Water Technologies & Solutions
technical paper
Optimizing mercury removal processes for industrial
wastewaters
This technical paper was developed in 2012.
Authors: Gerald Walterick, Jr. and Larry Smith, SUEZ.
Introduction
Mercury (Hg) removal from both air emissions and
industrial wastewater, especially coal-fired power
plants in the U.S., has been a topic of extensive study
for the last decade. Much of the initial focus has been
on controlling air emissions of mercury contaminants
from coal-burning power plants which were identified
as the single largest source of airborne mercury
emissions and specifically targeted by the U.S.
Environmental Protection Agency’s (EPA’s) Clean Air
Mercury Rule . This problem was addressed by the
1
installation of wet flue gas desulfurization (FGD)
systems at many coal-burning facilities. The FGD
process has resulted in a significant reduction in air
emission of mercury but has done this by transferring
the mercury contaminants to a wastewater stream.
Other industries such as petroleum refining, natural
gas recovery and other light and heavy industries also
generate mercury contaminated wastewaters. Much of
the recent research has been focused on removing
mercury from industrial wastewaters.
Mercury typically occurs at low parts per billion (ppb)
levels in industrial wastewaters. The severe toxicity of
some mercury compounds and the tendency of these
compounds to bioaccumulate in aquatic ecosystems
have led to very stringent wastewater discharge
regulations to keep mercury out of the environment.
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TP1198EN.docx Oct-22
The Ohio River Valley Sanitation Commission
(ORSANCO) standard of 12 parts per trillion (ppt)
discharge limit on Hg for discharges into the Ohio
River and the Great Lakes Water Quality Initiative
standard of 1.3 ppt Hg for discharges into bodies of
water in the Great Lakes Basin are examples of U.S.
guidelines.
Meeting these limits presents a significant challenge
to many industries. This paper will describe the use
of available technology, which includes a patented
chemical product developed by SUEZ to aid in the
removal of mercury to these low levels in industrial
wastewaters. Known as MetClear* MR2405, this
metals precipitant, when used in conjunction with
other unique coagulants and flocculants from the
SUEZ portfolio, provides significant removal of both
soluble and insoluble mercury.
Mercury Occurrence and Speciation
The primary source of mercury contaminants in coal-
burning power plants is the coal. Mercury
concentrations vary with coal grade, chloride content
and origin, but are typically in the range of 0.05-0.2
micrograms per gram (μg/g), equivalent to 0.0001-
0.0004 lb. /ton. Although many organic and inorganic
2
mercury compounds exist, for the purpose of this
discussion, mercury contaminants will be
categorized into three different “species” that are
related to the chemical or physical process that
would remove them. These are: elemental mercury
(Hg ), ionic mercury (Hg ) and particulate mercury
0 +2
(Hg ).
p
 Figure 1: Coal combustion FGD system mercury speciation

oxidized to Hg . The flue gases then pass through an

2+

Figure 1 illustrates the fate of various Hg species

Electrostatic Precipitator (ESP) or Fabric filter (FF) to
through a typical coal combustion process. Prior to
remove "fly ash" particulates, including Hg . Many
p

combustion, mercury is primarily present in the raw

systems also include Flue Gas Desulfurization (FGD),
coal as naturally occurring mercuric sulfide, which
which is a process originally intended to remove
would be classified as particulate mercury (Hg ). p

sulfur dioxide, (SO ), from coal combustion

During combustion, most of the mercury associated 2

processes, but is also an effective means of removing

with the coal is volatilized to Hg and Hg . Some small
0 2+

mercury, particularly Hg which is soluble in the

2+

fines of Hg may carryover with the fly ash and a small

p

scrubber slurry. Oxidants and catalysts are often

amount of Hg may remain with the bottom ash. As the
p

incorporated into the process to promote oxidation of

combustion products proceed toward the exhaust
Hg to the more soluble Hg species. This enhances
0 2+

stack, they cool down and Hg may be

0

the removal of mercury by the FGD process.

Page 2 TP1198EN.docx
Waste Treatment Processes wastewaters are soluble mercury (Hg ) and 2+

particulate mercury (Hg ). Treatment processes to

p

A significant portion of the airborne mercury handle these wastewaters can be as simple as a
contaminants removed from flue gas is transferred to settling pond as shown in Figure 2, below.
aqueous waste streams that must be treated prior to
discharge. The mercury species of most concern in

Figure 2: settling pond diagram

A more complex wastewater treatment system specifically designed to incorporate chemical precipitation
reactions required for adequate treatment of highly contaminated FGD wastewater streams is shown in figure 3.

Figure 3: FGD wastewater treatment system

This type of system typically includes several separate precipitation, coagulation, clarification, and
unit operations, including desaturation (addition of lime filtration. Biological waste treatment processes may
to precipitate sulfate as gypsum), equalization (to also be included to remove organics, nitrogen
stabilize influent pH and water chemistry), metals compounds and selenium.

TP1198EN.docx Page 3
Chemical Additives • Test apparatus - Mercury removal studies were
done in a dedicated clean laboratory using
Proper selection and application of chemical additives customized apparatus designed and operated to
are critical to the success of a wastewater treatment minimize the potential for sample contamination.
program for mercury removal. Additives used to
• Samples for low-level mercury analysis were
enhance the removal of contaminants in conjunction
processed in a dedicated clean lab using EPA
with the unit operations described above may include
recommended protocols.
lime, coagulants, flocculants, and heavy metal
precipitants. Use of an appropriate precipitant is • Personal Protective Equipment (safety gloves,
essential to ensure that soluble mercury contaminants protective eyewear, and protective clothing) were
are reduced to low ppt concentrations. Several years of always worn by lab personnel.
lab, pilot and full-scale testing have determined that
• The jar test procedures used for mercury
some of the most effective mercury precipitants are
removal studies were customized for each
types like SUEZ’s metals precipitant, MetClear MR2405,
application using a proprietary computer
which has a very strong affinity for mercury and will
program to design mixing protocols that
also precipitate other heavy metals such as silver,
simulated the mixing conditions and reaction
cadmium, copper, lead, zinc, cobalt and nickel.
times of the full-scale wastewater treatment
process. The use of this program improves the
Experimental accuracy of bench tests and facilitates scale-up
Bench scale mercury removal studies (jar tests) were to full-scale processes.
conducted in the laboratory on samples of mercury-
contaminated wastewater from several industrial Results
sources. Due to the extremely low concentrations of
A variety of wastewaters were evaluated, including
mercury typically found in these wastewaters, great
power plant and refinery wastewaters. The range of
care was taken to ensure that the test apparatus and
chemical compositions of these wastewaters varied
sample bottles were meticulously clean. The
widely as shown in table 1.
procedures used for the studies reported here are
summarized below:
Table 1: composition of test substrates

Range of values
Parameter Low - High
pH 3.2 - 9.0
Specific Conductance (umhos @ 25C) 828 - 40,300
P Alkalinity (ppm as CaCO3) 0 - 920
M Alkalinity (ppm as CaCO3) 0 - 3640
Sulfur (ppm as SO4) 97 - 40,000
Chloride (ppm as Cl) 22 - 10,100
Hardness (ppm as CaCO3) 350 - 42,100
Calcium (ppm as CaCO3) 229 - 16,700
Magnesium (ppm as CaCO3) 119 - 33,100
Iron (ppm as Fe) < 0.05 - 1310
Sodium (ppm as Na) 24 - 1630
Potassium (ppm as K) 6.6 - 218
Aluminum (ppm as Al) < 0.1 - 403
Manganese (ppm as Mn) 0.09 - 129
Nitrate (ppm as NO3) 4.2 - 1,800
Phosphate (Total, ppm as PO4) < 0.4 - 201
Silica (ppm as SiO2) 4.7 - 576
Turbidity (ntu) 1.2 - > 4000

Mercury (ppt as Hg) 19.8 - 17,000

Page 4 TP1198EN.docx
Study results with various contaminated wastewaters
demonstrated that the low ppt Hg discharge
concentrations required for each wastewater could be
achieved with proper application of chemical additives.
In many cases, the target discharge concentrations
were achieved using existing plant unit operations.
Figure 5 shows results of tests with an FGD
wastewater that contained >14,000 ppt Hg. The target
Hg concentration of 1500 ppt was attained by
chemical treatment and settling. Increasing the
dosage of MetClear significantly improved Hg
removal.

Figure 4 shows test results for studies done with a pond

wastewater. Untreated, this wastewater contained 47
ppt Hg. With chemical treatment and settling, Hg was
reduced to 2.5 ppt. The improvement in Hg reduction
resulting from the MetClear treatment is clearly
evident.

Figure 5: FGD wastewater mercury removal

Figure 4: pond wastewater mercury removal

TP1198EN.docx Page 5
Figure 6 is a comparison of treatments with MetClear
to treatments with a competitive precipitant. In this FGD
wastewater MetClear treatment reduced Hg to below
the target concentration of 1500 ppt while Competitor
A’s product "leveled off" at > 4000 ppt Hg.

Figure 7: FGD wastewater mercury removal

As previously mentioned, the MetClear product is

Figure 6: FGD wastewater mercury removal
Another FGD wastewater containing 43,800 ppt Hg was
successfully treated to reduce Hg to < 150 ppt using the
MetClear product (Figure 7).
very effective for removing other heavy metals in
addition to mercury. Figure 8 shows the effect of
MetClear treatments on the removal of mercury,
beryllium, cadmium, copper, vanadium, zinc, cobalt,
and nickel.

Figure 8: MetClear affinity for heavy metals

Page 6 TP1198EN.docx
Key Treatment Considerations
When a mercury-contaminated wastewater stream(s)
is identified as a candidate for mercury removal
studies, several key steps must be followed to
determine the potential for successful treatment.
Periodic, routine, and historical sampling and analysis
of mercury contributing wastewater streams must be
implemented utilizing EPA approved protocols for
sampling, handling, and analysis. The U.S. EPA has
published guidelines for proper procedures regarding
this. Method 1669, titled “Sampling Ambient Water for
Trace Metals at EPA Water Quality Criteria Levels” is
commonly used as a guide for sampling techniques.
Analytical techniques to measure low parts per trillion
levels were evaluated and in a 2007 memorandum,
guidelines for use of these analytical techniques were
disclosed . Analytical method 1631E is currently the
10
method of choice for low level mercury analyses.
Common power plant FGD and ash pond systems have
a variety of incoming water quality characteristics as
shown in Table 1. This variability is one of the reasons
why it is so important to routinely analyze and conduct
evaluations in the laboratory and on-site to ensure
optimum removal is maintained.
Impact of Treatment System Equipment Design
To maintain consistent, optimized mercury removal
across any treatment system, all reaction tanks, clari-
fiers, filtration equipment and in the case of oil refining,
both primary and secondary wastewater systems, must
be in excellent operating condition. Removal of mer-
cury, other heavy metals, and total suspended solids
(TSS) are all impacted by the system design and the se-
lection of chemical additives, but that is not the whole
answer for achieving effective removal. For pond sys-
tems, like bottom ash ponds in coal fired power plants,
it is also important to ensure the right chemical feed
points are chosen and optimal dosages are maintained.
Enough residence time under quiescent conditions is
required to facilitate settling of precipitated metals and
other suspended solids. Due to the large size of many
settling ponds, settling time is typically not a limiting
factor.
TP1198EN.docx
Pilot Studies
On-system application of the treatment programs
developed in laboratory jar testing is commonly
conducted through plant trials or pilot studies,
leading to extended or continuous treatment. Several
applications are outlined below to demonstrate the
effectiveness of the trialed programs for removal of
total mercury. Often the requirements for meeting
final discharge permit limits are accomplished by
treating each candidate stream individually. Treated
water may either be combined or discharged
separately. In many cases, immediately after the
precipitation process, results show excellent
removal even though the final discharge limits are
not met at that point in the system. Depending on the
downstream design, further removal is obtained, and
lower mercury levels are realized.
FGD system # 1
This coal fired power plant FGD system has a
traditional design with equalization, reaction tanks
and circular clarifier. The treatment program
includes the use of a coagulant, MetClear MR2405
and a SUEZ flocculant to remove TSS and mercury.
Specific regulatory discharge limits for mercury have
not yet been established at this site. Treatment
results for several heavy metals in this wastewater
are shown in Figure 9. Mercury removal of more than
99% on average has been accomplished, from
approximately 30 ppb to less than 0.2 ppb. The inlet
loading of most other heavy metals is not significant
(less than 1 ppb), compared to iron and mercury.
Results indicate that boron, selenium, and arsenic
are also removed by the combined treatment
approach.
Page 7
 Figure 10: FGD total mercury removal

Figure 9: FGD wastewater treatment system results

FGD system #2 Conclusion

This FGD system includes equalization, desaturation, a The use of chemical technology has been shown to
primary clarifier, a chemical reaction tank, a secondary be an effective method for removing mercury from
clarifier, and a continuous backwash sand filter. This several industrial wastewaters. Incorporating this
filtered effluent is discharged through ash ponds. In type of treatment into an overall wastewater
this system only the secondary clarifier is treated with treatment program should significantly improve
chemicals. Additives include lime for pH adjustment, mercury removal. The industry generating the
MetClear MR2405, a coagulant and a SUEZ flocculant. wastewater, the design of the wastewater treatment
Target levels for mercury are less than 200 ppt Hg out plant, the operating conditions of the plant and the
of the treated clarifier. Results have shown that mercury concentration and speciation in the influent
mercury can be removed from an inlet range of 230 to wastewater are all factors that have an impact on the
350 ppt down to as low as 65 ppt after the clarifier and efficacy of a treatment program. Understanding the
as low as 45 ppt after the filters, well below the target unique characteristics of each system and the
goal of 200 ppt. variability of the contaminant loading is vital to the
FGD system #3 successful removal of mercury from industrial
wastewaters.
This FGD wastewater treatment system includes
equalization, reaction tanks, clarifier and sand filter
prior to discharge. This system also utilizes a
coagulant, MetClear MR2405 and a SUEZ flocculant to
remove mercury, other heavy metals and TSS. Results
from treatment are shown in Figure 10. Mercury
removal more than 99.91% was achieved with
treatment. Average influent mercury of 84,800 ppt was
reduced to 78 ppt across the clarifier then to 18 ppt
through the sand filter. This site is also not currently
regulated for mercury removal.

Page 8 TP1198EN.docx
References
1. www.epa.gov/camr/basic.htm “Basic information
(Clean Air Mercury Rule)”
2. Schwalb, A.M. and Withum, J.A., "The Evolution of
Mercury from Coal Combustion Materials and By-
products", Mercury Control Technology R&D
Program Review Meeting, August 12-12, 2003.
3. www.uwp.edu/departments/geosciences/mercury.
cfm “Mercury Awareness”
4. http://library.acaa-usa.org/2-
Factors_Affecting_Mercury_Chemistry_and_Captu
re_in_Wet_FGD_Systems.pdf Blythe, G., “Factors
Affecting Mercury Chemistry and Capture in Wet
FGD Systems”
5. USEPA, “EPA’s Clean Air Rules: An Update”,
DOE/NETL 2007 Mercury Control Technology
Conference, December 11, 2007.
6. Pavlish, John H.; Sondreal, Everett A,\.; Mann,
Michael D.; Olson, Edwin S.; Galbreath, Kevin C.;
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8. Diaz-Somoano, Mercedes; Unterberger, Sven;
Hein, Klaus; “Using Wet-FGD systems for mercury
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9. Goodarzi, Fariborz; “Characteristics and
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10. http://water.epa.gov/scitech/methods/cwa/metals
/mercury/upload/2007_10_02_pubs_mercurymem
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