### N ew 

### Y ork 

### S tate 

### e NergY 

### r eSearch aNd 

### d evelopmeNt 

### a uthoritYThe New York State Energy Research and Development Authority (NYSERDA) is a public benefit corporation created in 1975 by the New York State Legislature. NYSERDA derives its revenues from an annual assessment levied against sales by New York’s electric and gas utilities, from public benefit charges paid by New York rate payers, from voluntary annual contributions by the New York Power Authority and the Long Island Power Authority, and from limited corporate funds. NYSERDA works with businesses, schools, and municipalities to identify existing technologies and equipment to reduce their energy costs. Its responsibilities include:
• Conducting a multifaceted energy and environmental research and development program to meet New York State’s diverse economic needs.
• The New York Energy $martSM program provides energy efficiency services, including those directed at the low-income sector, research and development, and environmental protection activities.
• Making energy more affordable for residential and low-income households.
• Helping industries, schools, hospitals, municipalities, not-for-profits, and the residential sector, implement energy-efficiency measures. NYSERDA research projects help the State’s businesses and municipalities with their energy and environmental problems.
• Providing objective, credible, and useful energy analysis and planning to guide decisions made by major energy stakeholders in the private and public sectors.
• Since 1990, NYSERDA has developed and brought into use successful innovative, energy-efficient, and environmentally beneficial products, processes, and services.
• Managing the Western New York Nuclear Service Center at West Valley, including: overseeing the State’s interests and share of costs at the West Valley Demonstration Project, a federal/State radioactive waste clean-up effort, and managing wastes and maintaining facilities at the shut-down
• State-Licensed Disposal Area.
• Coordinating the State’s activities on energy emergencies and nuclear regulatory matters, and monitoring low-level radioactive waste generation and management in the State.
• Financing energy-related projects, reducing costs for ratepayers.
For more information, contact the Communications unit, NYSERDA, 17 Columbia Circle, Albany, New York 12203-6399; toll-free 1-866-NYSERDA, locally (518) 862-1090, ext. 3250; or on the web at www.nyserda.org

S tate of N ew Y ork e NergY r eSearch aNd d evelopmeNt a uthoritY David A. Paterson, Governor Vincent A. DeIorio, Esq., Chairman Francis J. Murray, Jr., President and Chief Executive Officerii NOTICE This report was prepared by NESCAUM in t he course of performing work contracted for and sponsored by the New York State Energy Research and Development Authority (hereafter “NYSERDA”). The opinions expressed in this report do not necessarily reflect those of NYSERDA or the State of New York, and reference to any specific product, service, process, or method does not constitute an implied or expressed

recomm endation or endorsement of it. Further, NYSERDA, the State of New York, and the contractor make no warranties or representations, expressed or implied, as to the fitness for particular purpose or merchantability of any product, apparatus, or service, or the usefulness, completeness, or accuracy of any processes, methods, or other information contained, described, disclosed, or referred to in thi s report. NYSERDA, the State of New York, and the contractor make no representation that the use of any product, apparatus, process, method, or other information will not infringe privately owned rights and will assume no liability for any loss, injury, or damage resulting from, or occurring in connection with, the use of information contained, described, disclosed, or referred to in this report.iii ABSTRACT AND KEYWORDS Trace elements, including mercury, lead and arsenic, pose significant public health risk due to inhalation toxicity or carcinogenicity of certain compou nds containing these elements. Recent studies of crude oil in North American markets have shown mercury levels to be substantially lower than those used in emission factors for distillate and residual oils. While mercury emissions may be lower than previously estimated, nickel and vanadium from oil combustion are rising in concern. Recent research is suggesting an association between nickel and vanadium concentrations in fine particulate matter and average daily mortality risk.
This work was undertaken to determine whether or not available emission factors for oil are appropriate for use to develop trace elemental emissions inventories in New York State. The substantial market for both oils in th e N ortheast, particularly in the New York City area, supports a measurement campaign to better understand the emissions potential for mercury and other trace elements that may be of concern. Trace elemental profiles from in

- use oils could also prove useful to scientists performing source apportionment analysis of fine particulates (PM 2.5 ).
Working with major oil distributors in the New York market, samples of various oil grades were collected, including home heating oil, biodiesel, o nroad diesel , and residu al oil. Samples were analyzed for sulf ur content and trace elements. The elemental analysis (vanadium, ma n ganese , cobalt , nickel , zinc , arsenic , antimony, selenium , lead , mercury ) employe d a standard instrumental technique capable of detecting trace elemen ts down to a few parts per billion in a sample. Even so, a number of samples contained mercury below the detection limits of the instrument, so a subset of samples were analyzed for mercury using a more sensitive technique. In general, the trace elemental composition of light distillates appears to be somewhat lower than standard emission factor s given in compilations by the U.S. Environmental Protection Agency . As expected, the trace elemental composition of residual oil far exceed s that of lighter distill ates. These current elemental measurements can be used along with existing fuel use in New York State to better understand the relative importance of different sources of trace elements in the overall emissions inventory.

Keywords : heating oil, distillate oil, residual oil, biodiesel, ultra

- low

- sulfur diesel, mercury, nickel, vanadium, sulfur, trace elements, metals, emission inventoryiv ACKNOWLEDGEMENTS For their many contributions in developing the scope of this project, NESCAUM thank s Ray Albrecht, P. E. (NYSERDA

- retired), Ned Bulmer ( Irving Oil ) , Bernie Kelly (Global Companies, LLC), and Steven Levy ( Sprague Energy Corp. ) . We particularly thank the fuel oil distributors Global Companies LLC, Irving Oil, and Sprague Energy Corp. for providing support an d fuel oil samples for elemental analysis. NESCAUM also thanks the New England Fuel Institute and the National Oilheat Research Alliance for helpful comments and advice in developing the project design.v TABLE OF CONTENTS

EXECUTIVE SUMMARY
......................................................................................................................... ix Fuel Oil Consumption and the Public Health Context

.............................................................................. ix Sulfur

................................................................................................ .................................................... ix Mercury in Oil

................................................................................................ ....................................... x Other Trace Metals in Oil

.................................................................................................................... xi Summary of Fuel Oil Sampling Results

................................................................................................... xi Mercury

................................................................................................ ................................................... xii Sulfur

................................................................................................ ...................................................... xiii Implications and Future Directions

........................................................................................................... xv REFERENCES
................................................................................................ ......................................... xvii SECTION 1 : INTRODUCTION
.............................................................................................................. 1-1 Purpose of Assessme nt

........................................................................................................................... 1-1 Background on Mercury

......................................................................................................................... 1-1 Background on Trace Elements and Other HAPs

................................................................................... 1-4 Residential Fuel Use in New York State and the Northeast

................................................................... 1-7 Mercury and Trace Elements in Crude Oil

........................................................................................... 1- 13 Mercu ry
................................................................................................ ............................................ 1- 13 Trace Elements

................................................................................................ ................................ . 1- 15 Mercury and Trace Elements in Refined Petroleum Products

.............................................................. 1- 16 Mercury

................................................................................................ ............................................ 1- 16 Trace Elements

................................................................................................ ................................ . 1- 17 Mercury and Trace Elements in Natural Gas

........................................................................................ 1- 18 Mercury

................................................................................................ ............................................ 1- 18 Other Hazardous Trace Elements

..................................................................................................... 1- 19 Mercury and Trace Elements in Liquid Petroleum Gas (LPG)

............................................................. 1- 20 Current Emission Factors for Mercury and Trace Elements

................................................................ . 1- 20 REFERENCES
................................................................................................ ........................................ 1- 22 SECTION 2
................................................................................................ ................................................ 2-1 Fuel Oil Analytical Methods

.................................................................................................................. 2-1 Inductively Coupled Plasma Mass Spectrometry (IC P- MS) Analytical Methods for

Mercury and O ther Trace Elements

................................................................................................ 2-1 Cold Vapor Atomic Absorption Analytical Method for Mercury

...................................................... 2-3 X-r ay Fluorescence Analytical Methods for Sulfur

........................................................................... 2-3 Fuel Oil Sampling

................................................................................................ ................................... 2-4 REFERENCES
................................................................................................ .......................................... 2-6vi SECTION 3
................................................................................................ ................................................ 3-1 Results for Trace Element Content in Distillates and Residual Oil

........................................................ 3-1 Sample Reproducibility

...................................................................................................................... 3-1 Assessment of Trace Element Relationships with Sulfur Content

..................................................... 3-1 DETERMINATION OF EMISSION FACTORS

.................................................................................. 3-2 Trace Element Concentrations by Fuel Type

..................................................................................... 3-2 Comparison of Emission Factors

....................................................................................................... 3-4 Revision of 2002 New York State Mercury Emissions Inventory

.......................................................... 3-7 Estimated Reductions in New York State Sulfur Dioxide Emissions Based on

Ultra

- Low

- Sulfur

- Fuel

......................................................................................................................... 3-9 Comparison with Speciate Emission Profiles

....................................................................................... 3- 10 Summary

................................................................................................ ............................................... 3- 11 REFERENCES
................................................................................................ ........................................ 3- 12vii FIGURES Figure ES

- 1. General Source Category Contributions to the 2002 New York State Anthropogeni c Mercury Emissions Inventory

............................................................................................................ xiii Figure ES

- 2. General Source Category Contributions to the 2005 New York State Sulfur Dioxide Emissions Inv entory and Low Sulfur Potentia l

.................................................................................... xv Figure 1

- 1. Residential Distillate Fuel Oil Sales in 2008 in the Northeast.

................................................. 1-8 Figure 1

- 2. Shares of Household Heating Fuels in the Upper Northeast States in 2000.

............................ 1-9 Figure 1

- 3. Annual Residential Fuel Oil Sales in New York State, 1984

- 2008.

....................................... 1- 10 Figure 1- 4. Annual Residential Natural Gas Consumption in New York State, 1984

- 2008.

.................... 1- 11 Figure 1

- 5. Monthly New York Distillate Oil Retail Deliveries.

............................................................... 1- 12 Figure 1

- 6. Estimated 2008 Residential Distillate Fuel Oil Consumption by New York State County (Thousand Gallons).

......................................................................................................................... 1- 13 Figure 3

- 1. Trace Element Concentration versus S ulfur Content in Fuel Samples.

.................................... 3-2 Figure 3

- 2. Comparison of Measured Elemental Concentrations and Concentrations from AP

- 42 Emission Factors: Distillate Oil.

........................................................................................................ 3-6 Figure 3

- 3. Comparison of Measured Trace Element Concentrations and Concentrations from AP

- 42 Emission Factors: Residual Oil.

......................................................................................................... 3-7 Figure 3

- 4. General Source Category Contributions to the 2002 New York State Anthropogenic Mercury Emissions Inventory.

........................................................................................................... 3-8 Figure 3

- 5. General Source Category Contributions to the 2005 New York State Sulfur Dioxide Emissions Inventory.

.......................................................................................................................... 3-9viii TABLES

Table ES

- 1. Comparison of Emission Factors (EF) and Concentrations of Trace Elements for Distillate and Residual Fuel Oils

......................................................................................................... xii Table ES

- 2. Sulfur (S) Content in Fuel Oil Samples

................................................................................... xiv Table 1

- 1. 2008 Distillate and Residual Fuel Oil Sales in New York State Based on End Use

................ 1- 11 Table 1

- 2. Total Mercury in Crude Oil of Diffe rent Origins

..................................................................... 1- 15 Table 1

- 3. Trace Elements in Crude Oil

.................................................................................................... 1- 16 Table 1

- 4. Mercury in Refined Petroleum Products.

................................................................................. 1- 17 Table 1

- 5. Trace Elements in Refined Petroleum Products.

...................................................................... 1- 18 Table 1

- 6. Total Mercury in Natural Gas and Gas Condensate

................................................................ . 1- 19 Table 1

- 7. Reported Mercury Emission Factors for Distillate and Residual Oils

...................................... 1- 21 Table 1

- 8. Emission Factors of Trace Elements for Distillate and Residual Fuel Oils and Natural Gas.

................................................................................................ ..................................... 1- 21 Table 2

- 1. ICP

- MS Minimum Detection Limits for Trace Elements in No. 2 Heating Oil and Diesels

..................................................................................................................... 2-2 Table 2

- 2. ICP

- MS Minimum Detection Limits for Trace Elements in No. 6 Fuel Oil

.............................. 2-3 Table 2

- 3. Sampling Locations for No. 2 Home Heating Oil

...................................................................... 2-4 Table 2

- 4. Sampling Locations for No. 6 Fuel Oil and Diesel

.................................................................... 2-5 Table 3

- 1. Sulfur and Trace Element Analysis Comparison for 35 Distillate/Diesel Duplicat e Samples

.............................................................................................................................. 3-1 Table 3

- 2. Analytical Results of Trace Elements by ICP

- MS

..................................................................... 3-3 Table 3

- 3. Analytical Results of Trace Elements by I CP

- MS and Hg by CVAA

....................................... 3-4 Table 3

- 4. Emission Factors of Trace Elements for Distillate and Residual Fuel Oils

................................ 3-5 Table 3

- 5. Trac e Element Emissions Estimates from Distillate and Residual Oil Combustion in New York State, 2001.

..................................................................................................................... 3- 10 Table 3

- 6. Comparison of Emission Factors (EF) and Concentrations of Trace Elements for Distillate and Residual Fuel Oils.

..................................................................................................... 3- 11ix EXECUTIVE SUMMARY Policy

- makers rely on air emission inventories as a primary tool for air quality management. The quality of their decisions, however , is a direct reflection of the quality of the underlying inventories. Therefore, maintaining high

- quality emissions inventories represents a major priority for informed decision making

. Research results presented in this report provide up

- to

- date trace elemental composition of fuel oil s currently used in New York State as well as the northeastern United States. This information improves the understanding of the relative importance of oil combustion in regional emissions inventories for the analyzed elements, which are mercury , lead, arsenic, nickel, vanadium, cobalt, manganese, zinc , antimony, and selenium, along with fuel oil sulfur content

. Fuel Oil Consumption and the Public Health Context About 6.4 million households in the northeastern United States rely on home heating oil for heat ing needs, representing about 80% of the total U.S. households dependent upon home heating oil as their primary heating fuel, which is much higher than the 2005 national average of 7% (EIA 2010a). According to the Energy Information Administration (EIA), 8 2% of all residential fuel oil sales in 2008 occurred in the Northeast, 1

The top consuming state for home heating oil in the United States is New York State (23.5% of the sales), followed by its neighboring states Massachusetts, Pennsylvania, Connecticut and New Jersey (EIA 2009). In 2008, New York consumers bought a little over one billion gallons of home heating oil (No. 2 distillate fuel oil), or over one

- fifth of all home heating oil sold for residential use in the entire United States (EIA 2009). comprising about 3.8 billion gallons of heating oil sold to residential consumers (EIA 2010b). Note that this does not include heating oil sales to apartment and other large multi

- fam ily buildings; t he EIA attributes heating oil sales to these residential buildings under the commercial rather than residential
sector.

Sulfur Sulfate formed in the atmosphere from sulfur dioxide (SO 2 ) emissions when heating oil and other fossil fuels are burned is an important contributor to ambient fine particulate matter (PM 2.5 – particulate matter with a diameter less than 2.5 microns). These small particles can penetrate deeply into the lungs, thus potentially serving as a vector for delivering toxic metals and other hazardous air pollutant s into the body. Adverse health impacts due to PM 2.5 inhalation range from minor irritation to chronic disease , to even death.

1 For purpose s of this comparison, the Northeast region includes the District of Columbia and the states of Connecticut, Delaware, Maine, Maryland, Massachusetts, New Hampshire, New Jersey, New York, Pennsylvania, Rhode Island, and Vermont.x The overall mass of PM 2.5 in New York, New Jersey, and the New England states is typically comprised of at least 40 % sulfate, but sulfate can make up to two

- thirds of the total mass on the highest PM 2.5 days (NESCAUM 2006). Due to the linear relationship between the sulfu r content of fuel oil and SO 2 emissions, lowering the sulfur content of fuel oil can have significant impacts on SO 2 emissions and PM 2.5 formation

. Mercury in Oil Deserving special mention is mercury emitted from fuel oil combustion . Once in the atmosphere, mercury can be deposited locally or transported over long distances before falling back to the surface. When released into the environment and de posited or carried into water bodies, mercury can be converted to methylmercury, a particularly toxic form of mercury. Methylated mercury in the aquatic food chain bioaccumulate s in fish tissue to concentrations markedly higher than in the surrounding wate r.
Mercury is a potent neurotoxin in humans that is particularly damaging to the fetus and young child. A major route of exposure to mercury is through the eating of fish. Women of child bearing age are of special concern as methylmercury ingested by a mother can transport across the placenta into the brain of a developing fetus. In young children and fetuses, methylmercury inhibits the normal development of the nervous system, an effect that may occur even at low exposure levels. This damage frequently is not apparent until later in the developmental process, when motor and verbal skills are found to be delayed or abnormal. Developmental effects have been found in children exposed in utero, even though their mothers did not experience any symptoms of adult toxicity (USEPA 1997). Women in the Northeast have the highest mercury exposure in the U.S., with 19% exceeding blood organic mercury level considered safe for fetuses (Mahaffey et al. 2009).
Most of the mercury present in water bodies − and the fish within them − in New York State and the Northeast is deposited from the atmosphere (NESCAUM 2008). Atmospheric emissions of mercury come mainly from combustion sources including electric utility, industrial, commercial, and in stitutio nal boilers and municipal waste and sewage sludge incinerators. The mercury in combusted fossil fuels originates primarily from petroleum and coal. The U.S. Environmental Protection Agency ( USEPA ) Mercury Study Report to Congress ( USEPA 1997) determined th at the coal combustion in utility boilers constituted the largest source category for atmospheric mercury and also indicated there were, at the time, insufficient data and information available to estimate the amount of mercury emissions that result from t he combustion of liquid fossil fuels , such as home heating oil and diesel

. To address mercury in the environment and its threat to human health, New York State and surrounding
states have establis hed a regional Total Maximum Daily Load (TMDL) for mercury under the federal Clean Water Act. The regional mercury TMDL was set at a level that would decrease mercury levels in fish tissue low enough for states to lift their fish consumption advisories. To achieve the regional TMDL, it is projected that atmospheric deposition must be reduced up to 98% from 1998 levels (NEIWPCC 2007). Thisxi demonstrates a specific need to identify the major mercury air emission sources contributing to deposition in New York State and the surrounding region so that public health and ai r quality planners can efficiently expend limited resources to target the highest priority source sectors.
Inventory analysis identified residential fuel oil combustion as an important contributor to the mercury emissions in the region ( NESCAUM 2005 ). When added to estimated mercury emissions from oil used to fire boilers in the commercial, industrial, institutional, and electrical generating sectors, emissions derived from oil combustion comprised nearly one

- fourth of the regional inventory total.

These estimates were based on emission factors from the USEPA AP

- 42 database ( USEPA 1998 ). Emerging research on the mercury content of crude oil suggests much lower emissions from petroleum fuels. Th is indicate s a need to update the mercury emission factors for fu el oils in New York State and the Northeast to provide a firmer basis for informed decision making. The work presented in this report seeks to address this information need.

Other Trace Metals in Oil The sampling and analysis done to improve the level of knowledge for mercury in New York State’s fuel oils also provides an opportunity to improve understanding of other important trace metal s in fuel oils. Combustion of heating oil by necessity is co

- located with residential areas. Human exposure to toxic meta ls emitted during oil combustion will be relatively greater in areas where large amounts of heating oil are burned, such as in New York State and other areas of the Northeast. The uncertainty in emissions of toxic metals from oil combustion, however, can hinder assessments of public exposure to these air pollutants.
As an example, New York University researchers have implicated nickel and vanadium emissions from oil combustion with an increased risk in daily mortality (Lippmann et al. 200 6 ). In the U.S., N o. 6 residual oil combustion is the large st source of these emissions, with No. 2 distillate fuel oil having less of an impact. Improved knowledge on fuel content of these and other trace elements helps address and anticipate information needs as the healt h science of metals from petroleum combustion evolves.

A further area investigate d in this work is the potential relationshi p trace elements may have with differing fuel sulfur contents (e.g., ultra

- low

- sulfur diesel, biodiesel, No. 6 residual oil) . Specif ically, as regulatory requirements are implemented to require increasingly lower sulfur levels in petroleum fuels, we seek to answer whether mercury and other trace elements may predictably change (increase or decrease) in response to changes in the refini ng process to remove sulfur.

Summary of Fuel Oil Sampling Results Working with major oil distributors in the New York State market, samples of various oil grades were collected, including home heating oil, biodiesel, onroad diesel, and residual oil. Sample s were analyzed forxii sulfur content and the trace elements mercury (Hg), vanadium ( V) , m anganese (Mn), cobalt ( Co ) , nickel ( Ni ), z inc (Zn), arsenic ( As ) , a ntimony (Sb), s elenium (Se), and l ead (Pb).
A total of 137 fuel samples were collected and analyzed fr om fuel oil terminals in Albany, the Bronx, and Long Island, NY; and Revere and Quincy, MA , along with another 36 duplicate samples that were taken from the same storage tank, but collected, shipped, and analyzed separately. The results for distillates (ho me heating oil and diesels) and heavier residual oil (typically used in electric generating units and large industrial, commercial, and institutional boilers) are displayed in Table ES

- 1. Also included for comparative purposes are the emission factors and derived fuel oil concentrations of mercury and other trace elements based on U.S. Environmental Protection Agency’s (USEPA’s) “ AP

- 42 ” emission factors, which are the emission factors compiled by the USEPA and widely used for emissions inventory estimates.
In general, the trace elemental composition of light distillates appears to be 5- to

- 69 times lower than estimates based on the USEPA’s AP

- 42 emission factors

. T he trace elemental composition of residual oil typically far exceeds that of lighter distillates

. These current elemental measurements can be used along with existing fuel use to better understand the relative importance of different sources of trace elements in the overall emissions inventory.
Table ES

- 1. Comparison of Emission Factors (EF) and Conc entrations of Trace Elements for Di stillate and Residual Fuel Oils

Note : The blank entries indicate where samples had no detectable levels above the minimum detection limit

. Mercury
The mercury levels found in this study are sub stantially below those in previous inventory estimates in New York State. A comparison of emission factors and concentrations from this study and the USEPA AP

- 42 factors for #2 and #6 fuel oils are given in Table ES

- 1. Based on this study’s findings, t he m ercury emissions estimates for these source categories in New York State could be overestimated by a factor of 30 for #2 distillate oil (e.g., home heating oil) and by a factor of seven for #6 residual oil

. EF Conc. EF Conc. EF Conc. EF Conc. lb/10 6 gal ppb lb/10 6 gal ppb lb/10 6 gal ppb lb/10 6 gal ppb V n/a n/a 23.4 2,967 31.8 4,025 Mn 0.83 120 22.5 2851 3 380 Co n/a n/a 8.79 1113 6.02 762 Ni 0.0224 3.2 0.42 60 134 16,988 84.5 10,696 Zn 0.104 14.8 0.56 80 15.5 1,963 29.1 3,684 As 0.0147 2.1 0.56 80 1.36 172 1.32 167 Se 0.0303 4.3 2.08 295 0.945 119 0.683 86 Sb n/a n/a 70.1 8,873 5.25 665 Hg 0.014 2.0 0.42 60 0.016 2 0.113 14 Pb 1.25 179 1.49 188 1.51 191 #2 Distillate Oil #6 Residual Oil AP-42 Trace Element NESCAUM AP-42 NESCAUMxiii In order to illustrate the impact that the result s from this work have on emissions inventory data, we revisited the 2002 mercury inventory for New York State

. NESCAUM previously updated a baseline 1996 anthropogenic mercury emissions inventory for the State of New York to the year 2002 (NESCAUM 2005)

. I n the 2002 inventory, the USEPA AP

- 42 emission factors were employed to estimate the emissions from the oil combustion source categories, including industrial/commercial/institutional (ICI) oil

- fired boilers, electric utility oil

- fired boilers, and residen tial heating from distillate heating oil. Figure ES

- 1 presents the previous and revised 2002 New York State mercury emissions contributions by sector that reflects the change in fuel oil mercury emissions obtained from the fuel oil sampling results.

Figure ES

- 1. General Source Category Contributions to the 2002 New York State Anthropoge nic Mercury Emissions Inventory.
When adjusting the 2002 New York State inventory estimates using the emission factors determined in this work, the contributions of r esidential heating and ICI boilers to the overall state

- wide mercury emissions drop from 15 % and 7%, respectively, to only 1%

. These adjustments make the contributions from the other source categories relatively more significant; for example, the emissions from sewage sludge incineration after revision represen t 20% of the entire inventory rather than 15% in the original inventory. Municipal waste combustors continue to contribute the largest share of mercury air emissions in New York State, increasing from 27% to 34% of total state

- wide emissions when the fuel oil combustion contributions are adjusted to reflect the observed lower mercury content in fuel oil. Note that although the emission estimate of oil

- fired electric utility boilers was adjusted, the ma jority of mercury emissions from electric utility boilers in New York State are from coal

- fired boilers, so the total contribution from all electric utility boilers actually becomes relatively more significant after the revisions

.

Sulfur In this study, testing results found average concentrations of sulfur from the set of obtained home heating oil samples to be 2000 parts per million ( ppm ) and residual oil 50% greater ( Table ES

- 2). Ultra

- low

- sulfur Municipal Waste

Combustors 27%

Sewage Sludge

Incinerators 15% Medical Waste

Incinerators 1% ICI Boilers Total 7% Electric Utility Boilers Total 26% Total Manufacturing

Sources

4% Residential

Heating

15% Industrial Processes 5%

Municipal Waste Combustors 34%

Sewage Sludge

Incinerators 20% Medical Waste

Incinerators 1% ICI Boilers Total 1% Electric Utility Boilers Total 31% Total Manufacturing

Sources

5% Residential

Heating

1% Industrial Processes 7% 

### Original Inventory (1829 kg) Revised Inventory (1423 kg)xiv measurements were approximately six ppm and biodiesel somew hat higher at 27 ppm, consistent with previously reported values.
The fuel oil testing results found no strong relationship between the concentration of any trace element and the sulfur content of the fuel sample. On a more macroscopic scale, the trace ele ment concentrations in residual fuel oil are generally at least an order of magnitude higher than in distillate heating oil and diesel. Mercury is the exception, as it appears to be at comparable and relatively low levels in #2 distillate and #6 residual o ils.
Table ES

- 2. Sulfur (S) Content in Fuel Oil Samples

Note: Parentheticals in the table represent the number of samples obtained or that were used to calculate a particular value. *Averages calculated by substituting half the instrumental minimum detection limit for samples below the limit

.

Analysis of biodiesel constitutes one novel result for this study as this fuel represents an emerging market. Based on the results, bio fuel appears to have similar composition to ultra

- low

- sulfur diesel with trace elemental composition at or below that determined for home heating oil. Its sulfur level, however, appears on average to be higher than ultra

- low

- sulfur diesel, based on these limited samples and findings from other more extensive studies. Current USEPA regulations require all diesel fuel (highway and nonroad) meet a 15 ppm level as of June 2010 (Federal Register 2006) . R efined levels in ultra

- low

- sulfur diesel may need to be as low as five ppm to assure product at the pump meets t he 15 ppm requirement. The fuel sampling results in New York State indicate that biodiesel in and of itself may not necessarily be below ultra

- low

sulfur diesel regulatory levels if not subject to the same regulatory or certification requirements. Such

cer tification i s possi ble, with the biodiesel industry having developed a voluntary fuel accreditation program called BQ

- 9000 that includes certification testing for 15 ppm (as well as 500 ppm) sulfur content Type (n) Metric S Content (ppm) maximum 2899 minimum 807 average 1998 median 1920 maximum 3860 minimum 2780 average 3020 median 2970 maximum 8 minimum <3 (1) average 5.6 median 5 maximum 84 minimum 4 average 27.3* median 30.5 Home Heating/ Diesel (102)

Residual (16)

Ultra-low Sulfur (11)

Bio-diesel (8)xv in pure (100%) biodiesel (National Biodiesel Board 2008)

. Accreditation under t he BQ

- 9000 program requires that the fuel must meet the biodiesel certification levels established by the industry standard method ASTM D6751 ( ASTM International 2010 ).
Recently passed legislation in New York State mandates tha t all No. 2 distillate home heating oil meet the same ultra

- low

- sulfur fuel standard (15 ppm) as highway and nonroad diesel fuel by July 2012. This law carries significant public health, environmental, and other benefits (Batey and McDonald 2005). SO 2 and PM 2.5 emissions will be drastically reduced; for example, the annual SO 2 emissions from the residential home heating sector in New York are estimated to decrease to about 150 short tons SO 2 , which corresponds
to a 99 % reduction from 2005 levels

. This would diminish the residential sector’s share of the statewide SO 2 emissions inventory from 9% in 2005 to well less than 1% after the law is fully implemented

. Figure ES

- 2 illustrates the potential impact that using ultra low sulfur fuels in the residential an d commercial/institutional sectors has on the overall SO2 emissions inventory for New York State. This figure shows the 2005 SO2 emissions by sector from US EPA’s National Emissions Inventory (NEI) (left side) and the potential reduction in SO2 emissions if ultra

- low

- sulfur fuel was used in the residential and commercial/industrial sectors (right side). Other air pollutants, such as oxides of nitrogen ( NO x) and carbon dioxide ( CO2 ) , will decrease as well as the boilers and furnaces will operate more efficien tly on ultra

- low

- sulfur oil

. This also has the added benefit of requiring less equipment service, thus lowering the costs for maintenance.

Figure ES

- 2. General Source Category Contributions to the 2005 New York State Sulfur Dioxide Emissions Inve ntory and Low Sulfur Potential.

Implications and Future Directions With the information presented here specific to New York State and the region, air quality program
managers can factor into their work improved inventory estimates of mercury and other trac e metal emissions. Because t hese inventories form the basis for decisions, either by direct analysis or use in air 

## 2005 NEI Inventory Low Sulfur Potential

Commercial/Institutional 10%

Electric Utility 49% Industrial Boilers 18% Residential Fireplaces/Woodstoves 0% Residential Fuel

Combustion 9% Planes, Trains, & Ships 4%
Non-Road Equipment 2% Waste Disposal 1% On-Road Vehicles 1%

Miscellaneous 0% Indus Process 6%

Electric Utility 60% Planes, Trains, & Ships 4% Non-Road Equipment 2% On-Road Vehicles 2%

Miscellaneous 0%

Industrial Boilers 21% Waste Disposal 1%

Commercial/Institutional 3%

Residential Fireplaces/Woodstoves 0% Indus Process 7% Residential Fuel

Combustion 0%xvi quality modeling exercises , they require a reasonable degree of accuracy. Results for mercury , in particular, demonstrate the need to continu ally review and reassess available emission factors and associated emissions estimates. Improved estimates can be applied toward prioritization of control strategies as New York State addresses its regional goal of significantly reducing mercury releases a nd deposition from air into water bodies of the state and region

. In addition, the measurements of other trace elements provide a firmer foundation going forward in evaluating potential public exposure and source contributions to these elements as scientif ic understanding of their public health and ecological impacts evolve (e.g., nickel and vanadium).xvii REFERENCES

ASTM International. 2010. Method D6751

- 10: Standard Specification for Biodiesel Fuel Blend Stock (B100) for Middle Distillate Fuels . ASTM Interna tional. West Conshohocken, PA

. Batey, J.E. and R.J. McDonald. 2005. Low Sulfur Home Heating Oil Demonstration Project Summary Report . Energy Research Center, Inc. and Brookhaven National Laboratory, funded by the New York State Energy Research and Developm ent Authority. (EIA) Energy Information Administration, U.S. Department of Energy. 2009. New York Distillate Fuel Oil and Kerosene Sales by End Us e . EIA. Washington, DC. http:/ /tonto.eia.doe.gov/dnav/pet/pet_cons_821use_dcu_sny_a.htm (accessed May 12, 2010). (EIA) Energy Information Administration, U.S. Department of Energy. 2010 a
. Use of Energy in the United States Explained: Energy Use in Homes. EIA. Washington, DC. http://tonto.eia.doe.gov/energyexplained/index.cfm?page=us_energy_homes (accessed May 11, 2010). (EIA) Energy Information Administration, U.S. Department of Energy. 2010b. He ating Oil Explained: Use of Heating Oil

. EIA. Washington, DC. http://tonto.eia.doe.gov/energyexplained/index.cfm?page=heating_oil_use (accessed May 7, 2010). Federal R egister, 2006. Technical Amendments to the Highway and Nonroad Diesel Regulations; Final Rule and Proposed Rule. 71(83): 25706

- 25726. Lippmann , M. , K. Ito, J.S. Hwang, P. Maciejczyk, and L.C. Chen. 2006. Cardiovascular Eff ects of Nickel in Ambient Air. En vironmental Health Perspectives . 114(11): 1662

- 1669. Mahaffey, K.R., R.P. Clickner, and R.A. Jeffries. 2009. Adult Women’s Blood Mercury Concentrations Vary Regionally in the United States: Association with Patterns of Fish Consumption (NHANES 1999

- 2004). Environmental Health Perspectives . 117: 47

- 53

. National Biodiesel Board. 2008. Specification for Biodiesel (B100) – ASTM D6751

- 09 . National Biodiesel Board. Jefferson City, MO. http://www.biodiesel.org/pdf_files/fuelfactsheets/BDSpec.pdf (accessed October 14, 2010). (NEIWPCC) New England Interstate Water Pollution Control Commission. 2007. Northeast Regional Mercury Total Maximum Daily Load . NEIWPCC. Lowell, MA. http://www.neiwpcc.org/mercury/MercuryTMDL.asp (accessed May 7, 2010). (NESCAUM) Northeast States for Coordinat ed Air Use Management. 2005. Inventory of Anthropogenic Mercury Emissions in the Northeast . NESCAUM . Boston, MA. http://www.nescaum.org/documents/inventory

- of

- anthropogenic

- mercury
- emissions

- in

- the

northeast/rp t051130ne2002mercury_invrpt.pdf (accessed May 10, 2010). (NESCAUM) Northeast States for Coordinated Air Use Management. 2006. Contributions to Regional Haze in the Northeast and Mid

- Atlantic United States: Mid

- Atlantic/Northeast Visibility Union (MANE

- VU ) Contribution Assessment . NESCAUM. Boston, MA.xviii http://www.nescaum.org/documents/contributions

- to

- regional

- haze

- in

- the

- northea st

- and

- mid

atlantic

-- united

- states/ (accessed August 19, 2010). (NESCAUM) Northeast States for Coordinat ed Air Use Management. 2008. Sources of Mercury Deposition in the Northeast United States . NESCAUM. Boston, MA. http://www.nescaum.org/documents/nescaum

- sources
- of

- hg

- depo

- in

- northeast_2008

- final.pdf/ (accessed May 10, 2010). (USEPA) U.S. Environmental Protection Agency. 1998. AP

- 42 Compilation of Ai r Pollutant Emission Factors, Volume 1: Stationary Point and Area Sources , 5 th edition , Chapter 1.3: External Combustion Sources – Fuel Oil Combustion

. USEPA. Research Triangle Park, NC. htt p://www.epa.gov/ttn/chief/ap42/ch01/index.html (accessed May 10, 2010) (USEPA) U.S. Enviro nmental Protection Agency. 1997

. Mercury Study Report to Congress

. USEPA. EPA

452/R

- 97

- 004.1

- 1 SECTION 1 INTRODUCT ION
Purpose of Assessment The purpose of this projec t is to assess the contents of mercury (Hg) and other trace elements including lead (Pb), arsenic (As), nickel (Ni), vanadium (V), cobalt (Co), manganese (Mn), antimony (Sb), selenium (Se), and zinc (Zn) as well as sulfur (S) in fuel oil used in New York S tate and the neighboring region. This will assist the region in better understanding the relative contributions of the source category to overa ll trace element emissions. The data can also be useful in assessing exposures to emissions that may have detrime ntal human health impact s.
About 6.4 million households in the northeastern United States rely on home heating oil for heating needs, representing about 80% of the total U.S. households dependent upon home heating oil as their primary heating fuel. Accordi ng to the Energy Information Administration (EIA), 82% of all residential fuel oil sales in 2008 occurred in the Northeast, comprising about 3.8 billion gallons of heating oil sold to residential consumers (EIA 2010a). The top consuming state for home heat ing oil in the United States is New York State, followed by its neighboring states Massachusetts, Pennsylvania, Connecticut and New Jersey. In 2008, New York consumers bought a little over one billion gallons of home heating oil (No. 2 distillate fuel oil) , or over one
- fifth of all heating oil sold in the entire United States (EIA 2009).
Combustion of heating oil by necessity is co

- located with residential areas. As a result, human exposure to toxic metals from oil combustion can be relatively greater in areas where large amounts of heating oil are combusted, such as in New York State and other areas of the Northeast. The uncertainty in emissions of toxic metals from heating oil, however, can hinder assessments of public exposure to these air pollutants. The work described in this report seeks to address these data gaps through representative sampling of heating oil streams at various distribution points in New York State and adjoining areas. A special emphasis is placed on measuring the Hg content in heating oil due to public and ecological health concerns over eating fish that have high Hg levels as a result of atmospheric deposition.

Background on Mercury Mercury is a toxic metal found in residential heating oil (and other fuel oils) that is emitted to the air when the oil is burned. Once in the atmosphere, Hg can be deposited locally or transported over long distances before falling back to the surface. When released into the environment and deposited or carried into water bodies, Hg can be converted to methylmercury, a particularly toxic form of Hg . Methylated Hg in the aquatic food chain can bioaccumulate in fish tissue to concentrations markedly higher than in the surrounding water.1

- 2 Mercury is a potent neurotoxin, particularly damaging to the fetus and yo ung child. A major route of exposure to Hg in humans is through the eating of fish. Women of child bearing age are of special concern as methylmercury ingested by a mother can transport across the placenta into the brain of a developing fetus. In young children and fetuses, methylmercury inhibits the normal development of the nervous system, an effect that may occur even at low exposure levels. This damage frequently is not apparent until later in the developmental process, when motor and verbal skills are found to be delayed or abnormal. Developmental effects have been found in children exposed in utero, even though their mothers did not experience any symptoms of adult toxicity (USEPA 1997a)

.

Women in the Northeast have the highest Hg exposure in the U.S., with 19% exceeding blood organic Hg level considered safe for fetuses (Mahaffey et al. 2009). This translates into over 84,000 newborns in the Northeast at risk for irreversible neurological deficits from exposure to Hg in the womb. Emerging data also sug gest a link between Hg exposure and increased risk of adverse cardiovascular effects (Salonen et al. 2000; Mozaffarian and Rimm 2006). Further, previous analyses confirmed that eating mercury

contaminated fish and shellfish is the primary route of accumula ting blood organic Hg for most people (Mahaffey et al. 2004). H umans are not the only ones at risk; Hg also threatens fauna at the top of food chain. Birds, such as common loons, and mammals, such as otters, that eat the fish can also have high levels of Hg in their bodies

.

Most of the Hg present in water bodies − and the fish within them − in New York State and the Northeast is deposited from the atmosphere ( Bookman et al. 2008; NESCAUM 200 8). Atmospheric emissions of Hg come mainly from combustion sources including electric utility, industrial, commercial, and i nstitutional boilers and municipal waste and sewage sludge incinerators. The Hg in combusted fuels originates primarily from petroleum and coal. The U S EPA Mercury Study Report to Congress (1997 a ) de termined that the coal combustion in utility boilers constituted the largest source category for atmospheric Hg and also indicated there were, at the time, insufficient data and information available to estimate the amount of Hg emissions that result from the combustion of liquid fossil fuels.
Given recent measurements showing elevated Hg levels in freshwater fish, New York State and many other states have issued health advisories that recommend limiting the consumption of fish from state water bodies (NYS DOH 2010; US EPA 2010a)

. This is the best immediate approach for limiting exposure to Hg that is already present in the environment. B ecause it is believed that about 80

- 90% of atmospheric Hg deposition in New York State arises from out

- of

- state sources , in cluding a major portion from sources outside the U.S . (NYSERDA 2002; 2005 ; Seigneur et al. 2003 ; 2004 ), broad regional as well as international efforts will be needed to reduce continuing Hg deposition to New York State water bodies

. While this is a daunti ng challenge, studies have found that , depending on the characteristics of a given watershed, the availability of mercury for uptake by aquatic biota can decline rapidly within a year of deposition, with previously stored mercury in the watersheds being a relatively small source ( Harris et al.1

- 3 2007; Orihel et al. 2007; Orihel et al. 2008 ). Several studies have tracked decreases in fish tissue mercury levels correlated with decreases in regional and local mercury emission reductions (MassDEP 2006; Evers
et a l. 2007). For these water bodies, decreases in mercury air emissions can lead to rapid (years) decreases in mercury fish tissue levels.
While some improvement in Hg content in fish with decreasing emissions has been observed , these results
may depend upon type of fish species and water shed characteristics , including land use patterns and changes, organic matter properties, acid/base (pH) levels, bacterial community, and water chemistry (Madison Declaration, 2007)

. Wide

- spread long

- term m onitoring is expens ive , limiting the ability to generalize broadly from results of specific fish tissue sampling studies ( NYSERDA 2010)

. There is limited knowledge on how factors such as climate change and weather extremes (freeze/tha w, drying/saturation, etc.) may affect me rcury levels , with modeling of physical attribute s (e.g., watershed characteristics and climatic variables) providing only relatively modest predictive power of variance in fish tissue Hg concentrations in lakes and reservoirs (Shanley et al. 2005). For si tes that have reported co

- located sediment and fish tissue sampling results, no relationship between sediment Hg and fish tissue Hg ha s been found (Kamman et al. 2005)

. Sulf ate reducing bacteria also play a role in methylating mercury, therefore reductions in emissions of sulf ur oxid es may influence the rate of Hg release or retention in soils and water bodies and ultimately fish tissue Hg concentrations ( Drevnick et al. 2007 ).
To address Hg in the environment and its threat to human health, New York State and surrounding states have pursued a number of initiatives aimed at the virtual elimination of Hg releases into the environment. In December 2007, the U.S. Environmental Protection Agency (USEPA) approved a request from New York State and the six New Engl and states to establish a regional Total Maximum Daily Load (TMDL) for Hg under the federal Clean Water Act. The regional Hg TMDL was set at a level that would decrease Hg levels in fish tissue low enough for states to lift their fish consumption advisorie s (NEIWPCC 2007). Subsequently in 2009, New Jersey also received approval from the USEPA for a Hg TMDL in 122 impaired waters within the state that was set at a comparable level to the regional Hg TMDL previously established by New York State and the six N ew England states (NJ DEP 2009).
As noted above, the dominant source of Hg in surface waters of New York State and other states in the region is from atmospheric deposition, with contributions on the global, regional, and local scales (Bookman et al. 2008 ; NESCAUM 2008; NYSERDA 2002; 2005; Seigneur et al. 2003 ). To achieve the regional TMDL, New York State and the other states in the Northeast project that atmospheric deposition needs to be reduced up to 98% from 1998 levels (NEIWPCC 2007).

In order to effe ctively target efforts that can reduce atmospheric deposition of mercury , air quality planners and modelers require accurate inventories of mercury air emission sources (Walcek et al. 2003). An i nventory analysis of air emission sources in the Northeast identified residential fuel oil combustion as an important contributor to the Hg emissions in the region (NESCAUM 2005a)

. When added to estimated Hg1

- 4 emissions from oil used to fire boilers in the commercial, industrial, institutional, and electrical generati ng sectors, emissions derived from oil combustion comprised nearly one

- fourth of the regional inventory total. The inventory estimates were based on emission factors from the USEPA’s AP

- 42 Compilation of Air Pollutant Emission Factors, commonly referred to as AP

- 42 (USEPA 1998). This is a comprehensive list of emission factors developed by the US EPA to estimate the quantity of pollutants released into the atmosphere from a given activity. Emission factors from this compilation serve as a primary resource fo r emissions inventory development in the United States.

In contrast to estimates based on USEPA’s AP

- 42 Hg emissions factor for oil combustion, more recent research on the Hg content of crude oil sponsored by the USEPA and Environment Canada suggests much lower emissions from petroleum fuels (Wilhelm et al. 200 7 ; Environment Canada 2007). These analyses indicate a need to update the Hg emission factors for petroleum distillates.

The Hg emissions from oil combustion in New York State and the Northeast in gen eral are difficult to estimate due to lack of data on concentrations of Hg compounds in liquid fuels. The concentration of Hg in crude oil is highly dependent on geologic location and can vary from 0.01 ppb to 10 ppm by weight (Wilhelm and Bloom 2000). An early estimate by the USEPA of Hg content in distillate oil was given as 120 ppb (USEPA 1997 b) . This level is much higher than later estimates find ing levels below one ppb (Liang et al. 1996; Rising et al. 2004). This report addresses this data inconsisten cy through direct measurements of representative distillate fuels used in New York State and the Northeast.

While less than 1% of Hg emitted in 2002 was attributed to the combustion of natural gas from all combustion sources (NESCAUM 2005 a ), it is included in this study because it is a major residential fuel in

s everal states in the Northeast. Therefore, the environmental importance of natural gas combustion cannot be ignored due to its proximity to population. In addition, Hg in natural gas is detrimental from an industrial standpoint. It can cause corrosion of aluminum structures and damage catalytic processes that have lead to expensive plant shut downs (Kinney 1975).

B ackground on Trace Elements and Other HAPs Trace elements pose significant public health risk due to inhalation toxicity or carcinogenicity of certain compounds containing these elements. The Clean Air Act Amendments of 1990 listed ten trace element compounds among its 188 hazardous air pollutants (HAPs ) . The Agency for Toxic Substances and Disease Registry (ATSDR) has developed 302 toxicological profiles including all the trace elements discussed in this report, with some of them updated recently. Much of the information regarding the health effects of trace elements is cited from the ATSDR, unless noted otherwise.

Lead is one of the oldest known environmental toxins (records date back to 4000 years ago), and because it was used in a broad variety of products, humans are still exposed to lead on a daily basis (Florea and Busselberg 2006) . It has been studied and regulated extensively. Its health impacts include, but are not1

- 5 limited to, neurotoxicity, developmental delays, hypertension, impaired hearing acuity, impaired hemoglobin synt hesis, and male reproductive impairment (USEPA 2004). Children are more vulnerable to lead poisoning, and a bigger proportion of swallowed lead can enter the blood in children than in adults (ATSDR 2007a).
Inorganic arsenic has been recognized as a human poison since ancient times. Small oral doses may lead to stomachache, nausea, vomiting, and diarrhea, while large doses can result in death. Breathing high levels of arsenic in the air is likely to lead to a sore throat and irritated lungs (ATSDR 2007b).

Re cent research suggests an association between nickel and vanadium concentrations in fine particulate matter and average daily mortality coefficients , with residual oil combustion being an important emissions source for these elements (Lippmann et al. 2006)

. A study in New York City suggest ed that increases in ambient level s of nickel and vanadium from residual heating oil and/or traffic may be associated with respiratory symptoms among very young children (Patel et al. 2009). ATSDR (2005a) reported that the most serious harmful health effects from exposure to nickel, such as chronic bronchitis and reduced lung function, have occurred in people who have breathed dust containing certain nickel compounds while working in nickel refineries. The levels of nickel in these workplaces, however, were much higher than usual levels in the environment. The most common harmful health effect on nickel in humans is an allergic reaction. ATSDR (2009) reported that breathing high levels of vanadium caused irritated lungs and eyes that can persist for days to weeks. Vanadium and vanadium compounds are hazardous, with the oxidized form of vanadium, vanadium pentoxide , more toxic than the elemental form (Moskalyk and Alfantazi 2003)

. A study on urban particles around Seville, Spain determined that vanadium, compared to the other metals, had the highest percentage (50.4%) in the soluble and exchangeable fraction, meaning that vanadium is the most available metal to the human body via respiration (Espinosa et al. 2002)

. The major sources of lead emissions have historically been motor vehicles (such as cars and trucks) and industrial sources. As a result of the USEPA’s regulat ory efforts to remove lead from gasoline, levels of lead in the air decreased by 92% between 1980 and 2008 (USEPA 2010 b ). For New York State in 2002, lead emissions from non

- road equipments and electricity generation comprised the top two biggest source

se ctors, with each contributing about 16 tons per year. The fossil fuel combustion and industrial processes are the third and fourth biggest source sectors, respectively, and each contributed about 12 tons per year. Coal combustion has been identified as the single largest emission source sector of most of the other trace elements except for lead. Emissions from oil combustion are generally small compared with coal, with the exception of the majority of nickel emissions coming from oil combustion (Friedman et al. 1993). While oil

- fired power plants and residual oil used in industrial, commercial, and institutional (ICI) boilers and

ocean
- going vessels are thought to be the primary oil combustion sources for trace element emissions, more information is needed t o assess the amount of trace elements emitted into the ambient air through the combustion of heating oil in New York State and the region.1

- 6 Respiratory effects, such as inflammation of the lungs, chronic bronchitis, and chronic emphysema, are the primary ef fects noted from chronic (long

- term) exposure to antimony in humans via inhalation (USEPA 2000). Acute (short

- term) exposure to antimony can result in effects on the skin and eyes. Some antimony compounds have been used as a medicine to treat infection wit h parasites (ATSDR 1992). While the USEPA has not classified antimony for carcinogenicity, antimony trioxide is a possible carcinogen to humans (IARC 1998).
Unlike other trace elements discussed in this report, cobalt, manganese, selenium, and zinc have bo th beneficial and harmful effects on human health. They are essential nutrients for normal growth of plants and animals. Ingesting too much, however, can affect health. Some symptoms are cited here for reference. (1) Serious effects on the lungs have been found in people exposed to 0.005 mg/m 3 of cobalt while working with hard metal. The general public, however, is not likely to be exposed to that high level of cobalt dust (ATSDR 2004). (2) The inhalation of a large quantity of dust containing manganese may cause irritation of the lungs that could lead to pneumonia (ATSDR 2008). (3) Chronic inhalation exposure to selenium dioxide or elemental selenium as dust may have respiratory effects such as irritation of the nose, respiratory tract, and lungs, bronchial spasms, and coughing (ATSDR 2003). (4 ) If large doses of zinc (10

- 15 times higher than the Recommended Dietary Allowance) are taken by mouth even for a short time, stomach cramps, nausea, and vomiting may occur (ATSDR 2005b).
Of all the elements analyzed in this study, sulfur has the highest prevalence in No. 2 home heating oil. In the past, the average sulfur content of heating oil hovered around 0.25 %, or 2500 ppm, although it has varied more in recent years (Batey and McDonald 2005). On average, at leas t 95% of the sulfur in the fuel converts to sulfur dioxide (SO 2 ) upon combustion, so there is a linear relationship between the sulfur content of the fuel and SO 2 emissions (USEPA 1998). The combustion of No. 2 distillate oil in residential and commercial burners and furnaces is the second largest source sector of SO 2 emissions in the NESCAUM region 2

Acute exposure to high levels of SO 2 (e.g., 100 ppm) is an immediate danger to health and can be life

threatening; chronic exposure to persistent levels can cause respiratory symptoms and decreased lung function (ATSDR 1998). Upon oxidation (and often association with ammonium), gaseous SO 2 can convert to particle sulfate (NARSTO 2003). In the NESCAUM region, t he overall mass of PM 2.5 (particulate matter with a diamet er of less than 2.5 microns) is typically comprised of at least 40 % sulfate and can be up to
two

- thirds of the tot al mass on the highest PM 2.5 days (NESCAUM 2006). (electric power plants are the largest source sector) at over 120,000 tons per year , or 15% of the regional inventory (NESCAUM 2005b).

2 The NESCAUM region is comp rised of the six New England States (Connecticut, Maine, Massachusetts, New Hampshire, Rhode Island, and Vermont) plus New Jersey and New York.1

- 7 Across the region, sulfate is a major component of PM 2.5 during the winter months, when sales of No. 2 distillate fuel oil are at their highest (see the next section). Due to the wintertime meteorology, lo cal sources of sulfate are increasingly important, because winter

- time low inversion layer s prevent vertical mixing , which inhibits dilution and dispersion of the accumulating pollution

. For example, in New York City o ne third of the total winter

- time PM 2.5 mass is urban (local) sulfate (i.e., not from long range transport) (NESCAUM 2006).

E xposure to PM 2.5 is associated with adverse human health effects. Research (including toxicological, clinical, and epidemiological studies) has found links to respirato ry and cardiac impacts, from minor irritation to chronic disease. Key health effects studies have also identified a positive relationship between mortality and PM 2.5 (Abbey et al. 1999; Dockery et al. 1993; Lipfert et al. 2000; Pope et al., 1995). PM 2.5 it self is complex in nature, so it is difficult to pinpoint a single component (if one exists) to explain all the health effects observed. Nevertheless , source apportionment based studies tend to identify sulfate

associated sources as the top PM 2.5 source li nked to daily mortality (Mar et al. 2006; Thurston et al. 2005). A Boston study determined that individual s with diabetes (which increases cardiovascular risk) are particularly vulnerable to sulfates; the researchers observed endothelium

- dependent and

- ind ependent vascular reactivity when diabetics exposed to sulfate particle increases (O’Neill et al. 2005).

Recent reports indicate that lowering the sulfur content of home heating oil will significantly reduce the public health and environmental impacts of P M 2.5 at a favorable cost

- benefit ratio (Batey and McDonald 2005; NESCAUM 2005b). There are also additional substantial benefits, including reduction of other air pollutants (80% in PM, 10% in NO x , 1

- 2% in CO 2 ) and decreased boiler and furnace fouling rates , which translates to significant savings in service costs for the home heating oil customer.
Currently, essentially all highway and nonroad diesel fuel is required by the USEPA to meet the ultra

- low

sulfur regulation (maximum content of 15 ppm) (Federal Register 2006)

. In July 2010, New York adopted

a law requiring that all No. 2 heating oil sold in the state contain no more than 15 ppm sulfur as of July 1, 2012 and all No.4 heating oil sold in New York City contain no more than 1500 ppm sulfur as of Octo ber 1, 2012 . S imilar legislation or regulations have already passed in Connecticut and Maine and have been proposed in New Jersey and Pennsylvania (EIA 2010b).

Residential Fuel Use in New York State and t he Northeast In the United States, the majority of h ome heating oil is used in New York State and neighboring areas of the Northeast. About 82% of residential distillate oil sales in the U.S. in 2008 occurred in the region, and New York State has the highest percentage (23.5%) of sales among all states nati onally (EIA 2009). Figure 1-1 gives the amount of fuel oil sales in the Northeast according to jurisdiction.

A prominent feature in the upper N ortheast (New Jersey, New York, and New England) is that the share of distillate oil as a home heating fuel is much higher than the 2005 national average of 7% (EIA 2010c). In1

- 8 New York State, about 33% of households use fue l oil (EIA 2010d), with an estimated 2.2 million households using fuel oil for home heating in 2001 (NYSERDA 200 7 ). D istillate oil is the primary home heating fuel in Connecticut, Maine, New Hampshire, and Vermont , with share s above 50 % ( Figure 1-2 ). The percentages of households that use fuel oil in Massachusetts and Rhode Island are around 40%, close to the sh are of natural gas.
Natural gas is a primary source of home heating in New York State and New Jersey , with percentage share s above the national average
. In New York State, natur al gas is use d in 52% of homes. The share of households using natural gas as the home heating fuel is below the national average level in the other states, with relatively low use in Maine, Vermont, and New Hampshire ( Figure 1-2 ).

0 200 400 600 800 1000 1200

CT DE DC ME MD MA NH NJ NY PA RI VTMillion Gallons

Source: EIA 2009 Figure 1-1
. Residential D istillate F uel O il S ales in 2008 in the Northeast.1

- 9 

### 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%Percent of Households



### CT ME MA NH NJ NY RI VT Other/None LPG Electricity Fuel Oil NaturalGas

Figure 1-2 . Shares of Household Heating Fuels in the Upper Northeast States in 2000.
With specific regard to New York State, a NYSERDA

- sponsored study assessing the petroleum storage and delivery infrastructure in the New York City, Long Island, and Hudson River regions looked into the interplay of natural gas and residential heating oil (distillate) as they competed for market share (ICF Consulting 2006). Based on 2004 data, the most recent data available at the time of the report, residential oil appeared to be holding its market share in terms of tota l volume, but was losing market share to natural gas with population growth. Since 2004, however, residential heating oil sales volume has dropped dramatically ( Figure 1-3 ). Heating oil sales have decreas ed by about 350 million gallons from 2004 to 2008 (a 24% decrease). The drop since the 1980s has been even larger, with a sales volume decrease of over one

third since a peak above 1.7 billion gallons in 1988 to a minimum of about 1.1 billion gallons in 20 08, its lowest sales volume in at least 25 years. By contrast, residential natural gas consumption in New York State has increased by about 20% since 1984 ( Figure 1-4 ).
Even though the residential sales v olume was at a minimum in 2008, residential use of distillate oil in New York State was nearly as much as in the transportation sector, with both sectors accounting for over 75% of total sales that year. Table 1-1 provides the 2008 New York State volumes and percentages in sales of distillate and residual fuel oils by end use. Figure 1-5 show s the seasonality in all sales; the volumes are highest in the wi nter months when residential usage peaks.

T he county

- level distribution of fuel oil consumption in New York State is shown in Figure 1-6 . The latest available data is for 2008 , and comes from the U.S. Ce nsus Bureau ’s American Community Survey (ACS)

. The ACS provides the number of households who primarily use fuel oil for heating (note that th e ACS is1

- 10 conducted only in counties with populations greater than 20,000). The average household distillate fuel oi l consumption was estimated by dividing the 2008 residential sales volume by the total number of households primarily using fuel oil. The geographic distribution plotted in the figure was estimated by applying this factor to the number of households per co unty. As expected, the six most populous counties are estimated to have the highest consumption

.

0 200,000 400,000 600,000 800,000 1,000,000 1,200,000 1,400,000 1,600,000 1,800,000 2,000,0001984198519861987198819891990199119921993199419951996199719981999200020012002200320042005200620072008Residential Fuel Oil Sales (1000 gal)

Source: EIA 2009 Figure 1-3 . Annual Residential Fuel Oil Sales in New York State, 1984

- 2008.1

- 11 0 50,000 100,000 150,000 200,000 250,000 300,000 350,000 400,000 450,0001984198519861987198819891990199119921993199419951996199719981999200020012002200320042005200620072008Natural Gas Residential Consumption (million cubic feet)

Source: EIA 2010e Figure 1-4 . Annual Residential Natural Gas Consumption in New York State, 1984

- 2008.

Table 1-1
. 2008 Distillate and Residual Fuel Oil Sales in New York State Based on End Use

Thousand Gallons Percentage (%) Thousand Gallons Percentage (%) Residential 1,088,618 37.0 Commercial 526,526 17.9 273,185 34.5 Industrial 48,999 1.7 43,983 5.6 Farm 41,076 1.4 Electric Power 16,793 0.6 103,837 13.1 Oil Company 877 0.0 467 0.1 Transportation 1,172,617 39.8 369,650 46.7 Military 3,929 0.1 0 0.0 Off-Highway 45,684 1.6 Other 0 0.0 27 0.0 TOTAL 2,945,119 100.0 791,149 100.0 Distillate Fuel Oil Residual Fuel Oil Sector

Source: EIA 20091

- 12 0 200 400 600 800 1000 1200

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov DecDistillate fuel (thousand gallons) 2005 2006 2007 2008 2009 2010

Source: EIA 2010f Figure 1-5
. Monthly New York Distillate Oil Retail Deliveries.1

- 13 Sources: EIA 2009; U.S. Census Bureau 2009 (gray- shaded counties have populations below 20,000 and were not covered in the Census Bureau’s American Community Survey). Figure 1-6
. Estimated 2008 Residential Distillate Fuel Oil Consumption by New York State County (Thousand G allons).

Mercury a nd Trace Elements i n Crude Oil Crude oil refers to the unrefined petroleum taken from the ground

. The trace amounts of Hg and other elements in crude oil are of interest not only because of the toxicity of these compounds but also because of harmful effects they can have on refining equipment and the impact on the market value of the fuel (Wilhelm and Kirchgessner 2003; Hardaway et al. 2004). Mercury and elements from crude oil can be released to the environment through combustion of the refined products or through oil spills. The amount of Hg and other trace elements in crude oil varies considerably and is dependant on its geologic location (Wilhelm et al. 2000).

Mercury
Levels of total Hg in crude oil have been reported as low as 0.1 μg/k g (Kelly et al. 2003) and as high as 10,000 μg/kg (Wilhelm and Bloom 2000). It can be found in crude oil in several different chemical forms. These forms differ in their chemical and physical properties and include elemental Hg , dissolved organic Hg , inorg anic Hg salts, complexed Hg , suspended Hg compounds, and suspended adsorbed Hg (USEPA 2001).1

- 14 Elemental Hg is soluble in hydrocarbon liquids to only a few parts per million (ppm) but can adsorb onto metallic surfaces or suspended solids in the liquid, resul ting in the suspended adsorbed form. In contrast, organic Hg compounds are highly soluble in liquid oil while having similar adsorptive properties to elemental Hg . Due to differences in solubilities and boiling points, organic Hg compounds can be separated from each other and from elemental Hg by distillation.
Inorganic Hg salts are soluble in liquid oil and can also be found in the suspended form or attached to suspended particles. Suspended Hg compounds are compounds insoluble in water and oil and thus ar e present as a suspended particle. The most common examples in this category are mercuric sulfide (HgS) and mercuric selenide (HgSe). Finally, complexed Hg refers to Hg bound to other constituents, such as an organic sulfide, thiol, or thiophene. These com plexes are only postulated to exist in crude oil and condensates but have not been identified with certainty. Their existence is inferred from chromatographic experiments and operational speciation experiments (Wilhelm and Bloom 2000).

Wilhelm et al. (2007 ) provides a recent analysis of Hg levels in domestic and imported crude oils processed in the United States in 2004. Based on 170 different oil streams, the researchers estimated a total mean of 7.3 μg/kg total Hg in crude oil. The individual measurements showed a range of <0.5 μg/kg to 600 μg/kg. Crude oils originating in the United States were found to contain, on average, 4.3 μg/kg total Hg with the highest concentrations found in crudes produced in California. Of the imported crude oil, the highest

con centrations of total Hg were found in Asian crudes, with an average concentration of 220 μg/kg. This average was dominated by reported concentrations of crude oil imported from Thailand (593 μg/kg) and Vietnam (66.5 μg/kg). Aside from domestic production, the largest contributor to the United States’ supply of crude oil is from the Middle East. The estimated average concentration in oil streams from Saudi Arabia, Iraq, and Kuwait was 0.8 μg/kg (Wilhelm et al. 2007).
Environment Canada sponsored a survey of Hg content of crude oil processed in Canada between November 2003 and March 2006 (Environment Canada 2007). The study looked at 32 different crude oil streams, comprising 70% of Canada’s total 2002 market volume. The study reported an average total Hg

conc entration of 2.6 ± 0.5 μg/kg in all crude oil processed in Canada. The total Hg content of crude oil produced in Canada was found to be lower on average than found in imported crudes. The range of Hg concentrations from domestic and imported fuels was foun d to be 0.1

- 50 μg/kg.
While Wilhelm et al. (2007) and Environment Canada (2007) provide the most recent estimates of total Hg levels in crude oil, several previous studies have characterized these concentrations in crude oil from several points of origin

. In the early 1970s, Shah et al. (1970) reported average concentrations of Hg ranging between 20 to 7500 μg/kg. Since then, analytical methods have improved dramatically and allowed for more accurate and sensitive methods for detecting Hg

. Table 1-2 below summarizes reported Hg levels in crude oils from a variety of sources and analyzed by different detection methods.1

- 15 Table 1-2 . Total Mercury in Crude Oil of Different Origins

Trace Elements Crude oils generally contain trace concentrations of elements in the part per billion (ppb) to part per million (ppm) range. Similarly to Hg, the content of the other trace elements in crude oil is a characteri stic of the location where the oil is produced and can be released to the atmosphere through combustion processes.

Of the other trace elements, nickel and vanadium are the most abundant metallic elements in crude oil (Shah et al. 1970; Filby et al. 1994). They are generally found in the ppm range. Arsenic, cobalt, manganese, lead, selenium, and antimony are generally found in crude oil in the ppb range. Table 1-3 below summarizes the levels of As, Pb, Mn, Ni, Zn, Co, V, Se, and Sb reported in the literature. Reference Source N Mean (ug/kg) Range (ug/kg) Method

Shah et al. 1970 US, California NA 7551 81-29688 Instrumental Neutron Activation Analysis

Shah et al. 1970 Libya NA 739 62.4-2078 Instrumental Neutron Activation Analysis

Shah et al. 1970 US, Louisiana NA 22.5 NA Instrumental Neutron Activation Analysis
Shah et al. 1970 US, Wyoming NA 76.8 NA Instrumental Neutron Activation Analysis Filby et al. 1994 United States, Heavy Crude 6 <47 NA ICP-MS Filby et al. 1994 United States, Light Crude 6 <27 NA ICP-MS Musa et al. 1995 Libya 7 3.1 0.1-12.2 Nuetron Activation Analysis Magaw et al. 1999 Middle East 2 <10 NA Cold Vapor Atomic Absorption Magaw et al. 1999 Africa 4 <10 NA Cold Vapor Atomic Absorption Magaw et al. 1999 North America 11 146 ND-1560 Cold Vapor Atomic Absorption Magaw et al. 1999 Asia 4 <10 NA Cold Vapor Atomic Absorption Magaw et al. 1999 South America 4 <10 NA Cold Vapor Atomic Absorption Magaw et al. 1999 North Sea 1 <10 NA Cold Vapor Atomic Absorption

Bloom 2000 NA 76 1505 NA Cold Vapor Atomic Fluorescence Spectrometry

Bloom 2000 NA 39 3009 NA Cold Vapor Atomic Fluorescence Spectrometry

Bloom 2000 NA 37 1.2 NA Cold Vapor Atomic Fluorescence Spectrometry Liang et al. 2000 NA 11 4.4 1.6-7.2 Thermal Decomposition and Atomic Fluorescence Spectroscopy Kelly et al. 2003 US, Texas 9 0.139 0.127-0.151 Isotope Dilution Cold-Vapor ICP-MS Kelly et al. 2003 US, Texas 18 0.129 0.119-0.140 Isotope Dilution Cold-Vapor ICP-MS Kelly et al. 2003 US, Texas 6 0.053 0.044-0.061 Isotope Dilution Cold-Vapor ICP-MS Kelly et al. 2003 US, Texas 11 0.042 0.039-0.046 Isotope Dilution Cold-Vapor ICP-MS

Wilhelm et al. 2007 Africa, 7 Countries 21 2.7 0.3-13.3 Combustion and Digestion Atomic Fluorescence

Wilhelm et al. 2007 Asia, 3 Countries 4 220.1 0.8-593.1 Combustion and Digestion Atomic Fluorescence

Wilhelm et al. 2007 Canada 32 2.1 NA Combustion and Digestion Atomic Fluorescence

Wilhelm et al. 2007 Europe, 3 Countries 9 8.7 3.1-19.5 Combustion and Digestion Atomic Fluorescence

Wilhelm et al. 2007 Mexico 9 1.3 NA Combustion and Digestion Atomic Fluorescence

Wilhelm et al. 2007 Middle East, 3 Countries 24 0.8 0.7-0.9 Combustion and Digestion Atomic Fluorescence

Wilhelm et al. 2007 South America, 5 Countries 28 5.3 1.1-16.1 Combustion and Digestion Atomic Fluorescence

Wilhelm et al. 2007 United States, 10 States 42 4.3 1.4-11.3 Combustion and Digestion Atomic Fluorescence Environment Canada, 2007 Canada 109 2.6 0.1-50 Cold Vapor Atomic Absorption and Fluorescence1

- 16 Table 1-3 . Trace Elements in Crude Oil

Reference Source As Pb Mn Ni (ppm) Zn Co V (ppm) Se Sb Shah et al . 1970 U.S. California 379 194 27985 3344 679 Shah et al . 1970 Libya 191 77 49234 92 517 Shah et al . 1970 U.S. Louisiana 46 345 3571 29 26 Shah et al . 1970 U.S. Wyoming 111 113 6820 90 321 Raghavan et al . 1979 India 6

- 8 Ugarković and Premerl 1987 Moslavina 4.5

- 11 0.02

- 2.5 Olajire and Oderinde 1993 Nigeria < 0.2 10

- 1400 2800

- 6200 5.0

- 11 < 10 14

- 99 Stacy 1994 Venezuela 284 150 210 117 692 178 1100 303 Filby et al . 1994 U.S. Heavy Crude 20 92 94 162 355 276 15 Filby et al . 1994 U.S. Light Crude 12 10 170 61 2.8 120 28 Musa et al . 1995 Libya 133 3.3 353 7 1.9 6 317 Al

- Swaidan 1996 Saudi Arabia, Heavy Crude 810 9.4 138

Al

- Swaidan 1996 Saudi Arabia, Medium Crude 440 6.9 8.8 Al

- Swaidan 1996 Saudi Arabia, Light Crude 300 3.1 11.3 Magaw et al

. 1999 Several Countries 60 32 20 270 63 160 11 Note : Concentrations shown in table are in μg/kg (ppb) unless indicated otherwise (Ni, V).
Mercury a nd Trace Elements i n Refined Petroleum Products Mercury Petroleum products resulting from the refining of c rude oils commonly contain Hg compounds in various chemical forms. Since the early 1980s, several estimates of Hg in No. 2 distillate oil have been published, describing a wide range of concentrations. The US EPA (1981) estimated the concentration of Hg in No. 2 oil as 400 ppb ( μ g/kg), and US EPA (1997b) estimated it as < 120 ppb. Several studies have been released reporting le vels well below these estimates. Liang et al. (1996) and Rising et al. (2004) reported values below one ppb (0.59 pp b and <0.2 ppb, res pectively). Bloom (2000 ) found Hg concentrations of 1.32 ppb (μ g/kg ) in all light distillates. In addition, total Hg levels in diesel fuel have been reported as high as 3.0
μ g/kg to as low as 0.034 μ g/kg while the levels in gasoline have been found at 0.04 – 3.2 μ g/kg (Liang et al. 1996; Kelly et al. 2003 ; Conaway et al. 2005 ). Table 1-4 below summarizes published estimates of Hg in No. 2 fuel oil and other refined petroleum products.1

- 17 Table 1-4 . Mercury in Refined Petroleum Products.
R ef er en ce F u e l T y p e N M e a n (μ g / k g ) M e th o d E P A 1997b N o

. 2 D is t illa t e O il < 120 Li ang et al

. 1996 H eat i ng oi l 1 0. 59 C VAF S B l oom 2000 L ig h t D is t illa t e s 14 1. 32 C VAF S R is in g et al

. 2004 G as T ur bi ne F uel ( N o. 2) 13 < 0

. 2 I C P- M S E P A 1997b R es i dual F uel O i l 4 B l oom 2000 U t ilit y F u e l O il 21 0. 67 C VAF S K e lly et al

. 2003 R es i dual F uel O i l 5 3. 46 I DCV

- I CP

- M S Li ang et al

. 1996 D ie s e l ( U

. S

. ) 1 0. 4 C VAF S Li ang et al

. 1996 D i es el 1 2. 97 C VAF S H oy er et al

. 2004 D i es el 1 0. 0050 K e lly et al

. 2003 D i es el 6 0. 034 I DCV

- I CP

- M S C onaw ay et al

. 2005 D i es el 19 0. 15 C VAF S W on et al

. 2007 D i es el 0. 219 Li ang et al

. 1996 G as ol i ne ( U

. S

. ) 5 0. 22- 1. 43 C VAF S Li ang et al

. 1996 G as ol i ne ( Monac o) 2 0. 72- 0. 96 C VAF S Li ang et al

. 1996 G as ol i ne ( S l ov eni a) 1 1. 20 C VAF S Li ang et al

. 1996 G as ol i ne ( A l ger i a) 1 3. 20 C VAF S H oy er et al

. 2004 G as ol i ne 3 0. 071- 0. 259 C onaw ay et al

. 2005 G as ol i ne 20 0. 5 C VAF S W on et al

. 2007 G as ol i ne 0. 781 Li ang et al

. 1996 K er os ene 1 0. 04 C VAF S O s l en et al

. 1997 N apht ha 4 15 I C P- M S T ao et al

. 1998 N apht ha 3 40 I C P- M S

T

race Elements While several studies have examined levels of trace elements in crude oil, information is sparse on the levels of these compounds in refined products, and is t abulated in Table 1-5

. Rising et al. (2004) collected No. 2 distillate oil samples from gas turbine installations in 10 U.S. states and analyzed the samples by ICP

- MS. They reported mean concentrations of 15.0 ppb for lead, 28.9 ppb for nickel, and 5.5 ppb for
manganese. Levels of arsenic and cadmium were reported at below the detection limit, 0.9 and 0.1 ppb, respectively. Heathcote et al. (2000) examined the levels of nine elements in motor

- vehicle fuels using ICP

MS. The analysis foun d concentrations in No. 2 diesel of 0.3 to 5.3 ppb for lead, below the detection limit of 2.0 ppb for nickel, 0.7 to 6.5 ppb for vanadium, below the detection limit of 2.0 ppb for manganese, and 5.1 to 12.7 ppb for zinc. Olaj ire and Oderinde (1993) found that the trace element concentrations in heavy distillate we re close to the levels in crude oil ( Table 1-3 ). The reason for high Ni and V concentrations in the light gas oil m easured by Ugarković and Premerl (1987) is unknown.1

- 18 Table 1-5 . Trace Elements in Refined Petroleum Products.
Reference Fuel type As Pb Mn Ni Zn Co V Se Sb Ugarković and Premerl 1987 (Moslavina) Light gas oil 2.0 (ppm) 0.15 (ppm)
Ugarković and Premerl 1987 (Moslavina) Heavy gas oil 1.8 (ppm) 0.3 (ppm)

Olajire and Oderinde 1993 (Nigeria) Heavy distillate < 0.2 10

- 1120 2.4

- 3.8 (ppm) 5.5

- 11 (ppm) < 10 14

- 99 (ppm)

Heathcote et al . 2000 (U.S.) Diesel 0.3

- 5.3 < 2.0 < 2.0 5.1

- 12.7 0.7

- 6.5 1.4
Rising et al. 2004 No. 2 fuel oil < 0.9 15.0 5.5 28.9 < 5 Note: Concentrations shown in table are in μg/kg (ppb) unless indicated otherwise.
Mercury and Trace Elements i n Natural Gas Mercury
In natur al gas, the elemen tal form of Hg is predominant. The organic form is rarely detected while trace amounts of dimethylmercury have been reported ( USEPA 2001 ). Mercury concentrations in natural gas vary geologically from 0 to > 300 μg/N m 3 , where ‘N’ means no rmal condition s corresponding to standard pressure and temperature. Table 1-6 lists the average Hg conten t measured in natural gas in different regions in the world. S ome of the highest concentrations occu r in Southeast Asia, e.g., Indonesia and the Gulf of Thailand. Some high Hg level gas fields a re also found in Europe

.

Because Hg can cause corrosion of aluminum structures and damage catalytic processes that have led to expensive plant shut downs ( Kinney 1975 ), many gas processing plants employ Hg removal processes consisting of adsorbents specific to Hg . The Hg removal processes are particularly important if the feeds contain high levels of Hg , if aluminum heat exchangers are used, or if downstream custom ers have Hg specifications. Mercury removal is required on almost all liquefied natural gas plants as the low temperatures they operate under usually condenses Hg (USEPA 2001). Abu El Ela et al. (2006) described Hg levels in natural gas before and after in stallation of Hg removal equipment at an Egyptian gas plant. They reported Hg concentration s in natural gas ranging b etween 17 and 71 μg/N m 3 before remo val and between 0.53 and 0.92 μ g/N m 3 after removal.1

- 19 Table 1-6 . Total Mercury in Natural Gas and Gas Condensate

R ef er en ce L o c a ti o n N at u r al G as μg / N m 3 G as C o n d e n s a te μ g / kg A t t ar i and C hao 1993 U

. S. <0

. 2 B i ngham 1990; G i j s el m an 1991 N et her l ands 0- 300 Muc hl i s 1981; S i t um or ang and Muc hl i s 1986 I ndones i an 180- 300

H enni c o et al

. 1991 Mi ddl e E as t <5 0 H enni c o et al

. 1991 S out h A f r i c a 100 H enni c o et al

. 1991 F ar E as t 50- 300 R y z hov et al

. 2003 R u ssi a 1. 2- 47 Ab u El El a et al

. 2006 E gy pt 17- 71 Ab u El El a et al

. 2006 E gy pt ( out l et ) 0. 53- 0. 92 Ab u El El a et al

. 2006 S out h A m er i c a 50- 120 50- 100 Ab u El El a et al

. 2006 G ul f of T hai l and 100- 400 400- 1200 Ab u El El a et al

. 2006 N or t h A f r i c a 50- 80 20- 50 S haf aw i et al

. 1999 U nk now n 10- 74 T ao et al

. 1998 U nk now n 18. 1- 256 Z e ttl i tz e r et al

. 1997 N or t h G er m an 4000- 9000 S ar r az i n et al

. 1993 U nk now n 10- 3000 W i l hel m 2001 U

. S

. oi l r ef i ner i es <1 0 W on et al

. 2007 V ehi c l e LP G 1. 82

F or natural gas condensate, the average Hg contents also vary in different regions in the world as listed in Table 1-6

. Several authors provided m ore detailed information. Shafawi et al. (1999) examined Hg levels in five commercially available natural gas condensates using atomic fluorescence spectrometry. They reported Hg levels of 7

- 50 μg/l (10

- 74 μg/kg) in the gas condensates from a variety of or ganic, inorganic, and elemental forms. Tao et al. (1998) looked at Hg speciation in natural gas condensate using GC

- ICP

- MS and identified five species of Hg in gas condensates – elemental Hg, mercury chloride, dimethylmercury, methylethylmercury, and dieth ylmercury.

Other Hazardous Trace Elements Arsenic was studied more intensively than other trace elements partly due to its extreme toxic effects on humans and wildlife and partly due to it being a catalyst poison like Hg and sulfur. It exists in natural ga s predominantly in the form of trialkylarsines, including trimethylarsine (As(CH 3 ) 3 , the major component), dimethylethylarsine, methyldiethylarsine, and triethylarsine (Bouyssiere et al. 2001; Trahan 2008). As Hg, arsenic content in natural gas varies geo graphically. Delgado

- Morales et al. (1994) reported that natural gas from a field in southeastern New Mexico contained arsenic at concentrations of 200 to 2500 μg/m 3 in the form of trialkylarsines. Irgolic et al. (1991) examined arsenic compounds in natural gas using hydride generation and GC

- MS detection. They found a wide range of concentrations from several wells at multiple gas fields, reporting a range of 10 to 63000 μg/m 3 total arsenic. They also noted that this estimate may be low due to the use of a luminum canisters when collecting the gas samples. The same investigators also determined natural1

- 20 gas concentrations from four gas wells using GC

- MS. They found that total arsenic concentrations ranged from 21 to 217 μg/m 3 across the four wells. It was fou nd that 55% to 80% of the arsenic was in the form of trimethylarsine and an additional 5% to 10% were from other forms of trialkylarsines. Attari and Chao (1993) reported total arsenic concentrations of less than five μg/m 3 in the United States. We note th at arsenic removal facilities have been applied at gas wells with high arsenic concentrations. Newpoint Gas (2007) reported an ability to reduce arsenic concentrations from 1200 μg/m 3 to < 10 μg/m 3

. Limited information on trace element levels other than arsenic in natural gas was found

. Häsänen et al. (1986 ) reported that trace elements were not released in significant amounts in the combustion of natural gas. The y examined emissions of SO 2 , NOx, Pb, Cd, Hg, Be, V, Ni, Cr, Mn, Zn, As, Co, Mo, U, Th, and

210 Po from combustion of peat, coal, heavy fuel oil, and natural gas. They concluded that the only significant emission from combustion of natural gas was NOx . Schmidt (1998) examined lead precipitates in natural gas , noting that the first estimates of lead i n natural gas were made in 1975 where average concentrations of 1 μ g/m 3 were reported in gases from fields in n orthwest Germany. Therefore, it was postu lated that the trace element ’ s concentrations in sales natural gas wa s relatively low.

Mercury a nd Trace Elements in Liquid Petroleum Gas (LPG ) There is very limited public information on Hg and other trace elements in liquid petroleum gas (LPG – a gas condensate comprised of propane and/or butane). Wilhelm (2001) estimated that the Hg content in LPG used on

site at refineries is less than 10 ppb. Won et al. (2007) reported a Hg content of 1.23 μg/l (~3 ppb) in vehicle LPG.

Curren t Emission Factors for Mercury a nd Trace Elements According to the US EPA (1997b), the emission factor for No. 2 distillate oil is 0 .86 lb/10 6 g allon, which roughly corresponds to Hg content of 120 μg/kg ( ppb ), which assum es 100% of the Hg is emitted to air from oil combustion. However, the Hg content used in the calculation of this emission factor is not likely representative of most No. 2 fuels. The more recent studies identified in this report have measur ed levels typically much lower than this, with estimat es of the Hg content in No. 2 oil at around 1 ppb. Other estimates of Hg emission factors in fuel oil can be found in Table 1-7

. The Hg content for each emission factor is listed for comparison with Table 1-4 . As is evident, the Hg contents implicit in the USEPA emission factors ar e much higher than the more recent studies. The emission factors for No. 6 residual oil and the corresponding Hg content found in different studies are also listed for reference.

The Hg emission factor for natural gas combustion is 2.6E

- 04 (lb/10 6 scf) in AP

- 42 ( USEPA 1998). The corresponding Hg content is 4.40 (μg/N m 3 ). 3

3 To convert from the emission factor (EF) in lb/10 6 scf to mercury content (MC) in μg/N m 3 for natural gas, 1 l b = 454
gram s (g) , and 1 scf = 0.026853 N m 3 are used. The standard temperature and pressure corresponding to normal cubic meters (N m 3 ) are 0°C (273.15 K) and 101.325 kPa (1atm), while they are 60°F and 1 atm for standard cubic feet (scf)

. MC = EF * 454 (g/lb)/0.026853 (N m 3 /scf) * 1.0E6 μg/g

. This value is likely to be close to the Hg content of most1

- 21 natural gas consumed in the U nited S tates . As described previously , due to the low Hg concentrations in natural gas produced do mestically in the U nited S tates and the removal of Hg at the natural gas processing plant, the Hg content in sales natural gas in the United States is likely to be around one ppb.

Table 1-7 . Reported Mercury E mission Factors for Distillate and Residual Oils
Reference #2 Distillate Oil #6 Residual Oil Emission factor

lb/10 6 gallon Hg content ppb Emission Factor lb/10 6 gallon Hg content ppb USEPA Hg Report to Congress1997a 0.96 136 0.93 118 USEPA L&E Rep ort 1997b 0.86 120 0.033 4.2 USEPA AP

- 42 1998 0.42 60 0. 11 3 14 NHDES 2003 0.013 1.4 0.025 3.2

Note : To convert from lb/10 6 gal to ppb, the density of #2 distillate oil is assumed to be 7.05 lb/gal, and the density of #6 residual oil is assumed to be 7. 9 lb/gal.

Table 1-8 lists emission factors for trace elements from distillate fuel oil and natural gas combustions as contained in AP

- 42 ( USEPA 1998). For distillate oil, the trace element contents assumed in the emission factors are much higher than the recently reported estimates as listed in Table 1-5 . On the other hand, the emission factors from natural gas combustion seem reasonable from the limited in formation collected for this report. The emission factors from residual oil combustion are also listed in Table 1-8 for comparison. As expected, the emission factors for trace elements for residual oil are higher than distillate oil due to the low volatility of these elements. As such, the emission factors for Sb, Co and V , available only for residual fuel oil in AP

- 42 , can be regarded as the upper limit s for distillate oil.

Table 1-8
. Emission Factors of Trace Elements for Distillate and Residual Fuel Oils and Natural Gas
.

E m i s s i on f ac t or E m i s s i on f ac t or E m i s s i on f ac t or E m i s s i on f ac t or E m i s s i on f ac t or E m i s s i on f ac t or l b/ 10 6 gal l b/ MMB t u l b/ 10 6 gal l b/ MMB t u l b/ 10 6 scf l b/ MMB t u V n/ a n/ a 31. 8 2. 12E

- 04 2. 3E

- 03 2. 2E

- 06 Mn 0. 83 6. E

- 06 3 2. E

- 05 3. 8E

- 04 3. 7E

- 07 Co n/ a n/ a 6. 02 4. 02E

- 05 8. 4E

- 05 8. 2E

- 08 Ni 0. 42 3. E

- 06 84. 5 5. 64E

- 04 2. 1E

- 03 2. 0E

- 06 Z n 0. 56 4. E

- 06 29. 1 1. 94E

- 04 2. 9E

- 02 2. 8E

- 05 As 0. 56 4. E

- 06 1. 32 8. 82E

- 06 2. 0E

- 04 1. 9E

- 07 Se 2. 08 1. 5E

- 05 0. 683 4. 56E

- 06 < 2. 4E

- 05 < 2. 3E

- 08 Sb n/ a n/ a 5. 25 3. 51E

- 05 n/ a n/ a Hg 0. 42 3. E

- 06 0. 113 7. 55E

- 07 2. 6E

- 04 2. 5E

- 07 Pb 1. 25 9. E

- 06 1. 51 1. 01E

- 05 5. 0E

- 04 4. 9E

- 07 #2 D i st i l l at e O i l #6 R esi d u al O i l N at u r al G as T r ace E l em en t

Source: AP

- 42, USEPA 1998.1

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- 1 SECTION 2

Fuel Oil Analytical Methods Analysis of fuel oils was performed by a certified and accredited testing laboratory (Intertek Caleb Brett) und er contract to NESCAUM. The testing was done in two phases. The initial phase (Phase I) covered three months and focused on determining the levels of mercury (Hg), lead (Pb), nickel (Ni), vanadium (V), zinc (Zn), cobalt (Co), arsenic (As), selenium (Se), s ulfur (S) and manganese (Mn) in primarily No. 2 home heating oil as well as a small set of ultra

- low

- sulfur and nonroad diesel samples. The structure of the second phase (Phase II) was based on results obtained from Phase I and extended for about a year after Phase I.
A subset of the home heating samples was analyzed for Hg by cold vapor atomic absorption as an independent measurement. In addition, sulfur content of the fuels was tested using X

- ray fluorescence if the distributors were not already performin g those tests.
Additional details on the methods, procedures, and locations of the two sampling phases are described in the following sections.
Inductively Coupled Plasma Mass Spectrometry (ICP

- MS) Analytical Methods for Mercury and Other Trace Elements
I nductively coupled plasma mass spectrometry (ICP

- MS) is a type of mass spectrometry that is highly sensitive and capable of detecting and quantifying a range of metals and several non

- metals at concentrations in the parts per billion range and below (Amman n 2007). A nebulizer sample droplet is introduced into a charged plasma created at high temperature (~10,000 C) within the instrument. The sample droplet and any solids within it vaporize at the high temperatures within the plasma, and break down into atom s. The plasma temperature is also sufficiently high enough to ionize an atom after vaporization into a singly charged ion with the loss of its most loosely bound electron. The positively charged ion is then passed through a mass spectrometer (typically a mass quadrupole) where trace element ions can be discriminated according to their mass and then electronically detected, with the detection signal proportional to the concentration of the atomic species in the sample droplet.

ICP

- MS method for No. 2 home he ating oil and diesels. The analytical method for No. 2 home heating oil and the diesel grades was ITM_1051, Intertek Caleb Brett’s standard method for ICP

- MS analysis by dilution in an organic matrix. Under the ITM_1051 method, the samples are diluted with semi

- conductor grade xylenes at a minimum dilution of 1:10 for analyzing by ICP

- MS. Sample introduction is by self

aspirating perfluoroalkoxy (PFA) nebulizer. Calibration standards are also prepared in xylenes from organometallic standards. Calibration ra nges vary by element and expected result, but are usually in the 0

- 25 ppb range using a four

- point curve, including a calibration blank. Minimum linearity for acceptance is

r 2 >= 0.995. A check standard is run before and after every sample set with ± 20% the accepted value required. A sample blank is prepared with the samples and is run with the samples. The sample blank value2

- 2 must be less than the minimum detection limit (MDL) for the data to be used. A minimum of one sample per ten is run in duplicate wit h the relative standard deviation (RSD) of the duplicate samples required to be less than 20% for any result higher than the MDL. A hydrogen (H 2 ) reaction cell is used to eliminate interferences for problematic elements.
For samples where the dilution is l ess than 1:10, the standard additions technique must be applied. A series of three sample spikes are run with an unspiked sample, all at the desired dilution and these data are used to generate a standard additions curve and result. The result is cross

- che cked by converting the standard curve to an external calibration, which is then applied to a spiked sample with the calculated spike recovery required to be 70

- 130% for acceptance. If multiple samples are being run with the same curve, each sample is run w ith a spiked sample so that recoveries can be used to qualify the additions curve as acceptable for other samples in the set. If spike recovery is inadequate, a separate additions curve must be generated using that specific sample.

The minimum detection li mits for the trace elements investigated by the ICP

- MS technique for No. 2 heating oil and the diesel grades are shown in Table 2-1

.

Table 2-1 . ICP

- MS Minimum Detection Limits for Trace Elements in No. 2 Heating Oil and Diesels
Element ppb As 1 Co 6 Hg 2 Mn 5 Ni 3 Pb 4 Sb 10 Se 5 V 4 Zn 6

ICP

- MS method for No. 6 fuel oil. Because No. 6 fuel oil is relatively heavy, it is more difficult to run a
trace element analysis by simple dilution as with No. 2 home heating oil and the diesel grades. To prepare a sample appropriate for analysis required a preliminary digestion step before analysis by ICP

- MS, which is Intertek Caleb Brett’s method ITM_1052. The IT M_1052 method covers eight different digestion techniques depending on analytical need. If samples require charring with sulfuric acid first, this is done in a closed vessel so that volatiles are not lost. The addition of sulfuric acid can interfere with t he Zn results, which can be largely avoided by employing a helium collision cell.2

- 3 After digestion, the samples are run by ICP

- MS. Calibration is by four

- point curve using standards prepared from commercially available multi

- element aqueous standards. Minimum linearity for acceptance is r2 >= 0.995. An independent check standard is run before and after every sample set with ± 20% the accepted value required. A sample blank is prepared with the samples and is run with the samples. The sample blank value must be less than the MDL for the data to be used. Minimum of one sample per ten is run in duplicate with the RSD of the duplicate samples required to be less than 20% for any result higher than the MDL. A minimum of one sample in ten has a spiked sample prepared with a measured recover of 70

- 130% required to validate the analysis. A H2 reaction cell is used to eliminate interferences for problematic elements.
The minimum detection limits for the trace elements investigated by the ICP

- MS technique for No. 6 fuel oil are given in Table 2-2 . Note that the MDLs for No. 6 fuel oil are higher than that of No. 2 heating oil and the diesel grades.

Table 2-2 . ICP

- MS Minimum Detection Limits for Trace Elements in No. 6 Fuel Oil
Element ppb As 20 Co 10 Hg 25 Mn 10 Ni 25 Pb 10 Sb 30 Se 100 V 10 Zn 125

Cold Vapor Atomic Absorption Analytical Method for Mercury Cold Vapor Atomic Absorption (CVAA) is a more sensitive me thod for detecting Hg than the ICP

- MS method, with a Hg detection limit of 1 ppb for all fuel oil types tested in this study. CVAA is an optical technique that measures the absorption of atomic elemental Hg entrained in a gas flow within the instrument. Th e fuel oil samples were treated according to a combustion

- amalgamation process given by Universal Oil Products (UOP) Method UOP 938.

X- ray Fluorescence Analytical Methods for Sulfur Sulfur concentrations in conventional No. 2 home heating oil and off

- road diesel were obtained by energy

dispersive X

- ray fluorescence spectrometry according to ASTM Method D4294 (ASTM International2

- 4 2003). This method is typically applied to a concentration range of 0.0150 to 5.00 mass % sulfur in fuel oils. Ultra

- low

- sulfur die sel (on

- road diesel and biodiesel) was analyzed using wavelength dispersive X

- ray fluorescence spectrometry according to ASTM Method D2622 (ASTM International 2005).

Fuel Oil Sampling The project began sampling in February 2008 and continued collection until November 2009, encompassing, in part, three different heating seasons and one full calendar year. Home heating oil represented the majority of samples, with limited numbers of on

- road diesel, biodiesel, and residual fuel samples.
Oil samples were shippe d to the Intertek Caleb Brett laboratory in Deer Park, TX for analysis. Sample chain of custody was maintained so that metals analyses and sulfur results could be tracked to each sample. Sample treatment and analysis followed the Intertek Caleb Brett in

- ho use standard operating procedures.
Sample collection sites included terminals in Albany, the Bronx, and Long Island, NY; and Revere and Quincy, MA. Samples were collected by Intertek Caleb Brett field staff who had received training in industry standard op erating procedures prior to sample collection. A total of 137 fuel samples were collected for analysis, along with another 36 duplicate samples, where a duplicate sample refers to a sample taken from the same storage tank, but collected, shipped, and analyzed separately. The samples included 95 home heating oil, 7 high sulfur diesel, 11 ultra

- low

- sulfur diesel, 8 biodiesel, and 16 residual oil samples. The terminals sampled by Intertek Caleb Brett for No. 2 home heating oil are given in Table 2-3 and the locations for No. 6 fuel oil and diesels are given in Table 2-4

.

Table 2-3 . Sampling Locations for No. 2 Home Heating Oil

Location Distributor Terminal No. 2

Albany, NY Sprague Sprague

– Albany Global Global – Albany

Boston, MA Global Global

– Revere Irving Irving

– Revere Boston, MA Sprague Sprague

– Quincy

Long Island, NY Sprague Sprague – Oceansid e Global Global

– Long Island Terminals Brooklyn, NY Global Global

– Brooklyn Metro2

- 5 Table 2-4
. Sampling L ocations for No. 6 Fuel Oil and D iesel

Location Distributor Terminal No. 6 New York, NY Sprag ue Sprague

– Stuyvesant

- Bronx Boston, MA Global Global

– Chelsea Biodiesel New Jersey Sprague Sprague

– Elizabeth, NJ Ultra
- Low Diesel New York, NY Sprague Sprague

– Stuyvesant

- Bronx Nonroad Diesel New York, NY Sprague Sprague

– Stuyvesa nt

- Bronx2

- 6 REFERENCES Ammann, A.A. 2007. Inductively C oupled P lasma M ass S pectrometry (ICP MS): a V ersatile T ool

. Journal of Mass Spectrometry . 42: 419

- 427

. ASTM International . 2003. Method D 4294

– 03 : Standard Test Method for Sulfur in Petroleum and Petrole um Products by Energy

- Dispersive X

- ray Fluorescence Spectrometry . ASTM International. West Conshohocken, PA

. ASTM International . 2005. Method D2622

- 05: Standard Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X

- ray Fluorescence Spectr ometry . ASTM International. West Conshohocken, PA

.3

- 1 SECTION 3

Results f or Trace Element Content in Distillates a nd Residual Oil Sample Reproducibility In order to validate the analysis results, quality assurance and quality control (QA/QC) checks must be followed. As described in Section 2, Intertek Caleb Brett followed procedures to test and verify the performance of its laboratory instrumentation. In addition, duplicate samples were collected to verify the collection and storage procedures. A total of 36 duplicate samples (34 distillate oil, one ultra

- low

- sulfur diesel, and one residual fuel oil) were drawn from the same storage tank but collected, shipped, and analyzed separately from the original samples. Table 3-1 shows the comparison of the trace element concentrations of the duplicate samples (distillate and diesel) with the corresponding original sample.
Table 3-1. Sulfur and Trace Element Analysis Compa rison for 35 Distillate/Diesel Duplicate Samples

Note : No paired samples were tested for antimony (Sb).
Unlike the residual fuel oil samples, many of the trace element concentrations in the distillate oil and diesel samples were below the method detection limit (MDL)

. The MDL for each trace element by ICP

- MS was provided in Table 2-1 and Table 2-2 . In all samples used in this dup licate comparison, the trace metal concentration of cobalt and lead were below the MDL, and for this reason, all 35 sample pairs were determined to have the same trace element concentration

. Therefore, the percent difference between the cobalt/lead concentration for each duplicate and original sample is 0%

. On the other end, all 35 pairs of samples had detectable amounts of sulfur; while only eight of the pairs had the same exact sulfur concentration, the average percent difference is only 1.1%

. Zinc has th e highest average percent difference for the duplicate samples at 30.7%

. Overall, the duplicate samples indicate that the trace element concentrations are reproducible

. The slight differences shown here are expected given some inhomogeneity of the storage tanks.
Assessment of Trace Element Relationships with Sulfur Content For this project, samples of varying sulfur content (from ultra

- low

- sulfur diesel to residual fuel oil) were purposely collected and analyzed. The intent behind this approach was to be able to assess if there are any relationships between the sulfur content of refined petroleum products and the trace element concentrations. Figure 3-1 displays the trace element concentration (only those with detectable concentrations) versus the sulfur content of the sample. The distillate oil and diesel samples are represented by circles, and the residual fuel oil samples are represented by triangles. S V Mn Co Ni Zn As Se Pb Hg Average Percent Difference 1.1% 0.0% 6.2% 0.0% 8.0% 30.7% 18.7% 10.1% 0.0% 11.0% Median Percent Difference 0.5% 0.0% 0.0% 0.0% 0.0% 12.2% 0.0% 0.0% 0.0% 0.0% Pairs with Same Conc. 8 35 31 35 27 11 25 23 35 31 Pairs with Measurable Conc. 35 7 5 0 15 19 26 19 0 13

- 2 Figure 3-1 . Trace Element Concentration versus Sulfur Content in Fuel Samples
.

Figure 3-1 shows that there is no strong relationship between the concentration of any trace element and the sulfur c ontent of the fuel sample. Instead, the figure best illustrates the differences between the residual fuel oil and the distillate oil/diesel samples. In general, the trace element concentrations in residual fuel oil are at least an order of magnitude higher than in distillate heating oil and diesel. Mercury is the exception, as it was below the ICP

- MS minimum detection level (MDL) in all the residual fuel oil samples. Although the Hg content was not detectable in most samples, the ICP

- MS MDL for Hg in residu al fuel oil was higher (25 ppb vs. 2 ppb) than in distillate oil (see Table 2-1 and Table 2-2 ), and none of the residual oil samples had detectable Hg lev els by ICP

- MS. Based on the refining method (where residual fuel oil is the remaining crude oil after the other fuel types are distilled off), it is reasonable to expect that the concentrations for these trace elements would be higher in residual fuel oils than in distillate oils. Mercury, being more volatile, could possibly distill out of the residual fuel oil, while the other trace elements tend to remain behind.

DETERMINATION OF EMISSION FACTORS Trace Element Concentrations by Fuel Type
Table 3-2 and Table 3-3 summarize the analytical results, according to fuel type

. The elements in Table 3-2 were those m ost frequently found in the samples, whereas the concentrations of the elements included in 1 10 100 1000 10000 100000

0 500 1000 1500 2000 2500 3000 3500 4000 Sulfur Concentration (ppm)Trace Element Concentration (ppb) Distillate/Diesel Residual V Mn Co Ni Zn As Se Pb Hg

1 10 100 1000 10000 100000

0 500 1000 1500 2000 2500 3000 3500 4000 Sulfur Concentration (ppm)Trace Element Concentration (ppb) Distillate/Diesel Residual V Mn Co Ni Zn As Se Pb Hg3

- 3 Table 3-3 were more likely to be below the MDL

. Table 3-3 also includes the Hg concentrations, as measured by the more sensitive CVAA technique.
Table 3-2 . Analytical Results of Trace Elements by ICP

- MS

Notes : Units are given in ppb except for S, which is in ppm

. Parentheticals in the table represent the number of samples with that measurement or that were used to create the value

. Averages and medians were not determined when a low percentage of samples above the detection limit were recorded

. Elements not detec ted in any samples are listed as ND in the maximum row.
* Averages calculated by substituting half MDL values for samples with undetectable levels.

In these tables, the quantity in parenthesis represents the number of samples with that measurement or, in the case of determining averages, the number of samples used in the calculation

. The tables show that a significant number of home heating/diesel, ultra

- low

- sulfur diesel, and biodiesel samples have trace element (excluding sulfur) concentrations below the MDL

. For example, less than 50% of the distillate oil samples had detectable amounts (>3 ppb) of nickel by ICP

- MS . Also, no distillate samples recorded cobalt or antimony levels above instrument detection limits, whereas they were measured in residual oil at relatively high concentrations. Averages marked by an asterisk (*) were calculated using half of the MDL as substitutes for samples with unquantifiable concentrations.

Type (n) Metric S Ni Zn As Se Hg maximum 2899 9 66 10 11 13 minimum 807 <3 (54) <6 (35) <1 (25) <5 (18) <2 (72) average 1998 3.2* 14.8* 2.1* 4.3* (75) 2.0* median 1920 <3 17 2. 0 7.0 <2 maximum 3860 22600 4960 523 197 ND m in imum 2780 11900 813 <20 (8) <125 (4) <25 (16) average 3020 16988 1963 172* 119* median 2 970 16650 1810 3 5 125 maximum 8 6 64 ND 5 (1) 4 minimum <3 (1) <3 (8) 6 <1 (11) <5 (8) <2 (9) average 5.6 24 median 5 19 maximum 84 5 50 1 ND ND minimum 4 <3 (6) <6 (1) <1 (7) <5 (8) <2 (8) average 27.3* 22.5* median 30.5 27 Home Heating/

Diesel (102) Residual ( 16)

Ultra-low Sulfur (11)

Bio-diesel (8)3

- 4 T able 3-3 . Analytical Results of Tr ace Elements by ICP

- MS and Hg by CVAA

Notes : Units are given in ppb. Parentheticals in the table represent the number of samples with that measurement or that were used to create the value

. Averages and medians were not determined when a low percentage of samples above the detection limit were recorded

. Elements not detected in any samples are listed as ND in the maximum row. *Averages calculated by substituting half MDL values for samples with un detect able levels.

As was illustrated in Figure 3-1 , Table 3-2 and Table 3-3 show that the trace element content for all species, except Hg, are higher i n residual fuel oils than in distillate oil and diesel fuels

. In comparing the two analytical approaches for Hg measurements, Hg was detected in just over 25% of the distillate oil samples by ICP

- MS, whereas it was measured in over 80% of the samples using the CVAA technique

. By substituting half of the MDL for samples without measurable levels, the average concentration of 2 ppb agrees for both methods

. As mentioned, none of the residual oil samples had detectable Hg levels by ICP

MS

. Of the three residual oil samples measured by CVAA, an average of 1.3 ppb was calculated.
Comparison of Emission Factors
Table 3-4 provides the emission factors of trace elements for distillate and residual fuel oils based upo n the average concentrations measured in this work.

Type (n) Metric V Mn Co Sb Pb Hg maximum 20 114 ND ND 144 5.5 minimum <4 (85) <5 (55) <6 (102) <10 (27) <6 (99) <1 (3) average 1.9* median 2 maximum 8940 4870 1650 16900 603 2 minimum 849 1820 697 3880 <10 (2) 1 average 2967 2851 1113 8873 (6) 188* 1.3 (3) median 2105 2755 1145 6930 181 1 maximum ND 5 ND ND ND minimum <4 (11) <5 (10) <6 (11) <10 (2) <4 (11) <1 (1) average median maximum ND 8 ND minimum <4 (8) <5 (7) <6 (8) (0) <4 (8) (0) average median Home Heating/

Diesel (102) Residual (16)

Ultra-low Sulfur (11)

Bio-diesel (8)3

- 5 Table 3-4 . Emission Factors of Trace Elements for Distillate and Residual Fuel Oils

Figure 3-2 and Figure 3-3 compare the trace element concentrations determined in this work with the concentrations based upon the emission factors provided in AP

- 42 for distillate heating oil and residual fuel oil, respectively ( see also Table 3-6 ). The black bar represents the maximum measured value and the gray bar represents the minimum value (most often half of the MDL)

. The green diamond and blue bar represent the average and median values based on the samples measured in this study

. The red bars indicate the trace element concentrations according to the AP

- 42 emission factors.
For home heating oil , Figure 3-2 illustrates that the trace elemental content based on the information provided in AP

- 42 exceeds the average measured concentration by almost an order of magnitude or more

. With the slight exception of Mn, the AP

- 42 concentrations ar e all greater than the maximum recorded levels

. Because the maximum emission from the combustion of fuel cannot exceed the trace element concentration in the fuel, using the AP

- 42 emission factors would clearly overestimate the trace element emissions from these in

- use distillate oil samples

. Even using the average measurement concentrations would represent an upper bound of emissions, because it assumes that all the trace elements are completely emitted during combustion.
Figure 3-3 illustrates better agreement between the measured concentrations and those derived from AP

- 42 emission factor s for trace elements in residual fuel oils

. For most elements, the AP

- 42 derived concentration s fall within the range of measured concentrations

. The measured average concentration for Pb and As aligns favorably with the emission factor estimate

. Still , for Ni , Sb, and Mn, the AP

- 42 concentration is lower for the measured range

. As is the case with distillate oils, the AP

- 42 concentration for Hg is significantly higher than the concentrations measured in the residual oil samples

. Based on this work, the average concentration of Hg for both No. 2 and No. 6 fuel oils is 2 ppb

. According to AP

- 42, the inferred Hg concentratio ns are 60 ppb and 14 ppb, respectively; therefore, using the AP

- 42 factors would overestimate the Hg emissions by factors of 30 and 7 for the combustion of these fuels. Emission Factor Concentration Emission Factor Concentration lb/10 6 gal ppb lb/10 6 gal ppb As 0.0147 2.1 1.36 172 Pb 1.49 188 Mn 22.5 2851 Ni 0.0224 3.2 134 16,988 Zn 0.104 14.8 15.5 1,963 Co 8.79 1113 V 23.4 2,967 Hg 0.014 2.0 0.016 2 Se 0.0303 4.3 0.945 119 #2 Distillate Oil #6 Residual Oil Trace Element3

- 6 Figure 3-2 . Comparison of Measured Elemental Concentrations and Concentrations from AP

- 42 Emission Factors: Distillate Oil.
Analysis of biodiesel constitutes one novel result for this study as this fuel represents an emerging market. Based on the results, this fuel appears to ha ve similar composition to ultra

- low

- sulfur diesel with trace elemental composition at or below that determined for home heating oil. The sulfur level in biodiesel, however, appears on average to be higher (27.3 ppm) than ultra

- low

- sulfur diesel (5.6 ppm), although the small number of samples ( eight ) may not be representative. A study on sulfur levels in biodiesel derived from a wide range of feedstocks (vegetable oils, grease, and animal fats) indicated that sulfur levels in at least some biodiesel feedstocks are relatively high compared to ultra

- low

- sulfur diesel ( ≤ 15 ppm), depending on growing conditions or processing. As such, biodiesel in and of itself may not necessarily meet ultra

- low

- sulfur diesel requirements (Thompson and He 2006; He and Van Gerpen 2008). Biodiesel

c ertification as a low sulfur fuel is possible, with the biodiesel industry having developed a voluntary fuel accreditation program called BQ

- 9000 that includes certification testing for 15 ppm (as well as 500 ppm) sulfur content in pure (100%) biodiesel (National Biodiesel Board 2008). Accreditation under the BQ

- 9000 program requires that the fuel must meet the biodiesel certification levels established by the industry 

# 1 10 100 1000

Ni Zn As Se Hg Mn PbConcentration (ppb) 

# maximum average median minimum #2 EF3

- 7 standard method ASTM D6751 (ASTM International 2010 a ). In addition, th e October 2008 revisions to the ASTM International specifications for diesel fuels (ASTM D975

- 08a) and fuel oils used for home heating and boiler applications (ASTM D396

- 08b) include the same requirements for blends up to 5% biodiesel (ASTM International 2 009; ASTM International 2010b). These bioblends must meet the same regulations as their non

- blended counterparts.

Figure 3-3 . Comparison of Measured Trace Element Concentrations and Concentrations from AP

- 42 Emission Factors: Residual Oil.

Revision o f 2002 New York State Mercury Emissions Inventory In order to illustrate the impact that the results from this work have on emissions inventory data, we revisited the 2002 Hg inventory for New York State

. NESCAUM previously updated a baseline 1996 anthropogenic Hg emissions inventory for the northeast states (Connecticut, Maine, Massachusetts, New Hampshire, New Jersey, New York, Rhode Island, and Vermont) to the year 2002 (NESCAUM 2005 )

. In the 2002 inventory, the AP

- 42 emission factors were employed to estimate the emissions from the oil 

# 1 10 100 1000 10000 100000

Ni V Zn Co Sb Mn Pb As Se HgConcentration (ppb) 

# maximum average median minimum #6 EF3

- 8 combustion source categories, including industrial/commercial/institutional (ICI) oil

- fired boilers, electric utility oil

- fired boilers, and residential heating from distillate heating oil

. The original 2002 inventory for New York State can be revised by adjusting the Hg emissions by factors of 30 or 7, depending upon the fuel type, based on the results of fuel sampling described in this report. For the adjustments, it was assumed that all of the fuel used by electric utility boilers is residual, that all of the fuel used in residential heating is distillate, and that the fuel combusted by ICI oil

- fired boilers (note that EIA classifies apartment buildin gs as commercial) is 75% distillate and 25% residual

. Figure 3-4 displays the percent each general source category represents of the entire 2002 New York State inventory before and after the revisions

.

W hen adjusting the 2002 New York State inventory estimates using the emission factors determined in this work, the contributions of residential heating and ICI boilers to the overall state

- wide Hg emissions drop from 15 % and 7%, respectively, to only 1%

. Th ese adjustments make the contributions from the other source categories relatively more significant; for example, the emissions from sewage sludge incineration
represen t 20% of the entire inventory rather than 15% after the revisions. Municipal waste combu stors continue to contribute the largest share of Hg air emissions in New York State, increasing from 27% to 34% of total state

- wide emissions when the fuel oil combustion contributions are adjusted to reflect the observed lower Hg content in fuel oil. Not e that although the emission estimate of oil

- fired electric utility boilers was adjusted, the majority of Hg emissions from electric utility boilers in New York State are from coal

- fired boilers, so the total contribution from all electric utility boilers actually becomes more significant after the revisions

.

Figure 3-4 . General Source Category Contributions to the 2002 New York State Anthropogenic Mercury Emissions Inventory. Municipal Waste Combustors 27%

Sewage Sludge

Incinerators 15% Medical Waste

Incinerators 1% ICI Boilers Total 7% Electric Utility Boilers Total 26% Total Manufacturing

Sources

4% Residential

Heating

15% Industrial Processes 5%

Municipal Waste Combustors 34%

Sewage Sludge

Incinerators 20% Medical Waste

Incinerators 1% ICI Boilers Total 1% Electric Utility Boilers Total 31% Total Manufacturing

Sources

5% Residential

Heating

1% Industrial Processes 7% 

### Original Inventory (1829 kg) Revised Inventory (1423 kg)3

- 9 Estimated Reductions i n New York State Sulfur Dioxide Emissions Based o n Ultra

- Low

- Sulfur

- Fuel As discussed in Section 1, New York State recently passed legislation establishing an ultra

- low

- sulfur (15 ppm) fuel standard for No. 2 home heating oil by July 2012. By examining the Ne w York’s new requirement relative to a recent state SO 2 emissions inventory, the projected impact of th e new law can be quantified. According to the US EPA ’s 2005 National Emissions Inventory (NEI), a total of 34,814 short
tons of SO 2 (~9% of the total stat e inventory) w ere attributed to residential fossil fuel combustion in New York State in 2005 (USEPA 2009). In 2005, 1,471,188 thousand gallons of distillate fuel oil were sold for residential use. If the sulfur level in this fuel was 15 ppm, a maximum of 1 50 short tons SO 2 w ould have been released by residential combustion of distillate fuel. This calculation indicates that New York’s new law would result in a 99% SO 2 emissions reduction from the residential sector such that this sector’s share of the total state

- wide SO 2 emissions inventory would drop to less than 1%

. The reduction is illustrated in Figure 3-5 , which compares the original 2005 NEI SO 2 emissions inventory for New York State with a hypotheti cal adjusted inventory incorporating a lower sulfur fuel content level. Note that in the adjusted inventory, the SO 2 emissions from the commerci al/institutional category were also recalculated based on the volume sales (distillate and residual fuel oils) for that sector according to the EIA. A sulfur content of 15 ppm and 3, 020 ppm (the average level based on the data in this study) w ere assumed for distillate oil and residual oil, respectively. For other categories burning fuel oil (i.e., industrial boile rs and electric utility), it is difficult to separate the fuel oil SO 2 emissions in these categories from the coal combustion emissions; therefore, the SO 2 emissions from all other categories remained unchanged from the original inventory.


### 2005 NEI Inventory Low Sulfur Potential

Commercial/Institutional 10%

Electric Utility 49% Industrial Boilers 18% Residential Fireplaces/Woodstoves 0% Residential Fuel

Combustion 9% Planes, Trains, & Ships 4%
Non-Road Equipment 2% Waste Disposal 1% On-Road Vehicles 1%

Miscellaneous 0% Indus Process 6%

Electric Utility 60% Planes, Trains, & Ships 4% Non-Road Equipment 2% On-Road Vehicles 2%

Miscellaneous 0%

Industrial Boilers 21% Waste Disposal 1%

Commercial/Institutional 3%

Residential Fireplaces/Woodstoves 0% Indus Process 7% Residential Fuel

Combustion 0%

F igure 3-5 . General Source Category Contributions to the 2005 New York State Sulfur Dioxide Emissions Inventory
. It is important to keep in mind that the residential distillate fuel oil reductions will be largest dur ing the heating season (winter months). As mentioned in Section 1, sulfate is a significant component of PM 2.53

- 10 during the wintertime , with a large local contribution under stagnant meteorological conditions. In addition, b ecause residential oil combustion emissions occur in close proximity to where people live, reductions in sulfur emissions result in targeted reductions in public exposure to these pollutants.

Comparison w ith Speciate Emission Profiles
As mentioned above , the measured trace element concentr ations in the fuel samples should represent the upper limit of the emissions, assuming that all trace elements are emitted to the air during combustion

. It is interesting to compare the fuel

- based emission factors determined in this work with current sourc e profiles, largely obtained by in

- stack measurements

. SPECIATE is a US EPA database of speciated emissions profiles of air pollution sources (Hsu and Divita 2009)

. Recently, Reff et al. (2009) used the source profiles in SPECIATE to create a national emiss ions inventory of fine particulate matter (PM 2.5 ) for the year 2001. We were provided with the emissions estimates for New York for 2001 from both distillate oil combustion and residual oil combustion

. Using the total amounts of distillate oil and residual fuel oil consumed by New York State in 2001 as provided by the Energy Information Administration (EIA), trace element emissions were estimated using the emission factors determined in this work

. Table 3-5 compares the total 2001 New York State emissions estimates for trace elements from combustion of distillate and residual fuel oils from the calculations in this work with the SPECIATE

- based calculations.

Table 3-5 . Trace Element Emissions Estimates from Distillate and Residual Oil Combustion in New York State, 2001

With the exception of zinc emissions from distillate oil, all of the trace element estimates based on the SPECIATE profiles are less than the values determined from the measurements made in this work

. It is reasonable that the SPECIATE estimates are lower, because those estimates are based on stack measurements and it is possible that trace elements are not completely emitted during combustion , or completely captured in the stack measurements. Given that zinc was the only trace element studied in this work that was also listed in the SPECIATE source profile for distillate oil, it is difficult to interpret whether zinc is an outlier in the source profile or if the entire profile may need to be examined

. NESCAUM SPECIATE NESCAUM SPECIATE ton/yr ton/yr ton/yr ton/yr As 0.0251 0.86 Pb 0.942 Mn 14.2 0.0873 Ni 0.0383 84.7 1.14 Zn 0.0178 4.26 9.8 0.174 Co 5.56 V 14.8 1.93 Hg 0.0239 0.0101 Se 0.0518 0.597 #6 Residual #2 Distillate3

- 11 Of special note is that the SPECIATE estimates give relatively more emissions of V than Ni from residual fuel oil combustion, whereas the estimates from this work indicate Ni content is greater than V content by a factor of five . I t has been s ee n that the ratio of V to Ni in crude oil varies over a wide range (0.17 – 6.67), which may be correlated with the maturity of the crude oil (i.e., age of the reservoir rock) such tha t the V/Ni ratio decreases with increasing geologic time (Musa et al. 1995)

. Interestingly, all of the residual oil samples measured in this work, which presumably derive from diverse production fields , had higher Ni content than V content.

Summary
This wo rk provides an up

- to

- date estimate of trace elemental composition of distillate fuels used in the state of Ne w Yor k and surrounding areas . The fuel composition results for residual oil reasonably agree with existing emission factors, except for Sb, Mn and Hg. For home heating oil, however, the existing emission factors may exceed the true concentration in the fuel currently used in the Northeast. This confirms the importance of trace elemental emission s from residual oil and reveals its relative contributio n to be even greater than previously estimated when compared to emissions from home heating oil.

Table 3-6 summarizes and compares mercury and other trace element emission factors from AP

- 42 and the fuel s ampling results for New York State and the Northeast described in this report. With this state and region

- specific information, the fuel sampling results can be employed by air quality program managers in their work to develop improved inventories of emiss ions. Because t hese inventories form the basis for decisions, either by direct analysis or use in air quality modeling exercises , they require a reasonable degree of accuracy. Results for Hg, in particular, demonstrate the need to continually review and re assess available emission factors and associated emissions estimates. The evaluation process becomes especially critical once the emissions of well

- characterized major source categories have been reduced or controlled.

Table 3-6 . Comparison of Emission Factors (EF) and Concentrations of Trace Elements for Distillate and Residual Fuel Oils

EF Conc. EF Conc. EF Conc. EF Conc. lb/10 6 gal ppb lb/10 6 gal ppb lb/10 6 gal ppb lb/10 6 gal ppb V n/a n/a 23.4 2,967 31.8 4,025 Mn 0.83 120 22.5 2851 3 380 Co n/a n/a 8.79 1113 6.02 762 Ni 0.0224 3.2 0.42 60 134 16,988 84.5 10,696 Zn 0.104 14.8 0.56 80 15.5 1,963 29.1 3,684 As 0.0147 2.1 0.56 80 1.36 172 1.32 167 Se 0.0303 4.3 2.08 295 0.945 119 0.683 86 Sb n/a n/a 70.1 8,873 5.25 665 Hg 0.014 2.0 0.42 60 0.016 2 0.113 14 Pb 1.25 179 1.49 188 1.51 191 #2 Distillate Oil #6 Residual Oil AP-42 Trace Element NESCAUM AP-42 NESCAUM3

- 12 REFERENCES

ASTM International. 2009. D396

- 09a: Standard Specification for Fuel Oils . ASTM Int ernational. West Conshohocken, PA. ASTM International. 2010 a . Method D6751

- 10: Standard Specification for Biodiesel Fuel Blend Stock (B100) for Middle Distillate Fuels . ASTM International. West Conshohocken, PA

. ASTM International 2010b. D975

- 10a: Standard Specification for Diesel Fuel Oils . ASTM International. West Conshohocken, PA. He, B.B. and J. Van Gerpen. 2008. Biodiesel Quality Affected by Sulfur Content Originated from Different Feedstocks and a Database for the Same

. National Institute for Advanced Transportation Technology , University of Idaho

. Final Report KLK432 N08

- 04

. Hsu, Y. and F. Divita Jr. 2009. SPECIATE 4.2: Speciation Database Development Documentation

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. http://www.epa.gov/ttn/chief/net/2005inventory.html (accessed August 23, 2010).For information on other NYSERDA reports, contact: New York State Energy Research and Development Authority 17 Columbia Circle Albany, New York 12203-6399 toll free: 1 (866) NYSERDA local: (518) 862-1090

fax: (518) 862-1091 info@nyserda.org www.nyserda.org