AMBIENT WATER QUALITY ADVISORY
METHYLENE CHLORIDE
OFFICE OF WATER REGULATIONS AND STANDARDS
CRITERIA AND STANDARDS DIVISION
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
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NOTICES
This document has been reviewed by the Criteria and Standards
Division, Office of Water Regulations and Standards, U.S.
Environmental Protection Agency, and approved for distribution.
Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
This document is available to the public through the Criteria and
Standards Division, Office of Water Regulations and Standards,
U.S. EPA, Washington, DC.
ii
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FOREWORD
The Criteria and Standards Division of the Office of Water
Regulations and Standards has instituted water quality advisories
as a vehicle for transmitting the best available scientific
information concerning the aquatic life and human health effects
of selected chemicals in surface waters. Advisories are prepared
for chemicals for which information is needed quickly, but for
which sufficient data, resources, or time are not available to
allow derivation of national ambient water quality criteria.
Data supporting advisories are usually not as extensive as
required for derivation of national ambient water quality
criteria, and the strength of an advisory will depend upon the
source, type, and reliability of the data available. We feel,
however, that it is in the best interest of all concerned to make
the enclosed information available to those who need it.
Users of advisories should take into account the basis for
their derivation and their intended uses. Anyone who has
additional information that will supplement or substantially
change an advisory is requested to make the information known to
us. An advisory for an individual chemical will be revised if any
significant and valid new data make it necessary.
We invite comments to help improve this product.
Edmund M. Notzon, Director
Criteria and Standards Division
iii
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ACKNOWLEDGMENTS
AQUATIC LIFE
Mary D. Balcer, author
University of Wisconsin-Superior, Superior, WI
iv
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CONTENTS
Page
Notices
ii
Foreword
iii
Acknowledgments
iv
I.
Advisories
1-1
II.
General Information
II-l
A.
Biological, Chemical and Physical Properties
11-1
Ill .
Aquatic Toxicity
III-l
IV.
References
IV-1
V.
EPA Contacts
V-l
V
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SECTION I. Advisories
AQUATIC LIFE
If the estimated or^TrTeasured ambient concentration of
methylene chloride exceeds/770^ g/L in fresh or salt water, one
or more of the following^op/tions must be completed within a
reasonable period of time:
1. Obtain more measurements of the concentration.
2. Improve the estimate of the concentration.
3. Reduce the concentration.
4. Obtain additional laboratory and/or field data on the
effect of methylene chloride on aquatic life so that a
new aquatic life advisory or water quality criterion
can be derived.
After a reasonable period of time, unless a consideration of all
the available data concerning the ambient concentration and the
effects of methylene chloride on aquatic life indicates that the
ambient concentration is low enough, it must be reduced.
1-1
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SECTION II. GENERAL INFORMATION
A. Biological. Chemical, and Physical Properties
The following information on the properties of methylene
chloride (dichloromethane) and its persistence in the aquatic
environment was obtained from the Handbook of Chemistry and
Physics~ha~s or from the QSAR system~hb~s on August 13, 1987. Some of the
values were calculated using structure-activity relationships.
Property
Molecular Weight
Relative Density (20C)
Log P
Melting Point
Boiling Point
Vapor Pressure
Heat of Vaporization
pKa
Solubility in Water
BCF
Absorption Coef.[Log (Koc)]
Value
Source
84.93 g/mole
1.25
-95.0 °C
40.0 °C
436. mm Hg
6,666. cal/mole
(not applicable)
15.32 g/L
3.86
2.02
Calculated
Measured
Measured
Measured
Calculated
Calculated
Calculated
Calculated
Hydrolysis Half-life = 1000 days
Hydrolysis is not likely to be an important
mechanism for this chemical.
transformation
Biodegradation Half-life Analysis
This chemical has two halogens and all chemicals in the data
base with two halogens have a half-life > 15 days.
Log 10 (Henry's Constant) = -2.50 atmm~h3~s/mole
It could be concluded that a chemical with these properties
will vaporize rapidly from and will not persist in open
water.
Neely 100-day Partitioning Pattern
Air = 56.67%
Water = 43.15%
Ground = 0.09%
Hydrosoil = 0.08%
a Handbook of Chemistry and Physics, 67th Ed.
Raton, FL. 1986-1987.
CRC Press, Boca
For information on the QSAR system, see: Hunter, R., L.
Faulkner, F. Culver and J. Hill. Draft user manual for the
QSAR system. Center for Data Systems and Analysis, Montana
State University. November, 1985.
II-l
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SECTION III. AQUATIC TOXICITY
Introduction
Aquatic life advisory concentrations are conceptually
different from national aquatic life water quality criteria.
Aquatic life criteria are based on toxicity and bioconcentration
data for a sufficiently diverse group of animals and plants to
provide reasonable confidence in the appropriateness of the
criteria. Advisories are issued for selected chemicals for which
sufficient data are not available to allow derivation of national
water quality criteria for aquatic life. Because aquatic life
advisories are intended to be used to identify situations where
there is cause for concern and where appropriate action should be
taken, the advisory concentration for a chemical is derived to be
equal to or lower than what the Criterion Continuous Concentra-
tion (Stephan et al. 1985) would be if a national water quality
criterion for aquatic life could be derived for the chemical. If
the concentration of a chemical in a variety of surface waters is
found to exceed the aquatic life advisory concentration, this may
indicate that the U.S. EPA should consider deriving aquatic life
water quality criteria for that chemical.
The literature searching and data evaluation procedures used
in the derivation of aquatic life advisories are identical to
those used in the derivation of water quality criteria for
aquatic life (Stephan et al. 1985). However, advisories do not
contain a section on "Unused Data" as in a criteria document.
This aquatic life advisory concentration for methylene chloride
was derived using the procedures described in the "Guidelines for
Deriving Ambient Aquatic Life Advisory Concentrations" (Stephan
et al. 1986). A knowledge of these guidelines is necessary in
order to understand the following text, tables, and calculations.
The latest comprehensive literature search for information for
this aquatic life advisory was conducted in April, 1987.
The physical and chemical properties of methylene chloride
suggest that it is quite volatile and its concentration in static
exposures may decline rapidly (Section III A). Based on nominal
concentrations. Alexander et al. (1978) reported a 96-hr LC50 of
310,000 /M^g/L) for fathead minnows tested in a static exposure. In
a flow-through measured exposure, they calculated a 96-hr LC50 of
193,000
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According to the advisory guidelines, data from such static
exposures should be multiplied by a factor obtained by dividing a
flow-through 96-hr LC50 by a comparable 96-hr LC50 derived from a
static test that was measured at 0 hr. At the present time, data
are not available to allow the calculation of this adjustment
factor. Therefore, toxicity data derived from static, unmeasured
tests could not be adjusted, and their use in the derivation of
an aquatic life advisory concentration may lead to an
underestimate of the actual toxicity of methylene chloride.
Effects on Freshwater Organisms
Data on acute toxicity of methylene chloride to freshwater
organisms are available for one invertebrate and two species of
fish (Table 1). In static, unmeasured exposures, the cladoceran
Daphnia magna had a 48-hr LC50 of 220,000 g/L while the
bluegill (Lepomis macrochirus) and fathead minnow (Pimephales
promelas) had 96-hr LC50s of 230,000 and 310,000 g/L,
respectively. In a flow-through exposure, Alexander et aiv (1978)
reported an LC50 of 193, OOO'^Tyg/L and an EC50 of 99,000*7 yg/L for
the fathead minnow. Dill eVal. (1987) also conducted ^a flow-
through test with fathead minnows and obtained a 96 hr LC50 of
502,000|Q g/L.
In an early life-stage test with fathead minnows (Dill et
al. 1987) the wet weight of fish exposed to 142,000 g/L was 29%
less than the controls (Table 2). Survival was reduced at
methylene chloride concentrations greater than 209,000 g/L. Due
to the absence of any adverse effects at 82,500 g/L, a chronic
value of 108,000 can be calculated for fathead minnows. Division
of the acute value determined by these authors (502,000 g/L) by
the chronic value results in an acuta^hronic ratio of 4.648.t-—"'
Data are available describing other lethal and sublethal
effects of methylene chloride on freshwater organisms (Table 4).
Algal population growth, carbon 14 uptake, and chlorophyll a
content were affected by con- centrations of 550,000 to 2,292,000
g/L, while protozoan cell replication was inhibited by levels of
500,000 to > 8,000,000 g/L. Birge et al. (1980) and Black et
al. (1982) exposed embryos of rainbow trout (Salmo gairdneri).
fathead minnows, five species of frogs, and the northwestern
salamander (Ambystoma qracile) to methylene chloride in a flow-
through measured exposure. They determined EC50s (death and
deformity) for each species at hatching and at 4 days post-hatch
(Table 4). The EC50s ranged from 13,160 g/L for rainbow trout
to > 48,000 g/L for the leopard frog (Rana pipiens).
111-2
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Effects on Saltwater Organisms
Data on acute toxicity of methylene chloride to saltwater
animals are available for an invertebrate and a fish tested in
static, unmeasured exposures (Table 1). The 96-hr LC50s for the
mysid, Mvsidopsis bahia. and the sheepshead minnow, Cyprinodon
variegatus. were 256,000 and 330,000 g/L, respectively.
No data are available on chronic toxicity or other lethal or
sublethal effects of methylene chloride on saltwater organisms.
Calculation of Provisional Advisory Concentration
Due to the volatile nature of methylene chloride, data from
static, unmeasured tests should not be used in the calculation of
the advisory concentration. Although a total of five Species Mean
Acute Values (SMAVs) and Genus Mean Acute Values (GMAVs) are
available for freshwater and saltwater organisms (Table 3), only
dat$ with the fathead minnow were obtained from flow-through
tests. Therefore, according to the advisory guidelines, there are
not sufficient data available to calculate an advisory
concentration for methylene chloride.
However, if data from static unmeasured tests are included,
a provisional advisory may be calculated as follows. The lowest
GMAV (99,000 g/L) is divided by a factor of 9.0, in accordance
with the advisory guidelines, resulting in a provisional Advisory
Acute Value (AAV) of 11,000 g/L. The reported acute-chronic
ratio (4.648) is combined with two empirical ratios of 25 to
derive an Advisory Acute-Chronic Ratio (AACR) of 14.27. Division
of the provisional AAV (11,000 g/L) by the AACR (14.27) results
in a provisional Advisory Concentration of 770 g/L. Due to the
use of static unmeasured data in these calculations, this
concentration may underestimate the actual toxicity of methylene
chloride to aquatic life and, therefore, should be used with
caution.
111-3
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liable 1. Acute Toxicity of Methylene Chloride to Aquatic totals
PBEsanam species
Species
Cladoceran
(< 24 hr),
Daphnia magna
Fathead minnow
(adult),
Pimephales pronelas
Fathead minnow
(adult),
Pinephales pronelas
Fathead minnow
(adult),
Pimephales pronelas
Fathead minnow
(juvenile),
Pinephales pronelas
Bluegill
(Young of year),
Lepomis macrochirus
Method8 Qwlcal
s, u
s. u
F. M
F. M
F, M
S, U
Reagent
(>99.9%)
Hanhraw
(*g/L as
173
96
96
96
73-82
32-48
LC50
or BCSO
AsGd-
220,000
310,000
(LC50)
193,000
(LC50)
99,000
(BCSO
equilibriun)
502,000b
(LC50)
230,000
Species Mean
Vblue
Acute
220,000
99,000
230,000
Reference
LeBlanc 1980
Alexander et al.
1978
Alexander et al.
1978
Alexander et al.
1978
Dill et al. 1987
Buccafusso et al.
1981
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Ibhle 1. (continued)
SftLTHMBR SPECIES
Sfrecles
Mysid,
Mvsldopsls bahla
Sheepshead minnow
(juvenile),
Cyprinodan variegatus
netted* Chodcal
s, u
s, u
Salinity
10-31
LCSO
or BCSO
/fe/L)
256.000
330.000
Spncif8
Acute Value
Ax/C\
256,000
330,000
Reference
U.S. EPA 1978
Heitnuller et al.
1981
S = static; F = flow-through; M = measured; U = unmeasured
Data were not used in the calculation of the Species Mean Acute Value due to the presence
of results from a more sensitive endpoint.
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Mile 2. Chronic TbKLclty off Methylene Chkriife to Anlmls
Fathead minnow
Plaepbales promelas
ELS
(> 99.9*)
(&L1
CMDj)
73-82
drailc
Afar
82,500-142,000
Clrailc VUoe
108,000
Dill et al. 1987
Acute-Chronic Ratios
(mg/L as tete VUoe Chronic Vblae
Stecles CaCOj) /fg/L) A&L) tetio
Fathead minnow, 73-82 502,000 108,000 4.648
Plmertwles promelas
a ELS = early life-stage.
k Results are based on measured concentrations of Methylene Chloride.
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Tfchle 3. Racked Genus ffeao Acute Values idth Species Nun Acute-Chronic Ratios
Gens Mean Sfeecies Ifean Species Mea
Acute %lue Acute ttilue Acute-Chron
Rank0 /fg/L) Species Ak/L) Ratio0
330,000 Sheepshead minnow, 330,000
Cyprlnodon varlegatus
256,000 Mysid, 256,000
Mysldopsis bahia
230,000 Blueglll, 230,000
Leponris macrochirus
220,000 Cladoceran, 220,000
Daphnia magna
99,000 Fathead minnow, 99,000 4.648
Pimephales promelas
a Ranked from most resistant to most sensitive based on Genus Mean Acute Value,
k Fran "Mile 1.
C From Table 2.
Provisional Advisory Acute Value = (99,OO^g/L)/ 9.0 = 11 ,OOO^g/L (see text).
Advisory Acute-Chronic Ratio =14.27
Provisional Advisory Concentration = (11.000^g/L)/ 14.27 = Tiy^g/L
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"Mile 4. Other Data on Effects of Netiylene Chloride on Aquatic Gt^nisas
CTBSaHflHt SFBCIES
Species
Blue-green alga,
Anacystls aeruginosa
Green alga,
Chlorella vulgaris
Green alga,
Chlanvdomonas angulosa
Green alga,
Scenedesmus
qiiafirjcauda
Green alga,
Selenastrum
caprloomutun
Protozoan,
Chilonnmas
Paramecium
Protozoan,
Pseudnmonas putida
Cladoceran
(24 hr).
Daphnla magna
Chnical
IhrrfawiQ
(me/L as
CaCO_)
9*—
286
Duration
8 days
3 hr
3 hr
8 days
96 hr
48 hr
16 hr
24 hr
Effect
Incipient
inhibition of
population growth
(Cr uptake)
^uptake)
Incipient
Inhibition of
population growth
EC50
(chlorophyll a)
Incipient
inhibition of
cell replication
Incipient
inhibition of
cell nailtlplicatIctn
EC50
(immobility)
ftBMWll Ml Ifl
550,000
2,292,000
1,477,000
1,450,000
> 662,000
> 8,000,000
500,000
2,270,000
Reference
Bringnann and Kiiin
1978a,b
Hutchinson et al.
1980
Hutchinson et al.
1980
Bringnann and Huhn
1978a,b;1977a
U.S. EPA 1978
Bringmarei et al.
1980
Bringnaim and Kuhn
1977a
Bringmann and Kuhn
1977b
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*fahle 4. (oantimed)
Species
Rainbow trout
(embryo),
Salmo ealrdneri
Rainbow trout
(enbryo-larva),
Salmo ealrdneri
Fathead minnow
(embryo),
Plmephales promelas
Fathead minnow
(embryo-larva),
Plmephales promelas
Fathead minnow
(juvenile),
Plmephales promelas
Bullfrog
(enbryo),
Rana catesblana
Bullfrog
(embryo-larva),
Rana catesblana
Chfical
Reagent
Hankiess
(¦g/L as
106
Duration
23 days
(to hatch)
Reagent 106 27 days
(4 days
post-hatch)
Reagent 95.3 5 days
(to hatch)
Reagent 95.3 9 days
(4 days
(post-hatch)
Reagent 73-82 192 hr
(> 99.9*)
Analytical 106.8 4 days
(to hatch)
Analytical 106.8 8 days
(4 days
post-hatch)
Pickerel frog
(embryo).
Rana palustris
Analytical
106.8
4 days
(to hatch)
Effect
EC50
(death and
and deformity)
ECSO
(death and
deformity)
EC50
(death and
deformity)
ECSO
(death and
deformity)
LC50
EC50
(death and
deformity)
ECSO
(death and
deformity)
ECSO
(death and
deformity)
13,510
13,160
> 34,000
34,000
471,000
30,610
17,780
> 32.000
Reference
Black et al. 1982
Black et al. 1982
Black et al. 1982
Black et al. 1982
Dill et al. 1987
Birge et al. 1980
Birge et al. 1980
Birge et al. 1980
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Tbhle 4. (continued)
Hartkiess
(mg/L as
Stoecies dim leal CaCO^)
Pickerel frog Analytical 106.8
(embryo-larva),
Rana palustrls
Leopard frog Reagent 95.8
(embryo),
Rana plpiens
Leopard frog Reagent 95.8
(emhryo-larva),
Rana plpiens
Fowler's toad Analytical 106.8
(embryo),
Bufo fowleri
Fowler's toad Analytical 106.8
(embryo-larva),
Bufo fowleri
African clawed frog Reagent 97.9
(embryo),
Xenopus laevls
African clawed frog Reagent 97.9
(embryo-larva),
Xenopus laevls
Duration
8 days
(4 days
post-hatch)
5 days
(to hatch)
9 days
(4 days
post-hatch)
3 days
(to hatch)
7 days
(4 days
post-hatch)
2 days
(to hatch)
6 days
(4 days
post-hatch)
Effect
Oanoentratlon
Ma.
} Reference
EC50
(death and
deformity)
> 32,000 Birge et al. 1980
EC50
(death and
deformity)
> 48,000 Black et al. 1982
EC50
(death and
deformity)
> 48,000 Black et al. 1982
EC50
(death and
deformity)
> 32,000 Birge et al. 1980
EC50
(death and
deformity)
> 32,000 Birge et al. 1980
BC50
(death and
deformity)
> 29,000 Black et al. 1982
EC50
(death and
deformity)
> 29,000 Black et al. 1982
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"table 4. (oantlmed)
Species Qalcal
Northwestern salamander Reagent
(embryo),
Ambystana graclle
Uarrfcifgw
{mg/L as
-3SV- tUrati<°
97.9 5.5 days
(to hatch)
Northwestern salamander Reagent 97.9
(embryo-larva),
Ambystana graclle
9.5 days
(4 days
post-hatch)
OoDoentxatlan
Effect /tg/L) Reference
EC50 23,860 Black et al. 1982
(death and
deformity)
EC50 17,820 Black et al. 1982
(death and
deformity)
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SECTION IV.REFERENCES
Alexander, H.C., W.M. McCarty and E.A. Bartlett. 1978. Toxicity
of perchloroethylene, trichloroethylene, 1,1,1-trichloroethane,
and methylene chloride to fathead minnows. Bull. Environ. Contam.
Toxicol. 20:344-352.
Birge, W.J., J.A. Black and R.A. Kuehne. 1980. Effects of organic
compounds on amphibian reproduction. PB80-147523. National
Technical Information Service, Springfield, VA.
Black, J.A., W.J. Birge, W.E. McDonnell, A.G. Westerman, B.A.
Ramey and D.M. Bruser. 1982. The aquatic toxicity of organic
compounds to embryo-larval stages of fish and amphibians. PB82-
224601. National Technical Information Service, Springfield, VA.
Bringmann, G. and R. Kuhn. 1977a. Limiting values for the
damaging action of water pollutants to bacteria (Pseudomonas
putida) and green algae (Scenedesmus guadricauda) in the cell
multiplication inhibition test. Z. Wasser Abwasser Forsch. 10:87-
98.
Bringmann, G. and R. Kuhn. 1977b. Results of the damaging effect
of water pollutants on Daphnia magna. Z. Wasser Abwasser Forsch.
10:161-166.
Bringmann, G. and R. Kuhn. 1978a. Limiting values for the noxious
effects of water pollutant material to blue algae (Microcystis
aeruginosa) and green algae (Scenedesmus guadricauda) in cell
propogation inhibition tests. Vom Wasser 50:45-60.
Bringmann, G. and R. Kuhn. 1978b. Testing of substances for their
toxicity threshold: Model organisms Microcystis (Diplocystis)
aeruginosa and Scenedesmus guadricauda. Mitt. Int. Ver. Theor.
Angew. Limnol. 21:275-284.
Bringmann, G., R. Kuhn and A. Winter. 1980. Determination of the
biological effect of water pollutants in protozoa. III. Saprozoic
flagellates. Z. Wasser Abwasser Forsch. 13:170-173.
Buccafusco, R.J., S.J. Ells and G.A. LeBlanc. 1981. Acute
toxicity of priority pollutants to bluegill (Lepomis
macrochirus). Bull. Environ. Contam. Toxicol. 26:446-452.
Dill, D.C., P.G. Murphy and M.A. Mayes. 1987. Toxicity of
methylene chloride to life stages of the fathead minnow,
Pimephales promelas Rafinesque. Bull. Environ. Contam. Toxicol.
39:869-876.
IV-1
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Heitmuller, P.T., T.A. Hollister and P.R. Parrish. 1981. Acute
toxicity of 54 industrial chemicals to sheepshead minnows
(Cyprinodon varieqatus). Bull. Environ. Contam. Toxicol. 27:596-
604.
Hutchinson, T.C., J.A. Hellebust, D. Tarn, D. Mackay, R.A.
Mascarenhas and W.Y. Shiu. 1980. The correlation of the toxicity
to algae of hydrocarbons and halogenated hydrocarbons with their
physical-chemical properties. Environ. Sci. Res. 16:577-586.
LeBlanc, G.A. 1980. Acute toxicity of priority pollutants to
water flea (Daphnia magna). Bull. Environ. Contam. Toxicol.
24:684-691.
Stephan, C.E., D.I. Mount, D.J. Hansen, J.H. Gentile, G.A.
Chapman and W.A. Brungs. 1985. Guidelines for deriving numerical
national water quality criteria for the protection of aquatic
organisms and their uses. PB85-227049. National Technical
Information Service, Springfield, VA.
Stephan, C.E., G.A. Chapman, D.J. Hansen and T.W. Purcell. 1986.
Guidelines for deriving ambient aquatic life advisory
concentrations. December 11 draft. U.S. EPA, Environmental
Research Laboratory, Duluth, MN.
U.S. EPA. 1978. In-depth studies on health and environmental
impacts of selected water pollutants. (Table of data available
from Charles E. Stephan, U.S. EPA, Duluth, MN.)
IV-2
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SECTION V. EPA CONTACTS
AQUATIC LIFE ADVISORIES
For further information regarding the aquatic life and fish and
water exposure advisories contact:
FTS 382-7144 (202)382-7144
FTS 475-7315 (202)475-7315
V-l
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