Source apportionment of carbonaceous aerosols during haze days in Shanghai based on dual carbon isotopes

Journal of Radioanalytical and Nuclear Chemistry - We present dual carbon isotope constrained (δ13C and Δ14C) source apportionment of organic carbon and elemental carbon in fine...     

Tracing biogenic links of natural organic substances at the molecular level with stable carbon isotopes : n-Alkanes and n-Alkanoic acids from sediments

The ¹³C/¹²C compositions of n-alkanes and n-alkanoic acids from Eocene sediments are correlated in the 20–29 carbon number range.     

Determination of the stable carbon isotopic compositions of 2‐methyltetrols in ambient aerosols from the Changbai Mountains

Isoprene is one of the most important non‐methane hydrocarbons (NMHCs) in the troposphere: it is a significant precursor of O₃ and it affects the oxidative state of the atmosphere. The diastereoisomeric 2‐methyltetrols, 2‐methylthreitol and 2‐methylerythritol, are marker compounds of the photooxidation products of atmospheric isoprene. In order to obtain valuable information on the δ¹³C value of isoprene in the atmosphere, the stable carbon isotopic compositions of the 2‐methyltetrols in ambient aerosols were investigated. The 2‐methyltetrols were extracted from filter samples and derivatized with methylboronic acid, and the δ¹³C values of the methylboronate derivatives were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The δ¹³C values of the 2‐methyltetrols were then calculated through a simple mass balance equation between the 2‐methyltetrols, methylboronic acid and the methylboronates. The δ¹³C values of the 2‐methyltetrols in aerosol samples collected at the Changbai Mountain Nature Reserves in eastern China were found to be ?24.66 ± 0.90‰ and ?24.53 ± 1.08‰ for 2‐methylerythritol and 2‐methylthreitol, respectively. Based on the measured isotopic composition of the 2‐methyltetrols, the average δ¹³C value of atmospheric isoprene is inferred to be close to or slightly heavier than ?24.66‰ at the collection site during the sampling period. Copyright © 2010 John Wiley & Sons, Ltd.     

Metabolic turnover rates of carbon and nitrogen stable isotopes in captive juvenile snakes

Metabolic turnover rates (m) of δ¹⁵N and δ¹³C were assessed in different tissues of newly hatched captive‐raised corn snakes (Elaphe guttata guttata) fed maintenance diets consisting of earthworms (Eisenia foetida) that varied substantially in δ¹⁵N (by 644‰) and δ¹³C (by 5.0‰). Three treatments were used during this 144 day experiment that consisted of the same diet throughout (control), shifting from a depleted to an enriched stable isotope signature diet (uptake), and shifting from an enriched to depleted stable isotope signature diet (elimination). Values of δ¹³C in the liver, blood, and muscle of the control snakes reached equilibrium with and were, respectively, 1.73, 2.25 and 2.29 greater than in their diet, this increase is called an isotopic discrimination factor (Δδ¹³C = δ¹³C_snake ? δ¹³C_food). Values of δ¹⁵N in snake tissues did not achieve equilibrium with the diets in any of the exposures and thus Δ¹⁵N could not be estimated. Values of metabolic turnover rates (m) for δ¹³C and δ¹⁵N were greater in liver than in muscle and blood, which were similar, and relative results remained the same if the fraction of ¹⁵N and ¹³C were modeled. Although caution is warranted because equilibrium values of stable isotopes in the snakes were not achieved, values of m were greater for δ¹³C than δ¹⁵N, resulting in shorter times to dietary equilibrium for δ¹³C upon a diet shift, and for both stable isotopes in all tissues, greater during an elimination than in an uptake shift in diet stable isotope signature. Multiple explanations for the observed differences between uptake and elimination shifts raise new questions about the relationship between animal and diet stable isotope concentrations. Based on this study, interpretation of feeding ecology using stable isotopes is highly dependent on the kind of stable isotope, tissue, direction of diet switch (uptake versus elimination), and the growth rate of the animal. Copyright © 2009 John Wiley & Sons, Ltd.     

Glass transition and phase state of organic compounds: dependency on molecular properties and implications for secondary organic aerosols in the atmosphere

Recently, it has been proposed that organic aerosol particles in the atmosphere can exist in an amorphous semi-solid or solid (i.e. glassy) state. In this perspective, we analyse and discuss the formation and properties of amorphous semi-solids and glasses from organic liquids. Based on a systematic survey of a wide range of organic compounds, we present estimates for the glass forming properties of atmospheric secondary organic aerosol (SOA). In particular we investigate the dependence of the glass transition temperature T(g) upon various molecular properties such as the compounds' melting temperature, their molar mass, and their atomic oxygen-to-carbon ratios (O:C ratios). Also the effects of mixing different compounds and the effects of hygroscopic water uptake depending on ambient relative humidity are investigated. In addition to the effects of temperature, we suggest that molar mass and water content are much more important than the O:C ratio for characterizing whether an organic aerosol particle is in a liquid, semi-solid, or glassy state. Moreover, we show how the viscosity in liquid, semi-solid and glassy states affect the diffusivity of those molecules constituting the organic matrix as well as that of guest molecules such as water or oxidants, and we discuss the implications for atmospheric multi-phase processes. Finally, we assess the current state of knowledge and the level of scientific understanding, and we propose avenues for future studies to resolve existing uncertainties.     

Determination of aromatic acids and nitrophenols in atmospheric aerosols by capillary electrophoresis

A capillary zone electrophoresis method is developed for the determination of aromatic organic acids and nitrophenols in atmospheric aerosols. The procedure is based on sampling atmospheric particulate matter on quartz fiber filters and the extraction and analysis of the extracts by capillary electrophoresis. Separation conditions are optimized by varying the pH and acetonitrile content of the electrolyte buffer. Separations in a 20% acetonitrile-20 mM borate mixture (pH 9.9) are able to resolve all of the geometric isomers of hydroxybenzoic acid, phthalic acid, benzenetricarboxylic acid, and nitrophenol as well as 1,2,4,5-benzenetricarboxylic acid, m-toluic acid, and sulfosalicylic acid. A buffer consisting of 11% acetonitrile-20 mM borate (pH 9.9) is found to be most suitable for the analysis of atmospheric aerosol samples. Detection limits are in the order of 40 to 130 ng/mL. Intersample migration time reproducibility is generally better than 1.5%, with day-to-day variations under 3%. A general extraction scheme using diethyl ether-HCl in combination with a preconcentration step is developed. Recoveries of spiked standards range from 59% to 102%, with relative standard deviations ranging from 2% to 17% for five determinations. The method is applied towards the analysis of ambient aerosol samples as well as vehicle emission studies with promising results, thus showing it to be a potential complement to already existing methodology for the analysis of organic acids and nitrophenols in atmospheric aerosols.     

Periodicity of the stable isotopes

It is demonstrated that all stable (non-radioactive) isotopes are formally interrelated as the products of systematically adding alpha particles to four elementary units. The region of stability against radioactive decay is shown to obey a general trend based on number theory and contains the periodic law of the elements as a special case. This general law restricts the number of what may be considered as natural elements to 100 and is based on a proton:neutron ratio that matches the golden ratio, characteristic of biological and crystal growth structures. Different forms of the periodic table inferred at other proton:neutron ratios indicate that the electronic configuration of atoms is variable and may be a function of environmental pressure. Cosmic consequences of this postulate are examined.     

Fractionation and metabolic turnover of carbon and nitrogen stable isotopes in black fly larvae

Diet-tissue fractionation factors and metabolic turnover rates of delta15N and delta13C were assessed in laboratory-reared black fly (Simulium vittatum IS-7) larvae fed isotopically distinct diets. Five treatments consisted of using food with different delta15N signatures throughout the experiments (19-26 days), a sixth shifted from a low to high delta15N signature diet (uptake) on day 14, and the last shifted from a high to low delta15N signature diet (elimination) on day 14. In the larvae, diet-tissue fractionation factors for delta13C, which were in steady state with food, ranged from -0.61 to 2.0, with a median of 1.87. The delta15N diet-tissue fractionation factors were mostly negative, ranging from +2.85 to -24.96 per thousand, with a single positive value from the elimination treatment in which larval delta15N did not achieve steady state with the food. Diet-tissue fractionation factors also had a significant negative relationship (r2 = 0.98) with delta15N values in the food suggesting that nitrogen diet-tissue fractionation factors are 15N concentration-dependent. The delta15N of shed head capsules and feces were enriched in 15N and could be mechanisms for elimination of 15N by the larvae. For delta15N, metabolic turnover values based on the Hesslein model were highly consistent (0.40 to 0.43 delta15N*day(-1)) between uptake and elimination phases and across experiments and were an order of magnitude greater than growth rates. The rapid turnover of nitrogen in black fly larvae, which was orders of magnitude greater than measured in vertebrates, makes them an excellent indicator of short-term changes in nitrogen inputs to aquatic systems.     

Post-photosynthetic fractionation of stable carbon isotopes between plant organs--a widespread phenomenon

Discrimination against 13C during photosynthesis is a well-characterised phenomenon. It leaves behind distinct signatures in organic matter of plants and in the atmosphere. The former is depleted in 13C, the latter is enriched during periods of preponderant photosynthetic activity of terrestrial ecosystems. The intra-annual cycle and latitudinal gradient in atmospheric 13C resulting from photosynthetic and respiratory activities of terrestrial plants have been exploited for the reconstruction of sources and sinks through deconvolution by inverse modelling. Here, we compile evidence for widespread post-photosynthetic fractionation that further modifies the isotopic signatures of individual plant organs and consequently leads to consistent differences in delta13C between plant organs. Leaves were on average 0.96 per thousand and 1.91 per thousand more depleted than roots and woody stems, respectively. This phenomenon is relevant if the isotopic signature of CO2-exchange fluxes at the ecosystem level is used for the reconstruction of individual sources and sinks. It may also modify the parameterization of inverse modelling approaches if it leads to different isotopic signatures of organic matter with different residence times within the ecosystems and to a respiratory contribution to the average difference between the isotopic composition of plant organic matter and the atmosphere. We discuss the main hypotheses that can explain the observed inter-organ differences in delta13C.     

Annular diffusion denuder for simultaneous removal of gaseous organic compounds and air oxidants during sampling of carbonaceous aerosols

A specially designed annular diffusion denuder for simultaneous removal of organic gaseous compounds and atmospheric oxidants in carbonaceous aerosol sampling is presented. Various kinds of denuder coatings were compared with respect to the collection efficiency of both organic gaseous compounds and NO₂ and ozone. The optimum sorbent is a mixture of activated charcoal and sulfite on molecular sieve. To ensure high collection efficiency over long-term field operation, two annular diffusion denuders are combined in series. The first half of the first denuder is filled with Na₂SO₃ on molecular sieve (23 cm long layer) while the second half of the first denuder and the whole second denuder are filled with activated charcoal (the total length of the charcoal section is 67 cm).     

Determination of organic acids and ketones in contaminated soils

Hydrocarbons and metabolites from biodegradation in soil have been isolated and separated using Soxhlet extraction, with n-heptane and dichloromethane, combined with solid-phase extraction on silica gel and basic aluminum oxide using n-pentane, dichloromethane, methanol, and sulfuric acid – methanol as eluents. This procedure can be used for determination of metabolites both in laboratory-prepared soil samples containing mineral oils and in actual contaminated soil. After microbiological degradation, organic acids and ketones which were not original components of the diesel fuel and lubricating oil contaminating the soil samples were identified using capillary gas chromatography – mass spectrometry in batch-soil experiments. Predominantly alicyclic and branched-chain aliphatic organic acids and diacids, and aromatic ketones, were found to be formed after a few weeks degradation.     

Determination of organic,inorganic and particulate iodine in the coastal atmosphere of Japan

A reliable method for the sampling and analysis of atmospheric iodine species was developed. The air filtering system consisted of a 0.4 m Nuclepore^® filter, 47 mm in diameter, for particulate collection followed by two, 47 mm in diameter, cellulose filters for inorganic iodine collection. The latter filters had been impregnated with 1N LiOH in a 10% glycerol-water mixture. The organic iodine was collected by two beds holding 0.2 g of fibriform activated charcoal produced from phenol resin. Supplementation of the charcoal with triethylendiamine (TEDA) enhanced the sorption ability for gaseous iodine. The filters were analyzed by neutron activation analysis. The background radioactivity could be reduced by using the fibriform activated charcoal due to the low content of impurities in the phenol resin. The background count for¹²⁸I (443 keV) obtained from the fibriform activated charcoal was about one order of magnitude lower than that of the conventional granular one (plant origin). Approximate detection limits for particulate, inorganic and organic iodine were 1, 0.5 and 0.5 ng/m³, respectively, when 50 m³ of air was sampled by this system. The air was sampled at two locations along the coast of Ibaraki, Japan. The concentration ranges of particulate, inorganic and organic iodine were 0.3–3.4, 1.2–3.3 and 7.8–20.4 ng/m³, respectively. Almost 90% of the atmospheric iodine was in a gaseous form in which organic iodine was dominant.     

Determination of carbon and hydrogen in organic fluorine compounds

A rapid determination of carbon and hydrogen in organic fluorine compounds is described. Magnesium oxide is used both as an absorbent for fluorine and as an aid to complete combustion. The time required for one determination in series is under 30 min. The method is very widely applicable.     

Determination of urinary organic acids by HPLC

Summary A high-performance liquid chromatographic method for the simultaneous determination of urinary organic acids and creatinine for following the metabolism of aromatic solvents is reported. After extraction of acidified, filtered urine with diethylether followed by evaporation, the dried residue is dissolved in mobile phase. Hydroxybenzoic acid is used as internal standard. A column of Nucleosil C₁₈ is used with a precolumn of the same material. The mobile phase is acetonitrilephosphate buffer, pH 3.3 (1783). For determination of creatinine the sample is simply diluted 10-fold and the eluate monitored at 215 nm (UV). This technique gives highly reproducible results and is simple, reliable and useful for biological monitoring.     

Changes in carbon and nitrogen stable isotopes of chironomid larvae during growth, starvation and metamorphosis

We conducted experiments to determine isotope changes in the deposit-feeding chironomid larvae Chironomus acerbiphilus during feeding, starvation and metamorphosis. Isotope changes in chironomid larvae occurred mainly during growth and rarely afterward. This finding indicates that chironomid isotope turnover mainly occurs in conjunction with growth and suggests that chironomid larvae only break down newly assimilated food for energy during periods of no growth. Chironomid delta(13)C values significantly increased throughout the starvation experiment, indicating that chironomids preferentially break down components with lower delta(13)C content during starvation. We found significant changes in chironomid isotope ratios ((15)N enrichment) during pupation. This evidence suggests that the physiological condition of animals (such as during an active growth phase or pre- or post-molting) is important to their stable isotope ratios.