Hybrid Targeted/Untargeted Screening Method for the Determination of Wildfire and Water-Soluble Organic Tracers in Ice Cores and Snow.

Wildfires can influence the earth's radiative forcing through the emission of biomass-burning aerosols. To better constrain the impacts of wildfires on climate and understand their evolution under future climate scenarios, reconstructing their chemical nature, assessing their past variability, and evaluating their influence on the atmospheric composition are essential. Ice cores are unique to perform such reconstructions representing archives not only of past biomass-burning events but also of concurrent climate and environmental changes. Here, we present a novel methodology for the quantification of five biomass-burning proxies (syringic acid, vanillic acid, vanillin, syringaldehyde, and p-hydroxybenzoic acid) and one biogenic emission proxy (pinic acid) using solid phase extraction (SPE) and ultrahigh-performance liquid chromatography coupled with high-resolution mass spectrometry. This method was also optimized for untargeted screening analysis to gain a broader knowledge about the chemical composition of organic aerosols in ice and snow samples. The method provides low detection limits (0.003-0.012 ng g-1), high recoveries (74 ± 10%), and excellent reproducibility, allowing the quantification of the six proxies and the identification of 313 different molecules, mainly constituted by carbon, hydrogen, and oxygen. The effectiveness of two different sample storage strategies, i.e., re-freezing of previously molten ice samples and freezing of previously loaded SPE cartridges, was also assessed, showing that the latter approach provides more reproducible results.

A 320 Year Ice-Core Record of Atmospheric Hg Pollution in the Altai, Central Asia.

Anthropogenic emissions of the toxic heavy metal mercury (Hg) have substantially increased atmospheric Hg levels during the 20th century compared to preindustrial times. However, on a regional scale, atmospheric Hg concentration or deposition trends vary to such an extent during the industrial period that the consequences of recent Asian emissions on atmospheric Hg levels are still unclear. Here we present a 320 year Hg deposition history for Central Asia, based on a continuous high-resolution ice-core Hg record from the Belukha glacier in the Siberian Altai, covering the time period 1680-2001. Hg concentrations and deposition fluxes start rising above background levels at the beginning of the 19th century due to emissions from gold/silver mining and Hg production. A steep increase occurs after the 1940s culminating during the 1970s, at the same time as the maximum Hg use in consumer products in Europe and North America. After a distinct decrease in the 1980s, Hg levels in the 1990s and beginning of the 2000s return to their maximum values, which we attribute to increased Hg emissions from Asia. Thus, rising Hg emissions from coal combustion and artisanal and small-scale gold mining (ASGM) in Asian countries determine recent atmospheric Hg levels in Central Asia, counteracting emission reductions due to control measures in Europe and North America.

Squalene-hopene cyclases-evolution, dynamics and catalytic scope.

Herein we highlight recent mechanistic findings on the impact of solvent dynamics on catalysis displayed by squalene-hopene cyclases (SHCs). These fascinating biocatalysts that appeared early during the evolution of terpene biosynthetic machineries exploit a catalytic aspartic acid donating the anti-oriented proton to the terminal CC double bond of pre-folded isoprenoid substrates. We review how the unusual strength of this Brønsted acid can be used to harness a plethora of non-natural protonation-driven reactions in a plastic enzyme fold. Moreover, recent results underline how the reaction termination by deprotonation or water addition is governed by the spatial location of water in the active site. Site-directed mutagenesis of amino acids located in the hydrophobic binding pocket allows for the generation of novel catalytic function by active site reshaping with relatively small enzyme libraries. A deepened understanding of triterpene cyclase dynamics in concert with chemical expertise thus have a great potential to allow for the biocatalytic manufacturing of tailored building bricks that would expand the chemical repertoire currently found in nature.

Enantioselective Benzylic Hydroxylation Catalysed by P450 Monooxygenases: Characterisation of a P450cam Mutant Library and Molecular Modelling.

Cytochrome P450 monooxygenases can catalyse the stereoselective C-H activation of a very broad range of substrates. Prediction and control of enantioselectivity of this enzyme class is of great interest for the synthesis of high-value chiral molecules. Here we have used a combination of molecular dynamics simulations and experimental screening to study the enantioselectivity of a library of active-site mutants of chimeric P450cam-RhFRed towards the benzylic hydroxylation of structurally related regioisomers of ethylmethylbenzene. Small variations either in substrate structure or in enzyme active site architecture were shown to lead to dramatic changes in enantioselectivity; this was broadly in agreement with computational predictions. In addition to validating computational approaches, these studies have provided us with a deeper understanding of effects that might control stereoselectivity in these biooxidation reactions.

Active site diversification of P450cam with indole generates catalysts for benzylic oxidation reactions.

Cytochrome P450 monooxygenases are useful biocatalysts for C-H activation, and there is a need to expand the range of these enzymes beyond what is naturally available. A panel of 93 variants of active self-sufficient P450cam[Tyr96Phe]-RhFRed fusion enzymes with a broad diversity in active site amino acids was developed by screening a large mutant library of 16,500 clones using a simple, highly sensitive colony-based colorimetric screen against indole. These mutants showed distinct fingerprints of activity not only when screened in oxidations of substituted indoles but also for unrelated oxidations such as benzylic hydroxylations.

Pb pollution from leaded gasoline in South America in the context of a 2000-year metallurgical history.

Exploitation of the extensive polymetallic deposits of the Andean Altiplano in South America since precolonial times has caused substantial emissions of neurotoxic lead (Pb) into the atmosphere; however, its historical significance compared to recent Pb pollution from leaded gasoline is not yet resolved. We present a comprehensive Pb emission history for the last two millennia for South America, based on a continuous, high-resolution, ice core record from Illimani glacier. Illimani is the highest mountain of the eastern Bolivian Andes and is located at the northeastern margin of the Andean Altiplano. The ice core Pb deposition history revealed enhanced Pb enrichment factors (EFs) due to metallurgical processing for silver production during periods of the Tiwanaku/Wari culture (AD 450-950), the Inca empires (AD 1450-1532), colonial times (AD 1532-1900), and tin production at the beginning of the 20th century. After the 1960s, Pb EFs increased by a factor of 3 compared to the emission level from metal production, which we attribute to gasoline-related Pb emissions. Our results show that anthropogenic Pb pollution levels from road traffic in South America exceed those of any historical metallurgy in the last two millennia, even in regions with exceptional high local metallurgical activity.

A new sensitive method for the quantification of glyoxal and methylglyoxal in snow and ice by stir bar sorptive extraction and liquid desorption-HPLC-ESI-MS.

In this study, the development of a new sensitive method for the analysis of alpha-dicarbonyls glyoxal (G) and methylglyoxal (MG) in environmental ice and snow is presented. Stir bar sorptive extraction with in situ derivatization and liquid desorption (SBSE-LD) was used for sample extraction, enrichment, and derivatization. Measurements were carried out using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). As part of the method development, SBSE-LD parameters such as extraction time, derivatization reagent, desorption time and solvent, and the effect of NaCl addition on the SBSE efficiency as well as measurement parameters of HPLC-ESI-MS/MS were evaluated. Calibration was performed in the range of 1-60 ng/mL using spiked ultrapure water samples, thus incorporating the complete SBSE and derivatization process. 4-Fluorobenzaldehyde was applied as internal standard. Inter-batch precision was <12 % RSD. Recoveries were determined by means of spiked snow samples and were 78.9 ± 5.6 % for G and 82.7 ± 7.5 % for MG, respectively. Instrumental detection limits of 0.242 and 0.213 ng/mL for G and MG were achieved using the multiple reaction monitoring mode. Relative detection limits referred to a sample volume of 15 mL were 0.016 ng/mL for G and 0.014 ng/mL for MG. The optimized method was applied for the analysis of snow samples from Mount Hohenpeissenberg (close to the Meteorological Observatory Hohenpeissenberg, Germany) and samples from an ice core from Upper Grenzgletscher (Monte Rosa massif, Switzerland). Resulting concentrations were 0.085-16.3 ng/mL for G and 0.126-3.6 ng/mL for MG. Concentrations of G and MG in snow were 1-2 orders of magnitude higher than in ice core samples. The described method represents a simple, green, and sensitive analytical approach to measure G and MG in aqueous environmental samples.

Ice-core based assessment of historical anthropogenic heavy metal (Cd, Cu, Sb, Zn) emissions in the Soviet Union.

The development of strategies and policies aiming at the reduction of environmental exposure to air pollution requires the assessment of historical emissions. Although anthropogenic emissions from the extended territory of the Soviet Union (SU) considerably influenced concentrations of heavy metals in the Northern Hemisphere, Pb is the only metal with long-term historical emission estimates for this region available, whereas for selected other metals only single values exist. Here we present the first study assessing long-term Cd, Cu, Sb, and Zn emissions in the SU during the period 1935-1991 based on ice-core concentration records from Belukha glacier in the Siberian Altai and emission data from 12 regions in the SU for the year 1980. We show that Zn primarily emitted from the Zn production in Ust-Kamenogorsk (East Kazakhstan) dominated the SU heavy metal emission. Cd, Sb, Zn (Cu) emissions increased between 1935 and the 1970s (1980s) due to expanded non-ferrous metal production. Emissions of the four metals in the beginning of the 1990s were as low as in the 1950s, which we attribute to the economic downturn in industry, changes in technology for an increasing metal recovery from ores, the replacement of coal and oil by gas, and air pollution control.

Three centuries of Eastern European and Altai lead emissions recorded in a Belukha ice core.

Human activities have significantly altered atmospheric Pb concentrations and thus, its geochemical cycle, for thousands of years. Whereas historical Pb emissions from Western Europe, North America, and Asia are well documented, there is no equivalent data for Eastern Europe. Here, we present ice-core Pb concentrations for the period 1680-1995 from Belukha glacier in the Siberian Altai, assumed to be representative of emissions in Eastern Europe and the Altai. Pb concentrations and (207)Pb/(206)Pb ratios were strongly enhanced during the period 1935-1995 due to the use of Pb additives in Russian gasoline mined in the Rudny Altai. Comparable to Western Europe and North America, Eastern European Pb emissions peaked in the 1970s. However, the subsequent downward trend in Eastern Europe was mainly caused by the economic crisis in the U.S.S.R. and not by a phase-out of leaded gasoline. Pb concentrations in the period 1680-1935, preceding the era of intensified industrialization in Russia, reflect the history of local emissions from Rudny Altai mining and related metallurgical processing primarily for the production of Russian coins. During this time, Altai ore Pb contributed about 40% of the regional atmospheric Pb.