ASTM F1524-95(2013)
(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
SIGNIFICANCE AND USE
3.1 General—This guide contains information regarding the use of AOPs to oxidize and eventually mineralize hazardous materials that have entered surface and groundwater as the result of a spill. Since much of this technology development is still at the benchscale level, these guidelines will only refer to those units that are currently applied at a field scale level.
3.2 Oxidizing Agents:
3.2.1 Hydroxyl Radical (OH)—The OH radical is the most common oxidizing agent employed by this technology due to its powerful oxidizing ability. When compared to other oxidants such as molecular ozone, hydrogen peroxide, or hypochlorite, its rate of attack is commonly much faster. In fact, it is typically one million (106) to one billion (109) times faster than the corresponding attack with molecular ozone (1).2 The three most common methods for generating the hydroxyl radical are described in the following equations:
3.2.1.1 Hydrogen peroxide is the preferred oxidant for photolytic oxidation systems since ozone will encourage the air stripping of solutions containing volatile organics (2) . Capital and operating costs are also taken into account when a decision on the choice of oxidant is made.
3.2.1.2 Advanced oxidation technology has also been developed based on the anatase form of titanium dioxide. This method by which the photocatalytic process generates hydroxyl radicals is described in the following equations:
3.2.2 Photolysis—Destruction pathways, besides the hydroxyl radical attack, are very important for the more refractory compounds such as chloroform, carbon tetrachloride, trichloroethane, and other chlorinated methane or ethane compounds. A photoreactor's ability to destroy these compounds photochemically will depend on its output level at specific wavelengths. Since most of these lamps are proprietary, preliminary benchscale testing becomes crucial when dealing with these compounds.
3.3 AOP Treatment Techn...
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 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 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.
General Information
Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: F1524 − 95 (Reapproved 2013)
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 2.1.4 photoreactor—the core of the photoreactor is a UV
lamp that emits light in the broad range of 200 to 400 nm
1.1 This guide covers the considerations for advanced
wavelength range.
oxidation processes (AOPs) in the mitigation of spilled chemi-
2.1.5 radical species—a powerful oxidizing agent, princi-
cals and hydrocarbons dissolved into ground and surface
pally the hydroxyl radical, that reacts rapidly with virtually all
waters.
organic compounds to oxidize and eventually lead to their
1.2 This guide addresses the application of advanced oxi-
complete mineralization.
dation alone or in conjunction with other technologies.
2.1.6 scavengers—atermusedforsubstancesthatreactwith
1.3 The values stated in SI units are to be regarded as
hydroxyl radicals that do not yield species that propagate the
standard. No other units of measurement are included in this
chain reaction for contaminant destruction. Scavengers can be
standard.
either organic or inorganic compounds.
1.4 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.
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)
systems. 3 2 2 2
12 13 2
Fe 1H O→→OH·Fe 1OH ~Fenton’s Reaction! (3)
2.1.3 mineralization—the complete oxidation of an organic
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
stripping of solutions containing volatile organics (2). Capital
andoperatingcostsarealsotakenintoaccountwhenadecision
This guide is under the jurisdiction of ASTM Committee F20 on Hazardous
on the choice of oxidant is made.
Substances and Oil Spill Response and is the direct responsibility of Subcommittee
F20.22 on Mitigation Actions.
Current edition approved April 1, 2013. Published April 2013. Originally
approved in 1994. Last previous edition approved in 2007 as F1524–95 (2007). Theboldfacenumbersinparenthesesrefertothelistofreferencesattheendof
DOI: 10.1520/F1524-95R13. this standard.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
F1524 − 95 (2013)
TABLE 1 Rate Constants for the Hydroxyl Radical
3.2.1.2 Advancedoxidationtechnologyhasalsobeendevel-
+9 −1 −1
oped based on the anatase form of titanium dioxide. This Compound, m k , OH, (10 m s )
M
method by which the photocatalytic process generates hy- Benzene 7.8
Hydroperoxide Ion 7.5
droxyl radicals is described in the following equations:
Vinyl Chloride 7.1
1 2
Chlorobenzene 4.5
TiO 1hv1H O→OH·1H 1e (4)
2 2
1-Butanol 4.2
2 2
2e 12O 12H O→2OH·1O 12OH (5)
Trichloroethane 4.0
2 2 2
Nitrobenzene 3.9
3.2.2 Photolysis—Destruction pathways, besides the hy-
Pyridine 3.8
Toluene 3.0
droxyl radical attack, are very important for the more refrac-
Tetrachloroethane 2.3
tory compounds such as chloroform, carbon tetrachloride,
Carbonate Ion 0.39
trichloroethane, and other chlorinated methane or ethane com-
Dichloromethane 0.058
Bicarbonate 0.0085
pounds. A photoreactor’s ability to destroy these compounds
Chloroform ;0.005
photochemically will depend on its output level at specific
Carbon Tetrachloride NR
wavelengths. Since most of these lamps are proprietary,
preliminary benchscale testing becomes crucial when dealing
with these compounds.
tetrachloride, chloroform, and other chlorinated methane com-
3.3 AOP Treatment Techniques: pounds are quite resistant to degradation in the presence of the
3.3.1 Advancedoxidationprocesses(AOPs)maybeapplied hydroxyl radical and should be destroyed photochemically
alone or in conjunction with other treatment techniques as (that is, UV alone).
follows:
4.4 pH Adjustment—Adjusting the pH of the solution prior
3.3.1.1 Following a pretreatment step. The pretreatment
to treatment may significantly affect the performance of the
process can be either a physical or chemical process for the
treatment. A feed solution at a pH of 9 will tend to cause
removal of inorganic or organic scavengers from the contami-
precipitation of most inorganics, while a pH of 5 will cause
nated stream prior to AOP destruction.
themtoremaininsolutionthroughoutthetreatmentprocess.In
3.3.1.2 Following a preconcentration step. Due to the in-
situations where the inorganics are in a relatively low concen-
crease in likelihood of radical or molecule contact, very dilute
tration(lowpartspermillion),onewouldtendtolowerthepH,
solutionscanbetreatedcosteffectivelyusingAOPsafterbeing
while a higher pH would be preferable at the higher concen-
concentrated.
trations where the inorganics could be separated and removed.
3.4 AOP Treatment Applications—Advanced oxidation pro-
4.5 System Fouling—Generally, inorganic foulants, such as
cesses (AOPs) are most cost effective for those waste streams
iron,manganese,andcalcium,intheppmrange,causereduced
containing organic compounds at concentrations below 1%
flow, increased pressure and low performance of a treatment
(10000 ppm).This figure will vary depending upon the nature
system. This phenomenon is common in most organic treat-
of the compounds and whether there is competition for the
ment units regardless of the mechanism employed. Pretreat-
oxidizing agent.
ment systems usually involve chemical addition (that is, pH
adjustment) or membrane technology, or both, as they are
4. Constraints on Usage
generally the most economical and effective for inorganic
removal. Preliminary benchscale testing is commonly used to
4.1 General—Although AOPs are destruction processes, in
order for compound mineral
...
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