Photo-Driven Iron-Induced Non-Oxidative Coupling of Methane to Ethane.

Photo-driven CH4 conversion to multi-carbon products and H2 is attractive but challenging, and the development of efficient catalytic systems is critical. Herein, we construct a solar-energy-driven redox cycle for combining CH4 conversion and H2 production using iron ions. A photo-driven iron-induced reaction system was developed, which is efficient at selective coupling of CH4 as well as conversion of benzene and cyclohexane under mild conditions. For CH4 conversion, 94 % C2 selectivity and a C2 H6 formation rate of 8.4 µmol h-1 is achieved. Mechanistic studies reveal that CH4 coupling is induced by hydroxyl radical, which is generated by photo-driven intermolecular charge migration of an Fe3+ complex. The delicate coordination structure of the [Fe(H2 O)5 OH]2+ complex ensures selective C-H bond activation and C-C coupling of CH4 . The produced Fe2+ can be used to reduce the potential for electrolytic H2 production, and then turns back into Fe3+ , forming an energy-saving and sustainable recyclable system.

Molecular and Artificial Neural Networks Modeling of Sorption and Diffusion of Small Alkanes, Alkenes and Their Ternary Mixtures in ZIF-8 at Different Temperatures.

Numerical computations comprising of Grand Canonical-Monte Carlo (GCMC) and Canonical Statistical Ensemble (NVT) Molecular Dynamics (MD) simulations were used to study the diffusion and sorption characteristics primarily for methane, ethane, and ethene molecules and for their ternary mixtures at different temperatures in ZIF-8 porous material. Methane as pure component or in mixture proved to be the sorbed hydrocarbon with the higher molecular mobility at the temperature range of 273-373 K among alkanes and alkenes. In addtion, alkenes were the hydrocarbons with the higher self-diffusion coefficients compared to the respective alkanes. In the ternary mixtures ethane was preferentially sorbed in ZIF-8 at all temperatures studied. Direct comparisons of the self-diffusivity data obtained from the NVT-MD simulations with recently reported Magic Angle Spinning Pulsed Field Gradient Nuclear Magnetic Resonance (MAS PFG NMR) measurements showed reasonable agreement. Furthermore, the NVT-MD self-diffusivity coefficients in conjunction with the aforementioned MAS PFG NMR experimental measurements, and sorption thermodynamic data obtained from the present GCMC simulations were utilized for the development of individual Artificial Neural Networks (ANNs) predictive modeling procedures in order to provide additional quantitative and qualitative information regarding the diffusion and sorption of small alkanes, alkenes in ZIF-8. The ANNs predictions were in good agreement with the experimental measurements and with the molecular simulation data. The modeling and analysis capabilities of ANNs along with their fast computations using moderate computer resources can significantly assist the irreplaceable molecular simulation and experimental approaches to cope with complicated problems at the molecular level.

Twofold and Threefold Sinusoidal Patterns in Coupled Molecular Motions of 184,025 Structures of Phenylethane, Nitroethane, and Carboxylate Derivatives.

Scatter plot analyses for 14,169 phenylethanes of the substructure Cß-CαH2-Ph with three open coordination positions at Cß and 150,568 phenylethanes of Cß-CαHX-Ph with an additional open coordination position X at Cα have been performed, based on searches in the Cambridge Structural Database. The correlation of rotation angle ψ = Cß-Cα-Ci-Co with a pyramidalization angle θ = Co-Co'-Ci-Cα in a 360° rotation about the bond Cα-Ci reveals a sinusoidal pattern with three maxima and minima, whereas the correlation of rotation angle ψ with bond angle ω = Cß-Cα-Ci and bond length d = Cß-Cα results in sinusoidal patterns with two maxima and minima. A total of 3993 nitro derivatives of the substructure Cß-CαHX-NO2 confirm the results and show that atoms Ci/Co/Co' in the phenyl compounds can be replaced by atoms N/O/O' without any change in the two- and threefold patterns. In 15,295 methyl acetates of the substructure Cß-CαHX-C'(═O)OMe, pyramidalization of the group CαC'(═O)OMe results in a chiral flat tetrahedron with four different corners. (Rθ)/(Sθ) selectivity in the configuration of the tetrahedron is induced by the bonds Cα-Cß, Cα-H, and Cα-X, emanating from the tetrahedral center Cα. It is surprising that bonds as different as Cα-Cß, Cα-H, and Cα-X (X = H, C, N, O, S, etc.) give almost the same induction intensities.

Ethane-Bridged Hybrid Monolithic Column with Large Mesopores for Boosting Top-Down Proteomic Analysis.

Top-down proteomics is challenged by the high complexity of biological samples. The coelution of intact proteins results in overlapped mass spectra, and hence, an increased peak capacity for protein separation is needed. Herein, ethane-bridged hybrid monoliths with well-defined large mesopores were successfully prepared based on the sol-gel condensation of 1,2-bis(trimethoxysilyl)ethane and tetramethoxysilane, followed by two-step base etching of the Si-O-Si domain while maintaining the Si-C-C-Si domain in the structure. Relatively homogeneous macropores of 1.1 µm and large mesopores of 24 nm were obtained, permitting fast mass transfer of large molecules and efficient diffusion without obstruction. The use of less hydrophobic C1 ligand further sharpened the peak shape and improved peak capacity. A 120 cm-long capillary column was used for top-down proteomic analysis of E. coli lysates under low backpressure with 16 MPa. High peak capacity of 646 was achieved within 240 min gradient. With MS/MS analysis, 959 proteoforms corresponding to 263 proteins could be unambiguously identified from E. coli lysates in a single run. Furthermore, to illustrate the separation performance for large proteoforms, such monoliths were applied to top-down analysis of the SEC fraction of E. coli lysates with Mw ranging from 30 to 70 kDa. With highly effective separation, 347 large proteoforms with Mw higher than 30 kDa were detected in the single 75 min run. These results showed great potential for top-down proteomic analysis in complex samples.

Crystal structure of a key enzyme for anaerobic ethane activation.

Ethane, the second most abundant hydrocarbon gas in the seafloor, is efficiently oxidized by anaerobic archaea in syntrophy with sulfate-reducing bacteria. Here, we report the 0.99-angstrom-resolution structure of the proposed ethane-activating enzyme and describe the specific traits that distinguish it from methane-generating and -consuming methyl-coenzyme M reductases. The widened catalytic chamber, harboring a dimethylated nickel-containing F430 cofactor, would adapt the chemistry of methyl-coenzyme M reductases for a two-carbon substrate. A sulfur from methionine replaces the oxygen from a canonical glutamine as the nickel lower-axial ligand, a feature conserved in thermophilic ethanotrophs. Specific loop extensions, a four-helix bundle dilatation, and posttranslational methylations result in the formation of a 33-angstrom-long hydrophobic tunnel, which guides the ethane to the buried active site as confirmed with xenon pressurization experiments.

Discovery of novel purinylthiazolylethanone derivatives as anti-Candida albicans agents through possible multifaceted mechanisms.

An unprecedented amount of fungal and fungal-like infections has recently brought about some of the most severe die-offs and extinctions due to fungal drug resistance. Aimed to alleviate the situation, new effort was made to develop novel purinylthiazolylethanone derivatives, which were expected to combat the fungal drug resistance. Some prepared purinylthiazolylethanone derivatives possessed satisfactory inhibitory action towards the tested fungi, among which compound 8c gave a MIC value of 1 µg/mL against C. albicans. The active molecule 8c was able to kill C. albicans with undetectable resistance as well as low hematotoxicity and cytotoxicity. Furthermore, it could hinder the growth of C. albicans biofilm, thus avoiding the occurrence of drug resistance. Mechanism research manifested that purinylthiazolylethanone derivative 8c led to damage of cell wall and membrane disruption, so protein leakage and the cytoplasmic membrane depolarization were observed. On this account, the activity of fungal lactate dehydrogenase was reduced and metabolism was impeded. Meanwhile, the increased levels of reactive oxygen species (ROS) and reactive nitrogen species (RNS) disordered redox equilibrium, giving rise to oxidative damage to fungal cells and fungicidal effect.

Selective Oxidation of Ethane to Acetic Acid Catalyzed by a C-Scorpionate Iron(II) Complex: A Homogeneous vs. Heterogeneous Comparison.

The direct, one-pot oxidation of ethane to acetic acid was, for the first time, performed using a C-scorpionate complex anchored onto a magnetic core-shell support, the Fe3O4/TiO2/[FeCl2{κ3-HC(pz)3}] composite. This catalytic system, where the magnetic catalyst is easily recovered and reused, is highly selective to the acetic acid synthesis. The performed green metrics calculations highlight the "greeness" of the new ethane oxidation procedure.

A procedure and double-chambered device for macromolecular crystal flash-cooling in different cryogenic liquids.

Flash-cooling of macromolecular crystals for X-ray diffraction analysis is usually performed in liquid nitrogen (LN2). Cryogens different than LN2 are used as well for this procedure but are highly underrepresented, e.g., liquid propane and liquid ethane. These two cryogens have significantly higher cooling rates compared with LN2 and may thus be beneficial for flash-cooling of macromolecular crystals. Flash-cooling in liquid propane or liquid ethane results in sample vitrification but is accompanied by solidification of these cryogens, which is not compatible with the robotic systems nowadays used for crystal mounting at most synchrotrons. Here we provide a detailed description of a new double-chambered device and procedure to flash-cool loop mounted macromolecular crystals in different cryogenic liquids. The usage of this device may result in specimens of better crystal- and optical quality in terms of mosaic spread and ice contamination. Furthermore, applying the described procedure with the new double-chambered device provides the possibility to screen for the best flash-cooling cryogen for macromolecular crystals on a routine basis, and, most importantly, the samples obtained allow the usage of state-of-the-art robotic sample-loading systems at synchrotrons.

Ethyl esters production catalyzed by immobilized lipases is influenced by n-hexane and ter-amyl alcohol as organic solvents.

Lipase stability in organic solvent is crucial for its application in many biotechnological processes as biocatalyst. One way to improve lipase's activity and stability in unusual reaction medium is its immobilization on inert supports. Here, lipases from different sources and immobilized through weak chemical interactions on hydrophobic and ionic supports had their transesterification ability dramatically dependent on the support and also on the solvent that had been used. The ethanolysis of sardine oil was carried out at the presence of cyclohexane and tert-amyl alcohol, in which Duolite A568-Thermomyces lanuginosa lipase derivative achieved 49% of ethyl esters production after 24 h in cyclohexane. The selectivity of immobilized lipases was also studied and, after 3 h of synthesis, the reaction with Duolite A568-Thermomyces lanuginosa derivative in cyclohexane produced 24% ethyl ester of eicosapentaenoic acid and 1.2% ethyl ester of docosahexaenoic acid, displaying a selectivity index of 20 times the ethyl ester of eicosapentaenoic acid. Different derivatives of Candida antarctica lipases fraction B (CALB) and phospholipase Lecitase® Ultra (Lecitase) were also investigated. Along these lines, a combination between these factors may be applied to improve the activity and selectivity of immobilized lipases, decreasing the total cost of the process.

Competitive aptasensor with gold nanoparticle dimers and magnetite nanoparticles for SERS-based determination of thrombin.

It is known that the intensity of surface-enhanced Raman scattering (SERS) of monomeric gold nanoparticles (GNPs) is insufficient for ultrasensitive analysis. The authors describe dimeric GNPs for use in a competitive SERS and aptamer based assay for thrombin. The reagent 1,2-bis(4-pyridyl) ethylene serves as both the coupling agent and the Raman reporter on the GNP dimers. In the presence of thrombin, the hybridization of two aptamers, one attached to the GNP dimers, the other to magnetic nanoparticles, is competitively prevented. This method takes advantage of the unique "hot spots" of the GNP dimers to amplify the Raman signal. This results in an ultra-sensitive thrombin assay when compared to assays using GNP monomers. The limit of detection is as low as 1 fM of thrombin. The Raman intensity, best measured at 1612 cm-1, increases linearly in the 1 fM to 10 nM thrombin concentration range. The method was applied to the determinaiton of thrombin in spiked simulated body fluid and human serum. Graphical abstract This method takes advantage of the unique "hot spots" of the gold nanoparticle dimers to amplify the Raman signal. The dimers are linked to the magnetic nanoparticles via an aptamer. The use of both competitive displacement and magnetic separation greatly improves the sensitivity of the thrombin assay.

Encapsulation of Upconversion Nanoparticles in Periodic Mesoporous Organosilicas.

(1) Background: Nanomedicine has recently emerged as a promising field, particularly for cancer theranostics. In this context, nanoparticles designed for imaging and therapeutic applications are of interest. We, therefore, studied the encapsulation of upconverting nanoparticles in mesoporous organosilica nanoparticles. Indeed, mesoporous organosilica nanoparticles have been shown to be very efficient for drug delivery, and upconverting nanoparticles are interesting for near-infrared and X-ray computed tomography imaging, depending on the matrix used. (2) Methods: Two different upconverting-based nanoparticles were synthesized with Yb3+-Er3+ as the upconverting system and NaYF4 or BaLuF5 as the matrix. The encapsulation of these nanoparticles was studied through the sol-gel procedure with bis(triethoxysilyl)ethylene and bis(triethoxysilyl)ethane in the presence of CTAB. (3) Results: with bis(triethoxysilyl)ethylene, BaLuF5: Yb3+-Er3+, nanoparticles were not encapsulated, but anchored on the surface of the obtained mesoporous nanorods BaLuF5: Yb3+-Er3+@Ethylene. With bis(triethoxysilyl)ethane, BaLuF5: Yb3+-Er3+ and NaYF4: Yb3+-Er3+nanoparticles were encapsulated in the mesoporous cubic structure leading to BaLuF5: Yb3+-Er3+@Ethane and NaYF4: Yb3+-Er3+@Ethane, respectively. (4) Conclusions: upconversion nanoparticles were located on the surface of mesoporous nanorods obtained by hydrolysis polycondensation of bis(triethoxysilyl)ethylene, whereas encapsulation occurred with bis(triethoxysilyl)ethane. The later nanoparticles NaYF4: Yb3+-Er3+@Ethane or BaLuF5: Yb3+-Er3+@Ethane were promising for applications with cancer cell imaging or X-ray-computed tomography respectively.

Enhanced hydrolysis of 1,1,2,2-tetrachloroethane by multi-walled carbon nanotube/TiO2 nanocomposites: The synergistic effect.

Once released into the environment, engineered nanomaterials can significantly influence the transformation and fate of organic contaminants. To date, the abilities of composite nanomaterials to catalyze environmentally relevant abiotic transformation reactions of organic contaminants are largely unknown. Herein, we investigated the effects of two nanocomposites - consisting of anatase titanium dioxide (TiO2) with different predominantly exposed crystal facets (i.e., {101} or {001} facets) anchored to hydroxylated multi-walled carbon nanotubes (OH-MWCNT) - on the hydrolysis of 1,1,2,2-tetrachloroethane (TeCA), a common groundwater contaminant, at ambient pH (6, 7 and 8). Both OH-MWCNT/TiO2 nanocomposites were more effective in catalyzing the dehydrochlorination of TeCA than the respective component materials (i.e., bare OH-MWCNT and bare TiO2). Moreover, the synergistic effect of the two components was evident, in that the incorporation of OH-MWCNT increased the TeCA adsorption capacity of the nanocomposites, significantly enhancing the catalytic effect of the deprotonated hydroxyl and carboxyl groups on nanocomposite surfaces, which served as the main catalytic sites for TeCA hydrolysis. The findings may have important implications for the understanding of the environmental implications of composite nanomaterials and may shed light on the design of high-performance nanocomposites for enhanced contaminant removal.

1-Aryl-2-(triisopropylsilyl)ethane-1,2-diones: Toward a New Class of Visible Type I Photoinitiators for Free Radical Polymerization of Methacrylates.

1-Aryl-2-(triisopropylsilyl)ethane-1,2-diones (SEDs) are proposed here as a new class of visible Type I photoinitiators (PIs) for free radical polymerization under air upon exposure to blue (@455 nm) and green (@520 nm) LEDs. Remarkably, these new systems present good polymerization performances and excellent bleaching properties compared to camphorquinone-based systems, and transparent polymers are obtained upon visible light irradiation. Real-time Fourier transform infrared spectroscopy is used to monitor the polymerization profiles. Molecular orbital calculations are also carried out for a better understanding of the structure/reactivity relationship of the photoinitiators.

Structural Transformations in the Thermal Dehydration of [Cu2(bpa)(btec)(H2O)4]n Coordination Polymer.

Reactions between pyridinic ligands such as 1,2-bis(4-pyridyl)ethane (bpa) and transition metal cations are a very widespread technique to produce extended coordination polymers such as Metal-Organic Frameworks. In combination with a second ligand these systems could present different topologies and behaviors. In this context, the use of 1,2,4,5-benzenetetracarboxylic acid (H4btec) gave us a novel 2D compound, [Cu2(bpa)(btec)(H2O)4]n (1), which was prepared by microwave-assisted synthesis and structurally characterized by means of single crystal X-ray diffraction. Its thermal behavior was analyzed through thermogravimetric analysis and variable temperature powder X-ray diffraction, concluding that thermal stability is influenced by the coordination water molecules, allowing two sequential thermochromic phase transformations to take place. These transformations were monitored by electronic paramagnetic resonance spectroscopy and magnetic susceptibility measurements. In addition, the crystal structure of the anhydrous compound [Cu2(bpa)(btec)]n (1.ah) was determined. Finally, a topological study was carried out for the bpa ligand considering all the structures deposited in the Cambridge Structural Databased. More than 1000 structures were analyzed and classified into 17 different topologies, according to the role of the ligand.

Anaerobic oxidation of ethane by archaea from a marine hydrocarbon seep.

Ethane is the second most abundant component of natural gas in addition to methane, and-similar to methane-is chemically unreactive. The biological consumption of ethane under anoxic conditions was suggested by geochemical profiles at marine hydrocarbon seeps1-3, and through ethane-dependent sulfate reduction in slurries4-7. Nevertheless, the microorganisms and reactions that catalyse this process have to date remained unknown8. Here we describe ethane-oxidizing archaea that were obtained by specific enrichment over ten years, and analyse these archaea using phylogeny-based fluorescence analyses, proteogenomics and metabolite studies. The co-culture, which oxidized ethane completely while reducing sulfate to sulfide, was dominated by an archaeon that we name 'Candidatus Argoarchaeum ethanivorans'; other members were sulfate-reducing Deltaproteobacteria. The genome of Ca. Argoarchaeum contains all of the genes that are necessary for a functional methyl-coenzyme M reductase, and all subunits were detected in protein extracts. Accordingly, ethyl-coenzyme M (ethyl-CoM) was identified as an intermediate by liquid chromatography-tandem mass spectrometry. This indicated that Ca. Argoarchaeum initiates ethane oxidation by ethyl-CoM formation, analogous to the recently described butane activation by 'Candidatus Syntrophoarchaeum'9. Proteogenomics further suggests that oxidation of intermediary acetyl-CoA to CO2 occurs through the oxidative Wood-Ljungdahl pathway. The identification of an archaeon that uses ethane (C2H6) fills a gap in our knowledge of microorganisms that specifically oxidize members of the homologous alkane series (CnH2n+2) without oxygen. Detection of phylogenetic and functional gene markers related to those of Ca. Argoarchaeum at deep-sea gas seeps10-12 suggests that archaea that are able to oxidize ethane through ethyl-CoM are widespread members of the local communities fostered by venting gaseous alkanes around these seeps.

Elucidating the dechlorination mechanism of hexachloroethane by Pd-doped zerovalent iron microparticles in dissolved lactic acid polymers using chromatography and indirect monitoring of iron corrosion.

The degradation mechanism of the pollutant hexachloroethane (HCA) by a suspension of Pd-doped zerovalent iron microparticles (Pd-mZVI) in dissolved lactic acid polymers and oligomers (referred to as PLA) was investigated using gas chromatography and the indirect monitoring of iron corrosion by continuous measurements of pH, oxidation-reduction potential (ORP), and conductivity. The first experiments took place in the absence of HCA, to understand the evolution of the Pd-mZVI/PLA/H2O system. This showed that the evolution of pH, ORP, and conductivity is related to changes in solution chemistry due to iron corrosion and that the system is initially cathodically controlled by H+ mass transport to Pd surfaces because of the presence of an extensive PLA layer. We then investigated the effects of Pd-mZVI particles, temperature, initial HCA concentration, and PLA content on the Pd-mZVI/PLA/HCA/H2O system, to obtain a better understanding of the degradation mechanism. In all cases, HCA dechlorination first requires the production of atomic hydrogen H*-involving the accumulation of tetrachloroethylene (PCE) as an intermediate-before its subsequent reduction to non-chlorinated C2 and C4 compounds. The ratio between Pd-mZVI dosage, initial HCA concentration, and PLA content affects the rate of H* generation as well as the rate-determining step of the process. A pseudo-first-order equation can be applied when Pd-mZVI dosage is much higher than the theoretical stoichiometry (600 mg for [HCA]0 = 5-20 mg L-1). Our results indicate that the HCA degradation mechanism includes mass transfer, sorption, surface reaction with H*, and desorption of the product.

Optimising sampling patterns for bi-exponentially decaying signals.

A recently reported method, based on the Cramér-Rao Lower Bound theory, for optimising sampling patterns for a wide range of nuclear magnetic resonance (NMR) experiments is applied to the problem of optimising sampling patterns for bi-exponentially decaying signals. Sampling patterns are optimised by minimizing the percentage error in estimating the most difficult to estimate parameter of the bi-exponential model, termed the objective function. The predictions of the method are demonstrated in application to pulsed field gradient NMR data recorded for the two-component diffusion of a binary mixture of methane/ethane in a zeolite. It is shown that the proposed method identifies an optimal sampling pattern with the predicted objective function being within 10% of that calculated from the experiment dataset. The method is used to advise on the number of sampled points and the noise level needed to resolve two-component systems characterised by a range of ratios of populations and diffusion coefficients. It is subsequently illustrated how the method can be used to reduce the experiment acquisition time while still being able to resolve a given two-component system.

Exploration of M(100)-2×1 (M=Si, Ge) surface termination through hydrogen passivation using ethane and ammonia-borane derivatives: A theoretical approach.

Termination process of Si(100)-2 × 1 as well as Ge(100)-2 × 1 reconstructed surfaces have been explored comprehensively through the dehydrogenation of ethane and ammonia-borane and their several analogues by employing density functional theory (DFT). From our study, it is evident that the termination of Si-surface via the dehydrogenation of aforementioned ethane and NH3BH3 derivatives is more feasible compared to Ge-surface. For ethane, the investigation shows that the substitution of non-participating hydrogens with +I group (electron donating) causes an enhancement in the kinetic and thermodynamic feasibility of the termination process, whereas the implementation of -I substituent (electron withdrawing) makes an adverse effect. While exploring the termination of Si- as well as Ge-surfaces through the dehydrogenation of NH3BH3 and its derivatives, it is noticed that from both the kinetic as well as thermodynamic perspectives, the termination processes are more feasible than that of ethane and its derivatives. We have further examined the detailed mechanism of each termination process by analyzing the geometrical parameters and NPA charges. From bonding evaluation, it is evident that the hydrogen abstraction from ethane by both the surfaces is symmetric in nature, where both the hydrogens show slightly positive charge. But for NH3BH3 the hydrogen abstraction process becomes asymmetric, where the boron associated hydrogen is abstracted as hydride by the electrophilic surface Si (Ge) and the hydrogen bonded with the N-centre is abstracted as proton by the nucleophilic surface Si (Ge). Overall, the present theoretical work reveals one of the efficient chemical processes for terminating Si as well as Ge(100)-2 × 1 reconstructed surfaces through the formation of non-polar SiH bonds.

The role of the central metal ion of ethane-bridged bis-porphyrins in histidine sensing.

Ethane-bridged bis-porphyrin derivatives are reported for the selective detection of various analytes in sensing applications. The central metal ion is able to rule specific molecular arrangements upon analyte binding. Three bis-porphyrin compounds: a free base (metal free), Ni complex, and Cu complex, have been tested for histidine detection in aqueous media. Histidine is involved in various biological processes, including such deadly disease as lung cancer. The conformational changes of bis-porphyrins, induced by histidine binding, can be detected by monitoring the Soret band position. The spectroscopic characterization, at the air-water subphase interface, indicates that, in the presence of histidine, the Ni and Cu metallated derivatives undergo conformational changes. This behaviour was confirmed when these two derivatives were deposited onto the solid support by Langmuir-Schaefer (LS) technique. A prototypal Surface Plasmon Resonance (SPR) detection system for histidine based on these two porphyrin LS films was developed. The Cu substituted compound based SPR system allows the histidine sensing down to nanomolar concentration. Furthermore, a SPR response of the Ni bis-porphyrin shows a semilogarithmic dependence on the histidine concentration up to 10-6 M proposing the use of these two porphyrins in a sensor array for the monitoring of histidine levels in plasma.

Large changes in biomass burning over the last millennium inferred from paleoatmospheric ethane in polar ice cores.

Biomass burning drives changes in greenhouse gases, climate-forcing aerosols, and global atmospheric chemistry. There is controversy about the magnitude and timing of changes in biomass burning emissions on millennial time scales from preindustrial to present and about the relative importance of climate change and human activities as the underlying cause. Biomass burning is one of two notable sources of ethane in the preindustrial atmosphere. Here, we present ice core ethane measurements from Antarctica and Greenland that contain information about changes in biomass burning emissions since 1000 CE (Common Era). The biomass burning emissions of ethane during the Medieval Period (1000-1500 CE) were higher than present day and declined sharply to a minimum during the cooler Little Ice Age (1600-1800 CE). Assuming that preindustrial atmospheric reactivity and transport were the same as in the modern atmosphere, we estimate that biomass burning emissions decreased by 30 to 45% from the Medieval Period to the Little Ice Age. The timing and magnitude of this decline in biomass burning emissions is consistent with that inferred from ice core methane stable carbon isotope ratios but inconsistent with histories based on sedimentary charcoal and ice core carbon monoxide measurements. This study demonstrates that biomass burning emissions have exceeded modern levels in the past and may be highly sensitive to changes in climate.