Chemical Characteristics of Fine Particles (PM1) from Xi'an,China

Daily mass concentrations of water-soluble inorganic (WS-i) ions, organic carbon (OC), and elemental carbon (EC) were determined for fine particulate matter (PM₁, particles < 1.0 μm in diameter) collected at Xi'an, China. The annual mean PM₁ mass concentration was 127.3 ± 62.1 μg m^–3: WS-i ions accounted for ～38% of the PM₁ mass; carbonaceous aerosol was ～30%; and an unidentified fraction, probably mostly mineral dust, was ～32%. WS-i ions and carbonaceous aerosol were the dominant species in winter and autumn, whereas the unidentified fraction had stronger influences in spring and summer. Ion balance calculations indicate that PM₁ was more acidic than PM_2.5 from the same site. PM₁ mass, sulfate and nitrate concentrations followed the order winter > spring > autumn > summer, but OC and EC levels were higher in autumn than spring. Annual mean OC and EC concentrations were 21.0 ± 12.0 μg m^?3 and 5.1 ± 2.7 μg m^–3 with high OC/EC ratios, presumably reflecting emissions from coal combustion and biomass burning. Secondary organic carbon, estimated from the minimum OC/EC ratios, comprised 28.9% of the OC. Positive matrix factorization (PMF) analysis indicates that secondary aerosol and combustion emissions were the major sources for PM₁.     

Tailpipe emission characteristics of PM2.5 from selected on-road China III and China IV diesel vehicles

Eighteen China III and IV diesel vehicles, including light-duty diesel trucks (LDDTs), medium-duty diesel trucks (MDDTs), heavy-duty diesel trucks (HDDTs) and buses, were tested with real-world measurements using a portable emission measurement system (PEMS). The emission factors (EFs), chemical components and surface morphology of emitted particles from these vehicles were characterized. Measured features included organic carbon (OC), elemental carbon (EC), water soluble ions (WSIs) and trace elements of PM_2.5. The modelling system MOtor Vehicle Emission Simulator (MOVES) was also employed to estimate the PM_2.5 EFs from these vehicles. Carbonaceous content made up 35.8–110.8% of PM_2.5, the largest contribution of all the determined chemical components; WSIs and elements accounted for less than 10%. The average PM_2.5 EFs of MDDTs and HDDTs were 0.389 g·km^?1 and 0.115 g·km^?1, respectively, approximately one order of magnitude higher than that of LDDTs. The PM_2.5 EFs of China III buses were much lower than those of China III MDDTs and HDDTs, indicating that the inspection maintenance program (I/M) system was carried out effectively on public diesel vehicles. Moreover, the chemical composition of 9.2–56.2% of the PM_2.5 mass emitted from China IV diesel trucks could not be identified in the present study. It was possible this unidentified mass was particle bound water, but this hypothesis should be confirmed with further measurements. The SEM images of PM_2.5 samples presented a loose floc structure. In addition, the trends of variation of estimated PM_2.5 EFs derived from the MOVES simulation were essentially consistent with those of tested values.

Copyright © 2018 American Association for Aerosol Research     

Can litter production and litter decomposition improve soil properties in the rubber plantations of different ages in Côte d’Ivoire?

Litter production and litter decomposition influence the availability of nutrients in the soil. The investigation aimed at characterizing the dynamics of leaf litter decomposition, and soil physico-chemical and biological parameters in rubber plantations of different ages. During a 12-months’ period, field studies were done in 7-, 12-, and 25-year-old rubber plantations. For measuring of litter decomposition and input from aboveground, 324 litter bags and 27 litter traps (1 m?×?1 m) were placed in 3 sampling areas per age class of rubber plantations. The soil parameters were also characterized. The results showed that the annual litter production and the amounts of organic carbon in leaves increased with the aging of the plantations. The annual decomposition constant (k) ranged from 0.0381?±?0.0040 year^?1 in the 25-year-old plantations to 0.0767?±?0.0111 year^?1 in the 7-year-old plantations. The annually decomposed litter mass varied between 2.7?±?0.3 t ha^?1 year^?1 in the 12-year-old plantations to 4.2?±?0.3 t ha^?1 year^?1 in the 25-year-old plantations. The soil of the 25-year-old plantations showed higher values of most physico-chemical and biological variables as compared to the 7-year-old plantations: annual litter production (+?32%), annual litter mass decomposed (+?11%), annual carbon (+?15%) and nitrogen (+?11%) inputs, soil organic carbon (+?52%), total nitrogen (+?32%), soil organic matter (+?52%), soil water content (+?74%), and the total density of soil invertebrates (+?121%). The results indicate an improvement of soil properties with the aging of the rubber plantations and the importance of this agricultural system for carbon sequestration.     

Grazing effects on the greenhouse gas balance of a temperate steppe ecosystem

Although a significant fraction of the global soil?Catmosphere exchange of greenhouse gases (GHGs) occurs in semi-arid zones little is known about the magnitude of fluxes in grazed steppe ecosystems and the interference with grazing intensity. In order to assess GHG burdens and to identify options of climate-optimized livestock farming, GHG emissions of sheep grazing in Inner Mongolia steppe were analyzed. Carbon sequestration and field-fluxes of methane (CH₄) and nitrous oxide (N₂O) were measured at a range of steppe sites differing in grazing intensity and management, i.e. ungrazed (UG), ungrazed with hay cutting (HC), lightly grazed (LG), moderately grazed (MG), and heavily grazed (HG). In addition, GHG emissions from enteric fermentation, manure management, and farming inputs (i.e. fossil fuels) were quantified for LG, MG, and HG. Monte Carlo simulation was used to estimate uncertainty. Sheep grazing changed the net GHG balance of the steppe from a significant sink at UG (?1476?±?2481?kg CO_2eq ha^?1?year^?1) to a significant source at MG (2350?±?1723?kg CO_2eq ha^?1?year^?1) and HG (3115?±?2327?kg CO_2eq ha^?1?year^?1). In a similar way, the GHG intensity increased from 8.6?±?79.2?kg CO_2eq?kg^?1 liveweight gain at LG up to 62.2?±?45.8 and 62.6?±?46.7?kg CO_2eq?kg^?1 liveweight gain at MG and HG, respectively. GHG balances were predominantly determined by CO₂ from changes in topsoil organic carbon. In grazing systems, CH₄ from enteric fermentation was the second most important component. The results suggest that sheep grazing under the current management changes this steppe ecosystem from a sink to a source of GHGs and that grazing exclusion holds large potential to restore soil organic carbon stocks and thus to sequester atmospheric CO₂. The balance between grazing intensity and grazing exclusion predominantly determines GHG balances of grass-based sheep farming in this region. Therefore, a high proportion of ungrazed land is most important for reducing GHG balances of sheep farms. This can be either achieved by high grazing intensity on the remaining grazed land or by confined hay feeding of sheep.     

Treatment of dyehouse waste‐water by supercritical water oxidation: a case study

BACKGROUND: Supercritical water oxidation (SCWO) of dyehouse waste‐water containing several organic pollutants has been studied. The removal of these organic components with unknown proportions is considered in terms of total organic carbon concentration (TOC), with an initial value of 856.9 mg L^?1. Oxidation reactions were performed using diluted hydrogen peroxide. The reaction conditions ranged between temperatures of 400–600 °C and residence times of 8–16 s under 25 MPa of pressure. RESULTS: TOC removal efficiencies using SCWO and hydrothermal decomposition were between 92.0 and 100% and 6.6 and 93.8%, respectively. An overall reaction rate, which consists of hydrothermal decomposition and the oxidation reaction, was determined for the hydrothermal decomposition of the waste‐water with an activation energy of 104.12 ( ± 2.6) kJ mol^?1 and a pre‐exponential factor of 1.59( ± 0.5) × 10⁵ s^?1. The oxidation reaction rate orders for the TOC and the oxidant were 1.169 ( ± 0.3) and 0.075 ( ± 0.04) with activation energies of 18.194 ( ± 1.09) kJ mol^?1, and pre‐exponential factor of 5.181 ( ± 1.3) L^0.244 mmol^?0.244 s^?1 at the 95% confidence level. CONCLUSION: Results demonstrate that the SCWO process decreased TOC content by up to 100% in residence times between 8 and 16 s under various reaction conditions. The treatment efficiency increased remarkably with increasing temperature and the presence of excess oxygen in the reaction medium. Color of the waste‐water was removed completely at temperatures of 450 °C and above. Copyright © 2010 Society of Chemical Industry     

Characteristics of Fine Particle Growth Events Observed Above a Forested Ecosystem in the Sierra Nevada Mountains of California

Atmospheric aerosols from natural and anthropogenic processes have both primary and secondary origins, and can influence human health, visibility, and climate. One key process affecting atmospheric concentrations of aerosols is the formation of new particles and their subsequent growth to larger particle sizes. A field study was conducted at the Blodgett Forest Research Station in the Sierra Nevada Mountains of California from May through September of 2002 to examine the effect of biogenic volatile organic compounds on aerosol formation and processing. The study included in-situ measurements of concentration and biosphere-atmosphere flux of VOCs, ozone, aerosol size distribution, aerosol physical and optical properties, and meteorological variables. Fine particle growth events were observed on approximately 30 percent of the 107 days with complete size distribution data. Average particle growth rates measured during these events were 3.8 ± 1.9 nm hr^?1. Correlations between aerosol properties, trace gas concentrations, and meteorological measurements were analyzed to determine conditions conducive to fine particle growth events. Growth events were typically observed on days with a lesser degree of anthropogenic influence, as indicated by lower concentrations of black carbon, carbon monoxide, and total aerosol volume. Days with growth events also had lower temperatures, increased wind speeds, and larger momentum flux. Measurements of ozone concentrations and ozone flux indicate that gas phase oxidation of biogenic volatile organic compounds occur in the canopy, strongly suggesting that a significant portion of the material responsible for the observed particle growth are oxidation products of naturally emitted very reactive organic compounds.     

Spatio-temporal variability in atmospheric abundances of EC,OC and WSOC over Northern India

The atmospheric abundances of elemental carbon (EC), organic carbon (OC) and water-soluble organic carbon (WSOC) have been measured in aerosol samples collected during wintertime (December–March) from selected sites (urban, rural and high-altitude) in northern India. A characteristic feature of their abundance pattern, at urban sites, is reflected in the OC/EC ratios (range: 2.4–14.5, Av=7.8±2.4, n=77) indicating dominant contribution from biomass burning sources (wood-fuel and agriculture waste). This is in sharp contrast to the OC/EC ratios at a rural site (range: 2.1–4.0, Av=3.1±0.6, n=7) influenced by emissions from coal-fired industries. The long-term measurements made from a high-altitude site (～2000 m amsl) reveal significantly lower abundances of EC and OC; suggesting that boundary layer dynamics (during wintertime) play an important role in efficient trapping of pollutants within the Indo-Gangetic Plain (northern India). The WSOC/OC ratios are fairly uniform (～0.35) in aerosols over urban sites but relatively enhanced contribution of WSOC and higher ratios (～0.5) at a high-altitude site emphasizes the significance of secondary organic aerosols. The comprehensive data set on EC, OC and WSOC/OC ratios from northern India is crucial to improve model parameterization of carbonaceous aerosols for atmospheric scattering and absorption of solar radiation on a regional scale.     

On the Importance of Organic Oxygen for Understanding Organic Aerosol Particles

This study shows how aerosol organic oxygen data could provide new information about organic aerosol mass, aqueous solubility of organic aerosols, formation of secondary organic aerosol (SOA) and the relative contributions of anthropogenic and biogenic sources. For more than two decades, atmospheric aerosol organic mass (OM) concentration has been estimated by multiplying the measured carbon content by an assumed (OM)-to-organic carbon (OC) factor, usually 1.4. However, this factor can vary from 1.0 to 2.5 depending on location. This large uncertainty about aerosol organic mass limits our understanding of the influence of organic aerosol on climate, visibility and health. New examination of organic aerosol speciation data shows that the oxygen content is responsible for the observed range in the OM-to-OC factor. When organic oxygen content is excluded, the ratio of non-oxygen organic mass to carbon mass varies very little across different environments (1.12 to 1.14). The non-oxygen-OM-to-OC factor for all studied sites (urban and non-urban) averaged 1.13. The uncertainty becomes an order of magnitude smaller than the uncertainty in the best current estimates of organic mass to organic carbon ratios (1.6 ± 0.2 for urban and 2.1 ± 0.2 for non-urban areas). This analysis suggests that, when aerosol organic oxygen data become available, organic aerosol mass can be quite accurately estimated using just OC and organic oxygen (OO) without the need to know whether the aerosol is fresh or aged. In addition, aerosol organic oxygen data will aid prediction of water solubility since compounds with OO-to-OC higher than 0.4 have water solubilities higher than 1 g per 100 g water.     

Nitrous oxide and methane emissions from cultivated seasonal wetland (dambo) soils with inorganic,organic and integrated nutrient management

In many smallholder farming areas southern Africa, the cultivation of seasonal wetlands (dambos) represent an important adaptation to climate change. Frequent droughts and poor performance of rain-fed crops in upland fields have resulted in mounting pressure to cultivate dambos where both organic and inorganic amendments are used to sustain crop yields. Dambo cultivation potentially increases greenhouse gas (GHG) emissions. The objective of the study was to quantify the effects of applying different rates of inorganic nitrogen (N) fertilisers (60, 120, 240 kg N ha^?1) as NH₄NO₃, organic manures (5,000, 10,000 and 15,000 kg ha^?1) and a combination of both sources (integrated management) on GHG emissions in cultivated dambos planted to rape (Brassica napus). Nitrous oxide (N₂O) emissions in plots with organic manures ranged from 218 to 894 µg m^?2 h^?1, while for inorganic N and integrated nutrient management, emissions ranged from 555 to 5,186 µg m^?2 h^?1 and 356–2,702 µg m^?2 h^?1 respectively. Cropped and fertilised dambos were weak sources of methane (CH₄), with emissions ranging from ?0.02 to 0.9 mg m^?2 h^?1, while manures and integrated management increased carbon dioxide (CO₂) emissions. However, crop yields were better under integrated nutrient management. The use of inorganic fertilisers resulted in higher N₂O emission per kg yield obtained (6–14 g N₂O kg^?1 yield), compared to 0.7–4.5 g N₂O kg^?1 yield and 1.6–4.6 g N₂O kg^?1 yield for organic manures and integrated nutrient management respectively. This suggests that the use of organic and integrated nutrient management has the potential to increase yield and reduce yield scaled N₂O emissions.     

Estimation of the Monthly Average Ratios of Organic Mass to Organic Carbon for Fine Particulate Matter at an Urban Site

Two independent methods are used to estimate the seasonality of the ratio of fine particulate organic matter (OM) to fine particulate organic carbon (OC) for atmospheric particulate matter collected at the St. Louis—Midwest Supersite. The first method assumes that all of the fine particulate matter mass that cannot be attributed to sulfate ion, nitrate ion, ammonium ion, elemental carbon and metal oxides is organic matter. Using this method, 98 daily samples were used to estimate the annual average fine particulate matter OM/OC ratio to be 1.81 ± 0.07 with a summer average of 1.95 ± 0.17 and a winter average of 1.77 ± 0.13. The second approach to estimating fine particle OM/OC employed OC source apportionment results and estimates of source specific OM/OC, including primary sources and secondary organic aerosol. The OM/OC estimate that was based on 98 daily source apportionment calculations over a two year period yielded an annual average ratio of 1.96 ± 0.03. Methods used in the study yielded a relatively stable annual average estimate of the OM/OC ratio for fine particulate matter in the St. Louis area. The source apportionment results indicate that the similar OM/OC ratio for St. Louis in the summer and winter results from an increased relative contribution of secondary organic aerosol in the summer months that is balanced by the higher woodsmoke in the winter. Although the estimated OM/OC ratios that were determined for St. Louis cannot be directly applied to other locations, the methodologies used to estimate OM/OC can be broadly applied given the necessary data for these calculations.     

Characterization of Male and Female Jojoba Plants Employing Antioxidants,Lipid Peroxidation and Physiological Studies

Jojoba, [Simmondsia chinensis (Link) Schneider] is a commercially important dioecious, desert shrub which is mainly cultivated for liquid wax (oil) present in its seeds (40–60 %). The oil is being utilized by the cosmetic, pharmaceuticals, and other industries for certain formulations. In this study, gender based differences in biochemical and physiological parameters were examined in relation to natural drought conditions. The amount of protein, proline, cysteine, chlorophyll a and b, carotenoids and enzymatic activities were evaluated in leaves of male and female Jojoba genotypes. Significant differences between genders were found which was attributed to higher drought tolerance of males than females. Males showed higher contents of protein (113.05 ± 0.88 mg g^?1 FW), proline (95.13 ± 2.33 µmol g^?1 FW), cysteine (42.47 ± 2.69 µmol g^?1 FW) than females (proteins: 70.77 ± 0.52 mg g^?1 FW, proline: 66.61 ± 1.75 µmol g^?1 FW, cysteine: 17.84 ± 3.00 µmol g^?1 FW). Malondialdehyde (MDA) content was lower in male genotypes (18.29 ± 0.53 µmol g^?1 FW) than female genotypes (23.02 ± 0.70 µmol g^?1 FW). Higher activities of catalase (CAT) [0.088 ± 0.005 nkat mg^?1 protein], guaiacol peroxidase (GPX) [0.006 ± 0.001 nkat mg^?1 protein], glutathione reductase (GR) [9.02 ± 0.04 nkat mg^?1 protein], ascorbate peroxidase (APX) [4.28 ± 0.08 nkat mg^?1 protein] and superoxide dismutase (SOD) [151.75 ± 3.58 nkat mg^?1 protein] were found in males compared to females [CAT: 0.007 ± 00 nkat mg^?1 protein, GPX: 0.003 ± 00 nkat mg^?1 protein, GR: 6.40 ± 0.06 nkat mg^?1 protein, APX: 3.08 ± 0.06 nkat mg^?1 protein, SOD: 52.51 ± 1.73 nkat mg^?1 protein]. Chlorophyll b content was also higher in males than females.     

Chemically Resolved Particle Fluxes Over Tropical and Temperate Forests

Chemically resolved submicron (PM₁) particle mass fluxes were measured by eddy covariance with a high resolution time-of-flight aerosol mass spectrometer over temperate and tropical forests during the BEARPEX-07 and AMAZE-08 campaigns. Fluxes during AMAZE-08 were small and close to the detection limit (<1 ng m^?2 s^?1) due to low particle mass concentrations (<1 μg m^?3). During BEARPEX-07, concentrations were five times larger, with mean mid-day deposition fluxes of ?4.8 ng m^?2 s^?1 for total nonrefractory PM₁ (V_ex,PM1 = ?1 mm s^?1) and emission fluxes of +2.6 ng m^?2 s^?1 for organic PM₁ (V_ex,org = +1 mm s^?1). Biosphere–atmosphere fluxes of different chemical components are affected by in-canopy chemistry, vertical gradients in gas-particle partitioning due to canopy temperature gradients, emission of primary biological aerosol particles, and wet and dry deposition. As a result of these competing processes, individual chemical components had fluxes of varying magnitude and direction during both campaigns. Oxygenated organic components representing regionally aged aerosol deposited, while components of fresh secondary organic aerosol (SOA) emitted. During BEARPEX-07, rapid in-canopy oxidation caused rapid SOA growth on the timescale of biosphere-atmosphere exchange. In-canopy SOA mass yields were 0.5–4%. During AMAZE-08, the net organic aerosol flux was influenced by deposition, in-canopy SOA formation, and thermal shifts in gas-particle partitioning. Wet deposition was estimated to be an order of magnitude larger than dry deposition during AMAZE-08. Small shifts in organic aerosol concentrations from anthropogenic sources such as urban pollution or biomass burning alters the balance between flux terms. The semivolatile nature of the Amazonian organic aerosol suggests a feedback in which warmer temperatures will partition SOA to the gas-phase, reducing their light scattering and thus potential to cool the region.

Copyright 2013 American Association for Aerosol Research     

Removal of C.I. Basic Blue 41 from aqueous solution by supercritical water oxidation in continuous-flow reactor

Oxidation of aqueous solution of C.I. Basic Blue 41 (BB41), which is model azo dye pollutants, was studied in a continuous-flow reactor that was operated between 400 and 650 °C at a fixed pressure of 25 MPa. The total organic carbon (TOC) concentration of BB41 was in the range of 30.60 and 152.97 mmol/L in the feed stock solution. Hydrogen peroxide (H₂O₂) was used as an oxygen source and the oxidant concentrations were between 73.53 and 489.64 mmol/L in the feed stock solution. The results demonstrated that supercritical water oxidation (SCWO) process decreases the TOC up to 99.87% in very short reaction times (at residence times of 9–19 s). According to the wastewater and oxidant concentrations, the global rate expression was regressed from the complete set of data for each dye solution. As a result of regression analysis, the reaction rate expression for the oxidation of BB41 was determined with the activation energy of 18.88 (±0.9) kJ/mol and the pre-exponential factor of 2.8 (±0.5) mmol^?0.16 L^0.16 s^?1; and the reaction orders for BB41 (based on TOC) and the oxidant were 0.84 (±0.03) and 0.32 (±0.05) in a 95% confidence level.     

Gas-Wall Partitioning of Oxygenated Organic Compounds: Measurements,Structure–Activity Relationships,and Correlation with Gas Chromatographic Retention Factor

Gas-wall partitioning of 50 oxygenated organic compounds was investigated by using gas chromatography to monitor time-dependent gas-phase concentrations of authentic standards added to a large Teflon environmental chamber. Compounds included C₈–C₁₄ monofunctional ketones and alcohols, C₅–C₉ monoacids, and C₄–C₁₀ diols with linear and cyclic structures. Measured time constants for reaching gas-wall partitioning equilibrium ranged from ～10 to 100 min with an average value of ～30 min and exhibited no obvious trend with compound structure, whereas the extent of equilibrium partitioning to the walls ranged from ～0 to 100% and increased with increasing carbon number and with functional group composition in the order ketones < alcohols < monoacids < diols. When results were modeled using an approach analogous to one commonly used to describe absorptive gas-particle partitioning in terms of compound vapor pressure and aerosol mass loading it was determined that the absorptive properties of the Teflon film walls were equivalent to 2–36 mg m^?3 of liquid organic aerosol particles. These results, when combined with those obtained in previous studies, indicate that most multifunctional products formed from the oxidation of atmospherically important hydrocarbons including isoprene, monoterpenes, aromatics, and alkanes have the potential to undergo significant partitioning to the walls of Teflon chambers and thus be lost from further chemical reaction and secondary organic aerosol formation as well as from gas and particle analyses. Two approaches for estimating equilibrium gas-wall partitioning in such studies are presented: one is a structure–activity relationship based on the absorptive gas-wall partitioning model and the other involves the use of observed correlations between gas-wall partitioning and compound retention on a gas chromatographic column.

Copyright 2015 American Association for Aerosol Research     

Modelling NH<Subscript>3</Subscript> volatilisation within a urine patch using NZ-DNDC

Urea concentrations in urine patches deposited during animal grazing can be over ten times higher than typical fertiliser application rates, potentially leading to large ammonia (NH₃) losses. The process-based NZ-DNDC model was modified to better simulate soil pH changes and ammonia (NH₃) emissions following urine application using data collected from a New Zealand field trial. After modification, simulated 30-day NH₃ emissions decreased from 506 to 117 kg N ha^?1 compared to measured emissions of 78 ± 3 kg N ha^?1 (mean ± standard error) and the Nash–Sutcliffe Efficiency (NSE) for daily NH₃ emissions increased from ?7.11 to +0.97 for the parameterisation dataset. However, modified model correctly estimated the cumulative emissions for the first 7 days. Using the same parameterisation on an independent dataset from a nearby site gave cumulative 18-day NH₃ emissions of 84 kg N  ha^?1 compared to the measured 48 ± 2 kg N ha^?1 (mean ± standard error). However, the NSE for daily NH₃ emissions was ?0.71, indicating site specific parameterisation might be needed. The sensitivity of NH₃ emissions to ±5 and ±10% errors in 4 model parameters was tested. The sensitivities ranged from ?0.36 to +0.71. The highest sensitivity was to the rate of NH₃ transfer from the soil solution to the atmosphere and the lowest sensitivity was to the rate of urea hydrolysis.     

Investigating a Liquid-Based Method for Online Organic Carbon Detection in Atmospheric Particles

A Particle-Into-Liquid Sampler (PILS) was modified and coupled with a Total Organic Carbon (TOC) Analyzer (Sievers 800T, GE Water Systems, Boulder, CO), in an attempt to measure particulate organic carbon (OC) online. The PILS droplet collection system was changed from an inertial impactor to a miniature cyclone to increase the efficiency of transferring insoluble carbonaceous aerosol to the liquid sample stream. The performance of the modified PILS was investigated with a variety of calibration aerosols through comparison with the Sunset Labs ECOC technique (NIOSH method 5040). Linear regression slopes of water-soluble organic compounds compared well with Sunset Labs measurement, agreeing to within 5%. However, a size dependence was observed when comparing insoluble carbonaceous aerosol (polystyrene latex spheres, PSL). The new method did not effectively measure insoluble particles with aerodynamic diameters greater than ～ 110 nm due to inefficient analysis by the TOC. The OC measurement method was also compared with online Sunset Labs organic carbon (OC) measurements in two urban locations: Atlanta, GA, and Riverside, CA. Linear regression slopes between the PILS technique and Sunset Labs were near unity (101% to 93% ± 2 and 5%, respectively), and not statistically different from unity considering the measurement uncertainty of each method. However there was a significant (0.6 to 1.7 μ gC m ^{? 3} ) non-zero intercept, with the Sunset Labs instrument measuring higher concentrations, possible due to the inability of the PILS to measure large, insoluble particles or positive artifacts with the non-blank corrected Sunset Labs filter-based collection method.     

Near real-time measurement of carbonaceous aerosol using microplasma spectroscopy: Application to measurement of carbon nanomaterials

A sensitive, field-portable microplasma spectroscopy method has been developed for real-time measurement of carbon nanomaterials. The method involves microconcentration of aerosol on a microelectrode tip for subsequent analysis for atomic carbon using spark emission spectroscopy (SES). The spark-induced microplasma was characterized by measuring the excitation temperature (15,000–35,000 K), electron density (1.0 × 10¹⁷–2.2 × 10¹⁷ cm^?3), and spectral responses as functions of time and interelectrode distance. The system was calibrated and detection limits were determined for total atomic carbon (TAC) using a carbon emission line at 247.856 nm (C I) for various carbonaceous materials including sucrose, EDTA, caffeine, sodium carbonate, carbon black, and carbon nanotubes. The limit of detection for total atomic carbon was 1.61 ng, equivalent to 238 ng m^?3 when sampling at 1.5 L min^?1 for 5 min. To improve the selectivity for carbon nanomaterials, which mainly consist of elemental carbon (EC), the cathode was heated to 300°C to reduce the contribution of organic carbon to the total atomic carbon. Measurements of carbon nanotube aerosol at elevated electrode temperature showed improved selectivity to elemental carbon and compared well with the measurements from the thermal optical method (NIOSH Method 5040). The study shows the SES method to be an excellent candidate for development of low-cost, hand-portable, real-time instrument for measurement of carbonaceous aerosols and nanomaterials.     

Synthesis and Structure Determination of the Adducts of Dibenzo[a,l]pyrene Diol Epoxides and Deoxyadenosine or Deoxyguanosine

Abstract

(±)?Syn?dibenzo[a,l]pyrene diol epoxide (DB[a,l]PDE) and (±)?anti?DB[a,l]PDE were reacted with deoxyadenosine (dA) or deoxyguanosine (dG) in dimethylformamide at 100 °C for 30 min. The crude products were purified by reverse phase HPLC under gradient and isocratic conditions. The structure of each adduct was assigned by 1D and 2D NMR spectra and by fast atom bombardment mass spectrometry. Five adducts were isolated from the reaction of (±)?syn?DB[a,l]PDE and dA: syn?DB[a,l]PDE?N⁶dA?1, syn?DB[a,l]PDE?N⁶dA?2, syn?DB[a,l]PDE?N⁶dA?3, syn?DB[a,l]PDE?N⁶dA?4 and syn?DB[a,l]PDE?N7Ade. Four adducts were isolated from the reaction of (±)?anti?DB[a,l]PDE and dA: anti?DB[a,l]PDE?N⁶dA?1, anti?DB[a,l]PDE?N⁶dA?2, anti?DB[a,l]PDE?N⁶dA?3 and anti?DB[a,l]PDE?N⁶dA?4. Two adducts were isolated from the reaction of (±)?syn?DB[a,l]PDE and dG: (±)?11,12,13?trihydroxy?tetrahydroDB[a,l]P?14?N²dG and (±)?11,12,13?trihydroxy?tetrahydroDB[a,l]P?14?N7Gua. Two adducts were isolated from the reaction of (±)?anti?DB[a,l]PDE and dG: (±)?11,12,13?trihydroxy?tetrahydroDB[a,l]P?14?N²dG and (±)?11,12,13?trihydroxy?tetrahydroDB[a,l]P?14?N7Gua.     

A novel miniature inverted-flame burner for the generation of soot nanoparticles

Lab-scale soot nanoparticle generators are used by the aerosol research community to study the properties of soot over a broad range of particle size distributions, and number and mass concentrations. In this study, a novel miniature inverted-flame burner is presented and its emitted soot particles were characterized. The burner consisted of two co-annular tubes for fuel and co-flow air and the flame was enclosed by the latter. The fuel used was ethylene. A scanning mobility particle sizer (SMPS) and an aerodynamic aerosol classifier (AAC) were used to measure mobility and aerodynamic size distribution of soot particles, respectively. Particle morphology was studied using transmission electron microscopy (TEM). The elemental carbon (EC) and organic carbon (OC) content of the soot were measured using thermal-optical analysis (TOA). The burner produced soot particles with mobility diameter range of 66–270?nm, aerodynamic diameter range of 56–140?nm, and total concentration range of 2?×?10⁵–1?×?10⁷?cm^?3. TEM images showed that most soot particles were sub-micron soot aggregates. Some soot superaggregates, typically larger than 2?µm in length, were observed and their abundance increased with ethylene flow rate. TOA showed that the concentration of EC in the generated soot increased with ethylene flow rate, and the soot was observed to have high EC fraction at high ethylene flow rates. The miniature inverted-flame burner was demonstrated to produce soot nanoparticles over a range of concentrations and sizes with high EC content, making it a practical device to study soot nanoparticle properties in different applications.

Copyright © 2019 American Association for Aerosol Research     

Is Differential Use of Juniperus monosperma by Small Ruminants Driven by Terpenoid Concentration?

Differential plant use by herbivores has been observed for several woody plant species and has frequently been attributed to plant secondary metabolites. We examined the relationship between terpenoid concentration and Juniperus monosperma herbivory by small ruminants. Two groups of animals (10 goats or 5 goats plus 4 sheep) browsed 16 paddocks (20?×?30 m) containing one-seed juniper for six days during two seasons. Juniper leaves were sampled from 311 saplings immediately after browsing. Saplings were categorized by size (short [<0.5 m], medium [0.5–1.0 m], or tall [>1.0 m]), and by browsing intensity (light [<33 %], moderate [33–66 %], or heavy [>66 %]). Juniper bark was collected from 12 saplings during spring. Total estimated terpenoid concentrations in leaves and bark were 18.3?±?0.3 and 8.9?±?0.8 mg/g, respectively, and the dominant terpene in both tissues was α-pinene (11.1?±?0.2 and 7.6?±?0.7 mg/g, respectively). Total terpenoid concentration of juniper leaves was greater in spring than summer (20.6?±?0.5 vs. 16.7?±?0.3 mg/g, respectively) and was lower in short saplings than medium or tall saplings (16.5?±?0.6 vs. 19.8?±?0.4 and 19.5?±?0.4 mg/g, respectively). Total terpenoid concentration of leaves also differed among the three defoliation categories (21.2?±?0.6, 18.7?±?0.5, and 16.1?±?0.4 mg/g for light, moderate, and heavy, respectively). The smallest subset of terpenoids able to discriminate between light and heavy browsing intensity categories included eight compounds ([E]-β-farnesene, bornyl acetate, γ-eudesmol, endo-fenchyl acetate, γ-cadinene, α-pinene, cis-piperitol, and cis-p-menth-2-en-1-ol). Our results suggest terpenoid concentrations in one-seed juniper are related to season, sapling size, and browsing by small ruminants.