' -4?
Journal of Environmental Management (1999) 56, 79—95
Article No. jema.1999.0274, available online at httpvywww.idealibrary.com on
Issues in  managing  the  risks
associated  with  perchlorate  in
drinking  water1
E. T. Urbansky* and M. R. Schock
Perchlorate (CIO4~) contamination of ground and surface waters has placed drinking water supplies at risk
in communities throughout the US, especially in the West. Several major assessment studies of that risk in
terms of health and environmental impact are expected to be released by the US Environmental Protection
Agency in early 1999, and preparations for how best to manage and minimize that risk are underway.
Perchlorate salts are used in rocket and missile propulsion; therefore,  it is believed that the pollution is
derived primarily from defense and supporting industry. Due to the perchlorate anion's fundamental physical
and chemical nature, the contamination is difficult to treat or remediate. The current work describes the
evolution of the unique team-based governmental response to the problem and the rapidity of its development.
Technologies under consideration that may prove feasible  for treating contaminated water supplies are
discussed and evaluated.  The impact of these treatment technologies on other regulatory compliance
matters and limitations  of space,  cost, and other resources are considered.  Practical guidelines for
approaching the problem are outlined, and current research needs are identified.

Keywords: perchlorate, risk management, risk assessment, drinking water, potable water,
biodegradation,  electroreduction,  anion exchange, electrodialysis, membrane filtration, water
treatment, regulatory impact, infrastructure, water utility.
Introduction

At least 11 American states have sites where
perchlorate-contaminated   effluents  have
been discharged into sewage streams or nat-
ural waters and where aquifers or waterways
may be contaminated with this  species. The
perchlorate ion (C1O4~,  Figure 1) is likely to
be found in locations where perchlorate salts
have ever been manufactured or used. Per-
chlorate salts are used as energetics boosters
or solid oxidants in rockets and missiles; con-
sequently, the  source of the pollution is tied
largely to the  military,  space program and
supporting industries.  The US Air  Force
(USAF), National Aeronautics and Space Ad-
ministration (NASA), and a host of defense
  lrThis work was completed by US Government em-
ployees acting in their official capacities. As such, it
is in the public  domain and not subject to copyright
restrictions.
contractors   and  perchlorate  salt  man-
ufacturers2 are potentially responsible for the
release and site clean up (Fields, 1998). It is
undeniable that an important way of dealing
with such water pollution is to prevent it in
the first place by keeping the water from
contacting polluted soil or industrial waste,
as might be accomplished with impermeable
barriers, for instance. While such efforts must
be part  of overall risk management, this
paper will focus on issues dealing with water
that has already been contaminated with per-
chlorate and making that water safe for con-
sumption, primarily  by various treatment
processes.
  We explore a variety of issues that must
be faced by anyone who drinks, treats, uses
or regulates drinking water. In addition, we
address regulatory compliance issues and the

  2 The industrial potentially responsible parties include
Aerojet, Alliant Techsystems, American Pacific/Western
Electrochemical  Company,  Atlantic Research Cor-
poration, Kerr-McGee Chemical Corporation, Lockheed
Martin, Thiokol Propulsion Group and United Tech-
nologies Chemical Systems (Fields, 1998).
* Corresponding author

United States
Environmental Protection
Agency (EPA), Office of
Research and
Development, National
Risk Management
Research Laboratory,
Water Supply and Water
Resources Division,
Treatment Technology
Evaluation Branch,
Cincinnati, Ohio 45268,
USA

Received 10 November
1998; accepted 5 March
1999
0301-4797/99/060079+17 $30.00

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80  E. T. Urbansky and M. R. Schock
                    Figure 1.  Structure of the perchlorate ion. This
                    drawing  of a  space-filling  model  shows  the
                    tetrahedral orientation of the  four oxygen  atoms
                    around the central chlorine(VII). The oxygen atoms
                    sterically block reductant molecules from direct
                                attack at the chlorine.
                    difficulties in making technologies work to-
                    gether so that one does not adversely affect
                    another. Risk management for potable water
                    (like any other risk) is dependent upon avail-
                    able resources: space, time, money. How much
                    should a glass of water cost? How pure must
                    it be? We discuss the issues for consumers,
                    water utilities  and regulatory  agencies  as
                    well as  some guidelines we hope will prove
                    useful in resolving them. We offer general
                    information on  individual treatment strat-
                    egies, including applicability, advantages and
                    disadvantages—framed in  terms  of regu-
                    latory  and other restrictions.  Risk man-
                    agement for drinking water has traditionally
                    focused on treatment of contaminated water;
                    however, we suggest that there are a number
                    of ways of managing risk that, taken together,
                    can meet the ultimate goal of protecting pub-
                    lic health.
                      Much of the  recent federally funded re-
                    search has focused on the toxicological and
                    ecological  impact of  perchlorate  contam-
                    ination  and  therefore  is directed  towards
                    assessing risk, rather than managing it. The
                    primary target organ appears to be the thy-
                    roid gland, although other effects are known
                    (Urbansky, 1998; Von  Burg, 1995, and ref-
                    erences therein). Until a final reference dose
                    (RfD) or a no observable adverse effects level
                    (NOAEL) is established by the  US En-
                    vironmental  Protection Agency (EPA) Na-
                    tional Center for Environmental Assessment
                    (NCSA), risk management must  aim for a
                    moving target. Risk management has focused
                    on technologies that can lower perchlorate
                    concentrations to those levels which are un-
                    detectable by ion chromatography, i.e. below
5 ng ml"1 (jag I"1). Regardless of what NOAEL
is set  and  whether  perchlorate is  ever
regulated,3 water utilities in California and
Nevada have expressed interest in  lower-
ing perchlorate to undetectable  levels.  In
addition,  a number of consumer interest,
conservationist and environmentalist organ-
izations advocate setting  a level of zero  as
the goal for treated potable water. This com-
bined effort is driving the development of
technologies that will lower perchlorate con-
centrations to <5 ng ml"1 while ensuring that
total water quality is not compromised.
Evolution of governmental
response

When the  analytical  capabilities  of  ion
chromatography (1C) methods had improved
sufficiently that   aqueous  solution   con-
centrations as low as 5 ng ml"1 could be meas:
ured  reliably, studies  by the industry and
California agencies showed a number of con-
taminated  aquifers, wells and  surface wa-
terways. The EPA Region 9 office4 was already
aware of some of  these sites on account of
other contaminants, such as volatile organic
compounds. Shortly thereafter, the EPA Na-
tional Exposure Research Laboratory became
involved in a search for confirmatory tech-
niques and methods of chemical analysis.
At the same time, the USAF and Air Force
Research Laboratories were refining 1C work
and considering what studies might be neces-
sary.
  In the meantime, a perchlorate issue group
was assembled by local utilities6 to examine
the problem.  It issued a report  proposing
certain strategies  and identifying  several
areas of research need, based on information
available at the time. Subsequently, Congress
appropriated $2 million to one of these util-
ities (E VWD) to begin to carry out appropriate

  3 The EPA Office of Water added perchlorate to the
Contaminant Candidate List (CCL) as of 2 March 1998;
however, it is unknown whether this will lead to the
promulgation of a maximum contaminant level (MCL)
for potable water (US EPA, 1998a).
  4 Region 9 includes the states of California, Nevada,
Arizona and Hawaii and the protectorates of American
Samoa and Guam.
  5 The utilities were the East Valley Water District,
Main San Gabriel Watermaster, Metropolitan Water Dis-
trict of Southern California, San Bernardino Valley Mu-
nicipal Water District and Southern  Nevada Water
Authority.

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                                                                     Perchlorate risk management issues   81
studies.6 As the  health effects  and eco-
toxicology of perchlorate had been only min-
imally explored, a group of scientists was
convened to propose  and rank the studies
necessary to accurately assess the risks as-
sociated with perchlorate in the environment.
At  present, eight separate investigations
have been conducted  (funded by the USAF
and guided  by NCEA), and results are an-
ticipated to  be released in early  1999 after
completion  of the  external peer  review
(Fields, 1998; US EPA, 1998a). Since fall
1997, there  has been  a sense of urgency as-
sociated with this process, and the timeframe
for the risk  assessment  has  been  un-
precedented for the EPA (Farland, 1998).
A case study in cooperation

There are two particularly unique qualities
to the process that has followed the discovery
of this pollutant. First and foremost has been
the team approach. There has been a strongly
interactive,  cooperative spirit  among the
agencies and employees involved. The for-
mation of the Interagency Perchlorate Steer-
ing Committee (IPSC) with representatives
from throughout the federal government (see
Table 1) is an unprecedented development in
the history of dealing with water pollution.
Although statutory obligations require that
agencies maintain budgetary and adminis-
trative control over their respective domains,
the interaction has proved invaluable in en-
suring the rapid dissemination of information
and the  up-front consideration of alternate
(and sometimes conflicting) requirements. By
involving interested parties from the start, it
has ensured that all concerns and obligations
have been met, and  it has minimized last
minute objections to  recommendations and
conclusions. It is worth pointing out that
the formalization of the IPSC was a gradual
evolution as more agencies became involved
and roles took shape; it was not a directive
from senior management. Initially, it began
as a combined effort among the staffs of vari-
ous agencies to find out how much was known,
  6 The East Valley Water District (EVWD) has con-
 tracted with the American Water Works Association
 Research Foundation (AWWARF)  to carry out this
 research. Projects can he found at the AWWARF
 internet website: http://www.awwarf.corn/newprojects/
 perchlor.html
who was doing what,  and what should be
done next. By early 1998, it had become clear
that there was in fact a fairly well-defined
team with similar goals  and a commitment
to accomplishing them.
  The IPSC has thus far proven itself to be
a model for  attacking future pollution prob-
lems. Interagency Perchlorate Steering Com-
mittee meetings have remained open; PRPs,
government and university researchers, pri-
vate organizations, industry and corporate
representatives, and state and local agencies
have all been free to address the full com-
mittee or to inquire about the status of pro-
jects or action items.  Professionals  from a
wide variety of backgrounds  and expertise
were brought in at the beginning, including
risk management  (water treatment and re-
mediation) and exposure (chemical analysis
and occurrence)  among  others. This has
helped to balance the vision  as opposed to
the more traditional linear approach in terms
of  completing  detailed  risk  assessment
(health  effects), then developing analytical
methods and  determining occurrence, and
finally managing risks.
  The second unique quality has been the ex-
tremely rapid progression of events. This has
been made possible only through concurrent
work in several fields. Of course, this could not
have been done without the integrated ap-
proach and inclusion of so many people up
front. Since the discovery of the expanding
low-level perchlorate plumes in late  1996, a
network of perchlorate manufacturers, con-
sumers, researchers and regulators has been
established. The risk  assessment is  nearly
complete. There is a large body of analytical
chemistry  data  to draw  on,  and  inter-
laboratory method validation is well on its
way. Sites likely to be contaminated have been
identified, and there is a fairly comprehensive
body of data on occurrence throughout the
nation. Initial strategies for risk management
have been identified, and pilot scale tests are
underway for some technologies. As informa-
tion has been shared from the start, the regu-
latory community is prepared to receive the
risk assessment and is  familiar with tech-
nologies available for risk management. Of
course,  refinement and  eventual   imple-
mentation of risk management technologies
for water treatment and site remediation will
require the risk assessment results expected
in early 1999.

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82   E. T. Urbansky and M. R. Schock
                     Table 1.  Principal agencies involved in cooperative planning and discussion over how to handle perchlorate
                     pollution0

                     US military and space programs
                       US Air Force (USAF) and Air Force Research Laboratories (AFRL)
                       US Army
                       US Navy
                       National Aeronautics and Space Administration (NASA)
                      IS Environmental Protection Agency
                       Office of Research and Development (ORD)
                       National Center for Environmental Assessment (NCEA)
                       National Risk Management Research Laboratory (NRMRL)
                       National Exposure Research Laboratory (NERL)
                       National Health and Environmental Effects Research Laboratory (NHEERL)
                       Region 6 office6
                       Region 9 office0
                       Office of Solid Waste and Emergency Response (OSWER)
                       Office of Emergency and Remedial Response (OERR)
                       Office of Water (OW)
                       Office of Science Policy (OSP)
                      undry US federal research agencies
                       National Institute of Environmental and Health Sciences (NIEHS)
                       Oak Ridge National Laboratory (ORNL)
                       Lawrence Livermore National Laboratory (LLNL)
                       Agency for Toxic Substances and Disease Registry (ATSDR)
                       National Institute for Environmental and Health Sciences (NIEHS)
                       US Geological Survey (USGS)
                      tate agencies
                       Utah Department of Environmental Quality
                       Utah Department of Health Laboratories
                       Nevada Division of Environmental Protection
                       California Department  of Health Services
                       Arizona Department of Environmental Quality
                      ocal authorities
                       East Valley Water District
                       Main San Gabriel Watermaster
                       Metropolitan Water District of Southern California
                       San Bernardino Valley  Municipal Water District
                       Southern Nevada Water Authority
                       Las Vegas Valley Water District

                      • Many agencies have been involved along the way, including state and county health or environmental protection
                     departments or public utilities; however, the agencies listed here have been responsible for and continue to guide this
                     effort. Some of the agencies listed in this table have been involved primarily in technical or scientific consulting roles.
                     Note that the IPSC is comprised only of US federal agencies.
                      6 Region 6 includes the states of Arkansas, Louisiana, New Mexico, Oklahoma and Texas.
                      c See footnote 4.
                     Physical and chemical properties of
                     perchlorate

                     The chemistry of perchlorate was reviewed
                     in-depth  in a previous  paper  (Urbansky,
                     1998). Nevertheless, several key points neces-
                     sary  for  understanding  risk  management
                     strategies bear  repeating  here. The  per-
                     chlorate ion (C1O4~) is the most oxidized form
                     of chlorine that exists in water. It is a strong
                     oxidizing  agent (oxidation state  +7). Other
                     Cl711 compounds,  namely, C1F7 and C12O7, are
both hydrolyzed to perchlorate. When re-
duced to chloride in acidic solution it has a
standard reduction potential of 1-29 V (Bard
et al,  1985;  Emsley,  1989),  making it  a
stronger oxidant than oxygen, but  not so
strong as dichromate:


C1O4- + 8e- + 8H+ -+Cl- +4H2O E° = 1-29V
                                         (1)

When dilute (<10% w/w) or in weakly acidic
to basic (pH> 1) aqueous solution, perchlorate

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                                                                     Perchlorate risk management issues  83
is so non-labile as an oxidizing agent—, i.e., it
reacts so slowly—with most reducing agents
that no reaction is observable (Schilt, 1979).
Only extremely reactive air-sensitive trans-
ition metal species show any observable redox
reaction, making perchlorate famous for its
lack of lability (Urbansky, 1998). This be-
havior results from the high strength of the
chlorine-oxygen bonds and the requirement
that reduction must proceed initially by oxy-
gen atom abstraction rather than a direct
involvement  of the central chlorine  atom.
This kinetic behavior is illustrated in Figure
2.  The abscissa marks the progression of a
reaction between  a perchlorate  ion and a
general reducing  agent R, capable of  ac-
cepting an oxygen atom. The conversion to
chlorate shown in Equation (2) is generally
regarded as the first step in perchlorate re-
duction:
                                       (2)
The reaction is thermodynamically favored
as shown by AE<0, i.e. the products have
lower  internal energy  than the reactants.
Nonetheless, the reaction rate is controlled
by the kinetic barrier of the high activation
energy Ea of the transition state, the location
of which  is marked by the diesis  (f). Sub-
sequent steps in the process are much less
kinetically hindered.
                Reaction progress
 Figure 2.  Energy profile for the rate-limiting step
 in perchlorate reduction [Equation (2)], abstraction
 of the first oxygen atom. The kinetic barrier is the
 result of the high activation energy, Ea, despite the
 fact that the  reaction is driven forwards by the
          release of energy,  i.e., AE<0.
Available treatment
technologies

Ideally, a technology should be able to handle
concentrations  ranging  from  ^Sngml"1
(Ugl-1) all the way to  ~10mgml-1  (gT1).
Most of the affected regions have perchlorate
concentrations  below 0-5 nig ml"1; however,
concentrations  as high  as S-Tmgml"1 have
been encountered. The  Colorado River and
several California wells  show concentrations
in the range of 8-30 ng ml"1 (ng I"1). Current
technologies can be divided into two primary
categories:  destruction  and removal.  De-
struction is generally regarded as a preferable
process because it  eliminates the need for
subsequent disposal  of removed material,
which  is regarded as a  hazard in this case.
Each of the techniques is described briefly,
and the strengths and  weaknesses of these
technologies are summarized  in Table  2.
Regulatory  and other impacts some of these
techniques  will be addressed  or expanded
upon in a later section.
Chemically destructive processes

As perchlorate does not exhibit its oxidizing
properties under the conditions found in con-
taminated raw and treated waters, it cannot
be reduced with common agents,  such  as
thiosulfate  (S2O32-), sulfite (SO32-) or ele-
mental metals (e.g. Fe, Zn, Cu). To be a can-
didate for consideration in drinking water
treatment,  a technique must demonstrate
that it can overcome the high activation en-
ergy associated with perchlorate reduction.
The speed of the rate limiting step [such as
that shown in Equation (2)] must be in-
creased.
Biological reduction

At the present time, biological reduction ap-
pears to  hold the most promise for large-
scale treatment of perchlorate-laden waters.
Several genera of micro-organisms are cap-
able of using perchlorate as an oxidant (elec-
tron acceptor) for metabolism (Logan, 1998;
Urbansky, 1998). It is generally accepted that

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84   E. T. Urbansky and M. R. Schock
                    Table 2.  Pros and cons of currently available drinking water treatment technologies

                    Technique                  Pros                    Cons

                    Biological reduction
                    Electroreduction
                    Anion exchange
                    Membrane filtration
                    Electrodialysis
Selective
Fairly rugged
Fairly fast
Other contaminants also
  destroyed
Low operating cost
No waste products
Low maintenance
Easily implemented
Moderate maintenance
Fairly inexpensive
Existing technology
Existing technology
Highly effective
Fast
Ideal for point-of-use
Existing technology
Highly effective
Fast
Ideal for point-of-use
Unknown pathogenesis
Food source needed
O2 competition
Unknown byproducts
Moderate/high monitoring and maintenance
Insufficiently developed at this time
Difficult to implement in existing facilities
  with high output
Electricity consumption/high operating cost
Worker safety
Difficult to implement in existing facilities
  with high output
Insufficiently developed at this time
Regeneration/down time
Hard to make selective
Waste disposal (from regeneration)

Maintenance
Membrane corruption
Concentrate disposal
Not selective
Electricity consumption/moderate operating
  cost
Membrane corruption
Concentrate disposal
Not very selective at this time
                    these microbes possess a reductase (an en-
                    zyme) that allows  them to  lower  the ac-
                    tivation energy of perchlorate reduction and
                    thereby make use of the energy for cellular
                    respiration. In addition, at least some strains
                    make use of  a  chlorite (C1O2~) dismutase,
                    which allows direct conversion of chlorite to
                    chloride and water, without formation of cyto-
                    toxic hypochlorous acid (HOC1).
                      Unfortunately, some of these  organisms
                    cause disease and/or prefer oxygen. When
                    incoming water contains a significant con-
                    centration  of  dissolved oxygen,  a  large
                    amount of reductant (food) may be consumed
                    by the organisms without any reduction of
                    perchlorate. Any organisms known or found
                    to be pathogenic  are likely to be excluded
                    for obvious reasons. Even if  the water is
                    subsequently  subjected to  disinfection,  it
                    seems ill-advised to intentionally introduce a
                    pathogenic organism. The bacterial genera
                    that are the likely candidates remain un-
                    studied at this time, but all are anticipated
                    to be non-pathogenic. Harding Lawson As-
                    sociates, an engineering firm operating  in
                   Region 9, has developed bioreactors based on
                   organisms found in sludges (Catts, 1998). The
                   US Air  Force  has developed a bioreactor,
                   isolated the active microbe and identified it as
                   the bacterium  Wolinella succinogenes HAP-
                   1 (Wallace et al, 1996). The fluidized bed
                   biological reactor (FBBR) is  a popular ap-
                   paratus  for biodegradative treatment.  The
                   USAF process is geared towards wastewater
                   treatment; nonetheless,  there is reason to
                   believe it is applicable to potable water and
                   some research  is directed along these lines.
                   Both the  USAF and Harding Lawson reactors
                   were able to reduce effluent perchlorate con-
                   centrations to below 5 ng ml"1. Shown in Fig-
                   ure  3,  the usually  funnel-shaped  FBBR
                   makes use of an inert support medium (e.g.
                   granular carbon)  on  which microbiota are
                   grown. The FBBR's shape results in  high
                   influent  water velocity,  so that the water
                   suspends the medium. As the FBBR widens
                   towards  the top,  the  water  velocity is in-
                   sufficient to  suspend the  medium,  which
                   settles out. This  eliminates the need for a
                   filter to retain the bioactive medium. Smith

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                                                                       Perchlorate risk management issues   85
                               QP
Figure 3.   Fluidized bed biological reactor (FBBR).
Untreated water enters the bottom with high velocity,
which allows it to support the bed of supporting
medium (which the microbial population grows on).
Due to the shape of the FBBR, the  water loses
velocity with altitude, and the medium settles out
before  the  effluent is discharged. Although not
shown in the diagram, FBBRs are often constructed
with a recycle loop that increases the residence time
                of the water.
and Stewart (1998) constructed an FBBR
using Celite® as the support; they inoculated
their reactor with sludge from an anerobic
municipal waste digester  and fed  the mi-
crobes cheese whey. Their FBBR reduced per-
chlorate concentrations from l-Sngml"1 in
the influent to  rcSngml"1  in the effluent.
 Electrochemical reduction

 It is possible to reduce perchlorate to chloride
 using an electric current applied directly to
 the water by a cathode at high potential. A
 number of different materials have been used
 as cathodes, including platinum,  tungsten
 carbide, ruthenium, titanium, aluminum and
 carbon doped with  chromium(III)  oxide or
 aluminum oxide (Urbansky, 1998). There are
 several problems with electroreduction, most
 notably, the time required to get ions to the
electrode surface from the bulk water as well
as the time required for them to associate
with the surface. Electrode corrosion, surface
passivation  and  natural  organic  matter
(NOM) adsorption to the surface present tech-
nological  difficulties. Skillful design  could
likely overcome at least some these, however.
While  this technology is well-established for
such industrial processes as metal electro-
plating or brine electrolysis, it has not yet
been  implemented  in  the  potable  water
industry, probably because there has  never
been any real need. Figure 4 shows the ex-
pected oxidation and reduction half-reactions
for a simple electrolytic cell.  An actual elec-
trolytic cell used for this process would more
reasonably be modeled on a  diaphragm cell
used for brine electrolysis.
 Physical removal

 Physical removal processes work exactly as
 the name suggests; they physically separate
 the perchlorate ion from the drinking water.
 As these techniques do not destroy the per-
 chlorate, they create a subsequent need for
 disposal of both the perchlorate and any
 waste products  of the process. In addition,
 all of these techniques currently suffer from a
 lack of selectivity. Along with the perchlorate,
 they tend to remove or replace unacceptably
 large quantities of beneficial dissolved salts
 or their component parts. Deionized water
 presents a corrosion and disinfection problem
 for  distribution systems, resulting  in aes-
 thetic degradation of the  water,  and po-
 tentially  detrimental  health   effects  by
 increased mobilization of toxic trace metals
 (e.g. lead). Although these technologies are
 all well-established, they will be difficult to
 use in large systems, mainly because of the


Cathode ,

Reduction
C1O4" + 8e~ + 8H+ -»•
Cr + 4H20

!*
;;*

1 Anode

•'£•
.-, ,:{•*'
/*.

r;
Oxidation
(2H20-^02

-j'?
IN
*«

4-4

                                                                - 4H+) x 2
  Figure 4.  Simple electrolytic cell of the reduction of perchlorate. Electrons are applied direct y to the
  perchlorate at the cathode, which is maintained at high electrical potential (voltage) The reduction hal-
  reaction must be accompanied by an oxidation half-reaction, and the electrolysis of water is the most likely
                                          to occur.

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86   E. T. Urbansky and M. R. Schock
                             Anion exchange resin (stationary phase)
                             '      	
                                                                       CIO,
                     A perchlorate ion
                     is adsorbed to the
                     resin
                            CIO,
A chloride ion
is released
into the water
                    Figure 5.  Mechanism of anion exchange—chloride
                    for perchlorate. A chloride ion is released from the
                    quaternary ammonium moiety of  a  strong anion
                    exchange resin, and perchlorate ion takes the place
                      originally occupied by the chloride in the resin.
                    low concentration of perchlorate in the source
                    water and the lack of selectivity. Moreover,
                    their use is limited even in small water sys-
                    tems by pre-treatment and post-treatment
                    factors.
                   Anion exchange

                   With this technique, perchlorate is replaced
                   by an innocuous  anion, usually  chloride.
                   Water flows through a resin that contains a
                   high  concentration of this replacement ion.
                   Due to the relative concentration difference
                   of the two ions in the resin, the perchlorate
                   switches places with the other ion, which is
                   now released into the water (see Figure 5).
                   Eventually, the resin reaches an equilibrium
                   concentration where  no  more  perchlorate
                   can be extracted from the  water; at that
                   point, the  resin must  be regenerated.  The
                   used  regenerant solution contains  a high
                   concentration of perchlorate and must be dis-
                   posed of properly. While some highly selective
                   resins have been developed,  these are ex-
                   pensive  and  not  commercially available.
                   Those resins which are commercially avail-
                   able at this time are not sufficiently selective
                   for perchlorate. On account of  their relative
                   concentrations, harmless and even desirable
                   anions7 can be preferentially replaced over
                   perchlorate. Consequently, the resin's chlor-
                   ide supply is rapidly depleted, and the water
H,o
                                                                    HoO
                                                                           SO.
                 Incoming water
                                           Filtered water
              Figure 6.  Membrane filtration. In reverse osmosis
              and nanofiltration, influent water is forced through
              a membrane that is impermeable to dissolved salts.
              Exclusion is the result  of ionic size and charge.
                    Effluent water is relatively deionized.
              may be transformed into one having highly
              undesirable  chemical characteristics  (par-
              ticularly corrosiveness), as well as unpleasant
              taste. The US Department of Energy has
              developed an anion exchange resin and con-
              commitant process for rapid removal of per-
              technetate (99mTcO4-),  a  poorly aquated ion
              (a category into which perchlorate also fits),
              with minimal retention of strongly aquated
              ones6 (Brown, 1998). This custom-made trih-
              exyl/triethylammonium blend strong anion
              exchange  resin was found to remove per-
              chlorate from groundwater without affecting
              other anions (Gu et al, 1999). In this respect,
              it overcomes  the  selectivity problem  that
              plagues most commercially available  resins.
              Calgon Carbon Corporation has developed an
              anion exchange process that rotates columns
              to eliminate downtime and minimize waste
              from regeneration  (Betts,  1998). Despite the
              drawbacks, ion exchange systems are readily
              implemented into existing  potable  water
              treatment facilities. If highly selective resins
              can  be made cheaply on  a large  scale and
             regenerated  with minimal effort  and cost,
              anion exchange may prove to be an attractive
             option for drinking water treatment.
                    7 The list of harmless or beneficial anions that are
                  found in natural in water sources includes, but is not
                  limited to, the following: monohydrogen carbonate (bi-
                  carbonate), HCO3-; carbonate, CO32-; dihydrogen ortho-
                  phosphate, H2PO4 ; hydrogen ort/zo-phosphate, HPO42~-
                  and sulfate, SO,2-. All of these are highly aquated, i.e.
                  strongly associated with water molecules.
             Membrane filtration

             This includes such techniques as reverse os-
             mosis (RO) and nanofiltration. Water is forced
             through  a semiporous  polymer membrane;
             meanwhile, dissolved salts are unable to pen-
             etrate the membrane (Figure 6). Membrane
             permeability towards different anions  and

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                                                                     Perchlorate risk management issues  87
 +  +—   +— •*"
              _+
              ~
                              Concentrate

                               Diluate
                               Concentrate
Figure  7.  Electrodialysis. Water flows  through
alternate  semipermeable   membranes  (anion-
impermeable   unshaded;    cation-impermeable,
shaded) while under the influence of an electric field.
Cations migrate down; anions migrate up.  Ions
stop  migrating when  they reach their respective
impermeable membranes. Alternate layers of salty
and deionized water  form as the water moves
through the electrodialysis cell. The layers are drawn
     off separately, and the diluate is used.
cations can be adjusted in manufacture to
some degree;  however,  the filtrate (or per-
meate) is nearly always a relatively deionized
water. The concentrate  contains all rejected
dissolved matter, including the perchlorate.
Membrane  fouling by  alkaline earth  and
transition metal  compounds can present a
problem, depending on  their concentrations
in the water.  Additionally, high concentra-
tions of NOM and certain microbiota can
irreversibly foul  or damage the membrane
material, necessitating complete  replace-
ment. Work at the Metropolitan Water Dis-
trict  of Southern California (Liang  et al,
1998) showed that nanofiltration and RO
membranes were capable of removing 80% or
more of the perchlorate, but it did not meas-
ure the rejection  of other dissolved salts.
Electrodialysis

In electrodialysis, water is passed through
channels  of  alternating membranes  per-
meable to either anions or cations, all the
while being exposed to an electric field (see
Figure 7). This produces alternate channels
of nearly deionized water (the diluate or di-
alyzate)  and  salty water (the concentrate).
The diluate is used, and the concentrate is
discarded.
  Work is this  arena is  ongoing, and any
discussion of the 'current' state of the science
will necessarily be incomplete and somewhat
outdated by  the  time of publication.  Con-
ferences or meetings have been held by the
East Valley Water District, National Ground
Water Association,  and  American Water
Works Association (Water Quality Technology
Conference). The American Chemical Society
has scheduled a symposium for the August
1999 meeting. Many investigators and agen-
cies  are engaged in research and new de-
velopments occur continually. We expect to
see a number of advances regularly reported
at major scientific society meetings over the
course of the next few years.
Regulatory and engineering
constraints

The regulatory balancing act

The drinking water quality regulatory struc-
ture in the United States is organized around
specifying either a  permissible level  max-
imum as  an MCL or a treatment technique
(US EPA, 1994a,b). This approach is similar
to that practiced by many other countries or
international organizations. If the decision is
made to regulate perchlorate in the United
States by the promulgation of  an MCL, the
identification  of best available technologies
(BATs) may be undertaken, consistent with
the approach of other regulations governing
some specific contaminants  (US EPA, 1980).
Historically,  these   determinations  have
focused  only  on  individual  contaminants
of interest. While  some determination  of
treatment cost was included, the costs rarely
adequately reflected pre- and post-treatment
costs to adjust to needs of other regulations
in force, and the specific construction or ad-
aptation  needed for each treatment plant.
The new Safe Drinking Water Act Amend-
ments of 1996 (PL. 104-82) sought to balance
the burden of high cost and sophistication of
treatments  for smaller water systems  (serv-
ing under 10000 persons)  with allowances
for the use of variance technologies under
special different approval conditions. These
result when no  affordable technology can be
found that  will meet an MCL, but a tech-
nology or treatment system can be employed
which will achieve the maximum affordable
reduction given the size  of the system and

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88  E. T. Urbansky and M. R. Schock
                    quality of the source water (US EPA, 1997).
                    The terms of the variance agreement by the
                    primacy  agent  (i.e.  state or  federal  gov-
                    ernment) must assure adequate protection of
                    human health. This new approach could be
                    applicable to the problem with regulating
                    perchlorate.
                     The treatment technique approach has
                    been followed in the notable cases of the US
                    regulations for lead and copper (US EPA,
                    1991a,b,  1992, 1994b, 1998b,c), and newer
                    or upcoming regulations covering DBPs and
                    microbes such as Cryptosporidium. This ap-
                    proach has generally been selected either
                    when  the reduction of the contaminant to
                    the human health effects goal may not be
                    achievable with conscientious application of
                    the best known process technologies available
                    to water utilities (e.g. the case with  lead
                    from household plumbing), or when the direct
                    quantitative  measurement  of  the   con-
                    taminant is not possible at a level assuring
                    adequate safety (e.g. Cryptosporidium and
                    some other pathogenic microbes). This could
                    become a viable approach for perchlorate re-
                    gulation, and the pros and cons of treatment
                    technique versus the MCL approach must be
                    seriously debated.
                     Whatever the regulatory target for  per-
                    chlorate becomes, the challenge to the drink-
                    ing water system will  be to  develop an
                    integrated treatment process that will result
                    in successfully meeting all existing state or
                    federal drinking water quality regulations.
                    As many other regulations of serious health
                    consequences will already be in place [e.g.,
                    lead, copper, disinfection byproducts (DBPs),
                    microbial contaminants, other inorganics or
                    synthetic organics], much discretion is lost in
                    optimizing treatment purely for perchlorate
                   reduction or removal.
                     The  current schedule for new regulations
                   in the US is as  follows: (1)  disinfectants
                    and disinfection byproducts (D/DBP) rule—
                   stage 1, November 1998; stage 2, May 2002;
                   (2) enhanced  surface water treatment  rule
                   (ESWTR)—final   interim rule, November
                    1998;  final  long-term ESWTR, November
                   2000;  (3) groundwater  disinfection   rule
                   (GWDR)—final rule, January 2001; (4) ar-
                   senic—final rule, January 2001; (5)  radio-
                   nuclides other than radon—reproposed rules
                   for  uranium  and radium  by  December
                   2000.
 Producing acceptable drinking water full
 scale

 The lead and copper rule poses some of the
 most severe constraints to practical full-scale
 removal of perchlorate. Two of the most read-
 ily usable technologies, anion exchange and
 membrane filtration, can be expected to pro-
 duce water that is corrosive towards plumb-
 ing materials. Solubilization of pipe metals
 can adversely affect both health  and major
 distribution system materials such as unlined
 cast  or ductile iron, and  cement-based
 materials (AWWARF, 1990,1996).  Membrane
 permeates are frequently  low in pH relative
 to that essential for protection against the
 release of lead and copper. The  aggressive
 nature of high concentrations of chloride ion
 towards iron and copper, for instance, has
 been well-documented by corrosion studies
 goingback40 ormore years (AWWARF, 1996).
 The excessive removal of bicarbonate would
 result in the loss of buffering ability to control
 the pH  to non-corrosive  levels, and would
 remove an essential component of many pas-
 sivating films on metallic and cementitious
 piping materials (AWWARF, 1996), as would
 excessive loss of calcium hardness. Attack on
 unlined  iron pipe, a ubiquitous material in
 many American water distribution systems,
 can result  in the  premature loss  of  dis-
 infectant residual, dislodging of existing pipe
 scales  that might have micro-organisms en-
 trained within or adsorbed upon  them,  and
 increases in pH from cement leaching. Thus,
 water  quality can be degraded by iron  cor-
 rosion, increased turbidity,  poor  taste  and
 reduction in disinfection effectiveness. Cor-
 rosion  control treatment provides many be-
 nefits to distribution system water quality
 beyond  reduced lead  and  copper  levels
 (Schock, 1998). When a water system  has
 conducted monitoring for lead and  copper,
 and has optimized treatment based on his-
 torical or recently-improved corrosion control,
 major  changes in water chemistry  brought
 about by the installation of perchlorate treat-
ment could  have serious adverse health or
 distribution system water  quality impacts.
  Not  all regulatory interactions  are  ne-
cessarily negative. Water systems that have
problems with current and future regulated
contaminants  such  as DBP formation, ar-
senic, nitrate or with the potential for mi-
crobial contamination, may find it necessary

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Table 3.  Applicability of treatment technologies to different size systems
                                 Large3
  Medium"
                                                               Smallc
                                                                       Perchlorate risk management issues   89
Home"
Biodegradation
Electroreduction
Anion exchange
Membrane filtration
Electrodialysis
Combination8
y y
y y



y y


y
y
y
y


y
y
?

  a Large refers to systems serving >10000 persons, for example, metropolitan municipal systems.
  "Medium refers to systems serving ~ 1000-10000 persons, such as a rural township or county system.
  0 Small refers to systems serving a population in the hundreds, such as a village, corporate facility or residential
subdivision.
  dHome refers to systems serving under 20 people, including all point-of-use devices.
  8 Combination refers to two or more of the other techniques used together; see text for further explanation.
to employ enhanced membrane filtration or
other processes that could also reduce per-
chlorate  levels.  In these  cases,  re-optim-
ization of corrosion control for lead and copper
would be necessary in the regulatory frame-
work anyway, and the perchlorate removal
would not be the only factor driving up the
cost and complexity of treatment.
   It must be emphasized that the output
capacity of a water purification plant is one
of the most important factors in determining
which techniques are suited for perchlorate
treatment. In addition, physical space and
other  resources  play an important role in
making  this  decision.  Likewise,  influent
water quality also bears on this choice. If the
raw water has  an extremely high  level of
alkaline  earth metal cations (e.g.  Ca2+ or
Mg2+), membrane filtration will not be dir-
ectly applicable since fouling will occur. Other
obvious considerations include downtime for
systems requiring regeneration, operational
maintenance, operational staffing, staff cer-
tification, operational  cost,  electricity con-
 sumption, selectivity and speed. We  have
 attempted to rank these techniques in terms
 of applicability to different size systems in
 Table 3,  which provides a starting point for
 evaluating the reasonableness of  using any
 one technique or combination of techniques
 in a given size system.
   Caution must also be exercised in the se-
 lection of perchlorate removal technologies,
 lest the problem merely be shifted from one
 environmental  'compartment' to  another.
 Waste products  from removal or destruction
 processes may be  covered by a  variety of
 regulations  that do not relate to drinking
 water quality, and which may not necessarily
be under the economic control or regulatory
attention of the  drinking water production
utility. Additional complexity  is introduced
when different private companies  or public
governmental agencies are  responsible  for
source water  management and production,
drinking water treatment, wastewater treat-
ment and  discharge, and the disposal  of
process solids materials (such as waste treat-
ment sludges).
  In particular, the key drawback of physical
removal is that something must be done with
the removed perchlorate.  When these tech-
niques are applied in a home or point-of-use
(POU) membrane filtration or electrodialysis
system,  there is little concern as long  as
the raw influent water does not exceed the
permitted perchlorate discharge limits.  The
filtrate/dialysate and  concentrate are  es-
sentially recombined in the sewage stream
since nearly all  the  water that goes  into a
house goes down the drain. Accordingly, there
is  no  net  increase in  perchlorate  con-
centration in the sewage over the raw water.
However, in large or intermediate systems,
the local discharge of concentrate into a sew-
age system could have a disastrous impact
on the local ecology. In rural areas served by
a central water  utility, there  may not be a
central  sewage  treatment system, but in-
dividual septic tanks or  cesspools instead;
consequently, there would be no recombining
of the concentrate and filtrate streams.
 Combining technologies

 It is important to point out that the tech-
 nologies described above are not necessarily

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90  E. T. Urbansky and M. R. Schock
                    mutually exclusive in application. It is pos-
                    sible to physically separate perchlorate  by
                    membrane nitration and to subject the con-
                    centrate to subsequent biodegradation. Or it
                    is possible to remove perchlorate by anion
                    exchange and then  subject the spent re-
                    generant to  electrochemical reduction. The
                    decision to combine techniques must be made
                    after careful consideration of total water qual-
                    ity management, including the fundamental
                    characteristics of the influent water. In many
                    cases, the best approach may be a combina-
                    tion. This can especially benefit a facility that
                    has sufficient space to install ion exchange
                    columns, and who may, for example, hire a
                    contractor to regenerate them offsite. De-
                    velopment of an inexpensive, highly selective
                    anion exchange  resin could substantially
                    alter the applicability and attractiveness of
                    this technique.
                   Areas requiring research


                   While a number of investigators are currently
                   working on bioreduction, studies are needed
                   to identify and characterize more of the micro-
                   organisms  that reduce perchlorate so  as to
                   optimize conditions for maximal destruction
                   while  minimizing  byproduct  formation,
                   wasteful side-reactions  and nutrient  con-
                   sumption.  Presumably,  several  transition
                   metal complexes  act in key roles in the re-
                   duction process as active sites in reductases
                   or dismutases. Nevertheless, it is impossible
                   to know if the raw water provides a sufficient
                   supply of essential minerals and trace metals
                   since neither the waters nor the  organisms
                   are well-characterized at this time. Similarly,
                   it is  impossible to gauge the ongoing health
                   and reliability of a bioreactor without  well-
                   defined, measurable properties of the active
                   microbe populations.  Ideally,  some studies
                   should be  directed towards genetically en-
                   gineering and selecting for bacteria that pref-
                   erentially consume  perchlorate over oxygen
                   as a terminal oxidant (electron acceptor).
                     Biological degradation is already in use by
                   the USAF for wastewater treatment. Before
                   it can move to the arena of drinking water,
                   it will have to  demonstrate itself as a safe
                   and cost-effective tool. There are presently
                   too many unanswered questions  about the
                   organisms involved in the process to meet
 the regulatory needs of safe drinking water.
   More effort must  be expended in  elu-
 cidating the mechanism by which microbes
 reduce perchlorate, including the isolation,
 purification and characterization of the active
 enzyme(s). It may be  possible to exploit the
 mechanism whereby the bacteria are capable
 of overcoming the activation barrier, but only
 if we have a better understanding of that
 mechanism. Along these lines, chemical re-
 duction may become an option if suitable—
 that is, labile, non-toxic,  convenient, inex-
 pensive—reductants are found.
   Electrochemical  reduction   experiments
 have remained at the bench scale [see review,
 Urbansky (1998)]. Additional bench- (beaker)
 scale, intermediate- (bucket) scale, and pilot-
 (barrel and  tank)  scale  experiments  are
 needed to determine what electrodes can be
 practically constructed with cost constraints
 and how thoughtful designs to maximize sur-
 face area might be effectively used to obviate
 problems such as slow ion diffusion to  the
 cathode surface and poor association with the
 surface. It will be necessary to explore means
 of minimizing corrosion, surface deactivation
 and undesirable  competing redox reactions
 (e.g.  the  electrolysis of water  and sodium
 chloride)  under drinking water conditions.
 If electrolysis of sodium chloride  cannot be
 prevented, it will be necessary to recombine
 the NaOH with the C12; this could ultimately
 have some use in disinfection. Since pipe
 corrosion will be substantially influenced by
 other water components (i.e. pH; alkalinity;
 NOM, metal and salt content), a thorough
 characterization of influent water will also
 be essential, and the effects of influent water
 quality on the electroreduction process must
 be considered.
  The development of inexpensive and highly
 selective resins  for  anion  exchange should
 be pursued. While there are some nitrate-
 selective resins, this technology will require
 further refinement before it can be applied
 to perchlorate because of the much higher
 concentration permissible   and the  much
 lower concentration of perchlorate in the raw
 water in most cases. Similarly, since the semi-
 permeable membranes of electrodialysis are
based on ion exchange technology, they too
will  benefit from projects in this  area.  In-
tegrating these or other systems into existing
treatment  schemes  for utilities processing
large volumes of water daily needs  extensive

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                                                                      Perchlorate risk management issues   91
pilot scale or demonstration work, -with care-
ful attention paid to the net benefits relative
to the total costs.
  Because  some techniques,  such as elec-
trodialysis  or reverse osmosis, can  be  ex-
pected to dominate the home or POU system
market, the development of  standards for
perchlorate removal by commercially avail-
able units will be essential. This could logic-
ally be done as an extension of the voluntary
performance-based standards  for POU de-
vices that  already exist under  American
National Standards Institute/National San-
itation Foundation (ANS1/NSF) standards for
drinking water treatment units and related
products.8
   Little  is known  about the natural oc-
currence of perchlorate. It is not a significant
component of seawater,  but  solid deposits
are found in Chilean potassium nitrate (also
known as  Chile  saltpeter) (Schilt, 1979).
Given the celerity with  which perchlorate-
reducing microbes seem to appear in FBBRs
inoculated with sludge, one can only conclude
that these organisms evolved naturally from
exposure or have  a serendipitous advantage
in their ability to metabolize this ion.9 Since
the former seems more reasonable than the
latter, natural sources of perchlorate must be
in the environment. Additional investigation
into naturally occurring mechanisms for the
generation of perchlorate would be  helpful
in ascertaining whether  only anthropogenic
 sources   are  significant  contributors  to
pollution.  Moreover,  further  knowledge  of
natural background occurrence levels is re-
 quired. If it can be shown that perchlorate is
 produced naturally in the environment and
 yet levels are very low, we must conclude that
 natural attenuation is responsible  for the
 apparent  dichotomy. At present, little  is
 known about the ability  of normal flora and
   8 Relevant voluntary standards for certification of unit
 performance  developed by NSF International, Ann
 Arbor, Michigan, include ANS1/NSF Standard 53 (Drink-
 ing Water Treatment Units, Health Effects), ANS1/NSF
 Standard 58 (Reverse Osmosis Drinking Water Treat-
 ment Systems) and ANS1/NSF Standard 62 (Drinking
 Water Distillation Systems).
   9 We point out that chlorate salts are present in the
 environment and chlorate-reducing organisms are fairly
 abundant. It is possible that mechanisms that evolved
 in chlorate reducers are readily adapted to perchlorate
 reduction. Nevertheless, we feel that the chemical nature
 of perchlorate relative to other chlorine oxyanions makes
 this an unsatisfactory explanation.
fauna (macro- or microscopic) to consume per-
chlorate, regardless of the source. However,
the confirmed existence of several genera of
perchlorate-reducing monera in the laborat-
ory suggests that some organisms are already
present in the environment. Due to its aridity,
the western US is  not a choice place for
discovering these organisms; however, they
may play a significant role in moister regions
of the country. This remains largely  un-
known.
  Although ammonium perchlorate appears
to have been the original source for most of
the perchlorate in the environment, we do
not know what cation is presently responsible
for the charge balance. As ammonium is read-
ily biodegraded and has not been identified
at many sites, there is speculation that it has
been  replaced primarily by sodium.  While
this is not  an  unreasonable assertion per
se, one can view ammonium perchlorate as
ammonia and perchloric acid. If the ammonia
alone is biodegraded naturally, then remain-
ing cation is a proton (hydrogen ion). Since
perchloric  acid is a strong acid, whatever
basic anhydrides  (of alkaline earth,  trans-
ition, or other metals in low oxidation states)
are present in the soil will react to form the
respective metal perchlorate salts. Thus, the
composition of the surrounding soil and rock
will determine what cations are present.
 Managing risk: other issues
 for researchers, utilities,
 policy makers and regulators

 As of the writing of this paper, the EPA had
 not established a formal policy for the risk
 management of  perchlorate-tainted  water,
 and we do not intend to  propose one here.
 Nevertheless, we shall raise a  number of
 questions that apply to risk management de-
 cisions and that  will have to be considered
 in formulating policy or regulations  at any
 level—federal, state or local. In addition, it
 will be up to regulators and policy makers to
 address these issues (and probably others)
 when facing the public that consumes  the
 water, the utilities  that treat and produce
 the water and anyone else with an interest.
   Among some  consumer groups and even
 some water purveyors, there  is a growing

-------
92  E. T. Urbansky and M. R. Schock
                    desire to reduce perchlorate concentrations to
                    undetectable levels (<4ngml~1) with public
                    health  as  the  concern.  Suppose the  es-
                    tablished safe level10 is higher than the de-
                    tection limit (the provisional action level is
                    18 ngml"1). Is there then any benefit in treat-
                    ing water to reach perchlorate concentrations
                    below the safe level? Corrosion of the dis-
                    tribution system or other similar engineering
                    matters do not appear to apply, so seemingly
                    there are no secondary benefits to reducing
                    the perchlorate concentration below the safe
                    level. If there is no public health benefit, is
                    there any other reason to do it? If the benefit
                    is peace of mind, what cost is appropriate?
                    Depending on the answers to these questions,
                    many water supplies may require no treat-
                    ment at all.
                     How does  the risk from perchlorate com-
                    pare with other public health risks in drink-
                    ing water? Are financial resources better
                    devoted to other problems in potable water
                    production  systems?  Whatever  treatment
                    technologies  are eventually  employed must
                    be based on sound scientific reasoning, bear-
                    ing in mind that there will always be multiple
                    viewpoints of varying intensity. In terms of
                    economic resources, how can the opportunity
                    cost of treatment be justified?
                     Besides the treatment  technologies  de-
                    scribed here, which involve directly modifying
                    contaminated water, other options may be
                    available at  a particular  location.  For ex-
                    ample, can a contaminated water be blended
                   with a 'clean' water? For those utilities that
                   have the luxury of drawing from multiple
                   water sources, diluting a water that exceeds
                   the safe level with a water  containing less
                   perchlorate is a conceivable  option. As long
                   as blending would not substantially change
                   the background constituent  concentrations,
                   no new corrosion control studies would be
                   needed  (US   EPA,  1991a,b,  1992,  1994b,
                   1998b,c).
                     If a health advisory is eventually issued by
                   the EPA Office of Water, primacy agents will
                   have to ask: What other factors besides  the
                    10 Rather than choose a particular legal definition of
                   what is a safe level for drinking water, e.g. NOAEL or
                   MCL, we shall use the generic term safe level without
                   further elaboration, realizing that various public health,
                   regulatory and environmental authorities view this dif-
                   ferently. When we use this term, we mean a level that
                   has been established by government authority and that
                   ensures the protection of public health.
 concentration of perchlorate in the drinking
 water determine what is safe?
   Perchlorate exerts its effect not by reacting
 with  something,  but by  impeding another
 process. Cells in  the thyroid gland (as well
 as the salivary and gastric glands), possess
 an iodide pump which brings iodide ions into
 the cell for subsequent generation of iod-
 inated hormones. The pump discriminates
 among anions on  the basis of size;  con-
 sequently, perchlorate (and other large an-
 ions) interfere with this process by compet-
 ing for uptake (Foye, 1989; Orgiassi,  1990;
 Capen, 1994;  Cooper, 1996; Chiovato et al,
 1997). Presumably, the only adverse effects
 of perchlorate in drinking water  would be
 derived from its direct hindrance of the syn-
 thesis of thyroid hormones or secondary ef-
 fects resulting from decreased output of those
 hormones. As  a result of  decreased thyroid
 hormone production, the pituitary gland re-
 leases  more  thyroid-stimulating  hormone
 (TSH), causing the thyroid to  grow. In ro-
 dents, continued exposure to chemicals that
 bring about this effect has been shown to lead
 to the development of neoplasias or adenomas
 (Capen, 1994). At present, we do not know
 whether the perchlorate  concentrations in
 drinking water are capable of producing sim-
 ilar effects in humans.
   The medical literature has anecdotal re-
 ports of toxicity (especially aplastic anemia)
 from chemotherapeutic use in treating thy-
 roid problems  (Hobson, 1961; Johnson and
 Moore, 1961).  Despite these reports, potas-
 sium  perchlorate  (KC1O4)  has been  suc-
 cessfully   and   safely   used   to  treat
 thyrotoxicosis  induced  by  the cardiac  drug
 amiodarone, which  is used to treat arrhy-
 thmias; daily doses of 0-80-1 -00 g KC1O4 have
 resulted in  neither aplastic anemia nor
 nephrotoxicity  as the  earlier reports  sug-
 gested (Connell, 1981; Martino  et al,  1986;
 Martino et al, 1987; Harjai and Licata, 1997).
 A review of the toxicology  literature by Von
 Burg (1995) found that there is currently no
 evidence to suggest that perchlorate, when
 ingested at daily doses of less than 1 mg, will
 have any non-thyroid impact. A recent study
by Lamm et al. (1999) found that workers
in an ammonium perchlorate manufacturing
plant suffered no thyroid effects from inhala-
tion  of NH4C1O4 dust and that perchlorate
was    readily   egested   by    glomerulo-
nephrofiltration.

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                                                                      Perchlorate risk management issues   93
  Although  we   do  not  want  to  dis-
proportionately  emphasize  them,  several
questions remain: Are there likely to be any
effects, especially with chronic low-level ex-
posure over  a lifetime (rather than  acute
exposure)? Does the water contain any other
thyroid-interfering agents? Are there any po-
tentiators or synergistic agents in a water
supply that could make the effects worse?
Even if the answer to all three questions is not
likely or probably not, should an additional
safety net be built into a regulatory or risk
management position?
  Due to the competition between iodide and
perchlorate, it is clear that the safe level must
be influenced by the daily dietary intake of
iodide salts.  Increased  use of iodine-con-
taining   compounds  antiseptics,  non-pre-
scription drugs and foodstuffs has raised the
US daily intake to ~ 0-50-0-75 mg of iodide,
and it may be as high as 1-0 mg, up from
0-2 mg  10-15 years  ago  (Wartofsky,  1998;
Andreoli  et al, 1997). Meanwhile,  the  US
Department of Agriculture  recommended
dietary  allowance  (RDA) is 0-20 mg per  day
for a lactating woman and 0-15 mg for a 170 Ib
(77kg) adult man; thus, the average Amer-
ican ingests ~2-5 times the RDA (Andreoli
et al, 1997; USDA, 1998). The safe level set
overall  must  assume some  average iodide
intake for this purpose, which may not be
representative of the iodide consumption for
a particular  region. As the  dietary con-
sumption of iodide increases,  the competition
at the iodide pump is lessened. Accordingly,
is it possible that some regional populations
might be afforded a level of protection because
of a diet naturally high in iodide?
  We are familiar with the use of iodized salt
when local soils are too deficient to produce
crops that supply the daily iodide  require-
ment. Iodide supplements  are  cheap  and
readily  available. Therefore,  is it possible to
counter the effects of perchlorate simply by
supplementing the  diet with more iodide?
Iodide  supplementation  of  up to  0-50 mg
day"1 has shown no effect on thyroid func-
tion; consumption  of 40-150 mg day"1 for
1-3 weeks produced observable changes in
hormone levels, but these nonetheless re-
mained within normal physiological ranges
(Roti and Vagenakis, 1996). Although initial
dosing  inhibits iodine  organification  (the
Wolff-Chaikoff effect), continued administra-
tion of iodide results in escape from  this
inhibition (Nagataki and Yokoyama, 1996).
Does managing the risk associated with per-
chlorate-contaminated drinking  water  ne-
cessarily imply  treating  the  water or  can
other public health measures be viable so-
lutions?11
  There are no simple or straightforward an-
swers to the questions posed, and each com-
munity, utility or regulatory body will need
to wrestle with these questions as they work
towards specific solutions to  meet specific
needs. What works for Las Vegas, Nevada,
might not work for Magna, Utah  and vice
versa. As with most environmental problems,
dealing with  perchlorate contamination is
complex;  each  medium  (drinking  water,
wastewater, land, etc.) has its own  subset of
issues. There  is unlikely  to be any best so-
lution for any set of circumstances, but rather
a compromise of  competing  strategies for
meeting competing needs. Maintaining  a
reasonable "big-picture' perspective is one of
the most important things that researchers,
policy makers, and regulators alike can do.
  Authors'  note: Perchloric acid and per-
chlorate salts have a rich history in industry,
science, medicine, space exploration and de-
fense.  They function as inert  electrolytes in
chemical studies, catalysts in industrial and
synthetic processes  and boosters or solid ox-
idants in rockets and missiles. They are too
valuable to give up, and so we must find safe
ways to accommodate their use.
Acknowledgements
The authors, who sit on the IPSC, wish to acknow-
ledge several other committee members for their
contributions  to the  IPSC as well as for  in-
formation they have provided: Dan Rogers (USAF,
Judge Advocate's Office), Annie M. Jarabek (EPA,
NCEA), Michael Osinski (EPA, OW), Kevin P.
Mayer (EPA, Region 9) and Peter Grevatt (EPA,
OSWER).

© 1999 US Government
  11 We want to stress that neither the EPA nor the
 authors advocate the administration or consumption of
 iodide supplements as a preventive or curative measure
 without medical supervision. Nevertheless, we do con-
 sider it to be an area worthy of investigation and ex-
 ploration.

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94   E. T. Urbansky and M. R. Schock
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