Spatial Variation in Acidic Sulfate and Ammonia Concentrations within Metropolitan Philadelphia

Abstract

Acidic sulfate concentrations were measured in metropolitan Philadelphia during the summers of 1992 and 1993, as part of a continuing effort to characterize particle concentrations in urban environments. Sampling was performed simultaneously at eight sites located within and around metropolitan Philadelphia. Sites were selected based on their population density and on their distance and direction from the city center. Air pollution sampling was conducted every other day during the summer of 1992 and every day during the summer of 1993. All samples were collected for 24-h periods beginning at 9 a.m. (EDT). All acidic sulfate and ammonia samples were collected using modified Harvard-EPA Annular Denuder Systems (HEADS).

In this paper, we examine the spatial variation in acidic sulfate and ammonia concentrations within the metropolitan Philadelphia area. We also identify factors that may influence their variation and develop models to predict their concentrations. Outdoor sulfate (SO₄ ^2?) concentrations were uniform within metropolitan Philadelphia; however, aerosol strong acidity (H⁺) concentrations varied spatially. This variation generally was independent of wind direction, but was related to local factors, such as the NH₃ concentration, population density, and distance from the center of the city. Physico-chemical models, which were developed using data collected during the summer of 1992, were excellent predictors of 24-h and mean summertime H⁺ concentrations measured during the summer of 1993. Models accounted for 78% of the variation in 24-h H⁺ levels. Results suggest that a single stationary ambient (SAM) monitor would be sufficient to estimate SO₄ ^2? exposures for populations living in Philadelphia. For H⁺, however, multiple monitoring sites or models should be used to determine the outdoor H+ exposures of populations living in urban environments, although a single SAM site may provide an excellent index of H⁺ variation over time.     

Flow Injection Analysis of MWC Fly Ash Leaching Characteristics

Abstract

A completely mixed batch reactor leaching method utilizing flow injection analysis (the CMBR-FIA method) was developed to study the lead leaching characteristics of municipal waste combustor fly ash. Flow injection analysis (FIA) coupled with atomic absorption spectrophotometry enabled the determination of lead concentrations at one minute intervals. The pH and oxidation-reduction potential of the solution were continuously monitored to characterize the leaching conditions. Automatic titration was used to alter the solution pH to defined endpoints. The CMBR-FIA method offers the ability to immediately observe alterations to the leaching solution, and grants the freedom to study a number of parameters concurrently. The CMBR-FIA method is a rapid and reliable means to investigate leaching characteristics. This paper describes the method and demonstrates its use to monitor the leaching of lead from municipal solid waste combustor fly ash as a function of pH. Soluble lead concentrations are shown to increase quickly with decreasing pH.

A maximum of 50% of the total lead concentration was available in solution at pH 2. This value gradually decreased with time to over 35% of the total.     

Receptor Model Evaluation of the Southeast Michigan Ozone Study Ambient NMOC Measurements

Abstract

Large-scale studies like the Southeast Michigan Ozone Study (SEMOS) have focused attention on quantifying and spedating inventories for volatile organic compounds (VOCs). One approach for evaluating the accuracy of a VOC emission inventory is the development of a chemical mass balance (CMB) receptor model for ambient non-methane organic compound (NMOC) measurements. CMB evaluations of ambient hydrocarbon data provide a sample-specific allocation of emissions to individual source categories. This study summarizes the results of an application of the CMB model to the NMOC data from the SEMOS study. Comparison of CMB results with emission inventory values for the Detroit area show that vehicle emissions are well represented by the inventory, as are architectural coatings and coke ovens. Estimated emissions from petroleum refineries and graphic arts industries are much lower in the inventory than determined from the receptor allocation. Under-reporting of fugitive VOC emissions from petroleum refineries is an ongoing problem. Emissions from graphic arts industries are underestimated in the inventory partly because of the broad characterization of the emission factor (i.e., mass emitted/capita), which may be less useful when specific locations and days are under consideration. This study also demonstrates the effectiveness of the CMB approach when used prospectively to track the implementation of emission control strategies. While vehicle emission concentrations were unchanged from 1988 to 1993, measurement-based CMB results suggest a decrease in evaporative emissions during this time period resulting from Reid vapor pressure (RVP) reductions (from 11.0 psi in 1988 to 8.6 psi in 1993) and fleet turnover. Changes in emissions from coke plants and petroleum refineries were also seen in the CMB allocations for these sources.     

Method Comparisons for Particulate Nitrate,Elemental Carbon,and PM2.5 Mass in Seven U.S. Cities

ABSTRACT

Methods that measure PM₂₅ mass, total particulate NO₃ ^-, and elemental carbon (EC) were evaluated in seven U.S. cities from 1997 to 1999. Sampling was performed in Bakersfield, CA; Boston, MA; Chicago, IL; Dallas, TX; Philadelphia, PA; Phoenix, AZ; and Riverside, CA. Evaluating and validating methods that measure the components of fine mass are important to the effort of establishing a speciation-monitoring network. The Harvard Impactor (HI), which measures fine particle mass, showed excellent agreement (r² = 0.99) with the PM₂₅ Federal Reference Method (FRM) for 81 24-hr samples in Riverside and Bakersfield. The HI also showed good precision (4.8%) for 243 24-hr collocated samples over eight studies.

The Aethalometer was employed in six of the sampling locations to measure black carbon (BC). These values were compared to EC as measured from a quartz filter using thermal analysis. For the six cities combined, the two methods were highly correlated (r² = 0.94; 187 24-hr samples); however, the BC values were approximately 24% less than the EC measurements consistently across all six cites. This compares well to results observed for EC/BC measurements observed in other semi-urban areas. Par-ticulate NO₃ ^- was measured using the Harvard-EPA Annular Denuder System (HEADS). This was compared to the NO₃ ^- measured from the HI Teflon (DuPont) filter to assess NO₃ ^- artifacts. Significant NO₃ ^- losses (approximately 50% of total NO₃ ^-) were found in Riverside, Philadelphia, and Boston, while minimal artifacts were observed in the other sites. Two types of HEADS configurations were employed in five cities. One system used a Na₂CO₃-coated glass fiber filter, and the other type used a nylon filter to collect volatilized NO₃ ^- from the Teflon filter. The HEADS with the Na₂CO₃-coated filter consistently underestimated the total particulate NO₃ ^- by approximately 20% compared to the nylon HEADS.     

Contrasting structure and composition of the understory in species-rich tropical rain forests

In large samples of trees > or = 1 cm dbh (more than 1 million trees and 3000 species), in six lowland tropical forests on three continents, we assigned species with >30 individuals to one of six classes of stature at maturity (SAM). We then compared the proportional representation of understory trees (1-2 cm dbh) among these classes. The understory of the three Asian sites was predominantly composed of the saplings of large-canopy trees whereas the African and American sites were more richly stocked with trees of the smaller SAM classes. Differences in class representation were related to taxonomic families that were present exclusively in one continent or another. Families found in the Asian plots but not in the American plot (e.g., Dipterocarpaceae, Fagaceae) were predominantly species of the largest SAM classes, whereas families exclusive to the American plots (e.g., Melastomataceae sensu stricto, Piperaceae, and Malvaceae [Bombacacoidea]) were predominantly species of small classes. The African plot was similar to Asia in the absence of those American families rich in understory species, while similar to America in lacking the Asian families rich in canopy species. The numerous understory species of Africa were chiefly derived from families shared with Asia and/or America. The ratio of saplings (1-2 cm dbh) to conspecific canopy trees (>40 cm dbh) was lower in American plots than in the Asian plots. Possible explanations for these differences include phenology, moisture and soil fertility regimes, phyletic constraints, and the role of early successional plants in forest development. These results demonstrate that tropical forests that appear similar in tree number, basal area, and the family taxonomy of canopy trees nonetheless differ in ecological structure in ways that may impact the ecology of pollinators, dispersers, and herbivores and might reflect fundamental differences in canopy tree regeneration.     

Comparative biometry of Eunicella singularis (Gorgonian) sclerites at East Mediterranean Sea (North Aegean Sea, Greece)

The two forms of Eunicella singularis sclerites, spindles and clubs, were examined in two sites in East Mediterranean Sea, Greece. The comparison of the sclerites size was based on the hydrodynamic profile of the sites (the site of Arethoussa was exposed and the Phidonissi site was sheltered), on the sites bathymetry (AR 5–8 m, AR 9–13 m, PH 5–10 m, PH 11–13 m) and on the position occupied by the sclerites on the gorgonian colonies (top, middle and base). With the usage of image system analysis the following microfeatures were measured or calculated: projection, length, width, elongation factor, compactness factor, length × width and length/width. The present study confirms the hypothesis that spindles are involved in the recovering of the gorgonian colonies and clubs contribute to the flexion capacity of the colonies. The spindles of the shallow E. singularis colonies (AR 5–8 m) were significantly bigger (length, width) compared with the others, in order to assure the best recovery of the colonies after their flexion, induced by higher water current velocity in shallow water. The clubs occupy the intern part of the mesoglea and their size (length, width) increased in colonies from the shallow exposed site in order to facilitate the gorgonian flexion. The present study demonstrates the gorgonian adaptation (in a microscopic scale) to the environmental pressure of hydrodynamic conditions.     

Very low versus undetectable maternal serum alpha-fetoprotein values and fetal death

Very low maternal serum alpha-fetoprotein (MSAFP) levels (<10 ng/mL) are known to be associated with non-viable pregnancies, including conditions such as fetal death, molar pregnancies, and non-pregnancies. There has not been agreement, however, as to whether very low MSAFP levels indicate already existing fetal deaths or are actually predictive. We analysed 230 pregnancies with MSAFP levels <10 ng/mL from among 15 807 women (1.5 per cent) screened consecutively during a three-year period and identified 26 non-viable pregnancies, 22 of which were diagnosed sonographically as part of the screening process (17 missed abortions, 3 blighted ova, 2 non-pregnancies). Furthermore, 20 of these 22 pregnancies were associated with essentially undetectable MSAFP levels (<5 ng/mL). Our data indicate that pregnancies with MSAFP values <5 ng/mL are the group most strongly associated with fetal non-viability and that very low MSAFP values are not strongly predictive for fetal death.     

Terrain Discontinuity Effects in the Regional Flow of a Complex Karstified Aquifer

Karst aquifers are characterized by spatial heterogeneity due to the presence of highly permeable channels and conduits in low-permeable fractured rocks (matrix block). Recent studies have reported a close relationship between surface and subsurface water in karstic regions due to the water flow through a complicated network of paths formed by fracture intersections. Subsurface flow in karstified aquifers ranges between conduit flow, in large passages with relatively high flow velocities, and diffuse flow, in the matrix block where Darcy’s law is still valid. In this paper, we present the simulation of a complex karstified aquifer system in Crete, Greece, where the presence of main faults drastically affects the regional flow. A discrete fracture approach in conjunction with an equivalent porous medium approach was adopted to simulate the mixed flow in the area of interest. The simulation results have shown that the length and the orientation of the dominant faults, primarily during the rainy season, affect the flow field.     

Emissions of SO2, NO x and particulates from a pipe manufacturing plant and prediction of impact on air quality

Integrated pipe manufacturing industry is operation intensive and has significant air pollution potential especially when it is equipped with a captive power production facility. Emissions of SO₂, NO _x , and particulate matter (PM) were estimated from the stationary sources in a state-of-the-art pipe manufacturing plant in India. Major air polluting units like blast furnace, ductile iron spun pipe facility, and captive power production facility were selected for stack gas monitoring. Subsequently, ambient air quality modeling was undertaken to predict ground-level concentrations of the selected air pollutants using Industrial Source Complex (ISC 3) model. Emissions of SO₂, NO _x , and particulate matter from the stationary sources in selected facilities ranged from 0.02 to 16.5, 0.03 to 93.3, and 0.09 to 48.3 kg h^???1, respectively. Concentration of SO₂ and NO _x in stack gas of 1,180-kVA (1 KW = 1.25 kVA) diesel generator exceeded the upper safe limits prescribed by the State Pollution Control Board, while concentrations of the same from all other units were within the prescribed limits. Particulate emission was highest from the barrel grinding operation, where grinding of the manufactured pipes is undertaken for giving the final shape. Particulate emission was also high from dedusting operation where coal dust is handled. Air quality modeling indicated that maximum possible ground-level concentration of PM, SO₂, and NO _x were to the tune of 13, 3, and 18 μg/m³, respectively, which are within the prescribed limits for ambient air given by the Central Pollution Control Board.