Assessment of the use of ethanol instead of MTBE as an oxygenated compound in Mexican regular gasoline: combustion behavior and emissions.

The energy reforms implemented in Mexico promote the use of ethanol in gasoline but exclude the country's ozone nonattainment areas oxygenated with methyl-tert-butyl ether (MTBE) in view that further scientific studies are required. To address a potential implementation scenario in areas of ozone high VOC-sensitive regimes, the impact on performance and emissions characteristics between the regular MTBE fuel available and a formulated gasoline containing 10% v/v ethanol having similar Reid vapor pressure (RVP) were compared in a single cylinder spark-ignited engine and a set of tier I vehicles. Included in the assessment were the "criteria" pollutants (THC, CO, and NOx), toxic compounds, and speciated hydrocarbons in order to calculate the ozone-forming potential (OFP). The change in combustion speed of ethanol fuel vs. regular gasoline seems to be small and depends mainly on base gasoline formulation. Vehicle dynamometer testing showed no statistically significant differences in the average THC, CO, and NOx results when comparing both fuels. Statistically significant differences were seen in total speciated hydrocarbons, total carbonyls emitted, the increases in acetaldehyde emissions, and the decreases in OFP with E10. The results show roughly 20% increase in evaporative emissions when E10 is used, but the OFP of the emissions is lower than that of the Metropolitan Area of Mexico City fuel (MAMC). The increase in the oxygen content using ethanol fuel seems to have no deleterious effect on the vintage of vehicles tested. Taking into consideration that the evaporative emissions standard in Mexico is less stringent than that in other countries, the substitution of the actual regular gasoline for ethanol fuels should uphold the least volatile AA class in areas with ozone problems.

Long-term effects of discharges of produced water the marine environment from petroleum-related activities at Sonda de Campeche, Gulf of México.

Produced water from offshore oil platforms is a major source of oil and related chemicals into the sea. The large volume and high salinity of produced water could pose severe environmental impacts upon inadequate disposal. This study is based on direct field sampling of effluents released into the ocean in the years 2003 and 2013 at the Sonda de Campeche located in the southern part of the Gulf of Mexico. Metals and hydrocarbons were characterized in water, sediments, and fish tissues at the discharge site and compared with those obtained at two reference sites. Chemicals that exceeded risk-based concentrations in the discharge included the metals As, Pb, Cd, and Cr, and a variety of compounds polycyclic aromatic hydrocarbon (PAHs), including naphthalene, fluorenes, and low molecular weight PAHs. The values of low to high molecular weight polycyclic aromatic hydrocarbon (PAHs), and carbon preference index indicate that hydrocarbons in sediments of the discharge zone are originated from the produced water and combustion sources. Fish tissues at the discharge zone and reference site are contaminated with PAHs, dominated by 2- and 3-rings; 4-ring accounted for less than 1% of total PAHs (TPAHs) in 2003, but increased to 7% in 2013. Results suggest that, from 2003 to 2013, discharges of produced water have had a non-negligible impact on ecosystems at a regional level, so the possibility of subtle, cumulative effects from operational discharges should not be ignored.

The contribution of evaporative emissions from gasoline vehicles to the volatile organic compound inventory in Mexico City.

The strategy for decreasing volatile organic compound emissions in Mexico has been focused much more on tailpipe emissions than on evaporative emissions, so there is very little information on the contribution of evaporative emissions to the total volatile organic compound inventory. We examined the magnitudes of exhaust and evaporative volatile organic compound emissions, and the species emitted, in a representative fleet of light-duty gasoline vehicles in the Metropolitan Area of Mexico City. The US "FTP-75" test protocol was used to estimate volatile organic compound emissions associated with diurnal evaporative losses, and when the engine is started and a journey begins. The amount and nature of the volatile organic compounds emitted under these conditions have not previously been accounted in the official inventory of the area. Evaporative emissions from light-duty vehicles in the Metropolitan Area of Mexico City were estimated to be 39 % of the total annual amount of hydrocarbons emitted. Vehicles built before 1992 (16 % of the fleet) were found to be responsible for 43 % of the total hydrocarbon emissions from exhausts and 31 % of the evaporative emissions of organic compounds. The relatively high amounts of volatile organic compounds emitted from older vehicles found in this study show that strong emission controls need to be implemented in order to decrease the contribution of evaporative emissions of this fraction of the fleet.

Application of the positive matrix factorization approach to identify heavy metal sources in sediments. A case study on the Mexican Pacific Coast.

During the last two decades, sediments collected in different sources of water bodies of the Tehuantepec Basin, located in the southeast of the Mexican Pacific Coast, showed that concentrations of heavy metals may pose a risk to the environment and human health. The extractable organic matter, geoaccumulation index, and enrichment factors were quantified for arsenic, cadmium, copper, chromium, nickel, lead, vanadium, zinc, and the fine-grained sediment fraction. The non-parametric SiZer method was applied to assess the statistical significance of the reconstructed metal variation along time. This inference method appears to be particularly natural and well suited to temperature and other environmental reconstructions. In this approach, a collection of smooth of the reconstructed metal concentrations is considered simultaneously, and inferences about the significance of the metal trends can be made with respect to time. Hence, the database represents a consolidated set of available and validated water and sediment data of an urban industrialized area, which is very useful as case study site. The positive matrix factorization approach was used in identification and source apportionment of the anthropogenic heavy metals in the sediments. Regionally, metals and organic matter are depleted relative to crustal abundance in a range of 45-55 %, while there is an inorganic enrichment from lithogenous/anthropogenic sources of around 40 %. Only extractable organic matter, Pb, As, and Cd can be related with non-crustal sources, suggesting that additional input cannot be explained by local runoff or erosion processes.

Impact of reformulated ethanol-gasoline blends on high-emitting vehicles.

In-use vehicles which are high emitters (HEVs) make a large contribution to the emissions inventory. It is not known, however, whether HEVs share common emissions characteristics, and particularly the effect of ethanol blends. We study this by first examining laboratory measurements of exhaust and evaporative emissions on ethanol blends containing 21%, 26% and 30% aromatics, and a reference fuel formulated with methyl-tertiary butyl ether (MTBE). Switching from MTBE to ethanol fuels on HEVs shows no effect on the total emissions of regulated pollutants, but 1,3-butadiene emissions would increased substantially while the emissions of total carbonyls would not be affected except in the case of acetaldehyde, which would increase with EtOH. The ozone-forming potential of exhaust and evaporative emissions would be less using the EtOH blends and specific reactivity will not be incremented. Lowering the vapour pressure of the gasoline and increasing the proportions of alkylate and isomerate in the composition produces an ethanol-blended fuel with lower environmental impact both in normal vehicles and HEVs.

Weighing the evidence of ecological risk from PAHs contamination in the estuarine environment of Salina Cruz Bay, México.

Results of bulk-phase chemical measurements, toxicological tests combined with bioaccumulation measures in fishes, were used to evaluate the toxicity of the 16 USEPA priority polycyclic aromatic hydrocarbons from the sediment collected from eight stations of the Ventosa Estuarine System, located close to the main center of processing oil in the Mexican Pacific coast. Levels of the sum of polycyclic aromatic hydrocarbons varied from 22 to 6,850 microg kg(-1) dry weight. Based on sediment quality guidelines, the compounds with high environmental priority were acenaphtylene, acenaphtene, and phenanthrene. Acute toxicity tests with Vibrio fischeri and Daphnia magna as well as chronic toxicity with Panagrellus redivivus were performed. The quantification of hepatic ethoxyresorufin O-deethylase activity was used to assess the induction of the mixed function oxygenase system of brown trout. However, because it is often difficult to blend the results from such very different assays into a unified decision about the potential for impacts, a weight-of-evidence (WOE) approach to sediment quality investigations was followed. These assays provided measurement endpoints that could be used to develop an overall evaluation of the potential for environmental impacts from the oil processing operations. WOE provides a valuable tool for assessing the results of environmental investigations because it provides a framework for considering the strengths and weaknesses of environmental measurements, an approach for addressing uncertainty in the measurements, and documentation of the evaluation and its assumptions.

Cold-start and chemical characterization of emissions from mobile sources in Mexico.

In this work tailpipe and evaporative emissions from a set of normal and high emitter vehicle models, year 2006-2008 (low mileage) certified when new to meet the Tier 1 emission standard, were characterized for criteria pollutants (carbon monoxide, nitrogen oxides and hydrocarbons), and a suite of unregulated emissions including aliphatic and aromatic aldehydes, monocyclic aromatic compounds, 1,3 butadiene, n-hexane and acrolein. Data were obtained under the three different driving conditions of the United States Federal Test Procedure, FTP-75 cycle. High emissions of both regulated and unregulated pollutants were observed in the cold-start phase of the driving cycle for low mileage Tier 1 normal and high emitters engines. Data were compared with results obtained for a set of MY > 1992-2005 that included vehicles with no catalytic converters, Tier 0 and MY 2000-5 Tier 1 emission standard with high mileage. The calculated average cold-start emissions for normal emitters in grams are 0.93, 8.21 and 1.06 for NMHC CO, and NOx, respectively for Tier 1 low mileage vehicles. The reductions in emissions for Tier 1 normal emitters are 76%, 56% and 56% for NMHC, CO and NOx, respectively, but 58%, 30% and 25% for the high emitters. Differences in emission can be ascribed to the mileage accumulation more than technological improvements. Cold-start emissions account in the USA roughly 10% of emissions from gasoline-powered vehicles. In Mexico the fractions are likely to be higher because one must account also for the contribution of Tier 0 and the running exhausts emissions of vehicles with no catalytic converters.

Assessment of benthic changes during 20 years of monitoring the Mexican Salina Cruz Bay.

In this work a non-parametric multivariate analysis was used to assess the impact of metals and organic compounds in the macro infaunal component of the mollusks benthic community using surface sediment data from several monitoring programs collected over 20 years in Salina Cruz Bay, Mexico. The data for benthic mollusks community characteristics (richness, abundance and diversity) were linked to multivariate environmental patterns, using the Alternating Conditional Expectations method to correlate the biological measurements of the mollusk community with the physicochemical properties of water and sediments. Mollusks community variation is related to environmental characteristics as well as lead content. Surface deposit feeders are increasing their relative density, while subsurface deposit feeders are decreasing with respect to time, these last are expected to be more related with sediment and more affected then by its quality. However gastropods with predatory carnivore as well as chemosymbiotic deposit feeder bivalves have maintained their relative densities along time.

Fluorescence characteristics in the deep waters of South Gulf of México.

Vertical profiles of deep-water fluorescence determined by the chlorophyll sensor, polycyclic aromatic hydrocarbons, biomarkers, and other miscellaneous parameters measured in the southern Gulf of Mexico are reported. In the course of the survey, unexpected deep fluorescences were recorded (>1100m depth) in half of the 40 stations studied, a novel finding in this area of the Gulf. Currently, the deep-water fluorescence phenomenon is not completely understood, however we observe linear correlation between the fluorescence intensity and chlorophyll-α concentrations and coincidence of higher number of hydrocarbonoclastic bacteria in samples collected precisely in the deep-water fluorescence. This information is particularly interesting in relation to the Deepwater Horizon oil spill in 2010, in view that the aftermaths of the spill can be observed till today as oil plumes trapped in deep water layers that may disturb the natural water ecosystem.

A driving cycle for vehicle emissions estimation in the metropolitan area of Mexico City.

A driving cycle derived from driving behavior and real traffic conditions in Mexico City (MC) is proposed. Data acquisition was carried out over diverse MC routes, representing travel under congested and uncongested conditions, using the chase-car approach. Thirteen different on-road patterns, including the four main access roads to MC, trips in both directions and different timetables, a total of 108 trips spanning 1044 km were evaluated in this study. The MC cycle lasts 1360 seconds with a distance of 8.8 km and average speed of 23.4 km h(-1). Both maximum speed (73.6 km h(-1)) and maximum acceleration (2.22 km h(-1)s(-1)) are lower than those of the new vehicles certification employed in Mexico ,FTP-75 cycle., that is, the MC cycle exhibits less cruising time and more transient events than the FTP cycle. A total of 30 light duty gasoline vehicles were classified into different technological groups and tested in an FTP-75 and MC driving cycles in order to compare their emission factors A potential concern is that in Mexico manufacturers design vehicles to meet the emission standards in the FTP, but emission levels increase significantly in a more representative cycle of present driving patterns in the Metropolitan Area of Mexico City (MAMC). The use of a more representative cycle during certification testing, would provide an incentive for vehicle manufacturers to design emissions control systems to remain effective during operation modes that are not currently represented in the official test procedures used in the certification process. Based on the results of the study, the use of MC cycle, which better represents current day driving patterns during testing of vehicle fleets in emissions laboratories, would improve the accuracy of emissions factors used in the MAMC emissions inventories.

Effect of methyl tertiary butyl ether concentrations on exhaust emissions from gasoline used in the metropolitan area of Mexico City.

In this work, the primary objective was to assess the impact of oxygenated fuel on the exhaust emissions from an important fraction of vehicles in the Metropolitan Area of Mexico City (MAMC). The results aim to provide information on the actual effect of MTBE on a fleet that represents more than 60% of the in-use vehicles in the MAMC. Ten vehicles were tested with a low-octane base gasoline, and 10 more with a regular-grade unleaded base gasoline. Three MTBE concentrations, 5, 10, and 15 vol %, were tested following the U.S. Federal Test Procedure (FTP). CO, total HC, and NOx from the exhaust gases were quantitatively evaluated and also characterized for FTP speciated organic emissions. From this data, the O3-forming potential of the fuels was calculated. Results show that for the fleet using low-octane gasoline, the addition of 10% MTBE substantially reduced CO emissions, but total HC concentration in the exhaust showed a modest decrease. For the regular gasoline, the 10% MTBE blend seemed to be the best choice, but there was not a significant decrease in emissions. The specific reactivity of each fuel, expressed in grams of O3 per gram of nonmethane organic gases, increased with MTBE concentration in both cases. This result is important to consider, especially for a region like Mexico City, which has high atmospheric O3 concentrations.

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.

An evaluation of the LPG vehicles program in the metropolitan area of Mexico City.

The environmental agency in the metropolitan area of Mexico City has launched a program to introduce more energy-efficient modes of transport, one of which is the use of alternative and less polluting fuels. With the perspective in mind, a liquefied petroleum gas (LPG) fleet of vehicles is exempt of the mandatory "one day without a car" program if the emission of pollutants is below the standard authorized for that specific purpose. Today, about 28,000 light-duty vehicles and heavy-duty trucks circulate in the area, most of them as aftermarket converted vehicles. In this work, we evaluated regulated exhaust emission and other parameters on 134 representative vehicles of that fleet. From the data obtained, an estimate of emission factors and their contribution to the global emission in the metropolitan area is provided. It is concluded that more than 95% of the in-use vehicles using LPG presented regulated emissions which exceeded in one or more the environmental regulations values required for certification. The poor maintenance of the vehicles and the type of conversion kit installed could be the culprits of the results obtained.

Long-term efficiency of catalytic converters operating in Mexico City.

A 1999 ordinance by the Government of Mexico City bans 1993 model-year vehicles from on-road operation if their catalytic converters are not replaced with new ones. To validate the benefits of this action, we examined three issues related to exhaust emissions of vehicles equipped with catalytic converters. After selecting representative fleets of in-use vehicles, a comparison between emissions and catalyst efficiency in cars with two categories of exhaust emission limits was carried out. For that purpose, two fleets were selected, each made up of 10 vehicles run under similar conditions. A third, larger fleet with emissions control systems was used to evaluate and simulate real-world conditions of vehicles in a controlled laboratory. Finally, the aging effect on the catalytic converter was studied on vehicles run for 100,000 km, replacing their old emission control devices for new ones. The 1991-1992 model-year vehicles showed a high percentage of compliance with the corresponding emissions standard (90%) in comparison with 1993 model-year and later vehicles (Tier 0). However, NOx emissions were higher for the newer vehicles. Fifty percent of the 1991-1992 model-year vehicles evaluated under the official inspection/maintenance (I/M) procedure did not meet the regulated emissions standard when the results were compared with those of the U.S. Federal Test Procedure FTP-75. Our results suggest that the replacement of old catalytic converters with new ones will have little effect on decreasing polluting emissions because these vehicles were in very bad mechanical condition. Results of catalytic activity as a function of mileage indicated inefficient catalyst performance for the fleets tested. All pollutant conversions were below 90% efficiency, and they deteriorated by an average of 30% after the vehicles were run for 100,000 km.

Contribution of the gasoline distribution cycle to volatile organic compound emissions in the metropolitan area of Mexico City.

Gasoline distribution in the metropolitan area of Mexico City (MAMC) represents an area of opportunity for the abatement of volatile organic compound (VOC) emissions. The gasoline distribution in this huge urban center encompasses several operations: (1) storage in bulk and distribution plants, (2) transportation to gasoline service stations, (3) unloading at service stations' underground tanks, and (4) gasoline dispensing. In this study, hydrocarbon (HC) emissions resulting from breathing losses in closed reservoirs, leakage, and spillage from the operations just listed were calculated using both field measurements and reported emission factors. The results show that the contribution of volatile HC emissions due to storage, distribution, and sales of gasoline is 6651 t/year, approximately 13 times higher than previously reported values. Tank truck transportation results in 53.9% of the gasoline emissions, and 31.5% of emissions are generated when loading the tank trucks. The high concentration of emissions in the gasoline transportation and loading operations by tank trucks has been ascribed to (1) highly frequent trips from distribution plant to gasoline stations, and vice versa, to cope with excessive gasoline sales per gasoline station; (2) low leakproofness of tank trucks; and (3) poor training of employees. In addition, the contribution to HC evaporative and exhaust emissions from the vehicles of the MAMC was also evaluated.

Contribution of LPG-derived emissions to air pollution in the metropolitan area of Guadalajara City.

Measurements of hydrocarbon (HC) emissions generated by the use of liquefied petroleum gas (LPG) in the metropolitan area of Guadalajara City (MAG) are presented in this work. Based on measurements in the course of distribution, handling, and consumption, an estimated 4407 tons/yr are released into the atmosphere. The three most important contributors to LPG emissions were refilling of LPG-fueled vehicles and commercial and domestic consumption. The MAG shows a different contribution pattern of LPG emission sources compared with that of the metropolitan area of Mexico City (MAMC). These results show that each megacity has different sources of emissions, which provides more accurate strategies in the handling procedures for LPG to decrease the impact in O3 levels. This work represents the first evaluation performed in Guadalajara City, based on current measurements, of the LPG contribution to polluting emissions.

Trends in exhaust emissions from in-use Mexico City vehicles, 2000-2006. A remote sensing study.

A remote sensing study was conducted in year 2006 in four locations of the Metropolitan Area of Mexico City (MAMC). Two of the sites were the same studied back by us in year 2000 and by others in year 1994. A database was compiled containing 11,289 valid measurements for the carbon monoxide (CO), total hydrocarbons (THC), and nitric oxide (NO) exhaust vehicles emissions. Valid measurements were binned for each pollutant by the vehicle specific power (between -5 and 20 kW tonne(-1)) for the 2000 and 2006 databases. The mean average CO, THC, and NO emissions for year 2006 were determined to be 1.10 +/- 0.18 vol.%, 299 +/- 88.4 ppm, and 610 +/- 115.0 ppm, respectively. Matching the vehicle driving patterns of the fleet measured in year 2000 with the emissions factors obtained in this work, allows estimating the trends in the exhaust emissions of vehicles in the MAMC. The adjusted results of the remote sensing study performed in year 2006 shows that the fleet has decrease 22% in CO and 17% in NO emissions, with small change in total hydrocarbons emissions. The improvements could be related with the introduction in year 2001 of vehicles that met tighter emissions standards, particularly for nitrogen oxides.

Environmental assessment of aromatic hydrocarbons-contaminated sediments of the Mexican Salina Cuz Bay.

Concentrations of total aromatic hydrocarbons and extractable organic matter in the water column and sediment were determined in samples collected in the course of the last 20 years from the Salina Cruz Harbor, México, to assess the degree of organic contamination. In sediments, organic compounds accumulate in shallow areas mostly associated with extractable organic matter and fine fractions. Calculated geocumulation index and enrichment factors suggest that contamination could be derived from anthropogenic activities attributed to harbor and ship scrapping activities, as well as transboundary source. Concentration of total aromatic hydrocarbons (as chrysene equivalents) ranged from 0.01 to 534 microg l(-1) in water, and from 0.10 to 2,160 microg g(-1) in sediments. Total aromatic concentration of 5 microg g(-1) is proposed as background concentration.

Assessment of new vehicles emissions certification standards in the metropolitan area of Mexico City.

Light duty gasoline vehicles account for most of CO hydrocarbons and NOx emissions at the Metropolitan Area of Mexico City (MAMC). In order to ameliorate air pollution from the beginning of 2001, Tier 1 emission standards became mandatory for all new model year sold in the country. Car manufacturers in Mexico do not guarantee the performance of their exhaust emissions systems for a given mileage. The purpose of this study was to assess whether the Tier 1 vehicles will stand the certification values for at least 162000 km with the regular fuel available at the MAMC. Mileage accumulation and deterioration show that certified carbon monoxide emissions will stand for the useful life of the vehicles but in the case of non-methane hydrocarbons will be shorter by 40%, and nitrogen oxides emissions above the standard will be reached at one third of the accumulated kilometers. The effect of gasoline sulfur content, on the current in use Tier 1 vehicles of the MAMC and the impact on the emissions inventory in year 2010 showed that 31000 extra tons of NOx could be added to the inventory caused by the failure of the vehicles to control this pollutant at the useful life of vehicles.

A predictive model to correlate fuel specifications with on-road vehicles emissions in Mexico.

Mexico is currently in the process of implementing its third air management program, which includes control measures targeting emissions reductions from mobile, point, and area sources. Achieving the program goals will require changes in the composition and in physical properties of gasoline and implementing an emissions reduction schedule. For that purpose a study was undertaken to support understanding of the effect of gasoline fuel parameters on exhaust emissions. Specifically, the relative impacts of Reid vapor pressure, distillation parameters, oxygen, sulfur, olefins, and aromatic contents on the exhaust emissions of in-use vehicles of the metropolitan area of Mexico City were investigated. The results were used to develop a model to predict CO, nitrogen oxides, total hydrocarbons, and toxic emissions such as benzene, 1,3-butadiene, formaldehyde, and acetaldehyde. Also a statistical model that predicts evaporative emissions was built. Results of the present model are compared with those obtained using the complex model of the United States Environmental Protection Agency.