Claxton 2015

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MUTREV-8085; No. of Pages 17
Mutation Research xxx (2014) xxxxxx
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Review
The history, genotoxicity and carcinogenicity of carbon-based fuels

and their emissions: Part 4 Alternative fuels
Larry D. Claxton *
LDC Scientic Services, 6012 Brass Lantern Court, Raleigh, NC 27606, United States
A R T I C L E I N F O A B S T R A C T
Article history: Much progress has been made in reducing the pollutants emitted from various combustors (including
Received 11 May 2014 diesel engines and power plants) by the use of alternative fuels; however, much more progress is needed.
Received in revised form 27 June 2014 Not only must researchers improve fuels and combustors, but also there is a need to improve the
Accepted 28 June 2014
toxicology testing and analytical chemistry methods associated with these complex mixtures. Emissions
Available online xxx
from many alternative carbonaceous fuels are mutagenic and carcinogenic. Depending on their source
and derivation, alternative carbonaceous fuels before combustion may or may not be genotoxic;
Keywords:
however, in order to know their genotoxicity, appropriate chemical analysis and/or bioassay must be
Alternative fuels
Genetic toxicology
performed. Newly developed fuels and combustors must be tested to determine if they provide a public
Carbonaceous fuels health advantage over existing technologies including what tradeoffs can be expected (e.g., decreasing
Emissions levels of PAHs versus increasing levels of NOx and possibly nitroarenes in ambient air). Another need is to
Health improve exposure estimations which presently are a weak link in doing risk analyses.
Cancer 2014 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
1.1. Alternative types of vehicles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
1.1.1. Conventional internal combustion engine vehicles (conventional ICEVs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
1.1.2. Conventional hybrid electric vehicles (HEVs). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
1.1.3. Plug-in electric vehicles (PHEVs and BEVs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
1.2. Types of alternative fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
1.2.1. Conventional alternative fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
1.2.2. Other biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
1.2.3. Coal-derived products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
1.2.4. Shale oil or kerogen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
2. Genetic toxicology of biofuels: carcinogenicity/mutagenicity of the raw (unprocessed) product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
3. The carcinogenicity and mutagenicity of biofuel emissions at the point of release . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
3.1. Synfuel and related products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
4. Electricity the other alternative? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
5. Effects of emission controls. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
6. Other studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
7. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 000
* Tel.: +1 919 839 8978.

E-mail addresses: ldcss@gmx.com, larryclaxton@gmail.com, bettyandlarry@yahoo.com
http://dx.doi.org/10.1016/j.mrrev.2014.06.003
1383-5742/ 2014 Elsevier B.V. All rights reserved.
Please cite this article in press as: L.D. Claxton, The history, genotoxicity and carcinogenicity of carbon-based fuels and their emissions:
Part 4 Alternative fuels, Mutat. Res.: Rev. Mutat. Res. (2014), http://dx.doi.org/10.1016/j.mrrev.2014.06.003
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2 L.D. Claxton / Mutation Research xxx (2014) xxxxxx
1. Introduction combustion engines (ICEs) operating with gasoline and diesel

fuels have powered almost all light-duty vehicles (LDVs) for a
Before the availability of inexpensive fossil fuels, our society century. The dominance of LDVs using petroleum fuels instead of
depended on plant biomass to meet its energy needs. The discovery steam and batteries has been due to petroleum fuels continuing to
of crude oil, in the 19th century, produced an inexpensive liquid have low cost, high energy density, a good distribution system, and
fuel source that aided in the industrialization of the world and the the ability to operate for long distances in a wide range of
improvement of living standards. In the mid-1800s, biomass environmental conditions [11]. Goldemberg [12] reported that the
supplied more than 90% of U.S. energy and fuel needs. Today, British Petroleum Statistical Review of World Energy showed that
because of declining petroleum reserves, increased demand for at constant production and consumption, the presently known
petroleum, political and environmental concerns, countries feel reserves of oil will last around 41 years, natural gas 64 years, and
that it is important to develop other economical and energy- coal 155 years. They also reported that in 2007 the world energy
efcient sources to supplement or replace fossil fuels. Huber et al. use was distributed as follows: oil, 35.03%; coal, 24.59%; gas,
[1] informs us that the U.S. could produce 1.3 109 metric tons of 20.44%; traditional biomass, 8.48%; nuclear, 6.33%; modern
dry biomass/year using its agricultural and forest resources and biomass, 1.91%; solar, 0.53%; small hydroelectric, 0.41%; wind,
still meet its food, feed, and export demands. While the U.S. 0.32%; geothermal, 0.23%; hydro and other renewables, 1.73%.
consumes 7 109 barrels of oil/year, this alternative biomass has Therefore, fossil fuels (oil, coal, and gas) represent 80.1% of the
the energy content equivalent to 3.8 109 boe (barrels of oil total world energy supply. The most likely alternatives to fossil
energy equivalent). Many developing countries use biomass as a fuels are renewable sources such as hydroelectric, biomass, wind,
primary energy source, and other more developed countries use solar, geothermal, and marine tidal [12]. In 2012, the revival of
biomass to meet a signicant percentage of their energy demands shale gas meant that the US had the largest increase in oil
(Sweden, 17.5%; Finland, 20.4%; and Brazil, 23.4%). The laws of production outside Organization of Petroleum Exporting Countries
supply-and-demand economics forecast that as petroleum (OPEC) for the third year in a row [13]. Renewable energy for power
reserves dwindle, the price of petroleum products will increase, generation rose by 17.7% and was driven by wind energy (+25.8%)
and biofuels eventually will be cost-competitive or even cheaper which accounted for more than half of the renewable power
than petroleum-derived fuels. CO2, H2O, light, air, and nutrients are generation for the rst time, with the US and China showing the
the components needed for biofuel production. In addition, energy largest increments [13]. Because of the Fukushima Daiichi nuclear
to power the vehicles needed for producing and distributing the power plant accident in Japan on March 11, 2011 (which triggered
biomass-derived fuels is needed. The effect on food production also a magnitude 9.0 earthquake, caused a tsunami, and caused a
must be considered. Biomass (produced not only on agricultural month-long discharge of radioactive materials into the atmo-
land but also on forest, aquatic, and arid lands) provides a wide sphere), world nuclear power generation declined by 4.3%
range of starting chemical constituents. Biotechnology and genetic worldwide. Japanese nuclear output declined by 44.3% [13].
engineering along with classical plant breeding is expected to Disaster reignited the international debate on the future of nuclear
deliver more plants with faster growth rates, and plants that energy [14]. In Germany, the federal government decided to
require less energy input. In an editorial for Science, Koonin [2] temporarily shut down the old-generation nuclear reactors and re-
reasons: Credible studies show that with plausible technology examine the safety of all national nuclear power facilities [14].
developments, biofuels could supply some 30% of global demand in German output from nuclear power plants fell by 23.2% [13].
an environmentally responsible manner without affecting food The LDV eet is responsible for about half the petroleum
production. To realize that goal, so-called advanced biofuels must consumed in the United States [11]. Many technologies, with
be developed from dedicated energy crops, separately and widely varying levels of current capability, cost, and commerciali-
distinctly from food. . . . There are major technological challenges zation, can reduce LDV petroleum consumption. However, any
in realizing these goals. . . . The combination of modern breeding transition efforts aimed at extensive reduction in petroleum
and transgenic techniques should result in achievements greater utilization are likely to take decades. The demand for biofuels is
than those of the Green Revolution in food crops, and in far less partly driven by the need to replace fossil fuels for: (1) cost,
time. reducing any dependence on higher-priced fossil fuels; (2)
To generate biomass fuels, the process usually can be described environmental concerns, lessening the impacts that come from
as three steps: (1) production of the biomass, (2) processing of the the use of non-renewable resources; and (3) political concerns,
biomass, and (3) use of the biomass fuel [3]. For example: having less dependence upon nations that are of political concern.
vegetable oil plants (rapeseed, soy, palm, sunower, etc.) are: (1) Present national goals being set are so ambitious that Europe and
harvested, (2) extracted and processed, and (3) the bio-oils are the U.S. are unlikely to produce enough biofuels to meet the targets
used for diesel fuels and in the cogeneration of electricity. For being set by developed countries. Because biofuels are from
biodiesel, the plant materials not only have to be extracted but also renewable resources, research may not examine the potential
esteried and puried. For bioethanol, the plant materials undergo health effects of these fuels adequately. Initially, programs will
fermentation and distillation. Biogases usually are produced from depend upon rst generation biofuel crops (food crops such as
manure, biowaste, and corn, which undergo anaerobic digestion maize, sugarcane, soybeans, rapeseed, and palm oil). Second
with the produced gas used for the cogeneration of electricity. See generation biofuel crops (from nonfood crops such as wood chips
the reviews by Huber et al. [1], Leal et al. [4], Tsai and Wu [5], and switch grasses), while competing with food crops for land and
Kerckhoffs and Renquist [6], Philp et al. [7], and Azadi et al. [8] for water are likely to have even less research aimed at health effects
more information on the science of biomass production. Biofuels (e.g., emissions from their use). The National Research Councils
can be thought of as either primary or secondary biofuels, and Committee on Transitions to Alternative Vehicles and Fuels [11]
secondary biofuels may be subdivided into rst-, second-, or third- recent analysis (while exploratory and having signicant uncer-
generation fuels (Table 1). tainty) indicated that the costs and benets of replacing petroleum
In spite of increases in cost and with efforts to reduce pollution, consumption with alternative fuels will be substantial, and these
crude oil remains the raw material for the production of todays analyses also suggested that policy will play a major role in
fuels because crude oil production and distribution has kept pace achieving these reductions [11]. Many biological-source fuels will
with demand. In addition, world reserves have actually expanded undergo either biochemical or thermo-chemical conversion when
as a result of ongoing technological progress [11]. Internal being produced. Biochemical conversion uses enzymes and/or
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L.D. Claxton / Mutation Research xxx (2014) xxxxxx 3
Table 1
Categories of alternative fuels.
Category Method used to categorize Examples
Primary biofuels Unprocessed fuels primarily for heating, cooking or Firewood, wood chips, pellets, animal waste, forest and
electricity production crop residues, landll gas
Secondary biofuels Fuels produced by the processing of biomass and are able to
be used in vehicles and various industrial processes.
Secondary biofuels can be categorized into three
generations on the basis of different parameters, such as the
type of processing technology, type of feedstock, or their
level of development
Secondary biofuels: 1st generation Conventional technologies using conventional sources Fermentation of starch (e.g., wheat, barley) or sugars (e.g.,
sugarcane, sugar beet, etc.) to yield bioethanol and butanol.
Transesterication of oil crops (rapeseed, soybeans, palm,
coconut, used cooking oil, etc.) to give biodiesel
Secondary biofuels: 2nd generation Conventional technologies but this generation is based on Bioethanol and biodiesel produced from conventional
novel starch, oil, and sugar crops technologies but based on novel starch, oil and sugar crops
such as Jatropha or Miscanthus
Using lignocellulosic materials (e.g., straw, wood, and
grass) to produce bioethanol or biobutanol
Secondary biofuels: 3rd generation Use of microbiological or newer methods to produce fuels Microalgae to give biodiesel, bioethanol, or hydrogen
Seaweeds to give bioethanol
Microbes to give hydrogen
Natural gas products Natural gas is a mixture of low molecular weight Liquid natural gas (LNG); compressed natural gas (CNG);
hydrocarbons with methane (CH4) the main one. The synthetic natural gas (SNG); propane (liqueed petroleum
advantages of natural gas are: it is clean burning, and it is gas or LPG)
commercially availability to end users. Because of its
volatility it must be stored either in a compressed gaseous
state (CNG) or a liqueed state (LNG). Propane, also known
as liqueed petroleum gas (LPG) has been used (in light and
medium-duty vehicles) for over 60 years. Propane usually is
a by-product of natural gas processing and crude oil
rening. Synfuel, synthetic fuel, is any liquid fuel derived
from coal or from natural gas
P-series fuels P-series fuels are blends of natural gas liquids, ethanol, and P-series fuels
methyltetrahydrofuran (MeTHF). P-series fuels are clear,
colorless, liquid blends designed to be used alone or mixed
with gasoline in any proportion. These fuels are not
currently being produced in large quantities and are not
widely used
Coal products (including synfuels) Synfuel, synthetic fuel, is any liquid fuel obtained from coal Synfuel
or from natural gas
Electricity: coal generated Coal energy converted to electricity Electricity
Electricity: non-carbonaceous types Electricity produced from some form of NG, hydroelectric Electricity
of generation sources, wind, wave energy, etc.
Electricity: battery powera Electrical energy stored in batteries or capacitors (modern Electricity
capacitors are electrochemical capacitors or ECs (also called
supercapacitors or ultracapacitors) which like other
capacitors physically store charge. Conventional capacitors
store charge on low-surface-area plates, but ECs store
charge in an electric double layer set up by ions at the
interface between a high-surface area carbon electrode and
a liquid electrolyte)
Solar energya Uses sun energy collector cells Solar panels
Hydrogena Hydrogen is a clean energy that can be found everywhere. Hydrogen fuel and engines
The technology needed to use it is neither simple nor cheap;
however, manufacturers are releasing the rst hydrogen car
models
Other types of alternative fuelsa Steam: external combustion heat engines based upon Mechanical energy or electricity
Rankines cycle. Steam engines burn a fuel which produces
heat which is used to raise the temperature of the working
uid (e.g., water) in a conned space, which increases the
pressure, and exerts a force against a piston in the engine
Steam engines generally use less volatile fuels
Based on information provided by Dragone et al. [9] and Colomar et al. [10].
a
Not reviewed in this series but given to make information in this table more complete.
microorganisms to break down lignocellulose into base polymers, very instructive. First, it is possible to develop automobiles (and
and then into monomeric sugars including glucose and xylose, other vehicles and engines) that use alternative fuels. Next,
which can be fermented into ethanol. Thermo-chemical conver- because of the energy content of each fuel, different mpg or mpge
sion exposes lignocellulosic biomass to severe heat in the presence (miles per gallon of gasoline equivalent) would result from the use
of air or oxygen to make a synthetic gas, which is cleaned and used of each type of fuel. With the source of each fuel being different,
as a chemical building block to make a range of fuels [3]. cost for a fuel will vary. Since the projections were based on 2006
In 2006, the staff at Popular Mechanics compared the cost and values, costs in the present market would be expected to be
the fuel needed to travel from New York to California (Table 2) different. Table 2 does not factor in other factors such as the cost of
using gasoline and some alternative fuels [15,16]. The results are the automobile, availability and the distribution of the fuel,
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Table 2
Popular Mechanics 2006 virtual trip (3000 miles) across the United States using gasoline and alternative fuels [15,16].
Type of fuel and automobilea Mpg or mpgeb, Approximation of what starting Fuel cost per trip in 2006
fuel needed material would be used U.S. dollars, approximate
fuel cost/mile (percent cost
relative to a gasoline engine)
Gasoline 87 octane, 2006 Honda Civic 33 mpg, 90.9 gal 4.5 barrels of crude oil $212.70, $0.071 (100)
Hydrogen fuel, GM HY-Wire 41 mpge, 73 gge 16,000 ft3 of hydrogen $804.00, $0.268 (377)
M85/methanol, 1998 Tauris M85 FFV 14 mpg, 214 gal 18,190 ft3 of natural gas and $619.00, $0.206 (290)
half barrel crude oild
E85/ethanol, 2005 Tauris FFV 17 mpg, 176 gal 53 bushels of corn and half $425.00, $0.142 (203)
barrel of crude oild
B100/biodiesel, 2006 Golf TDI 44 mpg, 68.2 gal 16.5 gal of used vegetable oil $231.00, $0.077 (108)
CNGc, Honda Civic GX 32 mpgeb, 88 gge 10,650 ft3 of natural gas $110.00, $0.037 (52)
Electricity, 1997 Honda EV Plus 202 mpge, 16.4 gge 1 ton of coal $60.00, $0.02 (28)
The data for this table was summarized and calculated from the supplemental material supplied with the main article [16].
a
Cars chosen for this virtual cross-country trip were as close in size and weight as possible.
b
To compare the alternative fuels, the energy content in gallon of gasoline equivalents, gge (the amount of fuel with the same energy content as a gallon of gasoline), was
calculated.
c
Compressed natural gas.
d
The half barrel of crude oil is because there is a need to add 15% of a petroleum product that would help in the starting of the automobile.
changes in the cost of a fuel over time, differences due to regional 1.1.2. Conventional hybrid electric vehicles (HEVs)
availability, etc. HEVs combine an ICE, electric motor(s), and a battery (or
ultracapacitor). Most HEVs have a stopstart system that shuts
1.1. Alternative types of vehicles off the engine when idling and restarts it rapidly when the
accelerator is depressed. Such hybrids need a higher capacity
The National Academy of Sciences (NAS) [11] said that the battery and starter motor than ICEVs. Stopstart systems are
different types of vehicles that can be expected to conserve energy rapidly growing and are likely to be universal by 2030 [11]. Other
include: (1) more efcient internal combustion engine vehicles approaches are: (1) having two electric machines connected via a
(ICEVs), (2) hybrid electric vehicles (HEVs), (3) plug-in hybrid planetary gearset to the engine and the powertrain, (2) having
electric vehicles (PHEVs), (3) battery electric vehicles (BEVs), (4) waste heat recovery systems, (3) having components that are more
fuel cell electric vehicles (FCEVs), and (5) compressed natural gas efcient (improved designs and control strategies), and (4)
vehicles (CNGVs). Plug-in electric vehicles (PEVs) include BEVs and improving drivetrains.
PHEVs collectively. ICEVs, HEVs, and PHEVs engines can use fuels
produced from petroleum, biomass, natural gas (NG), or coal; 1.1.3. Plug-in electric vehicles (PHEVs and BEVs)
while, BEVs, FCEVs, and CNGVs only operate on their specic fuel. HEVs, which include PHEVs and BEVs, rely on battery power for
For all types of vehicles, there are some important crosscutting propulsion. These types of vehicles are in production by some
issues (e.g., weight reduction and improvements in aerodynamic manufacturers, and other manufacturers are introducing electric
resistance). vehicles over the next several years. Improvements in battery
technology will be critical to the success of electric vehicles. PHEVs
1.1.1. Conventional internal combustion engine vehicles can travel up to 40 miles on electricity. When driven beyond the
(conventional ICEVs) charge depletion mode of the rst 40 miles, the vehicles operate as
There are multiple technological methods for improving the conventional hybrid vehicles. A BEV has no combustion engine, a
efciencies of ICEVs. Included in these improvements are direct signicant cost savings relative to PHEVs. However, currently a
injection systems (better fuel vaporization), turbocharging (in- SUV might require 100 kWh for a range of 200 miles. In the future,
creasing torque and power output and allowing engine down- a battery of 78 kWh of available energy would give a range of 300
sizing), friction reduction, increasing transmission efciency, and miles. Unfortunately, current technology and costs make this
vehicle weight reduction. A NAS report [11] says that over the past prohibitively expensive, heavy, and bulky for most applications. In
twenty years, reductions in engine friction has occurred at the rate addition, the unit cost of batteries is expected to decline with
of about 1% per year. Even greater reductions, however, are increased production and development; and the energy storage (in
possible. For example, laser texturing can etch a microtopograph kilowatt-hours) required for a given vehicle range will decline with
on material surfaces to guide lubricant ow [11]. EPA apportioned vehicle load reduction and improved electrical component
the energy losses and efciencies to engine thermal efciency, efciency. Several advanced battery technologies (e.g., lithium-
friction, pumping losses, transmission efciency, torque converter air) are being developed that would address some of the drawbacks
losses, and accessory losses [11]. of lithium-ion batteries, but their potential for commercialization
Todays diesels are about 1520% more efcient than gasoline by 2050 is still highly uncertain [11].
engines; however, the efciency advantage of the diesel will If the use of petroleum is greatly reduced, the retirement of
decrease in the future as gasoline engines improve [11]. Current crude oil production and a decline in distribution infrastructure
diesels have a much higher level of technology than gasoline engines will follow. With production and distribution infrastructure being
in order to deal with diesel drivability, noise, smell, and emission changed, much of the distribution systems and lling stations will
concerns. Diesel engines commonly have direct fuel injection, become obsolete, and this could have drastic effects on the
sophisticated turbocharging systems, and cooled exhaust gas economy [11]. Large increases in fuel economy are possible;
recirculation (EGR) systems. As this same level of technology therefore, a NAS report says that manufacturers will need
becomes common in the gasoline engine, the efciency advantage of incentives or regulatory standards or both to apply widely the
the diesel engine will decline. In addition, future development of the new technologies [11]. For example, as of February 2010, the
homogenous charge compression ignition engines will blur the United States had approximately 136 million cars, 110 million
distinction between gasoline and diesel engines. trucks, and 1 million buses (247,000,000 registered road vehicles).
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There were 159,006 retail gasoline outlets. This gave 1553 industry, and other groups must establish policies that are broad,
vehicles/gasoline outlet [11]. At the same time, the United States robust, and adaptive [11]. This is especially true for policies
had only 1327 NG lling stations with the majority for CNG (only concerning human health. The highest gains are expected when
60 of these were for LNG). For NG vehicles, a NAS report estimates the rst goal (efcient ICEs) is combined with the other goals (e.g.,
that approximately 19 million vehicles could be fueled by CNG use of an alternative fuels) and additional goals (e.g., load or weight
without signicantly affecting the price and supply of domestic NG reduction). Making any goals for reducing dependence on
[11]. In addition, electric vehicles estimates ranged up to petroleum fuels harder to achieve is the expectation that the
approximately 10 million total vehicles on the road; however, number of LDVs and the vehicle miles traveled (VMT) will nearly
this value is highly speculative. Hydrogen vehicles may number 2 double from 2005 to 2050 [11]. Direct replacement biofuels (direct
million vehicles on the road by 2025. This discussion is important replacements for gasoline or diesel fuels) produced from some type
because nearly 160 thousand older gasoline sites will need of biomass could lead to large reductions in petroleum use and
monitoring due to health concerns and nearly an equal number emissions. While they can be introduced without major changes in
of new sites may represent new or additional health concerns. the fuel-delivery infrastructure or engine design, the achievable
production levels are uncertain [11]. The petroleum fuels, gasoline
1.2. Types of alternative fuels and diesel, would almost be eliminated from the fuel mix when the
U.S. petroleum goal to reduce dependence upon petroleum fuels by
Remembering that alternative fuels include alcohols, hydrogen, 80% by 2050 is reached.
compressed or liquid natural gas, and gasoline and diesel derived LDVs account for almost half of petroleum use in the United
from coal, NG, biomass, electric power, and fuels derived from States, and about half of that fuel is imported [17]. Biofuel
crude oil or unconventional oils, most think of biofuels when production is expected to increase because of the Renewable Fuel
considering alternative fuels. Biofuels are alternative fuels Standard 2 (RFS2) passed as part of the 2007 Energy Independence
produced from vegetable oils and animal fats. The term and Security Act (EISA) [11].
Conventional biofuel usually refers to ethanol derived from
starch of corn grain (corn-grain ethanol). The term Advanced 1.2.1. Conventional alternative fuels
biofuels (newly applied biofuels) usually refers to renewable fuels
other than corn-grain ethanol and includes types of biofuels 1.2.1.1. Ethanol. Ethanol is regarded as a primary conventional
derived from such renewable biomass such as cellulose, hemicel- fuel. Ethanol (C2H5OH), a volatile liquid fuel used to replace rened
lulose, lignin, sugar, or any other starch that is not from corn, petroleum, can be obtained from many feedstocks including
biomass-based diesel, and coprocessed renewable diesel. Biofuels cereals, sugarcane, and sugarbeets plus cellulose materials,
normally consist of the monoalkyl esters formed by a catalyzed namely, wood and vegetable remnants [18]. One advantage of
reaction of the triglycerides in the oil or fat with a simple ethanol is that it can lower the concentration of aromatic products
monohydric alcohol. The reaction conditions generally involve a found in high octane gasolines [18]. Many researchers and
trade-off between reaction time and temperature. Much of the engineers consider ethanol as a less than optimal biofuel because
complexity of the process originates from contaminants in the it is corrosive and extremely hygroscopic. In addition, ethanol
feedstock (and found as impurities in the nal product). Developed creates many problems such as its transport and incorporation in
processes that produce biofuels from high free fatty acid feedstocks gasoline. The power energy of this molecule is insufcient to
include starting materials such as recycled restaurant grease, provide the energy needed to y an airplane. Its low energy yield is
animal fats, and soap stocks. because ethanol is already a partially oxidized derivative of carbon.
Huber et al. [1] provide a useful review of the chemistry, Because the European vehicle market is very focused on diesel
catalysts, and engineering associated with the synthesis of engines, this molecule represents only a moderate interest there
transportation fuels from biomass. They show, for example, that [19].
the conversion from cellulosic biomass (e.g., wood, crop residues, The largest effort to employ ethanol is a Brazilian program,
grasses, sugar cane, water hyacinth, etc.) can proceed along any of started in the 1970s [12]. See the Goldemberg paper [12] described
three paths. The rst path is gasication, which produces Syngas, above for more information. The new renewable energy sources
which in turn can be used to produce alkanes, methanol, and amount to 16 exajoules (1 EJ = 1018 J), or 3.4% of the total.
hydrogen. The second path is pyrolysis of biomass materials to Renewables are also more labor intensive, requiring more work-
produce bio-oils (e.g., aromatics, tars, alcohols, aldehydes) which forces per unit of energy than conventional fossil fuels (3).
supplement liquid fuels. The third path uses hydrolysis, which Although technologically mature, some of the renewable sources
produces aqueous sugars and lignin. The aqueous sugars can be of energy are more expensive than energy produced from fossil
fermented to yield ethanol, can be dehydrogenated to provide fuels. This is particularly the case for the new renewables.
aromatic hydrocarbons, or go through other processing to give However, a simple calculation shows that expanding the Brazilian
liquid alkanes or hydrogen. ethanol program by a factor of 10 (i.e., an additional 30 million
A National Research Council (NRC) report [11] gives the hectares of sugarcane in Brazil and in other countries) would
potential for reducing petroleum consumption and reducing supply enough ethanol to replace 10% of the gasoline used in the
GHG emissions by the U.S. LDV eet by 80% by 2050. This report world. This land area is a small fraction of the more than 1 billion
examines the technologies that could achieve these two goals and hectares of primary crops already harvested on the planet.
the barriers that might hinder their adoption. Four pathways could Conversion to ethanol does allow the phasing-out of lead additives
contribute to attaining both goals: (1) highly efcient ICEs, (2) and MTBE and the reducing of sulfur, particulate matter, and
vehicles operating on biofuels, (3) vehicles operating on electricity, carbon monoxide emissions.
or (4) vehicles operating on hydrogen. The report acknowledges
that NG vehicles could contribute to the goal of reducing 1.2.1.2. Methanol. Although methanol (CH3OH) is mainly obtained
petroleum consumption. The writers of this document said, by synthesis from NG, it can be produced from a wide range of raw
Driving costs per mile will be lower, especially for vehicles materials (dry biomass in general, coal, etc.) [18]. Compared to
powered by NG or electricity, but vehicle cost is likely to be a ethanol, methanol is less volatile, can be extinguished with water,
signicant issue for consumers for at least a decade. Because it is pollutes less, and it also has no sulfur content [18]. In addition to
impossible to know which technologies will succeed, regulatory, decades of use in motor racing, the public in California used
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methanol for 25 years. According to the Energy Information States produces 35.3 billion pounds per year of vegetable oil and
Administration (EIA) [20], the dramatic increases in NG prices (the animal fat (combined) and could provide 4.6 billion gallons of
starting material for most of the methanol) prompted methanols biodiesel, the on-highway diesel fuel consumed yearly in the
decline at least in part. Methanol is one of the alternative fuels United States is about 33 billion gallons. All of the vegetable oil and
currently pursued by China. Methanol has a high octane number animal fat produced in the U.S. would only provide 13% of the
(114) and has about half of gasolines volumetric energy content current demand for on-highway diesel fuel [21]. Although FAME
(2.01 gal CH3OH = 1 gge). Methanol can be used with gasoline in can be produced from many types of oils, RME is the most common
different proportions (e.g., neat or 100% methanol, 85% methanol in Europe and SME in the U.S. Undesirable byproducts (e.g.,
with 15% gasoline, and 85% gasoline with 15% methanol). glycerin and water) are removed from the fuel. FAME can be used
Methanol also can be made from coal. With the abundant pure (B100) in diesel engines, but it is more often used as a mix
resources of NG and coal in the United States, the supply of with diesel fuel. In summary, biodiesel is produced by transester-
methanol would be ensured. Because methanol is less volatile ication of triglycerides from vegetable oils usually with methanol
than gasoline, it has a re safety advantage. Methanol has some [19,23,24], resulting in a fuel with similar properties as mineral oil
drawbacks. Methanol is hygroscopic, a solvent for some plastics, derived fuels [24,25]. See other publications if there is a desire to
and corrodes aluminum. Therefore, methanol is incompatible learn more about the production of biodiesel [21,26].
with some automotive materials. The major concerns with
methanol as an automobile fuel focus on environmental and 1.2.2.3. Algae fuels. Algae fuel is referred to as a third-generation
health issues. Although ingested methanol is well understood, biofuel [19]. The membrane components of microalgae, similar to
there is insufcient data about the health effects of inhaled and those of animal and vegetable oils, contain lipids and fatty acids
skin-penetrated methanol. Predictions show that methanol will as sources of energy. In addition, algal oils can be processed in a
be plentiful and cheap; therefore, methanol will likely remain manner similar to other biodiesel fuels. Even though the use of
under consideration as an alternative fuel. algae to make fuel was discussed more than 50 years ago, efforts
to use algal oils did not begin until the 1970 oil crisis when the US
1.2.2. Other biofuels Department of Energy (USDOE) began research efforts in Golden,
Within this review, the other biofuels are renewable fuels other Colorado [27]. From 1990 to 2000, the Japanese government
than corn-grain ethanol and methanol. Usually, they are chosen to funded algae research looking for an alternative fuel. However,
achieve a 50% reduction in GHG emissions. Advanced biofuels none of these approaches have proven to be economical on a
include biofuels derived from such renewable biomass as cellulose, large scale. The USDOE program closed in 1996 [27]. The closure
hemicellulose, lignin, sugar, or any other starch that is not from of these programs is due in part because these systems could not
corn, biomass-based diesel, and co-processed renewable diesel. compete with the cheap crude oil of the late 1990s [28].
However, because genetic engineering has improved and the cost
1.2.2.1. Vegetable oils. Vegetable oil can be obtained from more of fossil fuels may increase, the production of algal oils can yield
than 300 different plant species. Pure (rened and deslimed) more oil per acre of land than other biofuels. Therefore, algal oils
vegetable oils can be used directly in some diesel engines or mixed may be examined again [19,27,29]. Articles on the genotoxicity
with fossil diesel fuels. Pure vegetable oil, however, cannot be used and carcinogenicity of algal oils or their emissions were not
in direct-injection diesel engines. Some pure vegetable oils can be found.
used as lubricants and as hydraulic oils. These oils are mainly
contained in fruits and seeds with the highest oil yields obtained 1.2.2.4. Natural gas, liquid natural gas, and synthetic natural gas. An
from tree crops, such as palms, coconuts, and olives. However, option to other alternative fuels is NG. NG can be liqueed by
there are a number of eld crops containing oils. Vegetable oils can refrigerating it to approximately 259 8F at atmospheric pressure.
also be used in the esteried form achieved by cracking procedures Liquefaction of the gas will shrink about 625 cubic feet of gas into
or by treating the oil with an alcohol transesterication process. 1 cubic foot of liquid [30]. This makes the transport of NG feasible.
Transesterication is usually a less expensive way of transforming For residential, commercial, and industrial sectors, NG which is
the large, branched molecular structure of the bio-oils into smaller, predominantly methane (CH4) has proven itself as an important
straight-chain molecules of the type required in regular diesel energy source. Liqueed natural gas (LNG) is NG that has been
combustion engines. Rape oil methyl-ester (RME) and sunower converted to liquid form for ease of storage and/or transport.
methyl-ester (SME) are two frequently used biodiesel fuels derived Synthetic natural gas (SNG) is a proposed alternative to NG and
from their corresponding oil seeds. LNG. NG currently provides 24% of the energy used by United
States homes (1).
1.2.2.2. Biodiesel or FAME. A common example of a biofuel is There are several opportunities, direct and indirect, to use
biodiesel. Biodiesel is produced by chemically reacting a vegetable natural gas in LDVs, including producing electricity for PEVs and
oil or animal fat with an alcohol such as methanol. In addition to producing hydrogen for FCEVs. In addition, the USDOE estimates
methanol, other alcohols (e.g., propanol, isopropanol, butanol, and that in the coming decades the United States NG demand for
pentanol) can be used [21]. After reaction requiring a catalyst and electricity generation will increase [31]. Estimates also suggest
usually a strong base (such as sodium or potassium hydroxide), that NG supply will increasingly come from imported LNG [31].
this reaction produces methyl esters (generally known as fatty- Additional supplies of NG could come domestically from the
acid methyl ester or FAME). It is these esters that came to be known production of synthetic natural gas (SNG) via coal gasication
as biodiesel [21], and the process is called transesterication. methanation [31]. There was a surge in construction of natural-
Knothe in the Belgian Congo described how ethyl esters were used gas-red power plants: between 1992 and 2003, coal-red
as diesel fuel substitutes as early as 1937 [21,22]. Since the carbon capacity increased only from 309 to 313 GW, and natural-gas-
(in the vegetable oil or animal fat) originated from carbon dioxide red capacity more than tripled, from 60 to 208 GW [31]. Adding to
in the air, many believe that biodiesel contributes much less to this was the EIA prediction of continued low NG prices through
global warming than fossil fuels. Diesel engines operated on 2020, lower capital costs, shorter construction times, and generally
biodiesel have lower emissions of carbon monoxide, unburned lower air emissions for natural-gas-red plants allowing power
hydrocarbons, particulate matter, and air toxics than when generators to meet the clean air standards [31]. Demand from
operated on petroleum-based diesel fuel. Although the United electricity generators is projected to grow and the U.S. demand can
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only be met with alternative sources of NG, such as imported LNG available, (3) fuel distribution pipelines are in place and can meet
or SNG. initial requirements, and (4) emissions are lower when compared to
NG is extracted from wells and sent to processing plants where petroleum-based gasoline. The main disadvantages for CNG include:
water, carbon dioxide, sulfur, and other hydrocarbons are (1) CNG fuel stations are few and expensive to build, (2) there is
removed. The produced NG then enters the transmission system much design work that must be done on vehicles that use CNG (e.g.,
[32]. The U.S. transmission system includes some storage of NG in engines, trunk space, range), and (3) CNG vehicles are not
underground facilities (such as reconditioned depleted gas economical [11].
reservoirs, aquifers, or salt caverns) to meet seasonal and/or
sudden short-term demand. From the transmission and storage 1.2.2.5. Hydrogen. The hydrogen reciprocating engine has the
system, some NG goes directly to large-scale consumers, like potential of replacing conventional gasoline and diesel engines
electric power generators. The rest goes into local distribution in part due to reducing dependence on petroleum and other less
systems that deliver it to residential and commercial consumers regulated emissions. Before 2050, the cost and operating costs of
via low-pressure, small-diameter pipelines. The use of liqueed FCEVs could be lower than the cost of an equivalent ICEV. As a fuel,
natural gas (LNG) adds additional life-cycle stages to the NG life- hydrogen has several desirable properties (e.g., a high ame
cycle stages noted above: (1) after NG is produced and processed to velocity, high ignition temperature, and low ignition energy).
remove contaminants, the NG is transported by pipeline a Concerns for hydrogen engines revolve around NOx and PM
relatively short distance and liqueed. Liquefaction plants are emissions from the lubricating oil and from operating concerns
generally located in coastal areas of LNG exporting countries, (2) such as backre, pre-ignition, and knocking [33]. Other papers that
LNG ocean tankers transport the LNG to the United States, and (3) can be consulted are Crabtree et al. [34], Mao [35], Premkartikku-
upon arriving, the LNG tankers ofoad their cargo and the LNG is mar et al. [36], Verhelst et al. [37], Kumar et al. [38], and Verhelst
regasied [32]. At this point, the regasied LNG enters the U.S. NG [39].
transmission system. The coal life-cycle is usually simpler than the
NG life-cycle, consisting of three main steps: (1) coal mining and 1.2.3. Coal-derived products
processing (U.S. coal is produced from surface mines, 67%; or Faced with crude oil shortages and dwindling supplies of NG,
underground mines, 33% and the mined coal is processed to many argued that we must utilize our vast coal energy reserves
remove impurities), (2) transportation (via rail, 84%; barge, 11%; [30]. Coal is the United States most abundant energy source, with
and trucks, 5%), and (3) use (90% of the coal used in the United enough proven reserves to meet energy needs for hundreds of
States is used by the electric power sector) [32]. The life-cycle of years [30]. The energy in coal can be utilized in three ways [30]: (1)
SNG can be considered a combination of the coal life-cycle and the direct burning: in the past coal was used directly for residential
NG life-cycle [32]. Coal is mined, processed, and transported to the and industrial heating. However, the transporting and distributing
SNG production plant. Then the syngas is produced by gasication of coal to the residential and industrial market was very costly, and
and converted, via methanation. The SNG is then sent to the NG the environmental impact was extremely high; (2) the burning of
transmission system, described above, and on to consumers. coal to generate electrical power: this is a viable alternative only if
If CNGVs can be made competitive (with respect to both vehicle power generation plants are tted with after-treatments that
cost and refueling opportunities), CNGVs offer a quick and protect the environment and the publics health. Another
economical way for reducing petroleum use. With currently disadvantage to this alternative is that the thermal efciency of
envisioned technology, some think that sufcient biofuels are generating electricity from any fossil fuel is quite low, ranging from
likely be produced by 2050 to meet the United States goal of 80% 35 to 42% for the best of designs. Nonetheless, societys need for
reduction in petroleum use [11]. Environmental issues associated electrical power will mandate the use of coal to generate power
with shale gas extraction (fracking) must be resolved, including until alternatives are developed and accepted; (3) the conversion
leakage of NG, itself a potential contaminator of groundwater [11]. of coal into a substitute natural gas (SNG or synfuel products) for
NG and coal conversion to liquid fuel (GTL, CTL) may be used as a residential and industrial heating: coal gasication is about 70%
direct replacement for petroleum gasoline, but the GHG emissions thermally efcient. Therefore, a coal gasication plant is much
from these fuels are slightly greater than those from petroleum. more environmentally desirable than a coal-red power plant
Therefore, these fuels will play only a small role in reducing [30,40].
petroleum use even if GHG emissions are reduced simultaneously.
The NAS committee [11] nds that Meeting the study goals 1.2.3.1. Synfuels and coal gasication. The commercial gasication
requires a massive restructuring of the fuel mix used for of coal has been practiced for nearly one hundred years. Low-
transportation. Petroleum-based fuels must be largely eliminated pressure coal gasiers date back to the 1920s [30]. Most coal
from the fuel mix. Other alternative fuels must be introduced such gasication plants involve using chemical reactions which
that the average GHG emissions from a gallon equivalent of fuel are combine the carbon from the coal with hydrogen from steam to
only about 40% of todays level. form methane, which constitutes 97 vol% of the product SNG. The
The volume of economic NG from shale deposits within the amount of coal used for producing the energy from a SNG plant is
United States has been increasing rapidly. Based on 2009 estimates, very specic to the particular coal being used [30,40]. Synthetic
the probable NG reserves would provide about 86 years of usable NG fuels, for purposes of the Synthetic Fuels Corporation, were dened
if the consumption rate stays at 2009 levels. In 2011, this estimate as any solid or liquid that could be used as a substitute for crude oil
increased to 90 years of probable reserves existing based on 2010 or natural gas and that was produced by chemical or physical
consumption. Many earlier estimates for alternative fuels did not transformation primarily from coal, oil shale, or tar sands,
include NG as a possible source for LDV fuel for mainly two reasons: including heavy oil (Energy Security Act Conference Report, No. 96-
(1) a belief that only a very limited domestic supply existed and (2) 824, June 19, 1980, 22) [41]. Synthetic fuels did not include solar,
the use of NG would cause a substantial price increase in electricity wind, renewable, or nuclear.
and residential heating costs. Because of increasing domestic With the dwindling of petroleum and NG supplies during the
production, NG now is a viable option for providing transportation 1970s, came an awareness of an opportunity to develop synthetic
fuels [11]. The most efcient use of NG is direct use as CNG. The main fuels from coal. In 1980, President Carter and the U.S. Congress
advantages of CNG include: (1) 1 gge of CNG is cheaper than 1 gal of created the $20 billion Synthetic Fuels Corporation. The goal was to
petroleum-based gasoline, (2) the needed technology is proven and use coal to produce 700 million barrels of oil per year by 1992. The
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corporation spent $2 billion on demonstration projects in carbonate (see http://en.wikipedia.org/wiki/Marl or http://www.

California, Louisiana, and North Dakota. But management scandals answersingenesis.org/articles/cm/v22/n2/geology). A typical oil
and battles between the corporation and the White House during shale contains about 15 wt% kerogen and 85 wt% of carbonates,
the Reagan Administration, and the falling price of oil caused feldspars, quartz and clays. Deposits in the western United States are
Congress to stop funding. Experts said the only thing that would thick and yield more than 25 gal of crude shale oil per ton of rock
revive synfuels was $100-a-barrel oil [42]. Therefore, a multibil- (rich shale oil deposits). Over 15 nations around the world have
lion-dollar U.S. effort to turn coal into gasoline ended in the 1980s extensive shale oil reserves, the largest of which are: USA (2000
because the effort was plagued by mismanagement, political billion barrels), Brazil (342 billion barrels), and Zaire (103 billion
wrangling, and falling oil prices [42]. In addition, environmental- barrels) [30]. Some of these deposits yield nearly 100 gal per ton of
ists concerned about the impact of additional coal mining cheered rock [51]. At current national oil consumption rate of about 18
the end of the synthetic fuels program, which was aimed at cutting million barrels a day, the Green River Formation (deposits in the USA
U.S. dependence on oil from the Middle East [42]. China is building states of Colorado, Utah and Wyoming) represents about a 300 year
up to 23 synfuel plants. With todays economy and dwindling supply of in-place oil. Beginning as early as 1840 in France and
crude oil reserves, a few U.S. energy companies have plans for Scotland, commercial shale oil production was practiced for many
synfuels plants that would produce millions of barrels of the years. Beychok [30] estimates that the disposal wastes from shale oil
alternative fuels annually. The synfuel process begins by turning processes will be 54,000 tons/day.
coal into gas, which creates carbon monoxide and hydrogen gases. Presently, the only way found to recover oil from the kerogen is
Traditional synfuel plants make syngas from coal; however, to heat (retort) the kerogen to very high temperatures, and then to
industry contemplates the using of large amounts of plant biomass treat with hydrogen which creates a stable synthetic crude oil. The
along with coal and storing in the ground the CO2 emitted during synthetic crude can be rened into gasoline and other petroleum
the production of synfuels. The gas would then be catalyzed into products in a manner similar to conventional crude oils [51]. The
various liquid fuels such as diesel fuel, jet fuel, or chemical average percentages for chemical classes are: n-alkanes, 3.43.9%;
feedstocks. The use of cooler gasiers could generate problems, branched and cyclic alkanes, 23.630.3%; aromatic oils, 2.73.3%;
because lower temperatures mean that less of the feedstock (coal resins, 54.457.4%; and asphaltenes (including fatty acids), 9.0
or biomass) is converted into syngas [42]. The remaining toxic, 12.5% [52]. The n-alkanes, resins, and asphaltenes are not likely to
carbonaceous muck and its disposal also present an undesirable contain a detectable amount of carcinogens. The cyclic alkanes and
cost. Some processes produce mainly sulfur, ash, ammonia, and aromatic oils may contain detectable amounts of mutagens and
slag as by-products. A process, called the Lurgi process, also carcinogens [30].
produces other by-products (tars and oils) through the volatiliza-
tion and condensation of organic compounds from the feed coal. 2. Genetic toxicology of biofuels: carcinogenicity/mutagenicity
These tars and oils present some unique problems in the process of the raw (unprocessed) product
stream cleanup which in turn could present potential health
hazards for workers and the general population [43]. In contrast to During the late 1970s and 1980s, Oak Ridge National Laboratory
the CO2 from a standard generating plant which must be separated (ORNL) did seminal research for the USDOE examining synfuels.
from other ue gases, the CO2 that synfuel plants create, could take Much of their efforts were documented in ORNL reports [5356]. In
advantage of the fact that the process creates a concentrated CO2 a 1979 progress report [54], Epler reported that it was feasible to
stream that can simply be injected into deep underground use short-term mutagenicity assays to isolate and identify the
formations. But the amount of CO2 needed to be stored by a potential biohazards of complex materials. He noted that
new generation of synfuels plants is much larger than any current fractionation procedures are used to characterize the mutagens
projects. Even if the CO2 generated could be stored, many say that present with the bioassay being used as a tool to follow the activity
the effects of expanding coal mining could be harmful to the and guide the separations. The mutagenicity tests were intended to
environment [42]. function as (a) predictors of profound long-range health effects
Because many publications describe the non-genotoxic aspects such as mutagenesis and/or carcinogenesis, (b) a mechanism to
of biofuels and other alternative fuels, the reader may have a need rapidly isolate and identify hazardous biological agents in a
to consider these other sources of information. Included in these complex mixture, and (c) as a measure of biological activity that
publications are Brazon [44], Koonin [2], Priddy [41], Ros et al. [45], could correlate base-line data with changes in process conditions.
Kaniyal et al. [46], Li and Li [47], Hook et al. [48], Tchapda and He said, The investigator can accumulate information on the
Pisupati [49], and Yang et al. [50]. actual compounds responsible for the biological effect. Thus, the
mutagenicity tests will also aid in identifying the specic
1.2.4. Shale oil or kerogen hazardous compounds involved and in establishing priorities for
Geologically speaking, oil shale is not shale, and oil shale more denitive . . . testing, for mutagenesis and carcinogenesis.
contains virtually no oil. Instead, it is sedimentary rock containing The researchers at ORNL also recommended a tier system to test
a material called kerogen [30]. When heated, this solid organic the mutagenicity and carcinogenicity associated with fuel
material yields substantial amounts of hydrocarbon crude oil and technologies. Using such systems, their results implicated chemi-
gas (typically 1060 gal of crude oil per ton of shale). Eons ago, oil cals in the basic (ether-soluble) and the neutral fractions of coal-
shale began in a manner similar to crude oil, when organic matter derived fuels as potential genetic hazards. They showed that: (1)
was deposited in large lakes; however, the oil shale deposits were alkaline constituents of petroleum substitutes are major con-
not subjected to the heat and pressure essential for forming tributors to the Salmonella mutagenic activity, (2) subfractions of
petroleum [30]. Instead, the organic matter was transformed into ether-soluble bases from shale- and coal-derived oil had concen-
the solid hydrocarbon kerogen and locked into a marlstone trated the bioactive constituents into a subfraction contained in
matrix. The geological term for our Western oil shale is 0.5 wt% of the starting oil, and (3) nitrogen heterocyclics were the
kerogenous marlstone. Marlstone is a rock containing clay principal constituents of the active subfraction. They also summed
materials and calcium and magnesium carbonates, with approxi- the fractions to estimate the biological activity of the starting
mately the same composition as marl. Marl was originally an material. Applying mutagenicity testing of fractionated mixtures
old term loosely applied to a variety of materials; most are (from natural crude and synthetic oils, aqueous condensates,
loose, earthy deposits containing 3565% clay and 6535% process waters, leachates, and organic extracts of raw materials,
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wastes, and particulate materials) illustrated that specic activities Biodiesel also generates less air pollutants per net energy gain
(revertants per mg of fraction) can be summed to yield an estimate than ethanol.
of the mutagenic potential of the crude starting material. The total Transportation biofuels such as synfuel hydrocarbons or
activity varied from process to process, but basic and neutral cellulosic ethanol, if produced from low-input biomass grown
fractions consistently contained the bulk of the mutagenic activity. on agriculturally marginal land or from waste biomass, could
Metabolic activation with rat liver extracts was routinely required provide much greater supplies and environmental benets than
for activity. In a 1980 report [53], Epler et al. examined emerging food-based biofuels.
processes for producing energy from fossil fuels, namely a low Btu
industrial gasier. The electrostatic precipitator (ESP) tar samples 3. The carcinogenicity and mutagenicity of biofuel emissions
were mutagenic in the Salmonella assay (TA98, +S9) and showed at the point of release
(1) the mutagenic activity varied with different sampling dates, (2)
most mutagenic activity remained mainly in the basic fraction Clark et al. [64] used the Salmonella assay to evaluate the use of
indicating aromatic amines as the suspect agents, and (3) some ESP alcohol additives on the mutagenicity of particulate exhaust
tars exhibited signicant mutagenic activity in the neutral (PAH extracts. In this study, four typical gasoline engine vehicles were
fractions). This report also outlined some initial efforts by Hsie to operated on either 3 or 4 fuels (gasoline alone, 10% ethanol/90%
examine the mutagenicity and carcinogenicity of energy related gasoline, 10% methanol/90% gasoline, and a commercially available
pollutants in cultured mammalian cell systems and by L.B. Russell gasohol). The gasohol contained a different gasoline than that used
to examine in vivo screening for gene mutations in mouse germ in the ethanol blended fuels. Although all particulate extracts were
cells and somatic cells. In the 1981 report [56], Epler et al. reported mutagenic in strains TA100 and TA98, a decrease mutagenic
on their efforts with raw and hydrotreated coal (H-coal) product response was seen in the nitroreductase decient strains TA98NR
liquids. Direct coal liquefaction was one of the technologies and TA98DNPR. The decreases in the nitroreductase decient strains
investigated in an effort to generate clean and cost-competitive indicate that nitro-PAHs may be responsible for part of the
fuels from coal. To generate environmentally friendly products, mutagenicity. The response was higher in TA98 than in TA100
hydrogenation was used. Hydroprocessing results in at least two indicating that the majority of mutagens would be characterized as
major improvements: the reduction of aromatic content and the frame shift mutagens. The addition of S9 signicantly decreased the
reduction of heteroatom content by hydrogenolysis of hetero- mutagenic response in all the samples tested. Carbon monoxide and
molecules. Salmonella (TA98, +S9) results from chemical class particulate emission rates decreased with the use of alcohol fuel
fractions showed that any effects were generally reduced as the blends. Lower values for revertants per mile were seen with the
severity of hydrotreatment was increased. The data revealed that addition of alcohols to the gasoline, but this was mainly a result of
coal-derived distillates generated by the H-coal process are highly decreased particle mass per mile. Because of the small changes seen
carcinogenic to mouse skin, but wide differences were seen due to with the addition of ethanol or methanol to unleaded gasoline, the
the material composition. The 1986 report [55], presented results authors concluded that ethanol or methanol added (at 10%) to
for lifetime C3H mouse skin tumorigenicity assay of an H-coal unleaded gasoline does not appear to signicantly alter the genetic
series of oils and considered the relationships between tumorige- toxicity of particulate exhaust products.
nicity, chemistry, and processing. The report also documented the Gragg [65] reported on the testing of two CNG fueled Volvo
physical and chemical properties of the oils tested. Results of the buses equipped with oxidation catalysts. Using a transient driving
lifetime tumorigenicity assay demonstrated that even low-severity cycle that simulates a city bus driving pattern (average speed,
hydrotreatment reduced tumorigenicity; however, higher severity 22.5 km/h; maximum speed, 58.2 km/h; per cent idling, 22%; and
hydrotreatment led to no further reduction in tumorigenicity and driving distance 11 km), the NOx emission, CO emission, and the
may actually have increased tumorigenicity slightly. emission of particulate matter was low. Most of the HC was
Citing work done by the University of Idaho [57,58], Howell methane. The catalyst was not as efcient converting methane as
and Weber [59], the U.S. Bureau of Mines and the USEPA [60,61], converting CO. One of the buses underwent testing for unregulated
Kalligeros et al. [62] said the following, It is well known that emissions (alkenes, aldehydes, polycyclic aromatic hydrocarbons)
biodiesel is non-toxic, contains no aromatics, has higher and for Salmonella mutagenicity (TA98 and TA100, S9). The
biodegradability than fossil diesel, is less pollutant to water emission of alkenes, aldehydes, PAHs, and mutagenicity were low
and soil and does not contain sulfur. It offers safer handling in the [65]. The PAH emission was dominated by the semivolatiles
neat form and shows reduced oral and dermal toxicity, mutagenic phenanthrene and pyrene. The source of the pyrene and the
and carcinogenic compounds. It is the most suitable fuel in phenanthrene emission was not discernible.
environmentally sensitive areas (national parks, lakes, rivers) or Bunger et al. [66] examined the mutagenic and cytotoxic effects
in conned areas where environmental conditions and worker of diesel engine exhaust emissions from a passenger car using
protection must meet high standards (underground mines, biodiesel fuel (RME) and exhaust emissions of a petroleum-derived
quarries). See below for a summary of the published Kalligeros diesel fuel. After collecting the emitted particles on PTFE-coated
et al. [62] efforts. glass ber lters and extracting the lters with dichloromethane,
To be a viable alternative, a biofuel should provide a net energy the extracts mutagenicity was tested in the Salmonella assay
gain, have environmental benets, be economically competitive, (TA97a, TA98, TA100, and TA102). The extracts cellular toxicity
and be producible in large quantities without having negative was examined using mouse lung broblasts (L929) in the neutral
impacts (e.g., reducing food supplies). Hill et al. [63] compared red assay. In the Salmonella assay, a signicant increase of
ethanol to biodiesel using such criteria. They found that: mutations resulted when using emission extracts from both fuels,
but the petroleum-derived fuel gave results that were signicantly
Even dedicating all U.S. corn and soybean production to biofuels higher when compared to biodiesel fuel emissions. In some
would meet only 12% of gasoline demand and 6% of diesel comparisons, the biodiesel extracts showed slightly higher toxic
demand. effects in the neutral red assay. These results indicated a higher
Both biofuels when replacing petroleum would inuence food level of mutagenicity for the emissions of the petroleum-derived
supplies. diesel fuel compared to biodiesel. The authors attributed this to the
Ethanol yields 25% more energy than the energy invested in its lower content of polycyclic aromatic compounds (PAC) in biodiesel
production, whereas biodiesel yields 93% more. exhaust.
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Knowing that several PAHs are carcinogenic in rodents, and emissions. Although benzene was absent in RME, the emission of
PAHs are associated with various types of human cancer, Karahalil benzene increased with the amount of RME. In recent years it has
et al. [67] studied young workers exposed to PAHs in engine repair become clear that determining particle number and particle size
workshops. They compared exposed workers with non-exposed distribution may be more important than determining mass alone,
workers for urinary 1-hydroxypyrene (1-OHP), sister-chromatid because small particles reach pulmonary alveoli and deposit there.
exchange (SCE), and micronucleus (MN) levels. 1-OHP excretion is In comparison to diesel fuel, RME reduced hydrocarbon emissions
clearly an internal indicator of PAH exposure [6872]. The mean but increased aldehyde emissions; therefore, the authors found it
value SE of urinary 1-OHP excretions from workers was impossible to compare the ozone-formation potential of the two
4.71 0.53 mmol/mol creatinine and the mean value for controls fuels. Analyzed for 16 PAHs, DF and SME had higher total PAH
was 1.55 0.28 mmol/mol creatinine. Thus, a 4-fold increase in concentrations than RME. Concentrations of the individual
urinary 1-OHP excretion was seen. The mean values SE of SCE compounds varied from fuel to fuel. When using TA98, DF
frequency per cell in peripheral lymphocytes from the workers and revertant frequency was twice as high as for RME and SME. The
controls were 4.47 0.09 and 4.06 0.16, respectively. The mean revertant frequency for DF and SME without a catalytic converter
SE for MN (%) frequencies in peripheral lymphocytes from the was also signicantly elevated for tester strain TA100. The catalytic
workers and controls were 1.87 0.04 and 1.56 0.06, respectively. converter lead to decreased mutations for all particulate extracts.
Bunger et al. [73] compared a RME biodiesel fuel to a common In addition, Krahl et al. [76] used a test engine and two
fossil diesel fuel in a test tractor. Filter-sampled particles were agricultural tractors run on a RME (biodiesel) or conventional
extracted and tested using the Salmonella/microsome assay. The diesel fuel plus blends of the two. Their work compared for RME
extracts from the fossil diesel fuel emissions were signicantly and DF: (1) mutagenic potentials using the Salmonella assay, (2)
more mutagenic in TA98 and TA100 than the particulate extracts of particle mass as well as particle size and particle number
the engine emissions when biodiesel fuel was used. The extracts of distributions, (3) inuence of emissions on ozone formation, and
fossil diesel fuel showed a fourfold higher mutagenic effect in TA98 (4) different blend levels. Because of their median dynamic
(and a twofold effect in TA100) than extracts of the biodiesel fuel diameter (0.10.3 mm) the particles could be readily inhaled with
emissions. The authors attributed this lower mutagenic response about 10% deposited in the alveolar region of the lungs [76,77].
of the biodiesel to lower emissions of PAHs. However, the biodiesel Generally, emissions of regulated compounds changed linearly
extracts produced a fourfold stronger toxic effects on mouse with the blend level. The known positive and negative effects of
broblasts cell line L929 at idling but not at rated power than biodiesel varied accordingly. Overall, no optimal blend was found.
fossil fuel diesel extracts [73]. Increasing biodiesel content of the fuel caused a linear increase in
A study (also reported in 2000) of Bunger et al. [74] examined benzene emissions in the agricultural ve-mode engine test, an
the organic fraction of particulate emissions for polynuclear effect that may be explained from previous studies on precom-
compounds and mutagenic effects. Four different fuels were used bustion chemistry. In using the test engine, it was found that PM
(two biodiesel fuels, RME and SME; and two fossil diesel fuels, with from biodiesel had signicantly reduced mutagenic potential
the normal levels of sulfur (DF) and a low sulfur content fuel). The compared with that from diesel fuel; although in this work, PM
soluble fraction was analyzed for PAHs. Again, the Salmonella assay masses were found to be reproducibly higher for biodiesel from
(TA98 and TA100) was used. Compared with normal fossil diesel rapeseed oil compared with conventional diesel fuel. Ozone
fuel, the exhaust particles of the low sulfur fuel and the two precursors increased 1030% when using biodiesel compared
biodiesel fuels contained less insoluble material (mainly carbon with conventional diesel fuel. Emissions of aldehydes and alkenes
cores). Although individual polynuclear aromatic compounds are mainly responsible for this effect. N2O emissions increased
varied widely among the different exhaust extracts, the total when using a catalytic converter. However, even the combustion of
concentrations of PACs were approximately double for the fossil green fuels such as biodiesel leads to emissions of hazardous
diesel and soy biodiesel fuels when compared with low sulfur and gaseous compounds and particulate matter that may affect human
rapeseed fuels. The results indicated that diesel exhaust particles health. Other studies by Krahl and colleagues [7881] examining
from two biodiesel fuels and the low sulfur fossil fuels contained the effects of fuel composition upon regulated emissions and the
less black carbon, contained less total polynuclear aromatic mutagenicity of exhausts may be of interest to the reader [82].
compounds, and are signicantly less mutagenic in comparison Scientists have examined many species for the production of
with higher sulfur fossil fuel. biodiesel. For example, Cardone et al. [83] compared the
Two of the most used biodiesel fuels are RME and SME. Knowing performance of Brassica carinata oil-derived biodiesel with a
that it is necessary to judge the environmental and health effects commercial rapeseed oil-derived biodiesel and petroleum diesel
that derive from the use of biodiesel in combustion engines, Krahl fuels by examining engine performance, regulated exhaust
et al. [75] compared regulated (CO, HC, NOx, particulate matter, emissions, and unregulated exhaust emissions. B. carinata is an
benzene, methane, nitrous oxide, and aldehydes) and some non- oil crop that can be cultivated in coastal areas of central-southern
regulated emissions from different blends of RME and fossil diesel Italy, where it is more difcult to achieve the productivity
fuel (DF). The tests were carried out using a Fendt type 306 LSA potentials of the most common rapeseed cultivated in continental
tractor with a direct-injecting diesel engine. A comparison of the Europe (Brassica napus). Experimental tests used a turbocharged
particulate matter emissions (particle size and the particle number direct injection, passenger car diesel engine. The unregulated
distributions) from DF to those from RME was done. To estimate exhaust emissions were characterized by determining the soot, the
the genotoxic effects of diesel fuel and biodiesel particulate matter, soluble organic fraction content of the particulate matter, the
their mutagenic potencies were determined. They also studied content and speciation of polycyclic aromatic hydrocarbons,
whether biodiesel inuences ozone formation by quantizing ozone aldehydes, and ketones. B. carinata and a commercial biodiesel
precursors (e.g., ethene and formaldehyde). Although hydrocarbon behaved similarly as far as engine performance and regulated and
(HC) emissions declined with increasing RME content, the CO unregulated emissions were concerned. Compared with petroleum
emissions increased slightly. Independent of the catalytic convert- diesel fuel, the engine analysis did not show any appreciable
er, particulate matter rose with an increasing percentage of RME, variation of output engine torque values. However, there was a
but non-linearly. However, the organic insoluble matter decreased signicant difference in specic fuel consumption data. The
with an increasing RME. While varying the blend had almost no biofuels produced higher levels of NOx concentrations and lower
effect on NOx emissions, the catalytic converter doubled these levels of PM with respect to the petroleum diesel fuel. When
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compared with petroleum diesel fuel, biodiesel emissions contain In a 2012 review, Bunger et al. [87] compared the combustion of
less soot, and a greater fraction of the particulate soluble fraction. fatty acid methyl ester (FAME) fuels with common fossil diesel
The analysis and speciation of the soluble organic fraction of fuels for legally regulated and non-regulated emissions as well as
biodiesel particles suggest that the carcinogenic potential of the for toxic effects. They reviewed 62 publications on the chemical
biodiesel emissions were probably lower than that of petroleum analyses of diesel engine emissions, 18 in vitro toxicological
diesel. The performance of B. carinata biodiesel is quite similar to studies, and a small number of human studies and animal
commercial biodiesel making B. carinata a promising oil crop that experiments. In most studies, the use of biodiesel fuels reduced
takes advantage of Mediterranean agricultural areas [83]. Because legally regulated emissions of carbon monoxide, hydrocarbons,
of the drawbacks associated with individual biofuels, a number of and particulate matter but increased the production of nitrogen
other chemical substrates have been investigated as alternative oxides. The non-regulated emission aldehydes (e.g., formaldehyde)
liquid transportation fuels (e.g., for example, fatty acids, fatty increased, and polycyclic aromatic hydrocarbons decreased. There
alcohols, biobutanol, biopropanol, acetone, and methanol) [19]. were lower levels of mutagenicity compared to fossil fuel exhaust.
The equation for transesterication is given by Gerpen [21]. More recent studies of fossil diesel fuel showed lower levels of
Chen and Wu [84] examined the level of submicron particles mutagenicity. This may be caused by decreasing levels of sulfur in
(0.0081 mm) emitted from a direct injection diesel engine using present-day diesel fuels and new control technologies in diesel
either biodiesel or a commercially available petroleumdiesel fuel. engines [87].
The biodiesel fuel was a SME. Although the emitted particle sizes
for both fuels were about the same, the diesel engine using 3.1. Synfuel and related products
biodiesel reduced (2442%) the total number concentration and
the total mass concentration (4049%) of submicron particles. This Although Germany and South Africa were operating commer-
would indicate that the exposure to submicron particles would be cial scale coal gasication plants in the 1970s, little information
less when using soy-based biofuels. existed on possible health effects associated with gasication
Before 2003, RME had not been directly compared to a Swedish processes. Physical, chemical, and toxicological characterization of
low sulfur diesel fuel. Therefore, Krahl et al. [85] decided to compare fugitive emissions and potential waste efuents were needed for
the regulated and some non-regulated emissions of three fuels: evaluating potential health risks. In 1982, Vick and Epperly
biodiesel (RME), a common diesel fuel (DF), and Swedish low sulfur examined the genotoxicity of a liqueed coal process used to make
diesel fuel (MKI). They also reported the mutagenicity results a synthetic fuel [88]. Four process streams were evaluated using
observed. The test engine was a four cylinder Daimler-Chrysler the Salmonella assay and the Syrian hamster embryo morphologic
engine OM 904 LA. For the rst time, Swedish diesel fuel MKI and transformation assay. Three high boiling liquids (>200 8C) were
RME were compared after combustion in a diesel engine. MKI active in both assays, but a hydrotreated naphtha sample (<200 8C)
showed a higher mutagenic potential in the Salmonella assay than was not active in either assay. Dermal carcinogenesis studies also
RME, and the results of four modes of the 13-mode test indicate a showed positive results with the three high boiling liquids.
tendency to slightly more advantages for RME versus MKI and DF. However, a lack of quantitative agreement stemmed from the fact
Kalligeros et al. [62] examined the exhaust emission and fuel that the dermal carcinogenic activity of coal-derived synthetic
consumption measurements from a single cylinder, stationary, fuels is predominantly associated with neutral polycyclic aromatic
diesel engine (a Petter engine, model AV1-LAB). The engine was hydrocarbons, and the activity in the Salmonella assay is strongly
fueled with pure marine diesel and mixtures containing 10%, 20%, inuenced by the presence of aromatic amines and nitroaromatic
and 50% of biodiesel methyl esters from either sunower oil or compounds [89]. Benson et al. [43] examined the gasication of
olive oil. The two biodiesel fuels performed in a similar manner. coal using the Salmonella assay (TA98, S9). The coal gasier used
The biodiesel fuels decreased particulate matter, carbon monoxide, was a pressurized stirred-bed gasier. The higher-molecular-weight
hydrocarbon, and nitrogen oxide emissions but had a slight tars were removed from the gas stream by a tar trap, and the lower-
increase of the volumetric fuel consumption. In an abstract of molecular-weight tars were removed by a Venturi scrubber. An
research that used a LDV, Bunger et al. [86] compared the electrostatic precipitator removed small particles from the gas
Salmonella mutagenicity of the particulate emissions while using stream. Samples collected at ve sequential points in the cleanup
four different fuels (two were designed diesel fuels, one was a system were rinsed from the sampling devices with acetone.
biodiesel, and one was a fossil diesel fuel). While only the biodiesel Fractionated samples were used for chemical analysis and mutage-
fuel showed a decrease in the mass of particle emissions, the level nicity testing. All mutagenic materials required metabolic activation.
of mutations was higher for the fossil diesel fuel emissions than for Because there was no detectable mutagenesis in the nal gas
the emission extracts of the other three fuels. combustion products, the authors concluded that Health risks to the
Bunger et al. [25] used the Salmonella mutagenicity assay (TA98 general population resulting from exposure to gas combustion
and TA100) to examine the particle extracts and the gas phase products are expected to be minimal [43].
condensates from the following fuels: a common type of fossil Because of the difculties in doing cancer epidemiology on
diesel fuel, a NG derived fuel, a RME fuel, a rapeseed oil fuel, and a environmental mixtures, other approaches have been employed.
preheated rapeseed oil fuel. Compared to the common diesel fuel, One approach is the use of a tier system that determines which
the rapeseed oil fuel emissions signicantly increased (up to 59 bioassays are used for genotoxic substances [9097]. Epler et al. [98]
in TA98 and up to 22.3 in TA100) the mutagenicity of the particle tested this approach for complex environmental mixtures, namely,
extracts. In addition, the gas phase condensates of the rapeseed oil synthetic fuel technologies. They coupled chemical and biological
and the preheated rapeseed oil emissions were more mutagenic analysis of the products, process streams and efuents of existing or
than the reference fuel. The RME emission extracts had a moderate proposed energy-generating or energy-conversion systems. In order
but signicantly higher mutagenic response (TA98, +S9; TA100, to test large numbers of substances, they established a tier system
S9). The NG derived fuel samples did not differ signicantly from for mutagenicity testing. They listed fourteen bioassays they
the common diesel fuel. The authors concluded that the increase of believed were suitable for tier 1, eleven for tier 2, and three for
mutagenicity using rapeseed oil fuels as diesel fuels compared to tier 3. Fourteen substituted nitroso compounds (N-nitrosopiper-
the reference common diesel fuel causes deep concern on future idines) were compared in tier 1 Salmonella and yeast systems and in
usage of this biologic resource as a replacement of established the tier 2 Drosophila sex-linked lethal system. Results were
diesel fuels. compared to known carcinogenicity bioassay outcomes. Salmonella
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bioassay agreed with carcinogenicity data 13 of 14 times with 1 false it a unique component of everyday life and a major source of
positive. Saccharomyces cerevisiae results agreed 11 of 13 times with energy in industrialized societies.
carcinogenicity results, and Drosophila melanogaster agreed for 12 of However, since the 1920s, environmental concerns have grown
the 14 compounds. The authors noted the importance of exogenous continuously, and the electric power sector has been implicated in
metabolic activation with in vitro short-term assays and that many of the most important issues [101]. Everyone is well aware of
sensitivity is lowered when the oxygen-substituted compounds are the acute health effects, such as accidents. However, some contend
tested. They also examined the feasibility of using short-term that the production and distribution of electricity generates
genetic assays to predict, isolate, and identify the chemical hazards. chronic health risks to workers and the general public. This
Coupling the analytical chemistry separation procedure with burden of chronic diseases is more difcult to estimate [102]. For
bioassay results set priorities for identifying genotoxicants. They example, the risk of cancer is difcult because: (1) cancer has a long
stated, The working hypothesis was that sensitive detection of latency period from initial exposure to diagnosis, (2) there is an
potential mutagens in fractionated complex mixtures could be used inability to identify the causative agents of toxic concern, (3) a
to isolate and identify the biohazard. In addition, the information single exposure may cause several types of cancers and the same
could be helpful in establishing priorities for further testing, either cancer can be due to different types of exposures/agents, and (4)
with other genetic assays or with carcinogenic assays. Finally, the the relative rareness of most cancer types makes it difcult to have
procedures might show utility in monitoring plant processes, statistical signicance in epidemiology studies [102105]. To make
efuents, or personnel early in the formation of the engineering and a complete risk assessment on electricity, it also necessary to
environmental technology that will eventually evolve in the examine all the steps involved in this type of energy production:
synthetic fuels industry. Finally, they examined a crude synfuel i.e., the carcinogenicity associated with raw materials, raw
and two fractions (a basic fraction and a neutral fraction) from the material transportation (e.g., emissions from transportation
synfuel. The Salmonella mutagenicity assay showed that all three sources), electricity generation, waste disposal, accidents and
samples were mutagenic. Except where samples were too toxic to misuse of the energy sources [102,106]. Low estimates of risk may
test, other assays (S. cerevisiae; D. melanogaster sex-linked recessive reect lack of knowledge or lack of risk.
lethals, CHO cells using 6-thioguanine resistance, human leukocytes Industrialized countries generally use electricity (on an energy
chromosome aberrations, and Mus musculus dominant lethals) per capita basis) to a much higher degree than developing
agreed with Salmonella results. The authors conclude, as a countries. For example, Bangladesh uses less than 100 kilowatt-
prescreen to aid investigators in ordering their priorities, the hours (kWh) while Norway uses more than 25,000 kWh per capita
short-term tests appear to be a valid approach to testing the large per year. In comparative assessments of electric power, one would
number of hazardous compounds and complex mixtures that man expect that developing countries will continue to expand their
encounters in his environment. Fry et al. [99] reported, as part of the electricity production and use, and industrialized countries will
ORNL report to the USEPA, the provisional results for the skin continue to increase their energy production and use. In Europe, it
carcinogenicity and toxicity that resulted from protracted dermal is estimated that 60% of sulfur dioxide emissions and 30% of
exposures. Skin tumors resulted from exposures to shale oil crude nitrogen oxide emissions come from electricity generation [100].
(both the hydrotreated crude and hydrotreated residue). The effects Most understand that authorities must try to bring objective
of the distillates proved more complicated due to the dermal toxic assessments and data into the discussions [100]. Several facts that
effects (e.g., inammation and hyperplasia). Previous studies are obvious are:
showed that polycyclic aromatic primary amines and basic multi-
ring N-heterocyclics in basic fractions, and neutral multi-ring N- Electricity provides energy to our houses, work places, and
heterocyclics in neutral fractions are important contributors to the recreational areas (lighting to prolong our days, energy for
mutagenicities of synthetic fuel materials. refrigerators that preserve our food, televisions for entertain-
ment and news, and many other items that make our life more
4. Electricity the other alternative? comfortable).
A global increase in population leads to an increasing demand for
Electricity is actually an energy carrier, or secondary fuel electricity.
source, rather than a primary fuel source. There are signicant To increase the standard of living and the quality of life, more
losses in the conversion of primary fuels to electricity and in the electricity will be needed in developing countries and developed
transmission and distribution of electricity to the consumer. countries.
However, electricity is more efcient and exible in end use, and Efciency gains from using modern technologies (e.g., LED
switching to electricity permits the saving of primary energy. lighting) will not neutralize increased demand.
Moreover, there are often signicant environmental gains, as the
end use of electricity is very clean (e.g., the use of electric trolley It is not surprising that the use of electricity increases faster
buses instead of diesel buses). Blix stated at the Senior Expert than the use of energy in general. In many industrial processes,
Symposium on Electricity and the Environment, held in Helsinki switching to electricity permits the saving of primary energy,
from 13 to 17 May 1991, If I were allowed two wishes for the because electricity is more efcient and exible in end use. Blix
environment, the rst would be for an economically viable electric [100] gives an illustration that applies to not only residential use of
car and the second for a system of fast electric trains linking electricity but also to the industrial use of electricity. His
countries and continents and reducing the need to lift people to illustration is, Each new refrigerator will consume less electricity,
10,000 meters altitude at high energy cost for traveling even yes, but there will be so many more refrigerators that the increased
moderate distances. [100]. As Blix said, The reality is that number of refrigerators will use a greater total amount of
electricity transports energy to our doorsteps and houses [100]. electricity. For example, China has the ambition to ensure that
Articial lighting prolongs our days outdoors and indoors. each household has a refrigerator. Even if these appliances were
Refrigerators and deep freezers keep our food fresh thus reducing the most current and efcient models and were modest in size,
spoilage. Television, radio, computers, and communication devices they would call for a base load electric capacity of some 20,000
allow us to see and meet the whole world. Electric stoves, irons, megawatts-electric (MWe). Therefore, electricity needs will
vacuum cleaners, and innumerable other items make our lives increase, particularly in developing countries. Efciency gains,
more comfortable [100]. Electricitys versatility and usability make although necessary, will not neutralize needs arising from
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increased demand. The availability of electricity offers a signicant mutagenicity) that in some cases were greater than that found
improvement in the standard of living and the quality of life with a similar diesel bus equipped with either an oxidation catalyst
wanted by all people. Another basic factor leading to an increased (OC) or a particulate lter using a ultra-low sulfur diesel fuel.
demand for electricity is the expected population increase. In the Because of these initial results, CARB researchers explored the
last 10 years of the twentieth century, the human population effectiveness of an OC for a CNG-engine bus [112,113]. Results
increased roughly as much as it did during the preceding 1900 showed that an OC reduced total PM, total hydrocarbons, carbon
years. These two factors (i.e., increased standards of living and monoxide, and formaldehyde emissions. 1,3-Butadiene emissions
population increases) will demand increases in electricity [100]. were reduced to levels below detection. Toxic aromatic HCs such as
benzene appeared reduced by the catalyst, but the results were not
5. Effects of emission controls statistically signicant. The OC had little effect on methane and
NOx levels [112]. For a CNG bus without an OC, formaldehyde was
Bagley et al. [107] used an indirect injection diesel engine (like 8692% of all carbonyl emissions. In contrast, an OC was 96%
those used in underground mines) to examine a soy-derived, fatty- effective in reducing formaldehyde from the emissions from a
acid mono-ester (biodiesel) fuel and an oxidation catalytic Detroit Diesel bus without after-treatment [112]. In another report
converter (OC). Compared to emissions with the diesel fuel by CARB researchers, after-treatment reduced emissions for both
without the OC, both the diesel (D2) and biodiesel fuel with the OC CNG and diesel heavy-duty engines; however, the magnitude of
had similar reductions (5080%) in total particulate matter (TPM). these reductions differed by pollutant and driving cycle [113,114].
The solid matrix of the TPM was lowered with the biodiesel fuel. Only the Diesel bus and the uncontrolled CNG bus had mutagenic
Whether or not the OC was used, the particulate PAHs and 1- activity (Salmonella typhimurium TA98, +S9) in the volatile phase
nitropyrene emissions were lower with use of the biodiesel fuel as [113]. The OC reduced the mutagenic activity in both the volatile
compared to the D2 fuel. Vapor-phase PAH emissions also were and PM phase [113].
reduced (up to 90%) when the OC was used with either fuel.
Salmonella mutagenicity (TA98) was reduced >50% in both particle 6. Other studies
and vapor-phase with both fuels by when OC was used. Vapor-
phase mutagenicity was not detected with the biodiesel samples; One approach to reduce the nations dependence on coal and
and only a very low level of mutagenic activity was detected when other fossil fuels is for utility companies to core (either directly or
the D2 fuel and the OC were used. The OC caused a slight shift in the indirectly) a percentage of their total fuel requirements using
particle size to smaller particles for the diesel fuel; therefore, a biomass. Recognizing the tremendous coal requirements to
larger percentage of the particles would reach lung alveoli, but produce electricity and process steam in the United States, even
fewer particles would be emitted. Use of the biodiesel fuel in this small biomass co-ring rates would have a signicant impact both
study, did not increase any of the potentially toxic, health-related environmentally and economically. Therefore, Klasson and
emissions that were monitored as part of this study. For PAH Nghiem [115] examined the possibility of using zoo animal waste
compounds, seven of the nine monitored compounds were found for a biomass source. Because animal waste has the greatest
in the D2 and biodiesel samples obtained both with and without potential for methane production (yielding from 0.3 to 0.4 m3
the OC (i.e., all). Only one nitro-PAH compound (1-nitropyrene) methane/kg volatile solids) when compared to other types of
was found at quantiable levels. The levels of the soluble organic biomass, methane yields from animal waste have been studied
fraction and volatile compounds decreased with OC use; however, (although these studies have targeted primarily toward domesti-
the amount of PAH and nitro-PAH per unit mass actually increased cated animals). Klasson and Nghiem used elephant and rhinoceros
with OC use for the biodiesel fuel [107]. dung to investigate the feasibility of generating methane from the
Bunger et al. [108] knew from earlier studies that particle dung of zoo animals. They observed that the methane yield for this
emissions from diesel engines contain PAHs and that these dung was approximately 0.033 L biogas/g dung (0.020 L CH4/g
compounds cause Salmonella mutagenicity. Therefore, they ex- dung). The Knoxville Zoo produces 30 cubic yards (23 m3) of
plored what effect nitrogen oxides and an oxidation catalytic herbivore dung per week and cost of disposal of this dung is
converter had on the mutagenicity. The engine was fueled with US$105/week. The estimated weight of this dung is approximately
common fossil diesel fuel, low-sulfur diesel fuel, or one of two 1050 ton/year. This annually generated dung could potentially
biodiesel fuels (RME or SME) and run at ve different load modes in generate 17,400 m3 methane, and the energy value for this
two series with and without installation of an oxidation catalytic methane is 6.6 108 kJ (6.2 108 Btu). Because biomass repre-
converter. The mutagenicity of the extracts was examined with the sents a clean fuel source which can reduce SOx, NOx, and methane,
Salmonella assay (TA98 and TA100). Although the lowest numbers the authors noted that such co-ring supports policies of the Clean
of revertant colonies were with the biodiesel fuels (without Air and Energy Policy Act [115]. Readers may want to review other
oxidation catalytic converter), the number of revertant colonies documents related to this subject [116118].
also was low in extracts of low sulfur diesel fuel emissions. Usually, Many herders in the Tibetan Plateau still follow traditional
engine operation with the oxidation catalytic converter led to a lifestyle practices, including living in tents and burning yak dung
reduction of the mutagenicity. However, direct-acting mutagenic for fuel. Kang et al. [119] reported on a study of indoor air quality in
effects were signicantly increased for rapeseed biodiesel and soy the nomadic tents in the Nam Co region, inland Tibetan Plateau.
biodiesel under heavy duty conditions. Direct-acting mutagenicity The results showed very high concentrations of total suspended
also increased for common fossil diesel fuel and low sulfur diesel particles (TSP), averaging at 4.45 mg/m3 during the cooking/
fuel under heavy duty conditions when emissions were treated heating period (with daily value of 3.16 mg/m3). Elevated
with the oxidation catalytic converter. Because the oxidation concentrations of toxic elements (Cd, As, and Pb) were found
catalytic converter increased formation of direct-acting mutagens within the tents, averaging 3.16 mg/m3, 35.00 mg/m3, and
(probably nitroaromatics), the authors expressed concern over the 81.39 mg/m3 for a day, respectively, which was more than 104
use of oxidation catalytic converters with diesel engines [108]. 106 times higher than the outdoor air level in the Nam Co area
California Air Resources Board (CARB) researchers [109111] [119].
reported that tailpipe emissions from a compressed natural gas Such fuels, including dried cow dung, coconut shell and husk,
(CNG) fueled transit bus without after-treatment had levels of rice and other cereal straws, tobacco stalks, and jute sticks are
toxicants (e.g., formaldehyde, nanoparticles, and Salmonella often burned in open res or unvented cookstoves inside the home.
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Table 3 estimating the health effects associated with a particular type of

Summary of selected mutagenicity results
fuel (or engine).
(S. typhimurium, TA98 S9) from Bell and
Kamens [125] in revertants per mg extract. 4. Because results are limited, results cannot be used to infer
differences for vehicles as a whole. That is, for example, not all
Fuel S9 +S9
diesel engines produce the same results (quantitatively or
Dried dunga 0.16 0.33 qualitatively).
Coconut shell 1.56 2.61 5. Other factors (e.g., after-treatment durability, deterioration,
Crop residue 0.04 0.28
vehicle maintenance, etc.) have not been adequately explored.
Pine 0.48 1.20
Red oak 0.09 0.81 6. Newly developed fuels and combustors must be tested to
Peat 0.25 0.38 determine if they provide a public health advantage over
a
An average of samples from two sources. existing technologies including what tradeoffs can be
expected (e.g., decreasing levels of PAHs versus increasing
levels of NOx and possibly nitroarenes in ambient air).
The resulting human exposures to combustion gases and particles 7. Investigators should determine if after-treatments will decrease
from indoor burning can be 100-fold higher than pollutant levels toxicants over extended periods rather than just immediately
typically experienced in polluted urban air [120124]. Dichlor- following instillation.
omethane extracted 97% (370.0 mg extract/379.8 mg particles) of 8. Because mutation is linked to heritable conditions, birth rates,
the mass of the cow-dung-smoke particles and 35.3% (50.0 mg birth defects, and many other health conditions, researchers and
extract/141.8 mg particles) of the coconut-shell-smoke particles. decision makers should not limit their efforts to the cancer
In studies at UNC [125], it was observed that soft, slow-burning process when mutagens are identied.
fuels often produce particles with higher extractable organic
content than do hard, fast-burning fuels. Bell and Kamens also Much progress has been made in reducing the pollutants
examined these fuels using the Salmonella bioassay using TA98, emitted from various combustors (including diesel engines and
S9 (Table 3). power plants) by the use of alternative fuels; however, much more
progress is needed. Not only must researchers improve fuels and
combustors, but also there is a need to improve the toxicology
7. Summary
testing and analytical chemistry methods associated with complex
mixtures. Another need is to improve exposure estimations which
Charles [126] in a public policy paper questioned the use of
presently are a weak link in doing risk analyses.
biofuels as a replacement for petroleum fuels. While looking at the
proposed benets and disadvantages of biofuels, Charles says that
the use of biofuels may inhibit the development and maturation of Conict of interest statement
needed longer-term technologies [126]. In a scientic news article,
Dan Charles wrote, Last week, the California Air Resources Board The author declares that there are no conicts of interest.
(CARB) adopted a low-carbon fuel standard that requires greater
use of fuels that cause lower greenhouse emissions, compared with Acknowledgements
gasoline. . .. Corn-based ethanol doesnt meet that test and wont
benet from the new standard, CARB says, because diverting corn Special thanks go to Mutation Research and the editors (David
into ethanol production increases deforestation and the clearing of DeMarini and Mike Waters) and the journals reviewers for their
grasslands [127]. CARB, using a Purdue University model, encouragement and assistance. I want to think all researchers and
developed and concluded that corn-based ethanol produces decision makers worldwide who have contributed to the efforts
slightly more greenhouse emissions than does gasoline, with that have helped to protect the publics health through protecting
about 30% of those emissions occurring as farmers clear land for the air breathed, the water ingested, and the soils contacted. As
crops. One researcher found that corn ethanol produces twice the John Locke once said, It is one thing to show a man that he is in an
greenhouse gas emissions of gasoline, for every mile driven, once error, and another to put him in possession of the truth.
emissions from land conversion are counted [128]. This nding is
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MUTREV-8085; No. of Pages 17

Mutation Research xxx (2014) xxxxxx

Contents lists available at ScienceDirect

Mutation Research/Reviews in Mutation Research

The history, genotoxicity and carcinogenicity of carbon-based fuels

* Tel.: +1 919 839 8978.

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1. Introduction combustion engines (ICEs) operating with gasoline and diesel

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Category Method used to categorize Examples

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corporation spent $2 billion on demonstration projects in carbonate (see http://en.wikipedia.org/wiki/Marl or http://www.

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Table 3 estimating the health effects associated with a particular type of

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