fluoride concentrations in the ambient air

The body of the information presented in this paper is of general interest to those concerned with air quality. This paper reports data for ambient atmospheric concentrations of water-soluble fluorides determined in samples of suspended particulate matter collected on glass-fiber filters by the National Air Surveillance Network. Data for over 12,000 samples collected in calendar years 1966, 1967, and 1968 are examined. The purpose of the examination of the data is to give an estimation of current air quality with respect to fluoride content.

The samples are extracted with pure boiling water, and the fluoride concentration of the extracts measured using a fluoride-ion selective electrode. The data engendered are tabulated on an annual basis, and a table is presented summarizing the results. Comparative data will be presented showing the distribution of urban and non-urban stations that exhibit various specified fluoride levels. The results show that the fluoride content in the majority of the samples is below the minimum detectable amount of 0.05 µgF/m³. Conclusions that can be drawn include the observations that: few of the urban samples contain over 1.00 µg/m ³ of fluoride, very few of all samples exceeded 1.00 µ/m³ of fluoride, and no non-urban sample contained over 0.16 µg/m³ of fluoride. It was also concluded that only in rare instances would the fluoride concentrations at the sites sampled be in excess of published standards.     

A two-step approach for relating tapered element oscillating microbalance and dichotomous air sampler PM2.5 measurements

A method for transforming continuous monitoring (CM) fine particulate matter (aerodynamic diameter <2.5 μm; PM_2.5) data (i.e., by tapered element oscillating microbalance [TEOM]) obtained from the Canadian National Air Pollution Surveillance (NAPS) program to meet the data quality objective (DQO) of R² > 0.8 against the co-located federal reference method (i.e., dichotomous air sampler) is described. By using a two-step linear regression to account for the effect of the ambient temperature, 16 out of the 23 examined sites met the common model adequacy threshold of R² > 0.8. After the transformation, 20 out of the 23 examined sites met the DQO of R² > 0.7, as recommended by the U.S. Environmental Protection Agency (EPA). A combined two-step statistical approach was also examined and revealed similar results. The methods described herein show that the CM data can be successfully transformed to meet DQOs for representative sites across Canada using year-round (both summer and winter) data.

Implications:This study provides a transformation approach to correct ambient TEOM data against the federal reference method without dividing the ambient data according to warm and cold seasons. This transformation approach will significantly improve the correlation coefficient between TEOM and dichotomous air sampler data. It is possible that TEOM data at many Canadian locations can be transformed to meet the EPA data quality objective, thus making this transformation approach useful for comparisons of ambient PM data across jurisdictions.     

A simple HPLC method for determination of permethrin residues in wine

An isocratic High Performance Liquid Chromatographic (HPLC) method was optimized for 3-phenoxybenzyl (1RS)-cis-trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate (permethrin) residues identification and quantification in wine matrix. Analytical reverse phase (RP) C-18 column was used (25 cm × 4 mm i.d., 5 μ m) with mobile phase consisting of acetonitrile and water in ratio 70 %/30 % (v v^?1), flow-rate 2.0 mL min^?1, UV-detection at 215 nm and controlled oven temperature at 25°C. The peaks of isomers were identified with the retention times as compared to standard cis-/trans- mixture and confirmed with characteristic spectra using photodiode array detector. Under these conditions, permethrin isomers were well separated with resolution 2.8 and no interference with the naturally present wine compounds was observed. The method was validated for linearity, precision, accuracy, limit of detection (LOD) and limit of quantification (LOQ). Linear regression analysis data proved a good linear relationship (correlation coefficients, r², for cis- and trans-isomer are: 0.9995 and 0.9997, respectively) between response of the detector and concentration of permethrin isomers over a wide concentration range for both isomers (0.55 mg L^?1 ?4.40 mg L^?1). Experimental data showed mean recoveries between 93.95% and 96.58% with RSD values in range: 0.89% ?3.69%. The effect of ethanol content in the solvent on permethrin isomers peak areas was also studied and 60% v v^?1 ethanol was found to be optimal for sample preparation. The method was successfully tested on 20 commercial wine samples from the market in which no permethrin was detected. Thus, it was proved that it is suitable for routine permethrin residues analysis. The proposed method is suitable for routine analysis because of the simple sample preparation, acceptable run-time, low cost and its applicability with conventional instruments.     

A new environmental chamber for evaluation of gas-phase chemical mechanisms and secondary aerosol formation

A new state-of-the-art indoor environmental chamber facility for the study of atmospheric processes leading to the formation of ozone and secondary organic aerosol (SOA) has been constructed and characterized. The chamber is designed for atmospheric chemical mechanism evaluation at low reactant concentrations under well-controlled environmental conditions. It consists of two collapsible 90 m³ FEP Teflon film reactors on pressure-controlled moveable frameworks inside a temperature-controlled enclosure flushed with purified air. Solar radiation is simulated with either a 200 kW Argon arc lamp or multiple blacklamps. Results of initial characterization experiments, all carried out at 300–305 K under dry conditions, concerning NO_x and formaldehyde offgasing, radical sources, particle loss rates, and background PM formation are described. Results of initial single organic–NO_x and simplified ambient surrogate–NO_x experiments to demonstrate the utility of the facility for mechanism evaluation under low NO_x conditions are summarized and compared with the predictions of the SAPRC-99 chemical mechanism. Overall, the results of the initial characterization and evaluation indicate that this new environmental chamber can provide high quality mechanism evaluation data for experiments with NO_x levels as low as 2 ppb, though the results indicate some problems with the gas-phase mechanism that need further study. Initial evaluation experiments for SOA formation, also carried out under dry conditions, indicate that the chamber can provide high quality secondary aerosol formation data at relatively low hydrocarbon concentrations.     

Kinetics of OH-initiated oxidation of oxygenated organic compounds in the aqueous phase: new rate constants, structure–activity relationships and atmospheric implications

The kinetics of OH oxidation of several organic compounds of atmospheric relevance were measured in the aqueous phase. Relative kinetics were performed using various organic references and OH sources. After validation of the protocol, temperature-dependent rate constants for the reactions of OH radical with ethyl ter-butyl ether (, E_a/R=580 (±560) K), n-butyl acetate ( (±0.4)×10⁹ M⁻¹ s⁻¹, E_a/R=1000 (±200) K), acetone ( (±0.05)×10⁹ M⁻¹ s⁻¹, E_a/R=1400 (±500) K), methyl ethyl ketone (, E_a/R=1200 (±200) K), methyl iso-butyl ketone (, E_a/R=1200 (±300) K) and methylglyoxal (, E_a/R=1100 (±300) K) were determined. A non-Arrhenius behavior was found for phenol, in good agreement with the contribution of an OH addition to the mechanism, which also includes H-abstraction by OH radicals. Global rate constants of acetaldehyde, propionaldehyde, butyraldehyde and valeraldehyde were studied at 298 K only, as these compounds partly hydrate in the aqueous phase. All the obtained data (except those of phenol) complemented by literature data were used to investigate three methods to estimate rate constants for H-abstraction reactions of OH radicals in aqueous solutions when measured data were not available: Evans-Polanyi-type correlations, comparisons with gas-phase data, structure activity relationships (SAR). The results show that the SAR method is promising; however, the data set is currently too small to extend this method to temperatures other than 298 K. The atmospheric impact of aqueous phase OH oxidation of water-soluble organic compounds is discussed with the determination of their global atmospheric lifetimes, taking into account both gas- and aqueous-phase reactivities. The results show that atmospheric droplets can act as powerful photoreactors to eliminate soluble organic compounds from the atmosphere.     

Industrial Pollution Prevention! A Critical Review

Abstract

Pyrolytic product distribution rates and pyrolysis behavior of tire-derived fuels (TDF) were investigated using thermogravimetric analyzer (TGA) techniques. A TGA was designed and built to investigate the behavior and products of pyrolysis of typical TDF specimens. The fundamental knowledge of TGA analysis and principal fuel analysis are applied in this study. Thermogravimetry of the degradation temperature of the TDF confirms the overall decomposition rate of the volatile products during the depolymerization reaction. The principal fuel analysis (proximate and ultimate analysis) of the pyrolytic char products show the correlation of volatilization into the gas and liquid phases and the existence of fixed carbon and other compounds that remain as a solid char. The kinetic parameters were calculated using least square with minimizing sum of error square technique. The results show that the average kinetic parameters of TDF are the activation energy, E = 1322 ± 244 kJ/mol, a pre-exponential constant of A = 2.06 ± 3.47 × 10¹⁰ min^?1, and a reaction order n = 1.62 ± 0.31. The model-predicted rate equations agree with the experimental data. The overall TDF weight conversion represents the carbon weight conversion in the sample.     

A study of the atmospheric reaction of CH3S with O3 as a function of temperature

The atmospheric reaction of the methylthiyl radical (CH₃S) with O₃ was investigated as a function of temperature (259–381 K), in the pressure range of 25–300 Torr, using the technique of laser photolysis/laser-induced fluorescence. The resulting Arrhenius expression, with an uncertainty of ±2σ, was k₁(T=259–381 K)=(1.02±0.30)×10⁻¹² exp[(432±77) K/T] cm³ molecule⁻¹ s⁻¹. The obtained rate constant k₁ was independent of pressure over the limited range employed. Our results are compared with the previous studies carried out, at single temperature and as a function of temperature, by different techniques.     

A Simple Technique for Stack Design in Complex Terrain

The main objective of this study is to apply neutral electrolyzed water (NEW) spraying to inactivate bioaerosols. We evaluated the inactivation efficiency of NEW applied to inactivate two airborne bacterial Escherichia coli and Bacillus subtilis aerosols inside an environmental-controlled chamber in the study. Generated with electrolyzing 6.15 M sodium chloride brine, the NEW with free available chlorine (FAC) concentration 50, 100, and 200 ppm was pumped with an air pressure of 70 kg/cm² through nozzle into the chamber to inactive E. coli and B. subtilis aerosols precontaminated air (initial counts of 3?×?10⁴ colony-forming units [CFU]/m³). Bacterial aerosols were collected and cultured from chamber before and after NEW spray. The air exchange rate (ACH, hr^?1) of the chamber was set to simulate fresh air ventilating dilution of indoor environment. First-order concentration decaying coefficients (Ka, min^?1) of both bacterial aerosols were measured as an index of NEW inactivation efficiency. The result shows that higher FAC concentration of NEW spray caused better inactivation efficiency. The Ka values under ACH 1.0 hr^?1 were 0.537 and 0.598 for E. coli of FAC 50 and 100 ppm spraying, respectively. The Ka values of FAC 100 ppm and 200 ppm spraying for B. subtilis were 0.063 and 0.085 under ACH 1.0 hr^?1, respectively. The results indicated that NEW spray is likely to be effective in inactivation of bacterial airborne contamination. Moreover, it is observed in the study that the increase of ventilation rate and the use of a larger orifice-size nozzle may facilitate the inactivation efficiency.

Implications: Bacterial aerosols have been implicated in deterioration of air quality and occupational health. Effective, safe, and economic control technology is highly demanded, especially for agricultural and food industries. In the study, NEW mist spraying performed effectively in controlling E. coli and B. subtilis modeling bioaerosols contamination. The NEW revealed its potential as an alternative airborne disinfectant worth being discovered for improving the environmental quality in the future.     

A Correlation of Field Observations of Plume Rise

Data from 137 sets of plume observations, comprising nearly 1 500 data points, are correlated with two simple formulae. These formulae, one for the buoyancy-dominated rise region and the other for the stratification-dominated levelled-off region of a plume, represent an approximate form of the entrainment theory of Hoult, et al. (1968)¹ for the case of uniform atmospheric stratification and zero wind shear. The observations, which are those of the Tennessee Valley Authority and of Bringfelt (1968),⁶ were made of plumes whose source strengths ranged from 0.4 to 111 Mw and which were emitted from stacks of heights between 21 and 183 m. The two formulae are found to correlate the data equally well over all values of the stack exit and meteorological parameters, provided only that the bulk mean velocity of the stack gases exceeds the mean wind speed by at least 20%. The ratio of observed to calculated plume rise is found to be distributed log normally about the mean value.

The median rise at large distances downstream was found to differ insignificantly from that given by the effective stack height formula recommended recently¹¹ for large buoyant plumes. Based upon the correlation, two formulae are recommended for computing median plume rise at all distances downstream of the stack. The formulae include an estimate of the expected uncertainty in the predicted rise.     

Malathion dermal permeability in relation to dermal load: Assessment by physiologically based pharmacokinetic modeling of in vivo human data

Estimates of dermal permeability (K_p), obtained by fitting an updated human PBPK model for malathion to previously reported data on excreted urinary metabolites after 29 volunteers were dermally exposed to measured values of [¹⁴C]malathion dermal load (L), were used to examine the empirical relationship between K_p and L. The PBPK model was adapted from previously reported human biokinetic and PBPK models for malathion, fit to previously reported urinary excretion data after oral [¹⁴C]malathion intake by volunteers, and then augmented to incorporate a standard K_p approach to modeling dermal-uptake kinetics. Good to excellent PBPK-model fits were obtained to all of 29 sets of cumulative urinary metabolite-excretion data (ave. [±1 SD] R² = 0.953 [±0.064]). Contrary to the assumption that K_p and L are independent typically applied for dermally administered liquids or solutions, the 29 PBPK-based estimates of K_p obtained for malathion exhibit a strong positive association with the 2/3rds power of L (log-log Pearson correlation = 0.925, p = ～0). Possible explanations of this observation involving physico-chemical characteristics and/or in vivo cutaneous effects of malathion are discussed. The PBPK model presented, and our observation that K_p estimates obtained by fitting this model to human experimental urinary-excretion data correlate well with L^2/3, allow more realistic assessments of absorbed and metabolized dose during or after a variety of scenarios involving actual or potential dermal or multi-route malathion exposures, including for pesticide workers or farmers who apply malathion to crops.     

Is Daily Mortality Associated Specifically with Fine Particles? Data Reconstruction and Replication of Analyses

ABSTRACT

In 1996, Schwartz, Dockery, and Neas¹ reported that daily mortality was more strongly associated with concentrations of PM_2.5 than with concentrations of larger particles (coarse mass [CM]) in six U.S. cities (“original paper'V'original analyses”). Because of the public policy implications of the findings and the uniqueness of the concentration data, we undertook a reanalysis of these results. This paper presents results of the reconstruction of these data and replication of the original analyses using the reconstructed data. The original investigators provided particulate air pollution data for this paper. Daily weather and daily counts of total and cause-specific deaths were reconstructed from original public records. The reconstructed particulate air pollution and weather data were consistent with the summaries presented in the original paper. Daily counts of deaths in the reconstructed data set were lower than in the original paper because of restrictions on residence and place of death. The reconstruction process identified an administrative change in county codes that led to higher numbers of deaths in St. Louis. Despite these differences in daily counts of deaths, the estimated effects of par-ticulate air pollution from the reconstructed dataset, using analytic methods as described in the original paper, produced combined effect estimates essentially equivalent to the originally published results. For example, the estimated association of a 10 |j.g/m³ increase in 2-day mean particulate air pollution on total mortality was 1.3% (95% confidence interval [CI] 0.9-1.7%, t = 6.53) for PM₂₅ based on the reconstructed dataset, compared to the originally reported association of 1.5% (95% CI 1.1-1.9%, t = 7.41). For coarse particles, the estimated association from the reconstructed dataset was 0.4% (95% CI -0.2-0.9%, t = 1.43) compared to the originally reported association of 0.4% (95% CI -0.1-1.0%, t = 1.48). These results from the reconstructed data suggest that the original results reported by Schwartz, Dockery, and Neas¹ were essentially replicated.     

Festuca arundinacea,glutathione S-transferase and herbicide safeners: A preliminary case study to reduce herbicidal pollution

The expression of glutathione S-transferase (GST) activity in Festuca arundinacea was investigated in response to the following herbicide safeners: benoxacor, cloquintocet-mexyl, fenchlorazol-ethyl, fenclorim, fluxofenim and oxabetrinil. All the above compounds enhanced the GST activity tested towards the “model” substrate 1-chloro-2,4-dinitrobenzene (CDNB). Assays of GST activity towards the herbicides terbuthylazine (N ²-tert-butyl-6-chloro-N ⁴-ethyl-1,3,5-triazine-2,4-diamine) and butachlor (N-butoxymethyl-2-chloro-2′,6′-diethylacetanilide) as substrates also showed the ability of the safeners to enhance the enzyme activity towards both these herbicides, with the exception of cloquintocet-mexyl for the enzyme activity towards butachlor. As a consequence of the above effects at a macro-scale level, decreased herbicide accumulation and persistence were ascertained in response to the addition of the safener benoxacor to both terbuthylazine and butachlor treatments. These results are discussed in terms of capacity of benoxacor to induce herbicide detoxification in Festuca arundinacea with a view to utilizing them in reducing herbicide pollution.     

Bulgarian emergency response models–validation against ETEX first release

In the paper, the performance of two Bulgarian dispersion models is tested against European Tracer Experiment (ETEX) first release data base. The first one is the LED puff model which was the core of the Bulgarian Emergency Response System during all releases of ETEX. The second one is the newly created Eulerian dispersion model EMAP. These models have two important features: they are PC-oriented and they use quite a limited amount of input meteorological information. First, a number of runs with various source configurations are made on meteorological data produced by ECMWF. The aim of these runs is to verify the models’ ability to simulate reliably ETEX first release. To this end, a set of statistical criteria selected in ATMES (Atmospheric Transport Models Evaluation Study, see Klug et al., 1992 are used. The best runs for both models are obtained when the source is presented as a column towering from the ground to heights of 400–700 m. These runs took part in the second phase of ETEX (ETEX-II), the so called ATMES-type exercise where EMAP ranked ninth and LED - fourteenth among 34 models. Here, additional sets of EMAP are presented where in the first run the value of the horizontal diffusion coefficient is varied and in the other runs different meteorological data sets are tested. The results obtained from the first run show that the values of K_h=4–6×10⁴ m² s^-1 produce fields which fit experimental data best. The other sets of runs show that the higher the frequency of the meteorological data, the better the simulation. The results can be improved by linear interpolation of the meteorological parameters with time, the best fitting obtained with interpolation at each time step.     

Uranium and neptunium retention mechanisms in Gallionella ferruginea/ferrihydrite systems for remediation purposes

The ubiquitous β-Proteobacterium Gallionella ferruginea is known as stalk-forming, microaerophilic iron(II) oxidizer, which rapidly produces iron oxyhydroxide precipitates. Uranium and neptunium sorption on the resulting intermixes of G. ferruginea cells, stalks, extracellular exudates, and precipitated iron oxyhydroxides (BIOS) was compared to sorption to abiotically formed iron oxides and oxyhydroxides. The results show a high sorption capacity of BIOS towards radionuclides at circumneutral pH values with an apparent bulk distribution coefficient (K_d) of 1.23 × 10⁴ L kg^?1 for uranium and 3.07 × 10⁵ L kg^?1 for neptunium. The spectroscopic approach by X-ray absorption spectroscopy (XAS) and ATR FT-IR spectroscopy, which was applied on BIOS samples, showed the formation of inner-sphere complexes. The structural data obtained at the uranium L_III-edge and the neptunium L_III-edge indicate the formation of bidentate edge-sharing surface complexes, which are known as the main sorption species on abiotic ferrihydrite. Since the rate of iron precipitation in G. ferruginea-dominated systems is 60 times faster than in abiotic systems, more ferrihydrite will be available for immobilization processes of heavy metals and radionuclides in contaminated environments and even in the far-field of high-level nuclear waste repositories.

     

Inhibition of pancreatic carboxypeptidase A: A possible mechanism of interaction between penicillic acid and ochratoxin A

Abstract

Penicillic acid and ochratoxin A are environmentally important toxic fungal metabolites (mycotoxins) that are synergistic in combination. The effects of penicillic acid on the pancreatic enzyme, :arboxypeptidase A were investigated in vitro and in vivo. A broad range of inhibition in vitro of the enzyme by PA was demonstrated with a half‐maximal inhibitory concentration equal to 1.1 x 10^‐4M PA. Inhibition of carboxypeptidase A was time and temperature dependent, and resulted in decreased conversion of parent ochratoxin A to the non‐toxic metabolite, ochratoxin alpha. Studies in vivo demonstrated a penicillic acid‐dependent inhibition of pancreatic carboxypeptidase A activity in the mouse and the chicken following multiple oral exposure. It is postulated that the mode of toxic interaction of the two mycotoxins may be due, in part, to impaired detoxification of ochratoxin A through peni‐cillic acid depletion of carboxypeptidase A activity.     

Moist Olive Husks Addition to a Silty Clay Soil: Influence on Microbial and Biochemical Parameters

To investigate the effects of moist olive husks (MOH-residues) on soil respiration, microbial biomass, and enzymatic (o-diphenoloxidase, β-glucosidase, dehydrogenase and alkaline phosphatase) activities, a silty clay soil was incubated with 0 (control), 8 × 10³ (D), 16 × 10³ (2D) and 80 × 10³ (10D) kg ha^?1 of MOH-residues on a dry weight basis. Soil respiration and microbial biomass data indicated that the addition of MOH-residues strongly increased microbial activity proportionally to the amounts added. Data of qCO₂ suggested that the respiration to biomass ratio of the microbial population was strongly modified by MOH-residues additions during the first 90 days of incubation. The qCO₂ data suggested a low efficiency in energy yields from C oxidation during the first 2 months of soil incubation. qFDA seemed to be relatively unaffected for treatments D and 2D as compared to the control, but was significantly lowered by the application of 10D, showing the lowest hydrolytic activity of microbial biomass in this treatment up to 360 days of incubation.

o-Diphenoloxidase activity was delayed, and this delay was extended with the addition of larger quantities of MOH-residues. Alkaline phosphatase, β-glucosidase and dehydrogenase activities were in line with the findings on microbial biomass changes and activities. The biological and biochemical data suggest that the addition of a large quantity of MOH-residues (80 × 10³ kg ha^?1) strongly modifies the soil characteristics affecting the r- and K-strategist populations, and that these changes last for at least the 360 days of incubation. The data also suggest that application rates exceeding 16 × 10³ kg ha^?1 are not recommended until the agro-chemical and -physical functions of the soil are further studied.     

The role of wind field, mixing height and horizontal diffusivity investigated through two lagrangian particle models

Two Lagrangian particle models, APOLLO and MILORD, were used to simulate the first ETEX experiment. The role played by wind field, mixing height h and horizontal diffusivity K_H appeared to be the most important aspects to be studied. The sensitivity to the accuracy of the input advection field was studied through the application of APOLLO using different ECMWF data sets differing in space and time resolution and in being forecasted or analysed, corresponding to the real-time, emergency-like condition, and to the a posteriori benchmark simulation. The role of h and K_H was investigated by running both APOLLO and MILORD with different parameterisations, and comparing the model results between them and with the available observations.The model evaluation was carried out through a set of statistical indexes computed on three hourly average concentrations paired in space and time and time-integrated concentrations. It was found that the quality of the input wind field plays a major role in predicting with sufficient accuracy the plume position and extension after the first 24 h from the beginning of the release. The best-model results are obtained with large values of K_H (in the range of 2.5×10⁴–4.5×10⁴ m² s^-1), which confirms the need to enhance the horizontal diffusion, in order to include the advection fluctuations unresolved by large-scale meteorological fields. A fixed value of h in the range 1000–1500 m seems to be more efficient than space and time variable h computed with standard algorithms. A reasonable explanation for this result is given, based on the consideration that in the long range, particles diffuse also in the residual layer above the stable nocturnal boundary layer.     

Black carbon emissions in gasoline vehicle exhaust: A measurement and instrument comparison

A pilot study was conducted to evaluate the performance and agreement of several commercially available black carbon (BC) measurement instruments, when applied to the quantification of BC in light-duty vehicle (LDV) exhaust. Samples from six vehicles, three fuels, and three driving cycles were used. The pilot study included determinations of the method detection limit (MDL) and repeatability. With respect to the MDL, the real-time instruments outperformed the time-integrated instruments, with MDL = 0.12 mg/mi for the AE51 Aethalometer, and 0.15 mg/mi for the Micro Soot Sensor (MSS), versus 0.38 mg/mi for the IMPROVE_A thermal/optical method, and 0.35 mg/mi for the OT21_T Optical Transmissometer. The real-time instruments had repeatability values ranging from 30% to 35%, which are somewhat better than those of the time-integrated instruments (40–41%). These results suggest that, despite being less resource intensive, real-time methods can be equivalent or superior to time-integrated methods in terms of sensitivity and repeatability. BC mass data, from the photoacoustic and light attenuation instruments, were compared against same-test EC data, determined using the IMPROVE_A method. The MSS BC data was well correlated with EC, with R ² = 0.85 for the composite results and R² = 0.86 for the phase-by-phase (PBP) results. The correlation of BC, by the AE51, AE22, and OT21_T, with EC was moderate to weak. The weaker correlation was driven by the inclusion of US06 test data in the linear regression analysis. We hypothesize that test-cycle-dependent BC:EC ratios are due to the different physicochemical properties of particulate matter (PM) in US06 and Federal Test Procedure (FTP) tests. Correlation amongst the real-time MSS, PASS-1, AE51, and AE22 instruments was excellent (R² = 0.83–0.95), below 1 mg/mi levels. In the process of investigating these BC instruments, we learned that BC emissions at sub-1 mg/mi levels can be measured and are achievable by current-generation gasoline engines.

Implications: Most comparison studies of black carbon (BC) measurement methods were carried out in the ambient air. This study assesses the agreement among various BC measurement instrument in emissions from light-duty gasoline vehicles (LDGVs) on standard test cycles, and evaluates applicability of these methods under various fuel types, driving cycles, and engine combustion technologies. This research helps to fill in the knowledge gap of BC method standardization as stated in the U.S. Environmental Protection Agency (EPA) 2011 Report to Congress on Black Carbon, and these results demonstrate the feasibility of quantification of BC at the 1 mg/mi PM standard in California Low Emission Vehicle III regulations.     

A Comparative Validation of the RAM and PTMTP Models for Short-Term SO2 Concentrations in Two Urban Areas

A comprehensive and comparative model validation of two EPA models for short-term SO₂ concentrations was performed. The two models tested were RAM (Urban version) and PTMTP (Terrain version). Both are multiple source, multiple receptor gaussian plume models, recommended in the EPA Guideline On Air Quality Models. ¹ The principal difference between the two models is in their use of empirical dispersion coefficients. It was because of the potential for markedly different predicted maximum SO₂ concentrations, and the absence of any testing data on the RAM model, that the validation analysis was undertaken. The current study utilized a full year of air quality data from monitoring sites in two Indiana cities, Michigan City and Indianapolis. Cumulative frequency distributions for each site and model were prepared and comparisons made. The results indicate that the RAM (Urban) model was highly inaccurate in predicting maximum short-term SO₂ concentrations. The PTMTP model, although conservative in its estimates, produces results which more closely resemble the distribution of observed SO₂ concentrations. The body of information presented in this paper is directed to environmental scientists responsible for air quality modeling, and to those persons who set policy on the use of models in air quality studies.     

Diffusion of tritiated water and Na through non-degraded hardened cement pastes

Diffusion experiments through hardened cement pastes (HCP) using tritiated water (HTO) and ²²Na⁺, considered to be conservative tracers, have been carried out in triplicates in a glove box under a controlled nitrogen atmosphere. Each experiment consisted of a through-diffusion test followed by an out-diffusion test.The experimental data were inversely modelled applying an automated Marquardt–Levenberg procedure. The analysis of the through-diffusion data allowed the extraction of values for the effective diffusion coefficients, D_e, and the rock capacity factor, α. Good agreement between measured and calculated tracer breakthrough curves was achieved using both a simple diffusion model without sorption and a diffusion/linear sorption model. The best-fit K_d-values were found to be consistent with R_d-values measured in previous batch-sorption experiments.The best-fit values from the through-diffusion tests were then used to predict the results of subsequent out-diffusion experiments. Good agreement between experimental data and predictions was achieved only for the case of linear sorption.Isotopic exchange can only partially account for both the amount of tracer taken up in the batch-sorption tests and the measured retardation in the diffusion experiments and, hence, additional mechanisms have to be invoked to explain the data.