JUSTIFICATION FOR CREATION AND PROMULGATION OF NEW

AQUATIC LIFE AND HUMAN HEALTH CRITERIA FOR

PERCHLORATE

WATER QUALITY DIVISION

14 OCT 2006
JUSTIFICATION FOR CREATION AND PROMULGATION OF NEW AQUATIC
LIFE AND HUMAN HEALTH CRITERIA FOR PERCHLORATE

INTRODUCTION

Perchlorate is an inorganic chemical ion consisting of chlorine bonded to four oxygen atoms
(Figure 1). Because it is ionic, it is usually seen in association with a carrier ion such as sodium,
potassium, or ammonium and readily dissociates in water. Perchlorate occurs both naturally and
as a manmade compound. Manmade perchlorate compounds have been manufactured since
before the turn of the last century, primarily for use in defense activities and the aerospace
industry as a strong oxidizer of explosives and solid rocket boosters. It has also been found in
fireworks, airbag deployment charges in cars, road flares, and fertilizers.

Highly soluble and mobile in water, perchlorate is also very stable. An overview of the physical
properties of ammonium perchlorate can be seen in Attachment 1. Most of the attention focused
on perchlorate contamination concerns drinking water contamination. However, because of its
mobility and highly soluble nature, it can also be found in soil and vegetation. The potential for
perchlorate contamination in drinking water and food supplies is a human health concern,
because it can interfere with iodide uptake by the thyroid gland, and through this mode of action
result in decreased thyroid hormone production. Perchlorate was successfully used for decades
as a treatment for hyperthyroidism (Graves disease). Its specialized endocrine interference
capability was particularly effective in this application. It was still in widespread use into the
1960’s.

However, it is also a concern for fish and wildlife for similar reasons. Retardation in embryonic
development has been noted (Crane et. al, 2005) in Pimephales (fathead minnow) larvae as
well as Xenopis laevis, the African clawed frog (Goleman et. al, 2002). Developmental delays in
coloration, scale development, primary sexual characteristics and body size are among those
effective traits noted in various species.

In general, past management practices did not prevent the release of perchlorate to the
environment because it was not recognized or regarded as a contaminant of concern. Many out-
of-date munitions were simply buried and allowed to degrade naturally. Widespread perchlorate
contamination in the United States was observed after the spring of 1997 when an analytical
method was developed with a quantitation level (MQL) of 4 ppb. Additional sampling and
analysis techniques have since been developed that can detect perchlorate at concentrations of
1 ppb and lower.

The majority of the research attention of late has focused on the direct human health effects
through “end of tap” and other consumptive pathways. Most states are spending the majority of
their efforts establishing clean up targets.

While it was once thought to occur naturally only in one location in Chile, ongoing study has
found naturally occurring perchlorate in other locations as well. Various hypotheses have been
forwarded in an attempt to explain these developments and help in discriminating between
natural and anthropogenic sources. Lightening (Dasgupta et. al, 2005) is one of the more
interesting possibilities being offered at the current time. Walvoord (2003) suggests that
atmospheric ozone reacting with sodium chloride, carried aloft from ocean evaporation, may be

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Figure 1: A “Lewis dot structure”, with associated atomic charges, and a 3-D representation of
the perchlorate ion.

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responsible for creating significant amounts of perchlorate. Much of the “contamination” being
reported today may simply be the result of natural atmospheric processes and rainfall and more
sensitive testing technologies. Several authors have proposed chemical processes related to
arid landscapes and ancient marine sediments since there seems to be a widespread
appearance of naturally-occurring deposits (Orris et. al, 2003 and others).

McAlester Army Ammunition Plant (McAAP), ODEQ and OWRB staff have met and discussed
this issue since July 2004 when it became clear to McAAP that there was a pending Department
of Defense (DoD) requirement to modify the formulation of many of their explosives. This
modification, intended to make munitions more insensitive and “shock tolerant”, would require
them to add perchlorate (Stephen Maloney, U.S. Army Engineer Research and Development,
personal communication). They approached ODEQ staff for assistance in determining how
extensive the additional treatment works would have to be since conventional treatment is
ineffective for most concentrations that were expected in the effluent. The DoD, through
universities and research groups, had developed a process of treating wastewater contaminated
with perchlorate, but the size of the plant would be based upon the anticipated wasteload using
the final criterion as the target.

PROPOSAL

Beginning in 2004, OWRB technical staff have researched the feasibility of developing a set of
criteria for the perchlorate ion. These efforts were motivated by the need for McAlester Army
Ammunition Plant (McAAP) to begin incorporating ammonium perchlorate into their explosive
formulations. This change in the explosives formulation will result in a change in the nature of
their effluent and therefore will require a revision of their permit. Other locations in Oklahoma
have also come to light as possibly needing a permit limit for perchlorate, such as the former
Cardox manufacturing plant near Claremore (figure 1).

The Department of Defense recognizes their responsibility as a discharger and has gone to
great lengths to retain the necessary expertise to develop the treatment technology appropriate
for perchlorate. Parson’s Engineering, the Corps of Engineers, the University of Cincinnati and
other technical groups within the DoD itself have participated in this effort.

OWRB technical staff has investigated the various options for criteria development and
determined that formal scientific underpinnings are sufficiently evolved that they can be used to
justify promulgation.

Based upon extensive research and multiple meetings with staff from DEQ, McAAP and OWRB,
the results of our calculations and the subsequent proposals are as follows:

• Fish and Wildlife Propagation acute criterion, 6.6 mg/L applied at 7Q2 and
acute regulatory mixing zone,
• Fish and Wildlife Propagation chronic criterion, 1.8 mg/L applied at 7Q2 and
chronic regulatory mixing zone, and
• Fish Flesh and Water criterion, 9µg/L applied at long-term average receiving
stream flow and complete mix.

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Figure 1: A map of perchlorate detections and users across EPA Region 6.

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JUSTIFICATION

I. Aquatic Life Criteria

Provisions currently exist in Oklahoma’s Water Quality Standards, found in Title 785 Oklahoma
Administrative Code 45-5-12(f)(6), that allow for calculation of criteria for parameters not listed
in the WQS. Specifically,

“(D) For toxicants not specified in Table 2 of Appendix G of this Chapter,

concentrations of toxic substances with bio-concentration factors of 5 or less shall not
exceed 0.1 of published LC50 value(s) for sensitive representative species using standard
testing methods, giving consideration to site specific water quality characteristics.
(E) Concentrations of toxic substances with bio-concentration factors greater than 5
shall not exceed 0.01 of published LC50 value(s) for sensitive representative species
using standard testing methods, giving consideration to site specific water quality
characteristics.”

As part of the research and development efforts initiated by the Department of Defense,
Parson’s Engineering was contracted to perform toxicity testing on a variety of organisms and,
following EPA guidance and protocol, propose a criterion maximum concentration (CMC) and a
criterion continuous concentration (CCC) for perchlorate. These are generally accepted as
being the acute and chronic criteria respectively.

The following is a recap of the pertinent findings of the Parsons paper (Dean et al., 2004).

Used EC50 (effective concentration) values in addition to LC50 for some applications
EC50 likely to be more conservative as it uses a sub-lethal end-point established prior to
testing
Acute EC50 for Ceriodapnia dubia (most sensitive of species tested) reported at 66 mg/L,
chronic EC50 reported at 18.2 mg/L
Draft paper confirms that BCF’s have not been calculated for species of concern but
existing evidence supports conclusion that most will be far less than “1” *
Calculated CMC (acute) = 20.0 mg/L and CCC (chronic) = 9.3 mg/L based upon their
test results

*based upon the octanol/water Partition coefficient Kow = 1.4 x 10-6, (log Kow = -5.84)

Using existing OWRB citation above, as well as data and reported LC50 values from Parson’s
report, the aquatic life acute criterion is suggested to be 6.6 mg/L and chronic criterion to
be 1.8 mg/L. This conservative approach will consider the sub-lethal effects on amphibians and
some fish larvae noted in some other publications.

Criteria are to be applied at edge of the appropriate regulatory mixing zone boundary.

II. Human Health Criteria

The goal of human health criteria is to protect a normal healthy population with a lifetime of daily
exposure while considering sensitive sub-populations (e.g. children and pregnant women). This
is a highly contentious issue, especially when considering that perchlorate is a substance that

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was used for decades as a medication for hyper-thyroidism (Grave’s disease) and the wide
variance in human responses and pharmacokinetics.

The following is a description of the USEPA (2000) formula for calculating an ambient water
quality criterion for human health protection for exposure to a non-carcinogenic substance
through consumption of fish flesh and water.

 
 BW 
AWQC = RfDxRSCx  4

 DI + ( FI xBAF ) 
 ∑
i =2
i i 


where:

RfD = reference dose for non-cancerous effects (mg/kg-day)

RSC = relative source contribution, states how much of the total exposure will be
accounted for through this route (may be multiplied or subtracted depending
upon whether multiple criteria are relevant to the chemical)
BW = body wt. (default 70kg for adult), may be altered to account for sensitive
populations (e.g. 25kg for children, etc)
DI = drinking water intake (2L/day for adult)
FIi = fish intake per trophic level (TL) of I (I=2,3, and 4),
Total intake defaults to 0.0175 kg/day for general public, 0.1424 kg/day for
subsistence fishermen
(TL2=0.0038 kg/day, TL3=0.0080 kg/day, TL4=0.0057 kg/day)
BAFi = lipid normalized bioaccumulation factor per trophic level (L/kg)

The first and most contentious variable used herein is the “reference dose”. This is defined as
the amount of a substance that a healthy individual can be exposed to without adverse effect.
Very few studies appear to adequately address this issue and there is a wide range of opinions
and testing results. For example, in a 2002 document still under external review, EPA proposed
a value of 0.00003 mg/kg/day (revised from 0.005 – 0.0002 range) while Greer (2002) proposed
0.007 and Dollarhide (2004) proposed 0.002. Of all these, only the Greer and Dollarhide studies
used actual human test subjects.

The “relative source contribution” (RSC) attempts to reflect the percentage of the total exposure
to be reflected by this route of exposure. It is limited by EPA guidance to 0.2 to 0.8 (20-80% of
total exposure) with 0.20 being the default.

While the “bioaccumulation factor” (BAF) is not currently published for any perchlorate
compound, a few taxa have “bioconcentration factors” (BCF’s) calculated (0.70 L/Kg for
Lepomis macrochirus, Dean et al., 2004), but very little has been published in a usable
framework for these purposes. One possible alternative is to default back to EPA national
guidance which allows for predicting BAF from a variety of methods. However, this process is
very complicated and produces results of only medium confidence.

The following table details the variables used in calculation:

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 RfD RSC BW DW INTAKE FISH BAF SUGGESTED
(mg/kg/day) (KG) (L) INTAKE (mg/kg) CRITERION
(kg/day) (mg/L)
0.00200 0.2 45 2 0.0175 1 0.009

 
 45 
AWQC = 0.002 x0.20 x  4
 = 9µg/L
 2 + (0.0175 x1) 
 ∑
i=2


The following are justification for the values used in calculation:

• most stringent RFD of valid human studies
• default RSC, based upon the assumption that the majority of exposure WILL NOT be
from fish flesh or water routes, no evidence to suggest otherwise
• default BW (70 KG) modified to 45kg to account for sensitive sub-populations
(children and pregnant women)
• default DW intake
• default fish intake (non-subsistence fishermen)
• BAF is conservative assumption, assumed to be “1” (flesh concentration equivalent
to water concentration) since most literature acknowledges some bio-accumulation
but only one was found that attempts to quantify it (Dean et al., 2004), no evidence of
long-term retention

Using the above justification and calculation, the proposed criterion for the perchlorate
ion for the protection of Fish Flesh and Water Beneficial Use is 9µg/L.

This criterion is to be applied in the stream after “complete mix”.

ECONOMIC CONSIDERATIONS

There are limited economic impacts anticipated for this proposal. McAlester Army Ammunition
Plant has already begun planning the expansion of their wastewater treatment processes to
include fluidized bed reactors to reduce perchlorate to a non-toxic by-product. Other current or
future permit holders could be affected by this action, but those activities are still under review to
determine if permit limits are appropriate and what the possible economic impacts could be.

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References

Crane, H.M., D.B. Pickford, T.H. Hutchinson and J. A. Brown. 2005. Effects of Ammonium
Perchlorate on Thyroid Function in Developing Fathead Minnows, Pimephales promelas.
Environmental Health Perspectives. Vol. 113 No. 4. 396-401.

Dasgupta, P.K., P. J. Nartubekabgim, W.A. Jackson, T.A. Anderson, K. Tian, R.W. Tock and S.
Rajagopalan. 2005. “The Origin of Naturally Occurring Perchlorate: The Role of Atmospheric
Processes,” Environmental Science and Technology 39(6): 1569-1575.

Dean, K. E., R. M. Palachek, J. M. Noel, R. Warbritton, J. Aufderheide, and J. Wireman. 2004.

“Development of Fresh Water-Quality Criteria for Perchlorate,” Environmental Toxicology
and Chemistry 23: 1441–51.

Dollarhide, J., Q. Zhao, and M. Dourson. 2004. Reference Dose for Perchlorate Based Upon
Human Studies. Toxicology Excellence for Risk Assessment. In review.

Greer, M., G. Goodman, R. Pleus, and S. Greer. 2002. Heath Effects Assessment For
Environmental Perchlorate Contamination: The Dose Response for Inhibition of Thyroidal
Radioiodine Uptake in Humans. Environmental Health Perspectives. Vol 110, no. 9. pp.
927-937.
Goleman WL, Urquidi LJ, Anderson TA, Smith EE, Kendall RJ, Carr JA. 2002. Environmentally
relevant concentrations of ammonium perchlorate inhibit development and metamorphosis
in Xenopus laevis. Environ Toxicol Chem 21:424–430.

Orris, G.J., G.J. Harvey, D.T. Tsui, and J.E. Eldridge. 2003. Preliminary Analaysis for
Perchlorate in Selected Natural Materials and Their Derivative Products. U.S. Geological
Survey Open File Report 03-314.

U.S.E.P.A. 2002. Perchlorate Environmental Contamination: Toxicological Review and Risk

Characterization. NCEA –1-0503. In review.

U.S.E.P.A. 2000. Methodology for Deriving Ambient Water Quality Protection for the Protection
of Human Health. EPA-822-B-00-004

Walvoord, M. A.; Phillips, F. M.; Stonestrom, D. A.; Evans, R. D.; Hartsough, P. C.; Newman, B.
D.; Striegl, R. G. A reservoir of nitrate beneath desert soils. Science 2003, 302, 1021-1024.

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Attachment 1: Properties of ammonium perchlorate

(NH4ClO4)
CAS No. 7790-98-9
Molecular Weight = 117.49 g/mol
White orthorhombic crystal
Density/SpecificGravity = 1.95 g/cm3
Solubility = 200 g/L @ 25°C (6.4 oz, 0.4 lb)
Sorption Capacity Very low
Octanol/Water Partition Coefficient Kow = 1.4 x 10-6 (log Kow = -5.84)*
(EXTREMELY HYDROPHYLIC, VERY LOW BCF)
Inorganic salt, non-conservative but difficult to remove from solution because it’s so
hydrophylic
Biologically reduced to chloride

* from Risk Analysis, Communication, Evaluation, and Reduction at LANL

(Perchlorate in Groundwater)
August 15, 2003
Kimberly A. Groff, Ph.D., EarthSolve, Inc.
Julie L. Wilson, Ph.D., CIH, EnviroIssues, Inc.
Peter Shanahan, Ph.D., P.E., HydroAnalysis, Inc.
Principal Investigator
John E. Till, Ph.D., Risk Assessment Corporation

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