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Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from stack flue gases of sinter plants.

This study investigated four sinter plants, classified into two categories--with selective catalytic reduction (SCR) (S1, S2 and S3) and without SCR (S4) as its air pollution control device. Polychlorinated dibenzofurans (PCDFs) are dominant in the stack flue gases of sinter plants with and without SCR. The polychlorinated dibenzofurans/polychlorinated dibenzo-p-dioxins (PCDFs/PCDDs) ratio exceeds 1 extremely. The degree of chlorination of the sinter plant without SCR is towards hepta and hexa congeners while that of the sinter plant with SCR is towards penta and hexa congeners. PCDD/Fs are indeed decomposed (75.5% and 69% on ng and ng TEQ bases, respectively) and not only reduced in degree of chlorination. The overall concentration in the stack flue gas of sinter plants with SCR (7.97-14.1 ng/Nm(3); 0.995-2.06 ng TEQ/Nm(3)) is lower than that of the sinter plant without SCR (28.9 ng/Nm(3); 3.10 ng TEQ/Nm(3)). In Taiwan, based on the emission factors of 0.970 microg TEQ/ton-feedstock (sinter plants with SCR) and 3.13 microg TEQ/ton-feedstock (sinter plant without SCR), the annual PCDD/F emission of 44.7 g TEQ/year from sinter plants is 60 and 121 times higher than those from municipal solid waste incinerators (0.750 g TEQ/year) and MWIs (0.369 g TEQ/year). These results show that sinter plants have become the dominating PCDD/F emission source since tighter emission limits have been applied to incinerators.

Air Pollutants↗

Chemicals and gases.

This article covers the major chemicals and gases that are considered to be of the most clinical relevance to the primary care provider. The reader is referred to other comprehensive textbooks of toxicology and occupational medicine for a complete discussion of the numerous additional products found in the workplace that may result in occupational exposure.

Gases↗

The perfluorocarbon gases in the treatment of retinal detachment.

Four straight chain perfluorocarbon gases that had been studied in animals were tried in 30 patients. The larger volumes injected into patients made for extended disappearance times. Two milliliters of CF4 diminished to half volume in six days and had a total disappearance time of 16 days; 0.8 ml of C2F6 diminished to half volume in 10 days and had a disappearance time of 40 days; 1 ml of C3F8 diminished to half volume in 35 days and disappeared in 70 days; 0.6 ml of C4F10 diminished to half volume in 45 days and disappeared in 120 days. The expansion potential was estimated to be the same as measured in the animal model.

Animals↗

Direct mass spectrometric measurement of gases in soil monoliths.

An integrated approach to gas analysis in soil cores was conducted to provide a novel method for observing the gas dynamics associated with upland soil ecosystems. Depth profiles of the O(2), Ar, CO(2), CH(4), N(2) and NO(x) concentrations in intact soil monoliths were obtained simultaneously using membrane inlet mass spectrometry (MIMS). This technique enables the direct measurement of multiple gas species throughout the soil core with minimal disturbance. Depth profiles provided data on the vertical heterogeneity of gas concentrations, while horizontal heterogeneity was monitored by comparison between profiles. Detailed descriptions of the modifications to current MIMS methods for in situ environmental monitoring of terrestrial soils are provided. These included a thorough examination of calibration of the MIMS probe in gas phase, stirred and unstirred H(2)O, or between glass beads immersed in H(2)O. Calibration was also carried out in sterile (autoclaved) soil. The mean concentrations of CO(2) and CH(4) in the soil monoliths increased from 27 microM and undetectable levels respectively at the surface, to maximum values of 3.6 mM and 4.3 microM at 12-cm depth. These changes corresponded with decreases in mean O(2), Ar and N(2) concentration from 300, 20 and 720 microM respectively to 0-6, 10 and 574 microM at 12-cm depth. These data indicated the presence of a gradient within the core from an aerobic environment to an O(2)-depleted, but not in all cases a completely anaerobic, one. This transition corresponded, to some extent, with that between the upper and lower soil horizons. The increased methane and CO(2) concentrations observed at depth are indicative of anaerobic environments. General trends associated with the gradually changing vertical heterogeneity of these gas profiles and the transition towards anaerobiosis did not provide evidence for the existence of localised microsites. Some evidence for microsite-specific microbial communities was however, provided by observation of broad zones of accumulation of NO(x) species, but only at concentrations close to the limit of detection of the method. The ratio of each gas, to argon was calculated at each depth. This was done to correct for physical parameters, which influence inert and biologically active gases, equally. The amount of di-nitrogen as a ratio to Ar was seen to increase with depth. This could be evidence for denitrification in the lower horizon. An example of the dynamic 'online' data collection capabilities is provided for diurnal oscillations in subsurface (5 cm) soil gas concentrations.

Gases↗

Membrane inlet ion trap mass spectrometry for the direct measurement of dissolved gases in ecological samples.

The use of an ion trap mass spectrometer with three different membrane inlet probes is described. Two methods of removing water from the sample are compared. One is the use of a PTFE-silicone rubber double membrane, PTFE is relatively impermeable to water and so reduces the amount entering with the gas sample (Probe A). The second is the use of a silicone rubber membrane covered long probe, which condenses water out of the sample (Probe B). Response times (100%) for dissolved N2O, O2, Ar and CO2 without He in the chamber vary from between 158 and 684 s with Probe A. For the same probe with He, the response times were between 283 and 551 s. In the gas phase response times were between 99 and 153 s with He and 117 and 122 s without He. Probe B had 100% response of between 122 and 152 s for dissolved gases. Further extension of the probe by 2 m slowed response times as did increasing the ionisation time. Response times for Probe B increased to between 99 and 340 s when ionisation time increased from 1000 to 24,930 microseconds. Plots of output against concentration showed the steepest line of response for the short single membrane covered probe with 1000 microseconds ionisation time. Increasing the ionisation time, extending the probe and the use of a double membrane all reduced the gradient of output against concentration for every gas tested. In an intact sediment core, concentrations of O2, N2O and CO2 rose at the start and the concentration of N2 fell. As the disturbed sediment settled, this was reversed. The initial increase in O2 concentration stimulated respiration and inhibited the final pathway in dentrification producing higher concentrations of N2O and reducing the concentration of N2.

Argon↗

Removal of ethylacetate vapor from waste gases by a trickle-bed air biofilter.

Biofilter system is a relatively new process that has been proven to be more cost-effective than traditional technologies such as carbon adsorption, liquid scrubbing, condensation, thermal incineration, and catalytic incineration for removing low-strength volatile organic compounds from waste gases. The trickle-bed air biofilter (TBAB) performance for ethylacetate (EA) removal was evaluated under different influent loadings. In the pseudo-steady states, the elimination capacity increased, but the removal efficiency decreased with increased influent loading. More than 95 and 90% removal efficiencies could be achieved for EA loadings below 490 and 810 g m(-3) h(-1), respectively. The TBAB appears to be very effective for controlling EA emission under low to high loading conditions, and the effectiveness could be maintained over 190 days of laboratory operation.

Acetates↗

Prediction of flammability of gases by using F-number analysis.

A novel method of predicting flammability limits has been proposed. This method utilizes a new flammability index called F-number. For this purpose, an empirical expression of F-number has been derived to account for the flammability characteristics of various organic substances. The analysis has been done by fitting to the observed values of F-number for a wide variety of organic gases and vapors. As a result, it has been found that F-number is an excellent tool to analyze the flammability characteristics of various substances. It has also been shown that the values of upper and lower flammability limits can be derived from F-number together with the stoichiometric concentration corrected for the effect of selective diffusion.

Fires↗

RF number as a new index for assessing combustion hazard of flammable gases.

A new index called RF number has been proposed for assessing the combustion hazard of all sorts of flammable gases and their mixtures. RF number represents the total expectancy of combustion hazard in terms of flammability limits and heat of combustion for each known and unknown compounds. The advantage of RF number over others such as R-index and F-number for classification of combustion hazard has been highlighted.

Fires↗

Calculation of minimum ignition energy of premixed gases.

The minimum ignition energy of premixed gases has been calculated by using two theoretical expressions and compared with the experimental data. One expression considers the amount of energy that the minimal flame should have, and the other the heat loss from the surface of the minimal flamelet. The former is a cubic function of the quenching distance while the latter is a quadratic function of quenching distance. It has been found that the latter expression gives a better fit to the experimental data than the former, though the discrepancy is considerable even for the latter expression. The calculated widths of the fronts of the minimal flame for various fuels were about one-order of magnitude smaller than the corresponding experimentally determined quenching distances, although no clear correlation relationship between the two quantities was found.

Fires↗

Off-site ignition probability of flammable gases.

A key step in the assessment of risk for installations where flammable liquids or gases are stored is the estimation of ignition probability. A review of current modelling and data confirmed that ignition probability values used in risk analyses tend to be based on extrapolation of limited incident data or, in many cases, on the judgement of those conducting the safety assessment. Existing models tend to assume that ignition probability is a function of release rate (or flammable gas cloud size) alone and they do not consider location, density or type of ignition source. An alternative mathematical framework for calculating ignition probability is outlined in which the approach used is to model the distribution of likely ignition sources and to calculate ignition probability by considering whether the flammable gas cloud will reach these sources. Data are collated on the properties of ignition sources within three generic land-use types: industrial, urban and rural. These data are then incorporated into a working model for ignition probability in a form capable of being implemented within risk analysis models. The sensitivity of the model results to assumptions made in deriving the ignition source properties is discussed and the model is compared with other available ignition probability methods.

Accidents, Occupational↗

Comparison of two standard test methods for determining explosion limits of gases at atmospheric conditions.

A comparison is made between two internationally accepted methods to determine the explosion limits of gases at atmospheric pressure and room temperature (20 l sphere - DIN 51649). Significant differences (about 1 vol.%) in the upper explosion limits (UEL) values are found for four hydrocarbons tested. A new criterion is proposed which leads to close agreement between the UEL values obtained by the two methods.

Atmospheric Pressure↗

An investigation of the presence of methane and other gases at the Uzundere-Izmir solid waste disposal site, Izmir, Turkey.

Izmir is a large metropolitan city with a population of 3,114,860. The city consists of 27 townships, each township has a population of not less than 10,000 inhabitants. The two major solid waste disposal sites are in the townships of Uzundere and Harmandali. The amount of solid waste that is disposed at each of these sites is about 800 and 1800 t/day, respectively. In Uzundere, compost is produced from the organic fraction of urban solid wastes while the residual material is deposited at a disposal site with a remaining capacity of 700,000 m(3) as of 2001. Gas monitoring and measurements were carried out at the disposal site in Uzundere. For this purpose, nine sampling wells were drilled on selected locations. Each well was furnished with perforated metal pipes suitable for gas monitoring and measurements. The following gases were monitored: O(2), CH(4), CO, CO(2), and H(2)S. The most important finding was that the concentrations of CH(4) in the wells ranged from 7 to 57%. Dilution of the CH(4) by O(2) down to the LEL levels (5-15%) is always possible and poses a continuing risk at the site. Furthermore, the levels of O(2) require that access to the site be limited to only authorized personnel.

Cities↗

Electrosurgery-induced generation of gases: comparison of in vitro rates of production using bipolar and monopolar electrodes.

STUDY OBJECTIVE: To compare rates of production of gases generated by VersaPoint bipolar hysteroscopic vaporizing electrodes using normal saline and monopolar vaporizing electrodes using 1.5% glycine. DESIGN: In vitro study (Canadian Task Force classification II-1). SETTING: Laboratory. MATERIAL: Bovine cardiac muscle. INTERVENTION: Fresh morbid bovine cardiac muscle was fully immersed in normal saline for the bipolar system and in 1.5% glycine for monopolar systems. Loop and bulk vaporizing electrodes were activated by radiofrequency electrosurgical units (ESUs) appropriate for each system, at standard powers and at settings higher than those in clinical use. MEASUREMENTS AND MAIN RESULTS: Rates of gas production were calculated and data analyzed by analysis of variance. For bulk vaporizing electrodes, the highest gas production rates at standard settings occurred with monopolar electrodes and the Force 2 generator at 300 W, and the Force FX at 200 W. At slightly higher than standard 200-W settings, the VersaPoint bipolar bulk vaporizing electrode was associated with lowest gas production rates in this category. Although there were statistically significant differences between loop electrodes, the magnitude remained small at similar ESU settings, and differences are thought to be clinically insignificant. CONCLUSION: Rates of gas production in this model appeared to vary most with ESU power output settings and relatively little with electrosurgical modality (bipolar or monopolar).

Animals↗

Infrared laser spectrometer with balanced absorption for measurement of isotopic ratios of carbon gases.

Measurement of the isotopic compositions of carbon dioxide and methane is a powerful tool for quantifying their atmospheric sources and sinks, which is especially important considering the dramatic increase in these greenhouse gases during the industrial era. Laser absorption spectroscopy is a technique which has demonstrated the high sensitivity needed for isotopic measurement. A significant problem in the spectroscopic measurement of isotopic abundances is the large difference in concentrations of the major and minor isotopic constituents. The measurement of two isotopic species using lines of similar strength but very unequal concentrations leads to low precision, with either the minor constituent having too small an absorption depth, or the major constituent having too great an absorption depth. If lines with unequal strength are chosen to compensate for the absorption depth imbalance, then precision tends to suffer due to the greater temperature sensitivity of the weaker line strength. We describe the development of a compact instrument for isotopic analysis CO2 and CH4 using tunable infrared laser absorption spectroscopy which combines novel optical design and signal processing methods to address this problem. The design compensates for the large difference in concentration between major and minor isotopes by measuring them with pathlengths which differ by a factor of 72 within the same multipass cell. We have demonstrated the basic optical design and signal processing by determining delta13C (CO2) isotopic ratios with precision as small as 0.2/1000 using a lead salt diode laser based spectroscopic instrument.

Carbon Isotopes↗

Response calculations of electronic and vibrational transitions in molecular oxygen induced by interaction with noble gases.

The Einstein coefficient for the singlet oxygen emission a1Deltag-->X3Sigmag- at lambda=1270 nm and b1Sigmag+-->X3Sigmag- emission at lambda=750 nm were calculated by quadratic response (QR) multiconfiguration self-consisted field (MCSCF) method for a number of collision complexes O2+M, where M=He, Ne, Ar. Interaction with He clusters was studied in order to simulate cooperative effect of the environment on the oxygen emission. Calculations of the dipole transition moment for the Noxon band, b1Sigmag+-a1Deltag, by linear response (LR) MCSCF method were also performed for a number of collision complexes. Spin-orbit coupling (SOC) between the b1Sigmag+ and X3Sigmag- (MS=0) states does not change much upon collisions, thus the a-X transition borrows intensity mostly from the collision-induced Noxon band b-a. The a-X intensity borrowing from the Schumann-Runge transition is negligible. The calculations show that the b-a and a-X transition probabilities are enhanced approximately by 10(5) and 10(3) times by O2+M collisions. An order of magnitude differences occur for both transitions for noble gases with large difference in polarizability. A strong cooperative effect is obtained when few He atoms perturb the oxygen molecule. Depending on mutual orientation of the partners it can be a complete quenching of the a-->X emission or strong non-additive enhancement. Collision-induced infrared vibrational transitions in a number of molecular oxygen excited states were studied and shown to be state selective.

Models, Molecular↗

Mass spectrometer characterization of halogen gases in air at atmospheric pressure.

We have developed a new interface for a commercial ion trap mass spectrometer equipped with APCI capable of real-time measurements of gaseous compounds with limits of detection on the order of pptv. The new interface has been tested using the detection of Br2 and Cl2 over synthetic seawater ice at atmospheric pressure as a model system. A mechanical pump is used to draw gaseous mixtures through a glass manifold into the corona discharge area, where the molecules are ionized. Analysis of bromine and chlorine in dry air show that ion intensity is affected by the pumping rate and the position of the glass manifold. The mass spectrometer signals for Br2 are linear in the 0.1-10.6 ppbv range, and the estimated 3sigma detection limit is 20 pptv. The MS signals for Cl2 are linear in the 0.2-25 ppbv range, and the estimated 3sigma detection limit is 1 ppbv. This new interface advances the field of analytical chemistry by introducing a practical modification to a commercially available ion trap mass spectrometer that expands the available methods for performing highly specific and sensitive measurements of gases in air at atmospheric pressure.

Air↗

Selective detection of alkanolamine vapors by ion mobility spectrometry with ketone reagent gases.

The ion mobility (IMS) spectra of the alkanolamines, monoethanolamine (MEA), 3-amino-1-propanol (PRA), 4-amino-1-butanol (BUA), and 5-amino-1-pentanol (PEA) with acetone and 4-heptanone reagent gases have been measured using a hand-held spectrometer. Monomer and dimer peak patterns were observed for all the alkanolamines with acetone reagent gas. Drift times of monomer and dimer ion clusters for each alkanolamine increased linearly in order of size of alkyl group. Ammonia, Freon 22, and F76 diesel vapors, having similar or coincident mobilities, caused severe interference. Replacement of acetone with 4-heptanone reagent gas resulted in good separation by the altering drift times of product ions. The limit of detection was 0.005 ppm having a linear range of 0.005-0.7 ppm, and signal saturation occurred above 0.88 ppm. Detection was reversible, with a response time of 4 min and a slower recovery time of > 60 min, at vapor levels of 0.7 ppm and ambient nozzle and drift-region temperatures. In contrast to acetone chemistry, single-peak patterns were observed for the alkanolamines with the 4-heptanone reagent. Further, drift times unexpectedly remained stagnant with increasing alkyl-group size. From atmospheric pressure chemical ionization (APcI) tandem mass spectral identifications and collision induced studies, dynamic changes in product-ion equilibria in the IMS drift region compensated by differences in collision cross sections were suggested as the governing causes of the unusual mobility effect.

Acetone↗

Gas transport below artificial recharge ponds: insights from dissolved noble gases and a dual gas (SF6 and 3He) tracer experiment.

A dual gas tracer experiment using sulfur hexafluoride (SF6) and an isotope of helium (3He) and measurements of dissolved noble gases was performed at the El Rio spreading grounds to examine gas transport and trapped air below an artificial recharge pond with a very high recharge rate (approximately 4 m day(-1)). Noble gas concentrations in the groundwater were greater than in surface water due to excess air formation showing that trapped air exists below the pond. Breakthrough curves of SF6 and 3He at two nearby production wells were very similar and suggest that nonequilibrium gas transfer was occurring between the percolating water and the trapped air. At one well screened between 50 and 90 m below ground, both tracers were detected after 5 days and reached a maximum at approximately 24 days. Despite the potential dilution caused by mixing within the production well, the maximum concentration was approximately 25% of the mean pond concentration. More than 50% of the SF6 recharged was recovered by the production wells during the 18 month long experiment. Our results demonstrate that at artificial recharge sites with high infiltration rates and moderately deep water tables, transport times between recharge locations and wells determined with gas tracer experiments are reliable.

Environmental Monitoring↗