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Aerosol particles affect the Earth's energy balance by absorbing and scattering radiation according to their chemical composition, size, and shape. It is generally believed that their optical properties could be deduced from the molecular composition of the complex organic matter contained in these particles, a goal pursued by many groups via high-resolution mass spectrometry, although: (1) absorptivity is associated with structural chromophores rather than with molecular formulas, (2) compositional space is a small projection of structural space, and (3) mixtures of polar polyfunctional species usually exhibit supramolecular interactions. Here we report a suite of experiments showing that the photolysis of aqueous pyruvic acid (a proxy for aerosol alpha-dicarbonyls absorbing at lambda300 nm) generates mixtures of identifiable aliphatic polyfunctional oligomers that develop absorptions in the visible upon standing in the dark. These absorptions and their induced fluorescence emissions can be repeatedly bleached and retrieved without carbon loss or ostensible changes in the electrospray mass spectra of the corresponding mixtures and display unambiguous signatures of supramolecular effects. The nonlinear additivity of the properties of the components of these mixtures supports the notion that full structural speciation is insufficient and possibly unnecessary for understanding the optical properties of aerosol particles and their responses to changing ambient conditions.

Herein, we report the efficient synthesis of RNA bases and functionalized s-triazines from 0.1 M urea solutions in water after subjection to freeze-thaw cycles for three weeks. The icy solution was under a reductive, methane-based atmosphere, which was subjected to spark discharges as an energy source for the first 72 h of the experiment. Analysis of the products indicates the synthesis of the s-triazines cyanuric acid, ammeline, ammelide, and melamine, the pyrimidines cytosine, uracil, and 2,4-diaminopyrimidine, and the purine adenine. An experiment performed as a control at room temperature, with the urea solution in the liquid phase and with the same atmosphere and energy source, led to the synthesis of hydantoins and insoluble tholin, but there was no evidence of the synthesis of pyrimidines or triazines. The synthesis of pyrimidines from urea is possible under a methane/nitrogen atmosphere only at low temperature, in the solid phase. The generation of both pyrimidines and triazines in comparable yields from urea, together with a possible role for triazines as alternative nucleobases, opens new perspectives on the prebiotic chemistry of informational polymers.

The carboxylic acids produced by the reductive tricarboxylic acid (rTCA) cycle are possibly a biosynthetic core of initial life, although several steps such as the reductive kinetics of oxaloacetate (OAA) to malate (MA) are problematic by conventional chemical routes. In this context, we studied the kinetics of this reaction as promoted by ZnS mineral photoelectrochemistry. The quantum efficiency φMAof MA production from the photoelectrochemical reduction of OAA followed φMA=0.13 [OAA] (2.1×10−3+[OAA])−1and was independent of temperature (5 to 50°C). To evaluate the importance of this forward rate under a prebiotic scenario, we also studied the temperature-dependent rate of the backward thermal decarboxylation of OAA to pyruvate (PA), which followed an Arrhenius behavior as log (k−2)=11.74–4956/T, wherek−2is in units of s−1. These measured rates were employed in conjunction with the indirectly estimated carboxylation rate of PA to OAA to assess the possible importance of mineral photoelectrochemistry in the conversion of OAA to MA under several scenarios of prebiotic conditions on early Earth. As an example, our analysis shows that there is 90% efficiency with a forward velocity of 3 yr/cycle for the OAA→MA step of the rTCA cycle at 280 K. Efficiency and velocity both decrease for increasing temperature. These results suggest high viability for mineral photoelectrochemistry as an enzyme-free engine to drive the rTCA cycle through the early aeons of early Earth, at least for the investigated OAA→MA step.

It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3–4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively shallow boundary layer. Field and laboratory experiments have determined that the origin of the observed NOx flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.

Natural and anthropogenic emissions of aromatic hydrocarbons from biomass burning, agro-industrial settings, and fossil fuel combustion contribute precursors to secondary aerosol formation (SOA). How these compounds are processed under humid tropospheric conditions is the focus of current attention to understand their environmental fate. This work shows how catechol thin films, a model for oxygenated aromatic hydrocarbons present in biomass burning and combustion aerosols, undergo heterogeneous oxidation at the air-solid interface under variable relative humidity (RH = 0-90%). The maximum reactive uptake coefficient of O3(g) by catechol γO3 = (7.49 ± 0.35) × 10(-6) occurs for 90% RH. Upon exposure of ca. 104-μm thick catechol films to O3(g) mixing ratios between 230 ppbv and 25 ppmv, three main reaction pathways are observed. (1) The cleavage of the 1,2 carbon-carbon bond at the air-solid interface resulting in the formation of cis,cis-muconic acid via primary ozonide and hydroperoxide intermediates. Further direct ozonolysis of cis,cis-muconic yields glyoxylic, oxalic, crotonic, and maleic acids. (2) A second pathway is evidenced by the presence of Baeyer-Villiger oxidation products including glutaconic 4-hydroxy-2-butenoic and 5-oxo-2-pentenoic acids during electrospray ionization mass spectrometry (MS) and ion chromatography MS analyses. (3) Finally, indirect oxidation by in situ produced hydroxyl radical (HO(•)) results in the generation of semiquinone radical intermediates toward the synthesis of polyhydoxylated aromatic rings such as tri-, tetra-, and penta-hydroxybenzene. Remarkably, heavier polyhydroxylated biphenyl and terphenyl products present in the extracted oxidized films result from coupling reactions of semiquinones of catechol and its polyhydroxylated rings. The direct ozonolysis of 1,2,3- and 1,2,4-trihydroxybenezene yields 2- and 3-hydroxy-cis,cis-muconic acid, respectively. The production of 2,4- or 3,4-dihdroxyhex-2-enedioic acid is proposed to result from the sequential processing of cis,cis-muconic acid, 2- and 3-hydroxy-cis,cis-muconic acid. Overall, these reactions contribute precursors to form aqueous SOA from aromatics in atmospheric aerosols and brown clouds.

Cracking, flaking, and separation of paint films containing lead white from the substrate on medieval parchment manuscripts and other works of art have been frequently reported by conservators. In this study, Fourier transform infrared spectroscopy (FTIR) was used to follow up the changes induced by the pigment on some properties of proteinaceous binding media commonly mentioned in medieval treatises. Evidence of the removal of water molecules from the vicinity of the peptide linkage groups C=O and CNH, with a small change in the protein's secondary structure due to aggregation, was obtained. The properties of the lead white-binder samples were compared to those of massicot-contain- ing mixtures. Massicot was also found to promote aggregation of the binders, though it induces a smaller change than does lead white in the hydrogen- bonding characteristics of the peptide CNH group.

Snow in the environment acts as a host to rich chemistry and provides a matrix for physical exchange of contaminants within the ecosystem. The goal of this review is to summarise the current state of knowledge of physical processes and chemical reactivity in surface snow with relevance to polar regions. It focuses on a description of impurities in distinct compartments present in surface snow, such as snow crystals, grain boundaries, crystal surfaces, and liquid parts. It emphasises the microscopic description of the ice surface and its link with the environment. Distinct differences between the disordered air–ice interface, often termed quasi-liquid layer, and a liquid phase are highlighted. The reactivity in these different compartments of surface snow is discussed using many experimental studies, simulations, and selected snow models from the molecular to the macro-scale. Although new experimental techniques have extended our knowledge of the surface properties of ice and their impact on some single reactions and processes, others occurring on, at or within snow grains remain unquantified. The presence of liquid or liquid-like compartments either due to the formation of brine or disorder at surfaces of snow crystals below the freezing point may strongly modify reaction rates. Therefore, future experiments should include a detailed characterisation of the surface properties of the ice matrices. A further point that remains largely unresolved is the distribution of impurities between the different domains of the condensed phase inside the snowpack, i.e. in the bulk solid, in liquid at the surface or trapped in confined pockets within or between grains, or at the surface. While surface-sensitive laboratory techniques may in the future help to resolve this point for equilibrium conditions, additional uncertainty for the environmental snowpack may be caused by the highly dynamic nature of the snowpack due to the fast metamorphism occurring under certain environmental conditions. Due to these gaps in knowledge the first snow chemistry models have attempted to reproduce certain processes like the long-term incorporation of volatile compounds in snow and firn or the release of reactive species from the snowpack. Although so far none of the models offers a coupled approach of physical and chemical processes or a detailed representation of the different compartments, they have successfully been used to reproduce some field experiments. A fully coupled snow chemistry and physics model remains to be developed.

Recently, Griffith et al. reported that acetoin is a major product of the photolysis of aqueous pyruvic acid (PA), and proposed that its mechanism of formation involves the thermal decarboxylation of α-acetolactic acid (AL) intermediate (1). This finding is in contrast with a previous study by Guzman et al., based on experiments performed under similar conditions, which reported the formation of two major products: 2,3-dimethyl tartaric acid ( A ) and 2-(3-oxobutan-2-yloxy)-2-hydroxypropanoic acid ( B ) (2⇓–4). Both A and B result after triplet radical pairs are formed via long-range (proton-coupled) electron transfer between carbonyl groups (5). Product B can thermally decompose into acetoin, but its carbonyl chromophore absorbs at λmax ∼ 285 nm vs. 276 nm for acetoin (2). In fact, Guzman et al. had shown … [↵][1]1To whom correspondence should be addressed. E-mail: marcelo.guzman{at}uky.edu. [1]: #xref-corresp-1-1

Ice and snow in the environment are important because they not only act as a host to rich chemistry but also provide a matrix for physical exchanges of contaminants within the ecosystem. This review discusses how the structure of snow influences both chemical reactivity and physical processes, which thereby makes snow a unique medium for study. The focus is placed on impacts of the presence of liquid and surface disorder using many experimental studies, simulations, and field observations from the molecular to the micro-scale.

During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air-water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO(2), NaNO(3), NaClO(4), and NaIO(4). The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (f(X(-))) and their correlation with ion properties. Although no correlation exists between f(X(-)) and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions R(X(-)), dehydration free-energy ΔG(dehyd), and polarizability α, follows the order: R(X(-))(-2)R(X(-))(-1)R(X(-))ΔG(dehyd)α. The same pure physical process is observed in H(2)O and D(2)O. The factor f(X(-)) does not change with pH (6.8-8.6), counterion (Li(+), Na(+), K(+), and Cs(+)) substitution effects, or solvent polarity changes in methanol- and ethanol-water mixtures (0 ≤ x(H(2)O) ≤ 1). Sodium polysorbate 20 surfactant is used to modify the structure of the interface. Despite the observed enrichment of I(-) on the air-water interface of equimolar solutions, our results of seawater mimic samples agree with a model in which the interfacial composition is increasingly enriched in I(-)Br(-)Cl(-) over the oceanic boundary layer due to concentration effects in sea spray aerosol formation.

The reaction of glyoxylate with carbon dioxide to produce lactate is promoted when zinc sulfide is irradiated by ultraviolet light. These results, representing a model for the action of colloidal mineral semiconductors on early Earth, complete a consecutive series that culminates in entry-point molecules of the reductive tricarboxylic acid cycle.

Laboratory experiments show that the optical absorptivity of model organic matter is not an intrinsic property, but a strong function of relative humidity, temperature, and insolation. Suites of representative polyfunctional C_(x)H_(y)O_(z) oligomers in water develop intense visible absorptions upon addition of inert electrolytes. The resulting mixtures reach mass absorption cross sections σ(532 nm) ~ 0.1 m^(2)/gC in a few hours, absorb up to 9 times more solar radiation than the starting material, can be half-bleached by noon sunlight in ~ 1 h, and can be repeatedly recycled without carbon loss. Visible absorptions red-shift and evolve increasingly faster in subsequent thermal aging cycles. Thermochromism and its strong direct dependences on ionic strength and temperature are ascribed to the dehydration of >CH−C(OH)< groups into >C═C< unsaturations by a polar E1 mechanism, and bleaching to photoinduced retrohydration. These transformations are deemed to underlie the daily cycles of aerosol absorption observed in the field, and may introduce a key feedback in the earth’s radiative balance.

The abnormal spikes detected in some CO and CO_2 polar ice core records indicate persistent chemical activity in glacial ice. Since CO and CO_2 spikes are correlated, and their amplitudes scale with reported CO/CO_2 yields for the photolysis of dissolved natural organic matter, a common photochemical source is implicated. Given that sufficient actinic radiation is constantly generated throughout ice by cosmic muons (Colussi and Hoffmann, 2003), it remains to be shown that the photolyses of typical organic contaminants proceed by similar mechanisms in water and ice. Here we report that the photodecarboxylation of pyruvic acid (PA, an ubiquitous ice contaminant) indeed leads to the same products nearly as efficiently in both media. CO_2 is promptly released from frozen PA/H_2O films upon illumination and continues to evolve after photolysis. By analogy with our studies in water (Guzman et al., 2006b), we infer that ^3PA* reacts with PA in ice producing CH_3C(O)C(O)O· and (CH_3C•(OH)C(O)OH) radicals. The barrierless decarboxylation, CH3C(O)C(O)O· → CH_3C(O)· + CO_2, accounts for prompt CO_2 emissions down to ∼140 K. Bimolecular radical reactions subsequently ensue in fluid molecular environments, both in water and ice, leading to metastable intermediates that decarboxylate immediately in water, but protractedly in ice. The overall quantum yield of CO_2 production in the λ ~313 nm photolysis of PA in ice at 250 K is ∼60% of that in water at 293 K. The in situ photolysis of natural organic matter is, therefore, a plausible explanation of CO and CO_2 ice core record anomalies.

Ice is selectively intolerant to impurities. A preponderance of implanted anions or cations generates electrical imbalances in ice grown from electrolyte solutions. Since the excess charges are ultimately neutralized via interfacial (H(+)/HO(-)) transport, the acidity of the unfrozen portion can change significantly and permanently. This insufficiently recognized phenomenon should critically affect rates and equilibria in frozen media. Here we report the effective (19)F NMR chemical shift of 3-fluorobenzoic acid as in situ probe of the acidity of extensively frozen electrolyte solutions. The sign and magnitude of the acidity changes associated with freezing are largely determined by specific ion combinations, but depend also on solute concentration and/or the extent of supercooling. NaCl solutions become more basic, those of (NH(4))(2)SO(4) or Na(2)SO(4) become more acidic, while solutions of the 2-(N-morpholino)ethanesulfonic acid zwitterion barely change their acidity upon freezing. We discuss how acidity scales based on solid-state NMR measurements could be used to assess the degree of ionization of weak acids and bases in frozen media.

The 320 nm-band photodecarboxylation of aqueous pyruvic acid (PA), a representative of the alpha-oxocarboxylic acids widely found in the atmospheric aerosol, yields 2,3-dimethyltartaric (A) and 2-(3-oxobutan-2-yloxy)-2-hydroxypropanoic (B) acids, rather than 3-hydroxy-2-oxobutanone as previously reported. A and B are identified by liquid chromatography with UV and ESI-MS detection, complemented by collisionally induced dissociation and 2H and 13C isotope labeling experiments. The multifunctional ether B gives rise to characteristic delta approximately 80 ppm 13C NMR resonances. Product quantum yields are proportional to [PA](a + [PA])(-1) in the range [PA] = 5-100 mM. CO2(g) release rates are halved, while A and B are suppressed by the addition of1.5 mM TEMPO. A and B are only partially quenched in air-saturated solutions. These observations are shown to be consistent with an oligomerization process initiated by a bimolecular reaction between 3PA and PA producing ketyl, CH3C(OH)C(O)OH, and acetyl, CH3C(O)*, radicals, rather than by the unimolecular decomposition of 3PA into 1-hydroxyethylidene, 3HO(CH3)C: (+CO2), or [CH(3)C(O)* + *C(O)OH] pairs. A arises from the dimerization of ketyl radicals, while B ensues the facile decarboxylation of the C8beta-ketoacid formed by association of acetyl radicals with the ketyl radical adduct of PA. Since the radical precursors to A and B are scavenged by O2 with a low probability per encounter (k(sc) approximately 1 x 10(6) M(-1) s(-1)), PA is able to accrete into multifunctional polar species in aerated aqueous media under solar illumination.

The lambda300 nm photolysis of h4- or d4-pyruvic acid aqueous glasses at 77 K yields identical electron magnetic resonance (EMR) spectra arising from distant (r greater or similar 0.5 nm) triplet radical pairs. Spectra comprise: (1) well-resolved quartets, X, at g approximately ge, that closely match the powder spectra of spin pairs interacting across r approximately 1.0 nm with D approximately 3.0 mT, E approximately 0 mT zero field splittings (ZFS), and (2) broad signals, Y, centered at g approximately 2.07 that display marked g-anisotropy and g-strain, exclude D greater or similar 20.0 mT values (i.e., r less or similar 0.5 spin nm separations), and track the temperature dependence of related g approximately 4 features. These results imply that the n-pi excitation of pyruvic acid, PA, induces long-range electron transfer from the promoted carbonyl chromophore into neighboring carbonyl acceptors, rather than homolysis into contact radical pairs or concerted decarboxylation into a carbene. Since PA is associated into hydrogen-bonded dimers prior to vitrification, X signals arise from radical pairs ensuing intradimer electron transfer to a locked acceptor, while Y signals involve carbonyl groups attached to randomly arranged, disjoint monomers. The ultrafast decarboxylation of primary radical ion pairs, 3[PA+* PA-*], accounts for the release of CO2 under cryogenic conditions, the lack of thermal hysteresis displayed by magnetic signals between 10 and 160 K, and averted charge retrotransfer. All EMR signals disappear irreversibly above the onset of ice diffusivity at approximately 190 K.

The chemisorption of O2 on nanoscale n-doped CdS semiconductors is computed in terms of a Wolkenstein isotherm coupled to the Schrodinger Poisson equation. Present numerical results show the dependence of the chemisorbed charge and the differential capacitance on oxygen partial pressure. A comparison against the classical Poisson-Boltzmann approach shows a higher chemisorbed charge in the quantum model, but a greater differential capacitance in the classical case.