Bioremediation of chlorinated pesticide–contaminated soil using anaerobic sludges and surfactant addition

Methanogenic granular sludge and wastewater fermented sludge were used as inocula for batch tests of anaerobic bioremediation of chlorinated pesticide contaminated soil. Results obtained for both types of biomass were similar: 80 to over 90% of γ -hexachlorocyclohexane (γ-HCH), 1,1,1-trichloro-2,2-bis-(4-methoxyphenyl)ethane (methoxychlor) and 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane (DDT) removed in 4–6 weeks. Residual fractions of these pesticides persisted till the end of the 16-week experiment. DDT was degraded through 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethane (DDD). Accumulation of this product corresponded stoichiometrically only to 34–53% of removed DDT, supposedly due to its further transformations, finally resulting in formation of detected 4,4′-dichlorobenzophenone (DBP). Addition of 0.5 mM Tween 80 nonionic surfactant resulted in about a twofold decrease of γ -HCH and methoxychlor residual concentrations, as well as considerably lower DDD accumulation (7–29%) and higher DBP production. However, 1.25 mM dose of this surfactant applied together with granular sludge brought DDD levels back to that observed for treatments with the sludge alone, also impairing DBP formation.     

Improved xenobiotic-degrading activity of Rhodococcus opacus strain 1cp after dormancy

The goals of the present work were as follows: to obtain the dormant forms of R. opacus 1cp; to study the phenotypic variability during their germination; to compare phenotypic variants during the growth on selective and elective media; and to reveal changes in the ability of the strain to destruct xenobiotics that had not been degradable before dormancy. It was shown that Rhodococcus opacus 1cp (the strain degrading chlorinated phenols) became able to utilize a broader spectrum of xenobiotics after storage in the dormant state. Germination of the dormant forms of R. opacus 1cp on an agarized medium was followed by emergence and development of phenotypic variants that could grow on 4-chlorophenol and 2,4,6-trichlorophenol without adaptation. The cells of R. opacus 1cp phenotypic variants also utilized all of the tested chlorinated phenols: 2,3-, 2,5-, and 2,6-dichloro-, 2,3,4- and 2,4,5-trichloro-, pentachlorophenol, and 1,2,4,5-tetrachlorobenzene in concentrations up to 60 mg/L, though at the lower rates than 4-CP and 2,4,6-TCP. The improved degradation of chlorinated phenols by R. opacus strain 1cp exposed to the growth arrest conditions demonstrates the significance of dormancy for further manifestation of the adaptive potential of populations. A new principle of selection of variants with improved biodegradative properties was proposed. It embraces introduction of the dormancy stage into the cell life cycle with subsequent direct inoculation of morphologically different colonies into the media with different toxicants, including those previously not degraded by the strain.     

Estimating the concentration of indoor particles of outdoor origin: A review

Recent toxicological results highlight the importance of separating exposure to indoor- and outdoor-generated particles, due to their different physicochemical and toxicological properties. In this framework, a number of studies have attempted to estimate the relative contribution of particles of indoor and outdoor origins to indoor concentrations, using either statistical analysis of indoor and outdoor concentration time-series or mass balance equations. The aim of this work is to review and compare the methodologies developed in order to determine the ambient particle infiltration factor (F _INF) (i.e., the fraction of ambient particles that enter indoors and remains suspended). The different approaches are grouped into four categories according to their methodological principles: (1) steady-state assumption using the steady-state form of the mass balance equation; (2) dynamic solution of the mass balance equation using complex statistical techniques; (3) experimental studies using conditions that simplify model calculations (e.g., decreasing the number of unknowns); and (4) infiltration surrogates using a particulate matter (PM) constituent with no indoor sources to act as surrogate of indoor PM of outdoor origin. Examination of the various methodologies and results reveals that estimating infiltration parameters is still challenging. The main difficulty lies in the separate calculation of penetration efficiency (P) and deposition rate (k). The values for these two parameters that are reported in the literature vary significantly. Deposition rate presents the widest range of values, both between studies and size fractions. Penetration efficiency seems to be more accurately calculated through the application of dynamic models. Overall, estimates of the infiltration factor generated using dynamic models and infiltration surrogates show good agreement. This is a strong argument in favor of the latter methodology, which is simple and easy to apply when chemical speciation data are available.

Implications: ?Taking into account that increased health risks may be related with ambient particles, a reliable estimation of the main parameters governing ambient particle infiltration indoors may assist towards the development of appropriate regulation and control measures, targeted to specific sources/factors contributing to increased exposures. The overall study of the methodological approaches estimating particle infiltration indoors suggests that dynamic models provide a more complete and realistic picture of ambient particle infiltration indoors, whereas the use of specific PM constituents to act as surrogates of indoor particles of outdoor origin seems also a promising new methodology.     

Effects of pen bedding and feeding high crude protein diets on manure composition and greenhouse gas emissions from a feedlot pen surface

Greenhouse gas (GHG) emissions from concentrated animal feeding operations vary by stage of production and management practices. The objective of this research was to study the effect of two dietary crude protein levels (12 and 16%) fed to beef steers in pens with or without corn stover bedding. Manure characteristics and GHG emissions were measured from feedlot pen surfaces. Sixteen equal-sized feedlot pens (19?×?23 m) were used. Eight were bedded approximately twice a week with corn stover and the remaining eight feedlot pens were not bedded. Angus steers (n = 138) were blocked by live weights (lighter and heavier) with 7 to 10 animals per pen. The trial was a 2?×?2 factorial design with factors of two protein levels and two bedding types (bedding vs. non bedding), with four replicates. The study was conducted from June through September and consisted of four ?28-day periods. Manure from each pen was scrapped once every 28 days and composite manure samples from each pen were collected. Air samples from pen surfaces were sampled in Tedlar bags using a Vac-U-Chamber coupled with a portable wind tunnel and analyzed with a greenhouse gas gas chromatograph within 24 hr of sampling. The manure samples were analyzed for crude protein (CP), total nitrogen (TN), ammonia (NH₃), total volatile fatty acid (TVFA), total carbon (TC), total phosphorus (TP), and potassium (K). The air samples were analyzed for methane (CH₄), carbon dioxide (CO₂), and nitrous oxide (N₂O) concentrations. The concentration of TN was significantly higher (p < 0.05) in manure from pens with cattle fed the high protein diets. The volatile fatty acids (VFAs) such as acetic, propionic, isobutyric, butyric, isovaleric, and valeric acids concentrations were similar across both treatments. There were no significant differences in pen surface GHG emissions across manure management and dietary crude protein levels.

Implications: Livestock manure produces odor and emits GHGs (CO₂, CH₄, and N₂O) at different stages of production and management practices that have significant environmental concerns. Thus, it is important to measure GHG contributions from different sources and develop appropriate mitigation strategies for minimizing GHG contribution from livestock production facilities. Two dietary protein levels (12 and 16%) fed to beef steers in pens with or without corn stover bedding were studied. The results indicated that dietary protein levels and bedding vs. no bedding had very little effect on GHG emissions and manure composition under open feedlot conditions in North Dakota climatic conditions and management practices.     

A Monte-Carlo Simulation of the Ozone Attainment Process

A Monte-Carlo simulation of the approach to attainment of the National Ambient Air Quality Standard for ozone has been performed for the California Bay Area Air Quality Management District. Four compliance tests together with different design values are used in the simulation. The results show that the present compliance test requiring a zero-percent chance of violation and the design value represented by the fourth highest value in three years makes both the standard and the control requirement much more stringent than generally assumed. In fact, to attain the standard on a long-term basis would require annual means and annual second-highest values that are close to those of the rural background ozone. The simulation also shows that by taking into account the fluctuation of ozone concentrations in the compliance test, such as a t test, and by using a design value consistent with the test, a standard defined in terms of the three-year mean of the annual second-highest values not only is more consistent with the currently- perceived stringency of the present standard, but may also be attainable with a more reasonable control requirement.     

Chemical Dynamics of Clouds at Mt. Mitchell,North Carolina

The role of clouds as the primary pathway for deposition of air pollutants into ecosystems has recently acquired much attention. Moreover, the acidity of clouds is highly variable over short periods of time. Cloud water collections were made at Mt. Mitchell State Park, North Carolina, using a real-time cloud and rain acidity/ conductivity (CRAC) analyzer during May to September 1987, 1988 and 1989 in an effort to explore extremes of chemical exposure. On the average, the mountain peak was exposed to cloud episodes about 70 percent of experimental days. The lowest pH of cloud water in nearly real-time (～10 min.) samples was 2.4, while that in hourly integrated samples was 2.6. The cloud pH during short cloud events (mean pH 3.1), whjch results from the orographic lifting mechanism, was lower than that during long cloud events (mean pH 3.5), which are associated with mesoscale or synoptic atmospheric disturbances. On the average, the pH values in nonprecipitating cloud events were about 0.4 pH unit lower than those in precipitating cloud events. Sulfate, nitrate, ammonium and hydrogen ions were found to be the major constituents of cloud water, and these accounted for -90 percent of the ionic concentration. Total ionic concentrations were found to be much higher in non-precipitating clouds (670-3,010 μeq/L) than those in precipitating clouds (220-370 μeq/L). At low acidity, ionic balance is sometimes not obtained. It is suggested that organic acids may provide this balance.

The profile of cloud water ionic concentration versus time was frequently observed to show decrease at the beginning and rising toward the end during short cloud events. Before the dissipation of clouds, a decrease in cloud water pH and an increase in ionic concentration were found. At the same time, temperature and solar radiation increased, and relative humidity and microphysical parameters (liquid water content, average droplet size, and droplet concentration) decreased. These observations suggest that evaporative dissipation of cloud droplets leads to acidification of cloud water. Mean pH of cloud water was 3.4 when the prevailing wind was from the northwest direction, and it was 3.9 when the wind was from the west direction. The effects of variations in cloud liquid water content have been separated from variations in pre-cloud pollutant concentrations to determine the relationship between source intensity and cloud water concentrations.     

Validation of Three New Methods for Determination of Metal Emissions Using a Modified Environmental Protection Agency Method 301

Abstract

Three new methods applicable to the determination of hazardous metal concentrations in stationary source emissions were developed and evaluated for use in U.S. Environmental Protection Agency (EPA) compliance applications. Two of the three independent methods, a continuous emissions monitor-based method (Xact) and an X-ray-based filter method (XFM), are used to measure metal emissions. The third method involves a quantitative aerosol generator (QAG), which produces a reference aerosol used to evaluate the measurement methods. A modification of EPA Method 301 was used to validate the three methods for As, Cd, Cr, Pb, and Hg, representing three hazardous waste combustor Maximum Achievable Control Technology (MACT) metal categories (low volatile, semivolatile, and volatile). The modified procedure tested the methods using more stringent criteria than EPA Method 301; these criteria included accuracy, precision, and linearity. The aerosol generation method was evaluated in the laboratory by comparing actual with theoretical aerosol concentrations. The measurement methods were evaluated at a hazardous waste combustor (HWC) by comparing measured with reference aerosol concentrations. The QAG, Xact, and XFM met the modified Method 301 validation criteria. All three of the methods demonstrated precisions and accuracies on the order of 5%. In addition, correlation coefficients for each method were on the order of 0.99, confirming the methods’ linear response and high precision over a wide range of concentrations. The measurement methods should be applicable to emissions from a wide range of sources, and the reference aerosol generator should be applicable to additional analytes. EPA recently approved an alternative monitoring petition for an HWC at Eli Lilly’s Tippecanoe site in Lafayette, IN, in which the Xact is used for demonstrating compliance with the HWC MACT metal emissions (low volatile, semivolatile, and volatile). The QAG reference aerosol generator was approved as a method for providing a quantitative reference aerosol, which is required for certification and continuing quality assurance of the Xact.     

Near-source air quality impacts of large olefin flares

Large petrochemical flares, common in the Houston Ship Channel (the Ship Channel) and other industrialized areas in the Gulf of Mexico region, emit hundreds to thousands of pounds per hour of highly reactive volatile organic compounds (HRVOCs). We employed fine horizontal resolution (200 m?×?200 m) in a three-dimensional (3D) Eulerian chemical transport model to simulate two historical Ship Channel flares. The model reasonably reproduced the observed ozone rise at the nearest monitoring stations downwind of the flares. The larger of the two flares had an olefin emission rate exceeding 1400 lb/hr. In this case, the model simulated a rate of increase in peak ozone greater than 40 ppb/hr over a 12 km?×?12 km horizontal domain without any unusual meteorological conditions. In this larger flare, formaldehyde emissions typically neglected in official inventories enhanced peak ozone by as much as 16 ppb and contributed over 10 ppb to ambient formaldehyde up to ～8 km downwind of the flare. The intense horizontal gradients in large flare plumes cannot be simulated by coarse models typically used to demonstrate ozone attainment. Moreover, even the relatively dense monitoring network in the Ship Channel may not be able to detect many transient high ozone events (THOEs) caused by industrial flare emissions in the absence of stagnant air recirculation or stalled sea breeze fronts, even though such conditions are unnecessary for the occurrence of THOEs.

Implications: Flare minimization may be an important strategy to attain the U.S. federal ozone standard in industrialized areas, and to avoid inordinate exposure to formaldehyde in neighborhoods surrounding petrochemical facilities. Moreover, air quality monitoring networks, emission inventories, and chemical transport models with higher spatial and temporal resolution and more refined speciation of HRVOCs are needed to better account for the near-source air quality impacts of large olefin flares.