Chlorinated naphthalene formation from the oxidation of dichlorophenols

Polychlorinated naphthalenes (PCNs) formed along with dibenzo-p-dioxin and dibenzofuran products in the slow combustion of dichlorophenols (DCPs) at 600 degrees C were identified. Each DCP reactant produced a unique set of PCN products. Major PCN congeners observed in the experiments were consistent with products predicted from a mechanism involving an intermediate formed by ortho-ortho carbon coupling of phenoxy radicals; polychlorinated dibenzofurans (PCDFs) are formed from the same intermediate. Tautomerization of the intermediate and H2O elimination produces PCDFs; alternatively, CO elimination to form dihydrofulvalene and fusion produces naphthalenes. Only trace amounts of tetrachloronaphthalene congeners were formed, suggesting that the preferred PCN formation pathways from chlorinated phenols involve loss of chlorine. 3,4-DCP produced the largest yields of PCDF and PCN products with two or more chlorine substituents. 2,6-DCP did not produce tri- or tetra-chlorinated PCDF or PCN congeners. It did produce 1,8-DCN, however, which could not be explained.     

Low NOx,High Efficiency Multistaged Burner: Fuel Oil Results

A multistaged combustion burner designed for in-furnace NO_x control and high combustion efficiency is being evaluated for high nitrogen content fuel and waste incineration application in a 0.6 MW package boiler simulator. A low NO_x precombustion chamber burner has been reduced in size by approximately a factor of two (from 600 to 250 ms first-stage residence time) and coupled with (1) air staging, resulting in a three-stage configuration, and (2) natural gas fuel staging, yielding up to four stolchlometric zones. Natural gas, doped with ammonia to yield a 5.8 percent fuel nitrogen content, and distillate fuel oil, doped with pyridine to yield a 2 percent fuel nitrogen content, were used to simulate high nitrogen content fuel/waste mixtures. The multistaged burner reduced NO emissions by 85 percent from emission levels from a conventional unstaged burner mounted on a commercial package bollerTA minimum NO emission level of 110 ppm was achieved in the fuel oil tests, from a level of 765 ppm for conventional firing. This is compared with a 160 ppm minimum NO level achieved in gaseous fuel tests, from an uncontrolled level of 1000 ppm. Boiler fuel staging, or reburnlng, appears to be superior to air staging for high combustion efficiency due to its minimal fuel-rich core and second flame front in the boiler.     

Biogeochemical cycling constraints on stream ecosystem recovery

In systems where production is limited by the availability of a nutrient, nutrient input to and recycling within the system is related to the resilience, or speed of recovery, of a system to its steady state following a disturbance. In particular, it is shown that the return timeT _s of the system to steady state, or the inverse of the resilience, is approximately equal to the mean turnover time of the limiting nutrient in the system. From this relationship, it is possible to understand and predict how various properties of food webs and their environments affect resilience. These properties include nutrient input rate, loss rate, size of the detritus compartment, and trophic structure. The effects of these properties on resilience are described by using simple mathematical models. To test model predictions, experimental studies of the response of periphyton-dominated stream ecosystems to disturbance are being conducted on a set of laboratory streams in which nutrient inputs and grazing intensity are regulated at different levels. In streams without snail grazers (low-grazed streams), 90% recirculation of stream water to reduce nutrient inputs resulted in longer turnover times (T _r ) of phosphorus within the stream compared with once-through flow. However, in streams with snail grazers (high-grazed streams), there were no differences in phosphorus turnover time between once-through and partially recirculated treatments. Results on the rate of recovery of periphyton from a flood/scour disturbance to each stream partially support the model prediction of a positive relationship between ecosystem return time (T _s ) and nutrient turnover time (T _r ) within the streams.     

Upland disturbance affects headwater stream nutrients and suspended sediments during baseflow and stormflow

Because catchment characteristics determine sediment and nutrient inputs to streams, upland disturbance can affect stream chemistry. Catchments at the Fort Benning Military Installation (near Columbus, Georgia) experience a range of upland disturbance intensities due to spatial variability in the intensity of military training. We used this disturbance gradient to investigate the effects of upland soil and vegetation disturbance on stream chemistry. During baseflow, mean total suspended sediment (TSS) concentration and mean inorganic suspended sediment (ISS) concentration increased with catchment disturbance intensity (TSS: R2= 0.7, p = 0.005, range = 4.0-10.1 mg L(-1); ISS: R2= 0.71, p = 0.004, range = 2.04-7.3 mg L(-1)); dissolved organic carbon (DOC) concentration (R2= 0.79, p = 0.001, range = 1.5-4.1 mg L(-1)) and soluble reactive phosphorus (SRP) concentration (R2= 0.75, p = 0.008, range = 1.9-6.2 microg L(-1)) decreased with increasing disturbance intensity; and ammonia (NH4+), nitrate (NO3-), and dissolved inorganic nitrogen (DIN) concentrations were unrelated to disturbance intensity. The increase in TSS and ISS during storms was positively correlated with disturbance (R2= 0.78 and 0.78, p = 0.01 and 0.01, respectively); mean maximum change in SRP during storms increased with disturbance (r = 0.7, p = 0.04); and mean maximum change in NO3- during storms was marginally correlated with disturbance (r = 0.58, p = 0.06). Soil characteristics were significant predictors of baseflow DOC, SRP, and Ca2+, but were not correlated with suspended sediment fractions, any nitrogen species, or pH. Despite the largely intact riparian zones of these headwater streams, upland soil and vegetation disturbances had clear effects on stream chemistry during baseflow and stormflow conditions.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta—Seasonal variations at urban,suburban, and rural ambient air monitoring sites

Twenty-eight polycyclic aromatic hydrocarbons (PAH) and methylated PAHs (Me-PAH) were measured in daily PM_2.5 samples collected at an urban site, a suburban site, and a rural site in and near Atlanta during 2004 (5 samples/month/site). The suburban site, located near a major highway, had higher PM_2.5-bound PAH concentrations than did the urban site, and the rural site had the lowest PAH levels. Monthly variations are described for concentrations of total PAHs (∑PAHs) and individual PAHs. PAH concentrations were much higher in cold months than in warm months, with average monthly ∑PAH concentrations at the urban and suburban-highway monitoring sites ranging from 2.12 to 6.85 ng m^?3 during January–February and November–December 2004, compared to 0.38–0.98 ng m^?3 during May–September 2004. ∑PAH concentrations were found to be well correlated with PM_2.5 and organic carbon (OC) within seasons, and the fractions of PAHs in PM_2.5 and OC were higher in winter than in summer. Methyl phenanthrenes were present at higher levels than their un-substituted homologue (phenanthrene), suggesting a petrogenic (unburned petroleum products) input. Retene, a proposed tracer for biomass burning, peaked in March, the month with the highest acreage and frequency of prescribed burning and unplanned fires, and in December, during the high residential wood-burning season, indicating that retene might be a good marker for burning of all biomass materials. In contrast, potassium peaked only in December, indicating that it might be a more specific tracer for wood-burning.     

Spatial PM2.5 mobile source impacts using a calibrated indicator method

Motor vehicles are major sources of fine particulate matter (PM_2.5), and the PM_2.5 from mobile vehicles is associated with adverse health effects. Traditional methods for estimating source impacts that employ receptor models are limited by the availability of observational data. To better estimate temporally and spatially resolved mobile source impacts on PM_2.5, we developed an approach based on a method that uses elemental carbon (EC), carbon monoxide (CO), and nitrogen oxide (NO_x) measurements as an indicator of mobile source impacts. We extended the original integrated mobile source indicator (IMSI) method in three aspects. First, we generated spatially resolved indicators using 24-hr average concentrations of EC, CO, and NO_x estimated at 4 km resolution by applying a method developed to fuse chemical transport model (Community Multiscale Air Quality Model [CMAQ]) simulations and observations. Second, we used spatially resolved emissions instead of county-level emissions in the IMSI formulation. Third, we spatially calibrated the unitless indicators to annually-averaged mobile source impacts estimated by the receptor model Chemical Mass Balance (CMB). Daily total mobile source impacts on PM_2.5, as well as separate gasoline and diesel vehicle impacts, were estimated at 12 km resolution from 2002 to 2008 and 4 km resolution from 2008 to 2010 for Georgia. The total mobile and separate vehicle source impacts compared well with daily CMB results, with high temporal correlation (e.g., R ranges from 0.59 to 0.88 for total mobile sources with 4 km resolution at nine locations). The total mobile source impacts had higher correlation and lower error than the separate gasoline and diesel sources when compared with observation-based CMB estimates. Overall, the enhanced approach provides spatially resolved mobile source impacts that are similar to observation-based estimates and can be used to improve assessment of health effects.

Implications: An approach is developed based on an integrated mobile source indicator method to estimate spatiotemporal PM_2.5 mobile source impacts. The approach employs three air pollutant concentration fields that are readily simulated at 4 and 12 km resolutions, and is calibrated using PM_2.5 source apportionment modeling results to generate daily mobile source impacts in the state of Georgia. The estimated source impacts can be used in investigations of traffic pollution and health.     

Prediction of polychlorinated dibenzofuran congener distribution from gas-phase phenol condensation pathways

A model for predicting the distribution of dibenzofuran and polychlorinated dibenzofuran (PCDF) congeners from a distribution of phenols was developed. The model is based on a simplified chemical mechanism. Relative rate constants and reaction order with respect to phenol precursors were derived from experimental results using single phenols and equal molar mixtures of up to four phenols. For validation, experiments were performed at three temperatures using a distribution of phenol and 19 chlorinated phenols as measured in municipal waste incinerator exhaust gas. Comparison of experimental measurements and model predictions for PCDF isomer distributions and homologue pattern shows agreement within measurement uncertainty. The R-squared correlation coefficient exceeds 0.9 for all PCDF isomer distributions and the distribution of PCDF homologues. These results demonstrate that the distribution of dibenzofuran and the 135 PCDF congeners from gas-phase condensation of phenol and chlorinated phenols can be predicted from measurement of the distribution of phenol and the 19 chlorinated phenol congeners.     

Chlorination of dibenzofuran and dibenzo-p-dioxin vapor by copper (II) chloride

Dibenzofuran (DF) is formed from phenol and benzene in combustion gas exhaust streams prior to particle collection equipment. Subsequent chlorination at lower temperatures on particle surfaces is a potential source of chlorinated dibenzofuran (CDF). Gas streams containing 8% O₂ and approximately 0.1% DF vapor were passed through particle beds containing copper (II) chloride (0.5% Cu, mass) at temperatures ranging from 200 to 400 °C to investigate the potential for CDF formation during particle collection. Experiment duration was sufficient to provide an excess amount of DF (DF/Cu=3). The efficiency of DF chlorination by CuCl₂ and the distribution of CDF products were measured, with effects of temperature, gas velocity, and experiment duration assessed. Results of a more limited investigation of dibenzo-p-dioxin (DD) chlorination by CuCl₂ to form chlorinated DD (CDD) products are also presented.

The efficiency of DF/DD chlorination by CuCl₂ was high, both in terms of CuCl₂ utilization and DF/DD conversion. Total yields of Cl on CDF/CDD products of up to 0.5 mole Cl per mole CuCl₂ were observed between 200 and 300 °C; this suggests that nearly 100% CuCl₂ was utilized, assuming a conversion of two moles of CuCl₂ to CuCl per mole Cl added to DD/DF. In a short duration experiment (DF/Cu=0.3), nearly 100% DF adsorption and conversion to CDF was achieved. The degree of CDF chlorination was strongly dependent on gas velocity. At high gas velocity, corresponding to a gas–particle contact time of 0.3 s, mono-CDF (MCDF) yield was largest, with yields decreasing with increasing CDF chlorination. At low gas velocity, corresponding to a gas–particle contact time of 5 s, octa-CDF yield was largest. DF/DD chlorination was strongly favored at lateral sites, with the predominant CDF/CDD isomers within each homologue group those containing Cl substituents at only the 2,3,7,8 positions. At the higher temperatures and lower gas velocities studied, however, broader isomer distributions, particularly of the less CDD/CDF products, were observed, likely due to preferential destruction of the 2,3,7,8 congeners.     

Metal-mediated chlorinated dibenzo-p-dioxin (CDD) and dibenzofuran (CDF) formation from phenols

Heterogeneous formation of chlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs) on CuCl2 from three phenols without ortho chlorine and one phenol with two ortho chlorines was studied in a flow reactor over a temperature range of 325-450 degrees C. Heated nitrogen gas streams containing 8% oxygen, 1.5% benzene vapor, and equal amounts of phenol, 3-chlorophenol, 3,4-dichlorophenol and 2,4,6-trichlorophenol vapor (700 ppmv, each) were passed through a 1 g particle bed of silica and 0.5% (Cu mass) CuCl2. Maximum product yields of greater than 1.4% phenol conversion to CDD and 5.7% phenol conversion to CDF were observed between 400 and 450 degrees C. CDDs formed with loss of one chlorine atom were favored. While total CDD/F yield varied with temperature, CDD/F homologue and isomer distributions did not vary significantly with temperature. Based on the results of experiments with single phenol precursors, phenol precursors could be assigned to all PCDD/F products. Of the chlorinated phenols without ortho chlorine that were studied, 3,4-dichlorophenol was found to have the greatest propensity to form CDFs.     

Assessment of non-occupational exposure to polycyclic aromatic hydrocarbons through personal air sampling and urinary biomonitoring

Non-occupational inhalation and ingestion exposure to polycyclic aromatic hydrocarbons (PAHs) has been studied in 8 non-smoking volunteers through personal air sampling and urinary biomonitoring. The study period was divided into 4 segments (2 days/segment), including weekdays with regular commute and weekends with limited traffic related exposures; each segment had a high or low PAH diet. Personal air samples were collected continuously from the subjects while at home, at work, and while commuting to and from work. All urine excretions were collected as individual samples during the study. In personal air samples, 28 PAHs were measured, and in urine samples 9 mono-hydroxylated metabolites (OH-PAHs) from 4 parent PAHs (naphthalene, fluorene, phenanthrene and pyrene) were measured. Naphthalene was found at higher concentrations in air samples collected at the subjects' residences, whereas PAHs with four or more aromatic rings were found at higher levels in samples taken while commuting. Urinary OH-PAH biomarker levels increased following reported high inhalation and/or dietary exposure. On days with a low PAH diet, the total amount of inhaled naphthalene during each 24-hour period was well correlated with the amount of excreted naphthols, as was, to a lesser extent, fluorene with its urinary metabolites. During days with a high dietary intake, only naphthalene was significantly correlated with its excreted metabolite. These findings suggest that this group of non-occupational subjects were exposed to naphthalene primarily through indoor air inhalation, and exposed to other PAHs such as pyrene mainly through ingestion.