BioSafe Environmental Solutions

White Paper

Recovering Soluble Mercury from

Wastewater Streams

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Author
Don Wilson, President

Biosafe Environmental Solutions inc.

Introduction

Background Information
Biosafe Environmental Solutions (biosafe) is a small R&D
application research company located in the Province of Ontario.
Zorbtech and Don Wilson, the lead scientist who invented this
environmental technology, have been conducting application
research in the mercury abatement field for the last 6 years. Mr
Wilson has developed a wastewater treatment process which
uses a highly effective adsorbent () which can reduce the level of
mercury in wastewater streams to extremely low levels.

The biosafe technology and treatment process , according to the

research team, can also be used to purify drinking water.
Currently there are no drinking water purification systems which
have the capability to remove heavy metals from potable water.

Proof-of -Concept
In order to prove that this technology ( adsorbent) can in fact
remove soluble mercury from wastewater streams to extremely
low levels, a wastewater demonstration pilot plant was designed
and installed at a wastewater treatment plant located in the
State of Ohio in 2012. The site chosen for the demonstration was
the wastewater treatment plant operated by the City of Elyria in
the State of Ohio. The plant manager agreed to allow the pilot
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plant to be installed with the intent to evaluate the capability of

the technology in terms of removing soluble mercury down to
the required limits as set out in their permit from the Ohio EPA.
The Ohio EPA also supported the installation of the pilot plant and
encouraged Zorbtech to submit the results of the research study.
This was the first pilot plant demonstration site in the State of
Ohio which was set up to illustrate how one technology could in
fact reduce the level of mercury to the required regulations of
the Great Lake Initiative ( GIL) of 1.3ppt.

The technology process and more importantly, the results of the

demonstration were validated by an independent testing
laboratory located in Twinsburg Ohio. Mercury One is a world
leader in the area of detecting low-level mercury and the one of
the only testing facilities in North America which can perform real
time testing on site. This is the pilot plant study which is being
submitted as part of an application for the evaluation of
technology by the Ministry of Environment in the Province of
Ontario.

Technology Breakthrough
Although numerous bench tests exist which illustrated how a
particular technology can remove mercury removed from
various aqueous streams, this is the first implementation of a
real pilot plant demonstration in North America, which illustrates
the use of how one particular technology can be used for the
removal of mercury from an actual wastewater treatment plant.

Location of Pilot Plant

The pilot plant was conducted at City of Elyria Wastewater
Treatment Plant in the State of Ohio. The data from this pilot was
submitted to the OHIO Environmental Protection Agency ("EPA").
The OHIO EPA supported Zorbtech in the implementation of this
pilot plant. The USEPA also supported this pilot plant. The Ohio
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EPA indicated that Zorbtech is the only company in North America

which has published real time data illustrating the use of an
adsorbent for the reduction of mercury to extremely low levels in
an actual operating wastewater treatment facility.

Major Benefits from the Pilot Plant Study

The benefits and more importantly the information generated
from the modifications to the hardware during this trial allowed
the research team to arrive at a set of conclusions which could
lead to the design and engineering of a full scale wastewater
treatment process. Not only did the technology process prove to
be highly effective in terms of reducing the level down to the
1.3ppt as set out in the GIL regulation, but, also in terms as to
how cost effective the process could be in a full scale operation.
This pilot study represents for the first time that the economics
of implementing a new wastewater treatment technology could be
cost effective.

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Scientific Description of Technology

The Zorbtech Environmental Solutions wastewater treatment
process technology is based on the two new innovative
technologies; (a) development of new dithiocarbamate which
adsorbs mercury on to it surface, (b) a process whereby the
aqueous stream is reacted with dithiocarbamate to adsorb the
soluble mercury on to its surface.

In the scientific community, this process to make these new

class of dithiocarbamates is known as Self-Assembled
Mercaptan on Mesoporous Silica( SAMMS) for Mercury Removal
from Aqueous Streams. In general terms, SAMMS is a process
whereby certain organic monolayers( films) are applied to a
synthetic substrate. In scientific terms, the coated substrate is
known as a dithiocarbamate. Hundreds of dithiocarbamates have
been synsethsized and used in numerous fields. The class of
dithiocarbamates which attract heavy metals such as mercury are
relatively new to the game and have never been tested in the
field, particularly in terms of removing soluble mercury from an
actual wastewater stream.

This pilot plant represents for the first time the actual use of a
dithiocarbamate in a real time wastewater treatment plant. Don
Wilson, the primary investigator and research scientist has
invented one of these new dithiocarbamates specifically to adsorb
soluble mercury. His method to coat the surface of the substrates
is unique as he uses natural materials.

Mr. Wilson has broken the cost barrier which has prevented the
development of any treatment technologies for the last 25 years
which are aimed at removing mercury from aqueous streams. In
summary, this new dithiocarbamate invented by Mr. Don Wilson,
not only involves the coating of the surface of mesoporous
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material with functionalized organic monolayers, but has resulted

on the development of extremely efficient material which can
adsorb high volumes of soluble mercury and other heavy toxic
metals found in aqueous stream. The technology can also be
applied to potable water treatment facilities.

Description of the Science

The following figure represents the reaction of the mercury
molecule ( HG+2) with the adsorbent.

The above graphical representation illustrates how the mercury

molecules are bonded to the surface of the adsorbent. In the
above case, synthetic silica is used as the substrate support
system. However, in the Zorbtech process the material which is
used as the supporting substrate has a natural mesoporous

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support structure1. The monolayers which are bonded onto the

substrate are specifically tailored for mercury. ( See Figure 1).
The chemical functionality at one end in the monolayer has an
affinity for the surface of the support structure of the adsorbent,
while the other end has an affinity for the mercury thereby
bonding the mercury to the surface. In this pilot plant the
adsorbent is contained in a reaction tank.

Treatment Methodology
The method employed to treat wastewater streams using the
Zorbtech adsorbent comprise of three steps.

1. Removing, where appropriate all suspended solids from the

wastewater stream.

2. Reacting the outflow from the above the treatment with the
adsorbent in a reaction vessel

3. Removing spent adsorbent from the above vessel and

solidifying the adsorbent thereby encapsulating the mercury
laden compound.

Pilot Plant Setup and Operational Description

The following images represents the actual pilot plant and
the vessels used in the process. It was determined that in
order for the adsorbent to be highly efficient, a pre-
treatment filtration system would be needed in order to
remove the suspended solids The pre- treatment system
consisted of sand media contained in .5 micron media filter.

1 The use of a natural material to create the backbone of the development of this dithiocarbamate is
the essential cost saving factor in terms of using in the real world

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This is the first version of the tank which was used in Step 1
of the treatment process.

Figure 1

Figure 2

This is the second modification of the pilot plant showing a

much larger and taller reaction vessel. The problem
encountered during this phase of the demonstration was the
fact the research team could not determine how the
adsorbent was reacting with the water particular in terms of
employing the fluidized bed concept.

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Modification to Reaction Vessel

This is the final modified reaction vessel used in this pilot
plant

Figure 3

The above Reaction Vessel was modified in terms of

improving the reaction process in with the mercury and the
resin. As a result of this modification, Zorbtech was best
able to visually observe the dynamics surrounding the
adsorbent and the water.

The key technical challenge facing the research team was to

maintain the volume of resin in a suspended fluidized state
in such a manner that it would adsorb 99% the soluble the
mercury in the wastewater stream.

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Innovative Process Technology

Zorbtech discovered during the course operating this pilot
plant that if a fluidized bed was employed during the
reaction phase, a much larger volume of water could be
treated with a given volume of adsorbent and most
importantly, the bed did not create a severe back pressure
problem found in most filter type systems.

The following image represent a typical fluidized bed

treatment system

In this vessel the water from the filtration tank was pumped
to the bottom of the reaction and the treated water as
allowed to flow vertically where it was fed into an outlet port
located near the surface of water.

This improvement allowed a much larger volume wastewater

to be pumped through the pilot plant. The volume of
wastewater pumped through this pilot plant was
approximately 275,000 litres. In the above the image the
wastewater is pumped from the filtration tank (Figure 1) into

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the top of the reaction tank (Figure 4) through a pipe which

discharged the wastewater to the bottom surface of the
tank. The pressure was adjusted in order that the upward
flow stream of the water to keep the small particles in a
suspended state. The fluid velocity in the pilot plant was
adjusted to keep the particles in suspension. In actual
practice, the particles swirl around the bed in rapid motion
which creates the contact with the mercury molecules in the
wastewater stream. One of the key findings from this study
was a complete understanding of the fluid mechanics of
fluidization and how we could use this concept in the
implementation of the Zorbtech Wastewater treatment
process.

A sample of the treated water at this port and then is

analyzed to determine the level of mercury which is being
discharged in the final outfall located at the river edge.

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General Equipment Design

The technology can be scaled up to treat any volume of
water. In the Elyria Wastewater Plant, the average daily
volume was 3MGD (3,000,000 gallons per day). In a full
scale operation at this plant, a 250,000 gallon sand filter
system would remove 99% of all suspended solids.

Here is the image of a full scale fluidized bed reaction vessel

The above image represents the Zorbtech Treatment Process

using a full scale reaction tank, known as the Zorbtech
Mercury Removal System.

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Applications
The number of applications where the Technology can be
applied is as follows

1. Coal-Fired Power Plants

2. Cement Manufactures

3. Treating Mine Tailings containing high levels of mercury

4. Wastewater Treatment Plants

5. Pulp and Paper Discharging High levels of mercury in

wastewater

6. Chlor Alkali Plants

7. Large Industrial Companies Manufacturing Coal-Base

Compounds

8. Soil Remediation Sites containing high levels of heavy

metals including mercury

9. Large Oil Refinery Wastewater Treatment Plants

Technical Analysis and Discussion

The following sections will discuss the reasons and the current
problems surrounding the control of methyl mercury in the
environment.Ely

The Elyria Case Study

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The Elyria plant is an older plant that has a secondary wastewater

treatment facility which discharges it treated wastewater into the
Black River which flows into Lake Erie.

The Elyria plant has a discharge limit of 1.3 ng/L with a variance
permit which allows the plant to discharge up to 12ng/L in its
final outfall. The variance permit was granted based upon the
argument that the any wastewater treatment for the reduction
mercury to achieve the limit of 12 ng/L would be prohibitively
expensive.

Up until the recent development of a new class of adsorbents,

this was in fact true. The cost of mercury from wastewater
streams is based on a report prepared by Foster-Wheeler of the
Ohio EPA in 1999. In that study, is noted that it would cost
anywhere between 10-100 million dollars to remove a 500 grams
for mercury from wastewater streams.

Zorbtech was highly suspect to how these data were created as

no pilot has ever been implemented to provide a complete
economic cost analysis in terms how much it would cost to
remove 1 kilogram of mercury.

Cost of Removing Mercury from Wastewater Streams

In that context, Zorbtech incorporated a set of conditions
whereby an estimate could be made in terms of how much
mercury could be removed by the Zorbtech adsorbent. In order to
accomplish this goal, Zorbtech employed the services of Mercury
One to carry out the independent analysis of results. The
estimated mass of soluble mercury which could be captured by a
kilogram of DioZorb is 100grams. (See Appendix for actual field
data and calculations)

In comparison to the current standard, this represents a

tremendous reduction in the cost per kilogram as set out in the

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report published by the OHIO EPA in 1997. In that report it was

estimated it would cost 10 million dollars to remove 550 grams of
mercury from a wastewater stream.

The Adsorbent
As described above, Zorbtech formulated DioZorb specifically to
remove soluble mercury from wastewater streams. The adsorbent
has been tested in the laboratory and was found superior to
activated carbon and sulfurized carbon which has been the
adsorbent of choice. In bench tests, the DioZorb was more than
ten times more effective than sulfurized carbon and more than
100 times more effective than activated carbon. Bench tests are
useful but real application is critical.

Technological Challenges: Mercury Compounds Found in

Effluent Streams
All adsorbents designed to capture mercury are able to remove
dissolved mercury from wastewater streams. However, in most
cases soluble mercury is often trapped on suspended solids in the
water. As result wastewater treatment plants will have to install
post treatment processes utilizing some form of physical
separation. In most cases the physical separation process uses
an activated charcoal bed or a sand bed filter system. Having
tested wastewater streams which did not have sand filter bed and
streams which employed a filter system, Zorbtech and Mercury
One determine that a much higher capture rated occurred in the
water which had been pre-filtered and all the suspended solids
had be removed from the stream. Therefore the Zorbtech
treatment process must take into account the level of suspended
solids and employ a method to remove the suspended solids.

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Field Tests illustrating The Use of Pre-Treatment Filter

Beds
Mercury One tests the discharges from hundreds of wastewater
treatment plants and the key issue that they have tracked over
time is the level of suspended or total solids found in effluent
samples. When sand filers are employed, the level of mercury in
the effluent is substantially reduced. Although this study did not
quantitate the levels of total solids or suspended solids in various
effluents, Mercury Ones experience provided enough information
to indicate that the level of dissolved mercury in an effluent is
lower than the total level based upon studies commissioned by
clients.

The level of dissolved mercury also varied based upon the

condition of the effluent in terms of pH and influent conditions.
Some facilities have a relatively low influent mercury
concentration and a resulting low discharge level of mercury.
Some facilities have a higher influent total mercury concentration
and a resulting higher level of effluent mercury discharge.

Achieving Low-Level Mercury Numbers

Some of Mercury Ones clients have reduced their effluent
mercury discharge limits by reducing the influent level but have
not achieved the 1.3 ng/L limit in the Great Lakes. The number
of wastewater treatment plant clients that achieve the 1.3ng/L
limit on a routine basis is less than 10% of the over 200 clients
that Mercury One serves in the Great Lakes region. Though lower
influent mercury levels results in lower effluent mercury levels
may be common, there are some plants that have significantly
lowered their influent mercury levels and still have not achieved
the 1.3ng/L Great Lakes Initiative standard

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Improving the Current Wastewater Treatment Process:

Secondary versus Tertiary Treatment
The Elyria plant is a secondary treatment facility and was chosen
based upon the nature of its discharge and the historical data
accumulated by Mercury One. Based upon Mercury One data and
Elyrias willingness to allow the pilot study this became the facility
of choice. The average suspended solids content leaving the
facility was 10-8 mg/L. Further another local treatment plant
that has tertiary treatment have to lower their total suspended
solids content to 8-5mg/L.

These are examples of how some plants have employed tertiary

methods for lowering their suspended solids levels in the
effluent and thereby lowering the level of mercury
substantially, and , in fact the discharge levels of mercury was
reduced to 3 ng/L. Some other treatment facilities amongst
Mercury One clients have secondary or tertiary treatment and
meet the 1.3ng/L limit a majority of the time but have lower
influent mercury. There are other factors that contribute to these
variations but a majority of the time higher suspended solids
means higher effluent total mercury.

The Pilot Plant Concept

The initial concept of the study was to determine the capacity of
Diozorb in a real working environment. Mercury One determined
that at the Elyria plant a majority of the mercury in the effluent
was in the solids. Based upon their own data of comparing total
and dissolved solids for other clients this would normally be true.
However the mercury content dissolved in the Elyria effluent was
always above the 1.3ng/L limit regardless of suspended solids
content. In cases when the historical samples looked nearly
clear, (almost no visible solids) the total mercury level was not
necessarily lower than those with higher suspended or visible

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solids. The pilot plant was purposely designed to provide tertiary

filtration as well as mercury adsorption.

Pilot Plant Description

As described above, the plant consisted of two treatment tanks.
The first tank removed solids down to <5 microns. The second
tank contained the adsorbent. Three different trials were started
and data collected, however the first two trials ended in
equipment failure even though all final discharges were less than
1ng/L. During these first two trials 5000 gallons of water passed
through the two tanks. After a reconfiguration and design
improvement, the third trial got underway. The trail lasted 11
days. All Samples were collected by Elyria Personnel.

The Elyria chemist analyzed for other metals while Mercury One
analyzed only mercury. The mercury levels were consistently
below 1.3ng/L during trials 1 and 2. The third trial started out in
the same manner. For the sake of brevity, only some of the data
from trial three is shown below.

System Description
The effluent from the facilitys final outfall was pumped by the
facilitys pump to the first filtering tank (See Figure 1). The
discharge from the filtering tank (<5 micron solids and dissolved
Mercury) was pumped to the adsorbent reaction tank. The
discharge from adsorbent tank flowed by gravity to the drain.
Samples designated pre-filter were from the final outfall before
entering the first tank. Samples designated as post filter were
samples discharged from the adsorbent tank. The data is as
follows:

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Mercury Concentrations

Date Pre Filter Post

Filter
6/29/12 2.25ng/L <0.5ng/L
7/6/12 8.85ng/L 0.92ng/L
7/9/12 32.9ng/L 1.04ng/L
7/11/12 54.3ng/L 0.94ng/L

No further samples were taken. Elyria did not provide suspended

solids levels with this data. The plant chemist did confirmed that
the suspended solids content was higher the capacity of the resin
was never reached (no breakthrough). The volume of water
pumped through the system was 69,000 gallons. The Mercury
level never exceeded 1.3 ng/L.

The quantity of DioZorb used in this pilot plant demonstration was

400 grams.

The Zorbtech Treatment Advantages: Complete

Flexibility

The two tank system provided not only some significant answers
to the treatment of solids and mercury levels. The system
provides flexibility. Facilities that have only secondary treatment
may need to add tertiary treatment to remove as much solids as
reasonably possible. The pilot system provides the ability to

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determine if tertiary treatment is needed. In the system a

sampling port is added to test the mercury level between the pre-
treatment tank and the adsorbent tank. Thus the level of
mercury removed by simple filtration can be studied. The
adsorbent tank does a final polish and the mercury can meet
the Great Lakes 1.3ng/L limit as in the initial pilot test.

If a plant already has tertiary treatment, the adsorbent tank is

the only system needed. This polishing unit becomes the only
equipment needed for testing. The system is designed to treat
up to 1 million gallons using 1-3 kilograms of resin based upon
flow requirements. Thus it becomes a very cost effective pilot
test with results that can be easily engineered for flows over 12
million gallons per day.

Conclusion
Based upon current production and the data available at the
Elyria Plant, it is estimated that the treatment cost of the DioZorb
is approximately 0.0005$ per gallon of water. It is hoped that the
estimate is high in that true capacity under a pilot process was
not reached.

At the current estimated cost, exclusive of capital costs, the

DioZorb significantly reduces the perceived cost for the reduction
of mercury in wastewater. A secondary system such as Elyrias
would benefit greatly having a tertiary treatment system and a
final polishing system. As seen by the data, even when the
facility had high mercury levels in the secondary system, the
tertiary unit and final polishing unit still maintained a consistently
low level mercury discharge under the 1.3ng/L limit.

A plant with a tertiary system would only need a polishing unit to

remove the dissolved mercury which would reduce resin costs
further and thus cost per gallon. Zorbtech is looking at further
plant design and testing to generate data from such a plant. The
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simplicity of the physical plant itself renders it idea for any

wastewater treatment plant to use for study to reduce the level in
their outfall. More importantly the consistently low level mercury
discharge provides a great deal of comfort on a day to day basis.

The Zorbtech Technology: Investigating the Removal of

other Heavy Metals
During the course of this research study, a number of other
questions were addressed, namely in the area of what other
metals which could be removed by employing the Zorbtech
Wastewater Treatment Process? In that context, the Elyria
chemist also analyzed the pre and post samples for 15 other
metals. What was noted of significance is that Barium, Copper,
Chromium, Iron, Nickel, Titanium and Zinc were also reduced.

Further study of other metals in the Elyria system using the two
step system would also determine if the metals are removed
during the tertiary phase of the testing or during the polishing
stage. This data would also help determine if adsorbent like
DioZorb is affected by the other metals as these metals may take
up active sites on the adsorbent. What is significant to note is
that the iron content was reduced by nearly 90%. The average
iron content was 979 ug/L and was reduced consistently to 98
ug/L. Chromium was reduced to no -detect status though its
average concentration was only 1.3 ug/L.

A smaller pilot design that Zorbtech has developed can effectively

answer these questions and help older plants examine cost
effective up grades. The smaller design along with the testing
can make pilot studies cost effective and generate significant data
into the reduction of metals in the discharge and potentially
reduce the dissolved solids content of these discharges. This
versatility is part of the modular approach that Zorbtech has
taken for effective and low cost treatment solutions. Zorbtech has

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several modules for handling mercury discharges as high as 34

mg/L and reducing the final to less than 12 ng/L in very unique
ways. Such applications have been tried on Chlor-Alkali
discharges and power plant scrubber systems. Though the
systems are unique, they are effective.

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