Measurements of Sulfur Oxides,Nitrogen Oxides,Haze and Fine Particles at a Rural Site on the Atlantic Coast

During August, 1982 and January and February, 1983, General Motors Research Laboratories operated air monitoring sites on the Atlantic Coast near Lewes, Delaware and 1250 km to the east on the southwest coast of Bermuda. The overall purpose of this project was to study the transformations of the principal acid precipitation precursors, NO _x and SO _x species, as they transport under conditions not complicated by emissions from local sources. In this paper, the measurements of gas and particulate species from Lewes are described and the composition and sources of sulfate aerosol, which is the most important haze-producing species, are investigated.

On the average, the total suspended particulate (TSP) concentration was 27.9 μg/m³ while the PM₁₀ (mass of particles with a diameter less than or equal to 10 μm) concentration was 22.0 μg/m³ or 79 percent of the TSP. The PM₁₀ consisted of 6.1 μg/m³ of coarse particles (CPM, diameter = 2.5 ? 10μm) and 15.9 μg/m³ of fine particles (FPM, diameter < 2.5 μm).

On a mass basis the most important constituents of the fine particulate fraction were sulfate compounds, 50 percent, and organic compounds, 30 percent. The mean light extinction coefficient corresponds to a visual range of 18-20 km. Most of the extinction can be attributed to the sulfate (60 percent) and organic carbon (13 percent). Particle size measurements show that the mass median aerodynamic diameter for both species is 0.43 μm. This is a typical size for a hydrated sulfate aerosol. For carbon, however, this is a larger size than previously reported and results in a more efficient light scattering aerosol. Principal component analyses indicate that coal combustion emissions from the midwestern U.S. are the most significant source of sulfate in Lewes during the summer and winter.     

An intercomparison of formaldehyde measurement techniques at ambient concentration

A study was conducted to evaluate five techniques for determining ambient formaldehyde concentrations. One technique used a spectroscopic determination, and the other four techniques used derivatization followed by fluorometric analysis or high-performance liquid chromatography with detection by u.v. absorption. Formaldehyde was generated by two techniques. In the first technique, zero air was bubbled through a solution of aqueous formaldehyde to produce gas-phase formaldehyde. Various compounds serving as possible interferences were added singly or in combination to these air mixtures. In the second technique, formaldehyde was generated as a product from controlled irradiations of hydrocarbons and nitrogen oxides in a smog chamber operated in a dynamic mode. The study was conducted as a blind intercomparison with no knowledge by the participants of the HCHO concentrations or the interferences added.The data from each of the techniques were compared against mean values in each sampling period. For formaldehyde in zero air, average deviations for each of the techniques ranged between 15 and 30%. At a formaldehyde concentration of 10 ppb, each technique showed no evidence for interferences by O₃ (190 ppbv), NO₂ (300 ppbv), SO₂ (20 ppbv), and H₂O₂ (7 ppbv). The agreement for formaldehyde concentrations measured for the photochemical mixtures was similar to that of the mixtures in zero air.Ambient measurements were also performed on three evenings and for one 36-h period. Ambient formaldehyde concentrations ranged from 1 to 10 ppbv. Ambient H₂O₂ measurements were also performed. A strong correlation in the diurnal concentration profile for formaldehyde and H₂O₂ was observed over the 36-h period.     

Vermiremediation of dyeing sludge from textile mill with the help of exotic earthworm Eisenia fetida Savigny

The aim of present study was for the vermiremediation of dyeing sludge from textile mill into nutrient-rich vermicompost using earthworm Eisenia fetida. The dyeing sludge was mixed with cattle dung in different ratios, i.e., 0:100 (D₀), 25:75 (D₂₅), 50:50 (D₅₀), 75:25 (D₇₅), and 100:0 (D₁₀₀) with earthworms, and 0:100 (S₀), 25:75 (S₂₅), 50:50 (S₅₀), 75:25 (S₇₅), and 100:0 (S₁₀₀) without earthworms. Minimum mortality and maximum population build-up were observed in a 25:75 mixture. Nitrogen, phosphorus, sodium, and pH increased from the initial to the final products with earthworms, while electrical conductivity, C/N ratio, organic carbon, and potassium declined in all the feed mixtures. Vermicomposting with E. fetida was better for composting to change this sludge into nutrient-rich manure.     

Characterization of organic aerosol in Big Bend National Park,Texas

The Big Bend Regional Aerosol and Visibility Observational (BRAVO) Study was conducted in Big Bend National Park, Texas, July through October 1999. Daily PM_2.5 organic aerosol samples were collected on pre-fired quartz fiber filters. Daily concentrations were too low for detailed organic analysis by gas chromatography-mass spectrometry (GC-MS) and were grouped based on their air mass trajectories. A total of 12 composites, each containing 3–10 daily samples, were analyzed. Alkane carbon preference indices suggest primary biogenic emissions were small contributors to primary PM_2.5 organic matter (OM) during the first 3 months, while in October air masses advecting from the north and south were more strongly influenced by biogenic sources. A series of trace organic compounds previously shown to serve as particle phase tracers for various carbonaceous aerosol source types were examined. Molecular tracer species were generally at or below detection limits, except for the wood smoke tracer levoglucosan in one composite, so maximum possible source influences were calculated using the detection limit as an upper bound to the tracer concentration. Wood smoke was found not to contribute significantly to PM_2.5 OM, with contributions for most samples at <1% of the total organic particulate matter. Vehicular exhaust also appeared to make only minor contributions, with maximum possible influences calculated to be 1–4% of PM_2.5 OM. Several factors indicate that secondary organic aerosol formation was important throughout the study, and may have significantly altered the molecular composition of the aerosol during transport.     

Cloud condensation nucleus activity of organic compounds: a laboratory study

Critical or activation diameters of laboratory generated organic aerosols composed of succinic acid, adipic acid and glucose were determined. Measurements of sodium chloride and ammonium sulfate aerosols were performed for comparison. Our experimental approach involved producing single component aerosol particles of a known size, and measuring the fraction of aerosol number concentrations (CN) that act as CCN at several supersaturations. The particle diameter (D₅₀) at which the CCN/CN ratio of 0.50 is reached is defined as the critical, or activation, diameter. These experimentally derived diameters are compared with the theoretical critical diameter (D_C). The results indicate that highly water-soluble organic compounds exhibit critical diameters that approach that of ammonium sulfate.     

Surface chemistry of a pine-oil cleaner and other terpene mixtures with ozone on vinyl flooring tiles

Indoor environments are dynamic reactors where consumer products (such as cleaning agents, deodorants, and air fresheners) emit volatile organic compounds (VOCs) that can subsequently interact with indoor oxidants such as ozone (O₃), hydroxyl radicals, and nitrate radicals. Typically, consumer products consist of mixtures of VOCs and semi-VOCs which can react in the gas-phase or on surfaces with these oxidants to generate a variety of oxygenated products. In this study, the reaction of a pine-oil cleaner (POC) with O₃ (100 ppb) on a urethane-coated vinyl flooring tile was investigated at 5% and 50% relative humidity. These results were compared to previous α-terpineol + O₃ reactions on glass and vinyl surfaces. Additionally, other terpene and terpene alcohol mixtures were formulated to understand the emission profiles as seen in the POC data. Results showed that the α-terpineol + O₃ reaction products were the prominent species that were also observed in the POC/O₃ surface experiments. Furthermore, α-terpineol + O₃ reactions generate the largest fraction of oxygenated products even in equal mixtures of other terpene alcohols. This finding suggests that the judicial choice of terpene alcohols for inclusion in product formulations may be useful in reducing oxidation product emissions.     

Study on a new correlation between diffusion coefficient and temperature in porous building materials

The diffusion coefficient (D) and partition coefficient (K_ma) are the two important parameters used to predict the volatile organic compound (VOC) emission or sorption characteristics in porous building materials. D and K_ma may be strongly affected by temperature (T). In this study, we derived a new correlation between D and T based on the assumption that molecular diffusion is dominant, and evaluated this correlation using a series of existing experimental data. The modeling results using the new correlation agree well with the experimental data. The correlation would be useful for assessment of indoor air quality under different environmental (temperature) conditions.     

Product Guide/1975

Measurements conducted on full-scale hazardous waste incinerators have occasionally shown a relationship between carbon monoxide (CO) emissions and emissions of toxic organic compounds. In this study, four mixtures of chlorinated C₁ and C₂ hydrocarbons were diluted in commercial-grade heptane and burned in a water-cooled turbulent flame reactor (TFR) under two different excess air levels. No correlation between CO and organic emissions could be discerned. Reasons for this lack of observable correlations are discussed in terms of combustion and chemical reaction kinetic theory.     

Impact of clay mineral on air oxidation of PAH-contaminated soils

This work investigated the impact of a clay mineral (bentonite) on the air oxidation of the solvent extractable organic matters (EOMs) and the PAHs from contaminated soils. EOMs were isolated from two coking plant soils and mixed with silica sand or bentonite. These samples, as well as raw soils and bentonite/soil mixtures, were oxidized in air at 60 and 100 °C for 160 days. Mineralization was followed by measuring the CO₂ produced over the experiments. EOM, polycyclic aromatic compound (PAC), including PAH, contents were also determined. Oxidation led to a decrease in EOM contents and PAH concentrations, these diminutions were enhanced by the presence of bentonite. Transfer of carbon from EOM to insoluble organic matter pointed out a condensation phenomenon leading to a stabilization of the contamination. Higher mineralization rates, observed during the oxidation of the soil/bentonite mixtures, seem to indicate that this clay mineral had a positive influence on the transformation of PAC into CO₂.     

Influence of cosolvents on quinoline sorption by subsurface materials and clays

Quinoline sorption was measured on Na-saturated subsurface materials, a natural clay isolate, and montmorillonite, and was dominated by exchange of the quinolinium ion. In water/methanol and water/acetone mixtures, quinoline sorption on the subsoils and clays was lower than from water. In cosolvent, sorption followed the ionization fraction indicating the continued predominance of ion exchange. The reduction in quinoline sorption by cosolvent was similar for all the subsoils and clays indicating commonality in the surface-solute-solvent interaction. Conditional equilibrium constants (_cK_ex) for quinoline exchange on the subsoils in water/methanol mixtures decreased log-linearly with mole percent cosolvent up to 20% methanol. This decrease closely followed the increase in quinoline solubility in the cosolvent mixtures. Acetone caused greater reduction in sorption than methanol, at comparable mole percent, in accordance with its lower dielectric constant and enhanced solvating power. A generalized thermodynamic approach based on the concept of transfer activity coefficients was developed to account for the cosolvent effect on _cK_ex, and was successfully applied to the quinoline sorption data. The thermodynamic analysis suggested that enhanced solvation of the organic cation in the bulk solvent and desolvation of Na⁺ at the charged surface predominate the cosolvent effect.     

Feasibility of Soil Dust Source Apportionment by the Pyrolysis-Gas Chromatography/Mass Spectrometry Method

Abstract

This study tested the feasibility of using pyrolysis (Py)-gas chromatography (GC)/mass spectrometry (MS) to obtain organic chemical species data suitable for source apportionment modeling of soil-derived coarse particulate matter (PM₁₀) dust on ambient filters. A laboratory resuspension apparatus was used with known soils to generate simulated receptor filter samples loaded with ～0.4 mg of PM₁₀ dust, which is within the range of mass loading on ambient filters. Py-GC/MS at 740 °C generated five times more resolvable compounds than were obtained with thermal desorption GC/MS at 315 °C. The identified compounds were consistent with literature from Py experiments using larger samples of bulk soils. A subset of 91 organic species out of the 178 identified Py products was used as input to CMB8 software in a demonstration of source apportionment using laboratory-generated mixtures simulating ambient filter samples. The 178 quantified organic species obtained by Py of soil samples is an improvement compared with the 38 organic species obtained by thermal desorption of soils and the four functionally defined organic fractions reported by thermal/optical reflectance. Significant differences in the concentration of specific species were seen between samples from different sites, both geographically distant and close, using analysis of variance and cluster analysis. This feasibility study showed that Py-GC/MS can generate useful source profile data for receptor modeling and justifies continued method development.     

Solvophobic approach for predicting sorption of hydrophobic organic chemicals on synthetic sorbents and soils

The application of a solvophobic approach for predicting the sorption of hydrophobic organic compounds (HOC) was evaluated with data collected using synthetic sorbents and soils. The experimental data consisted of batch equilibrium sorption coefficients (K_D), as well as soil-TLC and reversed-phase liquid chromatographic (RPLC) retention factors (κ′). All data were collected using aqueous solutions and binary or ternary solvent mixtures of water, methanol, acetone, and acetonitrile. As predicted by the theory, the chromatographic retention factors and sorption coefficients for HOC decreased log-linearly with increasing fraction of organic cosolvent in binary solvents. Model parameters estimated from the binary solvent data could be used to predict sorption (or retention) from ternary solvents. Reasonable agreement was found between model parameters reported in the literature and those estimated using the data from batch sorption, soil-TLC, and RPLC studies.     

Characterization of Indoor Particle Sources Using Continuous Mass and Size Monitors

ABSTRACT

A comprehensive indoor particle characterization study was conducted in nine Boston-area homes in 1998 in order to characterize sources of PM in indoor environments. State-of-the-art sampling methodologies were used to obtain continuous PM_2.5 concentration and size distribution particulate data for both indoor and outdoor air. Study homes, five of which were sampled during two seasons, were monitored over week-long periods. Among other data collected during the extensive monitoring efforts were 24hr elemental/organic carbon (EC/OC) particulate data as well as semi-continuous air exchange rates and time-activity information.

This rich data set shows that indoor particle events tend to be brief, intermittent, and highly variable, thus requiring the use of continuous instrumentation for their characterization. In addition to dramatically increasing indoor PM₂₅ concentrations, these data demonstrate that indoor particle events can significantly alter the size distribution and composition of indoor particles. Source event data demonstrate that the impacts of indoor activities are especially pronounced in the ultrafine (d_a < 0.1 um) and coarse (2.5 < d_a < 10 |um) modes. Among the sources of ultrafine particles characterized in this study are indoor ozone/terpene reactions. Furthermore, EC/OC data suggest that organic carbon is a major constituent of particles emitted during indoor source events. Whether exposures to indoor-generated particles, particularly from large short-term peak events, may be associated with adverse health effects will become clearer when biological mechanisms are better known.     

Effects of Chronic Doses of Ozone on Field-Grown Loblolly Pine: Seedling Responses in the First Year

A study was designed to examine responses of loblolly pine (Pinus taeda) to chronic exposure to ozone (O₃) in the field. Seedlings of four full-sib families of loblolly pine were planted in a field near Raleigh, NC, and exposed daily (May 27 to October 24, 1985) in open-top chambers to O₃ ranging from 0.5 to 1.96 times the O₃ concentration in non-filtered (NF) air. One-fourth of the plants in each plot were removed during each of two harvests (August and October) to measure effects of O₃ on plant growth. Plants of each family exhibited foliar symptoms characteristic of O3 injury after five months of exposure to any greater-than-ambient O₃ concentration, and one family exhibited symptoms after five months of exposure to NF air. Ozone dose-plant response relationships were quantified by regression for stem height, stem diameter, biomass, and other plant morphological and yield characteristics. All relationships were linear for three families, but one family exhibited no significant growth response relationship of O₃ dose. Dose-response equations suggest a maximum growth suppression of 10 percent for NF air compared to charcoal-filtered air (i.e., 0.5 × NF) in the first season of exposure.     

Fine particle measurements at two background sites in Korea between 1996 and 1997

Five intensive field measurements were carried out at two background sites in Korea; Kosan and Kangwha during spring, fall, and winters of 1996 and 1997 to investigate the characteristics of long-range transport of air pollutants in northeastern Asia. Fine particles (PM_2.5) were collected by low-volume samplers and the concentrations of major ions, organic and elemental carbons, and nitric acid were quantified. The concentrations of anthropogenic species in PM_2.5 measured at both sites were generally higher than those at other background areas, Nagano, Japan and San Nicolas Is., USA due to continental outflow of air pollutants, but lower than those at an urban background site, Qingdao, China. The major components of PM_2.5 were sulfate, organic carbon (OC), and ammonium for Kosan and sulfate, OC, ammonium, and nitrate for Kangwha. The major fractions of sulfate at both sites are non-sea-salts (nss) sulfate. Based on the relationship among major anthropogenic species, analysis of the nss sulfate to total nitrate molar ratios, and backward air parcel trajectories, it was found that fine particles measured at both sites during the measurement periods are mainly coming from China. At Kosan, the concentrations of anthropogenic species were higher when air parcels were coming from southern China than when air parcels were from northern China. At Kangwha, however, the differences of the concentrations were not statistically significant since most air parcels were from northern China and local effects are prominent.     

Molecular diffusivities of Hg vapor in air,O2 and N2 near STP and the kinematic viscosity and thermal diffusivity of air near STP

Accurate knowledge of the coefficients of molecular diffusivity (D) of trace gases, the kinematic viscosity of air (ν) and the thermal diffusivity of air (k) has important application to modeling and observational studies of atmosphere–biosphere interactions. For example, leaf boundary-layer resistances are often parameterized in term of the Schmidt number for mass exchange and the Prandtl number for heat exchange. This study reviews and re-analyzes the historical data and some modeling results for D for Hg vapor in air, N₂ and O₂ and recasts results of an independent review of dynamic viscosity and thermal conductivity of air in a form that are consistent with one another and with this author’s previous study of D for simple gases and air, N₂ and O₂ near STP. Because D, ν and k are functions of temperature and pressure, all modeling results and data are corrected to 1 atmosphere pressure and then used with a one- and two-parameter regression model to determine optimal values for the temperature exponent and the value of D, ν and k at 0°C. Statistical/regression methods for treating data and modeling results follow this author’s previous study of D, except that data for D for Hg vapor is not restricted to values below 100°C.     

Organic carbon,total nitrogen,and water-soluble ions in clouds from a tropical montane cloud forest in Puerto Rico

Chemical characterization to determine the organic and nitrogen fractions was performed on cloud water samples collected in a mountaintop site in Puerto Rico. Cloud water samples showed average concentrations of 1.09 mg L^?1 of total organic carbon (TOC), of 0.85 mg L^?1 for dissolved organic carbon (DOC) and of and 1.25 mg L^?1 for total nitrogen (TN). Concentrations of organic nitrogen (ON) changed with the origin of the air mass. Changes in their concentrations were observed during periods under the influence of African dust (AD). The ON/TN ratios were 0.26 for the clean and 0.35 for the AD periods. Average concentrations of all these species were similar to those found in remote environments with no anthropogenic contribution. In the AD period, for cloud water the concentrations of TOC were 4 times higher and TN were 3 times higher than during periods of clean air masses associated with the trade winds. These results suggest that a significant fraction of TOC and TN in cloud and rainwater is associated to airborne particulate matter present in dust. Functional groups were identified using proton nuclear magnetic resonance (¹H NMR) spectroscopy. This characterization led to the conclusion that water-soluble organic compounds in these samples are mainly aliphatic oxygenated compounds, with a small amount of aromatics. The ion chromatography results showed that the ionic species were predominantly of marine origin, for air masses with and without African dust influence, with cloud water concentrations of NO₃^? and NH₄⁺ much lower than from polluted areas in the US. An increase of such species as SO₄^2?, Cl^?, Mg²⁺, K⁺ and Ca²⁺ was seen when air masses originated from northwest Africa. The changes in the chemical composition and physical properties of clouds associated with these different types of aerosol particles could affect on cloud formation and processes.     

A new detailed chemical model for indoor air pollution

A detailed chemical box model has been constructed based on a comprehensive chemical mechanism (the Master Chemical Mechanism) to investigate indoor air chemistry in a typical urban residence in the UK. Unlike previous modelling studies of indoor air chemistry, the mechanism adopted contains no simplifications such as lumping or the use of surrogate species, allowing more insight into indoor air chemistry than previously possible. The chemical mechanism, which has been modified to include the degradation reactions of key indoor air pollutants, contains around 15,400 reactions and 4700 species. The results show a predicted indoor OH radical concentration up to 4.0×10⁵ molecule cm⁻³, only a factor of 10–20 less than typically observed outdoors and sufficient for significant chemical cycling to take place. Concentrations of PAN-type species and organic nitrates are found to be important indoors, reaching concentrations of a few ppb. Sensitivity tests highlight that the most crucial parameters for modelling the concentration of OH are the light-intensity levels and the air exchange rate. Outdoor concentrations of O₃ and NO_X are also important in determining radical concentrations indoors. The reactions of ozone with alkenes and monoterpenes play a major role in producing new radicals, unlike outdoors where photolysis reactions are pivotal radical initiators. In terms of radical propagation, the reaction of HO₂ with NO has the most profound influence on OH concentrations indoors. Cycling between OH and RO₂ is dominated by reaction with the monoterpene species, whilst alcohols play a major role in converting OH to HO₂. Surprisingly, the absolute reaction rates are similar to those observed outdoors in a suburban environment in the UK during the summer. The results from this study highlight the importance of tailoring a model for its particular location and the need for future indoor air measurements of radical species, nitrated species such as PANs and organic nitrates, photolysis rates of key species over the range of wavelengths observed indoors and concurrent measurements of outdoor air pollutant concentrations.     

Participant-based monitoring of indoor and outdoor nitrogen dioxide,volatile organic compounds,and polycyclic aromatic hydrocarbons among MICA-Air households

The Mechanistic Indicators of Childhood Asthma (MICA) study in Detroit, Michigan introduced a participant-based approach to reduce the resource burden associated with collection of indoor and outdoor residential air sampling data. A subset of participants designated as MICA-Air conducted indoor and outdoor residential sampling of nitrogen dioxide (NO₂), volatile organic compounds (VOCs), and polycyclic aromatic hydrocarbons (PAHs). This participant-based methodology was subsequently adapted for use in the Vanguard phase of the U.S. National Children’s Study. The current paper examines residential indoor and outdoor concentrations of these pollutant species among health study participants in Detroit, Michigan.Pollutants measured under MICA-Air agreed well with other studies and continuous monitoring data collected in Detroit. For example, NO₂ and BTEX concentrations reported for other Detroit area monitoring were generally within 10–15% of indoor and outdoor concentrations measured in MICA-Air households. Outdoor NO₂ concentrations were typically higher than indoor NO₂ concentration among MICA-Air homes, with a median indoor/outdoor (I/O) ratio of 0.6 in homes that were not impacted by environmental tobacco smoke (ETS) during air sampling. Indoor concentrations generally exceeded outdoor concentrations for VOC and PAH species measured among non-ETS homes in the study. I/O ratios for BTEX species (benzene, toluene, ethylbenzene, and m/p- and o-xylene) ranged from 1.2 for benzene to 3.1 for toluene. Outdoor NO₂ concentrations were approximately 4.5 ppb higher on weekdays versus weekends. As expected, I/O ratios pollutants were generally higher for homes impacted by ETS.These findings suggest that participant-based air sampling can provide a cost-effective alternative to technician-based approaches for assessing indoor and outdoor residential air pollution in community health studies. We also introduced a technique for estimating daily concentrations at each home by weighting 2- and 7-day integrated concentrations using continuous measurements from regulatory monitoring sites. This approach may be applied to estimate short-term daily or hourly pollutant concentrations in future health studies.     

Diffusive transport through compacted Na- and Ca-bentonite

The effect of exchangeable cation — Na⁺ and Ca ²⁺ — on the diffusive transport of I⁻, Sr ²⁺ and ³H (as HTO) in compacted bentonite was examined using a through-diffusion method. Total intrinsic diffusion coefficients, D_i, were determined from the steady-state flux of the diffusants through the clays, and apparent diffusion coefficients, D_a, were obtained from the time lag technique. The clays were compacted to a dry bulk density of 1.3 Mg/m³, and Na-bentonite was saturated with a solution of 100 mol NaCl/m3 and Ca-bentonite with one of 50 mol CaCl₂/m³. The D_i values for all diffusants are 2 to 6 times higher in the Ca- than Na-clay. We attribute this to the larger quasicrystal, or particle, size of Ca- compared to Na-bentonite. Hence, Ca-bentonite has a greater proportion of relatively large pores; this was confirmed by Hg intrusion porosimetry. This means the diffusion pathways in Ca-bentonite are less tortuous than those in Na-bentonite. Moreover, in some cases the effective porosity, or the porosity available for diffusive transport, may be greater in Ca-bentonite. The D_a values are inversely proportional to the distribution coefficients of the diffusants with the clays.