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Detection of petroleum hydrocarbons at low ppb levels using quartz resonator sensors and instrumentation of a smart environmental monitoring system.

Petroleum hydrocarbon vapors at low ppb levels can be detected using a thickness shear mode resonator (TSMR) coated with a chemical-sensing overlayer, prepared by radiofrequency sputtering of porous sintered-polyethylene (PS-PE). The sensing capabilities of PS-PE sensors were profoundly affected by the sputtering methods; they were enhanced by the photo-excitation effect, and were reduced by carbonization and water treatment. The photo-assisted PS-PE sensor was extremely sensitive and could detect linear hydrocarbon (> C12) vapors below the ppb level. The time constant of the sorption curve, however, was large, indicating a slow sensing speed. Toward creating instrumentation for a smart environmental monitoring system, the TSMR sensors were arrayed on a circuit board equipped with a serial interface and signal processing chips of the oscillation drive and frequency counter. Co-sorption with water vapor at a relative humidity of about 10% has almost no effect on the sensing ability of PS-PE sensors for 1,2,4-trimethylbenzene. Conversely, it enhances the sensitivity of the TSMR sensor coated with a D-phenylalanine film. Upward shifts in the baseline are evident with elapsed time. However, a rigorous ten-cycle iteration test for 100 ppm toluene vapor demonstrated good reproducibility of the sensor's signals.

Air Pollution↗

Determination of organochlorinated compounds and petroleum hydrocarbons in sediment sample IAEA-408. Results from a world-wide intercalibration exercise.

A sediment sample from the intertidal mudflats of the Tagus estuary was prepared, homogenised and distributed globally to laboratories as the IAEA-408 intercomparison material for the analyses of organochlorinated pesticides, PCBs and petroleum hydrocarbons (PHs). A total of 48 laboratories from 36 countries reported their results. The data from participants show that there still remain some difficulties with the accurate determination of organic contaminants such as pesticides and polycyclic aromatic hydrocarbons (PAHs). More consistent interlaboratory results were obtained for PCBs congeners. The final results of this intercomparison exercise enable individual participants to assess their performance and, where necessary, to introduce appropriate modifications in their analytical procedures. Furthermore, as a series of statistical criteria was fulfilled for a number of compounds, the sample IAEA-408 can now be used as a reference material for quality control in the determination of some persistant organic pollutants (POPs) in marine sediment samples.

Calibration↗

Recycling of petroleum-contaminated sand.

The environmental impact of using petroleum-contaminated sand (PCS) as a substitute in asphalt paving mixtures was examined. An appreciable component of PCS is oily sludge, which is found as the dregs in oil storage tanks and is also produced as a result of oil spills on clean sand. The current method for the disposal of oily sludge is land farming. However, this method has not been successful as an oil content of < 1% w/w is required, and difficulty was encountered in reaching this target. The reuse of the sludge in asphalt paving mixtures was therefore considered as an alternative. Standard tests and environmental studies were conducted to establish the integrity of the materials containing the recycled sludge. These included physical and chemical characterization of the sludge itself, and an assessment of the mechanical properties of materials containing 0%, 5%, 22% and 50% oily sludge. The blended mixtures were subjected to special tests, such as Marshall testing and the determination of stability and flow properties. The experimental results indicated that mixtures containing up to 22% oily sludge could meet the necessary criteria for a specific asphalt concrete wearing course or bituminous base course. To maximize the assay from the recycled material, the environmental assessment was restricted to the 50% oily sludge mixture. Leachates associated with this particular mixture were assayed for total organic residue and certain hazardous metal contaminants. The results revealed that the organics were negligible, and the concentrations of the metals were not significant. Thus, no adverse environmental impact should be anticipated from the use of the recycled product. Our research showed that the disposal of oily sludge in asphalt paving mixtures could possibly yield considerable savings per tonne of asphalt concrete, and concurrently minimize any direct impact on the environment.

Conservation of Natural Resources↗

Water-soluble species and heavy metal contamination of the petroleum refinary area, Jordan.

The levels of lead, cadmium, copper, zinc, aluminum, chromium, and iron in street dust, soil, and plants in the Jordanian petroleum refinery were determined using flame and graphite-furnace atomic absorption spectrophotometry. Major cations (Li+, Na+, NH4+, K+, Mg2+, and Ca2+) and anions (F-, Cl-, NO3-, SO4(2-), and Br-) were also determined using suppression mode ion chromatography. Generally, higher levels of the heavy metals studied were found in street dust samples than in soil samples. On the other hand, except Cl-, and Li+ ions, other anions and cations showed higher concentrations in soil than in street dust samples. For plant samples, unwashed samples showed higher levels of heavy metals than their washed counterparts, indicating that dust fall is a source of heavy metal contamination.

Cities↗

Mechanisms for enhanced biodegradation of petroleum hydrocarbons by a microbe-colonized gas-liquid foam.

AIMS: A microbe-colonized gas-liquid foam formulation has been previously shown to provide enhanced biodegradation capabilities in soil microcosms. The present study considers the reservoir properties of this foam and how this affects hydrocarbon degradation rates. METHODS AND RESULTS: Oxygen solubility in protein hydrolysate solutions draining from aerated and oxygenated foams was measured. The suitability of oxygenated foam to enhance the degradation of n-hexadecane in soil microcosms was assessed. Sorption of bacterial isolates at the gas-liquid interface was also investigated using a range of microscopy techniques. CONCLUSIONS: Oxygenated bioactive foam enhanced biodegradation rates by improving oxygen availability and transfer. Biodegradation of n-hexadecane was also stimulated by the protein hydrolysate used and by the inclusion of known bacterial hydrocarbon-degrading bacteria. The interaction of bacteria with the gas-liquid interface was shown to be a significant factor governing the drainage of the bacteria from the bioactive foam. SIGNIFICANCE AND IMPACT OF THE STUDY: Protein hydrolysate-based bioactive foam may be a suitable treatment technology to enhance the biodegradation of petroleum hydrocarbons in soil.

Alkanes↗

A subacute inhalation exposure evaluation of a scrubbing solution used in petroleum refineries.

The potential for subacute toxicity and neurotoxicity of a potassium carbonate-based scrubbing solution used in petroleum refineries was evaluated in Sprague-Dawley Crl:CD BR rats. Exposures were to aerosols of a "used" scrubbing solution by wholebody inhalation, 6 h/d, for 21 consecutive days at target concentrations of 0 (filtered air-control), 0.1, 0.2, or 0.4 mg/L (30 animals/sex/group). A functional observation battery (FOB) and locomotor activities tests were conducted and monitored. No apparent adverse effects were noted at any exposure level as determined by clinical observations, food consumption, hematology, serum chemistry, ophthalmologic observations, and gross pathology. Statistically significant increases in lung weights were noted at all treatment levels but returned to control values upon cessation of exposure except for the 0.4 mg/L female group. There were no significant changes in other organ weights. Histopathologic findings were restricted to the respiratory tract and characterized by minimal to moderate epithelial hyperplasia, epithelial necrosis, and cytoplasmic vacuolation at levels I and II of the nasal cavities. Lung bronchiolization and alveolar macrophage infiltration were also observed. The respiratory-tract findings were considered a local response to the high alkalinity of the test material as substantiated by the return to normal upon cessation of exposure. Exposure to scrubbing solution had no adverse effect on FOB endpoints and locomotor activity evaluations, brain weight and size, and neuropathologic examinations. In conclusion, inhalation exposure to a used scrubbing solution aerosol for 21 d did not result in any persistent systemic toxicity or neurotoxicity in either male or female rats.

Animals↗

Developmental toxicity evaluation of a scrubbing solution used in petroleum refineries.

The developmental toxicity potential of a scrubbing solution used extensively in petroleum refineries to remove CO2 from hydrogen gas streams was evaluated via inhalation. Pregnant female CD (Sprague-Dawley) rats were exposed to aerosols of a "used" scrubbing solution at 0.05, 0.1, 0.2, or 0.3 mg/l for 6 h/d on d 6-19 of pregnancy. Control animals were exposed to filtered air under the same exposure conditions. Dams were sacrificed on d 20 of pregnancy and a laparohysterectomy was performed. The mass median aerodynamic diameter of the aerosol revealed that all particles ranged from 1.6 to 2.8 microm, with geometric standard deviations between 2.0 and 2.3 microm. The overall pregnancy rate was high (>95%) and equivalent across all groups. All pregnant dams had live litters, and 22-24 litters were examined in each group. Treatment-related clinical signs consisted of rales, observed at all exposure levels, and gasping noted only at the 0.3 mg/l exposure level. The occurrence of rales was presumably a localized effect on the respiratory tract and likely due to the irritating properties of the scrubbing solution. Maternal toxicity was exhibited in the 0.3 mg/l group, including reduced body weight, weight gain, and food consumption and one possible treatment-related death on gestation d 17. At scheduled necropsy, there were no treatment-related gross pathological observations and no statistically significant reproductive and developmental effects. The incidences of fetuses with skeletal variations involving the sternum were clustered in two litters at the highest exposure level with atypically low term fetal body weights. Under the conditions of this investigation, potassium carbonate scrubbing solution is not a selective developmental toxicant.

Accidents, Occupational↗

Contribution of liquefied petroleum gas to air pollution in the metropolitan area of Mexico City.

An estimation of hydrocarbon emissions caused by the consumption of liquefied petroleum gas (LPG) in the Metropolitan Area of Mexico City (MAMC) is presented. On the basis of experimental measurements at all points of handling, during the distribution process, and during the consumption of LPG in industrial devices and domestic appliances, an estimated 76,414 tons/year are released to the air. The most important contribution is found during the domestic consumption of LPG (70%); this makes the control initiatives available to the consumer. By developing a control program of LPG losses, a 77% reduction in emission is expected in a 5-yr period. The calculated amounts of LPG emissions when correlated with the consumption of LPG, combined with information from air samples from the MAMC, do not point to LPG emissions as the most important factor contributing to tropospheric ozone in the air in Mexico City.

Air Pollutants↗

Effect of liquefied petroleum gas on ozone formation in Guadalajara and Mexico City.

Leakages of liquefied petroleum gas (LPG) are suspected to contribute greatly to ozone (O3) formation in Mexico City. We tested such a hypothesis by outdoor captive-air irradiation (CAI) experiments in the two largest Mexican metropolitan areas: Guadalajara (GMA) in 1997 and Mexico City (MCMA) in 2000. O3 was monitored in each city for 20 days (8:00 a.m.-6:00 p.m.) in smog chambers containing unaltered morning air or morning air enriched with either commercial LPG or LPG synthetic mixture 60/40 (propane and butane). Tested additions of both components were 35% (by volume) in GMA and 60% (by volume) in MCMA. The addition effects on O3 (max) were compared with effects from diluting LPG components or total nonmethane hydrocarbons (tNMHCs) by 50%. Diluting tNMHCs had the greatest absolute effect at both cities: it lowered O3 (max) by 24% in GMA and 55% in MCMA. Adding commercial LPG increased O3 (max) by 6% in GMA and 28% in MCMA; whereas adding LPG synthetic mixture 60/40 caused a similar increase in O3 (max), 4 and 21% in GMA and MCMA, respectively. Compared with dilution of tNMHCs, dilution of LPG-associated compounds had a smaller decreasing effect on O3 (max), only 4% in GMA and 15% in MCMA. These results show that commercial LPG and LPG synthetic mixture 60/40 affect O3 formation to a lesser extent than estimated previously.

Air Pollutants↗

Biodegradation of petroleum hydrocarbons by two Pseudomonas aeruginosa strains with different uptake modes.

The uptake modes of alkanes by two strains (Pseudomonas aeruginosa S and Pseudomonas aeruginosa Y) were compared in this article. It was found that the strain of P. aeruginosa S showed low cell surface hydrophobicity and the surface tension of the broth decreased when the strain was cultivated on alkanes. On the contrary, P. aeruginosa Y showed higher cell surface hydrophobicity and the change in surface tension was not significant. This suggests that P. aeruginosa Y accessed hydrocarbon droplets by direct contact mode, while P. aeruginosa S engaged hydrocarbon droplets by biosurfactant-medium mode. The biodegradation of petroleum hydrocarbons by the two strains was also investigated. The results showed that irrespective of the substrate utilized: liquid hydrocarbons, solid hydrocarbons or crude oil in contaminated soil, the degradation by P. aeruginosa S was faster than that by P. aeruginosa Y. It was also deduced that the produced biosurfactant is advantageous in improving the biodegradation process.

Biodegradation, Environmental↗

Embryotoxic and teratogenic effects of petroleum hydrocarbons in mallards (Anas platyrhynchos).

Egg surface applications of microliter quantities of crude and refined oils of high aromatic content are embryotoxic to mallards (Anas platyrhynchos) and other avian species; applications of aliphatic hydrocarbons have virtually no effect. Mallard eggs at 72 h of development were exposed to a mixture of aromatic hydrocarbons or to aromatic compounds representative to those present in crude oil to assess their toxicity. The class composition of the mixture was similar to that of South Louisiana crude oil, an American Petroleum Institute reference oil. Application of 20 microliter of the mixture reduced embryonic survival by nearly 70%. The temporal pattern of embryonic death was similar to that after exposure to South Louisiana crude oil. Embryonic growth was stunted, as reflected by weight, crown-rump length, and bill length, and there was a significant increase in the incidence of abnormal survivors. When individual classes of aromatic hydrocarbons were tested, tetracyclics caused some embryonic death at the concentrations in the mixture. When classes were tested in all possible combinations of two, no combination appeared to be as toxic as the entire mixture. Addition of the tetracyclic compound chrysene to the aromatic mixture considerably enhanced embryotoxicity, but could not completely account for the toxicity of the crude oil. The presence of additional unidentified polycyclic aromatic hydrocarbons as well as methylated derivatives of polycyclic aromatic compounds such as chrysene may further account for the embryotoxicity of the crude oil.

Animals↗

Benzene and total hydrocarbon exposures in the upstream petroleum oil and gas industry.

Occupational exposures to benzene and total hydrocarbons (THC) in the Canadian upstream petroleum industry are described in this article. A total of 1547 air samples taken by 5 oil companies in various sectors (i.e., conventional oil/gas, conventional gas, heavy oil processing, drilling and pipelines) were evaluated and summarized. The data includes personal long- and short-term samples and area long-term samples. The percentage of samples over the occupational exposure limit (OEL) of 3.2 mg/m3 or one part per million for benzene, for personal long-term samples ranges from 0 to 0.7% in the different sectors, and area long-term samples range from 0 to 13%. For short-term personal samples, the exceedance for benzene is at 5% with respect to the OEL of 16 mg/m3 or five parts per million in the conventional gas sector and none in the remaining sectors. THC levels were not available for all sectors and had limited data points in others. The percentage exceedance of the OEL of 280 mg/m3 or 100 parts per million for THC as gasoline ranged from 0 to 2.6% for personal long-term samples. It is recommended that certain operations such as glycol dehydrators be carefully monitored and that a task-based monitoring program be included along with the traditional long- and short-term personal exposure sampling.

Benzene↗

Subchronic inhalation exposures to aerosols of three petroleum lubricants.

Subchronic inhalation studies were performed with three petroleum lubricants: generic cutting oil (GCO), generic gear oil (GO), and generic commercial engine oil (CEO). Each formulation had a mineral oil base. Sprague-Dawley rats were exposed 6 hours/day, 5 days/week for 13 weeks to aerosol concentrations of 0 (untreated controls), 0 (sham-exposed controls), approximately 50, 150, or 400-520 mg/m3. At necropsy, 15 rats/sex/group were sampled for serum chemistry (18 parameters), hematology, and weights of 13 organs. Testis and epididymis of males in the control and high-dose group were used for number of spermatids and morphology of epididymal sperm. Histopathological slides were evaluated for 22 or more organs. Pulmonary function tests were done on 10 additional males/group. Pulmonary hydroxyproline was measured in these rats for GCO and GO. Residual oil in the lungs was determined for GCO. The primary organ affected by exposures to these three formulations was the lung; the main observed effects were accumulation of foamy macrophages in pulmonary alveoli and alveolar walls, very mild thickening of alveolar walls due to foamy macrophages and a mixed cell infiltrate, and subtle epithelial hyperplasia. The foamy macrophages tended to group together in aggregates, and the aggregates seemed responsible for plaques seen visibly on the surface of the lung. These histological changes were accompanied by concentration-related increases in lung weight and pulmonary hydroxyproline, whereas pulmonary function tests were generally unaffected. Effects distal to the lung were more limited. These results indicated low toxicity of these aerosols in this model.

Aerosols↗

Correlation of fluorescence intensity and carcinogenic potency of synthetic and natural petroleums in mouse skin.

After standardized topical exposure of mouse skin to synthetic and natural petroleums, the penetration and persistence of the fluorescent components have been quantitated. Carcinogenicity of the same materials was determined by repeated skin application following by a period without treatment ot allow expression of malignantly transformed epidermal cells. No simple correlation was found for the materials between total specific fluorescence in either tissue or the test tube and their observed capacity to elicit skin necrosis or malignancy. The number of test materials was insufficient to allow generalization; however, the results do suggest that before fluorescence can be effectively employed as a tool for assessing potential occupational exposure to complex hydrocarbon mixtures, considerable refinement of the methodology will be required.

Animals↗

Fabric protectors. Part II - Propane, 1,1,1-trichloroethane, and petroleum distillates levels in air after application of fabric protectors.

Propane, 1,1,1-trichloroethane, and petroleum distillates levels in air which were generated during the use of aerosol type fabric protectors were monitored by means of the NIOSH charcoal tube, a glass bulb grab sampling, and the GASBADGE passive device techniques. Although 1982 ACGIH TLV-STEL were readily exceeded in an unventilated test room, when fabric was sprayed with 450 g of fabric protector in an unconfined area within a home the generated vapors quickly dispersed and STEL and 8-hour TWA-TLV were not exceeded.

Air Pollutants↗

A simple analytical test and a formula to predict the potential for dermal carcinogenicity from petroleum oils.

A correlation for predicting dermal carcinogenicity of petroleum oils in laboratory animals has been developed using two simple analytical tests. The tests are the Food and Drug Administration test (FDA) commonly used to measure white oil purity, and a viscosity test. In the correlation, FDA is a measure of aromaticity, and viscosity is used to account for molecular weight. The FDA test alone appears to be comparable to other predictors now in use, but incorporating viscosity significantly increases the accuracy of predicting dermal carcinogenicity. A formula is proposed, using both the FDA test results and viscosity, that predicts the percentage of mice which will develop neoplastic skin tumors.

Animals↗

Retrospective benzene and total hydrocarbon exposure assessment for a petroleum marketing and distribution worker epidemiology study.

A quantitative exposure-estimating algorithm for benzene and total hydrocarbons was developed for a case control study of petroleum marketing and distribution workers. The algorithm used a multiplicative model to adjust recently measured quantitative exposure data to past scenarios for which representative exposure measurement data did not exist. This was accomplished through the development of exposure modifiers to account for differences in the workplace, the materials handled, the environmental conditions, and the tasks performed. Values for exposure modifiers were obtained empirically and through physical/chemical relationships. Dates for changes that altered exposure potential were obtained from archive records, retired employee interviews, and from current operations personnel. Exposure modifiers were used multiplicatively, adjusting available measured data to represent the relevant exposure scenario and time period. Changes in exposure modifiers translated to step changes in exposure estimates. Though limited by availability of data, a validation exercise suggested that the algorithm provided accurate exposure estimates for benzene (compared with measured data in industrial hygiene survey reports); the estimates generally differed by an average of less than 20% from the measured values. This approach is proposed to quantify exposures retrospectively where there are sufficient data to develop reliable current era estimates and where a historical accounting of key exposure modifiers can be developed, but where there are insufficient historic exposure measurements to directly assess historic exposures.

Algorithms↗

Exposure assessment methods for a study of mortality and cancer morbidity in relation to specific petroleum industry exposures.

In 1987 a Canadian company implemented an exposure tracking and health information system. The exposure tracking method aligned closely with published concepts for describing workplace exposure, with over 1800 similar exposure groups being used to describe occupational exposures. The database has been actively maintained and is subject to a number of quality checks. Recently, the company initiated a cancer morbidity study, with one objective being to examine whether the exposure tracking data could be used to reconstruct exposure estimates for the cohort. Five agents--hydrogen sulfide, petroleum coke/spent catalyst, hydrocarbon solvents and fuels, hydrocarbon lubricants, and an index for exposure to operations derived from noise exposure--were selected for development of occupational exposure estimates for each cohort member. The cohort consisted of workers first employed between January 1964 and December 1994 and who were employed for at least 1 year. Work history records were associated with a similar exposure group, using human resources data and knowledge of local industrial hygienists. Only employees with >90% duration of their work history assigned were kept in the cohort (25,292 people out of a possible 25,617). For each similar exposure group inventory, the substances were identified that contributed to each of the five agents being studied. Exposure estimates before 1987 were modified using historic occupational exposure limits. Rules were created to sum the exposure from multiple substances found in any one similar exposure group. The validity of exposure estimates was tested via comparison with results documented in industrial hygiene survey reports. Industrial hygienists who were unaware of the derived exposure estimates evaluated several hundred industrial hygiene surveys and prepared benchmark information. The two lists were then evaluated for concordance, which was found to be significantly different from that occurring by chance. We conclude that the process described can create valid exposure estimates for use in epidemiology studies.

Cohort Studies↗