ASTM F1524-95(2001)
(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 2001)
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 (e) 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—a term used for substances that react
waters.
with hydroxyl radicals that do not yield species that propagate
1.2 This guide addresses the application of advanced oxi-
the chain reaction for contaminant destruction. Scavengers can
dation alone or in conjunction with other technologies.
be either organic or inorganic compounds.
1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
3. Significance and Use
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.
2. Terminology 3.2 Oxidizing Agents:
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 hy-
tive radical species and lead to the oxidation of waterborne
pochlorite, its rate of attack is commonly much faster. In fact,
contaminants (usually organic) in surface and ground waters.
6 9
itistypicallyonemillion(10 )toonebillion(10 )timesfaster
2.1.2 inorganic foulants—compounds,suchasiron,calcium
than the corresponding attack with molecular ozone (1). The
and manganese, that precipitate throughout a treatment unit
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
fibreglass mesh that is coated withTiO in photocatalyticAOP H O 1 hv→2OH· (1)
2 2 2
systems.
2O 1 H O →→2OH· 13O (2)
3 2 2 2
2.1.3 mineralization—the complete oxidation of an organic
12 13 2
Fe 1 H O →→ OH·Fe 1 OH ~Fenton’s Reaction! (3)
2 2
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
2.1.4 photoreactor—the core of the photoreactor is a UV
stripping of solutions containing volatile organics (2). Capital
lamp that emits light in the broad range of 200 to 400 nm
andoperatingcostsarealsotakenintoaccountwhenadecision
wavelength range.
on the choice of oxidant is made.
3.2.1.2 Advancedoxidationtechnologyhasalsobeendevel-
This guide is under the jurisdiction of ASTM Committee F20 on Hazardous oped based on the anatase form of titanium dioxide. This
Substances and Oil Spill Response and is the direct responsibility of Subcommittee
F20.22 on Mitigation Actions.
Current edition approved May 15, 1995. Published July 1995. Originally Theboldfacenumbersinparenthesesrefertothelistofreferencesattheendof
published as F1524–94. Last previous edition F1524–94. this standard.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
F1524–95 (2001)
method by which the photocatalytic process generates hy- 4.4 pH Adjustment—Adjusting the pH of the solution prior
droxyl radicals is described in the following equations: to treatment may significantly affect the performance of the
treatment. A feed solution at a pH of 9 will tend to cause
1 2
TiO 1 hv 1 H O→ OH· 1 H 1 e (4)
2 2
precipitation of most inorganics, while a pH of 5 will cause
2 2
2e 12O 12H O→2OH· 1 O 12OH (5)
2 2 2 themtoremaininsolutionthroughoutthetreatmentprocess.In
situations where the inorganics are in a relatively low concen-
3.2.2 Photolysis—Destruction pathways, besides the hy-
tration(lowpartspermillion),onewouldtendtolowerthepH,
droxyl radical attack, are very important for the more refrac-
while a higher pH would be preferable at the higher concen-
tory compounds such as chloroform, carbon tetrachloride,
trations where the inorganics could be separated and removed.
trichloroethane, and other chlorinated methane or ethane com-
4.5 System Fouling—Generally, inorganic foulants, such as
pounds. A photoreactor’s ability to destroy these compounds
iron,manganese,andcalcium,intheppmrange,causereduced
photochemically will depend on its output level at specific
flow, increased pressure and low performance of a treatment
wavelengths. Since most of these lamps are proprietary,
system. This phenomenon is common in most organic treat-
preliminary benchscale testing becomes crucial when dealing
ment units regardless of the mechanism employed. Pretreat-
with these compounds.
ment systems usually involve chemical addition (that is, pH
3.3 AOP Treatment Techniques:
adjustment) or membrane technology, or both, as they are
3.3.1 Advancedoxidationprocesses(AOPs)maybeapplied
generally the most economical and effective for inorganic
alone or in conjunction with other treatment techniques as
removal. Preliminary benchscale testing is commonly used to
follows:
determine the applicability and the cost-effectiveness of the
3.3.1.1 Following a pretreatment step. The pretreatment
different pretreatment systems.
process can be either a physical or chemical process for the
4.6 Off-Gas Analysis—Organic analysis of the exiting gas-
removal of inorganic or organic scavengers from the contami-
eous stream will assist the operator in modifying system
nated stream prior to AOP destruction.
parameters to maximize system performance and efficiency.
3.3.1.2 Following a preconcentration step. Due to the in-
This technique is also beneficial during preliminary testing as
crease in likelihood of radical or molecule contact, very dilute
it provides an indication of the AOP technology’s ability to
solutionscanbetreatedcosteffectivelyusingAOPsafterbeing
destroy the compounds as compared to simply stripping them
concentrated.
from the water phase into the air.
3.4 AOP Treatment Applications—Advancedoxidationpro-
4.7 Destruction Rate Constants—The reaction of the OH
cesses (AOPs) are most cost effective for those waste streams
radical with organic compounds is largely dependent upon the
containing organic compounds at concentrations below 1%
rate constant.Alist (3) of reaction rates for common contami-
(10000 ppm).This figure will vary depending upon the nature
nants is shown in Table 1.
of the compounds and whether there is competition for the
oxidizi
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