Evaluation of a sustainable remediation option: Beneficial reuse of petroleum-contaminated sediment as an energy source

The characteristics of petroleum-contaminated sediment (PCS) have been evaluated to assess whether the practice of its beneficial reuse as a sole or supplemental energy source is sustainable relative to other sediment remediation options such as monitored natural recovery (MNR), capping, or off-site disposal. Some of these remediation options for PCS are energy-intensive and/or require land utilization. The energy and compositional analysis results indicate a low carbon content (15–17%(wt)) and corresponding low energy values of 5,200 kJ/kg (2,200 Btu/lb) to 5,600 kJ/kg (2,400 Btu/lb). However, given other decision-making criteria, the sediment may contain enough value to be added as a supplemental fuel given that it is normally considered a waste product and is readily available.

The thermogravimetric profiles obtained under both combustion and pyrolytic conditions showed that the sulfur contents were comparable to typical low sulfur bituminous or lignite coals found in the United States, and most of the volatiles could be vaporized below 750°C. The heavy metal concentrations determined before and after combustion of the PCS indicated that further engineering controls may be required for mercury, arsenic, and lead. Due to the potential for reduction of public health and environmental threats, potential economic savings, and conservation of natural resources (petroleum and land), removal of PCS by dredging and beneficial reuse as a supplemental fuel clearly has merit to be considered as a sustainable remediation option.

Implications: This study will provide a logical evaluation process to determine whether petroleum-contaminated sediment can be reused as an energy source. The energy and emissions values were determined and evaluated whether the sediment could be combusted for viable and sustainable use, considering several factors pertinent to evaluate in the remediation decision process. Various analysis methods were employed to determine elemental compositions, heating values, thermal and emission characteristics. This evaluation process may be used as a general methodology for the determination of petroleum-contaminated sediment as a supplemental fuel that may have merit to be considered as a sustainable remediation option.     

Effects of pyrethroid insecticide seed treatments on Rhizobium japonicum and its symbiotic relationship with,and growth of soybean

Abstract

Two pyrethroid insecticides were compared with two fungicides for their effects on the rhizobial and seedling components of the N₂‐fixing symbiosis in soybeans (Glycine max Merr. variety Olinda). In vitro growth of Rhizobium japonicum RI16, was inhibited in the order of HgCl₂ > thiram > cypermethrin > permethrin. The emergence of the seedlings was stimulated by all chemicals tested. Also, none of the pesticides studied had any significant effect on N₂ fixation (acetylene reduction), at the dosages used. Consequently, yields of the various organs were also not significantly influenced by the chemicals.     

Economic Study of the Tunable Electron Beam Plasma Reactor for Volatile Organic Compound Treatment

ABSTRACT

A tunable electron beam generated plasma system has been developed for selective cold plasma treatment of dilute concentrations (1-3,000 ppm range) of hazardous compounds in gaseous waste treatment. This system, referred to as the Tunable Hybrid Plasma (THP), has shown a high degree of efficiency and effectiveness in both laboratory and field tests. Decomposition energy requirements are in the 100 eV per molecule range for treatment of carbon tetrachloride and 10 eV for treatment of trichloroethylene.

A cost comparison has been made between the Tunable Hybrid Plasma (THP) technology and three conventional technologies used for emission control of volatile organic compounds (VOCs): granular activated carbon, thermal incineration, and catalytic oxidation. In addition to its environmentally attractive features, THP technology has the potential to be lower cost than other technologies over a range of concentrations and flow rates. Cost projections for the THP system for decomposition of trichloroet-hylene are around 50 cents/lb for initial concentrations in the few hundred ppm range and flow rates of 5,000 cfm or greater and around $1/lb for 1,000 cfm flow rates. Cost projections for carbon tetrachloride and trichloroethane decomposition using the THP technology are several dollars per pound. The costs for THP treatment are generally significantly lower than costs for use of granular activated carbon and are also quite competitive with costs for thermal incineration and catalytic oxidation.     

Use of Noise Attenuation Modeling in Managing Missile Motor Detonation Activities

Abstract

The Sound Intensity Prediction System (SIPS) and Blast Operation Overpressure Model (BOOM) are semiempirical sound models that are employed by the Utah Test and Training Range (UTTR) to predict whether noise levels from the detonation of large missile motors will exceed regulatory thresholds. Field validation of SIPS confirmed that the model was effective in limiting the number of detonations of large missile motors that could potentially result in a regulatory noise exceedance. Although the SIPS accurately predicted the impact of weather on detonation noise propagation, regulators have required that the more conservative BOOM model be employed in conjunction with SIPS in evaluating peak noise levels in populated areas. By simultaneously considering the output of both models, in 2001, UTTR detonated 104 missile motors having net explosive weights (NEW) that ranged between 14,960 and 38,938 lb without a recorded public noise complaint. Based on the encouraging results, the U.S. Department of Defense is considering expanding the application of these noise models to support the detonation of missile motors having a NEW of 81,000 lb. Recent modeling results suggest that, under appropriate weather conditions, missile motors containing up to 96,000 lb NEW can be detonated at the UTTR without exceeding the regulatory noise limit of 134 decibels (dB).     

Hot Filter/Impinger and Dilution Sampling for Fine Particulate Matter Characterization from Ferrous Metal Casting Processes

Abstract

A study using two stack-sampling methodologies for collecting particulate matter (PM) emissions was conducted using a hot filter followed by a cold impinger sampling train and a dilution sampler. Samples were collected from ferrous iron metal casting processes that included pouring molten iron into a sand mold containing an organic binder, metal cooling, removal of the sand from the cooled casting (shakeout), and postshakeout cooling. The shakeout process contributed more to PM emissions than the metal pouring and cooling processes. Particulate matter less than 2.5 μm in aerodynamic diameter (PM_2.5) mass emissions for the entire casting cycle ranged from 3.4 to 4.7 lb/t of metal for the hot filter/impinger method and from 0.8 to 1.8 lb/t of metal for the dilution method. Most of the difference was due to PM captured by the impingers, much of which was probably dissolved gases rather than condensable vapors. Of the PM fraction captured by the impingers, 96–98% was organic in nature. The impinger PM fraction contributed 32–38% to the total suspended particle mass and caused a factor of 2–4 positive bias for PM_2.5 emissions. For the pouring and cooling processes only, the factor increased to over seven times.     

Effect of Periods of Non-Use on Biofilter Performance

Abstract

A biofilter does not operate as a true filter, but removes chemicals from gases by sorption and biologically degrades them. The objective of the research reported in this paper was to investigate the effect of periods of non-use on biofilter performance. The concept of non-use had two meanings in this research: "no chemical loading," which indicated that humidified air was passing through the biofilter with no chemicals, and "stagnant," which reflected that no flow at all was passing through the biofilter. Both instances of nonuse can require the microorganisms in the biofilter to reacclimate to differences in loading and type of chemical when a chemical load is re-applied. Acclimation time was compared with three different chemicals, initial acclimation was compared with re-acclimation following different periods of non-use, and the effect of humidification during the period of non-use was examined.

Bench scale testing produced results indicating that acclimation times ranged from several hours to longer than a day. Longer periods of biofilter non-use resulted in longer reacclimation periods and transition between different chemicals resulted in acclimation periods shorter than initial acclimation periods. Stagnant periods produced longer re-acclimation periods than periods of no chemical loading.     

Atrazine degradation in a containerized rhizosphere system

Abstract

The effect of atrazine (2‐chloro‐4‐ethylamino‐6‐isopropylamino‐s‐triazine) on rhizosphere microorganisms and its fate in a containerized rhizosphere system was studied. The rhizosphere system consisted of corn grown in pot containing a defined potting mix of sand and bark with atrazine. Sterilized potting mix and a container without plants served as controls. Atrazine was extracted and analyzed via HPLC. Fluorescent pseudomonad populations increased 100‐fold in the rhizposphere during a 60‐day incubation period as compared to the nonvegetated control. Atrazine degradation was higher in the rhizosphere system (half‐life of 7 days) compared to the nonvegetated control (half‐life of greater than 45 days). The major degradation product detected in the rhizosphere system was deisopropylatrazine; other products detected included deethylatrazine, deethylhydroxyatrazine, deisopropylatrazine and hydroxyatrazine. Hydroxyatrazine was detected in the nonvegetated and sterile controls. The containerized rhizosphere system provides an experimental system to study the fate of pesticidal chemicals as well as the effects on microbial populations.     

Fate of ochratoxin a in goats

Abstract

The fate of ochratoxin A (OA) was studied in goats given a single oral dose of ³H‐OA (0.5 mg/kg). More than 90% of the radioactivity was found to be excreted in 7 days and the majority (53%) was found in feces. Thirty‐eight percent, 6% and 2.26% of the activity was found in urine, milk and serum, respectively. The radioactivity in the liver and kidney 6 hours after feeding amounted to 1.5 and 0.5% of the total dose administered, respectively. Subsequent fractionation of liver and kidney homogenates revealed that microsomes, ribosomes and post‐ribosomal supernatant fractions contained most radioactivity. Thin layer chromatographic analyses revealed two additional radioactive spots with Upvalues and fluorescent characteristics different from OA, Oα and 4‐OH‐OA. Whereas OA was found as the unaltered molecule in feces, the metabolites were primarily found in urine and milk. Less than 0.03% of free OA was found in milk during the 7‐day period.     

Removal of Aldrin,Dieldrin, Heptachlor,and Heptachlor Epoxide Using Activated Carbon and/or Pseudomonas fluorescens Free Cell Cultures

Degradation of aldrin (1,2,3,4,10,10-Hexachloro-1,4,4a,5,8,8a-hexahydro-1,4:5-8-dimethanonaphthalene), heptachlor (1H-1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methano indene), dieldrin (1aα,2β,2aα,3β,6β,6aα,7β,7aα)-3,4,5,6,9,9-Hexachloro-1a,2,2a,3,6,6a,7,7a-octahydro-2,7:3,6-d-methanonaphtha[2,3-b]oxirene, and heptachlor epoxide (1aα, 1bβ,2α,5α,5αβ,6β,6aα-2,3,4,5,6,7,7-Heptachloro-1a,1b,5,5a,6,6a-hexahydro-2,5-methano-2H-inden[1,2-b]-oxirene) was tested using free cultures of Pseudomonas fluorescens under controlled conditions. Pesticide concentrations were monitored by gas chromatography during 120 h. Percentages of degradation and biodegradation rates (BDR) were calculated. Data showed a trend suggesting a relation between chemical structure and degradability. Degradation kinetics for each pesticide tested showed that the highest degradation rates were found in the first 24 h. Kinetics data were adjusted to an empirical equation in order to predict their behavior, and the correlation coefficients obtained were satisfactory. Gas chromatography/mass spectrometry (GC/MS) analysis of the final extracts allowed the identification of chlordene and monodechlorodieldrin, which have been reported as final metabolite produced in the biodegradation of this kind of compounds. Regarding adsorption of pesticides on activated vegetal carbon, we concluded that removal efficiencies between 95.45 and 97.18% can be reached, depending on the pesticide and the carbon dose applied. The values for K from the Freundlich equation were quite similar for the four pesticides (between 1.0001 and 1.04), whereas the n values were quite different for each pesticide in the following order of affinity: dieldrin > aldrin > heptachlor epoxide > heptachlor. Equilibrium times, very important for scaling up the process, were between 43 min and 1 h, for the heptachlor epoxide and the heptachlor, respectively.     

Nitrogen Oxides Emission Control Options for Coal-Fired Electric Utility Boilers

Abstract

Recent regulations have required reductions in emissions of nitrogen oxides (NO_x) from electric utility boilers. To comply with these regulatory requirements, it is increasingly important to implement state-of-the-art NO_x control technologies on coal-fired utility boilers. This paper reviews NO_x control options for these boilers. It discusses the established commercial primary and secondary control technologies and examines what is being done to use them more effectively. Furthermore, the paper discusses recent developments in NO_x controls. The popular primary control technologies in use in the United States are low-NO_x burners and overfire air. Data reflect that average NO_x reductions for specific primary controls have ranged from 35% to 63% from 1995 emissions levels. The secondary NO_x control technologies applied on U.S. coal-fired utility boilers include reburning, selective noncatalytic reduction (SNCR), and selective catalytic reduction (SCR). Thirty-six U.S. coal-fired utility boilers have installed SNCR, and reported NO_x reductions achieved at these applications ranged from 15% to 66%. Recently, SCR has been installed at >150 U.S. coal-fired utility boilers. Data on the performance of 20 SCR systems operating in the United States with low-NO_x emissions reflect that in 2003, these units achieved NO_x emission rates between 0.04 and 0.07 lb/10⁶ Btu.     

Leaching of fenamiphos,fenamiphos sulfoxide and fenamiphos sulfone in soil columns

Abstract

Leaching of fenamiphos and its thiooxidation products, sulfoxide and sulfone, has been studied in two different soils in laboratory conditions. Fenamiphos was much less mobile than its derivatives. A large volume of water was necessary to leach completely the three chemicals. Fenamiphos required an amount of water twice as large as that required by either sulfoxide or sulfone. Mobility and leaching efficiency of the chemicals examined were highly dependent on the properties of the two soils considered.     

Release of Mercury Vapor from Coal Combustion Ash

Abstract

The long-term stability of Hg in coal combustion byproducts (CCBs) was evaluated at ambient and near-ambient temperatures. Six CCB samples with atypically high levels of total Hg were selected for study assuming a greater potential for release of measurable amounts of Hg vapor. The samples selected included two fly ash samples from U.S. eastern bituminous coal, two fly ash samples from South African low-rank coal, one fly ash from Powder River Basin (PRB) subbituminous coal blended with petroleum coke, and one PRB subbituminous coal fly ash incorporated with flue gas desulfurization material.

Air scrubbed of Hg was passed through compacted 100-g aliquots of each sample at 1 mL/min and vented to a gold-coated quartz trap to collect released Hg vapor. The samples were maintained at ambient and near-ambient (37 °C) temperatures. All samples released low-picogram levels of Hg after 90 days. No pattern was evident to link the total Hg content to the rate of release of Hg vapor. An average of 0.030 pg Hg/g CCB/day was released from the samples, which equates to 2.2 x 10^-8 lb Hg/ton CCB/year. If this were applied to a coal-fired power plant production of 200,000 tons of fly ash per year, there would be a maximum potential release of 0.0044 lb, or 2.00 g, of Hg per year. Experiments are continuing to determine long-term vapor release of Hg from CCBs. All samples have been set up in duplicate at ambient temperature with an improved apparatus to reevalu-ate results reported in this article.     

Effects of some insecticides on microbial activities in sandy soil

Abstract

Laboratory tests were conducted with 14 insecticides applied to a sandy loam to determine whether these materials caused any effects on microbial activities related to soil fertility. The ammonification of soil native organic nitrogen was not inhibited by any of the insecticide treatments. Some insecticides showed an effect on nitrification during the second week of incubation which subsequently recovered to levels similar to those obtained in the controls. There was a significant effect on denitrification in a number of treated samples. However, recovery of denitrifying capacity was rapid. This recovery indicated that the indigenous soil microorganisms can tolerate the chemicals used for control of insect pests. No significant inhibition of sulfur oxidation was observed. Results indicated that the insecticide treatments at the level tested were not drastic enough to be considered deleterious to soil microbial activities important to soil fertility.     

Aerobic and anaerobic degradation of profluralin and trifluralin

Abstract

The degradation of profluralin [N‐(cyclopropylmethyl)‐α,α,α‐trifluoro‐2,6‐dinitro‐N‐propyl‐]p‐toluidine] and trifluralin (α,α,α‐trifluoro‐2,6‐dinitro‐N,N‐dipropyl‐p‐toluidine) was studied under aerobic and anaerobic soil conditions. Three soils (Goldsboro loamy sand, Cecil loamy sand, Drummer clay loam) were each treated with 1 ppmw herbicide; anaerobic conditions were maintained by flooding. Soil samples were extracted monthly and subjected to TLC analysis. No degradation was detected in sterile controls. Aerobic degradation of both herbicides was greatest in the Cecil loamy sand soil over the entire incubation period. Degradation of profluralin in Cecil soil under aerobic conditions was 86 percent after 4 months with three products detected; 83 percent of the trifluralin was degraded with two products detected. Anaerobic degradation accounted for 72 percent of the profluralin and 78 percent of the trifluralin after 4 months. Degradation of both herbicides increased with incubation time for the first 3 months and decreased slightly thereafter. Generally there was more extensive degradation (percent and in number of products formed) of profluralin than trifluralin under the conditions tested. More degradation products were detected for both herbicides under aerobic conditions than under anaerobic conditions.     

An overview of short‐term tests for the mutagenic and carcinogenic potential of pesticides

Abstract

In the last few years, marked progress has been made in the development of methods for evaluating the mutagenic and carcinogenic potential of pesticide chemicals. The correlation of genetic and related biological activity in short‐term tests with carcinogenic activity in whole animals allows the utilization of short‐term mutagenicity bioassays to prescreen chemicals for effects related to mutation induction and presumptive carcinogenicity. In addition, bioassays now available can measure directly the chemical transformation of normal cells in culture into cells capable of producing tumors when injected into animals.

This paper will review briefly the major types of relevant short‐term tests and will develop a rationale for a phased approach to the evaluation of the mutagenic and carcinogenic potential of environmental chemicals. This approach involves the sequential application of bioassays which are organized into a three‐level matrix emphasizing first detection, then confirmation, and finally hazard assessment. Chemicals demonstrating positive results in the short‐term detection systems and confirmatory bioassays are pursued in higher level whole animal tests. A core battery of tests is proposed to operationally define a negative result. The phased approach should facilitate a cost effective utilization of limited testing resources and provide protection for human health in proportion to the anticipated hazard.

Results obtained in evaluating a series of thirty‐eight pesticide chemicals according to the phased approach are discussed in detail.     

Estimation of Organic Compound Emissions from Waste Lagoons

Abstract

With the recent focus on fine particle matter (PM_2.5),new, self-consistent data are needed to characterize emissions from combustion sources. Such data are necessary for health assessment and air quality modeling. To address this need, emissions data for gas-fired combustors are presented here, using dilution sampling as the reference.The dilution method allows for collection of emitted particles under conditions simulating cooling and dilution during entry from the stack into the air. The sampling and analysis of the collected particles in the presence of precursor gases, SO₂, nitrogen oxide, volatile organic compound, and NH₃ is discussed; the results include data from eight gas fired units, including a dual-fuel institutional boiler and a diesel engine powered electricity generator. These data are compared with results in the literature for heavy-duty diesel vehicles and stationary sources using coal or wood as fuels. The results show that the gas-fired combustors have very low PM_2.5 mass emission rates in the range of ～10_-4 lb/million Btu (MMBTU) compared with the diesel backup generator with particle filter, with ～5 × 10_-3 lb/MMBTU. Even higher mass emission rates are found in coal-fired systems, with rates of ～0.07 lb/MMBTU for a bag-filter-controlled pilot unit burning eastern bituminous coal. The characterization of PM_2.5 chemical composition from the gas-fired units indicates that much of the measured primary particle mass in PM_2.5 samples is organic or elemental carbon and, to a much less extent, sulfate. Metal emissions are quite low compared with the diesel engines and the coal- or woodfueled combustors. The metals found in the gas-fired combustor particles are low in concentration, similar in concentration to ambient particles. The interpretation of the particulate carbon emissions is complicated by the fact that an approximately equal amount of particulate carbon (mainly organic carbon) is found on the particle collector and a backup filter. It is likely that measurement artifacts, mostly adsorption of volatile organic compounds on quartz filters, are positively biasing “true” particulate carbon emission results.     

Longterm effects of the herbicides Atrazine and Dichlobenil upon the phytoplankton density and physico-chemical conditions in compartments of a freshwater pond

Atrazine (1.1 mg · L^?1) and Dichlobenil (“DBN”) (4.3 mg · L^?1) were dosed in triplicates into the water of a compartimentalized pond. Maximum concentrations of the chemicals detected were 200 μg · L^?1 Atrazine and 4.2 mg · L^?1 DBN (on day 3 – 5 after dosing). Residues were monitored for 55 days, amounting to 60 μg Atrazine and 1.5 mg DBN per litre at the end of observation.O₂- and H⁺-concentrations were significantly lower for 35 and 30 days resp. in the treated water as compared to controls. The conductivity of the dosed water was significantly higher for at least 65 (DBN) and 120 days (Atrazine) than in the untreated compartments. Differences in phytoplankton abundance and diversity could be evaluated between controls and treated biotopes.     

Performance of two swine manure treatment systems on chemical composition and on the reduction of pathogens

Swine effluents must be correctly handled to avoid negative environmental impacts. In this study, the profiles of two swine manure treatment systems were evaluated: a solid–liquid separation step, followed by an anaerobic reactor, and an aerobic step (System 1); and a biodigester followed by serial lagoons (System 2). Both systems were described by the assessment of chemical, bacterial and viral parameters. The results showed that in System 1, there was reduction of chemicals (COD, phosphorus, total Kjeldhal nitrogen – TKN – and NH₃), total coliforms and Escherichia coli; however, the same reduction was not observed for Salmonella sp. Viral particles were significantly reduced but not totally eliminated from the effluent. In System 2, there was a reduction of chemicals, bacteria and viruses with no detection of Salmonella sp., circovirus, parvovirus, and torque teno virus in the effluent. The chemical results indicate that the treated effluent can be reused for cleaning swine facilities. However, the microbiological results show a need of additional treatment to achieve a complete inactivation for cases when direct contact with animals is required.     

Optimal Loading Rates and Economic Analyses for Anaerobic Digestion of Poultry Waste

ABSTRACT

Four combinations of litter and carcasses from broiler chickens were examined utilizing a thermophilic, stirred-tank digester of demonstration size of approximately 10,000 gal. Under computed optimal loading rates, litter with paper bedding had the highest daily production of methane over an 8-day retention period. The greatest methane production per lb of volatile solids was achieved over 10 days with litter and paper bedding combined with carcasses. This research found that sufficient poultry litter is generated within 20 mi (32 km) of Moorefield, WV, to support a commercial-sized digester operation. However, anaerobic digestion of poultry waste cannot be financially supported by methane production alone. To be financially viable, anaerobic digestion requires a disposal fee for poultry waste and/or the sale of the digested solid effluent as an organic fertilizer to retail markets.