Magnetic Isotope Effect Research Articles

Variation in the relationship between odd isotopes of tin in mass-independent fractionation induced by the magnetic isotope effect

Experimental results are presented showing the variation in the relationship between odd isotopes of tin (Sn) in mass-independent fractionation caused by the magnetic isotope effect (MIE), which has previously only been observed for mercury. These results are consistent with the trend predicted from the difference between the magnitudes of nuclear magnetic moments of odd isotopes with a nuclear spin. However, the correlation between odd isotopes in fractionation induced by the MIE for the reaction system used in this study (solvent extraction using a crown ether) was different from that reported for the photochemical reaction of methyltin. This difference between the two reaction systems is consistent with a theoretical prediction that the correlation between odd isotopes in fractionation induced by the MIE is controlled by the relationship between the spin conversion time and radical lifetime. The characteristic changes in the correlation between odd isotopes in fractionation induced by the MIE observed for Sn in this study provide a guideline for quantitatively determining fractionation patterns caused by the MIE for elements that have multiple isotopes with a nuclear spin. These results improve our understanding of the potential impact of the MIE on mass-independent fractionation observed in natural samples, such as meteorites, and analytical artifacts of high-precision isotope analysis for heavy elements.

Magnetic isotope effects: a potential testing ground for quantum biology.

One possible explanation for magnetosensing in biology, such as avian magnetoreception, is based on the spin dynamics of certain chemical reactions that involve radical pairs. Radical pairs have been suggested to also play a role in anesthesia, hyperactivity, neurogenesis, circadian clock rhythm, microtubule assembly, etc. It thus seems critical to probe the credibility of such models. One way to do so is through isotope effects with different nuclear spins. Here we briefly review the papers involving spin-related isotope effects in biology. We suggest studying isotope effects can be an interesting avenue for quantum biology.

Magnetic isotope effects and nuclear spin catalysis in living cells and biomolecular motors: recent advances and future outlooks: Nuclear spin catalysis.

Biomolecular nanoreactors are constructed from chemical elements many of which have magnetic and nonmagnetic stable isotopes. The magnetic isotope effects (MIE) were discovered in experiments with the cells enriched with different isotopes of magnesium, magnetic or nonmagnetic ones. The striking catalytic effect of the magnetic isotope, 25Mg, was revealed in the reaction of ATP hydrolysis driven by myosin, the biomolecular motor utilizing the chemical energy of ATP to perform the mechanical work. The rate of the enzymatic ATP hydrolysis with 25Mg as the enzyme cofactor is twice higher than the rates of the reactions with nonmagnetic 24Mg or 26Mg. A similar effect of the nuclear spin catalysis was revealed in the experiments with zinc as the myosin cofactor. MIE unambiguously indicate that, in the chemo-mechanical process catalyzed by the molecular motor, there is a limiting step which depends on the electron spin state of the reagents, and this step is accelerated by the nuclear spin of the magnetic isotope. The recent developments in this field highlight promising venues for future research of MIE in biophysics with possible applications of the magnetic isotopes in medical physics including radiation medicine and biomedical effects of electromagnetic fields.

Mass-independent Sn isotope fractionation and radiogenic 115Sn in chondrites and terrestrial rocks

Tin has ten stable isotopes, providing the opportunity to investigate and discriminate nucleosynthetic isotope anomalies from mass-dependent and mass-independent isotope fractionation. Novel protocols for chemical separation (based on TBP-resin) and MC-ICP-MS analyses are reported here for high precision Sn isotope measurements on terrestrial rocks and chondrites. Relative to the Sn reference standard (NIST SRM 3161a), terrestrial basalts and chondrites show isotope patterns that are consistent with mass-dependent and mass-independent isotope fractionation processes as well as with 115Sn radiogenic ingrowth from 115In.Two different mass-independent isotope effects are identified, namely the nuclear volume (or nuclear field shift) and the magnetic isotope effect. The magnetic isotope effect dominates in the two measured ordinary chondrites, while repeated analyses of the carbonaceous chondrite Murchison (CM2) display a pattern consistent with a nuclear volume effect. Terrestrial basalts show patterns that are compatible with a mixture of nuclear volume and magnetic isotope effects. The ultimate origin of the isotope fractionation is unclear but a fractionation induced during sample preparation seems unlikely because different groups of chondrites show distinctly different patterns, hence pointing towards natural geo/cosmochemical processes. Only the carbonaceous chondrite Murchison (CM2) shows a Sn isotope pattern similar to what expected for nucleosynthetic variations. However, this pattern is better reproduced by nuclear volume effects. Thus, after considering mass-independent and mass-dependent effects, we find no evidence of residual nucleosynthetic anomalies, in agreement with observations for most other elements with similar half-mass condensation temperatures.Most chondrites show a deficit in 115Sn/120Sn (typically −150 to −200 ppm) relative to terrestrial samples, with the exception of one ordinary chondrite that displays an excess of about +250 ppm. The 115Sn/120Sn data correlate with In/Sn, being consistent with the β− decay of 115In over the age of the solar system. This represents the first evidence of the 115In-115Sn decay system in natural samples. The radiogenic 115Sn signature of the BSE derives from a suprachondritic In/SnBSE, which reflects preferential partitioning of Sn into the Earth’s core.

Oligomerization of β-Like DNA Polymerases in the Presence of Fe2+ Ions

This work presents data on the relationship between the oligomeric state and catalytic activity of β-like DNA polymerases isolated from three cancer cell lines upon replacement of magnesium ions with iron. It was shown that the suppression of the catalytic activity of β-like DNA polymerases in the presence of divalent iron ions is related to enzyme oligomerization that can be responsible for the suppression of the magnetic isotope effect.

Mass-Independent Fractionation of Mercury Isotopes during Photoreduction of Soot Particle Bound Hg(II).

Soot and mercury (Hg) are two notorious air pollutants, and the fate and transport of Hg may be affected by soot at various scales in the environment as soot may be both a carrier and a reactant for active Hg species. This study was designed to quantify photoreduction of Hg(II) in the presence of soot and the associated Hg isotope fractionation under both atmospheric aerosol and aqueous conditions (water-saturated). Photoreduction experiments were conducted with diesel soot particulate matter under controlled temperature and relative humidity (RH) conditions using a flow-through semibatch reactor system. Mass-dependent fractionation resulted in the enrichment of heavier Hg isotopes in the remaining Hg(II) with enrichment factors (ε202Hg) of 1.48 ± 0.02‰ (±2 standard deviation) to 1.75 ± 0.05‰ for aerosol-phase reactions (RH 28-68%) and from 1.26 ± 0.11 to 1.50 ± 0.04‰ for aqueous-phase reactions. Positive odd mass-independent fractionation (MIF) was observed in aqueous-phase reactions, resulting in Δ199Hg values for reactant Hg(II) as high as 5.29‰, but negative odd-MIF occurred in aerosol-phase reactions, in which Δ199Hg values of reactant Hg(II) varied from -1.02 to 0‰. The average ratio of Δ199Hg/Δ201Hg (1.1) indicated that under all conditions, MIF was dominated by magnetic isotope effects during photoreduction of Hg(II). Increasing RH resulted in higher reduction rates but lower extents of negative MIF in the aerosol-phase experiments, suggesting that the reduction of soot particle-bound Hg(II) was responsible for the observed negative odd-MIF. Our results suggest that mass-independent Hg isotope fractionation during Hg(II) photoreduction varies with soot aerosol water content and that Hg-stable isotope ratios may be used to understand the transformational histories of aerosol-bound Hg(II) in the environment.

Mass-independent fractionation of oxygen isotopes during thermal decomposition of divalent metal carbonates: Crystallographic influence, potential mechanism and cosmochemical significance

Few physical or chemical processes defy well-established laws of mass-dependent isotopic fractionation. A surprising example, discovered two decades ago, is that thermal decomposition of calcium and magnesium carbonate minerals (conducted in vacuo, to minimise back-reaction and isotopic exchange) causes the oxygen triple-isotope compositions of the resulting solid oxide and CO2 to fit on parallel mass-dependent fractionation lines in ln(1 + δ17O) versus ln(1 + δ18O) space, with anomalous depletion of 17O in the solid and equivalent enrichment of 17O in the CO2. By investigating the thermal decomposition of other natural divalent metal carbonates and one synthetic example, under similar conditions, we find that the unusual isotope effect occurs in all cases and that the magnitude of the anomaly (Δ′17O) seems to depend on the room temperature crystallographic structure of the carbonate. A lower cation coordination number (as associated with smaller cation radius) correlates with a Δ′17O value closer to zero. Local symmetry considerations may therefore be influential. Relative to a reference fractionation line of slope 0.524 and passing through VSMOW, solid oxides produced by thermal decomposition of orthorhombic carbonates were characterised by Δ′17O = −0.367 ± 0.004‰ (standard error). The comparable figure from rhombohedral examples was −0.317 ± 0.010‰, whereas from the sole monoclinic (synthesised) specimen it was −0.219 ± 0.011‰. The numerical values are, to some extent, dependent on details of the experimental procedure. We discuss potential origins of the isotopic anomaly, including the possibility of hyperfine coupling between 17O nuclei and unpaired electrons of transient radicals (the ‘magnetic isotope effect’). A new mechanism based on the latter process is proposed. The associated transition state is compatible with that suggested by recent quantum chemical and kinetic studies of the thermal decompositions of calcite and magnesite. An earlier suggestion based on the magnetic isotope effect is shown to be incompatible with the generation of a 17O anomaly, regardless of the identity of the carbonate. We cannot exclude the possibility that a Fermi resonance between states leading to dissociation may additionally affect the magnitude of Δ′17O in some cases. Our findings have cosmochemical implications, with thermal processing of carbonates providing a potential mechanism for the mass-independent fractionation of oxygen isotopes in protoplanetary systems.

Mass-Independent Fractionation of Even and Odd Mercury Isotopes during Atmospheric Mercury Redox Reactions.

Mass-independent fractionation (MIF) of stable even mass number mercury (Hg) isotopes is observed in rainfall and gaseous elemental Hg0 globally and is used to quantify atmospheric Hg deposition pathways. The chemical reaction and underlying even-Hg MIF mechanism are unknown however and speculated to be caused by Hg photo-oxidation on aerosols at the tropopause. Here, we investigate the Hg isotope composition of free tropospheric Hg0 and oxidized HgII forms at the high-altitude Pic du Midi Observatory. We find that gaseous oxidized Hg has positive Δ199Hg, Δ201Hg, and Δ200Hg and negative Δ204Hg signatures, similar to rainfall Hg, and we document rainfall Hg Δ196Hg to be near zero. Cloud water and rainfall Hg show an enhanced odd-Hg MIF of 0.3‰ compared to gaseous oxidized HgII, potentially indicating the occurrence of in-cloud aqueous HgII photoreduction. Diurnal MIF observations of free tropospheric Hg0 show how net Hg0 oxidation in high-altitude air masses leads to opposite even- and odd-MIF in Hg0 and oxidized HgII. We speculate that even-Hg MIF takes place by a molecular magnetic isotope effect during HgII photoreduction on aerosols that involves magnetic halogen nuclei. A Δ200Hg mass balance suggests that global Hg deposition pathways in models are likely biased toward HgII deposition. We propose that Hg cycling models could accommodate the Hg-isotope constraints on emission and deposition fluxes.

Mechanistic Aspects Regarding the Ultraviolet Degradation of Polychlorinated Biphenyls in Different Media: Insights from Carbon and Chlorine Isotope Fractionation.

In this study, the carbon and chlorine isotope fractionation during ultraviolet-photolysis of polychlorinated biphenyls (PCBs, including PCB18, PCB77, PCB110, and PCB138) in n-hexane (Hex), methanol/water (MeOH/H2O), and silica gel was first investigated to explore their mechanistic processes. We observed a significant variation in ΛCl-C (εCl/εC) for the same PCBs in different photochemical systems, implying that PCB degradation processes in various photoreaction systems could differ. Although all substrates showed normal apparent carbon/chlorine kinetic isotope effects (C-/Cl-AKIE >1), the putative inverse C-AKIE of nondechlorinated pathways was suggested by 13C depletion of the average carbon isotope composition of PCB138 and corresponding dechlorinated products in MeOH/H2O, which might originate from the magnetic isotope effect. Significant negative correlations were found between C-AKIE and relative disappearance quantum yields ("Φ") of ortho-dechlorinated substrates (PCB18, PCB110, and PCB138) in Hex and MeOH/H2O. However, the C-AKIE and "Φ" of PCB77 (meta/para-dechlorinated congener) obviously deviated from the above correlations. Furthermore, significantly different product-related carbon isotope enrichment factors of PCB77 in Hex were found. These results demonstrated the existence of dechlorination position-specific and masking effects in carbon isotope fractionations.

Magnesium magnetic isotope effects in microbiology.

Two main properties of atomic nuclei-mass and nuclear magnetic moments-are origin of many biological effects. Mass-dependent isotope effects have been studied for a long time. The effect of magnetic isotopes having a magnetic moment and spin was first shown in the early twenty-first century for the magnetic isotope magnesium 25Mg on enzymatic ATP synthesis. This stimulated the search for experimental evidence and theoretical justification of magnetic nuclei influence on biological processes. This review contains the results of scientific research on the magnesium magnetic isotope effects in microbiology. Microorganisms have been found to be sensitive to the presence of nuclear magnetic moment of magnesium isotope 25Mg compared with non-magnetic 24,26Mg isotopes.

Isotopic effect of macro- and microelements in ecosystems

Isotopic effects occurring in living organisms due to metabolism are analyzed. The phenomenon of metabolism is considered in the classical sense as a combination of biochemical reactions (mainly enzyma­tic) that take place in the cells of living beings and provide the cleavage, synthesis and interconversion of complex compounds. The scope of use of natural isotopes is wide and diverse. Isotopes are carriers of information about the birth and transformation of molecules, and isotope fractionation is a chemical characteristic of a substance. Isotope metabolism consists in the intermolecular fractionation of isotopes at separate stages of biochemical reactions, namely the cleavage, synthesis and interconversion of complex compounds caused by differences in the structure and fundamental properties of isotope nuclei. It is proved that the fractionation of isotopes in chemical and biochemical reactions due to isotopic effects is based on two fundamental properties of atomic nuclei — mass and magnetic moment. The kinetic (mass-depen­ dent) isotopic effect distributes the isotopic nuclei by their masses, and the magnetic one fractionates the nuclei by their magnetic moments. The kinetic isotopic effect depends on the magnitude of the difference in the masses of isotopic molecules, temperature and the difference in the activation energies of isotopic forms. The magnetic isotope effect depends on the reaction rate in a single cell, its projection, magnetic moment and energy of electron-nuclear interaction. It is determined that the fractionation of isotopes in living organisms is that the relative content of one of the isotopes in this compound increases by reducing its content in the other. As a result, there is a fractionation of isotopes within one biological object.

Combined effect of magnesium isotopes and antibiotics on morphology of E. coli

In this paper, the morphology of Escherichia coli bacteria grown in the presence of magnesium isotopes (magnetic 25Mg, non-magnetic 24,26Mg and natural Mg), and antibiotics of various groups were studied. Atomic force microscopy (AFM) was used as the main method. When the bacteria were cultured in the presence of different groups of antibiotics, the following morphological changes were detected: filamentation, cell lysis, cell adhesion, cell wall damage, and the formation of “depressions” or pores. For E. coli bacteria cultured on a medium with tobramycin and lincomycin, a magnetic magnesium isotope effect 25Mg in bacteria morphology was detected, which was manifested as a change in the roughness of bacterial cells. Both of these antibacterial drugs act on the same intracellular system – protein synthesis. It has also been observed that the elongation of bacterial cells, when exposed to levofloxacin and ciprofloxacin, depends on the type of magnesium isotope in the nutrient medium. The combined action of the 25Mg magnetic isotope and quinolones on bacteria makes it possible to obtain the process followed by significant elongation of cells, thereby indicating improved antibiotic effect, as compared with the nonmagnetic 24,26Mg isotopes.

Magnetic-Isotope Effects of Magnesium and Zinc in Enzymatic ATP Hydrolysis Driven by Molecular Motors

The effects of different magnesium and zinc isotopes on the enzyme activity of myosin subfragment-1 have been explored. The rate of the enzymatic ATP hydrolysis in reaction media enriched with the magnetic isotope, 25Mg, is twice as high as it is in reaction media enriched with the nonmagnetic isotopes, 24Mg or 26Mg. A similar effect of nuclear spin catalysis has been detected in the experiments with zinc isotopes as cofactors of the enzyme. The rate of the enzymatic ATP hydrolysis with magnetic 67Zn increases by 40–50% compared to that with nonmagnetic 64Zn or 68Zn. The magnetic-isotope effects have been observed at the physiological concentration of magnesium and zinc chlorides (5 mM). The catalytic effect of the magnetic magnesium isotope 25Mg has been revealed in the experiments with Mg-dependent ATPase of myometrial plasma membranes. The magnetic-isotope effects indicate that there is a spin-selective rate-limiting step in the chemo-mechanical process driven by the “molecular motor” due to the energy of ATP hydrolysis and that nuclear spin catalysis causes acceleration of this stage. Some possible mechanisms of the nuclear spin catalysis are discussed.

Effect of Magnesium Isotopes on Antibiotic Sensitivity of E. coli

The effect of 25Mg, a magnetic magnesium isotope, on the sensitivity of Escherichia coli K12 TG1 to quinolone/fluoroquinolone (nalidixic acid and ciprofloxacin) and aminoglycoside antibiotics (amikacin and tobramycin) was found. In the case of fluoroquinolones, determination of antibiotic sensitivity by the disc diffusion method revealed the 7‒14% larger growth inhibition zones on the medium with the magnetic magnesium isotope than for the same antibiotics in the variants with 24Mg, 26Mg, or the natural Mg isotope. The effect of the magnetic magnesium isotope 25Mg on the increase in resistance to the quinolones/fluoroquinolones group of antibiotics was observed independently of the determining method: the growth rate of E. coli culture incubated in the medium with 25Mg and ciprofloxacin decreased by 80% compared to the control without antibiotics, while in the variants with 24Mg, 26Mg, and natural Mg the decrease did not exceed 50%. An increase in antibiotic resistance (opposite magnetic isotopic effect) was shown for amikacin, tobramycin, and clindamycin. In the variants with amikacin and clindamycin, the growth inhibition zones of bacteria enriched with 25Mg were 16‒17 and 17‒24% smaller, respectively. An increase in resistance to tobramycin (aminoglycosides) was observed for submerged E. coli cultures growing in the medium with 25Mg: at the antibiotic concentration two times lower than the MIC, the growth rate of E. coli was 86% of the control, while in the variants with nonmagnetic isotopes or natural magnesium it decreased by 40‒50%. The mechanisms of magnetic isotopic effects of 25Mg are discussed: its effect on the enzymatic activity of Mg-dependent enzymes involved in protection of the cells from the action of antibiotics.

Oxygen and sulfur mass-independent isotopic signatures in black crusts: the complementary negative Δ<sup>33</sup>S reservoir of sulfate aerosols?

Abstract. To better understand the formation and the oxidation pathways leading to gypsum-forming “black crusts” and investigate their bearing on the whole atmospheric SO2 cycle, we measured the oxygen (δ17O, δ18O, and Δ17O) and sulfur (δ33S, δ34S, δ36S, Δ33S, and Δ36S) isotopic compositions of black crust sulfates sampled on carbonate building stones along a NW–SE cross section in the Parisian basin. The δ18O and δ34S values, ranging between 7.5 ‰ and 16.7±0.5 ‰ (n=27, 2σ) and between −2.66 ‰ and 13.99±0.20 ‰, respectively, show anthropogenic SO2 as the main sulfur source (from ∼2 % to 81 %, average ∼30 %) with host-rock sulfates making the complement. This is supported by Δ17O values (up to 2.6 ‰, on average ∼0.86 ‰), requiring > 60 % of atmospheric sulfates in black crusts. Negative Δ33S and Δ36S values between −0.34 ‰ and 0.00±0.01 ‰ and between −0.76 ‰ and -0.22±0.20 ‰, respectively, were measured in black crust sulfates, which is typical of a magnetic isotope effect that would occur during the SO2 oxidation on the building stone, leading to 33S depletion in black crust sulfates and subsequent 33S enrichment in residual SO2. Except for a few samples, sulfate aerosols mostly have Δ33S values > 0 ‰, and no processes can yet explain this enrichment, resulting in an inconsistent S budget: black crust sulfates could well represent the complementary negative Δ33S reservoir of the sulfate aerosols, thus solving the atmospheric SO2 budget.

A Nuclear Magnetic Insight Towards the Cytostatic Potential of Medicinal Plant Extracts Replay to Al Wihibi et al Biomedica 2019;35(4):203-209

<p>Cytostatic activities of water and organic extracts prepared from medicinal higher plants including Ducrosia anethifolia should be analyzed by taking into account the “hidden” magnetic isotope effects of stable metal isotopes (25Mg, 43Ca, 67Zn …) pre-(bio) fractionated in the plant tissues. A multi-collector inductively coupled plasma mass spectrometry (MC – ICPMS) might be successfully employed to reveal and detail this specific peculiarity for further pharmacological applications.</p>

Mercury Isotope Fractionation during the Photochemical Reduction of Hg(II) Coordinated with Organic Ligands.

The photochemical reduction of Hg(II) is an important pathway in the environmental Hg cycle because it competes with Hg methylation and potentially limits the formation of bioaccumulative methylmercury. Hg stable isotope systematics have proven to be an effective tool for investigating the transport, transformation, and bioaccumulation of Hg. The dominant cause of mass independent isotope fractionation (MIF) of Hg in nature is the photochemical reduction of various species of Hg(II). However, it is difficult to fully interpret Hg stable isotope signatures due to the lack of mechanistic information about which Hg compounds are susceptible to MIF and why. This study investigates Hg isotope fractionation during the photochemical reduction of Hg(II) complexed to organic ligands, which are representative of the available binding sites in natural dissolved organic matter. The photochemical reduction of Hg(II) in the presence of cysteine resulted in both negative and positive MIF in residual Hg(II), where the sign depended on pH and dissolved oxygen level. In the presence of serine, either nuclear volume or magnetic isotope effects were observed depending on the wavelength of light and the extent of Hg(II) complexation by serine. In the presence of ethylenediamine, MIF was negative. Our Hg stable isotope results suggest that MDF and MIF are induced at different steps in the overall photochemical reduction reaction and that MIF does not depend on the rate-determining step but instead depends on photophysical aspects of the reaction such as intersystem crossing and hyperfine coupling. The behavior of Hg isotopes reported here will allow for a better understanding of the underlying reaction mechanisms controlling the Hg isotope signatures recorded in natural samples.

Magnetic Isotope Effect on the Repair of Radiation-Induced DNA Damage

The rate of DNA repair in human blood lymphocytes exposed to γ-radiation was shown to depend on the nuclear magnetic moment of magnesium ions. The decrease of DNA double-strand breaks occurs as a first-order reaction with the rate constants 1.1 × 10–3 s–1 and 1.6 × 10–3 s–1 for 25Mg2+ and 24Mg2+ ions respectively. Their ratio certifies magnetic isotope effect on the DNA repair; the latter occurs by 1.5 times slower with nuclear-magnetic 25Mg2+ ions than with nuclear nonmagnetic 24Mg2+ ions. The discovery of this effect is an irrefutable indicator that the DNA repair is spin-dependent and magneto-sensitive process, and its chemistry includes electron transfer and generation of radicals and radical pairs.

The Magnetic Isotopes Effect of Magnesium 25Mg on the Physiological Properties of Bacteria E. coli

Magnetic isotope effects of magnesium 25Mg on antibiotic resistance and biofilm formation of bacteria E. coli were discovered. The increase in antibiotic resistance in the presence of the ion 25Mg2+ was registered for E. coli cells incubated with quinolones, indicating the inhibiting effect of the magnetic moments of nuclei 25Mg on deoxyribonucleic acid (DNA) synthesis. It was discovered that the process of biofilm formation by the bacteria E. coli is magnetosensitive. Magnetic magnesium isotope presence in nutrient media stimulated formation of biofilm compared with nonmagnetic isotopes 24, 26Mg. As e result the enrichment of media by magnetic magnesium can be used to control the physiological properties of bacteria: biofilm formation and antibiotic resistance.

Carbohydrate pyrolysis mechanisms from isotopic labeling. Part 5. The pyrolysis of D-glucose: The origin of the light gases from the D-glucose molecule

Flash pyrolysis in air of the complete set of 13C1 isotopologs of D-glucose, monitored by GC/MS using an efficient column for separating the light gases, allowed us to determine the sources within D-glucose for a range of light hydrocarbons and carbon oxides. These include carbon monoxide (CO), carbon dioxide (CO2), ethyne, ethene, ethane, propadiene, propene, propane, various isomers of butene, 1,3-butadiene, 1,3-cyclopentadiene and benzene. Inasmuch as the pyrolysis product was swept into the chromatographic column as formed, changes in isotopic incorporation with temperature rise could be qualitatively observed as changes of isotopic content across the chromatographic peak. There was significant divergence in labeled origin of CO and CO2, suggesting substantial mutual independence of formation. For both, however, composition was dominated by the first four carbons of D-glucose. The high-temperature range of formation of these may reflect the composition of the underlying char undergoing combustion. Similarities in isotopic content of ethene and ethane, or of allene, propylene and propane or of the various C4 species suggest that the least saturated versions are formed initially, and then undergo free-radical chain induced hydrogenation. Concerted electrocyclic fragmentations were invoked to explain the dominant formation of ethene, ethyne, propadiene and 1,3-butadiene. CO formation was postulated to arise in part from the fragmentation of glyoxal. CO and CO2 showed strong evidence of preferential ionization of the 13C isotopologs relative to the 12C ipsologs under our conditions, due to the magnetic isotope effect. Overlaid on this was a partial chromatographic enrichment of 13CO2 in the leading edge of the chromatographic peak. The data were normalized to adjust for both effects.