Chemical Characterization of Exhaust Emissions from Selected

Article pubs.acs.org/est

Chemical Characterization of Exhaust Emissions from Selected Canadian Marine Vessels: The Case of Trace Metals and Lanthanoids Valbona Celo,*,† Ewa Dabek-Zlotorzynska,† and Mark McCurdy‡ †

Analysis and Air Quality Section, ‡Emissions Research and Measurement Section, Air Quality Research Division, Atmospheric Science and Technology Directorate, Science and Technology Branch, Environment Canada, 335 River Road, Ottawa, Ontario, Canada, K1A 0H3 S Supporting Information *

ABSTRACT: This paper reports the chemical composition of exhaust emissions from the main engines of five ocean going cargo vessels, as they traveled in Canadian waters. The emission factors (EFs) of PM2.5 and SO2 for vessels tested on various intermediate fuel oils (IFO), ranged from 0.4 to 2.2 g kW−1 hr−1 and 4.7 to 10.3 g kW−1 hr−1, respectively, and were mainly dependent on the content of sulfur in the fuel. Average NOx, CO, and CO2 EFs for these tests were 12.7, 0.45, and 618 g kW−1 hr−1, respectively and were generally below benchmark values commonly used by regulatory agencies. The composition of PM2.5 was dominated by hydrated sulfates, organic carbon and trace metals which accounted for 80−97% of total PM2.5 mass. A substantial decrease of measured emission factors for PM2.5 and SO2 was observed when the fuel was changed from IFO to marine diesel oil (MDO), in one of the tested vessels. The main component of PM2.5 in this case was organic carbon accounting for 65% of PM2.5 mass. In addition to commonly reported pollutants, this study presents EFs of the lanthanoid elements and showed that their distribution patterns in ship-exhaust PM2.5 were very similar to the PM2.5 emitted by oil refining facilities. Hence, using La:Ce:V tertiary diagrams and La/V ratios is necessary to distinguish ship plumes from primary emissions related to accidental and/or routine operation of oil-refining industry.

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INTRODUCTION

shipping causes a net global cooling impact throughout the period 1900−2050 that ranges from −0.03 to −0.3 °C. Commercial marine vessels typically burn heavy fuel oil (HFO) which is the petroleum product left after distillation of all other fractions of crude oil. Compared to gas and oil products used by other means of transportation, HFOs have high density, mean molecular weight and carbon/hydrogen ratio, and sulfur content that varies from 2 to 5%. HFOs also contain higher concentrations of organo-metallic compounds that derive from their natural presence in the original crude oils. The most abundant metal in crude oils is V, followed by Ni, Fe, K, and Na. This composition of the combustion oil explains the high content of SO2 in gaseous ship emissions and the predominance of sulfate, carbon-species and metals (e.g., V, Ni, Fe, Ca, Na) in the emitted particles. Other factors, such as type and technology of the engine, speed of operation and engine load also affect the chemical composition of ship exhausts, albeit to a lesser degree.5−10 In this study, we present regulated and nonregulated emission factors for main engines on selected large cargo ships that operate in Canadian waters. Special attention is given to emission factors of trace metals, particularly to V and Ni

Shipping is an important means of transportation around the globe, especially in the areas where road or air transportation is either impossible or very expensive. In Canada, ports and harbors are integral to the nation’s transportation system. They serve as vital links and gateways that facilitate domestic and international economic activities. The Great Lakes and St. Lawrence River water-ways are the major trade arteries for North America with an annual commerce that exceeds 200 million tons of raw materials, agricultural commodities and manufactured products.1 In the Canadian North, most nonperishable goods, fuel, equipment, and material are transported by ship during the short summer shipping season. The marine transport sector is a significant source of air pollution both globally and for coastal urban areas. In Canada, about 6.2% of the total SOx emissions are attributed to maritime traffic.2 Internationally, shipping accounts for about 15% of the world’s nitrogen oxides (NOx) emissions, for 5−8% of sulfur oxides (SOx) emissions from all fossil fuel sources, and for an annual emission of 1.2−1.6 million metric ton of particulate matter with aerodynamic diameter of 10 μm or less (PM10).3 A number of recent studies have linked ship emissions to both negative health effects for exposed populations, and to significant changes in climate patterns. For example, Corbett et al.3 showed that 3−8% of global PM2.5-related mortalities are attributable to marine shipping. Tronstad et al.4 estimated that Published 2015 by the American Chemical Society

Received: Revised: Accepted: Published: 5220

January 8, 2015 March 30, 2015 March 31, 2015 March 31, 2015 DOI: 10.1021/acs.est.5b00127 Environ. Sci. Technol. 2015, 49, 5220−5226

Environmental Science & Technology

Article

Table 1. Selected Properties and Chemical Composition of Fuels. Concentrations of Metallic Elements (Na to Mo) are expressed in mg/kga

a

vessel no. 1

vessel no. 2

fuel oil used for main engine

IFO180

IFO60

IFO180 no. 1

vessel no. 3 IFO180 no. 2

IFO180

vessel no. 4 MDO

vessel no. 5 IFO 380

density @ 15 °C (kg/m3) carbon (% weight) hydrogen (% weight) nitrogen (% weight) total sulfur (% weight) Na Mg Al Si Ti V Cr Fe Co Ni Cu Zn Mo

970.7 85.71 10.51 0.41 2.23 15.74 ND ND ND 3.12 109.4 ND 20.35 ND 50.3 ND ND 4.56

957.6 87.22 11.05 0.38 1.22 NR 5.5 NR NR NR 38.0 ND NR NR 21.0 NR 2.2 ND

964.8 87.18 11.17 0.23 1.48 ND ND 3.05 ND ND 55.8 ND ND ND 18.9 5.07 1.3 ND

973.7 86.78 10.7 0.38 2.21 13.23 ND 5.17 ND 1.36 102.4 ND 17.71 0.86 46.5 23.63 2.6 3.0

972.7 87.21 10.77 0.3 1.62 NR 4.5 NR NR NR 55.0 ND NR NR 29.6 NR 3.6 1.5

854.3 86.85 12.97 0.026 0.119 NR ND NR NR NR ND ND NR NR ND NR 2.7 ND

988 86.26 11.26 0.39 2.7 22.66 ND 7.06 ND 2.36 133.8 ND 31.44 1.16 63.2 29.51 2.1 5.5

NR, Not reported; ND, below detection limit.

which are typically used as tracers of ship emissions,9,11 and lanthanoids (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), the presence of which in PM emitted by marine vessels is rarely reported.10,12 The interest for analysis of lanthanoids in atmospheric PM2.5 increased significantly after 1985, when Olmez and Gordon suggested for the first time that the concentrations and distribution patterns of lanthanoids can be used as unique tracers for emissions from oil refining industry, which uses the fluid catalytic cracking (FCC) catalysts in the process of converting petroleum crude oils into gasoline or other commercial products.13 Further, several studies demonstrated that these elements are ideal tracers of both long-range and point source emissions, on an urban and a regional scale.14−19 In addition to the FCC catalysts released in the atmosphere during the refining process, it is plausible that part of the unused portion of the FCC catalysts remain in the HFOs and is released into the atmosphere together with other products of oil combustion. Hence, the objectives of this research are to provide a detailed insight into the elemental composition of particles emitted by large cargo ships, and to examine the possibility of including lanthanoids as markers of primary PM emissions by commercial marine shipping. In this research, tests were performed and samples were collected on-board vessels traveling their routine itineraries. The main engine was tested on commonly used fuels over one or more engine modes representing the typical range of in-use operating conditions. Thus, emission factors from this study should be helpful in developing emission models and in inventory calculations.

vessels was tested with the main engine operating with marine diesel oil (MDO). The fuel was switched during normal operations of the vessel, solely for the purposes of this study. The engine operating conditions were replicated to the extent possible between the two test fuels. Fuel properties and chemical composition for each tested ship are summarized in Table 1. Sampling and Gaseous Emissions Measurements. Exhaust emission samples were collected for 10 min per test repeat, using equipment and methods defined by ISO 8178− 1:200620 and ISO 8178−2:2008,21 with sample probe design guidelines from U.S. EPA CFR Title 40 Part 92.22 A partial-flow dilution tunnel system was used with the dilution ratio determined by simultaneous CO2 concentration measurements of the raw exhaust stream and the dilution tunnel. Dilution tunnel flow rates were also measured to verify the dilution ratio, which ranged from 6 to 10. PM2.5 samples were collected using an exhaust gas sample which was mixed in the dilution tunnel system with HEPA-filtered ambient dilution air for sample conditioning and to prevent condensation. The diluted exhaust stream was sampled for various analyses of samples collected on filters, on silica gel cartridges, and in stainless steel canisters. The samples for the raw gaseous analyzer and the dilution tunnel system were collected through straight multiholed sample probes, constructed from stainless steel extending across the exhaust duct. The raw exhaust gas sample was drawn through a heated filter and a heated transfer line to a chilled sample conditioning unit to remove moisture from the sample. A portable five-gas analyzer (Horiba PG-250, Horiba Instruments, Irvine, CA) was used to analyze the raw exhaust gas for several criteria air contaminants (CAC) and greenhouse gases (GHG) as described in Supporting Information Table S2. In every test, measurements were repeated at least four times and engines were operated in various loads, ranging from ∼40% to ∼90%. Also, emissions from both main and auxiliary engines operating with IFO or MDO were analyzed on selected vessels. In this paper we report only the average of measurements

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EXPERIMENTAL SECTION Vessels and Engines Description. Five marine vessels that travel in the Great Lakes - St. Lawrence Seaway and in the Canadian Arctic were tested in this study (Supporting Information, Table S1). During their normal routine operations, ships were using different intermediate fuel oils, with maximum viscosity measured at 50 °C of 60 (IFO60), 180 (IFO180) and 380 (IFO380) centistokes. Only one of the 5221

DOI: 10.1021/acs.est.5b00127 Environ. Sci. Technol. 2015, 49, 5220−5226


Article

Table 2. Comparison of Measured Emission Factors (g kW−1 hr−1)a with Literature Data this study

Vessel no. 1 Vessel no. 2 Vessel no. 3 Vessel no. 4 Vessel no. 5 Sippula et al.5 Khan et al.8 Agrawal et al.10 Agrawal et al.12 Moldanova et al.33 U.S. EPA30 CARB31

fuel type

PM2.5

SO2b

CO

NOx

IFO180 IFO60 IFO180 no. 1 IFO180 no. 2 IFO180 MDO IFO380 HFO HFO HFO HFO HFO

1.51 ± 0.07 0.37 ± 0.01 0.81 ± 0.02 0.94 ± 0.02 0.83 ± 0.01 0.30 ± 0.03 2.2 ± 0.2 0.72 to 1.90 1.42 ± 0.04 1.64 1.60 ± 0.08 1.03c 1.31 1.5

8.7 ± 0.1 4.7 ± 0.01 5.8 ± 0.07 8.7 ± 0.1 6.4 ± 0.1 0.47 ± 0.1 10.3 ± 0.03 NA 9.44 8.39 10.5 7.62 10.3 10.6

0.83 ± 0.01 1.31 ± 0.02 0.26 ± 0.01 0.30 ± 0.01 0.81 ± 0.03 1.2230 ± 0.02 0.00 1.2 NA 0.77 0.45 ± 0.03 0.42 1.4 1.4

16.3 ± 0.2 8.4 ± 0.03 11.4 ± 0.1 11.3 ± 0.1 12.2 ± 0.01 10.7 ± 0.04 16.7 ± 0.1 11.4 16.1 ± 0.1 18.21 19.87 ± 0.95 14.22 18.1 17.9

CO2 614 609 626 628 628 622 605 NA 600 658 625 667 621 623

± ± ± ± ± ± ±

1 1 7 9 1 1 1

±2 ± 25

Average ± st.dev (N = 4 replicates). bSO2 emission rates calculated from fuel consumption and fuel sulfur content as per recommendations in ISO8178−1:2006. cTotal PM.

a

performed with the main engine operated at its highest in-use operating load (Supporting Information, Table S1).23−26 Chemical Analysis of Particulate Matter. PM2.5 samples (four replicates for each test) were collected on Teflon filters (PALL Teflo, Pall Gelman, Ann Arbor, MI) and were subsequently gravimetrically analyzed in the laboratory for the particulate mass. Further on, one set of replicates was analyzed for water-soluble ions by ion chromatography and for water-soluble metals by inductively coupled plasma mass spectrometry (ICP-MS).27 The other set of replicates was acid digested and analyzed for total metals and lanthanoids by ICP-MS, following a previously reported method.28 Samples collected on quartz filters (PallflexTissuquartz Filters, Pall Gelman, Ann Arbor, MI) were analyzed for organic carbon (OC) and elemental carbon (EC) content following NIOSH 5040 protocols.29 Filter loading was taken into account for the OC and EC analysis to prevent incorrect OC/EC split. OC data were also corrected for positive artifact by subtracting the OC mass obtained from a secondary (backup) quartz filter. Calculations. Procedures outlined in ISO 8178−1:200620 and ISO 8178−2:200621 were followed for calculation of exhaust gas flow rates. Briefly, a carbon balance approach was used based on the concentration of measured species, fuel consumption, and fuel properties. Emission factors (EFs) are reported in grams per kilowatt-hour (gkW−1 h−1).23−26

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Figure 1. Emission factors of PM2.5, NOx, and SO2 as a function of fuel sulfur content, for vessels using HFOs and operating with the maximum engine load.

respectively 15% and 68% higher than U.S. EPA estimations. The higher sulfur content in the IFOs used by these two vessels and the strong correlation between PM2.5 emissions and fuel-S (Figure 1) explain the high PM2.5 emissions from these vessels. The SO2 emissions were also higher compared to the other vessels tested in this study, but were lower than values reported in the literature and did not exceed any of the U.S. EPA and CARB estimated EFs (Table 2). Changing to the lower sulfur content MDO fuel at high engine load, decreased the measured emissions of PM2.5 and SO2 by 3 and almost 15 times, respectively. NOx, CO, and CO2 emissions for vessels using IFOs were primarily related to the type of engines, with the slow speed engines having significantly higher NOx and slightly lower CO and CO2 emission factors than the medium speed engines (Figure 2). Emission factors for NOx and CO in this study were well below U.S. EPA and CARB values and lower than EFs reported in other similar studies. Switching from IFO to MDO fuel resulted in slightly lower NOx emission rates, whereas CO emissions increased by 1.5 times, possibly due to poor optimization of the engine parameters, such as fuel injection for operation on MDO fuel. Speciated Analysis of PM. While there are several publications about the CAC and GHG emission factors for ocean going vessels (OGV) of different types, sizes and

RESULTS AND DISCUSSIONS

PM2.5 and Gaseous Ship Emissions. The main pollutants of concern from marine diesel engines include PM2.5, SO2, NOx, CO, and CO2. PM2.5 and SO2 emissions are dictated by sulfur and ash content in fuel, by engine operating parameters, and composition/type of lubricating oil. NOx emissions are generally controlled by combustion temperature (thermal NOx) and fuel-bound nitrogen (fuel NOx), and the CO and CO2 emissions are typically related to combustion efficiency (or completeness of combustion).5,7,8 The emission factors for PM2.5, CO, NOx, SO2, and CO2 reported in this study are summarized in Table 2, together with literature data and the benchmark values commonly used by regulatory agencies for estimating emission inventories. The PM2.5 mass levels were generally lower than the U.S. EPA30 and California Air Resources Board (CARB)31 values (Table 2), except for Vessel No. 1 and Vessel No. 5 for which the measured EFs were 5222



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Figure 2. Emission factors of (a) NOx, (b) CO, and (c) CO2 for slow speed and medium speed engines. Error bars present the mean ±0.95 Confidence Interval (slow speed engines: N = 12 and medium speed engines N = 20 tests); the symbols (∗) present the measured data. Figure 4. (a) Distribution patterns of lanthanoids in PM2.5 emitted by marine vessels. The inset presents the distribution patterns for Vessel no. 4. (b) Distribution patterns for the Upper Continental Crust (UCC)43 and refinery-emitted PM2.515 are presented for comparison.

Figure 5. Three-component plot for marine exhaust PM2.5 samples analyzed in this study (closed circles). The composition of PM2.5 released during routine or episodic emissions from refineries15,17 and oil-fired plants,16 and the composition of a typical FCC16 (open circles) are presented for comparison.

the composition of PM emitted by the marine vessels was the type and quality of the fuel. The major components of PM for ships operating on IFOs (Supporting Information, Table S1) were hydrated sulfates (calculated as H2SO4 × 6.5H2O10), OC, EC, and trace metals, accounting for 80−97% of total PM2.5 mass. The average emission factor for hydrated sulfates was 0.65 g kW−1 hr−1 for vessels using IFO180 and 1.74 g kW−1 hr−1 for the vessel using IFO380. The portion of fuel-sulfur that is transformed in sulfate increased from 2.4% for IFO180 to 5.0% for IFO380 and

Figure 3. Emission factors of selected trace elements. Reference values are for main engines operating at the maximum reported load.

operation modes, the information about the composition of PM and concentration of trace elements in ship plumes is scarce. Results obtained in this study are summarized in Table S3 (Supporting Information). Based on our data, the age and speed of engine operation did not have a significant effect on the PM2.5 speciation. The main factor that considerably affected 5223



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increased with increasing the engine load, which is consistent with other studies.8,10,32 Hydrated sulfates which accounted for 50−75% of PM2.5 mass, were significantly correlated with the sulfur content in the fuel, as expected. The high transformation rates of fuel-sulfur to sulfates render particles emitted by marine vessels very acidic and amplify the implications of shipping to environmental sustainability and human health both globally and locally, particularly in coastal areas.4,7,11 The second most abundant component of the PM2.5 emitted by engines operating on IFOs was OC, accounting for 5−35% of the total mass. When the main engine was operated on MDO, the major component of PM2.5 was OC accounting for 65% of total mass. OC emission factors (ranging from 0.08 to 0.52 g kW−1 hr−1), were generally lower when the vessel operated at higher engine loads and increased slightly with the switch to MDO fuel. The EC emissions did not exceed 0.04 g kW−1 hr−1 and the average EC/OC ratio ranged from 0.03 to 0.1, depending on the type of fuel. These results are consistent with previous studies,8,10,12,33 and strongly distinguish marine combustion products from the on-road diesel engine emissions with typical EC/OC ratio ranging from 1 to 4.34 Total metals content (calculated as sum of all trace elements) accounted for 1.25−3.87% of the total PM2.5 mass, and as expected, was correlated to the concentration of metals in the fuel. Trace Metals. The EFs determined for the sum of the trace metals (including lanthanoids) ranged from (1.01 to 3.58) × 10−2 g kW−1 hr−1 for engines that used IFOs. The vessel that used IFO380 (i.e., the highest content of the bunker oil) had the highest emission factors for all elements (Figure 3), whereas operating the main engine with MDO decreased the emission of trace elements by about 14 times. These results are consistent with the study of Tao et al.7 which demonstrated that switching to lower sulfur fuels will significantly decrease the emissions of trace elements (such as V) by marine vessels. As shown in Figure 3, results of this study were generally lower than published emission factors of trace elements from slow and medium speed marine vessels.10,12 The higher EFs of V reported by Agrawal and Malloy10 are result of much higher content of this element in the HFO used by the vessel tested. EFs of Al were at least 1 order of magnitude lower than values reported by Agrawal and coauthors,10,12 whereas EFs for Mo and Zn were quite comparable. The most abundant elements in PM were V, Ni, and Fe followed by Al, Zn, and Mo. Vanadium contributed 30−70% of the sum of all trace elements followed by Ni (about 20%) and Fe (4−30%). Since V, Ni, and to a smaller extent Fe are known to be indigenous elements of crude oils, it was expected that the EFs of these elements were strongly correlated with their concentrations in the fuel (Supporting Information, Figure S1). The prevalence of V and Ni in ship plumes is also reported in a number of studies and is used as an indicator of the contribution of shipping to the PM 2.5 emissions.35 and references therein Aluminum and molybdenum accounted for 2−12% and less than 2% of trace elements in PM2.5, respectively and had EFs that were strongly correlated with their concentrations in the fuel. These elements are mainly derived in the fuel from the oil-processing catalysts and, as our results suggest, are released together with other combustion products in the emitted particles. EFs for Zn ranged from 0.08 to 0.68 × 10−4 mg kW−1 hr−1, and were not correlated with concentrations in the fuel, which is expected since Zn in shipemitted PM2.5 originates mainly from the partial combustion of lube oil.5

V/Ni ratios in the PM2.5 matched very closely their relative concentrations in the fuel, and ranged from 1.6 to 2.8, depending on the type of the fuel. These results agree with the ratio of V/Ni = 2.5−3 that is generally used to trace heavy oil combustion sources of PM2.59,35 and with V/Ni ratios reported for PM2.5 collected at Canadian sites in close proximity to major harbors and oil refining facilities.15,36,37 Agrawal et al.38 have also observed that the V/Ni ratio in the fuel (V/Ni = 2.28) is preserved in the exhaust on the tested marine vessel. Viana et al.9 reported V/Ni ratios in ambient ship-related PM 2.5 collected in close proximity to a Mediterranean harbor that vary from 2.5 to 5, depending on the shipping traffic, albeit remaining significantly different from this ratio in PM2.5 coming from land sources. Even though the water-soluble components of PM, particularly metals are strongly associated with the health effects of PM2.539,40 there are almost no data on the solubility of metals in ship exhaust. In this study, the PM samples from two vessels (Vessel no. 4 and Vessel no. 5) were also analyzed for water-soluble trace elements. Our results showed that most of the elements were more than 85% soluble in water, despite of the engine age, speed, engine load, or type of fuel. The only exceptions were Fe, As, Ti, and Mo, which were ∼70% soluble and Sb which was only 30% soluble. Selenium was the element with the lowest solubility of 17%. The high solubility of most of the metals in ship exhaust is expected because of the high acidity and hygroscopicity of the particles resulting from the heavy fuel oil combustion process,41 which in turn may make the ship related PM2.5 emissions even a greater concern for the health of coastal communities.42 Lanthanoid Elements. Emission factors for the sum of lanthanoids ranged from (0.34 to 3.6) × 10−5 g kW−1 hr−1, comprising only 0.02−0.2% of total elements emitted by marine vessels. The major lanthanoids were La and Ce for which the average emission factors were respectively 6.9 × 10−6 g kW−1hr−1 and 1.0 × 10−6 g kW−1hr−1. Operating the main engine with MDO (Vessel no. 4) decreased La and Ce emission factors by about 1 order of magnitude. The average Laenrichment factors (i.e., La/element ratios) for ship-exhaust PM2.5 samples were 2.6 for La/Ce and 19.5 for La/Sm, whereas typical values for Upper Continental Crust (UCC) are 0.5 and 6.7, respectively.43 Concentrations of lanthanoids and Laenrichment factors varied for different types of fuel oil used by the ship, and were not related to the operating speed or the age and type of the engine. Figure 4 shows that the distribution patterns of lanthanoids for vessels operating with IFOs are very similar to the typical patterns for refinery-emitted PM2.5.15,44 Consequently, lanthanoids alone cannot distinguish ship plumes from emissions related to accidental or routine operations of the oil-refining industry (Figure S2, Supporting Information). The other parameter often used to distinguish FCC from oil-combustion emission sources is La/V ratio. Kitto et al.16 showed that La/V ratios are typically ∼10 for FCC vs ∼0.02 for oil-fired power plants. Olmez and Gordon13 reported La/V ratios 0.3 ± 0.08 for coal-fired power plants, 0.045 ± 0.015 for oil fired power plants, and 20 ± 3 for refinery emissions. In our study, La/V in PM2.5 particles emitted from ships that use IFOs, varied from 1.2 × 10−4 to 8.5 × 10−3, depending on the type of fuel. For comparison, La/V ratio reported by Agrawal et al.10 was 4.5 × 10−3. This ratio was about 2 orders of magnitude lower than typical values reported for other oil combustion sources, and 5 orders of magnitude lower than FCC emission sources. Therefore, La:Ce:V tertiary 5224



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diagrams14,19,45 and La/V ratios could be used to distinguish shipping emissions from other oil-combustion sources or refinery emissions that have a similar distribution pattern of lanthanoids (Figure 5). Even though this study clearly demonstrated that the presence of FCCs is reflected in the composition of shipPM2.5 emissions, it should be noted that further investigations are needed to identify the sources of elevated concentrations of La in ship exhausts and to establish the relationship between concentration and distribution patterns of lanthanoids in the coastal areas-PM2.5 and shipping emissions.

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composition, and hygroscopicity of fine particles emitted from an oilfired heating plant. Environ. Sci. Technol. 2013, 47 (24), 14468−14475. (7) Tao, L.; Fairley, D.; Kleeman, M. J.; Harley, R. A. Effects of switching to lower sulfur marine fuel oil on air quality in the San Francisco Bay Area. Environ. Sci. Technol. 2013, 47 (18), 10171− 10178. (8) Khan, M. Y.; Giordano, M.; Gutierrez, J.; Welch, W. A.; AsaAwuku, A.; Miller, J. W.; Cocker, D. R. Benefits of two mitigation strategies for container vessels: Cleaner engines and cleaner fuels. Environ. Sci. Technol. 2012, 46 (9), 5049−5056. (9) Viana, M.; Amato, F.; Alastuey, A.; Querol, X.; Moreno, T.; Dos Santos, S. G.; Herce, M. D.; Fernández-Patier, R. Chemical tracers of particulate emissions from commercial shipping. Environ. Sci. Technol. 2009, 43 (19), 7472−7477. (10) Agrawal, H.; Malloy, Q. G. J.; Welch, W. A.; Wayne Miller, J.; Cocker Iii, D. R. In-use gaseous and particulate matter emissions from a modern ocean going container vessel. Atmos. Environ. 2008, 42 (21), 5504−5510. (11) Yau, P. S.; Lee, S. C.; Cheng, Y.; Huang, Y.; Lai, S. C.; Xu, X. H. Contribution of ship emissions to the fine particulate in the community near an international port in Hong Kong. Atmos. Res. 2013, 124, 61−72. (12) Agrawal, H.; Welch, W. A.; Miller, J. W.; Cocker, D. R. Emission measurements from a crude oil tanker at sea. Environ. Sci. Technol. 2008, 42 (19), 7098−7103. (13) Olmez, I.; Gordon, G. E. Rare earths: Atmospheric signatures for oil-fired power plants and refineries. Science 1985, 229 (4717), 966−968. (14) Bozlaker, A.; Buzcu-Güven, B.; Fraser, M. P.; Chellam, S. Insights into PM10 sources in Houston, Texas: Role of petroleum refineries in enriching lanthanoid metals during episodic emission events. Atmos. Environ. 2013, 69, 109−117. (15) Celo, V.; Dabek-Zlotorzynska, E.; Zhao, J.; Bowman, D. Concentration and source origin of lanthanoids in the Canadian atmospheric particulate matter: A case study. Atmos. Pollut. Res. 2012, 3, 270−278. (16) Kitto, M. E.; Andersen, D. L.; Gordon, G. E.; Olmez, I. Rare earth distributions in catalysts and airborne particles. Environ. Sci. Technol. 1992, 26 (7), 1368−1375. (17) Kulkarni, P.; Chellam, S.; Fraser, M. P. Tracking petroleum refinery emission events using lanthanum and lanthanides as elemental markers for PM2.5. Environ. Sci. Technol. 2007, 41 (19), 6748−6754. (18) Moreno, T.; Querol, X.; Alastuey, A.; Gibbons, W. Identification of FCC refinery atmospheric pollution events using lanthanoid- and vanadium-bearing aerosols. Atmos. Environ. 2008, 42 (34), 7851−7861. (19) Moreno, T.; Querol, X.; Alastuey, A.; de la Rosa, J.; de la Campa, A.M.; Minguillon, M. C.; Pandolfi, M.; Gonzales-Castanedo, Y.; Monfort, E.; Gibbons, W. Variations in vanadium, nickel and lanthanoid element concentrations in urban air. Sci. Total Environ. 2010, 408, 4569−4579. (20) ISO. Reciprocating Internal Combustion Engines. Exhaust Emission Measurement, Part 1: Test-Bed Measurement of Gaseous and Particulate Exhaust Emissions, ISO 8178-1:2006; International Organization of Standardization, 2006. (21) ISO. Reciprocating Internal Combustion Engines. Exhaust Emission Measurement, Part 2: Measurement of Gaseous and Particulate Exhaust Emissions under Field Conditions, ISO 8178-2:2008; International Organization of Standardization, 2008. (22) US-EPA. Code of Federal Regulations Title 40 − Protection of Environment Part 92.114; Environmental Protection Agency, 1998. (23) Evaluation of Exhaust Emissions from a Great Lakes SelfUnloading Bulk Cargo Vessel, ERMS Final Report No. 10-24; Emissions Research and Measurement Section Environment Canada: Ottawa, Ontario, Canada, 2011. (24) Evaluation of Exhaust Emissions from a Cargo Vessel Operating in Arctic Waters, ERMS Final Report No. 11-18; Emissions Research and Measurement Section Environment Canada: Ottawa, Ontario, Canada, 2013.

ASSOCIATED CONTENT

S Supporting Information *

Characteristics and routes traveled by the vessels tested in this study (Table S1); Sample collection and analysis methods used for chemical characterization of gaseous and particulate ship emissions (Table S2); Enrichment factors (g kW−1hr−1) obtained by speciation analysis of PM2.5 (Table S3); Emission factors of selected metals as a function of elemental fuel concentration (Figure S1); La−Ce−Sm three-component plot for marine exhaust PM2.5 samples analyzed in this study (Figure S2). This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*Phone: +1 613 949 1331; fax: +1 613 990 8568; e-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS Financial support for this study was provided through Environment Canada’s Clean Air Regulatory Agenda. Special thanks to the Canadian vessel operators involved in this study, and their environmental advisors, Captains, Chief Engineers, and vessel crews for providing outstanding support, assistance, and hospitality. We acknowledge the dedication of the ERMS field research teams in implementing the sampling on board.

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