Diagnostics for Determining Influential Species in the Chemical Mass Balance Receptor Model

ABSTRACT

The chemical mass balance (CMB) model can be applied to estimate the amount of airborne particulate matter (PM) coming from various sources given the ambient chemical composition of the particles measured at the receptor and the chemical composition of the source emissions. Of considerable practical importance is the identification of those chemical species that have a large effect on either the source contributions or errors estimated by the CMB model. This paper details a study of a number of influential diagnostics for application of the CMB software. Some of the diagnostics studied are standard regression diagnostics based on single-row deletion diagnostics. A number of new diagnostics were developed specifically for the CMB application, based on the pseudo-inverse of the source composition matrix and called nondeletion diagnostics to distinguish them from the standard deletion diagnostics. Simulated data sets were generated to compare the diagnostics and their response to controlled amounts of random error.

A particular diagnostic called a modified pseudoinverse matrix (MPIN), developed for this study, was found to be the best choice for CMB model application. The MPIN diagnostic contains virtually all the information present in both deletion and nondeletion diagnostics. Since the MPIN diagnostic requires only the source profiles, it can be used to identify influential species in advance without sampling the ambient data and to improve CMB results through possible remedial actions for the influential species. Specific recommendations are given for interpretation and use of the MPIN diagnostic with the CMB model software. Elements with normalized MPIN absolute values of 1 to 0.5 are associated with influential elements. Noninfluential elements have normalized MPIN absolute values of 0.3 or less. Elements with absolute values between 0.3 and 0.5 are ambiguous but should generally be considered noninfluential.     

Field Measurements of Particulate Matter Emissions,Carbon Monoxide,and Exhaust Opacity from Heavy-Duty Diesel Vehicles

ABSTRACT

Diesel particulate matter (PM) is a significant contributor to ambient air PM₁₀ and PM_2.5 particulate levels. In addition, recent literature argues that submicron diesel PM is a pulmonary health hazard. There is difficulty in attributing PM emissions to specific operating modes of a diesel engine, although it is acknowledged that PM production rises dramatically with load and that high PM emissions occur during rapid load increases on turbocharged engines. Snap-acceleration tests generally identify PM associated with rapid transient operating conditions, but not with high load. To quantify the origin of PM during transient engine operation, continuous opacity measurements have been made using a Wager 650CP full flow exhaust opacity meter. Opacity measurements were taken while the vehicles were operated over transient driving cycles on a chassis dynamometer using the West Virginia University (WVU) Transportable Heavy Duty Vehicle Emissions Testing Laboratories. Data were gathered from Detroit Diesel, Cummins, Caterpillar, and Navistar heavy-duty (HD) diesel engines. Driving cycles used were the Central Business District (CBD) cycle, the WVU 5-Peak Truck cycle, the WVU 5-Mile route, and the New York City Bus (NYCB) cycle. Continuous opacity measurements, integrated over the entire driving cycle, were compared to total integrated PM mass. In addition, the truck was subjected to repeat snap-acceleration tests, and PM was collected for a composite of these snap-acceleration tests. Additional data were obtained from a fleet of 1996 New Flyer buses in Flint, MI, equipped with electronically controlled Detroit Diesel Series 50 engines. Again, continuous opacity, regulated gaseous emissions, and PM were measured. The relationship between continuous carbon monoxide (CO) emissions and continuous opacity was noted. In identifying the level of PM emissions in transient diesel engine operation, it is suggested that CO emissions may prove to be a useful indicator and may be used to apportion total PM on a continuous basis over a transient cycle. The projected continuous PM data will prove valuable in future mobile source inventory prediction.     

Infant Mortality and Air Pollution: A Comprehensive Analysis of U.S. Data for 1990

ABSTRACT

This paper uses U.S. linked birth and death records to explore associations between infant mortality and environmental factors, based on spatial relationships. The analysis considers a range of infant mortality end points, regression models, and environmental and socioeconomic variables. The basic analysis involves logistic regression modeling of individuals; the cohort comprises all infants born in the United States in 1990 for whom the required data are available from the matched birth and death records. These individual data include sex, race, month of birth, and birth weight of the infant, and personal data on the mother, including age, adequacy of prenatal care, and smoking and education in most instances. Ecological variables from Census and other sources are matched on the county of usual residence and include ambient air quality, elevation above sea level, climate, number of physicians per capita, median income, racial and ethnic distribution, unemployment, and population density. The air quality variables considered were 1990 annual averages of PM₁₀, CO, SO₂, SO₄ ^2-, and “non-sulfate PM₁₀” (NSPM₁₀—obtained by subtracting the estimated SO₄ ^2-mass from PM₁₀). Because all variables were not available for all counties (especially maternal smoking), it was necessary to consider various subsets of the total cohort.

We examined all infant deaths and deaths by age (neonatal and postneonatal), by birth weight (normal and low [<2500 g]), and by specific causes within these categories. Special attention was given to sudden infant death syndrome (SIDS). For comparable modeling assumptions, the results for PM₁₀ agreed with previously published estimates; however, the associations with PM₁₀ were not specific to probable exposures or causes of death and were not robust to changes in the model and/or the locations considered. Significant negative mortality associations were found for SO₄ ^2-. There was no indication of a role for outdoor PM_2.5, but possible contributions from indoor air pollution sources cannot be ruled out, given higher SIDS rates in winter, in the north and west, and outside of large cities.     

Dissociation of Sulfur Hexafluoride Tracer Gas in the Presence of an Indoor Combustion Source

ABSTRACT

As an odorless, nontoxic, and inert compound, sulfur hexafluoride (SF₆) is one of the most widely used tracer gases in indoor air quality studies in both controlled and uncontrolled environments. This compound may be subject to reactions with water vapor under elevated temperature to form acidic inorganic compounds such as HF and H₂SO₄. Thus, in the presence of unvented combustion sources such as kerosene heaters, natural gas heaters, gas log fireplaces, candles, and lamps, the SF₆ dissociation may interfere with measurements of the emissions from these sources. Tests were conducted in a research house with a vent-free natural gas heater to investigate these potential interferences. It was observed that the heater operation caused about a 5% reduction of SF₆ concentration, which can be an error source for the ventilation rate measurement and consequently the estimated pollutant emission rates. Further analysis indicates that this error can be much greater than the observed 5% under certain test conditions because it is a function of the ventilation flow rate. Reducing the tracer gas concentration has no effect on this error. A simple theoretical model is proposed to estimate the magnitude of this error.

The second type of interference comes from the primary and secondary products of the SF₆ dissociation, mainly H₂SO₄, SO₂, HF, and fine particulate matter (PM). In the presence of ~5 ppm SF₆, the total airborne concentrations of these species increased by a factor of 4-10. The tests were performed at relatively high SF₆ concentrations, which is necessary to determine the interferences quantitatively. The second type of interference can be significantly reduced if the SF₆ concentration is kept at a low ppb level.     

Liability Theories in Contaminated Groundwater Litigation

Disputes regarding contaminated sites have given rise to an explosion of federal and state court litigation. Congress enacted the Resource Conservation and Recovery Act of 1976 ("RCRA"), 42 U.S.C. §§6901 et seq. , as a contemplated "cradle to grave" regulatory scheme for solid waste, and passed the Comprehensive Environmental Response, Compensation, and Liability Act ("CERCLA"), 42 U.S.C. §§9601 et seq. , to address the investigation and remediation of contaminated sites. RCRA and CERCLA each contemplate a strict, joint and several regulatory liability scheme to address sites that have required billions of dollars to investigate and remediate, and which will require additional billions in order to complete the job. Federal and state law cases involving groundwater contamination cases have presented special challenges to litigants and the Courts. Determining the source of groundwater contamination is often a matter of technical dispute, particularly in the case of commingled plumes or older plumes where original point source locations can no longer be located or where there has been a significant amount of contaminant degradation over time. Contaminated plumes derived in whole or in part from potential continuing sources can present difficult remedy selection issues and uncertainty regarding future cost obligations. While a variety of federal and state law theories of liability are available to address groundwater contamination, each presents certain benefits and limitations. For example, CERCLA claims can cover a wide spectrum of potentially responsible parties and are based on strict liability; however, CERCLA excludes petroleum from the scope of its liability scheme and limits recovery to necessary response costs consistent with the National Contingency Plan. RCRA claims can include petroleum contamination, but cannot seek recovery of past costs. Common law theories such as nuisance, trespass and negligence can permit recovery of a broader scope of potential damages and provide for joint and several liability, but they are not based on notions of strict liability and sometimes present difficult statute of limitations problems. This article identifies federal and California state law liability theories addressing responsibility for groundwater contamination, and reviews the elements of liability, potential limitations on available relief, and recent case law developments under these theories.     

Vascular function and short-term exposure to fine particulate air pollution

Exposure to fine particulate air pollution has been implicated as a risk factor for cardiopulmonary disease and mortality. Proposed biological pathways imply that particle-induced pulmonary and systemic inflammation play a role in activating the vascular endothelium and altering vascular function. Potential effects of fine particulate pollution on vascular function are explored using controlled chamber exposure and uncontrolled ambient exposure. Research subjects included four panels with a total of 26 healthy nonsmoking young adults. On two study visits, at least 7 days apart, subjects spent 3 hr in a controlled-exposure chamber exposed to 150-200 microg/m3 of fine particles generated from coal or wood combustion and 3 hr in a clean room, with exposure and nonexposure periods alternated between visits. Baseline, postexposure, and post-clean room reactive hyperemia-peripheral arterial tonometry (RH-PAT) was conducted. A microvascular responsiveness index, defined as the log of the RH-PAT ratio, was calculated. There was no contemporaneous vascular response to the few hours of controlled exposure. Declines in vascular response were associated with elevated ambient exposures for the previous 2 days, especially for female subjects. Cumulative exposure to real-life fine particulate pollution may affect vascular function. More research is needed to determine the roles of age and gender, the effect of pollution sources, the importance of cumulative exposure over a few days versus a few hours, and the lag time between exposure and response.     

Change of stream network connectivity under polder-type flood control measure

Polder is usually used for flood control in the river delta area. With the rapid development of urbanization, the dikes or pumps cut the original stream network system, and the stream network connectivity (SNC) and the river system pattern have changed. The dikes or pumps generally force up the river's water level, and regional flood formation mechanisms and processes have changed. In order to quantitatively describe the characteristics of polder-type flood control measure (PFCM) and the change law of SNC, firstly, the streams inside polders were generalized as virtual streams, a hydrological-hydrodynamic model was constructed by connecting Hydrologic Engineering Center-Hydrologic Modeling System and MIKE11 model. Secondly, an SNC evaluation model was constructed based on flow resistance and hydrological process. Finally, the SNC under different scenarios was simulated and evaluated to reveal the influence of the PFCM on SNC. And the dominance analysis method obtained the main control factors of SNC changes. The results showed that the pumps as the main drainage facility under the PFCM, SNC after the opening of the pumps were increased by 0.060, 0.103, and 0.311 for 50%, 30%, and 3% frequency flood scales compared with the pumps closed, respectively. However, compared with the natural stream (without the PFCM), the SNC decreased by 0.391, 0.456, and 0.487, respectively, at the same time of the same flood scale. The PFCM negatively impacted the SNC, and the number of pumps was the main control factor of the SNC.     

Buyer–supplier alliances in the automobile industry: how exit‐voice strategies influence interpersonal relationships

Although automobile manufacturers emphasize that they are building more cooperative, long‐term relationships with their suppliers, we hypothesized and found that buyers are actually pursuing a dual strategy approach, in which they use threats on out‐group suppliers while providing help to in‐group members. Our hypotheses were based on the exit, voice, and loyalty typology, and on research from leader–member exchange theory. We also found that the macro‐level strategy set the context for the micro‐level interactions between buyers and suppliers. The degree to which the buyers and suppliers interacted in a friendly, informal manner depended more on the in‐ or out‐group status of the supplier firm than on the interaction style preferences of the suppliers. These findings are consistent with Mischel's ( 1977 ) theory that individual differences predict behavior under weak environmental conditions but not under strong environments. Compared to buyers, suppliers were more likely to prefer a friendly, informal interaction style. These findings were predicted based on the research on emotional display rules and emotional labor. Copyright © 2000 John Wiley & Sons, Ltd.     

Environmental VOSCs--formation and degradation of dimethyl sulfide, methanethiol and related materials

Volatile organic sulfur compounds (VOSCs) play a major role in the global sulfur cycle. Two components, dimethyl sulfide (DMS) and methanethiol (MT) are formed in large amounts by living systems (e.g. algae, bacteria, plants), particularly in marine environments. A major route to DMS is by action of a lyase enzyme on dimethylsulfoniopropionate (DMSP). DMSP has other roles, for instance as an osmoprotectant and cryoprotectant. Demethiolation of DMSP and other materials leads to MT. A major transport process is release of DMS from the oceans to the atmosphere. Oxidation of DMS in the atmosphere by hydroxyl and nitrate radicals produces many degradation products including CO2, COS, dimethyl sulfoxide, dimethyl sulfone, organic oxyacids of sulfur, and sulfate. These materials also have roles in biotic processes and there are complex metabolic interrelationships between some of them. This review emphasizes the chemical reactions of the organic sulfur cycle. For biotic reactions, details of relevant enzymes are provided when possible.