F'll'J 'J.'t/032.770 i!,P,P, it> 0~ -'II-~ I ;J..¾,5 Aece; 11(:c/. WDNR., O'f/?.1 I01i Ac. h' UY1 : t 'I 7 April23,2004

Ms. Pam Mylotta Wisconsin Department of Natural Resources 2300 North Martin Luther King Jr. Street P.O. Box 12436 Milwaukee, Wisconsin 53212-0436

Re: Request for Source Area Chemical Injection Permit C & D Technologies, Inc. 900 Keefe A venue Milwaukee, Wisconsin 53212-1709

Dear Ms. Mylotta:

On behalf of the Johnson Controls Battery Group, Inc. (JCBGI) and C & D Technologies, Inc. (C&D), MWH Americas, Inc. (MWH) has prepared this request for an injection permit for groundwater treatment in the acid unloading area at the above referenced site. The purpose of the permit request is to provide information to the Wisconsin Department of Natural Resources (WDNR) for approval to conduct a pilot study and full-scale injection of sodium persulfate into the acid unloading area for treatment of volatile organic compounds (VOCs) in groundwater.

BACKGROUND INFORMATION

Soil and groundwater contamination were found to exist on the Facility property exceeding State environmental standards, based on the August 1999 Phase II Environmental Site Assessment (ESA) of the Facility.

In May and June 2001, remedial action was completed for the on-site lead, PCB, and VOC impacted soils. A summary of the remedial activities is contained in the February 2002 On­ Site Remedial Actions Construction Completion Report. Approximately 400 tons of VOC­ impacted soil was removed during this investigation.

Temporary wells were installed in July 2001 and November 2001 as part of the groundwater VOC characterization investigations documented in the June 2001 and October 2001 Work Plans, respectively. Results of these investigations suggested the potential for offsite migration of VOCs in groundwater.

Additional investigations were performed in May and June 2002 as documented in the Groundwater VOC Investigation Report (September 2002). The purpose of these investigations was to determine the extent and magnitude of groundwater VOC contamination and to evaluate the potential for natural attenuation. Based on the results of the groundwater VOC investigation, two areas were identified as sources of VOC contamination, the acid unloading area and the truck dock loading area. The analysis of

One Science Court Tel 608 231 4747 Del1ve r, ng Innovative Pro1ects and Solut1ons Worldw1ae P.O. Box 5385 Fax. 608 231 4777 Madison, Wisconsin 53705-::)385 remedial action alternatives for both source areas is discussed in the Remedial Action Options and Design Report (September 2003).

Vertical profiling was conducted by using hydraulic probe technology on May 12, 2003 to determine the presence of CVOCs in soils at depth at the truck dock loading area and the acid unloading area. Analytical results for soil samples from DB04 detected no VOC compounds at depths of 20 ft bgs to 30 ft bgs in the acid unloading area.

This permit is being prepared for the acid unloading source area for both a pilot study and full-scale injection, as described above. Refer to Drawing Bl2 for location of the acid unloading source area and the projected injection areas.

BENCH SCALE STUDY

A bench scale test was performed in December 2003 by ORIN Remediation Technologies (ORIN), on soil samples from two different areas in the acid unloading area for treatability testing for chemical injection. The Remedial Action Options and Design Report (September 2003) identified chemical injection using potassium permanganate to be a viable and effective chemical remedial action for remediation of VOC contaminated groundwater in the acid unloading area.

Based on results from this study (Appendix A), use of potassium permanganate in the chemical injection was determined to be cost prohibitive, as it must overcome the natural oxidant demand (NOD) as well as the contaminant demand. The NOD is likely from the reduced iron or ferrous iron present in the soils. The potassium permanganate preferentially reacts with the ferrous iron. Further discussion on the chemical reactions involving potassium permanganate and iron is located in Appendix A. Further testing concluded that sodium persulfate with chelated iron would be an effective, economically feasible alternative. The bench scale treatability study is included as Appendix A.

INJECTION PERMIT INFORMATION

There is no standard permit application apparently available for chemical injection treatment. However, MWH prepared a similar chemical injection treatment permit for the City of Hartford, Former Municipal Landfill (WDNR Facility ID: 00361, WDNR File Ref: 267059100), entitled Request/or Source Area Chemical Injection Permit dated October 24, 2000, which was approved by the WDNR. The City of Hartford permit application was used as a basis for creating this permit application for the C&D facility project site.

The following is a description of site activities and information required by the WDNR for the injection permit.

• Injection Chemical: Chemical injection treatment will be completed by ORIN. The chemical being used at this project will be catalyzed sodium persulfate. Chelated iron is added to the sodium persulfate, which catalyzes the reaction. Catalyzing the

Ms. Pam Mylotta April 23. 2004 Wisconsin Department of Natural Resources Page2 reaction produces sulfate radicals, which are highly reactive and have been shown to reduce levels of chlorinated compounds. The catalyzed sodium persulfate will be mixed with potable water from the City of Milwaukee municipal supply to obtain a slurry of 16% catalyzed sodium persulfate.

• Injection Point Design Specifications: The catalyzed sodium persulfate reagent will be installed using a direct push injection delivery system. The injection equipment used by ORIN is housed in a trailer that contains all of the necessary pumps, tanks, and valves to conduct the injection. Once on-site, the treatment chemistry will be mixed to the proper treatment blend and concentration, and injected into the zone of contamination. The direct push injection method consists of using a Geoprobe to insert the rods into the subsurface. Once the desired depth is reached (approximately 20 feet below ground surface for this site), the slurry of catalyzed sodium persulfate reagent and water is injected through the Geoprobe rods as they are slowly raised through the contaminated zone.

• Schematic of Injection Array and Rate: The injection area for the pilot study is approximately 20 feet by 20 feet. Based on an evaluation of contamination and physical subsurface characteristics, it was determined that approximately 1300 pounds of catalyzed sodium persulfate is needed for treatment of the targeted plume, through 8 direct injection delivery point locations. Based on the project design, 6.5-foot spacings and a 4-foot radius of influence is expected. Each point location will be injected with approximately 165 pounds (125 gallons of 16% catalyzed sodium persulfate slurry). The estimated target area and proposed injection locations are shown on Drawing Bl2.

The injection area for the full-scale injection is approximately 115 feet by 40 feet and will include approximately 92 direct injection delivery point locations. The spacing and footing is assumed to be the same as the pilot scale study. Each point location will be injected with approximately 125 gallons of the catalyzed Sodium Persulfate solution.

The following is a description of how the injection area was chosen in response to WDNR's letter "Investigations Results and Remedial Plans", dated April 20, 2004. The remedial objectives for the full scale injection are to:

• Reduce source area contamination.

• Prevent further off-site migration of CVOC-impacted groundwater to residential areas.

• Treat CVOC-impacted groundwater which is affected by the presence of residual CVOCs in source area soils.

• Minimize site operational disruptions.

• Obtain closure under NR 726 for the Facility within a "reasonable" time frame.

Ms. Pam Mylotta April 23, 2004 Wisconsin Department of Natural Resources Page3 The area for the full-scale chemical injection is based on groundwater quality results in the vicinity of the acid unloading area and evidence for migration of VOCs in groundwater. The results of groundwater monitoring are depicted on enclosed Drawing D13 (Total CVOCs Groundwater Isoconcentration Map, from the Groundwater VOC Investigation Report dated September 2002). · The treatment area is bracketed to the north and south, where isoconcentrations are 1 ppb or higher within the groundwater, as depicted by the isocontours. Drawing D13 indicates no migration of CVOCs to private property in the vicinity of temporary wells TW07 and TWOS, so chemical injection is not planned east of these temporary well locations. West of the temporary wells TW07 and TWOS, CVOCs is covered by a concrete cap, which can be considered a performance remedy. The CVOCs in this location have been in place for many years and show no evidence of migration at this time, here is no reason to believe they will begin to migrate at some time in the future. Therefore, this area was eliminated from the treatment area in the remedial design.

Abandoned well MW04 and OP24 both lie within the proposed chemical injection zone. OP23 is south of the proposed treatment zone by design and is in line with the remedial objectives for this source area (i.e., no migration exists due east of the source area in this location).

• No Temporary Exemption From NR 140 Groundwater Quality Standards: The sodium persulfate solution is a formulation composed of the following elemental constituents: sodium, sulfate, and oxygen. Of these elements, only sulfate has NR 140 groundwater quality standards (NR140, Table 2 - Public Welfare Groundwater Quality Standards). The sulfate related by-product that is generated by the overall reaction is in the form of sodium monosulfate that subsequently breaks down into sulfate ions. The surrounding area is industrial and is supplied with water by City of Milwaukee.

• Vapor Migration Monitoring Plan: This assessment will monitor the potential for vapor migration during the chemical injections:

1. Vapor Intrusion Exposure Pathway Assessment

Prior to the pilot study, this assessment will include onsite observations inside the building for possible vapor migration pathways, including foundation and floor cracks, doorways, and sumps/sewers that are in the vicinity of the footprint of each of the contamination source areas. A PID will be used to sniff suspected pathways for the presence of VOCs. In addition, an analysis of the potential for vapor migration routes and risks to occupants to residences to the east of the acid unloading area during chemical injection will be conducted.

Ms. Pam Mylotta April 23. 2004 Wisconsin Department of Natural Resources Page4 2. Chemical Injection Vapor Monitoring

a. Pilot Study -Vapor migration will be evaluated during the chemical injection pilot study and during the full-scale injection. During the pilot study, vapor monitoring probes will be installed inside and outside the building, for monitoring before, during and after treatment. This will include the installation of 2 probes into the subsurface, one inside the building and one outside the area of treatment in the direction of the residences to the east. These probes would be monitored for LEL with a multigas meter, pressure with a magnahelic gauge, and total VOCs with a PID.

The rationale for vapor migration monitoring from within the building and in the direction of residences to the east of the chemical injection area is to determine whether there is potential for migration to receptors as a result of the chemical injection process. According to our subcontractor for the chemical injection, the sodium persulfate injection should not cause vapor migration as a result of the injection process. Given the distance from the acid unloading area to nearby residences and the tight clay soil environment, it is unlikely that vapor intrusion would affect these residences.

b. Full-Scale Injection - The monitoring from the pilot study will be used to assess the potential for vapor migration during the full-scale injection. If the pilot study suggests that migration is not occurring during the pilot study, then a recommendation will be made that the monitoring need not be conducted during the full-scale injection.

The scope for the full-scale injection is anticipated to include 4 additional probes (for a total of 3 inside and 3 outside the building), unless exempted or changed by WDNR based on the results of the pilot-scale monitoring. The probes will be distributed in parallel, north to south lines.

The methods to be used for monitoring probe installations includes the following:

• Probe holes will be drilled through the concrete slab in the building or into the vadose zone of the unconsolidated soils outside.

• Stainless steel probes will be granted in place with flush mount fittings.

• Dedicated polyethylene tubing will be used to connect the probes to the appropriate meters.

The methods to be used for monitoring probe monitoring includes the following:

• Monitoring will occur just before, during and just after the injection.

Ms. Pam Mylotta April 23, 2004 Wisconsin Department ofNatural Resources Page 5 • Samples will be for monitored for LEL with a multigas meter, pressure with a magnahelic gauge, and total VOCs with a PID.

• Sample data will be recorded in field log books.

Groundwater monitoring may also be required inside the building, if additional source areas are found inside the building and subjected to chemical injection treatment. Additional investigation will be conducted beneath the building near the acid unloading area to determine the presence ofVOCs.

• Proposed Groundwater Monitoring Plan and Operational Plan:

a. Pilot Study - A monitoring plan to evaluate the chemical injection treatment during the pilot study will include collecting groundwater samples from an existing monitoring well location. Specifically, monitoring well MW04R, located in the acid unloading area, will be monitored for field parameters (dissolved oxygen, oxidation-reduction potential, pH, and temperature) and samples will be collected for laboratory analysis of volatile organic compounds (VOCs, method 8260). The schedule for this monitoring plan will be to collect samples prior to chemical injection, during the injection (at the end) and 30 days after treatment. The boring log and well construction details for monitoring well MW04R is included in the Remedial Action Options Report and Design Report, MWH, dated September 2003. The chemical injection treatment is anticipated to be a one-time event therefore, the monitoring plan and literature provided above and Attachment B 1s being used in lieu of an operational plan.

b. Full-Scale - Four groundwater monitoring wells will be installed downgradient of the chemical injection area to monitor the performance of the remedial action. Each of the monitoring wells will be installed to a depth of approximately 16 ft below ground surface. The wells will be constructed of2-in. diameter PVC well materials and a 10-ft well screen. The wells will be installed as flush-mount, so there will be no well stickups (see Drawing B12 for locations).

Groundwater sampling will be conducted during the full-scale chemical injection near the acid unloading area at the 4 new monitoring wells installed in the injection zone. The samples will be analyzed for field parameters pH, temperature, conductivity, redox, and dissolved oxygen and VOCs at an analytical laboratory. Samples will be collected and analyzed before, during (near the end of the injection) and approximately 30 days after the chemical injection.

• Specific Contaminant Types and Concentrations: Historic summary tables of site groundwater sample results are included in the Remedial Action Options Report and Design Report, MWH, dated September 2003. Contaminants of concern are chlorinated volatile organic compounds (CVOCs).

Ms. Pam Mylotta April 23. 2004 Wisconsin Department of Natural Resources Page 6 • Site Safety Plan: A Site Safety Plan (SSP) will be developed for the chemical injection of the acid unloading area of the site. The SSP will include project phone numbers and site personnel working.

• Proximity to underground utilities and residential buildings: The attached Drawing B 12 also shows the location of the source area, monitoring wells, underground utilities, and other surrounding features of the site. There are no public utilities located beneath the alleyway in this area. The site is located in an industrial area, consisting of primarily industrial buildings with some residential homes. The CVOCs that are being treated do not tend to create dangerous off-gas vapors during treatment like petroleum related contaminates may.

Please review the injection permit request and provide us with WDNR approval to proceed with the source area treatments as soon as possible. If there are any changes in the proposed full-scale treatment, based on the results of the pilot study than what is proposed in this permit application, we will advise you of the in writing before the full-scale treatment.

Please call us if you have any questions regarding this information.

Sincerely,

MWH AMERICAS, INC. ~G~ Alicia A. Gagne Daniel W. Hall Engineer Project Manager

Enclosures: Drawing B12 - Chemical Injection Area Drawing D13 -Total CVOCs Groundwater Isoconcentration Map Attachment A - Information on the ORIN treatability study Attachment B - Information on the ORIN catalyzed sodium persulfate injection process

cc: Barbara Grundl - Wisconsin Department of Natural Resources Pamela Reich - C & D Technologies, Inc. Timothy J. Lafond - JCBGI

WRB/vlr/ AAG/LBUDWH N:Vobs\208\230 I \2 1\ wp\ltr\86_Mylotta.doc 2082301 .214 7890 I-MAD I

Ms. Pam Mylotta April 23, 2004 Wisconsin Department of Natural Resources Page 7 / >( I LEGEND - • • - APPROXIMATE PROPERTY BOUNDARY

MONITORING WELL LOCATION AND NUMBER -st- / i: $-MW02 0 (SAMPLED 4/30/03) I n I I _J N I -$TW1 TEMPORARY GROUNDWATER MONITORING u_J WELL LOCATION AND NUMBER -st- (SAMPLED 11 /8/01) ~ 1: -$OFW10 C ..., -$OFW01 TEMPORARY OFFSITE GROUNDWATER 3 C (ND) ., I e 0 I TW11$ MONITORING WELL LOCATION AND NUMBER C E ., I. I _ (5.~ ~ (SAMPLED 5/23/02) 1ii a, '­ I l C" .C., I 0 "..., TEMPORARY VERTICAL PROFILING GEOPROBE ~ CX) ~ 0 • • -$-D801 "' • LOCATION AND NUMBER (DB01, DB02, ~ ~ ..,. DB03 AND DB04 SAMPLED 5/12/03, AND ~ 0 Area of • • DB05A, DB05B, DB06, AND DB07 ~ 0 I I') I') I N N • I • SAMPLED 6/14/03) . ' CX) I : 0 ..,. Injection N • I • ~ ~ CVOC CONCENTRATION IN ug/L • (1141) >, • CD ~ 't:I ., • • 1/) STREET TREE ., 't:I 0 C. C C • • 0 ~ 0 .; e ~ 'iii • • .,> C. ·;;:., LIGHT POLE C. ~ 3609 C <( ct: ct: .,3 .,'­ • I • I '> g' TRAFFIC LIGHT C • <> ct: " 55t OFW11 0~ , CATCH BASIN 0..., MW04R • • . $(4.8) • ·c ~ I I $-OFW05 .c ·~ 07 U 0 • ., '­ (150) .m• (260) HYDRANT I- c.. • I GAS LATERAL c!i c!i • ' I I • • "'~N 0 WATER LATERAL ..,.I ..,.I & • • 1 STREET NUMBER/ADDRESS •✓ 1 9 • APPRO XIMATE RESIDENTIAL LOT LINE PILOT INJECTION AREA • • ., - • • PROPOSED DOWNGRADIENT .g"E! ."2 • -$ PERFORMANCE WELL C 1/J • ...,"1/) ., • INJECTION POINT ~£ • • .c • ~ C. 't:I • :J c.,"" ~ NOTES 0 • • i;: • • 1. BASE MAP DEVELOPED FROM A SURVEY DRAWING w DATED FEBRUARY 25, 1998 PRODUCED BY NIENOW => • • z D8~ 4~ • ENGINEERING ASSOCIATES, A DIVISION OF McCLURE w • ENGINEERING ASSOCIATES, INC. OF MILWAUKEE, ~ • • WISCONSIN . w LLw • • 2. THE IN-SITU CHEMICAL INJECTION AREA IS w • • APPRO XIMATELY ~ • • 115 ' X 40'. !:: I :E 4 0:: • w $-TWOS ~ w u => a.~ z z I (ND) ~ w- C & D BUILDING z z (/)- <> (/)z 0 ow O i= 13 w u FORMER JOHNSO~ CONTROLS U O LL (I) ~ w _J w 3: FACILITY I "OW I i ~ z ~ - _J:r:1-t::J I ~ ~ I-

ATTACHMENT A

INFORMATION ON THE ORIN TREATABILITY STUDY ~ ORIN Remediation Technolo tes• :;,,

February 24, 2004

Ms. Alicia Gagne MWH Americas, Inc. One Science Court Madison, WI 53711

Subject: Treatability Study Report for the Keefe Avenue Site in Milwaukee, WI. MWH Project No. 2082301.21478901.

Dear Alicia,

ORIN Remediation Technologies (ORIN) is pleased to submit the bench scale treatability study results for the Keefe A venue site in Milwaukee, WI. The objective of this study was to evaluate the effectiveness of various chemical oxidants to reduce the concentrations of chlorinated solvents (PCE, TCE, cis 1,2- DCE, and Vinyl Chloride) at the site.

Background

MWH Americas (MWH) shipped samples from two different areas for treatability testing. Area AU-01 has contamination extending from 3-12 feet. Area AU-02 has contamination extending from 8-12 feet. The extent of the contamination is greater in Area AU-01 since the soils from AU-02 were excavated from 0-7 feet and filled. Groundwater is approximately 5-6 feet below ground surface (bgs).

Samples from both areas were received in multiple clear glass jars. AU-01 samples were collected at varying depth intervals: AU-01 (3-4'), AU-01 (6-8'), AU-01 (8-10'), AU-01 (10-12'), AU-01 (12-14'), and AU-01 (14-16'). Samples AU- 02 were collected at depth intervals of AU-02 (8-10'), AU-02 (10-12'), AU-02 (12- 14'), and AU-02 (14-16'). Depending on the depth, the samples consisted of fill material, clay or silty clay. The samples were collected on December 6, 2003 and received by ORIN on December 8, 2003. All samples were received on ice with no apparent headspace. The samples were kept refrigerated until treatment.

Field headspace analysis using a Photoionization Detector (PID) found the highest readings in sample AU-01 at depth intervals of 3-4', 6-8', 8-10', and 10- 12'. No detectable reading was observed at the 12-14' depth interval. PID

ORIN Remediation Technologies 25 Kessel Ct. Suite 105, Madison,WI 53711 Phone 608-819-0572 Fax 608-233-0502 I ~ ORIN Remediation Technolo 1es• ~

readings at area AU-02 found detectable levels at depth interval 8-10' and 10-12' only. The 12-14' and 14-16' intervals found no detectable headspace readings with the PID. Composites were prepared for the study from depth intervals that had positive PID readings. Composite sample AU-01 was prepared from samples AU-01 3-4', 6-8', 8-10', and 10-12'. The AU-02 composite was made from AU-02 8-10' and 10-12'.

The purpose of the study was to treat the soil with a variety of treatment chemistries to determine the chemistry and dosage that is most effective in reducing the concentrations of chlorinated solvents.

To reduce the levels of chlorinated contaminants, two permanganate treatment chemistries were proposed. The two permanganate chemistries were sodium permanganate and potassium permanganate. Permanganates have been shown to effectively reduce levels of chlorinated solvents. The major difference between the proposed chemistries is the solubility. Sodium permanganate is shipped as a 40% solution. The chemical is then diluted on site to meet the desired concentration. Potassium permanganate is a solid and is only soluble up to 2 to 3% under field conditions. Generally, higher contamination levels will require higher dosage levels. Therefore, when higher dosage levels are required, sodium permanganate is preferred. Lower contaminant levels can generally be treated with potassium permanganate, although high Natural Oxidant Demand (NOD) can require the use of sodium permanganate.

Two additional chemistries were added to the study after the initial round of testing. The two additional chemistries were hydrogen peroxide and sodium persulfate.

The procedure used and results for the study are provided below.

Procedure

The AU-01 composite was prepared by mixing equal amounts of AU-01 3-4', 6-8', 8-10', and 10-12'. The AU-02 composite was prepared using equal masses of AU- 02 8-10' and 10-12'. Each composite was prepared by thoroughly mixing the sample in a stainless steel bowl until the sample was homogeneous.

ORIN treated the composite with different treatment chemistries and in some cases, varying dosages of the same chemistry. In addition to treated samples, a control was analyzed to measure the concentration in the original sample and to

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account for any volatilization of the contaminant during the study. As discussed previously, two rounds of treatment where performed. The first round of treatment included potassium and sodium permanganate. The treatments dosages using sodium and potassium permanganate are shown in Table 1.

Table 1. Permanganate Dosage Rates

0.03% 0.1% 0.25% 0.5% Sample KMnO4 NaMnO4 NaMnO4 NaMnO4 AU-01 X X X X 2omposite AU-02 X X X X 2omposite NOTE: Dosage rates are on a wt./wt. basis

The second round of treatment included hydrogen peroxide and sodium persulfate. The dosage rates for these chemistries are shown in Table 2.

Table 2. Hydrogen Peroxide and Sodium Persulfate Dosage Rates

0.13% 0.22% 0.25% 0.28% Sample H2O2 H2O2 Na2S2O8 Na2SzO3 IAU-01 X X X X 2omposite IAU-02 X X X X 2omposite NOTE: Dosage rates are on a wt./wt. basis

Treatment was performed by mixing 100 g of sample with an amount of chemical that corresponded to the treatment dosage. The test jar containing the sample and treatment chemistry was topped off with water to reduce the headspace in the jar and to minimize volatilization. Samples were treated in a 4 oz glass amber bottles with a Teflon lid. After treatment, the treated samples were allowed to stand at ambient temperature with the cap screwed tight.

The initial treatment using the permanganate chemistries was permitted to continue for twelve days past the treatment date. After twelve days of treatment, the sample was preserved with methanol and analyzed for Volatile Organic

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Compound's (VOC). The second round of testing using hydrogen peroxide and sodium persulfate was permitted to react three days after treatment. After three days of treatment, the samples were preserved with methanol and analyzed for VOC's. VOC analysis was performed at EnChem, Inc., in Green Bay, WI.

Results The concentration for the control and permanganate treated samples for AU-01 are shown Table 3. Results for sample AU-02 are shown in Table 4. Only compounds of concern and compounds that were detected are reported.

As illustrate in Table 3, only PCE, TCE, and cis-1,2 DCE were detected in the control and treated samples. Vinyl Chloride was not detected in either the control or treated samples. The data also shows that the levels between the control and treated samples did not show significant treatment effectiveness. The difference between the control and the highest dosage level (0.5% NaMnO4) only found a reduction of PCE from 1,266 to 829 ug/Kg, a 35% reduction. Other compounds also showed little treatment effectiveness for the AU-01 composite sample at all treatment dosages. Sample AU-02 showed a similar response to treatment (Table 4). Compared to the control, little treatment was evident for all .compounds at each treatment dosage. The limited reduction in contaminant levels suggests that the soils have a high NOD. The high NOD is likely from reduced iron or ferrous iron present in the soils since there does not appear to be a significant amount of organic matter. The permanganate reacts with the ferrous iron, oxidizes it to ferric iron, and reduces the permanganate to manganese dioxide. In addition to the contaminant demand, the NOD must be overcome. This requires additional chemical. As found in this study, the dosage rate of permanganate needed to overcome both the contaminant loading and NOD is greater than 0.5% wt./wt. NaMnO4. Permanganate dosages greater than 0.5% become very cost prohibited and therefore not an economical solution.

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Table 3 VOC Concentrations After Potassium and Sodium Permanganate Treatment for Sample AU-01 Composite. Treatment Time of Twelve Days. 0.03% 0.1% 0.25% 0.5% :::::ompound Control KMnO4 NaMnO4 NaMnO4 NaMnO4 Tetrachloroethene (PCE) 1,266 1,249 1,124 1,001 829 CT'richloroethene (TCE) 680 727 594 524 558 b s-1,2 Dichloroethene (cis-1,2 DCE) 206 190 193 154 191 !Vinyl Chloride <40 <40 <40 <40 <40 NOTE: all results are reported as ug/kg wet wt. unless otherwise noted

Table 4 VOC Concentrations After Potassium and Sodium Permanganate Treatment for Sample AU-02 Composite. Treatment Time of Twelve Days. 0.03% 0.1% 0.25% 0.5% :::::ompound Control KMnO4 NaMnO4 NaMnO4 NaMnO4 Tetrachloroethene (PCE) 395 348 726 709 295 Trichloroethene (TCE) 641 348 330 379 100 cis-1,2 Dichloroethene (cis-1,2 DCE) 362 215 165 165 <41 Vinyl Chloride <41 <41 <41 <41 <41 NOTE: all results are reported as ug/kg wet wt. unless otherwise noted

Further testing was conducted using other proven chemical treatments. Two additional chemistries were tested. Hydrogen peroxide and sodium persulfate were evaluated on sample AU-01 (10-12') only. AU-01 (10-12') was the only sample interval remaining that was not opened in the initial round of testing. Other AU-01 samples that were previously opened may have lost significant levels of contaminants and therefore not used.

The purpose for the additional testing was to find a chemistry that reduces the contaminant levels while minimizing the NOD effect. Hydrogen peroxide and sodium persulfate were two good candidate chemistries since soluble iron catalyses each chemistry. Hydrogen peroxide will react with soluble iron and produce hydroxyl radicals through a Fenton's Reaction. Soluble iron will catalyze sodium persulfate to produce sulfate radicals. Both hydroxyl radicals

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and sulfate radicals are highly reactive and have been shown to reduce levels of chlorinated compounds.

Table 5 shows the results for the treatment of sample AU-01 with hydrogen peroxide and sodium persulfate. As the control data shows, the contaminant levels for PCE and TCE are roughly twice as much when compared to control in the permanganate testing. This is likely because the 10-12 foot depth interval is the most contaminated zone. Comparing the control to the treated samples shows the 0.22% hydrogen peroxide and both dosages of sodium persulfate reduced the levels of contaminants (Table 5). The total percent reduction of contaminants is also shown in Table 5. The 0.22% hydrogen peroxide removed 43% of the contaminants. The 0.17% and 0.28% sodium persulfate treatment removed 47% and 54%, respectively. A hydrogen peroxide dosage rate of 0.13% did not show a reduction. The data also suggests that the treatment reaction was not complete prior to sample analysis. The time between the treatment and analysis was three days. As evident in the persulfate treatment, the reduction of PCE was the greatest when compared to the control. The 0.17% persulfate treatment reduced the PCE from 2283 ug/Kg to 592 ug/kg, a 74% reduction. The reduction of TCE and cis-1,2 DCE found a reduction of 26% for TCE and an increase in cis-1,2 DCE. This observation suggests that the reaction was not complete and the formation of PCE daughter products (i.e., TCE and cis-1,2 DCE) are being formed. This was also observed in the 0.22% hydrogen peroxide and 0.28% sodium persulfate dosages.

Table 5. VOC Concentrations After Hydrogen Peroxide and Sodium Persulfate Treatment for Sample AU-01 (10-12'). Treatment Time of Three Days. 0.13% 0.22 % 0.17 % 0.28 % ~ompound Control H 2O2 H2O2 Persulfate Persulfate rI'etrachloroethene (PCE) 2283 2265 1002 592 682 rI'richloroethene (TCE) 1069 1344 809 795 668 cis-1,2-Dichloroethene (cis-1,2 DCE) 246 322 245 516 307 ~inyl Chloride <25 <25 <25 <25 <25 Total VOC's 3598 3931 2056 1903 1657 Total Percent Reduction - 0% 43% 47% 54% NOTE: all results are reported as ug/kg wet wt. unless otherwise noted

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~ .

As evident in the data, the treatment time needed to be extended to observe the full extent of contaminant reduction. Due to time restraints in the study, the samples were analyzed after three days of treatment. Although treatment was not complete after three days, given enough time a greater net reduction in all contaminants would be observed.

Discussion/Recommendations As the data in this study shows, permanganate is not a cost effective treatment chemistry since it appears the high NOD in the soil will require excessive permanganate to overcome the NOD and contaminant chemical demand. Hydrogen peroxide and sodium persulfate where shown to reduce the total VOC levels by roughly 50% over a three day period. Had the treatment time been extended, the reduction would likely be greater than reported here.

Based on this study, a minimum sodium persulfate dosage level of 0.17% wt./wt. is recommended. Hydrogen peroxide is not recommended for this site due to the proximity of the plume to buildings and off-site gas migration issues. The hydrogen peroxide reaction is very vigorous and can be detrimental to building foundations. Also, hydrogen peroxide requires vent wells for off gassing which would be undesirable for the nearby residential properties.

To ensure there is enough available iron to catalyze the persulfate reaction, ORIN recommends that chelated iron be added. Iron, in the form of ferrous sulfate, should be at a 200 mg/kg dosage rate. EDTA (chelator) should be added at a 1:1 molar ratio of the iron.

Sincerely,

ORIN Remediation Technologies

Andrew Wenzel Operations Manager /Senior Chemist

ORIN Remediation Technologies 25 Kessel Ct. Suite 105, Madison ,WI 53711 Phone 608-819-0572 Fax 608-233-0502 ATTACHMENT B

INFORMATION ON THE ORIN CATALYZED SODIUM PERSULFATE INJECTION PROCESS .PMC.

REUABLE SUPPLY Applications and Chemist ry Applications 4 Oxidation Chemistry 5 Free Radical Chemistry 5 Persulfate Chemical Structure 6

Physical and Chemicai Data Physical and Chemical Properties of Persulfates 7 Solubilities of Persulfate Salts 7 Density of Aqueous Solutions 8 Viscosity of Aqueous Solutions 8 Electrical Conductance of Aqueous Solutions 9 Heat Capacity of Aqueous Solutions 9 Conversion: Grams/Liter to Weight % 10 Decomposition Rates of 4 % Solutions 10 Decomposition Rates of 10% Solutions 11 Typical Analysis of Persulfates 11 Analytical Chemistry 12 Assay Procedures 12

Persulfate Handling and Safety 13 Personal Protective Equipment 13 First Aid 13 Disposal 13 Shipping 13 Containers and Packaging 13 Storage 14 Decomposition Hazard 14 Decomposition Prevention 14

Customer Support Ser,rices Quality Assurance 15 Distribution 15 Technical Services 15 Domestic and International Offices back cover

TABLE OF CONTENTS Leading the persulfate market with improved products and reliable supply.

Persulfates are the most chemically active of the peroxy­ gens, with great utility in a variety of chemical processes. FMC persulfates, backed by years of experience, are manu­ factured to strict specifications for thermal stability, mak­ ing them among the most stable available.

FMC Active Oxidants Sales 6 Marketing FMC is the leading producer of peroxygen chemicals and a major Pictured from left to right: researcher in active oxidant chemistry. We are the world 's largest Paula Sa,tt, Account Manager Rosanne Menzel, Senior Product Representative and North America's only producer of peroxydisulfates,' a group of Robert Mulholland, Acrount Manager chemicals commonly referred to as persulfates. FMC manufactures Richard White, Sales & Marketing Director ammonium, potassium, and sodium persulfates at a plant in Tonawanda, New York. Our dedicated plant employees contribute to FMC's 70 years of peroxygen production experience.

FMC provides a reliable supply of high-quality, stable persulfates to the global market The Tonawanda plant is an 1SO-9002 certified facil­ ity near the Niagara River outside Buffalo, NY. This location provides abundant local resources, including reliable supplies of hydroelectric power and cooling water.

FMC has been the world's leading producer of persulfates for decades, yet we continually find ways to improve our products, espe­ cially their safety.

Our research into the characteristics of peroxydisulfates has improved the quality and the stability of all FMC persulfates. An understanding of the crystalline structure of persulfates and the interplay with heat and moisture have changed quality control procedures, manufacturing processes, and storage requirements for these products. We have established new specifications for thermal stability which make persulfates among the most stable available.

Persulfates are strong oxidants, have excellent shelf life when stored properly, and are economical to use. These properties make persulfates suitable for a variety of applications.

FMC is committed to the principles of Product Stewardship and to manufacturing, transporting, storing, and using chemicals in a safe manner. The commitment begins with the manufacturing process and continues throughout the life cyde of our products. Our continu­ ing effort is to ensure that safety, health, and environmental issues are addressed wherever persulfates are handled or used.

INTRODUCTION

- .

- ... -- .. - - ~ ·: ,- - . . - . - ~ . - - ·-_ -- - .. ~ - . . , - - . - - - -~ -_ .. -· - -: - -_ - - : . - - ~ ·: - ~ - - _- - _~- - .,• Persulfates are used to dean and activate carbon and charcoal before and after their use as absorbents. Persulfates are key components in many industrial processes and commercial products. Cosmetics - The cosmetic industry has develbped formula­ tions which use persulfates to boost hair bleaching perform­ The polymer industry uses aqueous solutions of persulfates ance. as initiators in the polymerization of latex and synthetic rub­ ber. The electronics industry considers sodium persulfate an Organic synthesis - Persulfates are oxidizing agents in efficient microetchant in the manufacture of printed circuit the preparation of aldehydes, ketones, carboxylic acids, boards. The following examples further illustrate the chemical quinones, and a variety of other compounds. versatility of persulfates. The pharmaceutical industry uses sodium persulfate D ..-..L.,,.,...... o vi -s: ..,,l.l r, n as a reagent in the preparation of antibiotics. ;: ._.• ;_:-;;;o -;..,.: ;.;.. ;,...:.. ;,.:;-.....• ;: ()th .-:>r dnrdi,- '11'1f"\n c 0 Plastics and rubber - Ammonium, potassium, and sodium - - - ~ - - • i I • •-- - -• -...,.. persulfates are used as initiators for emulsion polymerization reactions in the preparation of acrylics, polyvinyl chlorides, Adhesive - Persulfates are used in the preparation of adhe­ polystyrenes, and neoprene. sive films and metal bonding adhesives. They are used as polymerization initiators in the manufacture Gas and oil production - In enhanced oil recovery, persul­ of synthetic rubber (styrene butadiene and isoprene) for auto­ fates are used "down hole" for gel forming and breaking. mobile and truck tires. Persulfate initiation is used to prepare latex polymers for Inks, pigments, and dispersants - Persulfates are used paints, coatings, and carpet backing. to graft substrates to polymers (for example, carbon black to sodium acrylate). Persulfates are used in the preparation Structural materials - Persulfates are used as initiators in of dispersants for ink jetting and toner formulations. polymeric concrete formulations. Mining - Persulfates can be used in nickel and cobalt sepa­ Inorganic chemicals and minerals - Persulfates are also ration processes. initiators for the polymeric coating of graphite filaments. Peroxymonosulfate - FMC developed a process Soil stabilization - Ammonium persulfate is used as a cur­ using ammonium and sodium persulfates to prepare peroxy­ ing agent in chemical grout systems used to stabilize soil near monosulfate solutions. This patented process dams, tunnels, and buildings. allows fast, efficient, on-site production of an alternative to Caro's acid and potassium caroate. O xidation Photography - Persulfates are used in many Surface preparation - The oxidation power of persulfates photographic applications, including bleaching solutions, solu­ is used to clean and microetch a variety of printed circuit tion regeneration, equipment deaning, and waste board substrates. water treatment. Persulfates are important oxidants in plating and coating Pulp and paper - Persulfates are used in the sizing of processes. They are also etchants for nickel, titanium, and paper, preparation of binders and coatings, and production zirik alloys. of special papers. Persulfates are used to dean and mill aluminum, brass, cop­ per, and many other metal surfaces prior to plating ...... or adhesive bonding .

APPLICATIONS AND CHEMISTRY An activated alkali metal persulfate effectively repulps neu­ The resulting solution is a useful replacement for tral/ alkaline wet-strength broke and decolorizes dyes and Caro's acid, H2S05 and potassium caroate, KHS05 . optical brightener.' Reactions at different pH : Textiles - Ammonium and sodium persulfates are used in ~~eutra! (pH 3 to 7) 2 the desizing and bleaching of textiles and the development S 0 - + H 0 ~ 2HS0 - + 1/20 of dyestuffs. 2 8 2 4 2 Dilute acid (pH > 0.3; [H+] < 0.5M) Swimming pools - Clear Advantage® shock treatment is 2 S 0 - + 2H 0 ~ 2HS0 - + H 0 used to oxidize non-filterable waste in swimming pools and 2 8 2 4 2 2 other recreational water. Clear Advantage® shock darifies Strong acid ([H+] > 0.5M) water and prevents the formation of combined chlorine. -2 - - S20 8 + H20 ~ HS04 + HSQ5 Environmental - Persulfates are very strong oxidants, Alkal ine (pH> 13) have excellent shelf life when stored properly, and are eco­ 2 2 nomical to use. These properties make persulfates suitable S20 8- +OH-~ HS04- + so4- + 1/202 for a variety of environmental applications, such as soil remediation and wastewater/groundwater deanup. Free Radical Chemistry Oxidation Chemistry Persulfates produce free radicals in many diverse reaction situations. The persulfate anion is the most powerful oxidant of When solutions of the persulfates are heated, free the peroxygen family of compounds. radicals are formed: The electromotive force data listed below compares three S 0 -2 +heat~ 2S0 •- commonly used peroxygens: 2 8 4 2 ln the presence of suitable monomers, the radical anions act S20 8- + 2W + 2e- ~ 2HS04- E = 2.12V as polymerization initiators to produce polymer molecules:

H202 2H+ + 2e- ~ 2H 0 0 + 2 E = 1.TN SQ • - + nCH =CH~ -0 SQ(CHi(CH) _ (CH C H) 4 2 3 0 1 2 HS0 - + 2W + 2e- ~ HS0 - + H 0 I I I 5 4 2 E = 1.44V R R R Free radicals suitable as polymerization initiators are also Many metals are oxidized by persulfate to form soluble generated in the presence of reducing agents, for example, metal sulfates, for example, copper: the bisulfite anion: 2 2 Cu+ s 0 - ~ CuS0 + so - 2 9 4 4 -2 - - •- S20 8 + HS03 + 1/202 ~ HS04 + 2S04 Under certain circumstances, hydrolysis of the persulfate anion will yield the bisulfate anion and hydrogen peroxide Free radicals can also be generated in the presence of a kinetically faster oxidant than persulfate: . transition metals: 2 2 S O -2 + Fe+2 ~ Fe+3 + SO -2 + SO .- S20 8- + 2H20 ~ 2HS04- + H20 2 2 8 4 4 Another reaction of note is the acid-catalyzed hydrolysis and mercaptans: of persulfate to form peroxymonosulfate anion. 2 S20 8- + 2RSH ~ 2HS04- + 2RS• Fast. high-temperature, acid hydrolysis followed by thermal quenching will yield solutions of peroxymonosulfate:

S 0 -2 + H 0 HS0 - + HS0 - 2 8 2 ~ 4 5

~ - _· ~~ · ~~ -' "' - . . .. •=•: • ~ C • - .,.::;, ·" ~ ~ '

APPLICATIONS AND CHEMISTRY Persulfate Chemical Structure

APPLICATIONS AND CHEMISTRY

•-•-:-••;-"'-"'...... ,.::'"'_..•--•-•• •,->•~-- _,.,,. _,, ~--••-~•.,.....••-_•••, ••-•~-••••.. •,-~- •~• • •••"'-••.,!;"'\"""~~t';°"(~•~,;•~--_.._,..,r>•".,.l~'•'f"""' ,-..- .,.. •r••• ._..,... "' • ,v••- •>" - ,. ,.~..,_,,-., __.,.,,-::,u:<.<:;•'f~•-•••••-••-•• ••• •-• : •• - • • --. ~,•- -~.--.!:=-::~;:~.,:r- .. ~r:,•"'~-- ~~-~· •··~~ ~-~~-M, r ;:::;,~~~-;:-- -~ --~~~~~•• -~~~~••-;::~~~~~~~~-: .. (.- .. :·_, ~~.::T_:--.,..~_ o:-~ ~ -- •·-·~- -.... ~.-- --• _ ·.,, v, .... • • ~ • _· ~ Physical and Chemical Data

FMC conducted physical and chemical studies of persulfates to provide ' .. the data for this section. You will find the data useful for applying · persulfate chemicals to various processes and products.

The density, viscosity, electrical conductance, and solution heat capacitf ·, data are presented in graphic and equation form. This formatenables you to view the general trend of the physical data. Then, with the aid of .:. equations, you can calculate the correct values for your application. , "

If you have any questions with regard to the information in this sectiop;: contact the FMC Research and Development Center in Princeton, NJ. Contact information is listed on the back cover.

Physical and Chemical Properties of Persulfates

Common name Ammonium persulfate Potassium persulfate Sodium persulfate

Chemical name Ammonium peroxydisulfate Potassium peroxydisulfate Sodium peroxydisulfate Physical fonn Crystalline (monoclinic) Crystalline (triclinic) Crystalline (monoclinic) Formula (NH4)2SPs K25iOs NaiSPs Molecular weight 228.2 270.3 238.1 Crystal density (g/cc) 1.98 2.48 2.59 Color Off-white White White Odor None None None Loose bulk density (glee) 1.05 1.30 1.12

Solubilities of Persulfate Salts

900 .------, Maximum solubility of persulfate salts in water 800 Solublllty Ammonium Potassium Sodium 700 Cg/100g of H20) Persulfate Persulfate Persulfate 25"C 85 6 73 C 0 50"C 116 17 86 .;e c., 400 u C 8 J OO 200

100o1L. __,_,, = ::=::_------______...! 0 10 20 JO 40 50 60 Temperature (0 C)

- Ammonium Persulfate Potusium Persulfiite ·-·- Sodium Persulfiite

PHYSICAL AND CHEMICAL DATA

~,.,.~_:•~: .:--:-:---~ --::-. ... ::.: -. :-----~ ',• =~~~:·:••-:-,:..~::.:•,..•~~-••:_:~::r•..: .. •P•:•: •:.,. :•••~ : __~ :_~::, .. __:-:,._~:'-:.:2.::•---~~- :~.: .. •~•-·•:.~-:•~.-... :~·~.. .:.' ... _~3::~:~.· --·------·------~- ~~ ,._. -·-····----~"--,_,...... ,~.-...-- ...... ,. -.···•·•-r.---'-'•--·--r--"t~~~-______~------·------.~·--···.Ci'-~'""-r- ·-r- --=------_.., .. ~ ... ~.. ··-•·-'-~- ...-----· ----=------.; ..~,.•.-r•.z .,.,. .... :-,~ .. •-i-• .:~~-•~,-,..... , ·------:.~-"t"~~~ -... 1 '!" - ,

Density of Aqueous Solutions

1.25 ,------EquaHon for 12lculallon of density 15 Density (g/ml.) = density Hp+ (A/1000)X + (B/1000)X , 1.20 where X = solution concentration in grams per liter (g/L.).

~ 1.15 Salt Constant 2s·c 3s•c 4s•c ~ Ammonium A 0.4903 0.4860 0 .4789 c 1.10 ·;;; B -2.6730 X 10-" -7.6254 X 10°" -5.0971 X 10°" .,i:: O 1.05 Potassium A 0 .6368 0.6273 0 .6294 3 3 B -1 .4934 X 10' -8.1965 X 10°" -1 .6472 X 10' 1.00 Sodium A 0.6709 0.6727 0.6610 3 3 0.95 ______, B · 1.4934 X 10' -1 .4909x 10· • 1 .0038 X 10°"

0 50 100 150 200 250 300 350 Concenlr.,lion (gill Density of water - Ammonium Persulfate 25°C 3s•c 45°C Potusium Persulfate Density H 0 0.99707 0.99406 0 .99025 - Sodium Persulfate 2

Viscosity of Aqueous Solutions

1.6 Equ.aHon for 12lculallon of vlsa>slty 05 15 Voscosity (cp) viscosity HiO + + DX+ EX , 1.5 = cx ©) where X = solution concentration in grams per liter (gll.). 1.4 Salt Constant 2s·c 3s·c 4s•c ci 1.3 ,!:o 3 3 3 Ammonium C • 1 .0686 X 10- 6.8050 X 10- 5.3134 X ,0· .g 1.2 25 D 1.7140 X 10°" -9.4542 X 10°" -5.8450 X 10°" ~ iii 1.1 5 5 5 5 E 2.4670 x 10- 5.9785x 10· 4.508Jx 10· 3 1.0 Potas.sium C 0 5.9187 X ,0·3 3.5413 X 10' 3 D 1.0661 X 10'3 -1.0551 X 10' -9.5623 X 10-5 0.9 5 E 9.8884 X 10' 1.0674 X 10°" 1.2477 X 10-5

0.8 3 3 2 0 50 100 150 200 250 300 350 Sodium C 4.3857 X 10' 6.1743 X 10- 1.3461 X 10- 3 3 Concentration (g/l) D ·1.2218 X 10' -4.6619 X 10°" -1 .9741 X 10· - Ammonium Persulfate E 1.5146x 10°" 8.1093 X 10-5 1.3540 X 10°" PoLlMium Persulfate

Sodium Persulfate Viscosity of water

25°C 3s·c 45°C

Viscosity Hp 0.8904 0 .7194 0.5960

PHYSICAL AND CHEMICAL DATA

- ' -- • ...... ,. ..,.,.,,.._,$ ----•-.-.,~-:.-•--••- --.•+•• .:.r.; .,. __ • .v-.,-. ~ _ ..,._.."""'".~.-••-H_... -•_.._.,.- __ ~,..,,.,...,..,. ___~~ -~~-,,.. • ,.,_..,.,,.. • ..., ._,..,,.,,..,..._, .., .. _ •- • . .,. -.- ~ - •.,. " ._. ,--.-<, -v ,_.._.., ,, __ ,_ __, ___ ,,.. ,...,- J!ll~

-~-·:~~.: )c ~ '

;:.,.,, ·' ;"""'°'.f;:<' -

Electrical Conductance of Aqueous Solutions

300 Equation for calrulall on of eledrlcal conductance

Conductance (mmho/an) = F + GX + HX2, 250 where X = solution concentration in grams per liter (g/1.J . E u c' .c 200 Salt Constant 25"C 3s·c 4s•c E 25© .s Ammonium F 3.9016 6.6081 6.2538 ., 150 u C G 0.8568 0.9804 1.1578 !l u X ~ H -6.2904 X 10--4 -7.1312 X 10--4 ,8.8912 10-4 "'C 100 C uC Potassium F 2.9603 3.7314 4.1673 50 G 0 .6704 o.79n 0 .9525 3 H -1 .0456 X 10'3 -1.1982 X 10'3 · 1.9173 X 10' 0 0 50 100 150 200 250 300 350 400 450 500 Sodium F 5 .9501 7.1826 8.1825 Concentration (g/l) G 0.5880 0.6967 0.8123 H -6.6193 X 10--4 -7.5821 X 10--4 -8.6226 X 10-4 - Ammonium Persulfate Potassium Persulf.lte Sodium Persulf.ite

. Heat Capacity of Aqueous Solutions

1.1 Equation for calrulallon of heat capadty 15 Heat capacity (cal/g "Q = K. LX + MX , 1.0 where X = solution concentration in grams per liter (g/1.J . 9 -!:!' 0.9 Salt Constant 25•c -;:; ~ :c Ammonium K 0.994 0.8 3 ·u L -1 .863 X 10· "'0. u"' M 4.531 X 10-5 0.7 16., Potassium K 0.997 l: L 1.150x 10·3 0.6 M 2.670 X 10-5 Sodium K 0 .997 0.5 3 () 11Xl 2

- Ammon ium Persulfate Conversion ca11g ·c =Btu/lb,== Jig ·c Potassiu m Persulf.lte 4.184 - Sodium Persulf.ite

PHYSICA L A ND CHEMICAL D ATA . II.

Conversion: Grams/Liter to Weight D/o 6()..------, - Ammonium Persulfate 50 Potassium Persulfate - Sodium Persulfate I 40 .gC 30 ~ E u "C 20 u0

10

0 0 I 00 200 300 400 500 600 700 Conr en1ra1ion (g/l) Conversion grams/liter ID weight percent Note: Potassium persulfate is the least soluble of the three FMC persulfate salts.

Ammonium persulfate (wt%) Potassium persulfate (wt%) Sodium persulfal!! (wt%) g/L 25·c 35•c 45•c 25·c 35•c 45•c 25•c 35·c 45•c 0 0 0 0 0 0 0 0 0 0 25 2.477 2.485 2.495 2.468 2.476 2.486 2.466 2.474 2.484 50 4.895 4.911 4.931 4.861 4.877 4.896 4.854 4.868 4.888 75 7.256 7.281 7 .311 7.183 7.208 7.237 7.167 7 .187 7.219 100 95 62 9.598 9.635 9.470 9.510 9.410 9.435 9 .479 125 11 .815 11 .863 11 .912 11 .668 11.719 11.586 11.616 11 .672 150 14.017 14.077 14.136 13.868 13.699 13.733 13.801 175 16.170 16.244 16.311 15.959 15.751 15.790 15.870 200 18.275 183 64 18.440 17.994 17.745 17.788 17.880 250 22.349 22.471 22.564 21.572 21 .620 21 .738 300 26.251 26.411 26.519 25.197 25250 25394 350 29.993 30.194 30.316 28.634 28.695 28.864 400 33.583 33.831 33.964 31 .910 31.969 32.164 450 37.031 37.329 37.473 35.026 35.087 35.307 500 40.346 40.699 40.850 37.998 38.060 383 05 550 43.536 43.946 44.104 40.836 40.898 41 .168 600 46.607 47.079 47.241 43.551 43.613 43.905 650 49.566 50.1 03 50.268 46.150 46.211 46.527 700 52.420 53.025 53.191 48.642 48.702 49.040

Decomposition Rates of 4 0/o Solutions

4.5

Ammonium Persulfate at 25°C i 4.0 Ammonium Persulfate at 50°C ! Potassium Persulfate at 25°C C 3.5 0 Potassium Persulfate al SO"C I Sodium Persulfate al 25°C u 3.0 ~ "C Sodium Persulfate at 50°C u0 C 0 2.5 '.§ 0 "' 2.0

1.5 0 5 10 15 20 25 30 ' Tim e (days) PHYSICAL AND CHEMICAL DATA

------

. - -. ~ - - - - ' . - - ...,.,_..,.~,~;'-'x,':\:.'l'.~\-:_t!-"'t~.-- "'''!"" •••~-'~:<'~"-.--.l---.,_- ~•,-,,,,-.,,- _, • ., •"~--:---':°" ,....,.::::r,- ___ • •~• •• f ,.,..,_ •~•t"•.-•••,.,,...,.,~!;:;n.--.~ ,,... .. ~J:,-•r,,., ,,_ •••-••-,,,--,-~ • • ------. - Decomposition Rates of 100/o Solutions

11.0 Ammonium Persulfale al 25°C 10.0 ;g- Ammonium Persulfale al SO"C 9.0 j Potassium Persulfate at SO"C C 8.0 0 Sodium Persulfate at 25°C ·g 7.0 Sodium Persulfale at 50°C C u "C 6.0 u0 C 5.0 0 ·5 4.0 0 "' 3.0

2.0 0 5 10 15 20 25 30 Time (days)

Typical Analysis of Persulfates

Analysis Ammonium persulfm Potassium persulfm Sodium persulfale

Purity% 99.5 99.5 99.4

Active oxygen (%) 6.98 5.90 6.68

Moisture(%) 0.02 0.02 0.0,

Ammonium persulfate ( % ) 0.14 0.0,

Sodium sulfate(%) 0.70

pH (1 % solution) 5.2 6.4 6.0

Iron (ppm) 3 2

lr=lubles (ppm) 21 18 29

Copper (ppm) <0.3 <0.2 <0.2

Chloride (ppm). <10 <10 <10

Heavy metals, as lead (ppm) <1 <1 <1

Manganese (ppm) <0.5 <0.5

Chromium (ppm) <0.5 <0.5 <0.5

Sodium (ppm) 20

Potassium (ppm) 50

Screen analysis Ammonium persulfm Potassium persulfm Sodium persulfale Mesh size % passing % passing % passing .

8 100 100 100

30 78 97 99

50 24 75 80

70 9 54 48

100 3 40 15

140 24 2

PHYSICAL AND CHEMICAL DATA

- - ~ -- . ------. -- ·------· . - - - . - - - - . - - , ..~,., .... • ,., •~::::,-•-,• K/""•' ~•• .. ••••+)• •~-•~••- ..... S • ,- • • ••·••~ ~---- • - • • •.• O -••· :,• .. ',<'•/ ,-.!:~--~-~-~--~~,.-~, ~,•...,,¥ ,- :-• • 0 Analytical Chemistry

Persulfates or their solutions can be conveniently assayed by the methods described below. In each method, persulfate is determined by titration of a standardized potassium permanganate or eerie ammonium sulfate solution with a standardized ferrous ammonium sulfate solution, a back­ titration technique. Reagents can be purchased prestandardized or prepared from commercially available chemicals. All reagents, chemicals, and apparatus used are common, off-the-shelf items, and can be purchased from commercial supply houses. Every phase of persulfate manufacwring is monitored and a,nfro/led electronically, Assay Procedures induding the aystallization and drying steps aitical to the product's thermal stability.

Solids (A - B)C x 0.8 % active oxygen = D To a 250 ml Erlenmeyer flask, add about 1 gram of (A - B)C x 11 .4 sample weighed to the nearest milligram and about % ammonium persulfate = D 50 ml of 1N H2SO4. Dissolve the sample and add exactly 40 ml of 0.5 N ferrous ammonium sulfate (A - B)C x 13.5 % potassium persulfate solution. Swirl constantly while adding the ferrous = D ammonium sulfate solution. Let this stand for one minute and titrate with 0.5 N KMnO to permanent (A - B)C x 11 .9 4 % sodium persulfate = D pink endpoint or with 0.5 N Ce(SOJ2 to a Ferroin indicator endpoint. The calculations require a blank titration on exactly 40 ml of ferrous ammonium A= ml KMnO or Ce(SO ) solution used for titrating the blank. sulfate solution, as used above, in 50 ml of 4 4 2 B = ml KMnO4 or Ce(SO4)2 solution used for titrating the sample. the 1 N H2SO 4. C = Normality of the KMnO4 or Ce(SO4)2 solution used. D = Weight of sample in grams.

(A - B)C x 8 Solutions g/L active oxygen ~=====·~~-~- = D To a 250 ml Erlenmeyer flask, pipette 2-20 ml of (A - B)C x 114 persulfate solution (depending on the approximate g/L ammonium persulfate = D solution concentration). Add about 50 ml of about 1 N H SO solution. Add exactly 40 ml of 0.5 N (A - B)C x 135 2 4 g/L potassium persulfate ferrous ammonium sulfate solution. Swirl constantly = D while adding the ferrous ammonium sulfate solution. (A - B)C x 119 Let stand for one minute and titrate with 0.5 N KMnO4 g/L sodium persulfate = D to a permanent pink endpoint or with 0.5 N Ce(SOJ2 to a Ferroin indicator endpoint. The calculations require a blank titration on exactly 40 ml of ferrous A= ml KMnO4 or Ce(SO4)2 solution used for titrating the blank. ammonium sulfate solution, as used above, in 50 ml B = ml KMnO4 or Ce(SO4)2 solution used for titrating the sample. of the 1 N H SO . 2 4 C = Normality of the KMnO4 or Ce(SO4)2 solution used. D = Volume of sample in milliliters.

PHYSICAL AND CHEMICAL DATA General Material Information

Persu lfate Handlin~ and Safety Disposal

Persulfates are oxidizing chemicals that require careful Persulfate crystals should never be discarded to trash bins . attention to all aspects of handling and use. For more Contact with moisture, contaminants, and/or reducing information, you may request a Material Safety Data agents can initiate a chemical reaction or a persulfate Sheet (MSDS) which is available from any FMC office. decomposition. Persulfate crystals which become a waste material are classified as hazardous waste because they are oxidizers. Persulfates which are spilled on the floor, Personal Protective Equipment or otherwise contaminated, are best dissolved in copious quantities of water. When handling persulfate chemicals, follow the guidelines listed here and in the MSDS. An acceptable disposal method for spent persulfate solu­ tions is to dilute with large quantities of water and dispose Protect your eyes - Wear chemical-type goggles or a via a treatment system. face mask whenever splashing, spraying, or any eye contact is possible. Any disposal method must be in full accordance with all local, state, and federal regulations. Protect your respiratory system - Use dust respirators approved by NIOSH/MSA whenever exposure may exceed the established standard listed Shipping in the current MSDS. The U.S. Department of Transportation classifies persulfates Protect your hands - Wear general purpose as OXIDIZER and regulates them as hazardous materials · neoprene gloves. for transport by air, water, and rail. The "Code of Federal Regulation - Title 49" details specific requirements for pack­ Protect yourself with proper clothing - Wear ordinary aging, marketing, labeling, and describing these materials work clothes with long sleeves and full-length pants. for shipment

Protect yourself with proper footwear - Wear shoes with neoprene soles. Containers and Packaging

FMC packages and ships crystalline persulfate chemicals First Aid in three different container types, according to customer requests. Eye contad - Flush with water for at least 15 minutes. If irritation occurs and persists, obtain medical attention. For more information, contact your nearest FMC · Sales Office. Skin contad - Wash with plenty of soap and water. If irritation occurs and persists, obtain medical attention. Wash clothing before reuse . Type Construction Persulfate Containers Persulfate wt/container per pallet wt/pallet Inhalation - Get fresh air. If breathing difficulty or discomfort occurs, call a physician. Bag Polypropylene 55 lbs 42 2,310 lbs

Ingestion - Drink one to two glasses of water. Do not Drum Fiber drums, 225 lbs 8 1,800 lbs induce vomiting. Do not give anything by mouth to an polyethylene liner unconscious individual. Call a physician immediately. IBC* Polyprop~ene sack, 1,000- 1 - 2 1,000- When properly handled and stored, persulfates and polyethy ne liner 2,200 lbs 2,200 lbs their solutions do not present serious health hazards. The MSDS provides information concerning exposure, • /BC = Intermediate Bulk Container, equipped with easy opening bottom emergency, first aid, and disposal of persulfates. spout for discharging into tanks or hoppers.

GENERAL MATERIAL INFORMATION Storage Decomposition Hazard

Persulfates should be stored in accordance with the National Overheating or contamination of persulfates can lead to Fire Protection Association's (NFPA) 430 Code for the a runaway decomposition. The persulfate salt will begin Storage of Solid and Liquid Oxidizers. FMC personnel can to effervesce with an acid-like odor. Persulfates decom­ provide additional support in reviewing storage facilities. pose to form solid sulfate salts and emit noxious fog or fumes of so. and NOx. This decomposition may form a high temperature melt. The material will flow like magma and may ignite nearby combustible materials such as wood or paper. Oxygen produced by persulfate decomposition can increase the intensity of the fire.

The only way to halt a decomposition event is to apply LARGE quantities of water to the reacting material. Eight pounds of water per pound of decomposin~ materi­ General Precautions - Persulfates should be kept in als is recommended, but no less than two pounds of a cool, dry storage area, in a configuration that is appro­ water should be applied. Insufficient amounts of priate for the sprinkler capacity of the building water will intensify the reaction and increase the acid per NFPA 430. mist concentration. Personnel should be trained to handle persulfates Please note that carbon dioxide (CO2) or other gas-filled safely, property dispose of spilled materials, and extinguishers will have NO effect on decomposing persul­ prevent contamination. fate. The use of water as an extinguishing agent is emphasized. Control of the melt and firefighting If material gets wet or spills, it must be isolated and dis­ efforts are enhanced if persulfates are stored within con­ posed of property. tainment areas.

Handling - To remove and transport persulfates from Persulfate decomposition will require emergency respon­ the shipping containers, use clean plastic or stainless ders wearing full protective rubber clothing, steel scoops, shovels, pails, etc. Cleanliness is essential. face and head protection, plus self-contained breathing apparatus (SCBA). Solution Storage - Aqueous solutions of ammonium persulfate are more susceptible to decomposition than the solid product. The recommended materials of con­ Decomposition Prevention struction for storage and conveyance equipment (tanks, pipelines, etc.) are 304 and 316 stainless steel. Other Observe the following precautions to prevent decomposi­ acceptable materials indude polyvinyl chloride, polyethyl­ tion: ene, Plexiglas4D plastic (or other suitable generic), Teflone Do not expose persulfates or their containers to resin (or other suitable generic), chemical stoneware, and moisture. Moisture significantly lowers the glass. Metals other than 304 and 316 stainless steel cause decomposition temperature. decomposition of the persulfate solutions or may be cor­ Do not store persulfates near incompatible materials roded by them. This is such as reducing agents, acids, bases, halide salt particularly true of Monel, copper, brass, and iron. solutions, organics, ammoniacal solutions, alkaline Do not store or process persulfate solutions in sealed cleansers, or other oxidizers. These materials can or closed containers or vessels. Normal solution decompo­ initiate decomposition. sition will release oxygen gas which may overpressurize a Do not store near point sources of heat such as steam sealed container and cause rupture. pipes, electrical appliances, heating vents, gas flames, Storage of persulfate solutions above 25°C will accelerate welding sparks, or radiant heaters. Do not store at ambi­ the rate of decompostition. See data on pages 10 and 11 . ent temperatures above 113°F or 45°C. Do not return spilled or unused portions of persulfates to the original container. Dirt, metal, moisture, or other contaminants can induce the decomposition of persulfates. Do not cross-contaminate with scoops, cups, or stirrers that may have been exposed to or used with other chem­ icals. Use only dedicated clean, dry plastic or stainless steel scoops and utensils for transfer. Do not grind or dry mix in equipment or machines that develop frictional heat.

,,2- _-. :,. ':;"~ / .= ~ -; I - . " t GENERAL MATERIAL INFORMATION Customer Support Services

database, enabling FMC to issue Certificates of Analysis Quality Assurance that are specific to each batch of materials received by our customers. FMC persulfate products are produced under an ISO 9002 certified quality system. Statistical Process Control (SPC) and FMC is the only persulfate producer that uses cutting­ a distributed control system combine to provide consistent edge technology to ensure that our products are stable process control. FMC operators monitor key parameters for storage or transport and use. We have established to ensure consistent quality for all products. new product safety standards for thermal stability to ensure a high-quality, stable persulfate. All materials-raw, intermediate and final-are checked and test­ ed in a new, modem laboratory Distribution .,.~. =: employing the latest analytical technology. Quality test results Domestic - All FMC persulfates are distributed - are maintained throughout North America. Our persulfate distribution facili­ II~ on each batch of product. ties are located in: Certificates of Analysis and DNV~• .r... *s other end-product information Bridgeview, Illinois ISO 9002 R.llGISTERED FIRM can be customized to meet Carteret, New Jersey your system requirements. Tonawanda, New York

Our production facility uses SPC methods to improve Minimum shipment from any domestic FMC distribution cen- and assure the quality of persulfate chemical products. ter is 24,000 lbs of FMC products. Persulfates may , FMC operators chart key operating parameters to maintain be any portion of the total weight. Contact us for more infor­ process control; this assures that quality is built in to each cus­ mation. tomer's order. International - Persulfates are also available from a The SPC system is designed to meet your specific quality network of chemical supply distributors that represent standards. Product is analyzed and identified as it leaves FMC persulfate products worldwide. the packaging areas. Product quality is maintained by batch number. The information is then stored in a computer

Technical Services All FMC customers have access to a staff of technical service representatives at the Research and Development Center in Princeton, NJ and at the plant in Tonawanda, NY. These chemists and engineers are experienced in the production, sale, and distribution of peroxygen chemicals. They are fully capable of answering questions on the safe handling and usage of persulfates. In fact. FMC specialists have helped our customers pioneer many successful applications for persulfate chemicals. Our engineering services include the design and construction of storage facilities, or the safety inspection of your present warehouse or production facilities. FMC also offers a complete list of technical artides, bulletins, data sheets, and patents. For more information, call or write the nearest FMC sales office.

Consistent process control and monitoring ensure a reliable supply of quality persulfates to a global market.

FMC's Tonawanda warehouse reflects state-of-the-art design, featuring monitors and detectors which close the fire doors in any emergency and sprinklers powerful enough to handle any fire or decomposition. Let FMC help you with your persulfate storage and warehousing.

CUSTOMER SUPPORT SERVICES Domestic Offices

FMC Corporation FMC Manufacturing Chemical Products Group FMC Active Oxidants Division 1735 Market Street 78 Sawyer Avenue Philadelphia, PA 19103 Town of Tonawanda, NY 14150 (215) 299-6000 (716) 879-0400 (215) 299-62n Fax (716) 879-0433 Fax

Technical Office

FMC Research and Development Active Oxidants Division Box 8 Princeton, NJ 08543 (800) 206-9980 (609) 951-3668 Fax

International Offices

Europe/ Africa Asia/ Pacific FMC Europe, N.V. Sales Office Avenue Louise 480-B9 FMC International, S.A. 1050 Brussels, Belgium 4th Floor, Pilipinas Bank Bldg. 011+ 32 2/645 9211 111 Paseo de Roxas 011+ 32 2/646 4454 Fax 1229 Makati City Metro Manila. Philippines 011+ 63 2/894 1615 011+ 63 2/894 1605 Fax

The persulfate applications referred to in this publication are solely for illustrative purposes. It is the responsibility of the user to determine whether a persulfate compound may be suitable for any specific application, in accordance with accepted good practices and applicable regulatory restrictions.

The information contained herein is, to our knowledge, true and accurate. However, we make no warranty or representation, expressed or implied, except that FMC products discussed herein conform to the chemical description shown on their labels. Nothing contained herein shall be construed as permission or recommendation to infringe any patenl No agent, representative or employee of this company is authorized to vary any of the terms of this notice.

4'MC:. is a "'gistered trademark of FMC Corporation. Plex~ ~ a registered trademark of Rohm and Haas Company. Teflon•~ a registered trademark of E.I . DuPont de Nemours and Company.

02001 FMC Corporation. All rights reserved. FMC9487-2500 12/01 Burgess