Key energy metabolisms in modern living microbialites from hypersaline Andean lagoons of the Salar de Atacama, Chile.

Microbialites are organosedimentary structures formed mainly due to the precipitation of carbonate minerals, although they can also incorporate siliceous, phosphate, ferric, and sulfate minerals. The minerals' precipitation occurs because of local chemical changes triggered by changes in pH and redox transformations catalyzed by the microbial energy metabolisms. Here, geochemistry, metagenomics, and bioinformatics tools reveal the key energy metabolisms of microbial mats, stromatolites and an endoevaporite distributed across four hypersaline lagoons from the Salar de Atacama. Chemoautotrophic and chemoheterotrophic microorganisms seem to coexist and influence microbialite formation. The microbialite types of each lagoon host unique microbial communities and metabolisms that influence their geochemistry. Among them, photosynthetic, carbon- and nitrogen- fixing and sulfate-reducing microorganisms appear to control the main biogeochemical cycles. Genes associated with non-conventional energy pathways identified in MAGs, such as hydrogen production/consumption, arsenic oxidation/reduction, manganese oxidation and selenium reduction, also contribute to support life in microbialites. The presence of genes encoding for enzymes associated with ureolytic processes in the Cyanobacteria phylum and Gammaproteobacteria class might induce carbonate precipitation in hypersaline environments, contributing to the microbialites formation. To the best of our knowledge, this is the first study characterizing metagenomically microbialites enriched in manganese and identifying metabolic pathways associated with manganese oxidation, selenium reduction, and ureolysis in this ecosystem, which suggests that the geochemistry and bioavailability of energy sources (As, Mn and Se) shapes the microbial metabolisms in the microbialites.

Connecting molecular biomarkers, mineralogical composition, and microbial diversity from Mars analog lava tubes.

Lanzarote (Canary Islands, Spain) is one of the best terrestrial analogs to Martian volcanology. Particularly, Lanzarote lava tubes may offer access to recognizably preserved chemical and morphological biosignatures valuable for astrobiology. By combining microbiological, mineralogical, and organic geochemistry tools, an in-depth characterization of speleothems and associated microbial communities in lava tubes of Lanzarote is provided. The aim is to untangle the underlying factors influencing microbial colonization in Earth's subsurface to gain insight into the possibility of similar subsurface microbial habitats on Mars and to identify biosignatures preserved in lava tubes unequivocally. The microbial communities with relevant representativeness comprise chemoorganotrophic, halophiles, and/or halotolerant bacteria that have evolved as a result of the surrounding oceanic environmental conditions. Many of these bacteria have a fundamental role in reshaping cave deposits due to their carbonatogenic ability, leaving behind an organic record that can provide evidence of past or present life. Based on functional profiling, we infer that Crossiella is involved in fluorapatite precipitation via urea hydrolysis and propose its Ca-rich precipitates as compelling biosignatures valuable for astrobiology. In this sense, analytical pyrolysis, stable isotope analysis, and chemometrics were conducted to characterize the complex organic fraction preserved in the speleothems and find relationships among organic families, microbial taxa, and precipitated minerals. We relate organic compounds with subsurface microbial taxa, showing that organic families drive the microbiota of Lanzarote lava tubes. Our data indicate that bacterial communities are important contributors to biomarker records in volcanic-hosted speleothems. Within them, the lipid fraction primarily consists of low molecular weight n-alkanes, α-alkenes, and branched-alkenes, providing further evidence that microorganisms serve as the origin of organic matter in these formations. The ongoing research in Lanzarote's lava tubes will help develop protocols, routines, and predictive models that could provide guidance on choosing locations and methodologies for searching potential biosignatures on Mars.

A multidisciplinary approach to the comparison of three contrasting treatments on both lampenflora community and underlying rock surface.

Removing lampenflora, phototrophic organisms developing on rock surfaces in tourist cavities due to the artificial lighting, is a challenge for sustainable and appropriate long-term management of caves. Photosynthetic-based biofilms usually cause rock biodeterioration and an ecological imbalance in cave ecosystems. In this work, a detailed investigation of the effects of the 3 most commonly used lampenflora cleaning operations (NaClO, H2O2 and UVC) was carried out in Pertosa-Auletta Cave (Italy). The application of NaClO showed good disinfection capability over extended periods of time without causing any appreciable rock deterioration. The H2O2 treatment showed to be corrosive for the rock surfaces covered with vermiculation deposits. The chemical alteration of organic and inorganic compounds by H2O2 did not remove biomass, favoring biofilm recovery after three months of treatment. Both NaClO and H2O2 treatments were effective at removing photoautotrophs, although the bacterial phyla Proteobacteria and Bacteroidetes as well as Apicomplexa and Cercozoa among the Eukaryotes, were found to be resistant to these treatments. The UVC treatments did not show any noticeable effect on the biofilms.

First Insights into the Bacterial Diversity of Mount Etna Volcanic Caves.

While microbial communities in limestone caves across the world are relatively understood, knowledge of the microbial composition in lava tubes is lagging behind. These caves are found in volcanic regions worldwide and are typically lined with multicolored microbial mats on their walls and ceilings. The Mount Etna (Sicily, S-Italy) represents one of the most active volcanos in the world. Due to its outstanding biodiversity and geological features, it was declared Natural Heritage of Humanity by the UNESCO in 2013. Despite the presence of more than 200 basaltic lava tubes, the microbial diversity of these hypogean systems has never been investigated so far. Here, we investigated bacterial communities in four lava tubes of Mount Etna volcano. Field emission scanning electron microscopy (FESEM) was carried out for the morphological characterization and detection of microbial features. We documented an abundant presence of microbial cells with different morphotypes including rod-shaped, filamentous, and coccoidal cells with surface appendages, resembling actinobacteria reported in other lava tubes across the world. Based on 16S rRNA gene analysis, the colored microbial mats collected were mostly composed of bacteria belonging to the phyla Actinomycetota, Pseudomonadota, Acidobacteriota, Chloroflexota, and Cyanobacteria. At the genus level, the analysis revealed a dominance of the genus Crossiella, which is actively involved in biomineralization processes, followed by Pseudomonas, Bacillus, Chujaibacter, and Sphingomonas. The presence of these taxa is associated with the carbon, nitrogen, and ammonia cycles, and some are possibly related to the anthropic disturbance of these caves. This study provides the first insight into the microbial diversity of the Etna volcano lava tubes, and expands on previous research on microbiology of volcanic caves across the world.

Fundamental Science and Engineering Questions in Planetary Cave Exploration.

Nearly half a century ago, two papers postulated the likelihood of lunar lava tube caves using mathematical models. Today, armed with an array of orbiting and fly-by satellites and survey instrumentation, we have now acquired cave data across our solar system-including the identification of potential cave entrances on the Moon, Mars, and at least nine other planetary bodies. These discoveries gave rise to the study of planetary caves. To help advance this field, we leveraged the expertise of an interdisciplinary group to identify a strategy to explore caves beyond Earth. Focusing primarily on astrobiology, the cave environment, geology, robotics, instrumentation, and human exploration, our goal was to produce a framework to guide this subdiscipline through at least the next decade. To do this, we first assembled a list of 198 science and engineering questions. Then, through a series of social surveys, 114 scientists and engineers winnowed down the list to the top 53 highest priority questions. This exercise resulted in identifying emerging and crucial research areas that require robust development to ultimately support a robotic mission to a planetary cave-principally the Moon and/or Mars. With the necessary financial investment and institutional support, the research and technological development required to achieve these necessary advancements over the next decade are attainable. Subsequently, we will be positioned to robotically examine lunar caves and search for evidence of life within Martian caves; in turn, this will set the stage for human exploration and potential habitation of both the lunar and Martian subsurface.

Organic geochemistry and mineralogy suggest anthropogenic impact in speleothem chemistry from volcanic show caves of the Galapagos.

The network of lava tubes is one of the most unexploited natural wonders of the Galapagos Islands. Here, we provide the first morphological, mineralogical, and biogeochemical assessment of speleothems from volcanic caves of the Galapagos to understand their structure, composition, and origin, as well as to identify organic molecules preserved in speleothems. Mineralogical analyses revealed that moonmilk and coralloid speleothems from Bellavista and Royal Palm Caves were composed of calcite, opal-A, and minor amounts of clay minerals. Extracellular polymeric substances, fossilized bacteria, silica microspheres, and cell imprints on siliceous minerals evidenced microbe-mineral interactions and biologically-mediated silica precipitation. Alternating depositional layers between siliceous and carbonate minerals and the detection of biomarkers of surface vegetation and anthropogenic stressors indicated environmental and anthropogenic changes (agriculture, human waste, and cave visits) on these unique underground resources. Stable isotope analysis and Py-GC/MS were key to robustly identify biomarkers, allowing for implementation of future protection policies.

Sulfidic Habitats in the Gypsum Karst System of Monte Conca (Italy) Host a Chemoautotrophically Supported Invertebrate Community.

The great diversity of the invertebrate community thriving in the deepest sections of the gypsum karst system of the Monte Conca sinkhole (Sicily, Italy) suggests the existence of a complex food web associated with a sulfidic pool and chemoautotrophic microbial activity. To shed light on the peculiarity of this biological assemblage, we investigated the species composition of the invertebrate community and surveyed trophic interactions by stable isotope analysis. The faunal investigation conducted by visual censuses and hand sampling methods led to the discovery of a structured biological assemblage composed of both subterranean specialized and non-specialized species, encompassing all trophic levels. The community was remarkably diverse in the sulfidic habitat and differed from other non-sulfidic habitats within the cave in terms of stable isotope ratios. This pattern suggests the presence of a significant chemoautotrophic support by the microbial communities to the local food web, especially during the dry season when the organic input from the surface is minimal. However, when large volumes of water enter the cave due to local agricultural activities (i.e., irrigation) or extreme precipitation events, the sulfidic habitat of the cave is flooded, inhibiting the local autotrophic production and threatening the conservation of the entire ecosystem.

Hydrophobicity of soils affected by fires: An assessment using molecular markers from ultra-high resolution mass spectrometry.

Soil water repellency (SWR) is a physical property due to a complex interaction of factors (e.g., fire, soil organic matter, soil texture) that reduces the soil water infiltration capacity. Traditionally, SWR is attributed to the accumulation and redistribution of hydrophobic compounds within soil profile. To obtain further insight into chemical compounds, which could be associated with SWR, a study was done on coarse (1-2 mm) and fine (< 0.05 mm) granulometric fractions of burned and unburned sandy soils under two Mediterranean vegetation biomes from Doñana National Park (Spain). The water drop penetration time (WDPT) test was used to assess the SWR. The molecular composition of extracted humic substances from the soil organic matter (SOM) was determined by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR/MS). Partial least squares (PLS) regressions showed that the SWR can be predicted (P = 0.006) solely based on the abundances of approximately 1200 common compounds determined by FT-ICR/MS. This model confirmed the significant correlation between a specific SOM molecular composition and the SWR. The comparative analysis revealed that the SWR in the burned samples was significantly (P < 0.05) related to the abundance of aromatic and condensed compounds, while in the unburned samples there was a significant influence of aromatic hydrocarbons and lignin compounds. In the fine fraction, lipid compounds were significantly associated with the SWR. Contrastingly, the coarse fraction did not show any correlation. Alternatively, soils with a high SWR were significantly related to the presence of lipids and lignin. This analysis showed that combining FT-ICR/MS molecular characterizations with statistical treatments is a powerful approach for exploratory analysis suggesting that the structural features associated with SWR in the studied soils are different depending on the types of vegetation or the soil physical fractions with different particle size.

Biochar ageing in polluted soils and trace elements immobilisation in a 2-year field experiment.

Biochar application to soils has become a focus of research during the last decade due to its high potential for C sequestration. Nevertheless, there is no exhaustive information on the long-term effects of biochar application in soils contaminated with trace elements. In this work, a 2-year field experiment was conducted comprising the application of different types of biochar to acidic and moderately acidic soils with high concentrations of As, Cu, Pb, Ba and Zn. In addition, representative samples of each biochar were buried in permeable bags that allowed the flow of water and microorganisms but not their physical interaction with soil aggregates. The biochars significantly adsorbed trace elements from polluted soils. However, given the high total concentration of these persistent trace elements in the soils, the application of biochars did not succeed in reducing the concentration of available metals (CaCl2 extractable fraction). After 2 years of ageing under field conditions, some degradation of the biochars from olive pit, rice husk and wood were observed. This study provides novel information concerning the biochar alterations during ageing in polluted soils, as the decrease of aryl C signal observed by 13C nuclear magnetic resonance (NMR) spectroscopy and the presence of O-containing groups shown by Fourier Transform mid-Infrared Spectroscopy (FT-IR) in aged biochar which enhanced trace elements adsorption. Scanning electron microscopy (SEM) revealed slight changes on surface morphology of aged biochar particles.

Microbial Community Characterizing Vermiculations from Karst Caves and Its Role in Their Formation.

The microbiota associated with vermiculations from karst caves is largely unknown. Vermiculations are enigmatic deposits forming worm-like patterns on cave walls all over the world. They represent a precious focus for geomicrobiological studies aimed at exploring both the microbial life of these ecosystems and the vermiculation genesis. This study comprises the first approach on the microbial communities thriving in Pertosa-Auletta Cave (southern Italy) vermiculations by next-generation sequencing. The most abundant phylum in vermiculations was Proteobacteria, followed by Acidobacteria > Actinobacteria > Nitrospirae > Firmicutes > Planctomycetes > Chloroflexi > Gemmatimonadetes > Bacteroidetes > Latescibacteria. Numerous less-represented taxonomic groups (< 1%), as well as unclassified ones, were also detected. From an ecological point of view, all the groups co-participate in the biogeochemical cycles in these underground environments, mediating oxidation-reduction reactions, promoting host rock dissolution and secondary mineral precipitation, and enriching the matrix in organic matter. Confocal laser scanning microscopy and field emission scanning electron microscopy brought evidence of a strong interaction between the biotic community and the abiotic matrix, supporting the role of microbial communities in the formation process of vermiculations.

Chemical, physical and morphological properties of biochars produced from agricultural residues: Implications for their use as soil amendment.

Biochar is a pyrogenous organic material resulting from the pyrolysis of organic residues, which is attracting the interest from researchers and farmers for its potential to sequester carbon and its use as soil ameliorant. Pyrolysis conditions and feedstock determine the properties of the biochars produced. In order to understand the relationship between these variables we analysed in detail the physical, chemical and surface characteristics of biochars produced from three contrasting agronomic residues abundantly generated in South Spain, such as rice husk (RH), olive pit (OP) and pruning remains of olive trees (mainly composed of olive branches and leaves; OB), using a temperature range from 350 to 600 °C and residence times from 0.5 to 4 h. High pyrolysis temperature (600 °C) and time resulted in the greatest pH and C content in the biochars. In general, elemental composition and ash content were dependent on the type of organic waste used as feedstock. 13C Nuclear Magnetic Resonance Spectroscopy and thermal (TG-DSC) analyses showed that temperatures ≥500 °C are needed to achieve a high degree of aromatization of the chars. Micro-computed tomography and field emission scanning electron microscopy revealed that the structure of RH was preserved during the pyrolysis process, favouring a greater porosity for these biochars. These data are very useful for the production of stable biochars obtained from residual biomass, maximising the value of residual biomass resources. These biochars show physical and chemical properties, such as adequate pH, high water retention capacity or high porosity, of interest for their use as soil amendments.

Impact of wildfires on subsurface volcanic environments: New insights into speleothem chemistry.

Siliceous speleothems frequently reported in volcanic caves have been traditionally interpreted as resulting from basalt weathering combined with the activity of microbial communities. A characteristic feature in lava tubes from Hawaii, Azores and Canary Islands is the occurrence of black jelly-like speleothems. Here we describe the formation process of siliceous black speleothems found in a lava tube from La Palma, Canary Islands, Spain, based on mineralogy, microscopy, light stable isotopes, analytical pyrolysis, NMR spectroscopy and chemometric analyses. The data indicate that the black speleothems are composed of a hydrated gel matrix of amorphous aluminum silicate materials containing charred vegetation and thermally degraded resins from pines or triterpenoids from Erica arborea, characteristic of the overlying laurel forest. This is the first observation of a connection between fire and speleothem chemistry from volcanic caves. We conclude that wildfires and organic matter from the surface area overlying caves may play an important role in the formation of speleothems found in La Palma and demonstrate that siliceous speleothems are potential archives for past fires.

Effect of pyrolysis conditions on the total contents of polycyclic aromatic hydrocarbons in biochars produced from organic residues: Assessment of their hazard potential.

The interest of using biochar, the solid byproduct from organic waste pyrolysis, as soil conditioner is significantly increasing. Nevertheless, persistent organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs), are formed during pyrolysis due to the incomplete combustion of organic matter. Consequently, these pollutants may enter the environment when biochar is incorporated into soil and cause adverse ecological effects. In this study, we examined the content of the 16 United States Environmental Protection Agency (USEPA) PAHs in biochars produced from rice husk, wood, wheat and sewage sludge residues using three different pyrolytic reactors and temperatures (400, 500 and 600 °C). The total concentration of PAHs (∑PAH) ranged from 799 to 6364 µg kg-1, being naphthalene, phenanthrene and anthracene the most abundant PAHs in all the biochars. The maximum amount of PAHs was observed for the rice husk biochar produced in the batch reactor at 400 °C, which decreased with increasing temperature. The ∑PAH value of the wood biochar produced via traditional kilns doubled compared with the wood biochar produced using the other pyrolytic reactors (5330 µg kg-1 in Kiln; 2737 µg kg-1 in batch and 1942 µg kg-1 in the rotary reactor). Looking for a more reliable risk assessment of the potential exposure of PAHs in biochar, the total toxic equivalent concentrations (TTEC) of the 14 produced biochars were calculated. When comparing the same feedstock and temperature, TTEC values indicated that the rotary reactor produced the safest biochars. In contrast, the biochars produced using the batch reactor at 400 and 500 °C have the greatest hazard potential. Our results provide valuable information on the potential risk of biochar application for human and animal health, as well as for the environment due to PAHs contamination.

Cellular Responses of the Lichen Circinaria gyrosa in Mars-Like Conditions.

Lichens are extremely resistant organisms that colonize harsh climatic areas, some of them defined as "Mars-analog sites." There still remain many unsolved questions as to how lichens survive under such extreme conditions. Several studies have been performed to test the resistance of various lichen species under space and in simulated Mars-like conditions. The results led to the proposal that Circinaria gyrosa (Lecanoromycetes, Ascomycota) is one of the most durable astrobiological model lichens. However, although C. gyrosa has been exposed to Mars-like environmental conditions while in a latent state, it has not been exposed in its physiologically active mode. We hypothesize that the astrobiological test system "Circinaria gyrosa," could be able to be physiologically active and to survive under Mars-like conditions in a simulation chamber, based on previous studies performed at dessicated-dormant stage under simulated Mars-like conditions, that showed a complete recover of the PSII activity (Sánchez et al., 2012). Epifluorescence and confocal laser scanning microscopy (CLSM) showed that living algal cells were more abundant in samples exposed to niche conditions, which simulated the conditions in micro-fissures and micro-caves close to the surface that have limited scattered or time-dependent light exposure, than in samples exposed to full UV radiation. The medulla was not structurally affected, suggesting that the niche exposure conditions did not disturb the lichen thalli structure and morphology as revealed by field emission scanning electron microscopy (FESEM). In addition, changes in the lichen thalli chemical composition were determined by analytical pyrolysis. The chromatograms resulting from analytical pyrolysis at 500°C revealed that lichen samples exposed to niche conditions and full UV radiation consisted primarily of glycosidic compounds, lipids, and sterols, which are typical constituents of the cell walls. However, specific differences could be detected and used as markers of the UV-induced damage to the lichen membranes. Based on its viability responses after rehydration, our study shows that the test lichen survived the 30-day incubation in the Mars chamber particularly under niche conditions. However, the photobiont was not able to photosynthesize under the Mars-like conditions, which indicates that the surface of Mars is not a habitable place for C. gyrosa.

Soil-borne fungi challenge the concept of long-term biochemical recalcitrance of pyrochar.

Pyrogenic organic matter (PyOM) is assumed to be biochemically recalcitrant, but recent studies indicated a quick decrease of PyOM in post-fire soils. Regardless erosion and abiotic degradation, microbial decomposition has been the explanation for this response, but no direct proof has been provided up to now. In the present study, we were able to demonstrate for the first time that the soil-borne fungus Fusarium oxysporum is not only colonizing the pore system of pyrochar (PyC) but is also involved in the degradation of its aromatic network. We showed that PyC not only stimulates microbial degradation of soil organic matter (SOM), but is also attacked and decomposed by microorganisms. Our observations are based on the chemical and morphological alterations of a sewage-sludge derived PyC produced at 600 °C after its amendment to a Calcic Cambisol by solid-state 13C nuclear magnetic resonance spectroscopy, analytical pyrolysis, elemental analysis, field emission scanning electron microscopy and DNA-based analysis of the isolated fungi. We showed that biofilms detected in the PyC play an essential role in the degradation process. These results are indispensable for a reliable assessment of the carbon sequestration potential of PyC in soils but also for improving global C cycling models.

Yellow coloured mats from lava tubes of La Palma (Canary Islands, Spain) are dominated by metabolically active Actinobacteria.

Microbial diversity in lava tubes from Canary Islands (Spain) has never been explored thus far offering a unique opportunity to study subsurface microbiology. Abundant yellow coloured mats developing on coralloid speleothems in a lava tube from La Palma Islands were studied by next-generation sequencing and DNA/RNA clone library analyses for investigating both total and metabolically active bacteria. In addition, morphological and mineralogical characterization was performed by field emission scanning electron microscopy (FESEM), micro-computed tomography, X-ray diffraction and infrared spectroscopy to contextualize sequence data. This approach showed that the coralloid speleothems consist of banded siliceous stalactites composed of opal-A and hydrated halloysite. Analytical pyrolysis was also conducted to infer the possible origin of cave wall pigmentation, revealing that lignin degradation compounds can contribute to speleothem colour. Our RNA-based study showed for the first time that members of the phylum Actinobacteria, with 55% of the clones belonging to Euzebyales order, were metabolically active components of yellow mats. In contrast, the DNA clone library revealed that around 45% of clones were affiliated to Proteobacteria. Composition of microbial phyla obtained by NGS reinforced the DNA clone library data at the phylum level, in which Proteobacteria was the most abundant phylum followed by Actinobacteria.

Effects of aging under field conditions on biochar structure and composition: Implications for biochar stability in soils.

The effects of aging on biochar (BC) properties, composition and carbon sequestration are still under debate. This study aimed at illustrating the qualitative alterations of five different BCs aged during a 24-month field experiment located in Southwest Spain. To determine the recalcitrance of each BC, physical fragmentation test, scanning electron microscopy, 13C NMR spectroscopy and CO2-respiration experiments were performed. The physical fragmentation values of all types of BC increased significantly over time at field conditions. FESEM examinations of aged BCs showed collapsed structures and the presence of entrapped soil material and microbial mats into the BC pores. The 13C NMR spectroscopy demonstrated an increase of the relative abundance of O-alkyl C and alkyl C at expenses of aromatic-C in aged BCs. The C losses of all BCs ranged from 27% to 11% of the initial C. In contrast, the nitrogen (N) content of wood-derived BCs significantly increased probably due to the sorption of nitrogen containing compounds into these highly-porous weathered chars. With the exception of that for the sewage sludge-BC, the pH of all aged BCs decreased from >9 to the soil pH, indicating a short lasting of the liming effect caused by BC addition. The respiration experiment revealed that BC recalcitrance was much lower than expected and, within the range of decades. Only wood-derived BCs significantly increased the mean residence time of the slow C pool of the Cambisol by factors between 3.4 and 7.7. Mediterranean climate conditions and the characteristics of the Cambisol used probably accelerated the microbial degradation of BCs.

Wildfire effects on lipid composition and hydrophobicity of bulk soil and soil size fractions under Quercus suber cover (SW-Spain).

Soil water repellency (hydrophobicity) prevents water from wetting or infiltrating soils, triggering changes in the ecosystems. Fire may develop, enhance or destroy hydrophobicity in previously wettable or water-repellent soils. Soil water repellency is mostly influenced by the quality and quantity of soil organic matter, particularly the lipid fraction. Here we report the results of a study on the effect of fire on the distribution of soil lipids and their role in the hydrophobicity grade of six particle size fractions (2-1, 1-0.5, 0.5-0.25, 0.25-0.1, 0.1-0.05 and <0.05mm) of an Arenosol under Quercus suber canopy at the Doñana National Park (SW-Spain). Hydrophobicity was determined using water drop penetration time test. Field emission scanning electron microscopy (FESEM) was used to assess the presence and morphology of the inorganic and organic soil components in the particle size fractions. Soil lipids were Soxhlet extracted with a dichloromethane-methanol mixture. Fatty acids (FAs) and neutral lipids were separated, derivatized, identified and quantified by gas chromatography/mass spectrometry and gas chromatography/flame ionization detection. The hydrophobicity values of soil samples and fractions were statistically different (P < 0.05), for both, the unburnt and burnt soils, and particle size fractions. All samples displayed a similar distribution of FAs, straight-chain saturated acids in the C14-C32 range, and neutral lipids (n-alkan-1-ols, n-alkanes), only differing in their relative abundances. Among possible biogeochemical mechanisms responsible for the changes in soil lipids, the observed depletion of long chain FAs (C≥24) in the coarse fraction is best explained by thermal cracking caused by the heat of the fire. The enrichment of long chain FAs observed in other fractions suggests possible exogenous additions of charred, lipid-rich, material, like cork suberin or other plant-derived macromolecules (cutins). Principal component analysis was used to study the relationships between hydrophobicity with soil organic matter and its different components. Extractable organic matter (EOM) and specifically long chain FAs content were positively correlated to soil hydrophobicity. Therefore, the latter could be used as biomarkers surrogated to hydrophobicity in sandy soils.

Assessing the effects of UVA photocatalysis on soot-coated TiO2-containing mortars.

The deposition of soot on building surfaces darkens their colour and leads to undesirable black crusts, which are one of the most serious problems on the conservation of built cultural heritage. As a preventive strategy, self-cleaning systems based on the use of titanium dioxide (TiO2) coatings have been employed on building materials for degrading organic compounds deposited on building surfaces, improving their durability and performance. In this study, the self-cleaning effect of TiO2-containing mortars coated with diesel soot has been appraised under laboratory conditions. The mortar samples were manufactured using lime putty and two different doses of TiO2 (2.5% and 5%). The lime mortars were then coated with diesel engine soot and irradiated with ultraviolet A (UVA) illumination for 30days. The photocatalytic efficiency was evaluated by visual inspection, field emission scanning electron microscopy (FESEM) and colour spectrophotometry. Changes in the chemical composition of the soot particles (including persistent organic pollutants) were assessed by analytical pyrolysis (Py-GC/MS) and solid state 13C NMR spectroscopy. The FESEM and colour spectrophotometry revealed that the soot-coated TiO2-containing mortars promoted a self-cleaning effect after UVA irradiation. The combination of analytical pyrolysis and 13C solid state NMR showed that the UVA irradiation caused the cracking of polycyclic aromatic structures and n-alkyl compounds of the diesel soot and its transformation into methyl polymers. Our findings also revealed that the inclusion of TiO2 in the lime mortar formulations catalysed these transformations promoting the self-cleaning of the soot-stained mortars. The combined action of TiO2 and UVA irradiation is a promising proxy to clean lime mortars affected by soot deposition.