Monitoring of Fogwater Chemistry in the Gulf Coast Urban Industrial Corridor: Baton Rouge (Louisiana)

Seventeen fog events were sampled in Baton Rouge, Louisiana during 2002–2004 as part of characterizing wet deposition by fogwater in the heavily industrialized corridor along the Louisiana Gulf Coast in the United States. These samples were analyzed for chemical characteristics such as pH, conductivity, total organic and inorganic carbon, total metals and the principal ion concentrations. The dominant ionic species in all samples were NH₄⁺, NO₃⁻, Cl⁻ and SO₄²⁻. The pH of the fogwater sampled had a mean value of 6.7 with two cases of acidic pH of 4.7. Rainwater and fogwater pH were similar in this region. The acidity of fogwater was a result of NO₃⁻ but partly offset by high NH₄⁺. The measured gaseous SO₂ accounted for a small percentage of the observed sulfate concentration, indicating additional gas-to-particle conversion of SO₂ to sulfate in fogwater. The gaseous NO_x accounted for most of the dissolved nitrate and nitrite concentration in fogwater. The high chloride concentration was attributable to the degradation of chlorinated organics in the atmosphere. The metal composition was traced directly to soil-derived aerosol precursors in the air. The major metals observed in fogwater were Na, K, Ca, Fe, Al, Mg and Zn. Of these Na, K, Ca and Mg were predominant with mean concentrations > 100 μM. Al, Fe and Zn were present in the samples, at mean concentrations < 100 μM. Small concentrations of Mn (7.8 μM), Cu (2 μM), Pb (0.07 μM) and As (0.32 μM) were also observed in the fogwaters, and these were shown to result from particulates (PM_2.5) in the atmosphere. The contribution to both ions and metals from the marine sources in the Louisiana Gulf Coast was minimal. The concentrations of all principal ionic species and metals in fogwater were 1–2 orders of magnitude larger than in rainwater. Several linear alkane organic compounds were observed in the fogwater, representing the contributions from petroleum products at concentrations far exceeding their aqueous solubility. A pesticide (atrazine) was also observed in fogwater, representing the contribution from the agricultural activities nearby.     

Air emission flux from contaminated dredged materials stored in a pilot-scale confined disposal facility

A pilot-scale field simulation was conducted to estimate the air emissions from contaminated dredged material stored in a confined disposal facility (CDF). Contaminated dredged material with a variety of organic chemicals, obtained from Indiana Harbor Canal, was used in the study. It was placed in an outdoor CDF simulator (i.e., a lysimeter of dimensions 4 ft x 4 ft x 2 ft). A portable, dynamic flux chamber was used to periodically measure emissions of various polynuclear aromatic hydrocarbons (PAHs). A weather station was set up to monitor and record the meteorological conditions during the experiment. The fluxes of several PAHs were monitored over time for 6 1/2 months. Initial 6-hr average fluxes varied from 2 to 20 ng/cm2/hr for six different PAHs. The flux values declined rapidly for all compounds soon after placement of the dredged material in the CDE Chemical concentrations derived from flux values were generally of low magnitude compared with ambient standards. Data obtained from the experiment were compared against those predicted using models for air emissions. Model simulations showed that initially the flux was largely from exposed pore water from saturated (wet) sediment, whereas the long-term flux was controlled by diffusion through the pore air of the unsaturated sediment. Model predictions generally overestimated the measured emissions. A rainfall event was simulated, and the dredged material was reworked to simulate that typical of a CDF operation. Increased flux was observed upon reworking the dredged material.     

N-doped mesoporous alumina for adsorption of carbon dioxide

N-doped mesoporous alumina has been synthesized using chitosan as the biopolymer template. The adsorbent has been thoroughly investigated for the adsorption of CO₂ from a simulated flue gas stream (15% CO₂ balanced with N₂) and compared with commercially available mesoporous alumina procured from SASOL, Germany. CO₂ adsorption was studied under different conditions of pre-treatment and adsorption temperature, inlet CO₂ concentration and in the presence of oxygen and moisture. The adsorption capacity was determined to be 29.4 mg CO₂/g of adsorbent at 55℃. This value was observed to be 4 times higher in comparison to that of commercial mesoporous alumina at a temperature of 55℃. Basicity of alumina surface coupled with the presence of nitrogen in template in synthesized sample is responsible for this enhanced CO₂ adsorption. Adsorption capacity for CO₂ was retained in the presence of oxygen; however moisture had a deteriorating effect on the adsorption capacity reducing it to nearly half the value.     

Effects of combustion parameters on polychlorinated dibenzodioxin and dibenzofuran homologue profiles from municipal waste and coal co-combustion

Variation in polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran (PCDD and PCDF) homologue profiles from a pilot scale (0.6 MW_t, 2×10⁶ Btu/h), co-fired-fuel [densified refuse derived fuel (dRDF) and high-sulfur Illinois coal] combustion system was used to provide insights into effects of combustion parameters on PCDD and PCDF pollutant formation. A 24-run, statistically designed test matrix varied dRDF and/or coal firing rates (at a constant targeted energy release rate) along with a range of process variables including calcium hydroxide injection, hydrogen chloride (HCl) concentration, flue gas temperature, quench, and residence time such that the results would be relatable to a wide variety of combustion conditions. Statistical analysis of the molar homologue profiles enabled interpretation based on non-confounding variables. A multivariate, generalized additive model, based on transformations of the design variables, described 83% of the variation of the profiles characterized by log ratios of the homologue molar concentrations. This method identifies the operating parameters that are most significant in determining the PCDD/F homologue profiles. The model can be exercised to predict homologue profiles through input of these system-specific operating parameters. For example, both higher HCl and sulfur dioxide concentrations favor higher relative formation of the lower chlorinated PCDF homologues.     

Volatilization of contaminants from suspended sediment in a water column during dredging

Remedial dredging of contaminated bed sediments in rivers and lakes results in the suspension of sediment solids in the water column, which can potentially be a source for evaporation of hydrophobic organic compounds (HOCs) associated with the sediment solids. Laboratory experiments were conducted in an oscillating grid chamber to simulate the suspension of contaminated sediments and flux to air from the surface of the water column. A contaminated field sediment from Indiana Harbor Canal (IHC) and a laboratory-inoculated University Lake (UL) sediment, Baton Rouge, LA, were used in the experiments, where water and solids concentration and particle size distribution were measured in addition to contaminant fluxes to air. A transient model that takes into account contaminant desorption from sediment to water and evaporation from the water column was used to simulate water and sediment concentrations and air fluxes from the solids suspension. In experiments with both sediments, the total suspended solids (TSS) concentration and the average particle diameter of the suspended solids decreased with time. As expected, the evaporative losses were higher for compounds with higher vapor pressure and lower hydrophobicity. For the laboratory-inoculated sediment (UL), the water concentrations and air fluxes were high initially and decreased steadily implying that contaminant release to the water column from the suspended solids was rapid, followed by evaporative decay. For the field sediments (IHC), the fluxes and water concentrations increased initially and subsequently decreased steadily. This implied that the initial desorption to water was slow and that perhaps the presence of oil and grease and aging influenced the contaminant release. Comparison of the model and experimental data suggested that a realistic determination of the TSS concentration that can be input into the model was the most critical parameter for predicting air emission rates.     

Organic composition of fogwater in the Texas–Louisiana gulf coast corridor

Fogwater and air samples were collected in Baton Rouge between November 2004–February 2005 and during February 2006 at Houston. Organic compounds present in the fog samples were detected, quantified and then grouped into different compound classes based on molecular size, solubility and polarity using gas chromatography/mass spectrometry, high performance liquid chromatography with diode array detection and ion chromatography. Organic compounds were grouped as n-alkanes, aromatics and polycyclic aromatics, carbonyls, alcohols, amides and esters. Organic compounds in fog and air samples in Houston indicated clear urban/industrial anthropogenic origin, while compounds detected in Baton Rouge fog and air samples showed a mix of both agricultural and urban/industrial anthropogenic inputs. Among the various polycyclic aromatic compounds detected, the total concentration of naphthalene and its derivatives was 2.8 μg m^?3 in Houston and 0.08 μg m^?3 in Baton Rouge air. Analysis of concentrations of organic compounds pre- and post- fog revealed that compounds with low vapor pressure had higher scavenging efficiency in fog sampled at the two locations. Concentrations of organic compounds in fog samples were higher than those predicted by conventional air-water Henry's law equilibrium. Observed higher concentrations in the aqueous phase were modeled accounting for surface adsorption and accumulation of gas phase species and the presence of humic-like substances in fogwater.     

Persistence of Violation and Crash Behavior Over Time

This analysis examines the ability of previous offenses to predict future high-risk offenses, and similarly, the ability of crashes to predict future high-risk crashes, using the complete driver history data (up to 9 years) for a set of young Michigan subjects. As expected, those with previous ticketed offenses or reported crashes are at greater risk for future offenses or crashes; with a previous-year serious offense doubling the odds of serious offenses during the subsequent year, and a previous-year at-fault crash increasing the odds of subsequent-year at-fault crashes by nearly 50%. There is modest evidence that serious offenses and at-fault crashes may better predict subsequent behavior in females and in more experienced drivers. This latter finding is also evidenced by the fact that records of these young drivers are less predictive of subsequent driving history than is true for records of all drivers in general found in other studies. This suggests that, in the early stages of driving, offenses and crashes are, at least in part, attributable to inexperience, and hence, characteristic of all beginning drivers.