical contaminants. One plastiglomerate with a PU matrix showed high concentrations of phthalates. All samples had high concentrations of polycyclic aromatic hydrocarbons (PAHs), likely due to the burning of the plastic in open fires. The burning leads to a change in the physical and chemical properties of the plastics contained in the plastiglomerates. Plastiglomerate and plastic waste of similar origin are therefore often more weathered and contaminated with organic pollutants than their parent polymers. The highest PAH concentration was found in a plastitar sample. Plastitar is defined as an agglomerate of tar and plastics that adheres to coastal rocks. In contrast, our study documents a more mobile, clastic plastitar type. This clastic plastitar could pose an additional ecological risk because of its mobility. These new types of plastic pollution could be an important vector for chemical contamination of nearby coastal habitats such as coral reefs, seagrass meadows, and mangroves.

Warm, not cold temperatures contributed to a Late Miocene reef decline in the Coral Sea.

Evidence shows that in the modern ocean, coral reefs are disappearing, and these losses are tied to climate change. However, research also shows that coral reefs can adapt rapidly to changing conditions leading some researchers to suggest that some reef systems will survive future climate change through adaptation. It is known that there were changes in the area covered by coral reefs in the past. Therefore, it is important to investigate the long-term response of coral reefs to environmental changes and high sea-surface temperatures (SSTs). However, because of diagenetic issues with SST proxies in neritic, metastable carbonate-rich environments, there is an incomplete and sometimes even incorrect understanding of how changes in SSTs affect carbonate reef systems. A good example is the Queensland Plateau offshore northeast Australia next to the threatened Great Barrier Reef. In the Late Miocene, between 11 and 7 Ma, a partial drowning caused the reef area on the Queensland Plateau to decline by ~ 50% leading to a Late Miocene change in platform geometry from a reef rimmed platform to a carbonate ramp. This reef decline was interpreted to be the result of SSTs at the lower limit of the modern reef growth window (20-18 °C). This article presents a new Late Miocene-ased SST record from the Coral Sea based on the TEX86H molecular paleothermometer, challenging this long held view. Our new record indicates warm tropical SSTs (27-32 °C) at the upper end of the modern reef growth window. We suggest that the observed temperatures potentially exceeded the optimal calcification temperatures of corals. In combination with a low aragonite supersaturation in the ocean, this could have reduced coral growth rates and ultimately lowered the aggradation potential of the reef system. These sub-optimal growth rates could have made the coral reefs more susceptible to other stressors, such as relative sea-level rise and/or changes in currents leading to reef drowning. Given that these changes affected coral reefs that were likely adapted to high temperature/low aragonite saturation conditions suggests that reefs that have adapted to non-ideal conditions may still be susceptible to future climate changes due to the interaction of multiple stressors associated with climate change.

Complete ammonia oxidization in agricultural soils: High ammonia fertilizer loss but low N2 O production.

The contribution of agriculture to the sustainable development goals requires climate-smart and profitable farm innovations. Increasing the ammonia fertilizer applications to meet the global food demands results in high agricultural costs, environmental quality deterioration, and global warming, without a significant increase in crop yield. Here, we reported that a third microbial ammonia oxidation process, complete ammonia oxidation (comammox), is contributing to a significant ammonia fertilizer loss (41.9 ± 4.8%) at the rate of 3.53 ± 0.55 mg N kg-1 day-1 in agricultural soils around the world. The contribution of comammox to ammonia fertilizer loss, occurring mainly in surface agricultural soil profiles (0-0.2 m), was equivalent to that of bacterial ammonia oxidation (48.6 ± 4.5%); both processes were significantly more important than archaeal ammonia oxidation (9.5 ± 3.6%). In contrast, comammox produced less N2 O (0.98 ± 0.44 µg N kg-1 day-1 , 11.7 ± 3.1%), comparable to that produced by archaeal ammonia oxidation (16.4 ± 4.4%) but significantly lower than that of bacterial ammonia oxidation (72.0 ± 5.1%). The efficiency of ammonia conversion to N2 O by comammox (0.02 ± 0.01%) was evidently lower than that of bacterial (0.24 ± 0.06%) and archaeal (0.16 ± 0.04%) ammonia oxidation. The comammox rate increased with increasing soil pH values, which is the only physicochemical characteristic that significantly influenced both comammox bacterial abundance and rates. Ammonia fertilizer loss, dominated by comammox and bacterial ammonia oxidation, was more intense in soils with pH >6.5 than in soils with pH <6.5. Our results revealed that comammox plays a vital role in ammonia fertilizer loss and sustainable development in agroecosystems that have been previously overlooked for a long term.

Salinity-driven ecology and diversity changes of heterocytous cyanobacteria in Australian freshwater and coastal-marine microbial mats.

N2 -fixing heterocytous cyanobacteria are considered to play a minor role in sustaining coastal microbial mat communities developing under normal marine to hypersaline conditions. Here, we investigated microbial mats growing under different salinities from freshwater mats of Giblin River (Tasmania) to metahaline and hypersaline mats of Shark Bay (Western Australia). Analyses of genetic (rRNA and mRNA) and biological markers (heterocyte glycolipids) revealed an unexpectedly large diversity of heterocytous cyanobacteria in all the studied microbial mat communities. It was observed that the taxonomic distribution as well as abundance of cyanobacteria is strongly affected by salinity. Low salinity favoured the presence of heterocytous cyanobacteria in freshwater mats, while mats thriving in higher salinities mainly supported the growth unicellular and filamentous non-heterocytous genera. However, even though mRNA transcripts derived from heterocytous cyanobacteria were lower in Shark Bay (<6%) microbial mats, functional analyses revealed that these diazotrophs were transcribing a substantial proportion of the genes involved in biofilm formation and nitrogen fixation. Overall, our data reveal an unexpectedly high diversity of heterocytous cyanobacteria (e.g. Calothrix, Scytonema, Nodularia, Gloeotrichia, Stigonema, Fischerella and Chlorogloeopsis) that had yet to be described in metahaline and hypersaline microbial mats from Shark Bay and that they play a vital role in sustaining the ecosystem functioning of coastal-marine microbial mat systems.

Fossil Biomarkers and Biosignatures Preserved in Coprolites Reveal Carnivorous Diets in the Carboniferous Mazon Creek Ecosystem.

The reconstruction of ancient trophic networks is pivotal to our understanding of ecosystem function and change through time. However, inferring dietary relationships in enigmatic ecosystems dominated by organisms without modern analogues, such as the Carboniferous Mazon Creek fauna, has previously been considered challenging: preserved coprolites often do not retain sufficient morphology to identify the dietary composition. Here, we analysed n = 3 Mazon Creek coprolites in concretions for dietary signals in preserved biomarkers, stable carbon isotope data, and macromolecular composition. Cholesteroids, metazoan markers of cholesterol, show an increased abundance in the sampled coprolites (86 to 99% of the total steranes) compared to the surrounding sediment, indicating an endogenous nature of preserved organics. Presence of unaltered 5α-cholestan-3ß-ol and coprostanol underline the exceptional molecular preservation of the coprolites, and reveal a carnivorous diet for the coprolite producer. Statistical analyses of in situ Raman spectra targeting coprolite carbonaceous remains support a metazoan affinity of the digested fossil remains, and suggest a high trophic level for the coprolite producer. These currently oldest, intact dietary stanols, combined with exquisitely preserved macromolecular biosignatures in Carboniferous fossils offer a novel source of trophic information. Molecular and biosignature preservation is facilitated by rapid sedimentary encapsulation of the coprolites within days to months after egestion.

Towards a more labor-saving way in microbial ammonium oxidation: A review on complete ammonia oxidization (comammox).

In the Anthropocene, nitrogen pollution is becoming an increasing challenge for both mankind and the Earth system. Microbial nitrogen cycling begins with aerobic nitrification, which is also the key rate-limiting step. For over a century, it has been accepted that nitrification occurs sequentially involving ammonia oxidation, which produces nitrite followed by nitrite oxidation, generating nitrate. This perception was changed by the discovery of comammox Nitrospira bacteria and their metabolic pathway. In addition, this also provided us with new knowledge concerning the complex nitrogen cycle network. In the comammox process, ammonia can be completely oxidized to nitrate in one cell via the subsequent activity of the enzyme complexes, ammonia monooxygenase, hydroxylamine dehydrogenase, and nitrite oxidodreductase. Over the past five years, research on comammox made great progress. However, there still exist a lot of questions, including how much does comammox contribute to nitrification? How large is the diversity and are there new strains to be discovered? Do comammox bacteria produce the greenhouse gas N2O, and how or to which extent may they contribute to global climate change? The above four aspects are of great significance on the farmland nitrogen management, aquatic environment restoration, and mitigation of global climate change. As large number of comammox bacteria and pathways have been detected in various terrestrial and aquatic ecosystems, indicating that the comammox process may exert an important role in the global nitrogen cycle.

A heterocyte glycolipid-based calibration to reconstruct past continental climate change.

Understanding Earth's response to climate forcing in the geological past is essential to reliably predict future climate change. The reconstruction of continental climates, however, is hampered by the scarcity of universally applicable temperature proxies. Here, we show that heterocyte glycolipids (HGs) of diazotrophic heterocytous cyanobacteria occur ubiquitously in equatorial East African lakes as well as polar to tropical freshwater environments. The relative abundance of HG26 diols and keto-ols, quantified by the heterocyte diol index (HDI26), is significantly correlated with surface water temperature (SWT). The first application of the HDI26 to a ~37,000 year-long sediment record from Lake Tanganyika provides evidence for a ~4.1 °C warming in tropical East Africa from the last glacial to the beginning of the industrial period. Given the worldwide distribution of HGs in lake sediments, the HDI26 may allow reconstructing SWT variations in polar to tropical freshwater environments and thereby quantifying past continental climate change.

Abundance and Functional Importance of Complete Ammonia Oxidizers and Other Nitrifiers in a Riparian Ecosystem.

The discovery of complete ammonia oxidation (comammox) has altered our understanding of nitrification, which is the rate-limiting process in the global nitrogen cycle. However, understanding the ecological role of comammox or its contribution to nitrification in both natural and artificial ecosystems is still in its infancy. Here, we investigated the community distribution and function of comammox bacteria in riparian ecosystems and analyzed interactions between comammox and other nitrogen cycling microorganisms. The comammox bacterial abundance and rate were higher in summer than in winter and higher in nonrhizosphere soils than in the rhizosphere. Fringe soils in the riparian zone comprise a comammox hotspot, where the abundance (2.58 × 108 copies g-1) and rate (0.86 mg N kg-1 d-1) of comammox were not only higher than at other sampling sites but also higher than those of other ammonia oxidation processes. The comammox rate correlated significantly positively with relative abundance of the comammox species Candidatus Nitrospira nitrificans but not with that of the species Candidatus Nitrospira nitrosa. Analysis of comammox interaction with other ammonia-oxidizing processes revealed ammonia-oxidizing archaea to dominate interface soils, comammox to dominate in fringe soils, and anaerobic ammonium oxidation (anammox) to dominate in interface sediments of the riparian zone. These results indicate that comammox may constitute an important and currently underestimated process of microbial nitrification in riparian zone ecosystems.

Epicuticular wax lipid composition of endemic European Betula species in a simulated ontogenetic/diagenetic continuum and its application to chemotaxonomy and paleobotany.

Plants are excellent climate indicators and their macro-remains or pollen accumulating in geological archives serve as recorders of environmental change. In Europe birch trees contribute importantly to Holocene plant successions. They constitute the dwarf species Betula nana and B. humilis, representing colder and two tree birches, B. pubescens and B. pendula indicative of more temperate climate. Birch pollen is highly similar preventing species differentiation. We obtained unambiguous chemotaxonomic differentiation of four European birch species via cuticular wax lipids. Dominating lipid classes in recent epicuticular birch waxes were n-alkanes (nC23 to nC33), n-alcohols and n-alkanoic acids (nC20 to nC32), and long-chain wax ester (nC36 to nC48) differing in amount and distribution. After plant senescence and in geological archives lipids undergo diagenetic alteration modifying the distributions found in recent plants. Long-chain wax esters via hydrolysis release bound n-alcohols and n-fatty acids, adding to their free analogues. Simulated release of bound lipids increased the pool of n-alcohol and n-fatty acids up to 400%. Such modification of primary lipid patterns is unaccounted for in most paleovegetation studies. Proceeding diagenesis, e.g. by decarboxylation will convert these functionalized primary and secondary lipids into their corresponding n-alkanes, the compound class mostly applied in paleoenvironment reconstruction. The simulated n-alkane pattern changed significantly, evidenced by an increase of mid-chain (nC23,nC25) homologues. Release of bound lipids may not only alter molecular but also isotopic composition, which may cause errors in paleoclimate reconstruction. We assessed the potential contribution of secondary (free lipid decarboxylation) and tertiary (bound lipid decarboxylation) wax metabolites and compared the cumulative n-alkane patterns with birch n-alkane distributions reported in the literature. Two statistically different patterns were separated, one dominated by primary, the other by secondary and tertiary formed n-alkanes. This may explain the inconsistency in previous birch wax analysis reported and needs consideration in paleoenvironment reconstruction.

δ13C of terrestrial vegetation records Toarcian CO2 and climate gradients.

Throughout Earth's history, variations in atmospheric CO2 concentration modulated climate. Understanding changes in atmospheric carbon cycle is therefore pivotal in predicting consequences of recent global warming. Here, we report stable carbon isotopes (δ13C) of molecular land plant fossils complemented by bulk organic and inorganic carbon fractions for early Toarcian (Early Jurassic) sediments that coincided with global warming and a carbon cycle perturbation. The carbon cycle perturbation is expressed by a negative excursion in the δ13C records established for the different substrates. Based on differences in the magnitude of the carbon isotope excursion recorded in land plants and marine substrates we infer that the early Toarcian warming was paralleled by an increase in atmospheric CO2 levels from ~500 ppmv to ~1000 ppmv. Our data suggest that rising atmospheric CO2 levels resulted from the injection of  12C-enriched methane and its subsequent oxidation to CO2. Based on the cyclic nature of the CIE we concluded that methane was released from climate sensitive reservoirs, in particular permafrost areas. Moderate volcanic CO2 emissions led to a destabilization of the labile permafrost carbon pool triggering the onset of Toarcian climate change only. The main carbon cycle perturbation then subsequently was driven by a self-sustained demise of a carbon-rich cryosphere progressing from mid to high latitudes as reflected by latitudinal climate gradients recorded in land plant carbon isotopes.

Anaerobic ammonium oxidation is a major N-sink in aquifer systems around the world.

Global-scale N-oxide contamination of groundwater within aquifers occurs due to the widespread use of N-bearing fertilizers and chemicals, threatening both human and environmental health. However, the conversion of these pollutants in active nitrogen (N) cycling processes in the subsurface biosphere still remains unclear. This study investigates the global occurrence of anaerobic ammonium oxidation (anammox) in aquifers, where anammox was found to be turned on and off between saturated and unsaturated soil horizons, and contributed 36.8-79.5% to N loss in saturated soil horizons, the remainder being due to denitrification which has traditionally been considered the main pathway for removal of N-pollutants from aquifers. Although anammox activity was undetectable in the unsaturated soil horizons, it could potentially be activated by contact with ascending groundwater. High-throughput pyrosequencing analysis identified Candidatus Brocadia anammoxidans as being the most abundant anammox bacterium in the saturated soils investigated. However, the anammox bacterial abundance was determined by the relative richness of Candidatus Jettenia asiatica. Isotopic pairing experiments revealed that coupling anammox with ammonium oxidation and respiratory ammonification enabled the formation of a revised N cycle in aquifer systems, in which respiratory ammonification acted as an important coordinator. Anammox can therefore contribute substantially to aquifer N cycling and its role in remediation of aquifers contaminated with N-oxides may be of global importance.

Heterocyte glycolipids indicate polyphyly of stigonematalean cyanobacteria.

The cyanobacterial phylum is currently divided into five subsections (I-V), with the latter two containing no or false-branching (nostocalean) and true-branching (stigonematalean) cyanobacteria. Although morphological traits (such as cellular division and secondary branches) clearly separate both types of heterocytous cyanobacteria, molecular evidence indicates that stigonematalean cyanobacteria (Subsection V) do not form a monophyletic group but instead are interspersed and nested within the nostocalean cyanobacteria (Subsection IV). To further resolve the phylogeny of heterocytous cyanobacteria, we here analyzed the distribution of heterocyte glycolipids (HGs) in the true-branching cyanobacterium Stigonema ocellatum SAG 48.90 (type genus of Subsection V) and compared it with the HG inventory of other stigonematalean and nostocalean cyanobacteria. The most dominant HGs in S. ocellatum SAG 48.90 were 1-(O-hexose)-27-keto-3,25-octacosanediol (HG28 keto-diol) and 1-(O-hexose)-3,25,27-octacosanetriol (HG28 triol), which together constituted ca. 94% of all HGs. In addition, 1-(O-hexose)-3-keto-27-octacosanols (HG28 keto-ols), 1-(O-hexose)-3,27-octacosanediols (HG28 diols), 1-(O-hexose)-3-keto-27,29-triacontanediol (HG30 keto-diol) and 1-(O-hexose)-3,27,29-triacontanetriol (HG30 triol) occurred in minor abundances. Heterocyte glycolipids previously reported to be unique for stigonematalean cyanobacteria, i.e. 1-(O-hexose)-3,29,31-dotriacontanetriols (HG32 triols) and 1-(O-hexose)-3-keto-29,31-dotriacontanediols (HG32 keto-diols), were not detected in S. ocellatum SAG 48.90. Comparison of the HG distribution pattern with those of other heterocytous cyanobacteria indicated that S. ocellatum SAG 48.90 is most closely related to the nostocalean families Rivulariaceae and Scytonemataceae, which is complementary to reconstructed 16S rRNA gene sequence phylogenies. Our HG-based data thus provides evidence for the polyphyly of stigonematalean cyanobacteria, independent from molecular approaches, and points to the need for a critical re-evaluation of the current taxonomy of heterocytous cyanobacteria.

Anammox and denitrification separately dominate microbial N-loss in water saturated and unsaturated soils horizons of riparian zones.

Fertilized agroecosystems may show considerable leaching of the mobile nitrogen (N) compound NO3-, which pollutes groundwater and causes eutrophication of downstream waterbodies. Riparian buffer zones, positioned between terrestrial and aquatic environments, effectively remove NO3- and serve as a hotspot for N2O emissions. However, microbial processes governing NO3- reduction in riparian zones still remain largely unclear. This study explored the underlying mechanisms of various N-loss processes in riparian soil horizons using isotopic tracing techniques, molecular assays, and high-throughput sequencing. Both anaerobic ammonium oxidation (anammox) and denitrification activity were maximized in the riparian fringe rather than in the central zones. Denitrifying anaerobic methane oxidation (damo) process was not detected. Interestingly, both contrasting microbial habitats were separated by a groundwater table, which forms an important biogeochemical interface. Denitrification dominated cumulative N-losses in the upper unsaturated soil, while anammox dominated the lower oxic saturated soil horizons. Archaeal and bacterial ammonium oxidation that couple dissimilatory nitrate reduction to ammonium (DNRA) with a high cell-specific rate promoted anammox even further in oxic subsurface horizons. High-throughput sequencing and network analysis showed that the anammox rate positively correlated with Candidatus 'Kuenenia' (4%), rather than with the dominant Candidatus 'Brocadia'. The contribution to N-loss via anammox increased significantly with the water level, which was accompanied by a significant reduction of N2O emission (∼39.3 ±â€¯10.6%) since N-loss by anammox does not cause N2O emissions. Hence, water table management in riparian ecotones can be optimized to reduce NO3- pollution by shifting from denitrification to the environmentally friendly anammox pathway to mitigate greenhouse gas emissions.

Resuscitation of anammox bacteria after >10,000 years of dormancy.

Water is essential for life on Earth, and an important medium for microbial energy and metabolism. Dormancy is a state of low metabolic activity upon unfavorable conditions. Many microorganisms can switch to a metabolically inactive state after water shortage, and recover once the environmental conditions become favorable again. Here, we resuscitated dormant anammox bacteria from dry terrestrial ecosystems after a resting period of >10 ka by addition of water without any other substrates. Isotopic-tracer analysis showed that water induced nitrate reduction yielding sufficient nitrite as substrate and energy for activating anammox bacteria. Subsequently, dissimilatory nitrate reduction to ammonium (DNRA) provided the substrate ammonium for anammox bacteria. The ammonium and nitrite formed were used to produce dinitrogen gas. High throughput sequencing and network analysis identified Brocadia as the dominant anammox species and a Jettenia species seemed to connect the other community members. Under global climate change, increasing precipitation and soil moisture may revive dormant anammox bacteria in arid soils and thereby impact global nitrogen and carbon cycles.

Palaeobiology of red and white blood cell-like structures, collagen and cholesterol in an ichthyosaur bone.

Carbonate concretions are known to contain well-preserved fossils and soft tissues. Recently, biomolecules (e.g. cholesterol) and molecular fossils (biomarkers) were also discovered in a 380 million-year-old concretion, revealing their importance in exceptional preservation of biosignatures. Here, we used a range of microanalytical techniques, biomarkers and compound specific isotope analyses to report the presence of red and white blood cell-like structures as well as platelet-like structures, collagen and cholesterol in an ichthyosaur bone encapsulated in a carbonate concretion from the Early Jurassic (~182.7 Ma). The red blood cell-like structures are four to five times smaller than those identified in modern organisms. Transmission electron microscopy (TEM) analysis revealed that the red blood cell-like structures are organic in composition. We propose that the small size of the blood cell-like structures results from an evolutionary adaptation to the prolonged low oxygen atmospheric levels prevailing during the 70 Ma when ichthyosaurs thrived. The δ13C of the ichthyosaur bone cholesterol indicates that it largely derives from a higher level in the food chain and is consistent with a fish and cephalopod diet. The combined findings above demonstrate that carbonate concretions create isolated environments that promote exceptional preservation of fragile tissues and biomolecules.

Lipid biomarker signatures as tracers for harmful cyanobacterial blooms in the Baltic Sea.

The recent proliferation of harmful cyanobacterial blooms (cyanoHABs) in the Baltic and other marginal seas poses a severe threat for the health of infested ecosystems as e.g. the massive export and decay of cyanobacterial biomass facilitates the spread of bottom water hypoxia. There is evidence that cyanoHABs occurred repeatedly in the Baltic Sea but knowledge of their spatiotemporal distribution and the cyanobacteria that contributed to them is limited. In this study, we examined representatives of the major bloom-forming heterocystous cyanobacteria (i.e. Aphanizomenon, Dolichospermum (formerly Anabaena) and Nodularia) to establish lipid fingerprints that allow tracking these environmentally important diazotrophs in the modern and past Baltic Sea. The distribution of normal and mid-chain branched alkanes, fatty acid methyl esters, bacteriohopanepolyols and heterocyst glycolipids permitted a clear chemotaxonomic separation of the different heterocystous cyanobacteria but also indicated a close phylogenetic relationship between representatives of the genera Aphanizomenon and Dolichospermum. Compared to the discontinuous nature of phytoplankton surveys studies, the distinct lipid profiles reported here will allow obtaining detailed spatiotemporal information on the frequency and intensity of Baltic Sea cyanoHABs as well as their community composition using the time-integrated biomarker signatures recorded in surface and subsurface sediments. As heterocystous cyanobacteria of the genera Aphanizomenon, Dolichospermum and Nodularia are generally known to form massive blooms in many brackish as well as lacustrine systems worldwide, the chemotaxonomic markers introduced in this study may allow investigating cyanoHABs in a great variety of contemporary environments from polar to tropical latitudes.

Inland navigation: PAH inventories in soil and vegetation after EU fuel regulation 2009/30/EC.

In January 2011, fuel quality in inland water vessels was changed by EU regulation 2009/30/EC, aiming at improving air quality along waterways. We hypothesized that the implementation of this regulation both lowered the total deposition of polycyclic aromatic hydrocarbons (PAHs) and changed their composition in river valleys. We analyzed parent-, alkylated- and thio-PAHs in soil and vine leaves, at two waterways (Rhine and Moselle, Germany), as well as in one ship-free reference area (Ahr, Germany). Samples were taken annually (2010-2013) in transects perpendicular to the rivers. We did not find any relation of PAH concentration and composition on vine leaves to inland navigation, likely because atmospheric exchange processes distorted ship-specific accumulation patterns. We did find, however, an accumulation of ship-borne PAHs in topsoil near the waterways (1543±788 and 581±252ngg-1 at Moselle and Rhine, respectively), leading to larger PAH concentrations at the Moselle Valley than at the reference area (535±404ngg-1) prior to EU fuel regulation. After fuel regulation, the PAH concentrations decreased in topsoils of the Moselle and Rhine Valley by 35±9 and 62±28%, respectively. These changes were accompanied by increasing proportions of dibenzothiophene (DBT) and low molecular weight PAHs. Both, changes in PAH concentrations and composition were traceable within 200 and 350m distance to the river front of Moselle and Rhine, respectively, and likely favored by erosion of topsoil in vineyards. We conclude that the EU regulation was effective in improving soil and thus also air quality within only three years. The impact was greater and spatially more relevant at the Rhine, which may be attributed to the larger traffic volume of inland navigation.

Glycerol monoalkanediol diethers: a novel series of archaeal lipids detected in hydrothermal environments.

RATIONALE: Recent advances in analytical techniques used to study archaeal membrane lipids have led to the identification of several novel di- and tetraether lipid structures. Here, we report the presence of a previously unknown series of archaeal diethers that have been detected exclusively in hydrothermally affected environments. METHODS: Polar lipid extracts were analyzed using high-performance liquid chromatography coupled to positive ion atmospheric pressure chemical ionization mass spectrometry (HPLC/APCI-MS). Identification of the novel archaeal diethers was achieved using a triple quadrupole mass spectrometer operated in MS/MS mode and by comparison of characteristic retention time patterns. RESULTS: Modern and fossil sediments deposited under hydrothermal conditions contained variable abundances of archaeal lipids including archaeol, glycerol trialkyl glycerol tetraether (GTGT-0), isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs), glycerol monoalkyl glycerol tetraethers (GMGTs) and glycerol dialkanol diethers (GDDs). In addition to these well-established archaeal lipids, we detected a novel series of archaeal diethers (i.e., glycerol monoalkanediol diethers (GMDs)) that are structurally related to GMGTs but which lack one terminal glycerol moiety and contain 0-2 cyclopentyl ring systems. CONCLUSIONS: The unique presence of GMDs in hydrothermally affected environments suggests that these compounds may constitute an exclusive and yet unknown component of the cell wall membrane of (hyper)thermophilic Archaea. The presented mass spectral characteristics will facilitate detection of these components in pure cultures of Archaea and natural environments.

Macroecology of methane-oxidizing bacteria: the ß-diversity of pmoA genotypes in tropical and subtropical rice paddies.

Studies addressing microbial biogeography haveincreased during the past decade, but research onmicrobial distribution patterns is still in its infancies,and many aspects are only poorly understood. Here,we compared the methanotroph community in paddysoils sampled in Indonesia, Vietnam, China and Italy,focusing on the distance­decay relationship.We usedthe pmoA gene as marker for methanotroph diversityin terminal restriction fragment length polymorphism,microarray and pyrosequencing approaches. Wecould observe a significant increase of ß-diversity with geographical distance across continents (12 000 km).Measured environmental parameters explained only asmall amount of data variation, and we found no evidencefor dispersal limitation. Thus, we propose historicalcontingencies being responsible for theobserved patterns. Furthermore, we performed anin-depth analysis of type II methanotroph pmoA distributionat the sequence level. We used ordinationanalysis to project sequence dissimilarities into athree-dimensional space (multidimensional scaling).The ordination suggests that type II methanotrophs inpaddy fields can be divided into five major groups.However, these groups were found to be distributed inall soils independent of the geographic origin. Byincluding tropical field sites (Indonesia and Vietnam)into the analysis, we further observed the firstpaddy fields harbouring a methanotroph communitydepleted in type II methanotrophs.