Selective extraction of levoglucosan and its isomers from complex matrices using ligand exchange-solid phase extraction for analysis by liquid chromatography-electrospray ionization-tandem mass spectrometry.

The analysis of trace quantities of monosaccharide anhydrides (MAs) in sediments is complicated by the lack of fast and reliable technologies to selectively extract these water-soluble non-ionic compounds from samples of complex composition. Here we describe a solid phase extraction method that takes advantage of the affinity between monosaccharide anhydrides (MAs) and immobilized Na+ ions related to ligand-exchange processes (LE-SPE). The capacity factor of LE-SPE columns was enhanced by using non-aqueous mobile phases such as DCM/MeOH mixtures. We have used the unique properties of LE-SPE columns to selectively extract MAs from lacustrine, coastal, and deep-sea oceanic sediment samples. The analytical procedure produces extracts with low ion suppression effects (0-20%), resulting in ideal conditions for MAs quantification with LC-ESI-MS/MS systems irrespective of the sedimentary matrix and MAs concentration. The analytical method yields repeatable concentration values (RSD of 9-23% for levoglucosan and 15-34% for mannosan and galactosan) and an IS recovery of 45-70%. The instrumental dynamic range is 10-10000 pg injected, but in practice, the methodological lower limit of quantification is constrained by sample contamination during processing. The combination of LE-SPE and LC-ESI-MS/MS has the potential to produce sensitive and reliable technologies to analyze saccharides and amino acids in environmental and biological samples.

Assessment of greenhouse emissions of the green bean through the static enclosure technique.

Urban green installations are extensively promoted to increase sustainable and accessible food production and simultaneously improve the environmental performance and liveability of city buildings. In addition to the multiple benefits of plant retrofitting, these installations may lead to a consistent increase in biogenic volatile organic compounds (BVOCs) in the urban environment, especially indoors. Accordingly, health concerns could limit the implementation of building-integrated agriculture. In a building-integrated rooftop greenhouse (i-RTG), throughout the whole hydroponic cycle, green bean emissions were dynamically collected in a static enclosure. Four representative BVOCs, α-pinene (monoterpene), ß-caryophyllene (sesquiterpene), linalool (oxygenated monoterpene) and cis-3-hexenol (LOX derivate), were investigated in the samples collected from two equivalent sections of a static enclosure, one empty and one occupied by the i-RTG plants, to estimate the volatile emission factor (EF). Throughout the season, extremely variable BVOC levels between 0.04 and 5.36 ppb were found with occasional but not significant (P > 0.05) variations between the two sections. The highest emission rates were observed during plant vegetative development, with EFs equivalent to 78.97, 75.85 and 51.34 ng g-1 h-1 for cis-3-hexenol, α-pinene, and linalool, respectively; at plant maturity, all volatiles were either close to the LLOQ (lowest limit of quantitation) or not detected. Consistent with previous studies significant relationships (r ≥ 0.92; P < 0.05) were individuated within volatiles and temperature and relative humidity of the sections. However, correlations were all negative and were mainly attributed to the relevant effect of the enclosure on the final sampling conditions. Overall, levels found were at least 15 folds lower than the given Risk and LCI values of the EU-LCI protocol for indoor environments, suggesting low BVOC exposure in the i-RTG. Statistical outcomes demonstrated the applicability of the static enclosure technique for fast BVOC emissions survey inside green retrofitted spaces. However, providing high sampling performance over entire BVOCs collection is recommended to reduce sampling error and incorrect estimation of the emissions.

Improving the Fertigation of Soilless Urban Vertical Agriculture Through the Combination of Struvite and Rhizobia Inoculation in Phaseolus vulgaris.

Soilless crop production is a viable way to promote vertical agriculture in urban areas, but it relies extensively on the use of mineral fertilizer. Thus, the benefits of fresher, local food and avoiding the transportation and packaging associated with food import could be counteracted by an increase in nutrient-rich wastewater, which could contribute to freshwater and marine eutrophication. The present study aimed to explore the use of mineral fertilizer substitutes in soilless agriculture. Phaseolus vulgaris (common bean) was fertilized with a combination of slow-releasing fertilizer struvite (a source of N, P, and Mg), which is a byproduct of wastewater treatment plants, and inoculation with Rhizobium (a N2-fixing soil bacteria). The experiment included three bean-production lines: (A) 2 g/plant of struvite and rhizobial inoculation; (B) 5 g/plant of struvite and rhizobial inoculation, both irrigated with a Mg-, P-, and N-free nutrient solution; and (C) a control treatment that consisted of irrigation with a full nutrient solution and no inoculation. Plant growth, development, yields, and nutrient contents were determined at 35, 62, and 84 days after transplanting as well as biological N2 fixation, which was determined using the 15N natural abundance method. Treatments A and B resulted in lower total yields per plant than the control C treatment (e.g., 59.35 ± 26.4 g plant-1 for A, 74.2 ± 23.0 g plant-1 for B, and 147.71 ± 45.3 g plant-1 for C). For A and B, the nodulation and N2 fixation capacities appeared to increase with the amount of initially available struvite, but, over time, deficient levels of Mg were reached as well as nearly deficient levels of P, which could explain the lower yields. Nevertheless, we conclude that the combination of struvite and N2-fixing bacteria covered the N needs of plants throughout the growth cycle. However, further studies are needed to determine the optimal struvite quantities for vertical agriculture systems that can meet the P and Mg requirements throughout the lifetime of the plants.

Soil organic carbon accumulation rates on Mediterranean abandoned agricultural lands.

Secondary succession on abandoned agricultural lands can produce climate change mitigation co-benefits, such as soil carbon sequestration. However, the accumulation of soil organic carbon (SOC) in Mediterranean regions has been difficult to predict and is subject to multiple environmental and land management factors. Gains, losses, and no significant changes have all been reported. Here we compile chronosequence data (n = 113) from published studies and new field sites to assess the response of SOC to agricultural land abandonment in peninsular Spain. We found an overall SOC accumulation rate of +2.3% yr-1 post-abandonment. SOC dynamics are highly variable and context-dependent. Minimal change occurs on abandoned cereal croplands compared to abandoned woody croplands (+4% yr-1). Accumulation is most prevalent within a Goldilocks climatic window of ~13-17 °C and ~450-900 mm precipitation, promoting >100% gains after three decades. Our secondary forest field sites accrued 40.8 Mg C ha-1 (+172%) following abandonment and displayed greater SOC and N depth heterogeneity than natural forests demonstrating the long-lasting impact of agriculture. Although changes in regional climate and crop types abandoned will impact future carbon sequestration, abandonment remains a low-cost, long-term natural climate solution best incorporated in tandem with other multipurpose sustainable land management strategies.

Appraisal of sedimentary alkenones for the quantitative reconstruction of phytoplankton biomass.

Marine primary productivity (PP) is the driving factor in the global marine carbon cycle. Its reconstruction in past climates relies on biogeochemical proxies that are not considered to provide an unequivocal signal. These are often based on the water column flux of biogenic components to sediments (organic carbon, biogenic opal, biomarkers), although other factors than productivity are posited to control the sedimentary contents of the components, and their flux is related to the fraction of export production buried in sediments. Moreover, most flux proxies have not been globally appraised. Here, we assess a proxy to quantify past phytoplankton biomass by correlating the concentration of C37 alkenones in a global suite of core-top sediments with sea surface chlorophyll-a (SSchla) estimates over the last 20 y. SSchla is the central metric to calculate phytoplankton biomass and is directly related to PP. We show that the global spatial distribution of sedimentary alkenones is primarily correlated to SSchla rather than diagenetic factors such as the oxygen concentration in bottom waters, which challenges previous assumptions on the role of preservation on driving concentrations of sedimentary organic compounds. Moreover, our results suggest that the rate of global carbon export to sediments is not regionally constrained, and that alkenones producers play a dominant role in the global export of carbon buried in the seafloor. This study shows the potential of using sedimentary alkenones to estimate past phytoplankton biomass, which in turn can be used to infer past PP in the global ocean.

Belowground biota responses to maize biochar addition to the soil of a Mediterranean vineyard.

Biochar is a high carbon material resulting from biomass pyrolysis that, when applied to croplands, can increase soil carbon and soil water retention. Both effects are of critical importance in semi-arid regions, where carbon decline and desertification are the main drivers of soil degradation. Since most environmental services provided by soil are mediated by belowground biota, effects of biochar on soil microbial and invertebrate communities must be evaluated under field conditions before its agricultural application can be recommended. We tested maize biochar for its mid-term effect on soil microbes and micro-arthropods of a Mediterranean vineyard. We applied biochar to three field plots with neutral sandy loam soils at a dose of 5 Mg ha-1. During two years, we monitored the abundance of functional groups of soil micro-arthropods and estimated the biomass of soil microbial groups. We also analyzed the δ13C value of microbial PLFA biomarkers to determine biochar-C utilization by each microbial group taking advantage of the δ13C natural abundance differences between the applied biochar and the soil. Biochar addition significantly reduced soil microbial biomass but did not alter the functional microbial diversity nor the abundance or biodiversity of soil micro-arthropods. The contribution of biochar-C to the diet of most microbial groups was very low through the monitoring period. However, two gram-negative bacterial groups increased their biochar-derived carbon uptake under extreme soil dryness, which suggests that biochar-C might help soil microbes to overcome the food shortage caused by drought. The decrease in microbial biomass observed in our experiment and the concomitant decrease of SOM mineralization could contribute to the carbon sequestration potential of Mediterranean soils after biochar addition.

First evidences of Amazonian wildlife feeding on petroleum-contaminated soils: A new exposure route to petrogenic compounds?

Videos recorded with infrared camera traps placed in petroleum contaminated areas of the Peruvian Amazon have shown that four wildlife species, the most important for indigenous peoples' diet (lowland tapir, paca, red-brocket deer and collared peccary), consume oil-contaminated soils and water. Further research is needed to clarify whether Amazonian wildlife's geophagy can be a route of exposure to petrogenic contamination for populations living in the vicinity of oil extraction areas and relying on subsistence hunting.

Oil pollution in soils and sediments from the Northern Peruvian Amazon.

Oil has been extracted from the Northern Peruvian Amazon for over four decades. However, few scientific studies have assessed the impacts of such activities in the environment and health of indigenous communities in the region. We have investigated the occurrence of petrogenic hydrocarbon pollution in soils and sediments from areas favoured as hunting or fishing grounds by local indigenous inhabitants. The study was conducted in one of the most productive oil blocks in Peru, located in the headwaters of the Amazon river. Soils and river sediments, in the vicinity of oil extraction and processing infrastructure, contained an oil pollution signature as attested by the occurrence of hopanes and steranes. Given the lack of any other significant source of oil pollution in the region, the sources of hydrocarbons are likely to be the activities of the oil industry in the oil block, from voluntary discharges or accidental spills. Spillage of produced water was commonplace until 2009. Moreover, petrogenic compounds were absent in control samples in sites far removed from any oil infrastructure in the oil block. Our findings suggest that wildlife and indigenous populations in this region of the Amazon are exposed to the ingestion of oil polluted soils and sediments. The data obtained supports previous claims that the local spillage of oil and produced waters in the water courses in the Corrientes and Pastaza basins could have eventually reached the main water course of the Amazon.

Dataset on the evidence of bee products processing: A functional definition of a specialized type of macro-lithic tool.

The database includes spatial, chronological and technological information about the analyzed tools in the article entitled "Evidence of bee products processing: a functional definition of a specialized type of macro-lithic tool" (Ache et al., 2017 [1]). The technological information refers to the tool type, its rock type, weight, state of preservation, morphology, metrical data and functional features. We also provide an index of acronyms to properly understand the dataset published here.

Abundance and Co-Distribution of Widespread Marine Archaeal Lineages in Surface Sediments of Freshwater Water Bodies across the Iberian Peninsula.

Archaea inhabiting marine and freshwater sediments have a relevant role in organic carbon mineralization, affecting carbon fluxes at a global scale. Despite current evidences suggesting that freshwater sediments largely contribute to this process, few large-scale surveys have been addressed to uncover archaeal diversity and abundance in freshwater sedimentary habitats. In this work, we quantified and high-throughput sequenced the archaeal 16S rRNA gene from surficial sediments collected in 21 inland waterbodies across the Iberian Peninsula differing in typology and trophic status. Whereas methanogenic groups were dominant in most of the studied systems, especially in organic-rich sediments, archaea affiliated to widespread marine lineages (the Bathyarchaeota and the Thermoplasmata) were also ubiquitous and particularly abundant in euxinic sediments. In these systems, Bathyarchaeota communities were dominated by subgroups Bathyarchaeota-6 (87.95 ± 12.71%) and Bathyarchaeota-15 (8.17 ± 9.2%) whereas communities of Thermoplasmata were mainly composed of members of the order Thermoplasmatales. Our results also indicate that Archaea accounted for a minor fraction of sedimentary prokaryotes despite remarkable exceptions in reservoirs and some stratified lakes. Copy numbers of archaeal and bathyarchaeotal 16S rRNA genes were significantly different when compared according to system type (i.e., lakes, ponds, and reservoirs), but no differences were obtained when compared according to their trophic status (from oligotrophy to eutrophy). Interestingly, we obtained significant correlations between the abundance of reads (Spearman r = 0.5, p = 0.021) and OTU richness (Spearman r = 0.677, p < 0.001) of Bathyarchaeota and Thermoplasmata across systems, reinforcing the hypothesis of a potential syntrophic interaction between members of both lineages.

Water contamination from oil extraction activities in Northern Peruvian Amazonian rivers.

Oil extraction activities in the Northern Peruvian Amazon have generated a long-standing socio-environmental conflict between oil companies, governmental authorities and indigenous communities, partly derived from the discharge of produced waters containing high amounts of heavy metals and hydrocarbons. To assess the impact of produced waters discharges we conducted a meta-analysis of 2951 river water and 652 produced water chemical analyses from governmental institutions and oil companies reports, collected in four Amazonian river basins (Marañon, Tigre, Corrientes and Pastaza) and their tributaries. Produced water discharges had much higher concentrations of chloride, barium, cadmium and lead than are typically found in fresh waters, resulting in the widespread contamination of the natural water courses. A significant number of water samples had levels of cadmium, barium, hexavalent chromium and lead that did not meet Peruvian and international water standards. Our study shows that spillage of produced water in Peruvian Amazon rivers placed at risk indigenous population and wildlife during several decades. Furthermore, the impact of such activities in the headwaters of the Amazon extended well beyond the boundaries of oil concessions and national borders, which should be taken into consideration when evaluating large scale anthropogenic impacts in the Amazon.

Molecular dynamics simulation study of the effect of glycerol dialkyl glycerol tetraether hydroxylation on membrane thermostability.

Archaeal tetraether membrane lipids span the whole membrane width and present two C40 isoprenoid chains bound by two glycerol groups (or one glycerol and calditol). These lipids confer stability and maintain the membrane fluidity in mesophile to extremophile environments, making them very attractive for biotechnological applications. The isoprenoid lipid composition in archaeal membranes varies with temperature, which has placed these lipids in the focus of paleo-climatological studies for over a decade. Non-hydroxylated isoprenoid archaeal lipids are typically used as paleo-thermometry proxies, but recently identified hydroxylated (OH) derivatives have also been proposed as temperature proxies. The relative abundance of hydroxylated lipids increases at lower temperatures, but the physiological function of the OH moiety remains unknown. Here we present molecular dynamics simulations of membranes formed by the acyclic glycerol-dialkyl-glycerol-tetraether caldarchaeol (GDGT-0), the most widespread archaeal core lipid, and its mono-hydroxylated variant (OH-GDGT-0) to better understand the physico-chemical properties conferred to the membrane by this additional moiety. The molecular dynamics simulations indicate that the additional OH group forms hydrogen bonds mainly with the sugar moieties of neighbouring lipids and with water molecules, effectively increasing the size of the polar headgroups. The hydroxylation also introduces local disorder that propagates along the entire alkyl chains, resulting in a slightly more fluid membrane. These changes would help to maintain trans-membrane transport in cold environments, explaining why the relative abundance of hydroxylated Archaea lipids increases at lower temperatures. The in silico approach aids to understand the underlying physiological mechanisms behind the hydroxylated lipid based paleo-thermometer recently proposed.

Links between media communication and local perceptions of climate change in an indigenous society.

Indigenous societies hold a great deal of ethnoclimatological knowledge that could potentially be of key importance for both climate change science and local adaptation; yet, we lack studies examining how such knowledge might be shaped by media communication. This study systematically investigates the interplay between local observations of climate change and the reception of media information amongst the Tsimane', an indigenous society of Bolivian Amazonia where the scientific discourse of anthropogenic climate change has barely reached. Specifically, we conducted a Randomized Evaluation with a sample of 424 household heads in 12 villages to test to what degree local accounts of climate change are influenced by externally influenced awareness. We randomly assigned villages to a treatment and control group, conducted workshops on climate change with villages in the treatment group, and evaluated the effects of information dissemination on individual climate change perceptions. Results of this work suggest that providing climate change information through participatory workshops does not noticeably influence individual perceptions of climate change. Such findings stress the challenges involved in translating between local and scientific framings of climate change, and gives cause for concern about how to integrate indigenous peoples and local knowledge with global climate change policy debates.

Polycyclic aromatic hydrocarbons, polychlorinated biphenyls and organochlorine pesticides in European hake (Merluccius merluccius) muscle from the Western Mediterranean Sea.

Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) were quantified in muscle tissue of European hake, an ecologically and commercially important species. Samples were collected from the Western Mediterranean, in seven different stations at different depths and a batch was bought in a local market. PCBs are the dominant pollutants, but the overall concentrations do not show significant differences between the different specimens analyzed from various locations, with the exception of the concentration of PCBs at a shallow station close to the River Besòs mouth. This probably suggests that generally the pollutants in hake from the Western Mediterranean derive from historical and non-point sources. The occurrence of pollutants is widespread in the samples but their concentration is below recommended legal limits for fish or other foodstuffs.

The emergence of modern sea ice cover in the Arctic Ocean.

Arctic sea ice coverage is shrinking in response to global climate change and summer ice-free conditions in the Arctic Ocean are predicted by the end of the century. The validity of this prediction could potentially be tested through the reconstruction of the climate of the Pliocene epoch (5.33-2.58 million years ago), an analogue of a future warmer Earth. Here we show that, in the Eurasian sector of the Arctic Ocean, ice-free conditions prevailed in the early Pliocene until sea ice expanded from the central Arctic Ocean for the first time ca. 4 million years ago. Amplified by a rise in topography in several regions of the Arctic and enhanced freshening of the Arctic Ocean, sea ice expanded progressively in response to positive ice-albedo feedback mechanisms. Sea ice reached its modern winter maximum extension for the first time during the culmination of the Northern Hemisphere glaciation, ca. 2.6 million years ago.

Bacterial dominance in subseafloor sediments characterized by methane hydrates.

The degradation of organic carbon in subseafloor sediments on continental margins contributes to the largest reservoir of methane on Earth. Sediments in the Andaman Sea are composed of ~ 1% marine-derived organic carbon and biogenic methane is present. Our objective was to determine microbial abundance and diversity in sediments that transition the gas hydrate occurrence zone (GHOZ) in the Andaman Sea. Microscopic cell enumeration revealed that most sediment layers harbored relatively low microbial abundance (10(3)-10(5) cells cm(-3)). Archaea were never detected despite the use of both DNA- and lipid-based methods. Statistical analysis of terminal restriction fragment length polymorphisms revealed distinct microbial communities from above, within, and below the GHOZ, and GHOZ samples were correlated with a decrease in organic carbon. Primer-tagged pyrosequences of bacterial 16S rRNA genes showed that members of the phylum Firmicutes are predominant in all zones. Compared with other seafloor settings that contain biogenic methane, this deep subseafloor habitat has a unique microbial community and the low cell abundance detected can help to refine global subseafloor microbial abundance.

Climate sensitivity estimated from temperature reconstructions of the Last Glacial Maximum.

Assessing the impact of future anthropogenic carbon emissions is currently impeded by uncertainties in our knowledge of equilibrium climate sensitivity to atmospheric carbon dioxide doubling. Previous studies suggest 3 kelvin (K) as the best estimate, 2 to 4.5 K as the 66% probability range, and nonzero probabilities for much higher values, the latter implying a small chance of high-impact climate changes that would be difficult to avoid. Here, combining extensive sea and land surface temperature reconstructions from the Last Glacial Maximum with climate model simulations, we estimate a lower median (2.3 K) and reduced uncertainty (1.7 to 2.6 K as the 66% probability range, which can be widened using alternate assumptions or data subsets). Assuming that paleoclimatic constraints apply to the future, as predicted by our model, these results imply a lower probability of imminent extreme climatic change than previously thought.

Southern Ocean dust-climate coupling over the past four million years.

Dust has the potential to modify global climate by influencing the radiative balance of the atmosphere and by supplying iron and other essential limiting micronutrients to the ocean. Indeed, dust supply to the Southern Ocean increases during ice ages, and 'iron fertilization' of the subantarctic zone may have contributed up to 40 parts per million by volume (p.p.m.v.) of the decrease (80-100 p.p.m.v.) in atmospheric carbon dioxide observed during late Pleistocene glacial cycles. So far, however, the magnitude of Southern Ocean dust deposition in earlier times and its role in the development and evolution of Pleistocene glacial cycles have remained unclear. Here we report a high-resolution record of dust and iron supply to the Southern Ocean over the past four million years, derived from the analysis of marine sediments from ODP Site 1090, located in the Atlantic sector of the subantarctic zone. The close correspondence of our dust and iron deposition records with Antarctic ice core reconstructions of dust flux covering the past 800,000 years (refs 8, 9) indicates that both of these archives record large-scale deposition changes that should apply to most of the Southern Ocean, validating previous interpretations of the ice core data. The extension of the record beyond the interval covered by the Antarctic ice cores reveals that, in contrast to the relatively gradual intensification of glacial cycles over the past three million years, Southern Ocean dust and iron flux rose sharply at the Mid-Pleistocene climatic transition around 1.25 million years ago. This finding complements previous observations over late Pleistocene glacial cycles, providing new evidence of a tight connection between high dust input to the Southern Ocean and the emergence of the deep glaciations that characterize the past one million years of Earth history.

Phase distribution of hydrocarbons in the water column after a pelagic deep ocean oil spill.

Spills from wrecks are a potential major source of pollution in the deep ocean. However, not much is known about the fate of a spill at several kilometers depth, beyond the oceans continental shelves. Here, we report the phase distribution of hydrocarbons released from the wrecks of the Prestige tanker, several years after it sank in November 2002 to depths between 3500 and 3800 m. The released oil reached the surface waters above the wrecks without any signs of weathering and leaving an homogenous signature throughout the water column. At depths of several kilometers below the sea surface, the occurrence and spread of the deep sea oil spill could be evaluated better by quantifying and characterizing the dissolved hydrocarbon signature, rather than just the investigation of hydrocarbons in the suspended particulate matter.

Subpolar link to the emergence of the modern equatorial Pacific cold tongue.

The cold upwelling "tongue" of the eastern equatorial Pacific is a central energetic feature of the ocean, dominating both the mean state and temporal variability of climate in the tropics and beyond. Recent evidence for the development of the modern cold tongue during the Pliocene-Pleistocene transition has been explained as the result of extratropical cooling that drove a shoaling of the thermocline. We have found that the sub-Antarctic and sub-Arctic regions underwent substantial cooling nearly synchronous to the cold tongue development, thereby providing support for this hypothesis. In addition, we show that sub-Antarctic climate changed in its response to Earth's orbital variations, from a subtropical to a subpolar pattern, as expected if cooling shrank the warm-water sphere of the ocean and thus contracted the subtropical gyres.