HomeMy WebLinkAbout2.d. CIP - Water Treatment Plant
EXECUTIVE SUMMARY
City Council Work Session: December 7, 2015
AGENDA ITEM: CIP - Water Treatment Plant AGENDA SECTION:
Discussion
PREPARED BY: Dwight Johnson, City Administrator
Patrick Wrase, Public Works Director/City
Engineer
AGENDA NO. 2.d.
ATTACHMENTS: Information forwarded by Councilmember
Demuth APPROVED BY: ddj
RECOMMENDED ACTION: Discuss Capital Improvement Plan-Water Treatment Plant and
direct staff on any changes to the proposed CIP
BACKGROUND
The Council reviewed the proposed 10 year Capital Improvement Plan on November 9th. One of the
items included in the plan is a possible Water Treatment Plant which was listed under the year 2019 for
construction. Subsequent to that meeting, Councilmember Demuth has forwarded additional information
to us and asked for re-consideration of the planned date for reconstruction. The additional information is
attached.
DISCUSSION (from Public Works Director/City Engineer Patrick Wrase)
The United States Environmental Protection Agency (EPA) is responsible for establishing water quality
standards to protect public health. The USEPA has not established legally enforceable Primary Drinking
Water Regulations for Maximum Contaminant Levels (MCL's) for manganese. The EPA has established
a non-enforceable Secondary Standard for Manganese at 0.05 mg/l. Secondary Standards are set to
provide technical guidance for regulating constituents that can cause aesthetic issues. Manganese is
regulated as a Secondary Standard at 0.05 mg/l as concentrations higher than this level can cause laundry
staining, scaling of fixtures and taste and odor issues. The Rosemount water system adds polyphosphates
to sequester manganese thereby reducing the formation of precipitates and avoiding typical aesthetic water
quality issues. As the extent of the Rosemount distribution system increases, the ability of polyphosphates
to control manganese precipitation will decrease as the polyphosphate reaction is time sensitive. Until this
point, the plan for implementation of a Rosemount Water Treatment plant was to coordinate with the
occurrence of manganese aesthetic concerns due to the deterioration of polyphosphate effectiveness.
Recently, the Minnesota Department of Health (MDH) has published guidance suggesting a manganese
Risk Assessment Advice (RAA) level of 0.1 mg/l for infants under one year of age and 0.3mg/l for adults
and children over one year of age. The MDH suggests that public water suppliers use these guidance
values to regulate groundwater use protection. They have also indicated that the EPA is reviewing the case
for enhanced regulation of manganese concentration in drinking water supplies and that future regulation
may be forthcoming.
2
The City of Rosemount has several wells with manganese concentrations greater than 0.1 mg/l. Testing of
limited home tap samples have indicated manganese concentrations ranging from 0.062 to 0.077 mg/l,
beneath the RAA infant level suggested recently by the MDH. With the various levels of manganese in the
city's wells and another well, well 16 coming on line within the next year, which has been tested with
manganese levels greater than 0.1 mg/l, it is possible that segments of the city's water system exceed the
MDH RAA infant level. If the council wishes to mitigate that condition, ahead of EPA regulations, a
water treatment plant can reduce manganese concentrations to a level considerable less than 0.1mg/l.
However, the North West Treatment Plant currently scheduled for 2019 in the city CIP will not be capable
for treating all wells located within the city. Additionally, operation controls such as limiting output from
high manganese concentration wells or mixing well water within the 1.5 million gallon reservoir planned
for construction in 2015 could help to mitigate manganese levels.
Prior to altering the implementation schedule for the North West Treatment Plant, staff suggests that a
facilities planning effort be commissioned. This plan would: document the current and anticipated
manganese concentrations throughout the distribution system under current conditions; examine
operational changes to possibly reduce system manganese concentrations; develop a well water treatment
plan including possible raw water main construction to achieve suitable manganese levels throughout the
city; and make a recommendation for the timing of the North West Water Treatment Plant in order to
meet either EPA requirements or MDH recommendations.
Manganese in Minnesota’s Groundwaters
Emphasizing the Health Risks of Manganese in Drinking Water
Prepared for the Minnesota Ground Water Association
September 2015
Acknowledgements
Manganese white paper work group members:
Dr. Mindy Erickson, US Geological Survey, chairperson
Bill Bangsund, Barr Engineering
Meghan Blair, Barr Engineering, lead writer
Vanessa Demuth, Dakota County
Dr. Sarah Johnson, Minnesota Department of Health
Linse Lahti, Minnesota Department of Natural Resources
Dave Lowell, retired
Jim Lundy, Minnesota Department of Health
White Paper Committee liaisons:
Mark Collins, retired
Bruce Olsen, retired
Other contributors:
Jeff Hill, Robert B. Hill Company
Prof. Patricia McGovern, University of Minnesota
Kate Sande, ECOLAB
Rich Soule, Minnesota Department of Health
Lisa Yost, ENVIRON International Corporation
Manganese in Minnesota’s Groundwaters: Emphasizing the Health
Risks of Manganese in Drinking Water
Glossary of Terms
1 Problem Statement and Definition
2 Background
3 Manganese and Human Health
4 Environmental Behavior of Manganese
Solid Phase Manganese
Aqueous Manganese
5 Regulation of Manganese in Water Supplies and Groundwater
Federal Regulations and Guidance
Minnesota Regulations and Guidance
Public Water Supplies
Private Drinking Water Supplies
Bottled Water
Groundwater Use Protection
Potential for Regulatory Action
6 Manganese Distribution in Groundwater
Statistical Observations
Spatial Distribution
7 Impact Mitigation
Impacted Community Education and Outreach
Impacted Water Supplies
Testing
Water Treatment
Methods Typically Used by Water Suppliers
Residential Treatment Considerations
Alternative Water Supply
8 Opportunities for Research
9 Review of Major Findings and Issues
Glossary of Terms
Adsorption: A water treatment method where undesirable constituents in water stick onto the surface of
particles. Activated carbon typically is the most effective adsorbent used
Ambient groundwater: Groundwater that is not impacted by any known point sources of pollution, such
as a chemical spill, surrounding a well or monitoring location
Anthropogenic: Caused by human activity
Aquifer: any water-bearing bed or stratum of earth or rock capable of yielding groundwater in sufficient
quantities that can be extracted (as defined in Minnesota Rules 6115.0630)
Bottled Water: Water that is intended for human consumption and sealed in bottles or other containers
with no added ingredients, except that it may contain a safe and suitable antibacterial agent (as
defined in Minnesota Rules 1550.3200)
CWI: Minnesota County Well Index, a database that contains information on water wells constructed in
Minnesota
DOC: dissolved organic carbon
Greensand: iron potassium phyllosilicate mineral, which usually has a green color
HA: Health Advisory, established by the United States Environmental Protection Agency; non-
enforceable guidance for other agencies for unregulated drinking water constituents
HBV: Health Based Value; established by Minnesota Department of Health; the concentration of a
chemical below which there is little or no risk to human health; not promulgated
HRL: Health Risk Limit; established by Minnesota Department of Health; the concentration of a chemical
that is likely to pose little or no risk to human health; promulgated
Ion exchange: process whereby one or more ions in water, such as calcium and magnesium, are
exchanged for other ions, usually sodium,using a media like a resin
MCL: Maximum Contaminant Level. Enforceable water quality standard set by the U.S. Environmental
Protection Agency under the Safe Drinking Water Act in 40 CFR 143 for public drinking water
supplies.
MDA: Minnesota Department of Agriculture
MDH: Minnesota Department of Health
mg/L: milligrams per liter; 1 mg/L is approximately 1 part per million (ppm) in dilute water
MGS: Minnesota Geological Survey
MGWA: Minnesota Ground Water Association
MN DNR: Minnesota Department of Natural Resources
MPCA: Minnesota Pollution Control Agency
Neurotoxicant: A toxic compound that can cause damage to the central nervous system
SDWA: Safe Drinking Water Act. Federal law originally passed in 1974, it requires EPA to set drinking
water quality standards and oversee states, municipalities, and other entities that implement the
standards.
SMCL: Secondary Maximum Contaminant Level. Non-enforceable water quality standards set by USEPA
under the SDWA in 40 CFR 143.
RAA: Risk Assessment Advice; established by Minnesota Department of Health; technical guidance
concerning exposures and risks to human health. RAA may be quantitative (e.g., a concentration of
a chemical that is likely to pose little or no health risk to humans) or qualitative (e.g., a written
description of how toxic a chemical is in comparison to a similar chemical).
Toxicity: The degree to which a substance can damage an organism
ug/L: Micrograms per liter; 1 ug/L is approximately part per billion (ppb) in dilute water
USEPA: United States Environmental Protection Agency
USGS: United States Geological Survey
UV: Ultraviolet light
Valence: the number of electrons required to create stability in the outer shell of an atom. The valence of
an atom is determined by the number of electrons the atom will lose, gain, or share when it forms
compounds.
EXECUTIVE SUMMARY
Manganese in Minnesota’s Groundwaters:
Emphasizing the Health Risks of Manga-
nese in Drinking Water
Manganese is a naturally-occurring element in the groundwater
that is well known for causing aesthetic problems with drinking
water. Much of Minnesota’s soil, bedrock, and groundwater com-
monly contains manganese. Water professionals recognize that
water supplies containing more than ~50 micrograms per liter
(ug/L) dissolved manganese can be a household nuisance because
atmospheric oxygen causes manganese in these water supplies to
precipitate in water mains, leading to stained laundry and fixtures,
and distinct aesthetic effects such as discoloration, odor, or taste
(Figure 1). More than 60% of ambient groundwater measurements
in Minnesota exceed 50 ug/L, suggesting that many water supplies
contain excess manganese.
There is increasing recognition of human health effects caused by
manganese. Acute neurological effects resulting from inhalation of
manganese have long been recognized, and recent studies indicate
that ingestion of excess manganese also poses a potential health
risk. These studies demonstrate that although manganese is essen-
tial for body functions, subtle decreases in memory, attention, and
motor skills are positively correlated with drinking water manga-
nese concentrations, especially above 100 ug/L (Figure 2). Infants
relying on powdered formula mixed with drinking water contain-
ing high levels of manganese are at highest risk; they are unable
to excrete excess manganese and they absorb ingested manganese
more readily than adults and children.
Non-enforceable guidance was developed to minimize the human
health and aesthetic problems associated with excessive levels of
manganese in water. Recognizing manganese as a potential public
health issue, the Minnesota Department of Health (MDH) devel-
oped tiered health-based risk assessment advice (RAA) for man-
ganese in drinking water in 2012: 300 ug/L for adults and children
one year of age or older, and 100 ug/L for infants, especially those
relying on reconstituted formula. The Environmental Protection
Agency (EPA) advises public water suppliers to treat water to less
than 50 ug/L manganese to maintain consumer acceptance of the
water. However, these are not enforceable health-based drinking
water standards. In fact, manganese levels in public and private
water supplies are not currently regulated and not required to be
monitored. Mitigation of the potential health risk through devel-
opment of enforceable standards is unlikely, at least within the
next five years. Instead, education, risk communication, testing,
and treatment are potential approaches to mitigate the potential for
health risks associated with manganese in drinking water.
The groundwater community in Minnesota can help educate the
water supply industry, water conditioning contractors, public
health professionals, educators, and community and political lead-
ers. The distribution of manganese in ambient ground water is not a
measure of manganese in tap water, which can change from source
to tap. However, these measurements can be used to target risk
communication, testing, and treatment efforts on regions of the
state that have relatively high ambient manganese concentrations
in groundwater. Manganese concentrations are variable, common-
ly exceeding 1,000 ug/L in Southwestern Minnesota while rarely
exceeding 50 ug/L in Southeastern Minnesota (Figure 3).
Informing health care providers and consumers about naturally
elevated manganese in groundwater can help them make better
Figure 1. Water containing elevated levels of manganese
sampled from a toilet tank in a residence.
Figure 2. Full Scale IQ as a function of the range of median tap
water manganese concentrations. Quintile groups are: 1st = 1,
0-2; 2nd = 6, 3-19; 3rd = 34, 20-66; 4th = 112. 67-153; and 5th =
216, 154-2700. Figure from Bouchard et al., 2011.
decisions about the health risk posed by the potential presence of
manganese in their drinking-water supply. Awareness of manga-
nese in drinking water is particularly important for families with
infants who may reconstitute formula.
Observation of nuisance and aesthetic effects might be used as an
indicator of potential health risk: using tap water that stains faucets
to mix infant formula may not be protective of health. In addition,
using this water as a drinking source also may not be protective of
adult and child health. When properly treated to reduce nuisance
and aesthetic effects, tap water manganese is likely to be below
health guidance values.
Testing for manganese in drinking water provides a definitive
method to assess the potential for manganese exposure. Water
samples can be tested at local labs for approximately $20. The
MDH provides information on laboratories and sampling.
For water supplies containing excess manganese, there are many
treatment methods. In public supplies, treatment systems are de-
signed to maintain consumer acceptance of the water and meet
enforceable standards for some chemicals. Treatment systems
used to reduce iron in water through oxidation, a common treat-
ment step in public water supplies, also reduces dissolved manga-
nese concentrations. Information about the efficiency of treatment
systems for reducing manganese to specific recommended health
standards is sparse. However, common treatment methods such
as carbon filtration, reverse osmosis, cation exchange or water
softening, adsorption, oxidation and filtration all likely decrease
manganese levels. A licensed water conditioning installer or con-
tractor can help determine the appropriate water treatment device.
Regardless of the treatment option installed, post-treatment testing
for manganese and regular maintenance are essential to ensure that
manganese levels are protective of health.
Alternatively, drinking water supplies containing excess manga-
nese can be replaced with bottled water. Manganese in bottled wa-
ter, which also can be sourced from groundwater in Minnesota,
is enforced to contain less than 50 ug/L by the Federal Food and
Manganese in Minnesota’s Groundwaters, cont.
Figure 3. Manganese in groundwater measured at 7,574 wells.
Samples collected at various times, for various studies. Data
collated and map prepared by MDH, February, 2015. Dashed
line encloses area of southeastern Minnesota with low (< 50
ug/L) manganese concentrations. Dashed ellipse encloses area
of southwestern Minnesota where manganese concentrations
exceed 1,000 ug/L.
Drug Administration or the Minnesota Department of Agriculture.
Families relying on formula for infant nutrition also may choose
to use liquid, ready-to-feed infant formula instead of powdered
formula. In some cases, replacing a troublesome water supply with
a new permanent water supply may be economical.
Understanding the potential health risk due to manganese in Min-
nesota’s drinking water will take time and careful consideration by
the public health, groundwater, and drinking water communities.
Potential investigation activities could include:
● Additional health studies, including a study of the neu-
rological effects of exposure in infants and children ex-
posed to low levels of manganese, and a comparison of
the effects of drinking water versus dietary exposure.
● Correlation of ambient groundwater manganese concen-
trations to tap water manganese concentrations to deter-
mine typical exposure concentrations.
● Additional assessment of the spatial distribution of man-
ganese in groundwater. This provides an effective way
to identify the populations that may be most at risk of
exposure to manganese in drinking water. Coordinating
between various ambient groundwater quality monitoring
programs within state agencies and local governments is
necessary. A concerted effort may be needed to increase
the density of ambient groundwater measurements in ru-
ral areas, and to assess the adequacy of the data to de-
velop geographical correlations based on geology.
● Evaluation of the effectiveness of manganese removal by
water softeners and readily-available pitcher or faucet fil-
ters, with specific reference to health-based water quality
concentrations.
1 Problem Statement and Definition
Manganese is widespread in the groundwater that many Minnesotans use for drinking.
Epidemiology and toxicology studies published in the past ten years have shown that dissolved
forms of manganese in drinking water pose a greater health risk than previously thought,
especially for formula-fed infants, whose exposure may include both manganese from formula
fortification and in the water used to mix formula. The widespread presence of manganese
above threshold health-based guidance values in Minnesota’s groundwater suggests that many
people may be exposed to a level that presents a health risk.
Many water supply professionals consider manganese in water as primarily an aesthetic issue,
not a health issue because of discoloration and staining associated with manganese-enriched
groundwater. Therefore, the message they provide to their customers is that manganese is a
“nuisance” contaminant in drinking water, rather than a health concern. The MDH, seeking to
alter this misconception, has provided information to professionals and the public regarding the
potential health risks associated with manganese in drinking water, and awareness of this public
health issue is growing.
The goal of this white paper is to provide information about this issue to facilitate awareness-
building and a better understanding among local public health officials, public utility operators,
water supply professionals, private well owners, and others. The white paper brings together
information about 1) the health effects of manganese in drinking water and the availability of
new health-based drinking water guidance, 2) the spatial distribution of manganese in
groundwater, including current monitoring programs that test for manganese in Minnesota
drinking water, and 3) effective ways to reduce exposure to manganese, especially for those
who may be using water with high manganese concentrations to prepare infant formula.
2 Background
Manganese is required for human health; however, several harmful neurotoxic effects of
excessive manganese exposure are recognized. Parkinson-like effects are caused by inhalation
exposure, especially in occupational settings. Recent work suggests more subtle, harmful
effects also are caused by ingestion of low levels of manganese, especially among infants.
Manganese is a ubiquitous component of soils, rocks and water. It can be leached from soil and
rock into the underlying groundwater, where mobilization of manganese is favored in
chemically-reducing conditions.
In Minnesota, groundwater commonly is used for drinking water supplies. Figure 1 depicts the
role pumping wells play within the context of the hydrologic cycle. Approximately 75% of
Minnesotans use groundwater for their drinking water supply (MDH, 2015).
Figure 1. The hydrologic cycle describes the movement of water above, upon, and below the surface of
the Earth. Groundwater aquifers supply water to wells, making them important sources of drinking water.
(Figure used with permission from the Illinois State Water Survey).
The wells used to extract the groundwater for water supplies generally are either managed by
municipalities or businesses or privately installed and operated to provide residential supply.
Municipalities and businesses generally manage public drinking water supplies, which are
broken into various categories:
● Community supplies: these are systems serving a minimum of 25 persons or 15 service
connections, year round. There are almost 1,000 community supplies in Minnesota.
● Non-community supplies: these are systems serving at least 25 people for a minimum of
60 days of the year. There are almost 6,000 non-community supplies in Minnesota. Non-
community supplies are further subdivided into:
○ transient supplies where consumers use the supplies only temporarily and
occasionally; these include gas stations, parks, resorts, campgrounds,
restaurants, and motels, and
○ nontransient supplies where 25 or more of the same people consume the well
water on a regular basis for at least six months out of a year; these include
schools, factories, and hospitals,.
In addition to private wells and public water supply wells, groundwater is used as a source for
bottled water distributed in Minnesota.
There is a considerable amount of available information on manganese concentrations in the
state’s groundwater. Many state and county organizations actively measure manganese
concentrations in groundwater to determine ambient water quality. These data can be used to
identify regions of the state where the potential for a public health risk related to manganese in
drinking water is highest. Education and outreach, testing and water treatment, alternative
drinking water supply, public policy, or regulatory changes might be targeted within these
regions.
Sources
Minnesota Department of Health, 2015. Minnesota Drinking Water 2015: Annual Report for 2014. 33pp.
3 Manganese and Human Health
Living organisms need manganese for their biological processes. Manganese is an essential
nutrient that is needed to create carbohydrates, amino acids and cholesterol, plus it is critical for
cartilage, collagen, and bone synthesis. Manganese deficiency can result in abnormal skeletal
growth and wound healing. In the developed world, people’s manganese requirements 1 are
easily met by consumption of nuts, legumes, tea, and whole grains.
Ingested manganese within the body can be absorbed by tissues or excreted. Children and
adults have fully functioning metabolisms that control the amount of manganese retained in the
body, with only 3-5% of ingested manganese absorbed in tissue. In contrast, infants’ immature
body systems limit their ability to excrete manganese; infants can absorb up to 40% of the
manganese they ingest from formula. (Health Canada, 2010, ATSDR, 2012).
While manganese is necessary, excessive ingestion of manganese can be harmful, especially
to infants. The neurotoxic effects of inhalation exposure to high doses of manganese have been
recognized for more than 100 years. In 1837, John Couper first described effects similar to
Parkinsonism among workers grinding manganese at a chemical factory (Guilarte, 2013).
Workers affected by manganese inhalation lost strength in their lower extremities, causing them
to lean forward when walking, which resulted in short, running steps. They also lost the ability to
speak loudly, and had paralyzed facial muscles. More recently, this constellation of health
effects, known as “manganism”, along with more subtle locomotor effects, has been reported
not only in human epidemiology studies, but
also in rodent and nonhuman primate studies.
Figure 2. IQ is plotted by median tap water
manganese concentration quintiles. The quintiles
are as follows: 1st, 1 (0-2); 2nd, 6 (3-19); 3rd, 34
(20-66); 4th, 112 (67-153); and 5th, 216 (154-2700).
Figure copied from Bouchard et al. (2011).
The neurotoxic effects of manganese ingested
at low levels have only recently been
recognized. Since the early 2000s, a handful of
epidemiological studies have examined the
effects of manganese on children. In 2011,
Bouchard and colleagues showed that children whose drinking water source contained more
than 200 ug/L manganese had a deficit of more than 6 IQ points compared to children whose
drinking water source contained less than 5 ug/L manganese (Figure 2) (Bouchard et al., 2011).
In a follow up study, they examined the same group of children and found that decreased
memory, attention, and motor skills correlated with increasing manganese water concentration,
with the steepest drop in these functions occurring at, or just above, 100 ug/L manganese in
drinking water (Oulhote et al., 2014).
1 The Institute of Medicine recommends a daily intake rate of 0.003 milligrams per day for infants under
the age of one, 1.2-1.9 milligrams per day for children, and 1.8-2.3 milligrams per day for adults.
Similar neurological effects were observed in direct experiments on 0-18 month old primates
(which is equivalent to children who are 0-6 years old). Golub and coworkers (2005) fed either
standard infant formula or manganese-enriched formula to the infant primates, and measured
the effects using a variety of sensitive neurobehavioral tests. Those treated with manganese-
enriched formula showed differences in consistency and type of play during group interactions
(rough vs. chase), changes to their day/night cycle, and impulsivity. The authors proposed that
the observed subtle neurological changes in social behavior and regulatory control were due to
alterations in brain chemicals sensitive to manganese.
The effects of neonatal (early-life) oral manganese exposure on behavior and cognition also
were tested using animal studies. Rats were exposed to manganese via oral ingestion from birth
until 23 days of age, and their performance on a series of learning and memory challenges was
recorded (Kern et al., 2010). The results of this study are applicable to human manganese
exposures: the study focused on low level exposure to manganese in the young animals, which
are the most sensitive population. The neurobehavioral endpoints measured in this study
included locomotor activity (movement), emotional reactivity (impulsivity), learning ability, and
behavioral disinhibition (a lack of restraint), The design of the study allowed for evaluation of
subtle effects that are relevant to humans, and the biochemical changes reported in the study
are similar to those reported in humans. The exposed young animals had increased locomotor
activity, consistent with hyperactivity, and a significant learning deficit. These effects were
attributed to manganese targeting pathways in the brain that control higher decision-making
functions.
It is clear from the studies in humans and animals that manganese, although a beneficial and
essential nutrient at low doses, is a neurotoxicant at high exposure levels for children and
adults. In comparison, even a low dose is a neurotoxicant for infants. While high level exposures
result in overt manganism, low level exposure effects are subtle, such as IQ loss, in infants and
children. At highest risk are infants, who lack the mature systems needed to excrete excess
manganese and avoid neurological effects.
Sources
Agency for Toxic Substances and Disease Registry (ATSDR) (2012). “Toxicological Profile for
Manganese.” http://www.atsdr.cdc.gov/toxprofiles/tp151.pdf
Bouchard, M.F., S. Sauve, B. Barbeau, M. Legrand, M.E. Broduer, T. Bouffard, E. Limoges, D.C.
Bellinger and D. Mergler (2011). “Intellectual impairment in school-age children exposed to manganese
from drinking water.” Environ Health Perspect 119(1): 138-143.
Golub, M.S., C.E. Hogrefe, S.L. Germann, T.T. Tran, J.L. Beard, F.M. Crinella and B. Lonnerdal (2005).
“Neurobehavioral evaluation of rhesus monkey infants fed cow’s milk formula, soy formula, or soy formula
with added manganese,” Neurotox Teratol 27(4): 615-627
Guilarte, T.R. (2013). “Manganese neurotoxicity: new perspectives from behavioral, neuroimaging and
neuropathological studies in humans and non-human primates,” Front. Aging Neurosci
Health Canada (2010). Human Health Assessment for Inhaled Manganese,
Institute of Medicine. (2001). “Dietary Reference Intakes: Elements.” from
http://www.iom.edu/~/media/Files/Activity%20Files/Nutrition/DRIs/DRI_Elements.pdf.
Kern, C.H., G.D. Stanwood, and D.R. Smith (2010). “Preweaning manganese exposure causes
hyperactivity, disinhibition, and spatial learning and memory deficits associated with altered dopamine
receptor and transporter levels.” Synapse 64(5): 363-378.
Oulhote, Y., D. Mergler, B. Barbeau, D.C. Bellinger, T. Bouffard, M.E. Brodeau, D. Saint-Amour, M.
Legrand, S, Suave and M.F. Bouchard (2014). “Neurobehavioral function in school-age children exposed
to manganese in drinking water.” Environ Health Perspect. 122(12): 1343-1350.
4 Environmental Behavior of Manganese
Manganese is an abundant element that occurs in the environment in both solid and aqueous
(dissolved in water) phases, typically with iron. The behavior of manganese and iron is strongly
driven by chemical reactions known as oxidation or reduction (“redox” reactions). Redox
reactions describe the transfer of electrons between atoms, molecules, or ions, where oxidation
is defined as the loss of electrons and reduction is defined as the gain of electrons. Manganese
ions change oxidation (valence) state by losing or gaining electrons, which affects its solid
properties and solubility in water.
Solid Phase Manganese
Manganese is found in over 100 types of minerals, including sulfides, oxides, carbonates,
silicates, phosphates, and borates. The most common manganese-bearing minerals on the
Earth’s surface are listed in Table 1 (Nadaska and Michalik, 2010). The amount of manganese
dissolved in the groundwater depends on how much of these minerals are present in the aquifer
materials as well as their ability to dissolved and their dissolution rate. Manganese’s dissolution
rate depends on environmental conditions like temperature, ionic strength, pH and redox state.
Table 1. Common forms of solid-phase manganese [Nadaska and Michalik 2010].
Aqueous Manganese
The two most important environmental conditions that control manganese behavior in water are
the water’s pH and its reduction or oxidation/reduction potential (ORP).
● pH is a measure of the acidity or alkalinity of a solution. It is presented as a range from 1
to 14, with pH of 7 considered neutral.
● ORP, expressed in voltage, indicates the relative presence of oxidants, such as
dissolved oxygen, and describes the oxidizing or reducing tendency of a water. It
determines the direction and rate of redox reactions. Its measurement provides a relative
indication of water’s redox state, where positive values are more oxidizing, and less
positive or more negative values are more reducing.
Groundwater generally has neutral pH;
therefore, ORP, also known as redox
potential or Eh, generally drives
manganese behavior. An Eh-pH
diagram, which describes these two
variables, is a graphical means of
showing the effect of changing redox
potential and pH on manganese
solubility in aqueous systems.
Figure 3. Eh-pH diagram describing the
stability of solid “(c)” and aqueous phases of
manganese as a function of redox potential
and pH, at standard temperature (25 °C) a
pressure (1 atmosphere). In the solid stabi
fields, manganese precipitates and forms the
insoluble compound. The stability fields of
the solids (solid lines) represent the
boundaries at a concentrations of 0.01 ppm
(parts per million) dissolved manganese (
ug/L). Dashed lines represent the stabili
field boundaries when dissolved Mn+2
concentrations are 0.10, 1.0, 10, and 100
ppm.
nd
lity
~10
ty-
oncentration
Figure 3 illustrates that the c
of dissolved manganese increases at low pH and at low redox potential. The Eh-pH diagram
also indicates that solid-form manganese can occur in several oxidation states (+2, +3, +4, or
+6), but the dominant dissolved species in natural waters is Mn+2 (Hem, 1985).
Manganese concentrations in surface waters generally are low. Surface water is more oxidized
than groundwater, which is isolated from atmospheric oxygen. Therefore, manganese
concentrations are generally low in surface waters because oxidation of Mn+2 to relatively
insoluble Mn+3/Mn+4 leads to spontaneous formation of particulate manganese oxides and
hydroxides. These particles drop out of suspension in surface waters, leaving the water
relatively depleted in manganese. Thus, in surface water and relatively oxygenated aquifer
systems, dissolved manganese does not accumulate.
In groundwater, manganese concentrations can be high when the aquifer has reducing
conditions. As surface water infiltrates downward into groundwater and becomes increasingly
isolated from the atmosphere, oxygen is depleted resulting in more reducing conditions (a
“downward” shift on the Y axis on Figure 3). Under these reducing conditions, manganese
converts to its more soluble form, Mn+2. Therefore, much higher dissolved manganese
concentrations commonly are found in groundwater that has low amounts of oxygen such as
deep, isolated aquifers (Nadaska and Michalik, 2010; Mitsch and Gosselink, 2007). The
Minnesota Pollution Control Agency (MPCA) performed ambient monitoring as part of the
Baseline Study in the early to mid-1990s to assess the hydrogeochemistry of the state’s
principal aquifers. The MPCA confirmed that manganese concentrations in groundwater
increased as ORP decreased.
It is really easy to see how redox conditions affect the various manganese forms in the water
just by pumping water from a deep well. The manganese oxidizes and precipitates once this
water is brought to the surface and placed into contact with air (and it
associated oxygen), resulting in the dark, cloudy water shown in Figure 4.
This cloudy, black-tinted water contains suspended particles of
manganese oxides/hydroxides. These are the stains and coatings that c
affect plumbing fixtures and laundry. This generally is referred to as the
“aesthetic” or “nuisance” effects of excessive manganese in water
supplies.
an
Figure 4. Water containing elevated levels of manganese sampled from a
residence.
Manganese also can dissolve into groundwater. This opposite reaction is
referred to as reductive dissolution. When an aquifer which is regularly
supplied with oxygenated recharge water suddenly becomes starved of
this water, the aquifer can become enriched in manganese. Oxygen
depletion in aquifers can happen because of land-use changes at the
surface or the release of organic substances (i.e., oil or other
contamination) into groundwater, which drives oxygen consumption by microbial communities.
In either case, oxygen depletion leads to a change in the overall redox state of groundwater,
which can dissolve solid-form manganese through reduction reactions.
Bacteria also can make some of the manganese coatings that develop on plumbing fixtures and
water treatment equipment. Certain bacteria derive their energy by reacting with soluble forms
of iron and manganese. These organisms thrive in waters that have high levels of iron and
manganese. The bacteria change the iron and manganese from a soluble form into thick mats
of black or reddish brown slimes. These slimes can clog plumbing and water treatment
equipment and can slough off in globs to create iron or manganese stains on laundry.
Precipitation caused by bacteria occurs fast and tends to concentrate staining. The elimination
of these bacteria from wells often is a difficult and expensive undertaking. (University of
Minnesota website see links)
Sources
Hem, John D., 1985. Study and Interpretation of the Chemical Characteristics of Natural Water; Third
Edition; USGD Water Supply Paper 2254.
Hem, John D., 1963. Chemical Equilibria and rates of Manganese Oxidation; US Geological Survey
Water Supply Paper 1667-A.
Mitsch, W.J., and Gosselink, J.G., 2007. Wetlands, 4th. Ed. John Wiley and Sons, Hoboken, New Jersey.
Nadaska, Lesny and Michalik, 2010. “Environmental Aspects of Manganese Chemistry”, Health and
Environmental Journal, Article ENV-100702-A.
5 Regulation of Manganese in Water Supplies and Groundwater
Manganese levels in drinking water supplies are not currently regulated or enforced in
Minnesota, with the exception of bottled water. The existing regulatory framework has resulted
in several federal and state threshold water quality concentrations which are used in various
ways to address the potential public health risks associated with prevalent manganese in
groundwater.
Federal Regulations and Guidance
The US Environmental Protection Agency (USEPA) is responsible for establishing drinking
water quality standards under Title XIV of the Public Health Safety Act, more commonly known
as the Safe Drinking Water Act (SDWA). Under the SDWA, the USEPA developed the National
Primary Drinking Water Regulations (“primary standards”), which are the legally-enforceable
water quality standards that apply to public water supplies. Primary standards are the basis for
Maximum Contaminant Levels (MCLs) that represent the highest contaminant levels allowable
in drinking water. There is no primary standard (and no enforceable MCL) for manganese.
The SDWA also sets non-enforceable standards. These are the National Secondary Drinking
Water Regulations (“secondary standards”), and are the basis for Secondary Maximum
Contaminant Levels (SMCLs). The SMCLs provide technical guidance for regulating
constituents that can cause unwanted cosmetic or aesthetic effects. A secondary standard
(SMCL) of 50 ug/L was established for manganese because concentrations above this level
typically cause laundry staining, scaling on fixtures, and deleterious appearance, odor, and/or
taste (USEPA, 2004). These aesthetic issues affect consumer acceptance of the water.
The USEPA also provides Health Advisory (HA) values for unregulated contaminants that may
cause non-cancerous health effects. HA values are set for a range of exposure times and
include a 1-day, a 10-day and a Lifetime Health Advisory value. For manganese, the Lifetime
HA value has been set to 300 ug/L to protect against neurological effects. The 1- and 10-day
HA value for acute, or short term, exposures is 1,000 ug/L (or 300 ug/L for infants under 6
months old; USEPA, 2004). The January 2004 US EPA Drinking Water HA concluded that the
recommendation to reduce manganese concentrations in water supplies to below 50 ug/L (the
SMCL), to avoid aesthetic effects, also is more than adequate to protect human health.
The SMCL and the HA values serve as technical guidance for local, state, and federal agencies,
who are responsible for implementing (enforcing) USEPA primary standards. The enforcement
agencies may establish higher or lower levels depending on the local conditions and goals, such
as unavailability of alternate water sources, provided that public health and welfare are not
adversely affected.
Minnesota Regulations and Guidance
The Minnesota Department of Health (MDH) enforces the primary drinking water quality
standards in the nearly 7,000 public water suppliers in the state. Public water suppliers,
however, are not required to treat drinking water for manganese because there is no primary
standard for this chemical.
The MDH does provide health-based guidance so water suppliers can understand the potential
health risks of unregulated chemicals, like manganese. Three types of health-based guidance
values have been established for manganese in drinking water by the MDH. Each type varies
based on the extent of information available, the methodologies used to establish guidance and
whether the guidance has been formally adopted by rulemaking (MDH, 2012), as outlined in
Table 2. Guidance values include Risk Assessment Advice (RAA), Health-Based Values (HBVs)
and Health Risk Limits (HRLs).
Table 2. Minnesota manganese guidance values.
Type Basis Manganese Values
Health Risk
Limits (HRL)
Formally adopted through the rulemaking
process, outlined in Minnesota’s Health Risk
Limit Rules
HRL93 = 100 ug/L
Health-Based
Values (HBV)
Have the same data requirements as HRLs, but
have not been formally adopted through the
rulemaking process
HBV08 = 300 ug/L
Risk
Assessment
Advice (RAA)
Based on more limited data or newer
methodologies and can be either numeric or
qualitative (9)
RAA12 = 100 ug/L for infants
under one year; 300 ug/L for
adults and children one year of
age or older
In 2012, the MDH re-evaluated health-based values for manganese and developed tiered 2
(meaning multiple values) health-based guidance. This approach was used to develop RAAs
(RAA12) of 100 ug/L for infants under one year of age, especially those that drink formula
reconstituted with tap water, and 300 ug/L for adults and children one year of age or older (or
infants who are breastfed). The value corresponding to the RAA12 of 300 ug/L was originally
adopted as a HBV in 2008 (HBV08=300 ug/L) while the more restrictive RAA12 is the same as
the manganese HRL issued by the MDH in 1993 (HRL93=100 ug/L). These health-based
guidance values can be used by public water suppliers, private well owners, and agencies that
regulate groundwater use protection.
Public Water Supplies
Many public water suppliers treat their water to mitigate the nuisance and aesthetic effects that
generally occur in water containing more than 50 ug/L of manganese, despite this lack of
specific regulation. There are currently 918 community suppliers in Minnesota that provide
drinking water from groundwater supplies. Not all of these supplies contains elevated
manganese; however, a total of 107 community suppliers report some type of “manganese
removal” and an additional 115 community suppliers report “manganese/iron removal” (personal
communication, Rindal, 2015). Based on populations served, approximately 25% of
2 The tiered based approach is unique to manganese. This unique methodology requires classification of
these guidance values as Risk Assessment Advice (RAA).
Minnesotans have access to drinking water that undergoes some sort of treatment to reduce
manganese levels.
Private Drinking Water Supplies
Approximately 1,350,000 Minnesotans obtain drinking water from private water wells. The
quality of water from these wells is not regulated, and sampling and monitoring is the
responsibility of well owners. It is common for private well owners to use treatment systems to
mitigate nuisance or aesthetic effects in their water.
Bottled Water
Bottled water, unlike public or private water supplies, is regulated by the Food and Drug
Administration (FDA) as a food product under the Federal Food, Drug and Cosmetic Act
(FFDCA). Bottled water is sourced from various types of water supplies - artesian waters,
mineral water, spring water, municipal water and groundwater. The FDA enforces a 50 ug/L
limit among those sources. Sources for bottled water production in Minnesota must be approved
by the Minnesota Department of Agriculture (MDA). The MDA enforces the federal
government’s allowable level of 50 ug/L for bottled water in Minnesota. Mineral water 3 ,
containing naturally elevated levels of total dissolved solids, is exempt from these standards
both at the federal and state level.
Groundwater Use Protection
The MPCA is charged with protecting the overall quality of Minnesota’s groundwater. In
Minnesota’s rules for Water Quality Standards (chapter 7050) all groundwater in Minnesota is
protected as a Class 1 (Domestic Consumption) resource. The applicable standards include the
MCLs and SMCLs. The SMCL for manganese, 50 ug/L, is considered by agencies in developing
groundwater quality monitoring requirements, intervention limits, and clean-up goals for the
remediation of groundwater contaminated by anthropogenic sources. Various state agency
programs also consider the direct use of the groundwater for drinking and may apply the health-
based guidance values administered by the MDH in setting site- and facility- specific
groundwater requirements.
Potential for Regulatory Action
The SDWA requires the USEPA to develop a Candidate Contaminant List (CCL) that identifies
unregulated contaminants that are known, or are likely to be found, in drinking water supplies.
This list is updated every five years and prioritizes the review and investigation efforts for
unregulated contaminants. The USEPA must evaluate at least five contaminants on the CCL
and make a regulatory determination on whether or not to issue primary standards for those
contaminants. Regulatory determinations are based on whether or not the contaminant has
adverse human health effects, widespread occurrence that could impact public health, and the
potential to reduce public health risks (USEPA, 2012a). If an affirmative regulatory
determination is made, the new primary standards must be adopted by rule (USEPA, 2012b).
3 "Mineral water" means water from one or more boreholes or springs, that contains not less than 250
parts per million total dissolved solids, and originating from a geologically and physically protected
underground water source. It is distinguished from other types of water by its constant level of minerals
and trace elements at the point of emergence from the source. (as defined in Minn. R. 1550.3200).
Since 1998, there have been three CCLs. Manganese was one of 60 contaminants included on
the first list, but a review of the data available at that time resulted in a negative regulatory
determination and no new standard. In February 2015, the USEPA published the draft of the 4th
CCL for public comment. Manganese was included on this list based on new information
regarding its occurrence and potential health effects. Although primary standards for
manganese may be developed in the future, changes to the manganese standard are unlikely
within the next five years.
Sources
USEPA, 2004. Drinking Water Health Advisory for Manganese. USEPA Office of Water Report: EPA-822-
R-04-003. Washington D.C.
http://water.epa.gov/action/advisories/drinking/upload/2004_02_03_support_cc1_magnese_dwreport.pdf
USEPA, 2012a. Regulatory Determinations for Priority Contaminants on the Second Drinking Water
Contaminant Candidate List. United States Environmental Protection Agency. Accessed 28 July 2014.
http://water.epa.gov/scitech/drinkingwater/dws/ccl/reg_determine2.cfm
USEPA, 2012b. Basic Information on CCL and Regulatory Determinations. United States Environmental
Control Agency. 8 May 2012. Accessed 28 July 2014.
http://water.epa.gov/scitech/drinkingwater/dws/ccl/basicinformation.cfm
MDH. Health Based Guidance for Water. Minnesota Department of Health, 2012. Accessed 28 July 2014.
http://www.health.state.mn.us/divs/eh/risk/guidance/gw/index.html
Rindal, Dave, MDH Community Water Supply Program 2015. Personal communication.
6 Manganese Distribution in Groundwater
The distribution of manganese can be described by analyzing the data collected by a variety of
ambient groundwater monitoring programs. Several county, state and federal programs with
available data are listed in Table 3. Collation and reduction of the data resulted in 8,222
individual manganese records representing untreated groundwater. Data reduction steps
included, for example, calculation of median values for wells sampled on more than one date.
The spatial distribution, sampling techniques, analytical methods, and laboratory reporting limits
for these programs vary, reflecting the research emphases of the various sponsoring agencies
and counties. Despite these variations, these data provide a very good statewide ambient
groundwater characterization. However, the actual human exposure to manganese may be less
in many cases. For example, many private well owners may have treatment devices installed
on their inside taps to remove excess manganese and prevent staining.
Table 3. Manganese Data Sets
Data Source Number of records Date Acquired Note
MDH 1809 January 2015 Safe Drinking Water Act compliance data
MDH 1120 January 2015 Source Water Protection investigative data
MDH 861 Minnesota Arsenic Research Study
(MARS)
Anoka County 190 1997 Marsh, 1997
MGS 59 1992 Lively, et. al, 1992
MDNR 2337 January 2015 County Geologic Atlas, LCCMR studies,
Regional Hydrologic Atlas, etc.
MPCA 42 1994 Wall and Regan, 1994
MPCA 1664 January 2015 Ambient Groundwater Monitoring
Program/Baseline Study
USGS 140 1995, 1998 Smith and Nemetz, 1995; Fong et al., 1998
Dakota County 788 February 2015 Ambient Groundwater Monitoring Program
Statistical Observations
Manganese concentrations in the state’s groundwater ranged from below reporting limits to
more than 5,000 ug/L, with a median value of 101 ug/L (Figure 5). Approximately 66% of the
samples were above the secondary MCL of 50 ug/L, 50% were above 100 ug/L, and 22% were
above 300 ug/L.
Figure 5. Frequency distribution of manganese concentrations in Minnesota’s groundwater.
Spatial Distribution
Figure 6 shows the spatial distribution of the ambient groundwater data, classified based on the
water quality standards and health-based guidance (50 ug/L, 100 ug/L, 300 ug/L). The data
density indicate a general emphasis on monitoring in more densely-populated regions of the
state.
In general, manganese concentrations in the groundwater are spatially quite variable,
sometimes over relatively short distances. The data show a few noticeable spatial patterns. In
Southeastern Minnesota, manganese concentrations rarely exceed 50 ug/L. In contrast,
concentrations commonly exceed 1,000 ug/L in portions of Southwestern Minnesota. In
addition, geostatistical analysis indicates there is some spatial correlation between manganese
concentrations in the dataset. The spatial correlation was used to develop a predictive model of
the distribution of manganese in groundwater, based on probability (Figure 7). For this dataset,
the probability of manganese concentration exceeding 100 ug/L is spatially correlated,
consistent with an exponential model 4 . Other variables, such as the well depth or aquifer, also
impact the probability estimated by ordinary kriging as a lumped parameter 5 .
4 https://en.wikipedia.org/wiki/Variogram
5 https://en.wikipedia.org/wiki/Kriging
Figure 6. Manganese in groundwater measured at 7,574 wells. Samples collected at various times, for
various studies. Data collated and map prepared by the Minnesota Department of Health, February,
2015. Dashed line encloses area of southeastern Minnesota with low (< 50 ug/L) manganese
concentrations. Dashed ellipse encloses area of southwestern Minnesota where manganese
concentrations exceed 1,000 ug/L.
Figure 7. Probability map indicating areas where manganese concentrations in the groundwater will
exceed 100 ug/L <25% of the time, 25%-50% of the time, 50%-75% of the time, and > 75% of the time.
The map was derived using a general model of spatial variation based on the variability of manganese
concentrations and the number of data points. Areas within 1 mile of a sampled well are shown as dots
with the most intense color, and shading decreases with distance from each well.
Sources
Fong, Alison L., Andrews, William J., and Stark, James R., (1998), Water-quality assessment of part of
the upper Mississippi River Basin, Minnesota and Wisconsin—Ground-water quality in the Prairie du
Chien-Jordan Aquifer, 1996, United States Geological Survey Water-Resources Investigations Report 98-
4248, 45 pp.
Hem, John D., (2005), Study and interpretation of the chemical characteristics of natural water, United
States Geological Survey Professional Paper 1473 (reprinted from 1970 edition), 363 pp.
Lively, Richard S., Jameson, Roy, Alexander, E.C., Jr., and Morey, G.B., (1992), Radium in the Mt.
Simon-Hinckley aquifer, east-central and southeastern Minnesota, Minnesota Geological Survey
Information Circular 36, 58 pp.
Marsh, Richard, (1997), Evaluation of trace metals and sulfates in individual water supplies, Anoka
County, Minnesota, Anoka County Community Health and Environmental Services Department, 50 pp.
Minnesota Department of Health (Messing R., R. Soule, J. Small-Johnson, D. Durkin, M. Salisbury (née
Erickson), L. Souther, J. Connett, B. Baker). December 2001. The Minnesota Arsenic Study (MARS):
Final Report to Agency for Toxic Substances and Disease Registry (ATSDR).
Smith, E.S., and Nemetz, D.A., (1996), Water quality along selected flowpaths in the Prairie du Chien-
Jordan Aquifer, southeastern Minnesota, United States Geological Survey Water-Resources
Investigations Report 95-4115, 76 pp.
Wall, D.B., and Regan, C.P., (1994), Water quality and sensitivity of the Prairie du Chien-Jordan Aquifer
in west-central Winona County, Minnesota Pollution Control Agency, Water Quality Division, 65 pp.
7 Impact Mitigation
Education and Outreach to Impacted Communities
The groundwater community in Minnesota can play a role by educating others about the
potential for health risks associated with manganese in drinking water. Awareness can be
improved especially among the water supply industry, physicians and public health
professionals, well owners, water conditioning installers or contractors, political and community
leaders and educators. Outreach efforts may be targeted in Southwestern Minnesota and other
regions of the state that have elevated ambient manganese concentrations in the groundwater.
Identifying and Mitigating Impacted Water Supplies
A water supply with manganese above the HRL of 100 ug/L also exceeds the SMCL of 50 ug/L;
therefore, water that poses a potential health risk likely will also have aesthetic issues such as
the tendency to stain fixtures or laundry. Many public water supplies containing high manganese
concentrations likely are treated to mitigate these aesthetic issues. However, water testing is the
only reliable method to provide assurance that water supplies contain levels of manganese
below health risk criteria. The results of testing provide a quantitative assessment of whether a
municipality is successfully reducing manganese to protective levels, or whether additional
treatment should be considered.
Testing
Testing for manganese in all water supplies currently is voluntary: there are no specific
requirements for testing for either public or private water supplies.6 The MDH has begun to
sample all new community public water supplies for manganese and only samples non-
community wells for manganese if they are investigating a water quality problem such as lead or
copper concerns.7 Water quality can change in transport from the wellhead to the household
tap, so sampling for individual supplies should take place at the individual drinking water tap.
New private residential wells are not required to be tested for manganese, and samples are
typically taken from wellhead, not the tap. Note that sampling ambient groundwater monitoring,
as discussed in Section 6, is also limited to samples taken from the wellhead, rather than from
the tap.
Local labs can test tap water samples relatively inexpensively (approximately $20). The MDH
provides information on qualified laboratories and detailed sampling information. There are no
regulatory penalties associated with voluntary testing: the MDH cannot enforce water quality
standards in private drinking water supplies or require treatment or replacement of the water
source (i.e., drilling a new well). However, if testing of tap water reveals that concentrations
exceed health-based guidance values, public water supply consumers or well owners,
6 per phone conversation with Basam Banat, Principal Engineer with MDH Community Public Water
Supply Unit on July 16, 2015
7 per phone conversation with Brenda Eschenbacher, Sanitarian with MDH Non-Community Public Water
Supply Unit on July 16, 2015
especially those who intend to use the water source to mix infant formula, could consider
treatment, or temporary alternative water supplies, such as bottled water.
Water Treatment
Specific information about the effectiveness of common treatment methods in removing
manganese from water is sparse. However, treatment used to remove iron in water through
oxidation, a common treatment step in public water supplies, also removes manganese
concentrations. The oxidation of iron tends to occur faster than the oxidation of manganese, so
treatment systems can be overwhelmed by iron and be less effective for decreasing
manganese.
Complex water quality problems require designing a sophisticated treatment system. An
example of a complex problem would be a non-community water-supply well producing a large
volume of water that contains both fecal coliform bacteria and manganese. Treatment would
begin with chlorination to eliminate the bacteria. The chlorination would also oxidize manganese
which would necessitate filtration of the manganese particles. The factors to consider in
selecting the appropriate treatment system include: concentration of manganese, volume to be
treated, other constituents present in the water, and cost. Sophisticated water treatment
systems, although commonly used to treat public water supplies, are rarely used to treat the
water obtained from private wells. Common water treatment options are listed in Table 4.
Regardless of the treatment used, post-treatment testing for manganese at the primary drinking
water tap is essential to ensure that manganese levels are protective of health.
Table 4. Typical water treatment options
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2
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5
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t
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p
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Ch
l
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2
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0
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.
4
Capital – High O&M – High
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s
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Methods Typically Used by Water Suppliers
Water treatment methods commonly used by water suppliers, such as ultra-violet radiation, air-
stripping, and carbon filtration have some capacity to remove manganese. The most common
methods for removing manganese include:
● Adsorption – manganese ions are sorbed onto a solid substrate;
● Ion exchange (water softening) – regular home water softeners are generally used to
remove calcium and magnesium because these contribute to hardness. Since calcium
and magnesium are both divalent ions, home water softeners also will generally remove
manganese;
● Suspension/sequestration – can be accomplished by adding polyphospates to the water
supply. This does not remove the manganese, but it isolates the ion to temporarily
prevent its oxidation. The effects upon human consumption are unknown.
● Oxidation, precipitation, and filtration or settling – Oxidation converts aqueous divalent
manganese to relatively insoluble manganese oxides/hydroxides. Common oxidizers,
like those listed in Table 5, have different reaction rates and optimal conditions for
effectiveness (Knocke et al, 1990).
Table 5. Common oxidants used in water treatment.
Oxidant Reaction Comments
Air (O2) 2Mn2+ + 2SO4-2+ 2Ca(HCO3)2 + O2 <=> 2MnO2(s)
+2CaSO4 + 2H2O + 4CO2
Very slow
Chlorine (HOCl) Mn2+ + HOCl + H2O <=> MnO2(s) + Cl - + 3H+Slow. Concerns regarding
trihalomethanes, residual
chlorine.
Potassium
Permanganate
(KMnO4)
3Mn2+ + 2MnO4- + 2H2O <=> 5MnO 2(s) + 4H+Fast
Chlorine dioxide
(ClO2) Mn2+ + 2ClO2 + 2H2O <=> MnO2(s) + 2ClO2- + 4H+Fast but temperature
dependent. DOC will interfere.
Ozone (O3) Mn2+ + O3 + H2O <=> MnO2(s) + 2O2 + 2H+Fast. DOC will interfere.
Residential Treatment Considerations
Household water treatment to decrease staining caused by manganese and iron typically is
designed to treat all of the water in the home (“whole house” treatment). Treatment options
include devices 8 purchased from a retailer or from a professional. A licensed water conditioning
8 Three independent water treatment certification agencies websites were consulted: Underwriter’s
Laboratories (UL), NSF International and the Water Quality Association. No devices are specifically
certified for reducing manganese; however, there are many water treatment devices that may reduce
manganese concentrations. As more states establish a drinking water standard for manganese, the
manufacturers of treatment systems may begin to have their treatment devices certified for manganese
removal.
installer or contractor9 can help determine the appropriate water treatment device by
considering the water quality and the consumer’s desired results. Regular maintenance is a
critical factor in maintaining effectiveness of any selected water treatment device. A low cost
alternative is to let water stand in a container until manganese particulates settle to the bottom,
making sure not to consume the accumulated sediment.
Alternative Water Supply
Drinking water containing elevated manganese concentrations can be replaced temporarily or
permanently with bottled water supplied from another source. Alternatively, a new well could be
installed in a different aquifer. In some locations, connection to a public water supply system
may be possible. For families relying on formula for infant nutrition, bottled water could be used
to reconstitute formula, or they may choose to use pre-mixed, “ready-to-feed” infant formula.
Table 6 provides additional consideration of these alternative water supplies.
Table 6. Costs and considerations related to alternative water supply options.
Alternative water supply Estimated Costs Notes
Supplied/bottled water Approximately $365 a year per person
($1/gal x 1 gal/day x 365 day/year)
Levels of manganese < 50ug/L, as
regulated by MDA or FDA
Connection to PWS Varies widely May be unavailable
Replacement well On the order of $5,000 to $15,000 No guarantee manganese
concentration will be lower in new well
9 The Minnesota Department of Labor and Industry licenses water conditioning installers and contractors.
Only licensed water conditioning persons can install and service water conditioning equipment in single-
family dwellings. There is guidance available for hiring a water treatment contractor.
8 Opportunities to Improve Understanding of the Issue
Understanding the potential health risk due to manganese in drinking water will likely take time
and careful consideration by the public health, groundwater, and drinking water communities.
The toxicity and health effects research outcomes related to manganese exposure through
ingestion is relatively new. Further study of the neurological effects of exposure in infants and
children exposed to low levels of manganese is warranted, along with comparison of the effects
of drinking water versus dietary exposure.
Understanding the spatial distribution of manganese in ambient groundwater provides an
effective way to identify the populations that may be most at risk of exposure to manganese in
drinking water. This effort could be refined to the degree that, perhaps with adequate data
distribution at the county-scale, predictions could be made about the occurrence of manganese
in groundwater. To improve this approach, coordination should take place between various
ambient groundwater quality monitoring programs (i.e., MDH, MPCA, MDA, MN DNR, local
governments, etc.). Additional considerations to this approach include:
● Correlation between groundwater and drinking water exposure: What is the correlation
between manganese concentrations in wells and the manganese concentrations in tap
water supplied from them?
● Data density: Spatial analysis is dependent on an abundance of accurately-located and
verified location data. The analysis could be refined by locating and sampling water wells
which have not yet been accurately located and verified. Additional sampling and
analysis for manganese from wells in sparsely-sampled areas will improve the data
distribution.
● Incomplete records: Inadequate well construction (e.g., dug-wells, multi-aquifer wells)
can cause problems with data interpretation. How does missing information on well
construction or geology for some wells affect the assessment?
● Understanding the correlation between geology and manganese-enriched groundwater:
Studies of how different geologic environments affect manganese concentrations in
groundwater. This may provide an aerial screening tool for elevated manganese
occurrences. Improved information about geochemical controls on manganese release
to groundwater. Improved information on the spatial and vertical distribution of
manganese-bearing minerals within Minnesota.
Further evaluation of the effectiveness of manganese removal by common treatment
technologies is warranted, especially with specific reference to health-based water quality
concentrations. Specific evaluations of common, and readily-available point-of-use treatment
methods, such as pitcher and/or faucet filtration units may provide information about relatively
simple treatment strategies.
9 Review of Major Findings and Issues
Health studies indicate neurological sensitivity to manganese exposure levels over 100 ug/L in
infants under the age of 1. These findings led the MDH to issue a tiered RAA for manganese:
100 ug/L for infants, and 300 ug/L for children and adults. The RAA takes into account the high
potential risk of exposure to infants: they may be relying on reconstituted formula as their
primary source of nutrition and exposed to manganese in both the drinking water and powdered
formula. The risk of neurological problems also is increased in infants because they readily
absorb ingested manganese and retain it, primarily in the tissues of the brain, longer than adults
and children.
Groundwater containing manganese above the RAA values is routinely used as a drinking water
source in Minnesota. Manganese in groundwater is largely controlled by the distribution of solid-
phase manganese in aquifers and local redox conditions. Ambient water quality monitoring and
other monitoring programs related to public water supplies form the basis for a statewide
assessment of manganese concentrations in groundwater. Ambient groundwater
measurements do not represent exposure conditions for people using groundwater as a drinking
water source because manganese concentrations may change from the groundwater source
(i.e., the supply well) to the drinking water source (i.e., the tap) in water distribution systems.
However, they can be used to identify potentially susceptible populations. The distribution of
manganese in ambient groundwater indicates that manganese concentrations in Southeastern
Minnesota typically are less than 50 ug/L, and commonly exceeds 1,000 ug/L in Southwestern
Minnesota.
Groundwater and water supply professionals are generally aware of the widespread occurrence
of manganese in groundwater because the manganese oxides/hydroxides precipitate from
water supplies containing more than about 50 ug/L. These precipitates cause staining and other
aesthetic effects. However, people may not be aware of the health implications related to
manganese in drinking water, especially for infants who rely on reconstituted formula for
nutrition. Although some public water suppliers may monitor levels of manganese for aesthetic
purposes, manganese levels are not regulated in drinking water supplies, with the exception of
bottled water supplies.
Healthcare providers and consumers, especially new parents, should be aware of the health risk
posed by manganese in their drinking water supply. When water supplies are treated to below
about 50 ug/L manganese to reduce aesthetic effects, these water supplies are adequately
protective of health. However, because manganese levels are not typically measured,
observation of stained fixtures or clothing should be used an indicator of potential health risk,
especially within areas of the state with high natural manganese concentrations in groundwater.
Using a tap water source that stains faucets to mix formula for infants is likely not protective of
health. Using this water as a drinking water source also may not be protective of adult and child
health.
Many effective technologies are available for treating water supplies. Carbon filtration, reverse
osmosis, cation exchange (water softening), adsorption, oxidation and filtering all likely remove
manganese, although data regarding the efficiency of manganese removal of those systems is
not available. Post-treatment testing would be required in most situations to ensure protective
levels. Alternative water supplies such as bottled water or “ready-to-feed” infant formula are also
practical solutions to mitigate or prevent exposure in formula-fed infants.
Helpful Links
Home Water Treatment Units: Point-of-Use Devices
http://www.health.state.mn.us/divs/eh/water/factsheet/com/pou.html
Deceptive Sales of Water Treatment Systems
http://www.health.state.mn.us/divs/eh/water/factsheet/com/pousales.html
Treatment systems for household water supplies: Iron and manganese removal
http://www.extension.umn.edu/environment/water/treatment-systems-for-household-water-supplies-iron-
and-manganese-removal/
MDH Information: information sheet on manganese in groundwater, and in fall of 2012 MDH published a
short article in their Waterline newsletter.
More recently MDH included an article on manganese in groundwater in their spring/summer 2014
Minnesota Well Management News publication.
Also see: http://www.health.state.mn.us/divs/eh/water/swp/manganese/index.html
MII{TVESOTA VALLEY TE STING LA B ORATORIE S,
1126 North Front St. - New U1m, MN 56073 - 800-752-3557 - Fax 507-359-2890
2616East Broadway Ave. - Bismarck, ND 58501 - 800-279-6885 - Fax 70I-258-9724
1201 Lincoln Hwy. " Nevada, IA 50201 " 800-362-0855 - Fax 515-382-3885
www.mvil.com
INC,
.]EFF LUEHRS
DAKOTA COI]NTY ENVIRON MGMT DEPT
14955 GALAXTE AVE W
APPLE VALLEY MN 55124
Reason for Testinq: MANGANESE
Report Date: 22 Altg 20L4
Lab Number: 14-A34293
Work Order #: 201-424L83
Account #: 023028
Date Recelved: 13 Aug 201-4
Time Received: 15:50
Date Sampled: 13 Aug 2014
Time Sampled: 9:00
Samplers Name: VD
Temperature at- Receipl:: 0.2 C
Sample Description: 14-I45
Site Address of Wel-I: N/A
VANESSA DEMUTH
Met.hod
I
Arral-yzed AnaLystAI]al-yte Resufts MCL
Manganese 0.050 200 .7
It
MCt is defined as Ehe Maximum Contaninant. Level allowed by the Safe Drinking Watser Act. RAL is t.he
Recomended Allo\^table Limit. For further information, contact your state or local health department
or call the EPA Safe Drinking water Hotline 1,-800-425-479L.
Approved by:
Oan O'Connell, Chemistry Latloratory Manager New Ulrn, MN
Analyses performed under our Minnesota Department of Health Accreditation conform to the current TNI standards
The reporting limit was elevated for any analyte requiring a dilution as coded below:
o.062 mg/L
@ = Due to sample matrix
! = Due to sample quantity
8/20/L4 14:52 RMV
i r i:.i i'
l1l i Li
# = Due to concentration of other analytes
+ = Due to internal standard response
CERTIFICATION: MN LAB # 027-015-125 Wl LAB # 999447680 ND MICRO # 1013-M ND WWDW # R-040
publication ofstatemcnls, conelusions or extracts tiom or regarding our repods is rcscned pendine our written approral.
MINNESOTA VALLEY TESTI]VG LABORATORIES,
1126 North Front St. - New Ulm, MN 56073 - 800-782-3557 - Fax 507-359-2890
2616East Broadway Ave. - Bismarck, ND 58501 - 800-279-6885 - Fax 701-258-9724
1201 Lincoln Hwy. - Nevada, IA 50201 - 800-362-0855 - Far 515-382-3885
www.mvil.com
INC,
E
,JEFF LUEHRS
DAKOTA COUNTY
14955 GALAXIE
APPLE VALLEY
ENVIRON MGMT DEPT
AVE W
MN 551_24
Report. Date: 22 Aug 2014
Lab Number: ]-4-A34294
Work Order #: 20]-424:.83
Account #: 023028
Date Received: 13 Aug 2014
Time Received: 15:50
Date Sampled: 13 Aug 2014
Ti me Samnl ed. 9: 00
Semn l Frs N^me . \/D
TFmnFr^Flrre Ar Reeei.Pt' O -2
Reason for Testi-nq: MANGANESE
Sample Descri-pt.ion: 14-146
Site Address of Well: N/A
VANESSA DEMUTH
RAL Method
C
Analyzed AnalystAnalyteResults
Manganese 0.077 mg/L NA 0.050 200.7 8/20/14 14 r52 RMV
'.t f l
, -till*rn-
-'J Jtvt;
-
,, ' I' ' ',:;'}
MCL is defined a6 the Maximum ContaminanE Level allowed by the Safe Drinking Water Act. RAL is the
Recomended Allowable Limit. For further informaEion, contact your state or locaI health departmen!
or calL tshe EPA Safe Drinking water Hotline L-800-426-479f.
Approved by:
Analyses performed under our Minnesota Department of Health Accreditation conform to the current TNI standards.
The reporting limit was elevated for any analyte requiring a dilution as coded below:
@ = Due to sample matrix # = Due to concentration of other analytes
! = Due to sample quantity + = Due to internal standard response
CERTIFICATION: MN LAB #027-015-125 Wl LAB # 999447680 ND MICRO # 1013-M ND WWDW # R-040
publicalion ol slatements. conclusions or exlracts from or regardinlt our rcporls is resened pcnding our *rittcn nppnx rl.
Dan C'Co:'iricll, Che;:i:stry l-aboratcry Mancger
Hardness
The hardness of water supplied by the City is 17 grains per gallon (g/g).
Iron / Manganese
Iron and manganese are minerals found in abundant quantities in groundwater
throughout the region. Although iron is not harmful to human health, water with iron
concentrations greater than 0.3 parts per million (ppm) can be a nuisance. Iron can
leave rust-colored stains on laundry, porcelain, and fixtures. Levels of manganese
greater than 0.05 ppm can tint the water, cause black spots in ice cubes, and cause
the water to have a bitter, metallic taste.
Water Properties
Component Before Treatment After Treatment
Iron 0.385 ppm 0.058 ppm
Manganese 0.091 0.035 ppm
Chlorine N/A 0.5 – 1.0 ppm
Fluoride 0.19 ppm 0.5 – 0.9 ppm
Hardness 17 grains/gallon 17 grains/gallon
Updated August 2015