Tank atmosphere perturbation: a procedure for assessing flashing losses from oil storage tanks

A new procedure to measure the total volume of emissions from heavy crude oil storage tanks is described. Tank flashing losses, which are difficult to measure, can be determined by correcting this value for working and breathing losses. The procedure uses a fan or blower to vent the headspace of the storage tank, with subsequent monitoring of the change in concentrations of oxygen or other gases. Combined with a separate determination of the reactive organic carbon (ROC) fraction in the gas, this method allows the evaluation of the total amount of ROC emitted. The operation of the system is described, and results from measurement of several storage tanks in California oil fields are presented. Our measurements are compared with those obtained using the California Air Resources Board (CARB) 150 method.     

Standards for Air Quality in California

Abstract

During the 1950s and 1960s, hundreds of thousands of underground storage tanks (and above-ground storage tanks) containing petroleum products and hazardous chemicals were installed. Many of these tanks either have been abandoned or have exceeded their useful lives and are leaking, thereby posing a serious threat to the nation’s surface and groundwater supplies, as well as to public health. Cleaning up releases of petroleum hydrocarbons or other organic chemicals in the subsurface environment is a real-world problem,

Biological treatment of hydrocarbon-contaminated soil is considered to be a relatively low-cost and safe technology; however, its potential for effectively treating recalcitrant wastes has not been fully explored. For millions of years, microorganisms such as bacteria, fungi, actinomycete, protozoa, and others have performed the function of recycling organic matter from which new plant life can grow.

This paper examines the biological treatment technology for cleaning up petroleum product-contaminated soils, with special emphasis on microbial enzyme systems for enhancing the rate of biodegradation of petroleum hydrocarbons. Classifications and functions of enzymes, as well as the microbes, in degrading the organic contaminants are discussed. In addition, the weathering effect on biodegradation, types of hydrocarbon degraders, advantages associated with enzyme use, methods of enzyme extraction, and future research needs for development and evaluation of enzyme-assisted bioremediation are examined.     

The Application of the Karl Fischer Oven for the Determination of Water in Consumer Products

Abstract

The direct Karl Fischer (KF) titration method has known interferences for measuring water content. In addition, in analyzing some paints, KF can fail to produce an accurate analysis. The California Air Resources Board (GARB) staff has developed a KF procedure that can be used to determine the water content of consumer products. The procedure uses an oven accessory to the titration system, and is based on a distillation method developed by the California Polytechnical University at San Luis Obispo (Cal Poly). Samples are diluted in l-methoxy-2-propanol (MPA), and an aliquot is injected into an enclosed oven system, where the MPA/water azeotrope is swept directly into the KF titration vessel. The technique is accurate and precise and, thus far, proves to be a fast and reliable method for analysis.     

Measurements show that marginal wells are a disproportionate source of methane relative to production

ABSTRACT

Oil and natural gas wells are a prominent source of the greenhouse gas methane (CH₄), but most measurements are from newer, high producing wells. There are nearly 700,000 marginal “stripper” wells in the US, which produce less than 15 barrels of oil equivalent (BOE) d^?1. We made direct measurements of CH₄ and volatile organic carbon (VOC) emissions from marginal oil and gas wells in the Appalachian Basin of southeastern Ohio, all producing < 1 BOE d^?1. Methane and VOC emissions followed a skewed distribution, with many wells having zero or low emissions and a few wells responsible for the majority of emissions. The average CH₄ emission rate from marginal wells was 128 g h^?1 (median: 18 g h^?1; range: 0– 907 g h^?1). Follow-up measurements at five wells indicated high emissions were not episodic. Some wells were emitting all or more of the reported gas produced at each well, or venting gas from wells with no reported gas production. Measurements were made from wellheads only, not tanks, so our estimates may be conservative. Stochastic processes such as maintenance may be the main driver of emissions. Marginal wells are a disproportionate source of CH₄ and VOCs relative to oil and gas production. We estimate that oil and gas wells in this lowest production category emit approximately 11% of total annual CH₄ from oil and gas production in the EPA greenhouse gas inventory, although they produce about 0.2% of oil and 0.4% of gas in the US per year.

Implications: Low producing marginal wells are the most abundant type of oil and gas well in the United States, and a surprising number of them are venting all or more of their reported produced gas to the atmosphere. This makes marginal wells a disproportionate greenhouse gas emissions source compared to their energy return, and a good target for environmental mitigation.     

Loss of Particle Nitrate from Teflon Sampling Filters: Effects on Measured Gravimetric Mass in California and in the IMPROVE Network

Abstract

The extent of mass loss on Teflon filters caused by ammonium nitrate volatilization can be a substantial fraction of the measured particulate matter with an aerodynamic diameter less than 2.5 μm (PM_2.5)or 10 μm (PM₁₀) mass and depends on where and when it was collected. There is no straightforward method to correct for the mass loss using routine monitoring data. In southern California during the California Acid Deposition Monitoring Program, 30-40% of the gravimetric PM_2.5 mass was lost during summer daytime. Lower mass losses occurred at more remote locations. The estimated potential mass loss in the Interagency Monitoring of Protected Visual Environments network was consistent with the measured loss observed in California. The biased mass measurement implies that use of Federal Reference Method data for fine particles may lead to control strategies that are biased toward sources of fugitive dust, other primary particle emission sources, and stable secondary particles (e.g., sulfates). This analysis clearly supports the need for speciated analysis of samples collected in a manner that preserves volatile species. Finally, although there is loss of volatile nitrate (NO₃ ^?) from Teflon filters during sampling, the NO₃ ^? remaining after collection is quite stable. We found little loss of NO₃ ^? from Teflon filters after 2 hr under vacuum and 1 min of heating by a cyclotron proton beam.     

Assessment of volatile organic compound and hazardous air pollutant emissions from oil and natural gas well pads using mobile remote and on-site direct measurements

Emissions of volatile organic compounds (VOCs) and hazardous air pollutants (HAPs) from oil and natural gas production were investigated using direct measurements of component-level emissions on pads in the Denver-Julesburg (DJ) Basin and remote measurements of production pad-level emissions in the Barnett, DJ, and Pinedale basins. Results from the 2011 DJ on-site study indicate that emissions from condensate storage tanks are highly variable and can be an important source of VOCs and HAPs, even when control measures are present. Comparison of the measured condensate tank emissions with potentially emitted concentrations modeled using E&P TANKS (American Petroleum Institute [API] Publication 4697) suggested that some of the tanks were likely effectively controlled (emissions less than 95% of potential), whereas others were not. Results also indicate that the use of a commercial high-volume sampler (HVS) without corresponding canister measurements may result in severe underestimates of emissions from condensate tanks. Instantaneous VOC and HAP emissions measured on-site on controlled systems in the DJ Basin were significantly higher than VOC and HAP emission results from the study conducted by Eastern Research Group (ERG) for the City of Fort Worth (2011) using the same method in the Barnett on pads with low or no condensate production. The measured VOC emissions were either lower or not significantly different from the results of studies of uncontrolled emissions from condensate tanks measured by routing all emissions through a single port monitored by a flow measurement device for 24 hr. VOC and HAP concentrations measured remotely using the U.S. Environmental Protection Agency (EPA) Other Test Method (OTM) 33A in the DJ Basin were not significantly different from the on-site measurements, although significant differences between basins were observed.

Implications: VOC and HAP emissions from upstream production operations are important due to their potential impact on regional ozone levels and proximate populations. This study provides information on the sources and variability of VOC and HAP emissions from production pads as well as a comparison between different measurement techniques and laboratory analysis protocols. On-site and remote measurements of VOC and HAP emissions from oil and gas production pads indicate that measurable emissions can occur despite the presence of control measures, often as a result of leaking thief hatch seals on condensate tanks. Furthermore, results from the remote measurement method OTM 33A indicate that it can be used effectively as an inspection technique for identifying oil and gas well pads with large fugitive emissions.     

Determining the Costs of Air Pollution Control

A general procedure has been described that can be followed for estimating the cost of reducing air pollution emissions within a metropolitan region. The six step procedure examines emission inventories, regional trends, control trends, alternate control schemes, control costs, and optimum cost-effectiveness. The procedure is illustrated for one emission source in the Delaware Valley. By application of “feasible controls,” automobile emissions were shown to be reduced from 4.5 billion pounds per year in the Region during 1968 to 1.5 billion pounds in the year 2000. Annual control costs during the same period will increase from $30 million to over $300 million per year. This represents a cost increase from $15 per registered vehicle in 1968 to about $58 per vehicle per year in 2000. A method was illustrated for determining minimum cost to achieve any desired degree of emission reduction where alternate feasible control schemes are available. This method is especially useful where the allocation of scarce resources is involved. The general procedure is applicable to any number of pollutants and emission sources, and may be useful for calculations in any metropolitan area. The objectives of the present study are to apply this method to other sources within the Delaware Valley and to determine total regional costs for various levels of emission reduction. As one example of a practical application for this type of analysis, the economic impact of regulatory schemes can be evaluated on a cost-effectiveness basis     

Loss of PM2.5 Nitrate from Filter Samples in Central California

Abstract

Evaporative loss of particulate matter (with aerodynamic diameter <2.5 μm, [PM_2.5]) ammonium nitrate from quartz-fiber filters during aerosol sampling was evaluated from December 3, 1999, through February 3, 2001, at two urban (Fresno and Bakersfield) and three nonurban (Bethel Island, Sierra Nevada Foothills, and Angiola) sites in central California. Compared with total particulate nitrate, evaporative nitrate losses ranged from <10% during cold months to >80% during warm months. In agreement with theory, evaporative loss from quartz-fiber filters in nitric acid denuded samplers is controlled by the ambient nitric acid-to-particulate nitrate ratio, which is determined mainly by ambient temperature. Accurate estimation of nitrate volatilization requires a detailed thermodynamic model and comprehensive chemical measurements. For the 14-month average of PM_2.5 acquired on Teflon-membrane filters, measured PM_2.5 mass was 8–16% lower than actual PM_2.5 mass owing to nitrate volatilization. For 24-hr samples, measured PM_2.5 was as much as 32–44% lower than actual PM_2.5 at three California Central Valley locations.     

Reverse phase high performance liquid chromatographic determination of Baygon in water

Abstract

A simple analytical procedure for determination of Baygon in water is described. The Baygon residues are extracted on a C₁₈ SEP‐PAK cartridge and subsequently analyzed by reverse phase high performance liquid chromatography using ultraviolet detection at 272 nm. Water samples spiked with Baygon are found to give greater than 90 percent recoveries.

Concentration levels as low as 20 ppb can be easily detected by this method.     

Accuracy Assessment of EPA Protocol Gases Purchased In 1991

ABSTRACT

Fixed-roof tanks are used extensively at manufacturing, waste management, and other facilities to store or process liquids containing volatile organic compounds. Federal and state air standards require the control of organic air emissions from many of these tanks. A common practice used for some fixed-roof tanks that are required to use controls is to vent the tank through an activated carbon canister. When organic vapors are adsorbed on activated carbon, heat is released. Under certain conditions, the temperature of the carbon bed can increase to a level at which the carbon or organic vapors spontaneously ignite, starting a fire in the carbon bed. Bed fires in carbon canisters are not uncommon and can present a significant safety hazard at facilities if proper safety measures are not implemented. This article discusses how carbon adsorber bed fires occur and presents general guidance on safety measures for carbon canisters installed on fixed-roof tanks to reduce the likelihood of a carbon bed fire and to minimize the impact in the event of a fire.     

Comparison of Aerobic and Anaerobic Biotreatment of Municipal Solid Waste

Abstract

To increase the operating lifetime of landfills and to lower leachate treatment costs, an increasing number of municipal solid waste (MSW) landfills are being managed as either aerobic or anaerobic bioreactors. Landfill gas composition, respiration rates, and subsidence were measured for 400 days in 200-L tanks filled with fresh waste materials to compare the relative effectiveness of the two treatments. Tanks were prepared to provide the following conditions: (1) air injection and leachate recirculation (aerobic), (2) leachate recirculation (anaerobic), and (3) no treatment (anaerobic). Respiration tests on the aerobic wet tank showed a steady decrease in oxygen consumption rates from 1.3 mol/day at 20 days to 0.1 mol/day at 400 days. Aerobic wet tanks produced, on average, 6 mol of carbon dioxide (CO₂)/kg of MSW as compared with anaerobic wet tanks, which produced 2.2 mol methane/kg of MSW and 2.0 mol CO₂/kg methane. Over the test period, the aerobic tanks settled on average 35%, anaerobic tanks settled 21.7%, and the no-treatment tank settled 7.5%, equivalent to overall mass loss in the corresponding reactors. Aerobic tanks reduced stabilization time and produced negligible odor compared with anaerobic tanks, possibly because of the 2 orders of magnitude lower leachate ammonia levels in the aerobic tank. Both treatment regimes provide the opportunity for disposal and remediation of liquid waste.     

强化生物通风修复过程中柴油衰减规律及其影响因素研究

强化生物通风技术对于修复因地下储油罐泄漏引起的土壤污染具有很大的应用前景。通过室内土柱模拟柴油泄漏污染土壤,从土柱中总石油烃（total petroleum hydrocarbon,TPH）剖面分布随时间的变化及降解模式角度,分析了其自然衰减和强化生物通风过程。结果表明：初始柴油浓度直接影响着各柱在自然衰减和强化生物通风过程中柱内的残余TPH平衡分布曲线的形状和浓度峰值位置;在前期自然衰减过程中（约1个月）,当土壤中的柴油浓度为5 000～40 000 mg油/kg土时,整个柱内TPH变化的主要原因是重力扩散迁移的结果;当土壤中的柴油浓度≤5 000 mg油/kg土时,其TPH的变化不仅是重力扩散迁移作用的结果,生物降解作用也存在;通风约2个月后,抽提作用对于保持土柱上部柴油浓度稳定变化的意义较为突出。     

Estimating Gas Emissions from Multiple Sources Using a Backward Lagrangian Stochastic Model

Abstract

Manure storage tanks and animals in barns are important agricultural sources of methane. To examine the possibility of using an inverse dispersion technique based on a backward Lagrangian Stochastic (bLS) model to quantify methane (CH₄) emissions from multiple on-farm sources, a series of tests were carried out with four possible source configurations and three controlled area sources. The simulated configurations were: (C1) three spatially separate ground-level sources, (C2) three spatially separate sources with wind-flow disturbance, (C3) three adjacent ground-level sources to simulate a group of adjacent sources with different emission rates, and (C4) a configuration with a ground level and two elevated sources. For multiple ground-level sources without flow obstructions (C1 and C3), we can use the condition number (k, the ratio of the uncertainty in the calculated emission rate to the uncertainty in the predicted ratio of concentration to emission rate) to evaluate the applicability of this inverse dispersion technique and a preliminary threshold of k < 10 is recommended. For multiple sources with wind disturbance (C2) or an even more complex configuration including ground level and elevated sources (C4), a low k is not sufficient to provide reasonable discrete and total emission rates. The effect of flow obstructions can be neglected as long as the distance between the source and the measurement location is greater than approximately 10 times the height of the flow obstructions. This study shows that the bLS model has the potential to provide accurate discrete emission rates from multiple on-farm emissions of gases provided that certain conditions are met.     

Direct Measurement of Fugitive Emissions of Hydrocarbons from a Refinery

Abstract

Refineries are a source of emissions of volatile hydrocarbons that contribute to the formation of smog and ozone. Fugitive emissions of hydrocarbons are difficult to measure and quantify. Currently these emissions are estimated based on standard emission factors for the type and use of equipment installed. Differential absorption light detection and ranging (DIAL) can remotely measure concentration profiles of hydrocarbons in the atmosphere up to several hundred meters from the instrument. When combined with wind speed and direction, downwind vertical DIAL scans can be used to calculate mass fluxes of the measured gas leaving the site. Using a mobile DIAL unit, a survey was completed at a Canadian refinery to quantify fugitive emissions of methane, C₂₊ hydrocarbons, and benzene and to apportion the hydrocarbon emissions to the various areas of the refinery. Refinery fugitive emissions as measured with DIAL during this demonstration study were 1240 kg/hr of C₂₊ hydrocarbons, 300 kg/hr of methane, and 5 kg/hr of benzene. Storage tanks accounted for over 50% of the total emissions of C₂₊ hydrocarbons and benzene. The coker area and cooling towers were also significant sources. The C₂₊ hydrocarbons emissions measured during the demonstration amounted to 0.17% of the mass of the refinery hydrocarbon throughput for that period. If the same loss were repeated throughout the year, the lost product would represent a value of US$3.1 million/yr (assuming US$40/bbl). The DIAL-measured hourly emissions of C₂₊ hydrocarbons were 15 times higher than the emission factor estimates and gave a different perspective on which areas of the refinery were the main source of emissions. Methods, such as DIAL, that can directly measure fugitive emissions would improve the effectiveness of efforts to reduce emissions, quantify the reduction in emissions, and improve the accuracy of emissions data that are reported to regulators and the public.     

Oxalic Acid in PM2.5 Particulate Matter in California

ABSTRACT

Ambient air monitoring for organic acids in PM₂₅ was conducted at several locations in California. During the study, it was found that oxalic acid (ethanedioc acid) was the most abundant organic acid found in the PM_{2 5} fraction. Samples from Azuza (in southern California), San Jose (in the San Francisco Bay area), and Fresno (in central California), a PM_2.5 Super Site, were collected in 1999 and analyzed. The results for oxalic acid concentrations during this monitoring effort are presented.     

14C‐dimethoate residues in olive oil during oil processing

Abstract

An olive tree was treated twice in the field with ¹⁴C‐dimethoate (237.7 (μCi, 2.4 g) and ¹⁴C residues were determined in the olive fruits at harvest. The fruits were crushed and pressed to extract the crude oil, then refined by neutralization, bleaching and deodorization. The crude oil contained 14.1% of the total ¹⁴C in the olive fruits. Neutralization resulted in a reduction of ¹⁴C by about 50% of the total ¹⁴C residues in oil. Bleaching and deodorization processes further reduced the ¹⁴C residues and the refined oil contained 31.6% (which corresponds to 4.4% of ^I4C residues of the total ¹⁴C in olive fruits) of the total ¹⁴C in the crude oil. Industrially extracted crude oil was fortified with ¹⁴C‐dimethoate at 1.8 mg kg^‐1 (0.02 μCi) level and subjected to the same refining process. A sharp decrease in the amount of ¹⁴C was observed by neutralization and the amount of ¹⁴C remaining in the refined oil was about 7.3% of the total ^l4C in the crude fortified oil. The data suggest that the ¹⁴C residues in the aged and the fortified oil amples were not of the same nature. The terminal ¹⁴C residue in the refined oil obtained from the field experiment did not contain dimethoate and/or its oxon.     

Determination of Nitrogen Oxides in Auto Exhaust

A new procedure for determining nitrogen oxides in automobile exhaust has been developed. The new procedure was included in a Bureau of Mines comparative study that aimed at evaluating various widely used methods for determining NO_x in auto exhaust. The methods included in the evaluation study follow: (1) Static oxidation in tank (ST method). The method involves oxidation of NO in residence with O₂ in a stainless steel tank. (2) Bureau of Mines method (BM method). The method involves application of the ST procedure in exhaust samples from which the hydrocarbons have been removed by combustion over catalyst. (3) Chevron Research method (CR method), as described in the literature. (4) Phenoldisulfonic acid method (PDS method), as described in the literature. The principal objective of this study was to generate experimental evidence which would lead to defining an optimum procedure for converting NO, present in exhaust gas, into NO₂; this conversion is desired so that the total of NO + NO₂ can be determined quantitatively in the form of NO₂. In pursuing this objective, the procedures prescribed by the foregoing methods were comparatively tested. The results indicated that all four methods are subject to error, the extent of which depends on the conditions employed. The BM method was superior from the standpoint of accuracy because it was less affected by interferences due to hydrocarbon-NO₂ reactions.     

Solid‐phase extraction and GC analyses of select agricultural pesticides and metabolites in stream water

Abstract

The occurrence of agricultural pesticides in surface waters around the USA has created a concern over the status of safe drinking water. Solid‐phase extraction (SPE) or liquid‐liquid extraction (LLE) is usually employed to concentrate trace levels of pesticides in water samples to concentrations that are measurable with advanced chromatographic instruments. We describe here a SPE and capillary gas chromatographic (GC) procedure to extract and concentrate trace levels of select agricultural pesticides and metabolites from stream water. Our SPE and GC method provides high sensitivity, with recoveries between 85% to 95%, and high reproducibility for 9 of the pesticides studied. The described method provided marginal recoveries of 19 and 60% for the atrazine metabolites.     

Contribution of Nitrate and Carbonaceous Species to PM2.5 Observed in Canadian Cities

ABSTRACT

At a variety of Canadian monitoring sites, carbonaceous compounds were estimated to account for an average of 50% of fine particle mass. These estimates were determined by subtracting the total fine particle mass associated with inorganic compounds from the total fine mass determined gravimetrically. This approach, which yields an upper limit estimate of the total amount of carbon-related mass was necessary since particulate carbon was not measured in the Canadian National Air Pollution Surveillance (NAPS) network. In this paper, total carbon estimates are evaluated against organic and elemental carbon measurements at locations in the Greater Vancouver area and Toronto. In addition, particle nitrate measurements at seven Canadian locations are used to determine the importance of nitrate relative to total mass and to examine the sampling artifacts due to the loss of particle nitrate from Teflon filters used in the NAPS di-chotomous samplers.

Measurements of organic and elemental carbon indicated that the total carbon estimation approach provides representative estimates of the average contribution by carbonaceous material to the total fine and coarse mass. The average total carbon among all Vancouver area measurements (N = 225) was 4.28 μg m^-3, while the estimated value was 4.34 μg m^-3. There was a larger discrepancy between Toronto total carbon measurements (12.1 μg m^-3) and estimates (8.8 μg m^-3), which is attributed in part to sampling of particles above 10 mm in diameter. However, the R² relating the measurements and estimates was about 0.71 for both areas. Linear regression slopes of 0.98 for Vancouver and 0.78 for Toronto (nonsignificant intercepts) indicate little bias in the Vancouver estimates, but a tendency for underestimation as the observed total carbon concentration increased in Toronto.

Annually, nitrate was responsible for 17% and 12% of the fine mass in the Vancouver area and Ontario, respectively. In contrast, at two rural locations in southern Quebec and Nova Scotia, only 6% of fine mass was associated with nitrate. Due to filter losses, nitrate concentrations determined through the NAPS dichot sampling were much lower than actual concentrations (0.44 μg m^-3 vs. 2.63 μg m^-3). As a result of these losses (attributed mostly to loss during laboratory storage), previous total carbon estimates for the Canadian NAPS sites were likely to have been overestimated on average by about 10%.