Development of a Sample Equilibration System for the TEOM Continuous PM Monitor

ABSTRACT

In recent years, scientific discussion has included the influence of thermodynamic conditions (e.g., temperature, relative humidity, and filter face velocity) on PM retention efficiency of filter-based samplers and monitors. Method-associated thermodynamic conditions can, in some instances, dramatically influence the presence of particle-bound water and other light-molecular-weight chemical components such as particulate nitrates and certain organic compounds. The measurement of fine particle mass presents a new challenge for all PM measurement methods, since a relatively greater fraction of the mass is semi-volatile.

The tapered element oscillating microbalance (TEOM) continuous PM monitor is a U.S. Environmental Protection Agency (EPA) PM₁₀ equivalent method (EQPM-1090-079). Several hundred of these monitors are deployed throughout the United States. The TEOM monitor has the unique characteristic of providing direct PM mass measurement without the calibration uncertainty inherent in mass surrogate methods. In addition, it provides high-precision, near-real-time continuous data automatically. Much attention has been given to semi-volatile species retention of the TEOM method.

While using this monitor, it is desirable to maintain as low an operating temperature as practical and to remove unwanted particle-bound water. A new sample equilibration system (SES) has been developed to allow conditioning of the PM sample stream to a lower humidity and temperature level. The SES incorporates a special low-particle-loss Nafion dryer. This paper discusses the configuration and theory of the SES. Performance results include high time-resolved PM_2.5 data comparison between a 30 °C sample stream TEOM monitor with SES and a standard 50 °C TEOM monitor. In addition, 24-hr integrated data are compared with data collected using an EPA PM_2.5 Federal Reference Method (FRM)-type sampler. The SES is a significant development because it can be applied easily to existing TEOM monitors.     

Benzo[b]fluoranthene,a Potential Alternative to Benzo[a]pyrene as an Indicator of Exposure to Airborne PAHs in the Vicinity of Söderberg Aluminum Smelters

ABSTRACT

Benzo[b]fluoranthene (B[b]F) was used in relative abundance ratios (RARs), a parameter obtained by dividing the concentration of individual polycyclic aromatic hydrocarbons (PAHs) found in a given sample by the concentration of B[b]F in the same sample. The B[b]F RARs were derived for PAH concentrations measured at stacks and sampling stations in the vicinity of two Söderberg aluminum horizontal stud smelters (HSSs). The samples collected were analyzed by high-performance liquid chromatography using UV and fluorescence detection. A total of 15 PAHs were analyzed, but, due to the inefficiency of the sampling method used in collecting gaseous PAHs, only particulate PAHs were considered. Comparisons between the B[b]F RARs obtained simultaneously at the source (stack) and those obtained at sampling stations at the two smelters showed that B[b]F degrades more slowly than or at the same rate as most other particulate PAHs monitored. Twenty-three months of urban sampling in the vicinity of one of the aluminum HSSs are also presented, and the results indicate that B[b]F is more stable than all other particulate PAHs investigated. Sampling conducted during a smelter shutdown period confirmed that B[b]F was a much better marker of this source than was benzo[a]pyrene (B[a]P), the usual indicator. The remarkable stability of the benzo[k]fluoranthene (B[k]F)/B[b]F ratio is also discussed.     

Total fuel-cycle analysis of heavy-duty vehicles using biofuels and natural gas-based alternative fuels

Heavy-duty vehicles (HDVs) present a growing energy and environmental concern worldwide. These vehicles rely almost entirely on diesel fuel for propulsion and create problems associated with local pollution, climate change, and energy security. Given these problems and the expected global expansion of HDVs in transportation sectors, industry and governments are pursuing biofuels and natural gas as potential alternative fuels for HDVs. Using recent lifecycle datasets, this paper evaluates the energy and emissions impacts of these fuels in the HDV sector by conducting a total fuel-cycle (TFC) analysis for Class 8 HDVs for six fuel pathways: (1) petroleum to ultra low sulfur diesel; (2) petroleum and soyoil to biodiesel (methyl soy ester); (3) petroleum, ethanol, and oxygenate to e-diesel; (4) petroleum and natural gas to Fischer-Tropsch diesel; (5) natural gas to compressed natural gas; and (6) natural gas to liquefied natural gas. TFC emissions are evaluated for three greenhouse gases (GHGs) (carbon dioxide, nitrous oxide, and methane) and five other pollutants (volatile organic compounds, carbon monoxide, nitrogen oxides, particulate matter, and sulfur oxides), along with estimates of total energy and petroleum consumption associated with each of the six fuel pathways. Results show definite advantages with biodiesel and compressed natural gas for most pollutants, negligible benefits for e-diesel, and increased GHG emissions for liquefied natural gas and Fischer-Tropsch diesel (from natural gas).     

Toxic masking and synergistic modulation of the estrogenic activity of chemical mixtures in a yeast estrogen screen (YES)

Background, aim and scope

Estrogenic and non-estrogenic chemicals typically co-occur in the environment. Interference by non-estrogenic chemicals may confound the assessment of the actual estrogenic activity of complex environmental samples. The aim of the present study was to investigate whether, in which way and how seriously the estrogenic activity of single estrogens and the observed and predicted joint action of estrogenic mixtures is influenced by toxic masking and synergistic modulation caused by non-estrogenic chemical confounders.

Materials and methods

The yeast estrogen screen (YES) was adapted so that toxicity and estrogenicity could be quantified simultaneously in one experimental run. Mercury, two organic solvents (dimethyl sulfoxide (DMSO) and 2,4-dinitroaniline), a surfactant (LAS-12) and the antibiotic cycloheximide were selected as toxic but non-estrogenic test chemicals. The confounding impact of selected concentrations of these toxicants on the estrogenic activity of the hormone 17ß-estradiol was determined by co-incubation experiments. In a second step, the impact of toxic masking and synergistic modulation on the predictability of the joint action of 17ß-estradiol, estrone and estriol mixtures by concentration addition was analysed.

Results

Each of the non-estrogenic chemicals reduced the apparent estrogenicity of both single estrogens and their mixtures if applied at high, toxic concentrations. Besides this common pattern, a highly substance- and concentration-dependent impact of the non-estrogenic toxicants was observable. The activity of 17ß-estradiol was still reduced in the presence of only low or non-toxic concentrations of 2,4-dinitroaniline and cycloheximide, which was not the case for mercury and DMSO. A clear synergistic modulation, i.e. an enhanced estrogenic activity, was induced by the presence of slightly toxic concentrations of LAS-12. The joint estrogenic activity of the mixture of estrogens was affected by toxic masking and synergistic modulation in direct proportion to the single estrogens, which allowed for an adequate adaptation of concentration addition and thus unaffected predictability of the joint estrogenicity in the presence of non-estrogenic confounders.

Discussion

The modified YES proved to be a reliable system for the simultaneous quantification of yeast toxicity and estrogen receptor activation. Experimental results substantiate the available evidence for toxic masking as a relevant phenomenon in estrogenicity assessment of complex environmental samples. Synergistic modulation of estrogenic activity by non-estrogenic confounders might be of lower importance. The concept of concentration addition is discussed as a valuable tool for estrogenicity assessment of complex mixtures, with deviations of the measured joint estrogenicity from predictions indicating the need for refined analyses.

Conclusions

Two major challenges are to be considered simultaneously for a reliable analysis of the estrogenic activity of complex mixtures: the identification of known and suspected estrogenic compounds in the sample as well as the substance- and effect-level-dependent confounding impact of non-estrogenic toxicants.

Recommendations and perspectives

The application of screening assays such as the YES to complex mixtures should be accompanied by measures that safeguard against false negative results which may be caused by non-estrogenic but toxic confounders. Simultaneous assessments of estrogenicity and toxicity are generally advisable.     

Methane generation in tropical landfills: simplified methods and field results

This paper deals with the use of simplified methods to predict methane generation in tropical landfills. Methane recovery data obtained on site as part of a research program being carried out at the Metropolitan Landfill, Salvador, Brazil, is analyzed and used to obtain field methane generation over time. Laboratory data from MSW samples of different ages are presented and discussed; and simplified procedures to estimate the methane generation potential, Lo, and the constant related to the biodegradation rate, k are applied. The first order decay method is used to fit field and laboratory results. It is demonstrated that despite the assumptions and the simplicity of the adopted laboratory procedures, the values Lo and k obtained are very close to those measured in the field, thus making this kind of analysis very attractive for first approach purposes.     

Impact of training programs on decision-making and situation awareness of trainee watch officers

This paper examines the impact of training programs on the ability of trainee watch officers to make decisions in collision avoidance situations.It draws on previous studies which have shown that experts are able to manage complex situations in an acceptable way. However, observations of students on simulators have revealed that many of them are unable to manage such situations or even to recall their main features. It is therefore necessary to identify new training tools that will give trainees the capacity to assess a situation quickly and accurately, and to perform satisfactory actions. These would be in addition to formal regulations.Exercises were designed to evaluate the impact of such tools on the decision-making process of trainees. The impact of the type of navigation experienced by trainees during their on-the-job training was also evaluated.Results showed that decision-making exercises did tend to improve the trainees’ capacity to analyse a complex situation; however, they did not have a clear impact on the manoeuvre performed. On the contrary, there was an obvious difference between the trainees who experienced complex avoidance situations during their on-the-job training period and those who did not.At a time where ship-owners are looking to reduce the length of the “on-the-job” training period, these results point to its vital importance.     

Soil-atmosphere trace gas exchange in semiarid and arid zones

A review is presented on trace gas exchange of CH4, CO, N2O, and NOx arising from agriculture and natural sources in the world's semiarid and arid zones due to soil processes. These gases are important contributors to the radiative forcing and the chemistry of the atmosphere. Quantitative information is summarized from the available studies. Between 5 and 40% of the global soil-atmosphere exchange for these gases (CH4, CO, N2O, and NOx) may occur in semiarid and arid zones, but for each of these gases there are fewer than a dozen studies to support the individual estimates, and these are from a limited number of locations. Significant differences in the biophysical and chemical processes controlling these trace gas exchanges are identified through the comparison of semiarid and arid zones with the moist temperate or wet/dry savanna land regions. Therefore, there is a poorly quantified understanding of the contribution of these regions to the global trace gas cycles and atmospheric chemistry. More importantly, there is a poor understanding of the feedback between these exchanges, global change, and regional land use and air pollution issues. A set of research issues is presented.     

Numerical Modeling of a Potential Geological CO 2 Sequestration Site at Minden (Germany)

We study opportunities for CO₂ sequestration in geological formations of the state North Rhine Westphalia in Germany. Simulations are performed for evaluating a potential site within the Bunter sandstone formation near the town of Minden in a depth?of around 3,000 m using the numerical simulator TOUGHREACT. Our focus is on three CO₂ storage mechanisms: (1) hydrodynamic trapping, (2) dissolution trapping, and (3) mineral trapping. The results show that due to buoyancy the injected CO₂ phase initially migrates towards the top of the reservoir and is hydrodynamically trapped beneath the confining layer of the cap rock. Then, the CO₂ spreads laterally and dissolves partially in the formation water. The dissolution of CO₂ results in an increase of the density of the brine causing a downward migration until it settles after 10,000 years at the bottom of the reservoir. The simulations indicate that after 10,000 years, 15% (17 Mt) from a total of 114 Mt injected CO₂ are trapped hydrodynamically, 20% (23 Mt) are trapped by dissolution, and 65% (74 Mt) are fixed in newly formed carbonates such as dawsonite, ankerite, and siderite. Within our study pressure increases near the injection well by a factor of 1.1 which is lower than the upper limit usually accepted in gas storage operations. The mineral reactions cause a net decrease of porosity and in turn a decrease of permeability down to 9% of the initial value in parts of the reservoir.     

Seagrass resource assessment using remote sensing methods in St. Joseph Sound and Clearwater Harbor,Florida, USA

In the event of a natural or anthropogenic disturbance, environmental resource managers require a reliable tool to quickly assess the spatial extent of potential damage to the seagrass resource. The temporal availability of the Landsat 5 Thematic Mapper (TM) imagery provided a suitable option to detect and assess damage of the submerged aquatic vegetation (SAV). This study examined Landsat TM imagery classification techniques to create two-class (SAV presence/absence) and three-class (SAV estimated coverage) SAV maps of the seagrass resource. The Mahalanobis Distance method achieved the highest overall accuracy (86%) and validation accuracy (68%) for delineating the seagrass resource (two-class SAV map). The Maximum Likelihood method achieved the highest overall accuracy (74%) and validation accuracy (70%) for delineating the seagrass resource three-class SAV map. The Landsat 5 TM imagery classification provided a seagrass resource map product with similar accuracy to the aerial photointerpretation maps (validation accuracy 71%). The results support the application of remote sensing methods to analyze the spatial extent of the seagrass resource.     

Use of cellular automata in the study of variables involved in land use changes

The study of changes in land use has been included lately in territorial processes in order to optimize future management decisions. The different functions that the territory plays (production, aesthetic, and natural functions, etc.) make planning choices more difficult. This work focuses on the selection and combination of a set of indicators to analyze the variables through which the changes occur in the land used in viticulture for wine production. The proposed approach makes use of the Geographic Information System (GIS) in the development of a map of land use scenario. It is applied to a case study through a model involving cellular automata (CA) implemented with maps of suitability for viticulture and Markov chains. The use in this case of the CA is aimed at validating the scenario map in order to deduce the variables and the orientations of the farmers in the field of wine production.