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Solid-phase extracted dissolved organic matter (SPE-DOM) was isolated from two depth profiles at the core and at the edge of an anticyclonic eddy (ACE) in the northern South China Sea. Non-target nuclear magnetic resonance (NMR) spectroscopy and Fourier transform ion cyclotron mass spectrometry (FTICR/MS) of SPE-DOM revealed a higher uniformity of DOM molecules within the ACE than at the edge of the ACE. Small-scale upwelling of external nutrients may have contributed to higher productivity and production of fresher DOM, with higher proportions of CHNO and CHNOS compounds and low molecular weight species at the edge of the eddy. Common SPE-DOM molecules of supposedly biological origin such as carbohydrates and olefins were most abundant in the chlorophyll maximum layer in both stations. An unusual suite of ~10 abundant and ~35 less abundant tert-butyl benzene derivatives with potential to act as endocrine disruptors within a marine food chain and ~two dozen ketones of putative bacterial origin was recognized at meso- and bathypelagic depths in single-digit micromolar concentrations, with a distinct maximum at 1000m depth at the edge of ACE. Downwelling might bring temporary large volumes of productive marine waters into deep waters, with micromolar concentration of abundant, microbial food web-specific metabolites (e.g. 2,4-di-tert-butylphenol etal.). In our study, these eventually added up to one quarter of common background biogeochemical marine organic matter even at bathypelagic depths and beneath and are significant food and energy sources for marine biota. Mesoscale chemical heterogeneity of marine water columns might extend to larger depths than currently anticipated and may create activity hotspots influencing biota, processing of DOM, and cycling of nutrients and trace elements.

Fe-doped TiO2 nanoparticles were successfully synthesized by the coprecipitation method. TiO2 was doped with a different molar ratio of iron amounts, namely 0.1% and 0.2%. An undoped TiO2 was also prepared for comparison. X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-visible diffuse reflectance spectroscopy techniques were used to characterize the as-synthesized nanoparticles. The XRD spectra revealed that the photocatalysts were mostly in a well-crystallized anatase phase. Optical properties of the powders shifted from UV to the beginning of the visible light (Vis-L) region. Absorption edge wavelengths between 392 and 380 nm were obtained for the Fe-doped TiO2 and TiO2-P25, corresponding to band gap energies between 3.17 and 3.26 eV. TEM images showed homogeneity with a certain degree of agglomeration for all the samples. The photocatalytic efficiency of the as-synthesized Fe-doped TiO2 nanoparticles was performed using azo dye methyl orange (MO) in an aqueous solution under Vis-L irradiation. The photocatalytic results showed that Fe-doped TiO2 nanoparticles effectively degrade MO under Vis-L excitation and follow pseudo-first order kinetics. Besides, kinetic comparison showed that pure TiO2 is less efficient than 0.1% and 0.2% Fe-doped TiO2 because they exhibit unequaled efficiency. Moreover, the photocatalyst at 0.2% Fe-doped TiO2 molar ratio revealed the highest photocatalytic efficiency, which was 4.2 times higher compared to pure TiO2. Different amounts of Fe induced different increases in the apparent first-order rate constant of the photocatalytic process.

Sulfate-reducing microorganisms (SRMs) often compete with methanogens for common substrates. Due to thermodynamic reasons, SRMs should outcompete methanogens in the presence of sulfate. However, many studies have documented coexistence of these microbial groups in natural environments, suggesting that thermodynamics alone cannot explain the interactions among them. In this study, we investigated how SRMs compete with the established methanogenic communities in sediment from a long-term, electron acceptor-depleted, asphalt-exposed ecosystem and how they affect the composition of the organic material. We hypothesized that, upon addition of sulfate, SRMs (i) outcompete the methanogenic communities and (ii) markedly contribute to transformations of the organic material. We sampled sediments from the test and proximate control sites under anoxic conditions and incubated them in seawater medium with or without sulfate. Abundance and activity pattern of SRMs and methanogens, as well as the total prokaryotic community, were followed for 6 weeks by using qPCR targeting selected marker genes. Some of these genes were also subjected to amplicon sequencing to assess potential shifts in diversity patterns. Alterations of the organic material in the microcosms were determined by mass spectrometry. Our results indicate that the competition of SRMs with methanogens upon sulfate addition strongly depends on the environment studied and the starting microbiome composition. In the asphalt-free sediments (control), the availability of easily degradable organic material (mainly plant-derived) allows SRMs to use a larger variety of substrates, reducing interspecies competition with methanogens. In contrast, the abundant presence of recalcitrant compounds in the asphalt-exposed sediment was associated with a strong competition between SRMs and methanogens, ultimately detrimental for the latter. Our data underpin the importance of the quality of bioavailable organic materials in anoxic environments as a driver for microbial community structure and function. © Copyright © 2020 Michas, Harir, Lucio, Vestergaard, Himmelberg, Schmitt-Kopplin, Lueders, Hatzinikolaou, Schöler, Rabus and Schloter.

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This paper proposes improved guidelines for dissolved organic matter (DOM) isolation by solid phase extraction (SPE) with a styrene–divinylbenzene copolymer (PPL) sorbent, which has become an established method for the isolation of DOM from natural waters, because of its ease of application and appreciable carbon recovery. Suwannee River water was selected to systematically study the effects of critical SPE variables such as loading mass, concentration, flow rate, and up-scaling on the extraction selectivity of the PPL sorbent. High-field Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) and proton nuclear magnetic resonance (1H NMR) spectroscopy were performed to interpret the DOM chemical space of eluates, as well as permeates and wash liquids with molecular resolution. Up to 89% dissolved organic carbon (DOC) recovery was obtained with a DOC/PPL mass ratio of 1:800 at a DOC concentration of 20 mg/L. With the application of larger loading volumes, low proportions of highly oxygenated compounds were retained on the PPL sorbent. The effects of the flow rate on the extraction selectivity of the sorbent were marginal. Up-scaling had a limited effect on the extraction selectivity with the exception of increased self-esterification with a methanol solvent, resulting in methyl ester groups. Furthermore, the SPE/PPL extract exhibited highly authentic characteristics in comparison with original water and reverse osmosis samples. These findings will be useful for reproducibly isolating DOM with representative molecular compositions from various sources and concentrations and minimizing potential inconsistencies among interlaboratory comparative studies.

Similarities between the Atacama Desert (Chile) and Mars include extreme aridity, highly oxidizing chemistry, and intense ultraviolet radiation that promoted the photochemical production of perchlorates and nitrates. Concentration of these ions under hyperarid conditions led to the formation of nitrate- and perchlorate-bearing deposits in ephemeral lakes, followed by later deposition of chlorides and sulfates. At some locations, such as the Salar Grande, hypersaline deposits have remained unaltered for millions of years. We conducted a drilling campaign in deposits of the Salar to characterize the preservation state of biological molecules. A 5 m deep discontinuous core was recovered and subjected to multitechnique analysis including the antibody microarray-based biosensor LDChip300 and the SOLID (Signs Of Life Detector) instrument, complemented by geophysical, mineralogical, geochemical, and molecular analysis. We identified two units based on the mineralogy: the upper one, from the surface to ~320 cm depth characterized by a predominance of halite and anhydrite, and the lower one, from 320 to 520 cm, with a drop in halite and anhydrite and an enrichment in nitrate and perchlorate. Organic compounds including biomolecules were detected in association with the different depositional and mineralogical units, demonstrating the high capacity for molecular preservation. Hypersaline environments preserve biomolecules over geologically significant timescales; therefore, salt-bearing materials should be high-priority targets for the search for evidence of life on Mars. Key PointsPreservation of biomolecules in salty deposits of AtacamaSame salty deposits are found in MarsMars salt-enriched deposits have a great astrobiological potential.

The IMOG is the official conference of the European Association of Organic Geochemists (EAOG) and one of the most important events on this subject in the world. After the previous IMOG meetings in Madrid (7th IMOG; 1975), San Sebastian (17th IMOG; 1995), Seville (22nd IMOG), Tenerife is proud to host the fourth IMOG edition in Spain during September 15-20, 2013. We would like to dedicate this IMOG edition to Prof. Dr. Geoffrey EGLINTON. In the early 60’, together with Dick HAMILTON and the local Prof. Antonio GONZÁLEZ-GONZÁLEZ (1917- 2002), Prof EGLINTON developed the biomarker proxi in organic geochemistry when analysing leaf waxes of Canarian endemic Crassulaceae species (see communication OP1-1). This book, divided in two volumes, encomprises all communications to the 26 IMOG. For this IMOG edition a grand total of 580 abstracts were submitted by authors from all around the world. During March 21 – 23 2013 the 26 IMOG Scientific Committee (SC) meet in Madrid (Residencia de Estudiantes CSIC) to review and discuss the distribution and form of presentation, and the Conference's general chart of events was produced.