Technical Memorandum

To: Kevin Bagby and Ryan O’Keefe, Tribar Technologies, Inc. (Tribar)
From: Don E. Richard and Teresa Kinder, Barr Engineering Co.
Subject: Conceptual Fate of Chromium in Wastewater
Date: August 11, 2022
Project: 22631032

The purpose of this memo is to provide an analysis of the fate and transformation processes encountered
by an industrial wastewater containing chromium beginning with a pretreatment system before
discharging into a sanitary sewer system leading to a publicly owned treatment works (POTW).

The three steps included in this process are:

• Pretreatment at the industrial wastewater facility,

• Conveyance and transformation during transport through the sanitary sewer, and
• Treatment at the POTW.

The processes encountered in each of these steps are described below. Where available, actual values are
calculated to quantify a known release of industrial wastewater that occurred on or about July 29, 2022,
from an industrial facility located in Wixom, MI.

Industrial pretreatment
A volume of 2,670 gallons of etch solution containing 53 oz/gal of chromic acid was removed from a
plating operation and stored in one of two influent equalization tanks (Tank A, approximately 15,000-
gallon capacity. See attached process flow diagram). This tank was used to pretreat industrial wastewater
containing hexavalent chromium. This volume of used acid was also mixed with approximately 7,000
gallons of rinse water that was used to clean out the etch tank after the acid was removed. The
concentration of total chromium in a total volume of 10,000 gallons is calculated to be 46.6 g/L. The total
mass of chromium was 3,892 pounds.

The etch solution and rinse water was stored for a total of seven days (July 23 through July 29 inclusive).
During the seven days that this material was in storage, several chemical processes were used to reduce a
portion of the hexavalent chromium (Cr+6) to trivalent chromium (Cr+3), including:

• Addition of chemical reducing agents – sodium bisulfite (SBS: NaHSO3) and sodium metabisulfite
(MBS: Na2S2O5)

Barr Engineering Co. 3005 Boardwalk Street, Suite 100, Ann Arbor, MI 48108 734.922.4400 www.barr.com
To: Kevin Bagby and Ryan O’Keefe, Tribar Technologies, Inc. (Tribar)
From: Don E. Richard and Teresa Kinder, Barr Engineering Co.
Subject: Conceptual Fate of Chromium in Wastewater
Date: August 11, 2022
Page: 2

• Addition of hydrogen peroxide

• Contact with granular activated carbon (GAC)

A total of 140 pounds of SBS (35lbs/day, July 25-29) and 55 pounds of MBS (July 29) was added to the
influent equalization tank and mixed using an air lance to facilitate chemical reduction. MBS in water is
converted to SBS which reduces hexavalent chromium via the following equation:

3NaHSO3+ 2H2CrO4>>> Cr2(SO4)3+ 3NaHSO4+ 5H2O

Based on the stoichiometry of this equation, 6.1 pounds of SBS or 2.8 pounds of MBS can convert one
pound of hexavalent chromium to trivalent chromium. Thus, the addition of these materials is calculated
to have reduced 43 pounds of hexavalent chromium to trivalent chromium.

Similarly, five gallons of 30 percent hydrogen peroxide were added to Tank A on July 29. In aqueous
solutions with low pH, hydrogen peroxide has been shown to reduce of Cr+6 to Cr+3. Finally, as the low pH
solution passed through a series of four treatment vessels containing GAC or an ion exchange resin,
surface reactions reduced Cr+6 to Cr+3, with a portion of the reduced chromium remaining sorbed to the
solid surface. A portion of the hexavalent and total chromium mass was also retained within the pore
space of these units.

Results of chemical analysis of the saturated GAC or ion exchange materials were used to calculate the
volume of industrial wastewater, and the corresponding mass of chromium, that was retained in these
vessels. A summary of these calculations is included in the following table.

Unit GAC/Resin Total Chromium Total Chromium Hexavalent Hexavalent

(kg) (mg/Kg) (lbs.) Chromium Chromium
(mg/Kg) (percent of
Total)
Cylinder 1 2,268 77,000 658 7,400 9.6
(GAC)
Cylinder 2 2,268 50,000 638 4,100 8.2
(GAC)
Cylinder 3 2,268 9,000 116 130 1.4
(GAC)
Cylinder 4 907 12,000 60 15 0.125
(resin)
Total (lbs.) 1,499

Subtracting the mass of chromium retained in these vessels from the total mass initially stored in Tank A,
the total mass of chromium potentially discharged is calculated to be 2,392 pounds. In addition, the low
percentage of hexavalent chromium present in the final cylinder supports the analysis that most of the

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To: Kevin Bagby and Ryan O’Keefe, Tribar Technologies, Inc. (Tribar)
From: Don E. Richard and Teresa Kinder, Barr Engineering Co.
Subject: Conceptual Fate of Chromium in Wastewater
Date: August 11, 2022
Page: 3

chromium in the industrial discharge was in the trivalent form. This observation is consistent with
analytical results for influent and effluent samples collected at the POTW, which are discussed further in
the following sections of this memo.

After passing through the four GAC/ion exchange units, the industrial wastewater was discharged at a rate
of approximately 60 gallons per minute to the sanitary sewer. At this rate of discharge, the entire volume
was released in approximately 167 minutes. The concentration total chromium and hexavalent chromium
in this liquid is calculated to be 28.6 g/L and 35 mg/L, respectively, based on the effluent mass of 2,392
pounds of total chromium released in 10,000 gallons and 0.12 percent of the total chromium remaining as
hexavalent chromium after passing through the GAC/ion exchange vessels.

Sanitary sewer conveyance

The industrial wastewater was discharged to the sanitary sewer system and conveyed to the POTW by
gravity flow within the sewer pipes. The aquatic environment within sanitary sewer systems is generally
low in oxygen due to the high concentrations of biodegradable organic matter and the presence of a high
density of microbial life. This environment would not be conducive to re-oxidation of trivalent chromium
to hexavalent chromium, but could potentially be suitable for microbial reduction of any remaining
hexavalent chromium to trivalent chromium. This process is not as rapid as chemical reduction using SBS
or GAC; however, with extended travel times, some portion of the remaining hexavalent chromium could
have been reduced.

The distance from the industrial facility to the POTW is approximately 4 .3 miles or 22,700 feet. Assuming
a typical travel speed of 1 foot per second for water flowing in the sewer system, the time required to
convey the discharge from the industrial pretreatment system to the POTW would be approximately 6.3
hours.

The average daily flow to the POTW is approximately 1.5 million gallons per day (MGD), or approximately
62,500 gallons per hour, although this varies throughout the day with higher flows typically in the
morning and in the late afternoon. This volume would have been combined with the average flow of
60 gallons per minute from the industrial discharge resulting in a total chromium concentration entering
the POTW of approximately 1,650 mg/L for total chromium and 2.1 mg/L for hexavalent chromium, for a
duration of approximately 3 hours. The actual pattern of the change in concentration before, during, and
after the arrival of the industrial discharge to the POTW is likely to have been spread out over longer
durations with a peak concentration likely lower than the calculated concentration based on the ratio of
industrial and municipal flows.

POTW treatment
The primary treatment processes included in the Wixom POTW include:

• Influent screening and grit removal

P:\Ann Arbor\22 MI\63\22631032 Storm Water Notice of Violat\WorkFiles\Tribar Plant 5\PIPP Notification\Fate Memo\Conceptual Mass Attenuation Model_08112022.docx
To: Kevin Bagby and Ryan O’Keefe, Tribar Technologies, Inc. (Tribar)
From: Don E. Richard and Teresa Kinder, Barr Engineering Co.
Subject: Conceptual Fate of Chromium in Wastewater
Date: August 11, 2022
Page: 4

• Combined primary (physical) and secondary (biological) treatment in two oxidation ditches (in
parallel).
• Clarification of primary/secondary solids generated in the oxidation ditch for recycle to the
oxidation ditch or removal for disposal.
• Tertiary clarification, filtration, and disinfection.

The processes to manage solids from the secondary clarifiers and tertiary clarification include:

• Dewatering
• Aerobic digestion
• Off-site disposal at GFL landfill

While hexavalent chromium is soluble in water, trivalent chromium is sparingly soluble. Due to its lower
solubility, trivalent chromium becomes bound (sorbed) to solid, particulate matter suspended in water.
During normal operations, the oxidation ditches facilitate the growth of suspended microbial organisms
that provide surface area for sorption that removes trivalent chromium from the water. Solids are
maintained at a high concentration (or density) within the oxidation ditch by recovery of solids in the
secondary clarifier that and recycling a portion of these solids to the oxidation ditch.

During the weekend of July 29-31, one of the two oxidation ditches was in operation while the other ditch
was out of service for maintenance. The total volume of one oxidation ditch is approximately 1.144 million
gallons. A combined water and solids sample was collected from the oxidation ditch on August 2 by
POTW staff. The results of this sample showed 15 mg/L of total chromium. Using the concentration of
15 mg/L throughout the volume of the oxidation ditch, a total of 143 pounds of chromium was retained in
the oxidation ditch.

The concentrations of hexavalent and total chromium measured in the two grab samples collected by
POTW staff from the influent to the POTW at 8:15 am and 6:06 pm on August 1 and one grab sample
from the POTW effluent, also collected at 6:06 pm on August 1, are summarized in the table below along
with the results from one influent and one effluent composite sample:

Location Collection Date Collection Time Total Chromium Hexavalent

(mg/L) Chromium (mg/L)
Influent Grab 8/1/2022 8:15 AM 120 <0.10
Influent Grab 8/1/2022 6:06 PM 1.7 <0.02
Effluent Grab 8/1/2022 6:06 PM 0.017 <0.02
Influent Composite 7/31 – 8/1/2022 6:56 AM 0.053 <0.020
Effluent Composite 7/31 – 8/1/2022 6:56 AM <0.005 <0.020

The influent grab sample concentration on August 1 is one order of magnitude below the calculated peak
concentration that could have been observed in the POTW effluent at the calculated peak concentration,

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To: Kevin Bagby and Ryan O’Keefe, Tribar Technologies, Inc. (Tribar)
From: Don E. Richard and Teresa Kinder, Barr Engineering Co.
Subject: Conceptual Fate of Chromium in Wastewater
Date: August 11, 2022
Page: 5

and has dropped by another two orders of magnitude (from 120 mg/L to 1.7 mg/L) in twelve hours. No
hexavalent chromium was detected in either influent grab sample or the influent composite sample. In
addition, the concentration of hexavalent chromium is at least three orders of magnitude less than the
concentration of total chromium, similar to what was observed in the effluent of the final vessel of the
industrial pretreatment system. Comparing the influent to the effluent also shows a decrease in the
concentration of total chromium confirming that the treatment processes in the POTW are removing
chromium from the water.

Conclusions
The results of this analysis produce the following conclusions:

• An estimated three pounds of hexavalent chromium were present in an industrial discharge to the
Wixom sanitary sever on July 29. 2022.
• The industrial discharge traveled approximately 4.3 miles via the sewer system to reach the POTW.
• An influent composite sample for the POTW did not have a concentration of hexavalent
chromium above the laboratory analytical detection limit of 0.020 mg/L for the period of July 31
through August 1.

The following documents were used to prepare this analysis (attached where noted):

• Spreadsheet of mass balance calculations (attached)

• Industrial wastewater treatment process flow diagram (attached)
• Eurofins laboratory analytical Job No. 190-29392-1 dated August 8, 2022, for wastewater samples
collected by POTW.
• Eurofins laboratory analytical Job No. 190-29452-1 dated August 10, 2022, for GAC samples
collected August 5, 2022, by Tribar.

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Tribar Plant 5 - July 23, 2022 Tank Maintenance/July 29, 2022 Discharge

DRAFT
Contents in Tank A from Etch Tank Units Tank 5
Tank Volume [1] gal 2,670
Chromic Acid Addition [2] oz/gal 53
Chromic Acid Addition in pounds lb/gal 3.3
Chromic Acid weight for etch tank lb 8,844
Chromium weight (44% of Chromic Acid) [3] lb 3,892

Notes:
[1] Size of etch tank 5 provided by Tribar as nameplate capacity
[2] Amount of chromium trioxide is 53 ounces/gallon provided by Tribar
[3] Chromium molecular weight is 44% of total Chromic Acid molecular weight.
Chromic Acid (H2CrO4) MW = 118.01
Cr (Cr+6) MW = 51.996
% Cr of Chromic Acid = 44%

Amount in Granular Activated Carbon (GAC)

1 Cylinder 5000 lb GAC 2268 kg GAC
Cylinder 1 A or B, 2 and 3 (total 3 cylinders of GAC) 15,000 lb GAC 6,804 kg GAC
Cylinder 4 (Resin) 2,000 lb GAC 907 kg GAC
Total GAC 17,000 lb GAC 7,711 kg GAC

Cylinder 1 Cylinder 2 Cylinder 3 Cylinder 4 Total

Potential Amount Discharged Estimated on GAC Sample GAC GAC GAC Resin (lb)
Percent Solids (weight%) 56.1% 39.1% 38.6% 39.8%
Percent Liquid (weight%) 43.9% 60.9% 61.4% 60.2%
Total Weight in Cylinder (lb) 8,913 12,788 12,953 5,025
Weight of Liquid in Cylinders (lb) 3,913 7,788 7,953 3,025
Weight of Liquid in Cylinders (kg) 1,775 3,532 3,608 1,372
GAC Bed Weight (kg) 2,268 2,268 2,268 907
Total Weight GAC + Liquid (kg) 4,043 5,800 5,876 2,279
Total Chromium Concentration (mg/kg) 77,000 50,000 9,000 12,000 Eurofins sample results of GAC
Hexavalent Chromium Concentration (mg/kg) 7,400 4,100 130 15 Eurofins sample results of GAC
Total Chromium in Cylinder (lb) 685 638 116 60 1,499

Potential amount discharged Cr (3,892 lb - 1,499 lb) 2,392

Potential amount discharged Cr+6 lb (based on % of hex Cr of Total Cr in Cylinder 4) 3

Conversion Factors
mg = 2.2E-06 lb
8.3 lb/gallon of liquid

Notes:
Eurofin August 10, 2022 sample analysis of Plant 5 granular activated carbon cylinders. Samples taken prior to replacement of the GAC.
Data is based on available information at the time of this evaulation.
 Process Wastewater Tribar Plant 5 Pretreatment Wastewater Flow Diagram
Legend
Acid Sulfuric Acid
Recycle from Final Discharge Tank Caustic Sodium Hydroxide
or Filter Feed Tank CR-Red Sodium Metabisulfite
Chem-1 Coagulant
Transfer Tank Floc Flocculant

Filter Press Filtrate CR-Red Chem-1 Chem-1

Acid Acid Acid

Caustic Caustic Caustic Floc

Rinse Waste Rinse Waste
Holding Tank Holding Tank To Filter Feed Tank
Tank A Interconnect Tank B

Chrome Treatment
14,923 gallons 14,923 gallons Tank Neutralization Tank Neutralization Tank Flocculator Tank
CRT N-1 N-2 Gravity Settler
Fiberglass Fiberglass
1,250 gallons 1,250 gallons 1,250 gallons 500 gallons

Polyethylene Polyethylene Polyethylene Polyethylene

Process Wastewater

Filter Press Filtrate

Spent Acid Holding

Tank Sludge Thickener
T-2 Transfer Tank

6,122 gallons 700 gallons 3,069 gallons

Chem-1
Fiberglass Polyethylene Filter Feed Tank Fiberglass
Acid
Spent Nickel Process Wastewater Tank A or B
Caustic
Floc

Spent Nickel
Holding Tank Filter Press
T-3 Batch Treatment
Tank
4,106 gallons 2.033 gallons

Fiberglass Fiberglass

Filter Press
Clean/Precoat Tank
360 gallons Transfer Tank
Polyethylene

Transfer Tank
Filter Feed Tank Caustic
Acid

1,250 gallons Recirculate back to Tank A or B

Final Neutralization
Polyethylene Tank
Final Discharge Granular
1,250 gallons Tank Sample to Determine if Recycle Activated Carbon
200 gallons or to Sewer Discharge GAC
Polyethylene Polyethylene Sewer Discharge