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.

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.

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.

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.

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.

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.

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.

Distribution, enrichment and accumulation of heavy metals in coastal sediments of Salina Cruz Bay, méxico.

Surface sediment samples collected from the Salina Cruz Bay in the last twenty years, were analyzed for the total available trace elements (Cr, Cu, Fe, Pb, Ni, V, and Zn) to evaluate metal contamination due to possible anthropogenic inputs. Normalization of metals to iron and fine-grained fraction (< 63 microm) indicated relatively high enrichment factors for lead during the last two decades. Sediment Quality Guidelines suggest that lead must be considered as a chemical of potential concern in the marine and estuarine ecosystem. Concentration levels of lead ranged from 5-124 microg/g, while Ni and V below 70 and 30 microg/g, respectively. Geoaccumulation and enrichment factors for the rest of elements show comparable values to those reported for sites with similar activities in the world. Spatial distribution suggests that in addition to harbor activities, a transboundary source for Pb must account for the observed trends.

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.

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.

Air emissions assessment from offshore oil activities in Sonda de Campeche, Mexico.

Air emission data from offshore oil platforms, gas and oil processing installations and contribution of marine activities at the Sonda de Campeche, located at the Gulf of Mexico, were compiled and integrated to facilitate the study of long range transport of pollutants into the region. From this important region, roughly 76% of the total Mexican oil and gas production is obtained. It was estimated that the total air emissions of all contaminants are approximately 821,000 tons per year. Hydrocarbons are the largest pollutant emissions with 277,590 tons per year, generated during flaring activities, and SOx in second place with 185,907 tons per year. Marine and aviation activities contribute with less than 2% of total emissions. Mass of pollutants emitted per barrel of petroleum produced calculated in this work, are in the range reported by similar oil companies.

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.

Remote sensing study of emissions from motor vehicles in the Metropolitan Area of Mexico City.

Remote sensing was employed for the first time to measure nitric oxide (NO) levels of on-road light-duty motor vehicles of the Metropolitan Area of Mexico City (MAMC). The sensor placed at 12 different sites also measured the concentration of CO2, CO, and total hydrocarbons (THC) in the exhaust emissions. A database was compiled containing 122 800 readings, of which 84 650 (69%) records were valid emissions measurements. CO, HC, and NO valid readings were 68.9, 63.4, and 62.9%, respectively, of the total attempted measurements. Furthermore, 42 822 vehicles were number-plate-matched to model year with the information provided by the Inspection/Maintenance Program. The mean emissions of total valid readings for CO, HC, and NO were determined to be 1.31 vol %, 440 ppm (propane), and 914 ppm, respectively. In 1991 and 1994, remote sensing measurements of CO and HC tailpipe emissions were performed in the MAMC in five different locations (30 000 valid readings). Large drops in both pollutants were observed for the intervening years, but sufficient vehicle information was not available at that time to fully explain the observed trends. Compared with those reports, our results point out to a steady decrease in CO and HC exhaust emissions with vehicle model year. The fleet emissions measured exhibit a gamma-distribution, with 10% of the most polluting fleet studied being responsible for 45%, 25%, and 29% of the CO, HC, and NO emissions, respectively. NO emissions in taxis are the highest among the vintage of vehicles, a matter of concern since according to the distance traveled per year, they represent 22% of the total activity in the MAMC.

Evaluation of the vehicle inspection/maintenance program in the Metropolitan Area of Mexico City.

The Inspection/Maintenance Program in the Metropolitan Area of Mexico City (MAMC) mandates a test every 6 months for all gasoline motor vehicles as one of the strategies to decrease emissions of vehicular pollutants. FTP-75 and ASM procedures were performed in our facilities to a fleet of 108 in-use motor vehicles before and after the approval of the I/M mandatory test When our laboratory-simulated ASM data were compared with those of the official certificate, a large difference was observed between them. On the other hand, audits at the test-only centers indicate poor maintenance of the analytical instruments and dynamometers. On the basis of our FTP results, an estimation of the emissions change for the MAMC fleet shows a net 4% decrease in CO emissions, while total hydrocarbons and NOx increased 9 and 8%, respectively. Our results indicate that the I/M system in the MAMC lacks the technical capability and investment to ensure that software and hardware are properly maintained, calibrated, and upgraded. Sometimes limited attention is paid to ensure adequate training of inspectors, auditors, and quality control staff.

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.

Environmental implications on the oxygenation of gasoline with ethanol in the metropolitan area of Mexico City.

Motor vehicle emission tests were performed on 12 in-use light duty vehicles, made up of the most representative emission control technologies in Mexico City: no catalyst, oxidative catalyst, and three way catalyst. Exhaust regulated (CO, NOx, and hydrocarbons) and toxic (benzene, formaldehyde, acetaldehyde, and 1,3-butadiene) emissions were evaluated for MTBE (5 vol %)- and ethanol (3, 6, and 10 vol %)-gasoline blends. The most significant overall emissions variations derived from the use of 6 vol % ethanol (relative to a 5% MTBE base gasoline) were 16% decrease in CO, 28% reduction in formaldehyde, and 80% increase in acetaldehyde emissions. A 26% reduction in CO emissions from the oldest fleet (< MY 1991, without catalytic converter), which represents about 44% of the in-use light duty vehicles in Mexico city, can be attained when using 6 vol% ethanol-gasoline, without significant variation in hydrocarbons and NOx emissions, when compared with a 5% vol MTBE-gasoline. On the basis of the emissions results, an estimation of the change in the motor vehicle emissions of the metropolitan area of Mexico city was calculated for the year 2010 if ethanol were to be used instead of MTBE, and the outcome was a considerable decrease in all regulated and toxic emissions, despite the growing motor vehicle population.