ASTM F1524-95(2007)
(Guide)Standard Guide for Use of Advanced Oxidation Process for the Mitigation of Chemical Spills
Standard Guide for Use of Advanced Oxidation Process for the Mitigation of Chemical Spills
SCOPE
1.1 This guide covers the considerations for advanced oxidation processes (AOPs) in the mitigation of spilled chemicals and hydrocarbons dissolved into ground and surface waters.
1.2 This guide addresses the application of advanced oxidation alone or in conjunction with other technologies.
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. In addition, it is the responsibility of the user to ensure that such activity takes place under the control and direction of a qualified person with full knowledge of any potential safety and health protocols.
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Designation: F1524 − 95(Reapproved 2007)
Standard Guide for
Use of Advanced Oxidation Process for the Mitigation of
Chemical Spills
This standard is issued under the fixed designation F1524; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 2.1.5 radical species—a powerful oxidizing agent, princi-
pally the hydroxyl radical, that reacts rapidly with virtually all
1.1 This guide covers the considerations for advanced
organic compounds to oxidize and eventually lead to their
oxidation processes (AOPs) in the mitigation of spilled chemi-
complete mineralization.
cals and hydrocarbons dissolved into ground and surface
2.1.6 scavengers—atermusedforsubstancesthatreactwith
waters.
hydroxyl radicals that do not yield species that propagate the
1.2 This guide addresses the application of advanced oxi-
chain reaction for contaminant destruction. Scavengers can be
dation alone or in conjunction with other technologies.
either organic or inorganic compounds.
1.3 This standard does not purport to address all of the
3. Significance and Use
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
3.1 General—Thisguidecontainsinformationregardingthe
priate safety and health practices and determine the applica-
use of AOPs to oxidize and eventually mineralize hazardous
bility of regulatory limitations prior to use.Inaddition,itisthe
materials that have entered surface and groundwater as the
responsibility of the user to ensure that such activity takes
result of a spill. Since much of this technology development is
placeunderthecontrolanddirectionofaqualifiedpersonwith
still at the benchscale level, these guidelines will only refer to
full knowledge of any potential safety and health protocols.
those units that are currently applied at a field scale level.
3.2 Oxidizing Agents:
2. Terminology
3.2.1 Hydroxyl Radical (OH)—The OH radical is the most
2.1 Definitions of Terms Specific to This Standard:
common oxidizing agent employed by this technology due to
2.1.1 advanced oxidation processes (AOPs)—ambient tem-
its powerful oxidizing ability. When compared to other oxi-
perature processes that involve the generation of highly reac-
dants such as molecular ozone, hydrogen peroxide, or
tive radical species and lead to the oxidation of waterborne
hypochlorite, its rate of attack is commonly much faster. In
contaminants (usually organic) in surface and ground waters. 6 9
fact, it is typically one million (10 ) to one billion (10 ) times
2.1.2 inorganic foulants—compounds,suchasiron,calcium
fasterthanthecorrespondingattackwithmolecularozone (1).
and manganese, that precipitate throughout a treatment unit
The three most common methods for generating the hydroxyl
and cause reduced efficiency by fouling the quartz sleeve that
radical are described in the following equations:
protects the lamp in photolytic oxidation AOP systems or the
H O 1hv→2OH· (1)
2 2
fibreglass mesh that is coated withTiO in photocatalyticAOP
2O 1H O→→2OH·13O (2)
3 2 2 2
systems.
12 13 2
Fe 1H O→→OH·Fe 1OH Fenton’s Reaction (3)
~ !
2 2
2.1.3 mineralization—the complete oxidation of an organic
compound to carbon dioxide, water, and acid compounds, that
3.2.1.1 Hydrogen peroxide is the preferred oxidant for
is, hydrochloric acid if the compound is chlorinated.
photolyticoxidationsystemssinceozonewillencouragetheair
stripping of solutions containing volatile organics (2). Capital
2.1.4 photoreactor—the core of the photoreactor is a UV
lamp that emits light in the broad range of 200 to 400 nm andoperatingcostsarealsotakenintoaccountwhenadecision
on the choice of oxidant is made.
wavelength range.
3.2.1.2 Advancedoxidationtechnologyhasalsobeendevel-
oped based on the anatase form of titanium dioxide. This
This guide is under the jurisdiction of ASTM Committee F20 on Hazardous method by which the photocatalytic process generates hy-
Substances and Oil Spill Response and is the direct responsibility of Subcommittee
droxyl radicals is described in the following equations:
F20.22 on Mitigation Actions.
Current edition approved Nov. 1, 2007. Published November 2007. Originally
approved in 1994. Last previous edition approved in 2001 as F1524–95 (2001). Theboldfacenumbersinparenthesesrefertothelistofreferencesattheendof
DOI: 10.1520/F1524-95R07. this standard.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
F1524 − 95 (2007)
1 2
TiO 1hv1H O→OH·1H 1e (4) 4.4 pH Adjustment—Adjusting the pH of the solution prior
2 2
2 2 to treatment may significantly affect the performance of the
2e 12O 12H O→2OH·1O 12OH (5)
2 2 2
treatment. A feed solution at a pH of 9 will tend to cause
3.2.2 Photolysis—Destruction pathways, besides the hy-
precipitation of most inorganics, while a pH of 5 will cause
droxyl radical attack, are very important for the more refrac-
themtoremaininsolutionthroughoutthetreatmentprocess.In
tory compounds such as chloroform, carbon tetrachloride,
situations where the inorganics are in a relatively low concen-
trichloroethane, and other chlorinated methane or ethane com-
tration(lowpartspermillion),onewouldtendtolowerthepH,
pounds. A photoreactor’s ability to destroy these compounds
while a higher pH would be preferable at the higher concen-
photochemically will depend on its output level at specific
trations where the inorganics could be separated and removed.
wavelengths. Since most of these lamps are proprietary,
4.5 System Fouling—Generally, inorganic foulants, such as
preliminary benchscale testing becomes crucial when dealing
iron,manganese,andcalcium,intheppmrange,causereduced
with these compounds.
flow, increased pressure and low performance of a treatment
3.3 AOP Treatment Techniques:
system. This phenomenon is common in most organic treat-
3.3.1 Advancedoxidationprocesses(AOPs)maybeapplied
ment units regardless of the mechanism employed. Pretreat-
alone or in conjunction with other treatment techniques as
ment systems usually involve chemical addition (that is, pH
follows:
adjustment) or membrane technology, or both, as they are
3.3.1.1 Following a pretreatment step. The pretreatment
generally the most economical and effective for inorganic
process can be either a physical or chemical process for the
removal. Preliminary benchscale testing is commonly used to
removal of inorganic or organic scavengers from the contami-
determine the applicability and the cost-effectiveness of the
nated stream prior to AOP destruction.
different pretreatment systems.
3.3.1.2 Following a preconcentration step. Due to the in-
4.6 Off-Gas Analysis—Organic analysis of the exiting gas-
crease in likelihood of radical or molecule contact, very dilute
eous stream will assist the operator in modifying system
solutionscanbetreatedcosteffectivelyusingAOPsafterbeing
parameters to maximize system performance and efficiency.
concentrated.
This technique is also beneficial during preliminary testing as
3.4 AOP Treatment Applications—Advanced oxidation pro-
it provides an indication of the AOP technology’s ability to
cesses (AOPs) are most cost effective for those waste streams destroy the compounds as compared to simply stripping them
containing organic compounds at concentrations below 1%
from the water phase into the air.
(10000 ppm).This figure will vary depending upon the nature
4.7 Destruction Rate Constants—The reaction of the OH
of the compounds and whether there is competition for the
radical with organic compounds is largely dependent upon the
oxidizing agent.
rate constant.Alist (3) of reaction rates for common contami-
nants is shown in Table 1.
4. Constraints on Usage
5. Practical Applicat
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