Environmental Issues—Persistent Problems and Emerging Challenges

Abstract

A field study was performed to evaluate indoor air concentrations and vapor intrusion (VI) of tetrachloroethylene (PCE) and other chlorinated solvents at a commercial retail site in Dallas, TX. The building is approximately 40 yr old and once housed a dry cleaning operation. Results from an initial site characterization were used to select sampling locations for the VI study. The general approach for evaluating VI was to collect time-integrated canister samples for off-site U.S. Environmental Protection Agency Method TO-15 analyses. PCE and other chlorinated solvents were measured in shallow soil gas, subslab soil-gas, indoor air, and ambient air. The subslab soil gas exhibited relatively high values: PCE ≤2,600,000 parts per billion by volume (ppbv) and trichloroethylene ≤170 ppbv. The attenuation factor, the ratio of indoor air and subslab soil-gas concentrations, was unusually low: approximately 5 x 10^-6 based on the maximum subslab soil-gas concentration of PCE and 1.4 x 10^-5 based on average values.     

Quantification of ventilation on distribution of gaseous pollutants emitted from stored swine manure

Abstract

This paper describes the quantification of the effects of ventilation on distribution of gaseous pollutants as a result of mass transfer from stored manure to ventilation air in a swine confinement building. A multiple airflow regions model is developed and used to simulate the dynamics of gaseous pollutants in any airspace within a ventilated slotted‐inlet enclosure. The model predictions compared favorably with the measured results adapted from a literature research at ventilation rates between 443 and 932 m³/hr (deviations of 5.1 ‐ 14.68%) for carbon dioxide and ammonia concentrations. A comparison between predictions and measured carbon dioxide concentrations derived from an environmental chamber test found deviations ranged from 3.1 ‐ 5.6% at ventilation rates between 281 and 995 m³/hr. The results suggest that the model can be experimentally applied between ventilation rates of 443 and 995 m³/hr. The model also capable of predicting air exchange rate required to maintain acceptable levels of gaseous pollutants in swine confinement buildings based on gas emission rates.     

Individual Measurements of the Emission Factor of Aerosol Black Carbon in Automobile Plumes

As automobiles passed a measuring point, we recorded the concentrations of carbon dioxide and aerosol black carbon (BC) in their dispersing exhaust plumes. After subtraction of background levels, the ratio of the increments of these species allows us to calculate the emission factor of BC per unit mass of fuel from each individual vehicle. These factors spanned a range of greater than two orders of magnitude, representing the emission of from 4 × 10^?6 to 10^?3 grams of aerosol black carbon per gram of carbon consumed in the fuel. Their distribution showed that 20 percent of the vehicles accounted for 65 percent of the emissions. The real-time measurement methodology allows for a determination of the distribution of emission factors across the actual population of sources. These results are similar to the wide range of carbon monoxide emission factors reported recently.     

Using variances in hydrocarbon concentration and carbon stable isotope to determine the important influence of irrigated water on petroleum accumulation in surface soil

Hunpu is a wastewater-irrigated area southwest of Shenyang. To evaluate petroleum contamination and identify its sources at the area, the aliphatic hydrocarbons and compound-specific carbon stable isotopes of n-alkanes in the soil, irrigation water, and atmospheric deposition were analyzed. The analyses of hydrocarbon concentrations and geochemical characteristics reveal that the water is moderately contaminated by degraded heavy oil. According to the isotope analysis, inputs of modern C3 plants and degraded petroleum are present in the water, air, and soil. The similarities and dissimilarities among the water, air, and soil samples were determined by concentration, isotope, and multivariate statistical analyses. Hydrocarbons from various sources, as well as the water/atmospheric deposition samples, are more effectively differentiated through principal component analysis of carbon stable isotope ratios (δ¹³C) relative to hydrocarbon concentrations. Redundancy analysis indicates that 57.1 % of the variance in the δ¹³C of the soil can be explained by the δ¹³C of both the water and air, and 35.5 % of the variance in the hydrocarbon concentrations of the soil can be explained by hydrocarbon concentrations of both the water and the air. The δ¹³C in the atmospheric deposition accounts for 28.2 % of the δ¹³C variance in the soil, which is considerably higher than the variance in hydrocarbon concentrations of the soil explained by hydrocarbon concentrations of the atmospheric deposition (7.7 %). In contrast to δ¹³C analysis, the analysis of hydrocarbon concentrations underestimates the effect of petroleum contamination in the irrigated water and air on the surface soil. Overall, the irrigated water exerts a larger effect on the surface soil than does the atmospheric deposition.     

Black Carbon Aerosol at McMurdo Station,Antarctica

ABSTRACT

Aerosol light absorption as black carbon (BC) was measured from November 19, 1995, to February 6, 1996, at a location 0.65 km downwind of the center of McMurdo Station on the Antarctic coast. The results show a bimo-dal frequency distribution of BC concentrations. Approximately 65% of the measurements were found in a mode at a low range of concentrations centered at ~20 ng/m³. These concentrations are higher than those found at other remote Antarctic locations and probably represent contamination from the station. The remaining measurements were in a high-concentration mode (BC ~300 ng/m³), indicating direct impact of local emissions from combustion activities at the station. High values of BC were associated with winds from the direction of the station, and the BC flux showed a clear directionality. Maximum BC concentrations occurred between 7:00 and 11:00 a.m. The "polluted" mode accounted for more than 80% of the BC frequency-weighted impact at this location.     

Engineered in situ bioremediation of a petroleum hydrocarbon-contaminated aquifer: assessment of mineralization based on alkalinity, inorganic carbon and stable carbon isotope balances

A concept is proposed to assess in situ petroleum hydrocarbon mineralization by combining data on oxidant consumption, production of reduced species, CH₄, alkalinity and dissolved inorganic carbon (DIC) with measurements of stable isotope ratios. The concept was applied to a diesel fuel contaminated aquifer in Menziken, Switzerland, which was treated by engineered in situ bioremediation. In the contaminated aquifer, added oxidants (O₂ and NO₃⁻) were consumed, elevated concentrations of Fe(II), Mn(II), CH₄, alkalinity and DIC were detected and the DIC was generally depleted in ¹³C compared to the background. The DIC production was larger than expected based on the consumption of dissolved oxidants and the production of reduced species. Stable carbon isotope balances revealed that the DIC production in the aquifer originated mainly from microbial petroleum hydrocarbon mineralization, and that geochemical reactions such as carbonate dissolution produced little DIC. This suggests that petroleum hydrocarbon mineralization can be underestimated if it is determined based on concentrations of dissolved oxidants and reduced species.     

Effect of Gas and Kerosene Space Heaters on Indoor Air Quality: A Study in Homes of Santiago,Chile

Abstract

The impact of outdoor and indoor pollution sources on indoor air quality in Santiago, Chile was investigated. Toward this end, 16 homes were sampled in four sessions. Each session included an outdoor site and four homes using different unvented space heaters (electric or central heating, compressed natural gas, liquefied petroleum gas, and kerosene). Average outdoor fine particulate matter (PM_2.5) concentrations were very high (55.9 μg·m^-3), and a large fraction of these particles penetrated indoors. PM_2.5 and several PM_2.5 components (including sulfate, elemental carbon, organic carbon, metals, and polycyclic aromatic hydrocarbons) were elevated in homes using kerosene heaters. Nitrogen dioxide (NO₂) and ultrafine particles (UFPs) were higher in homes with combustion heaters as compared with those with electric heaters or central heating. A regression model was used to assess the effect of heater use on continuous indoor PM_2.5 concentrations when windows were closed. The model found an impact only for kerosene heaters (45.8 μg m^-3).     

Determination of the Adsorption Isotherm of Vapor-Phase Mercury Chloride on Powdered Activated Carbon Using Thermogravimetric Analysis

Abstract

This study investigated the use of thermogravimetric analysis (TGA) to determine the adsorptive capacity and adsorption isotherm of vapor-phase mercury chloride on powdered activated carbon (PAC). The technique is commonly applied to remove mercury-containing air pollutants from gas streams emitted from municipal solid waste incinerators. An alternative form of powdered activated carbon derived from a pyrolyzed tire char was prepared for use herein. The capacity of waste tire-derived PAC to adsorb vapor-phase HgCl₂ was successfully measured using a self-designed TGA adsorption system. Experimental results showed that the maximum adsorptive capacities of HgCl₂ were 1.75, 0.688, and 0.230 mg of HgCl₂ per gram of powdered activated carbon derived from carbon black at 30, 70, and 150 °C for 500 µg/m³ of HgCl₂, respectively. Four adsorption isotherms obtained using the Langmuir, Freundlich, Redlich-Peterson, and Brunauer–Emmett–Teller (BET) models were used to simulate the adsorption of HgCl₂. The comparison of experimental data associated with the four adsorption isotherms indicated that BET fit the experimental results better than did the other isotherms at 30 °C, whereas the Freundlich isotherm fit the experimental results better at 70 and 150 °C. Furthermore, the calculations of the parameters associated with Langmuir and Freundlich isotherms revealed that the adsorption of HgCl₂ by PAC-derived carbon black favored adsorption at various HgCl₂ concentrations and temperatures.     

Clearance of atrazine in soil describing xenobiotic behavior

The primary aim of this study was to evaluate the “clearance concept” as a tool for describing the behavior of xenobiotic movement into and through soils. As an example, degradation of 2-chloro-4-ethylamino-6-isopropylamino-s-triazine (atrazine) with the formation of metabolites 2-chloro-6-isopropylamino-s-triazine (desethylatrazine) and 2-chloro-4-ethylamino-s-triazine (desisopropylatrazine) was investigated. Atrazine was sprayed post-emergently in doses of 0.125 or 0.5 g active ingredient/m² each on four test plots. Soil type was a sandy-loam, on which corn (Zea mays L.) was cultivated. Soil samples were taken as cores of 0.2 m depth 0, 1, 2, 4, 8, 12, 16 and 20 weeks after application of atrazine, and analyzed by HPLC. Soil concentrations of atrazine were highly correlated (r=0.993, p< 0.001) between the two applications of 0.125 g/m² and 0.5 g/m². Up to 50% of the atrazine was measured as metabolites during the whole vegetation period. Clearance of atrazine from soil was calculated as the total load of atrazine divided by the area under the soil atrazine concentration time curve. Soil atrazine clearance was calculated as 5.13 +/? SD 1.10 and 5.17 +/? SD 1.02 liter of soil per day for doses of 0.125 g/m² and 0.5 g/m², respectively (from a “soil unit” of 1 × 1 × 0.2 meter). The clearance concept might be a tool for risk assessment of xenobiotics.     

Evaluation of Trickle Bed Air Biofilter Performance as a Function of Inlet VOC Concentration and Loading,and Biomass Control

ABSTRACT

The 1990 Amendments to the Clean Air Act have stimulated strong interest in the use of biofiltration for the economical, engineered control of volatile organic compounds (VOCs) in effluent air streams. Trickle bed air biofilters (TBABs) are especially applicable for treating VOCs at high loadings. For long-term, stable operation of highly loaded TBABs, removal of excess accumulated bio-mass is essential. Our previous research demonstrated that suitable biomass control for TBABs was achievable by periodic backwashing of the biofilter medium. Backwashing was performed by fluidizing the pelletized biological attachment medium with warm water to about a 40% bed expansion. This paper presents an evaluation of the impact of backwashing on the performance of four such TBABs highly loaded with toluene. The inlet VOC concentrations studied were 250 and 500 ppmv toluene, and the loadings were 4.1 and 6.2 kg COD/m³ day (55 and 83 g toluene/m³ hr). Loading is defined as kg of chemical oxygen demand per cubic meter of medium per day. Performance deterioration at the higher loading was apparently due to a reduction of the specific surface of the attached biofilm resulting from the accumulation of excess biomass. For a toluene loading of 4.1 kg COD/m³ day, it was demonstrated that the long-term performance of biofilters with either inlet concentration could be maintained at over 99.9% VOC removal by employing a backwashing strategy consisting of a frequency of every other day and a duration of 1 hr.     

Biotrickling Filtration of Nitric Oxide

ABSTRACT

A biotrickling filter with blast-furnace slag packings (sizes = 20-40 mm and specific surface area = 120 m²/m³) was utilized to treat NO in an air stream. The operational stability, as well as the effects of gas empty-bed retention time (EBRT) and nutrient addition on the removal ability of NO, were tested. Approximately six weeks were required for the development of a biofilm for NO degradation, and a two-week organic carbon deficiency resulted in the detachment of biofilms from the packing surfaces. A steady removal rate of 80% was attained at specified influent NO concentrations of 892 to 1237 ppm and an EBRT of 118 sec. The effluent NO concentration diminished exponentially with enlarging EBRT, with influent NO concentrations of 203-898 ppm, and EBRTs of 25 to 118 sec. Nutrient addition is essential for efficient removal of the influent NO. Mass ratios of C: P: N = 7: 1: 30 and NaHCO₃: NO-N = 6.3 could be used for practical applications.     

Mineralisation of target hydrocarbons in three contaminated soils from former refinery facilities

This study investigated the microbial degradation of ¹⁴C-labelled hexadecane, octacosane, phenanthrene and pyrene and considered how degradation might be optimised in three genuinely hydrocarbon-contaminated soils from former petroleum refinery sites. Hydrocarbon mineralisation by the indigenous microbial community was monitored over 23 d. Hydrocarbon mineralisation enhancement by nutrient amendment (biostimulation), hydrocarbon degrader addition (bioaugmentation) and combined nutrient and degrader amendment, was also explored. The ability of indigenous soil microflora to mineralise ¹⁴C-target hydrocarbons was appreciable; ≥16% mineralised in all soils. Generally, addition of nutrients or degraders increased the rates and extents of mineralisation of ¹⁴C-hydrocarbons. However, the addition of nutrients and degraders in combination had a negative effect upon ¹⁴C-octacosane mineralisation and resulted in lower extents of mineralisation in the three soils. In general, the rates and extents of mineralisation will be dependent upon treatment type, nature of the contamination and adaptation of the ingenious microbial community.     

Degradation of Isobutanal at High Loading Rates in a Compost Biofilter

Abstract

Biofiltration has been increasingly used for cleaning waste gases, mostly containing low concentrations of odorous compounds. To expand the application area of this technology, the biofiltration of higher pollutant loading rates has to be investigated. This article focuses on the biodegradation of isobutanal (IBAL) in a compost biofilter (BF) at mass loading rates between 211 and 4123 g/m³/day (30– 590 ppm_v). At mass loading rates up to 785 g/m³/day, near 100% removal efficiencies could be obtained. However, after increasing the loading rate to 1500–1900 g/m³/day, the degradation efficiency decreased to 62–98%. In addition, a pH decrease and production of isobutanol (IBOL) and isobutyric acid (IBAC) were observed. This is the first report showing that an aldehyde can act as electron donor as well as acceptor in a BF. To study the effects of pH, compost moisture content, and electron acceptor availability on the biofiltration of IBAL, IBOL, and IBAC, additional batch and continuous experiments were performed. A pH of 5.2 reduced the IBAL degradation rate and inhibited the IBOL degradation, although adaptation of the microorganisms to low pH was observed in the BFs. IBAC was not degraded in the batch experiments. High moisture content (51%) initially had no effect on the IBOL production, although it negatively affected the IBAL elimination increasingly during a 21–day time–course experiment. In batch experiments, the reduction of IBAL to IBOL did not decrease when the amount of available electron acceptors (oxygen or nitrate) was increased. The IBAL removal efficiency at higher loading rates was limited by a combination of nutrient limitation, pH decrease, and dehydration, and the importance of each limiting factor depended on the influent concentration.     

Long Term Monitoring of Hydrocarbon Contamination Using Multi-Level Vapor Phase Piezometers

This study evaluated the feasibility of supplementing groundwater monitoring protocols by assessing the vadose zone for the extent of residual subsurface contamination. The study also characterized the response of the soil gas signatures with respect to different soil types and degrees of contamination.A field study was conducted at a former gasoline vending station located in Ottawa, Canada. The current state of contamination was determined by analysis of soil samples taken from boreholes. A series of 10 nested soil gas wells with monitoring depths of 0.75, 1.5, 2.25 and 3.0 m were then installed. Using these wells, soil gas surveys were performed at regular intervals over an extended period to quantify Gaseous TPH (TPH_g), oxygen and carbon dioxide concentrations in the soil gas.Results indicate that soil gas wells located near the source term exhibited characteristic soil gas signatures and significant fluctuations in TPH_g, oxygen, and carbon dioxide concentrations with time. Soil gas wells located beyond the soil contamination demonstrated limited correlation between TPH_g, oxygen and carbon dioxide concentrations and decreased seasonal variability.     

Removal of Volatile Organic Compounds at Extreme Shock-Loading Using a Scaled-Up Pilot Rotating Drum Biofilter

Abstract

A pilot-scale rotating drum biofilter (RDB), which is a novel biofilter design that offers flexible flow-through configurations, was used to treat complex and variable volatile organic compound (VOC) emissions, including shock loadings, emanating from paint drying operations at an Army ammunition plant. The RDB was seeded with municipal wastewater activated sludge. Removal efficiencies up to 86% and an elimination capacity of 5.3 g chemical oxygen demand (COD) m^?3 · hr^?1 were achieved at a filter-medium contact time of 60 sec. Efficiency increased at higher temperatures that promote higher biological activity, and decreased at lower pH, which dropped down to pH 5.5 possibly as a result of carbon dioxide and volatile fatty acid production and ammonia consumption during VOC degradation. In comparison, other studies have shown that a bench-scale RDB could achieve a removal efficiency of 95% and elimination capacity of 331 g COD m^?3 · hr^?1. Sustainable performance of the pilot-scale RDB was challenged by the intermittent nature of painting operations, which typically resulted in 3-day long shutdown periods when bacteria were not fed. This challenge was overcome by adding sucrose (2 g/L weekly) as an auxiliary substrate to sustain metabolic activity during shutdown periods.     

Characterization of Air Quality Problems in Five Finnish Indoor Ice Arenas

ABSTRACT

The air quality in five Finnish ice arenas with different volumes, ventilation systems, and resurfacer power sources (propane, gasoline, electric) was monitored during a usual training evening and a standardized, simulated ice hockey game. The measurements included continuous recording of carbon monoxide (CO), nitric oxide (NO), and nitrogen dioxide (NO₂) concentrations, and sampling and analysis of volatile organic compounds (VOCs). Emissions from the ice resurfacers with combustion engines caused indoor air quality problems in all ice arenas. The highest 1-hour average CO and NO₂ concentrations ranged from 20 to 33 mg/m³ (17 to 29 ppm) and 270 to 7440 µg/m³ (0.14 to 3.96 ppm), respectively. The 3-hour total VOC concentrations ranged from 150 to 1200 µg/m³. The highest CO and VOC levels were measured in the arena in which a gasoline-fueled resurfacer was used. The highest NO₂ levels were measured in small ice arenas with propane-fueled ice resurfacers and insufficient ventilation.

In these arenas, the indoor NO₂ levels were about 100 times the levels measured in ambient outdoor air, and the highest 1-hour concentrations were about 20 times the national and World Health Organization (WHO) health-based air quality guidelines. The air quality was fully acceptable only in the arena with an electric resurfacer. The present study showed that the air quality problems of indoor ice arenas may vary with the fuel type of resurfacer and the volume and ventilation of arena building. It also confirmed that there are severe air quality problems in Finnish ice arenas similar to those previously described in North America.     

The Steubenville Comprehensive Air Monitoring Program (SCAMP): Analysis of Short-Term and Episodic Variations in PM2.5 Concentrations Using Hourly Air Monitoring Data

Abstract

One-hour average ambient concentrations of particulate matter (PM) with an aerodynamic diameter <2.5 μm (PM_2.5) were determined in Steubenville, OH, between June 2000 and May 2002 with a tapered element oscillating microbalance (TEOM). Hourly average gaseous copollutant [carbon monoxide (CO), sulfur dioxide (SO₂), nitrogen oxide (NO_x), and ozone (O₃)] concentrations and meteorological conditions also were measured. Although 75% of the 14,682 hourly PM_2.5 concentrations measured during this period were ≤17 μg/m³, concentrations >65 μg/m³ were observed 76 times. On average, PM_2.5 concentrations at Steubenville exhibited a diurnal pattern of higher early morning concentrations and lower afternoon concentrations, similar to the diurnal profiles of CO and NO_x. This pattern was highly variable; however, PM_2.5 concentrations >65 μg/m³ were never observed during the mid-afternoon between 1:00 p.m. and 5:00 p.m. EST. Twenty-two episodes centered on one or more of these elevated concentrations were identified. Five episodes occurred during the months June through August; the maximum PM_2.5 concentration during these episodes was 76.6 μg/m³. Episodes occurring during climatologically cooler months often featured higher peak concentrations (five had maximum concentrations between 95.0 and 139.6 μg/m³), and many exhibited strong covariation between PM_2.5 and CO, NO_x, or SO₂. Case studies suggested that nocturnal surface-based temperature inversions were influential in driving high nighttime concentrations of these species during several cool season episodes, which typically had dramatically lower afternoon concentrations. These findings provide insights that may be useful in the development of PM_2.5 reduction strategies for Steubenville, and suggest that studies assessing possible health effects of PM_2.5 should carefully consider exposure issues related to the intraday timing of PM_2.5 episodes, as well as the potential for toxicological interactions among PM_2.5 and primary gaseous pollutants.     

Factors Influencing 2,4-D Sorption and Mineralization in Soil

Abstract

This study quantified 2,4-D [(2,4-dichlorophenoxy)acetic acid] sorption and mineralization rates in five soils as influenced by soil characteristics and nutrient contents. Results indicated that 2,4-D was weakly sorbed by soil, with Freundlich distribution coefficients ranging from 0.81 to 2.89 µg^1?1/n  g^?1 mL^{1/ n} . First-order mineralization rate constants varied from 0.03 to 0.26, corresponding to calculated mineralization half-lives of 3 and 22 days, respectively. Herbicide sorption generally increased with increasing soil organic carbon content, but the extent of 2,4-D sorption per unit organic carbon varied among the soils due to differences in soil pH, clay content and/or organic matter quality. Herbicide mineralization rates were greater in soils that sorbed more 2,4-D per unit organic carbon, and that had greater soil nitrogen contents. We conclude that the effect of sorption on herbicide degradation cannot be generalized without a better understanding of the effects of soil characteristics and nutrient content on herbicide behavior in soil.     

Presence of alkyllead in rural and urban air: Evaluation of some sources of alkyllead pollution of the atmosphere in Norway

Concentrations of alkyllead in ambient air were measured, as well as in car exhaust and in gasoline vapours. In Oslo the concentration in air ranged from 0.010 to 0.100 μg Pb m⁻³, and these values were compared to the concentrations (< 0.001 μg Pb m⁻³) measured in a low traffic rural area of Norway. The amount of alkyllead in car exhaust varied between 0.1 and 15 μg Pb m⁻³, which was between 0.01 and 0.5% of the amount of inorganic lead in exhaust. Evaporation of alkyllead from parked cars was estimated at 0.5 mg Pb per day per car. The concentrations of alkyllead in saturated gasoline vapour were found to be 10–20 mg Pb m⁻³ at ambient air temperatures.     

The Superfund Remedial Action Decision Process: A Review of Fifty Records of Decision

Abstract

Although the Superfund remedial action decision process is a complex process involving a variety of technical, political, and public health issues, the primary goal of remedial action is the protection of public health. We performed an in-depth analysis of 50 post-SARA Records of Decision in order to characterize the role of risk assessment in the decision-making process and determine whether decisions are being made in an effective and environmentally protective manner. Our findings indicate that the majority of decisions to remediate Superfund sites are based on the existence of contamination per se and not on actual public health risk. Although hypothetical risk is an essential consideration, this gray area is not well-defined in the current decision-making process.

The lack of assessment of the degree of risk reduction associated with the remedial alternatives evaluated and the lack of support indicating the effectiveness of the remedial alternatives selected also constitute major weaknesses in the majority of decisions. These inadequacies undermine rationales regarding the protectiveness and cost-effectiveness of the remedial alternatives selected. The fact that objectives beyond addressing public health risk are often unclear in the decision-making process also weakens rationales for costeffectiveness.