Metals emitted from heavy-duty diesel vehicles equipped with advanced PM and NOX emission controls

Emission factors for elemental metals were determined from several heavy-duty diesel vehicles (HDDV) of 1998–2007 vintage, operating with advanced PM and/or NO_X emissions control retrofits on a heavy-duty chassis dynamometer, under steady state cruise, transient, and idle conditions. The emission control retrofits included diesel particulate filters (DPF): catalyzed and uncatalyzed, passive and active prototype vanadium- or zeolite-based selective catalytic reduction (SCR) systems, and a catalyzed DPF fitted on a hybrid diesel electric drive vehicle. The prototype SCR systems in combination with DPF retrofits are of particular interest because they represent the expected emissions controls for compliance with PM and NO_X regulations in 2010. PM samples from a full-exhaust dilution tunnel were collected on bulk filters, and on a Personal Cascade Impactor Sampler (PCIS) for total and water-soluble elemental analysis. All the DPFs significantly reduced emissions of total trace elements (>85% and >95% for cruise and for the Urban Dynamometer Driving Schedule (UDDS), respectively). However, we observed differences in the post-retrofit metals emissions due to driving cycle effects (i.e., exhaust temperature) and type of retrofit. In general, the metals emissions over cruise conditions (which leads to higher exhaust temperatures) were substantially different from the emissions over a transient cycle or while idling. For instance, during cruise, we observed higher levels of platinum (1.1 ± 0.6–4.2 ± 3.6 ng km^?1) for most of the retrofit-equipped vehicle tests compared to the baseline configuration (0.3 ± 0.1 ng km^?1). The vanadium-based DPF + SCR vehicle during cruise operation exhibited emissions of vanadium (562 ± 265 ng km^?1) and titanium (5841 ± 3050 ng km^?1), suggesting the possible release of actual SCR wash-coat (V₂O₅/TiO₂) from the catalyst under the higher temperatures characteristic of cruise operation. The vanadium emissions exhibited a bi-modal mass size distribution, with modes at <0.25 μm and 1.0–2.5 μm size ranges for the vanadium-based SCR system. For the DPF + SCR systems, a greater fraction of the metal emissions from the zeolite-based system is water-soluble compared to emissions from the vanadium-based system.     

Transport and transformation of sulfadiazine in soil columns packed with a silty loam and a loamy sand

Concerning the transport of the veterinary antibiotic sulfadiazine (SDZ) little is known about its possible degradation during transport. Also its sorption behaviour is not yet completely understood. We investigated the transport of SDZ in soil columns with a special emphasis on the detection of transformation products in the outflow of the soil columns and on modelling of the concentration distribution in the soil columns afterwards. We used disturbed soil columns near saturation, packed with a loamy sand and a silty loam. SDZ was applied as a 0.57 mg L(-1) solution at a constant flow rate of 0.25 cm h(-1) for 68 h. Breakthrough curves (BTC) of SDZ and its transformation products 4-(2-iminopyrimidin-1(2H)-yl)aniline and 4-hydroxy-SDZ were measured for both soils. For the silty loam we additionally measured a BTC for an unknown transformation product which we only detected in the outflow samples of this soil. After the leaching experiments the (14)C-concentration was quantified in different layers of the soil columns. The transformation rates were low with mean SDZ mass fractions in the outflow samples of 95% for the loamy sand compared to 97% for the silty loam. The formation of 4-(2-iminopyrimidin-1(2H)-yl)aniline appears to be light dependent and did probably not occur in the soils, but afterwards. In the soil columns most of the (14)C was found near the soil surface. The BTCs in both soils were described well by a model with one reversible (kinetic) and one irreversible sorption site. Sorption kinetics played a more prominent role than sorption capacity. The prediction of the (14)C -concentration profiles was improved by applying two empirical models other than first order to predict irreversible sorption, but also these models were not able to describe the (14)C concentration profiles correctly. Irreversible sorption of sulfadiazine still is not well understood.     

A study of emissions from a Euro 4 light duty diesel vehicle with the European particulate measurement programme

The California Air Resources Board, CARB, has participated in a program to quantify particulate matter (PM) emissions with a European methodology, which is known as the Particulate Measurement Programme (PMP). The essence of the PMP methodology is that the diesel PM from a Euro 4 vehicle equipped with a Diesel Particulate Filter (DPF) consists primarily of solid particles with a size range greater than 23 nm. The PMP testing and the enhanced testing performed by CARB have enabled an increased understanding of both the progress that has been made in PM reduction, and the future remaining challenges for new and improved DPF-equipped diesel vehicles. A comparison of measured regulated emissions and solid particle number emissions with the results obtained by the PMP participating international laboratories was a success, and CARB’s measurements and standard deviations compared well with the other laboratories. Enhanced measurements of the influence of vehicle conditioning prior to testing on PM mass and solid particle number results were performed, and some significant influences were discovered. For example, the influence of vehicle preconditioning on particle number results was significant for both the European and USA test driving cycles. However, the trends for the cycles were opposite with one cycle showing an increase and the other cycle showing a decrease in particle number emissions. If solid particle size distribution and total particle numbers are to be used as proposed in PMP, then a greater understanding of the quality and errors associated with measurement technologies is advisable.In general, particle counting instruments gave results with similar trends, but cycle-to-cycle testing variation was observed. Continuous measurements of particle number concentrations during test cycles have given detailed insight into PM generation. At the present time there is significant variation in the capabilities of the particle counting instruments in terms of particle size and concentration.Current measurements show the existence of a large number of volatile and semi-volatile particles of yet-to-be-resolved chemical composition in diesel exhaust, especially during DPF regeneration, and these particles are not included in the PMP methodology because they are smaller than 20 nm. It will be very challenging to improve our understanding of this class of diesel particulate matter.     

Design And Performance Characteristics of High-Velocity,High-Efficiency Air Cleaning Precipitators

This paper presents an evaluation of four gaussian (GM, HIWAY, AIRPOL-4, CALINE-2), and three numerical (DANARD, MROAD 2, ROADS) models with the tracer gas data collected in the General Motors experiment. Various statistical techniques are employed to quantify the predictive capability of each of the above models. In general, the three numerical models performed rather poorly compared to the gaussian models. For this data set, the model with the best performance in accurately predicting the measured concentrations was the GM model followed in order by AIRPOL-4, HIWAY, CALINE-2, DANARD, MR0AD2, and ROADS. Although the GM model provides by far a better simulation than any of the models tested here, it is skewed toward underprediction. As a screening tool for regulatory purposes, however, HIWAY model would be useful since this model has the highest percentage in the category of overprediction if the concentration data in the range of 50th percentile through 100th percentile are included in the analysis. The present version of the HIWAY model for stable and parallel wind-road conditions warrants modifications to improve its predictive capability. Current studies indicate that the modified HIWAY model can be used with greater confidence by the regulatory agencies.     

The Validity of Several Plume Rise Formulas

The ground level concentration of pollutants downwind of a tall chimney decreases as the effective height of the stack increases. The effective height of the stack is the actual height plus the rise of the plume center-line due to momentum and buoyancy of the effluent. Over twenty formulas to predict plume rise from stack and meteorological parameters have been proposed; none is uniformly accepted. In this paper, 711 plume rise observations were used to test the ability of fifteen of the published and commonly used formulas to predict plume rise. The plume rise data were obtained from single stacks whose heat emission rate varied over four orders of magnitude. None of the formulas tested was found to be significantly better than the others. Research was performed under the auspices of the U.S. Atomic Energy Commission.     

Cost and Benefits of Road Dust Control in Seattle’s Industrial Valley

The paving of gravel roads with an average daily traffic (ADT) over 15 is a least cost method for reducing suspended particulate In the air in Seattle. It is also a good business investment when the ADT exceeds 100. Clean roads, gutters, and parking lots may reduce or eliminate Seattle’s most serious environmental constraint on economic development. In a study done in Seattle’s Duwamish Valley the impact of road dust on air quality was measured by obtaining dust emission factors for vehicles traveling at 10, 20, and 30 mph on gravel as well as dusty paved roads. A University of Washington Mark II Cascade Impactor was mounted on a trailer and towed behind a car to determine the concentration and size distribution of this dust. It was found that each vehicle mile at 20 mph on unpaved roads contributed 7.0 Ib of dust to the air, 1.9 Ib consisting of particles smaller than 10 microns in diameter and 0.24 Ib below 2 microns. Three to eight percent by weight of this respirable dust was free silica, which is potentially toxic. The quantity of dust generated varies as an exponent of the speed. The concentrations of dust found in the air near a dry gravel road with an ADT of 250 reached 584 μg/m3 for an 8 hr work day. A 24 hr suspended particulate reading of 463 μg/m3 total and 3.83 μg/m3 free silica was found beside a dusty paved road with an ADT of 18,000. Nineteen miles of gravel roads and 110 miles of dusty paved roads contributed 2700 tons/year of particulate, of which 700 tons were below 10 microns. Paving or oiling such roads will produce benefits of $3,881,000 yearly in household cleaning, health care, sewer, vehicle operation, and road maintenance costs as well as an increase in property values. Clean roads can lower the cost of clean air in Seattle.     

Characterization of air manganese exposure estimates for residents in two Ohio towns

This study was conducted to derive receptor-specific outdoor exposure concentrations of total suspended particulate (TSP) and respirable (d_ae ≤ 10 µm) air manganese (air-Mn) for East Liverpool and Marietta (Ohio) in the absence of facility emissions data, but where long-term air measurements were available. Our “site-surface area emissions method” used U.S. Environmental Protection Agency’s (EPA) AERMOD (AMS/EPA Regulatory Model) dispersion model and air measurement data to estimate concentrations for residential receptor sites in the two communities. Modeled concentrations were used to create ratios between receptor points and calibrated using measured data from local air monitoring stations. Estimated outdoor air-Mn concentrations were derived for individual study subjects in both towns. The mean estimated long-term air-Mn exposure levels for total suspended particulate were 0.35 μg/m³ (geometric mean [GM]) and 0.88 μg/m³ (arithmetic mean [AM]) in East Liverpool (range: 0.014–6.32 μg/m³) and 0.17 μg/m³ (GM) and 0.21 μg/m³ (AM) in Marietta (range: 0.03–1.61 μg/m³). Modeled results compared well with averaged ambient air measurements from local air monitoring stations. Exposure to respirable Mn particulate matter (PM₁₀; PM <10 μm) was higher in Marietta residents.

Implications: Few available studies evaluate long-term health outcomes from inhalational manganese (Mn) exposure in residential populations, due in part to challenges in measuring individual exposures. Local long-term air measurements provide the means to calibrate models used in estimating long-term exposures. Furthermore, this combination of modeling and ambient air sampling can be used to derive receptor-specific exposure estimates even in the absence of source emissions data for use in human health outcome studies.     

Identifying potential receptors and routes of contaminant exposure in the traditional territory of the Ouje-Bougoumou Cree: Land use and a geographical information system

Great concern has been raised with respect to the 13 traplines that constitute the traditional territory of the Ouje-Bougoumou Cree located in the James Bay region of northern Quebec, Canada, with respect to mine wastes originating from three local mines. As a result, an “Integrative Risk Assessment” was initiated consisting of three interrelated components: a comprehensive human health study, an assessment of the existing ecological/environmental database, and a land use/potential sites of concern study. In this paper, we document past and present land use in the traditional territory of the Ouje-Bougoumou Cree for 72 heads of households, including 13 tallymen, and use a Geographic Information System (GIS) to layer harvest/hunting and gathering/collecting data over known mining areas and potential sites of concern. In this way, potential receptors of contamination and routes of human exposure were identified. Areas of overlap with respect to land use activity and mining operations were relatively extensive for certain harvesting activities (e.g., beaver, Castor canadensis and various species of game birds), less so for fish harvesting (all species) and water collection, and relatively restrictive for large mammal harvesting and collection of firewood (and other collection activities). Potential receptors of contaminants associated with mining activity (e.g., fish and small mammals) and potential routes of exposure (e.g., ingestion of contaminated game and drinking of contaminated water) were identified.     

Temporal trends (1990-2000) in the concentration of cadmium, lead and mercury in mosses across Europe

The European heavy metals in mosses survey provides data on the concentration of 10 heavy metals in naturally growing mosses. The survey has been repeated at five-yearly intervals and in this paper we report on the temporal trends in the concentration of cadmium, lead and mercury between 1990 and 2000. Metal- and country-specific temporal trends were observed. In general, the concentration of lead and cadmium in mosses decreased between 1990 and 2000; the decline was higher for lead than cadmium. For mercury not enough data were available to establish temporal trends between 1990 and 1995, but between 1995 and 2000 the mercury concentration in mosses did not change across Europe. The observed temporal trends for the concentrations in mosses were similar to the trends reported for the modelled total deposition of cadmium, lead and mercury in Europe.     

The Role of Periphyton in Mediating the Effects of Pollution in a Stream Ecosystem

The effects of pollutants on primary producers ramify through ecosystems because primary producers provide food and structure for higher trophic levels and they mediate the biogeochemical cycling of nutrients and contaminants. Periphyton (attached algae) were studied as part of a long-term biological monitoring program designed to guide remediation efforts by the Department of Energy’s Y-12 National Security Complex on East Fork Poplar Creek (EFPC) in Oak Ridge, Tennessee. High concentrations of nutrients entering EFPC were responsible for elevated periphyton production and placed the stream in a state of eutrophy. High rates of primary production at upstream locations in EFPC were associated with alterations in both invertebrate and fish communities. Grazers represented >50% of the biomass of invertebrates and fish near the Y-12 Complex but <10% at downstream and reference sites. An index of epilithic periphyton production accounted for 95% of the site-to-site variation in biomass of grazing fish. Analyses of heavy metals in EFPC periphyton showed that concentrations of zinc, cadmium, copper and nickel in periphyton decreased exponentially with distance downstream from Y-12. Zinc uptake by periphyton was estimated to reduce the concentration of this metal in stream water ~60% over a 5-km reach of EFPC. Management options for mitigating eutrophy in EFPC include additional reductions in nutrient inputs and/or allowing streamside trees to grow and shade the stream. However, reducing periphyton growth may lead to greater downstream transport of contaminants while simultaneously causing higher concentrations of mercury and PCBs in fish at upstream sites.