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CASF FORUM 2010 The Chromium Electroplating Regulations and The PFOS Regulations P. J. Paine Environment Canada (819) 997-2295 CASF.

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Presentation on theme: "CASF FORUM 2010 The Chromium Electroplating Regulations and The PFOS Regulations P. J. Paine Environment Canada (819) 997-2295 CASF."— Presentation transcript:

1 CASF FORUM 2010 The Chromium Electroplating Regulations and The PFOS Regulations P. J. Paine Environment Canada Peter.paine@ec.gc.ca (819) 997-2295 CASF Environmental Forum 2010 Toronto, Ontario Thursday 28 th October 2010

2 Chromium Electroplating, Chromium Anodizing and Reverse Etching Regulations

3 Outline: Chromium Regulations Application Definitions Point Source Requirements Surface Tension Requirements Tank Covers Requirements Inspection and Maintenance Reporting and Record Keeping Summary

4 CHROMIUM ELECTROPLATING, CHROMIUM ANODIZING and REVERSE ETCHING REGULATIONS Regulations came into force on 4 th July 2009 Applies to any facility using more than 50 kg of chromium trioxide to carry out chromium electroplating (hard, decorative), chromium (i.e. chromic acid) anodizing and reverse etching Does not apply to any facility using less than 50 kg chromium trioxide per year The Chromium Regulations allow three approaches for compliance - Point Source Emission Limit - Surface Tension (ST) - Closed Cover (EEDs) Regulatee is to notify EC of which approach used (Control Method Notice) Regulatee to notify EC of which equipment to be used (stalagmometer or tensiometer) to measure ST Regulatee to notify EC of any change in approach used

5 CHROMIUM REGULATION Point Source Emission Limit Release limit: 0.03 mg/dscm to be complied with within 30 months of the coming into force of the regulation (i.e., 4 th January 2012) Release test: performed for each point source during “representative operating conditions” Release testing required every 5 years (on-going compliance testing) Reporting and Recording requirements Equipment Maintenance Plan Inspection Plan Note: Release test also required within 60 days of any of: replacing a control device; changing the number of tanks; mechanical changes to tank ventilation system; addition to /replacement of ductwork with tank

6 10/23/10 Page 6 RELEASE TEST AND ANALYSIS RELEASE TEST Performed in accordance with generally accepted standards of good scientific practice at the time of the sampling Sampler (i.e., stack testing company) trained and experienced in sampling for chromium Using a documented and validated method Three two-hour sampling runs (6 hr total) Minimum sample of 1.7 dscm per run The regulations do not specify that a particular method be used (i.e., US EPA Method 306) There is not as yet accreditation of stack testing companies in Canada

7 10/23/10 Page 7 RELEASE TEST AND ANALYSIS ANALYSIS Performed in accordance with generally accepted standards of good scientific practice at the time of the analysis Laboratory to be accredited to ISO 17025 ISO 17025: General requirements for the competence of testing and calibration laboratories Laboratory accreditation to include chromium analysis Analytical method precision and accuracy based on a minimum of seven replicate samples MDL: 8 µg/L chromium Precision: 5% relative standard deviation at 10 times the MDL Accuracy: 100% ± 5% based on analyte recovery at least 10 times the MDL

8 CHROMIUM REGULATION Surface Tension Maintain surface tension below specified value for each tank Measure and record ST “once every day” for each tank and readings to be 16 hours apart Stalagmometer: < 45 dynes/cm Tensiometer: < 35 dynes/cm Release test is not required Reporting and recordkeeping requirements Maintenance Plan: additions to bath Tank not used for more than 24 consecutive hours requires ST measurement before commencing operations ST results to be submitted to EC on a 6 month basis with reporting form

9 Surface Tension Measurement Stalagmometer Follow manufacturer’s instructions Kocur, Wilmad-Labglass Tensiometer ASTM International method ASTM D 1331 – 89 (Reapproved 2001), “Standard Test Methods for Surface and Interfacial Tension of Solutions of Surface-Active Agents” (except Method B) as amended from time to time This ASTM method is for the Du Nuoy Tensiometer In 2010, ASTM has “withdrawn” this method New Tensiometers (e.g., Kibron) are in the market place and there is no ASTM method for the Kibron tensiometer

10 SURFACE TENSION and CHROMIUM TRIOXIDE CONCn (USEPA, 1993)

11 WETTING AGENT CONCENTRATION VS. SURFACE TENSION (USEPA, 1993)

12 CHROMIUM REGULATION Closed Covers Developed in late 1980’s before EPA MACT “Merlin Cover” and “Chrome Dome” Emission Elimination Device (EEDs) Palm International Inc is the supplier USA : 5-10 installations (to date) EEDs suitable only for hard chromium plating and possibly anodizing EEDs use a tank adaptor and cover with openings for bus bars, agitation, tank evacuation Tank cover incorporates a PTFE membrane (0.1 micron) for hydrogen and oxygen egress Membrane area sized according to amperage Filters and membranes to be replaced at specified intervals

13 ELIMINATION EMISION DEVICE (EED’s)

14 SCHEMATIC OF EED’s

15 CHROMIUM REGULATION Closed Covers Regulation allows 6 months to install and comply Regulation states the components required for the cover ( seals; membrane; evacuation device) Inspection and Maintenance at end of daily operation or each plating cycle Compliance Test: Smoke test to be conducted every 3 months to ensure no leakage from seals and gaskets Continuous Compliance: Visual inspection of membrane during plating (concave up) and evacuation ( concave down)

16 Inspection and Maintenance Control Device Section 6 of the Regulations Prepare and implement an I & M plan requiring an inspection at least every three months I & M plan to cover Control device’s surfaces Ductwork between control device to the tank(s) Media within control device Visible signs of chromium at exit I & M plan by 4 th January 2012

17 Reporting and Record Keeping Reporting (Section 11) Release test report to be submitted within 75 days of completion of sampling Various information to be supplied for the release test report per S.11(1) (a) to (k) Surface Tension reports are submitted every 6 months For January 1 – June 30 - no later than July 31 For July 1- December 31 - no later than January 31 (following year) Reports submitted are to be signed by an authorized person and include information on title, address, phone, etc…

18 Reporting and Record Keeping Record Keeping All records, reports, inspection and maintenance plans, floor plans (showing location of tanks, etc…) test results and other information required by these Regulations, for a period of 5 years beginning on the date of their creation Person submitting the information must specify civic address (where these documents can be inspected) and identify the facility to which the information pertains

19 Inspection and Maintenance Tank Covers Section 9 of the Regulations The plan is to be in accordance with the manufacturer of the tank cover Plan to include Outward movement of membrane Drainage of air inlet and verify seal of the tank cover Inspect the access doors and membranes (for leaks and tears) Inspect membrane for perforations Inspect all clamps Inspect piping to and from the evacuation device Replace HEPA filter on evacuation device

20 ENVIRONMENT CANADA AND US EPS MACT: Release Limits Canada < 0.03 mg / dscm Regular release testing and results to Regulatory authority Pressure drop (across the control device) is not used No distinction between Large/Small or Old/New US < 0.03 mg / dscm < 0.015 mg / dscm < 0.01 mg / dscm One Release Test Pressure Drop is the Compliance Parameter (+/- 2 inches gauge) Release Limits = F( size, age)

21 ENVIRONMENT CANADA AND US EPA MACT: SURFACE TENSION Canada ST < 45 dynes/cm (Stalagmometer) ST< 35 dynes/cm (Tensiometer) Surface Tension (ST) measured once per day per tank Fume Suppressant for all plating/anodizing Closed Covers allowed No distinction in release limits between Hard, Dec, Anodizing US ST < 45 dynes / cm (Stalag) ST< 35 dynes / cm ( Tensio) ST can be measured once per 4hours to 40 hours MACT Amended to Include fume suppressant for Hard chromium Closed Covers allowed Emission Limits different for Hard, Dec, Anodizing

22 Summary The Chromium Regulation came into force 4 th July 2009 The EC Regulations are “similar” to the US EPA Release limit of < 0.03 mg/dscm and this will have to be complied with by 4 th January 2012 Surface Tension limits of < 35 dynes/cm (Tensiometer) and < 45 dynes/cm (Stalagmometer) and these limits are already in effect ASTM D 1331-89 has been withdrawn and a replacement has not been announced To date there are no Tank Covers in use in Canada Noticeable decline in the MFI sector (recession, China, US markets, etc…) Alternative processes (HVOF, Cr3+) as complete replacement? Over 80 years of successful chromium plating (from Cr6+) with excellent and probably non replaceable metrics

23 Perfluorooctane Sulfonate and its Salts and Certain Other Compounds Regulations (PFOS Regulations)

24 Outline: PFOS Regulations PFOS: Why the Assessment? PFOS: Background Risk Management Strategy for PFOS Production, Import, Use of PFOS Why was action needed? Exposure Sources PFOS and Metal Finishing PFOS Regulations in Canada Summary Page 24

25 What is PFOS? The PFOS (perfluorooctane sulphonate) anion: Page 25

26 PFOS: Why the Assessment? Emerging science indicated global distribution of PFOS with some of the highest concentrations recorded in the Canadian Arctic In 2000 The major North American manufacturer (3M) announced phase out of this chemistry US EPA supported 3M decision as data showed PFOS with a strong tendency to accumulate in humans and environment and potential long term harm to humans and environment Draft OECD hazard assessment of PFOS concurred with US EPA decision In 2004 in Canada, a screening assessment (environmental and health) was undertaken on PFOS and its salts under CEPA 1999 CEPA: Canadian Environmental Protection Act

27 PFOS: Background PFOS (salts and precursors) refers to a group of compounds that have a specialized fluorinated chemistry and belong to the fluorochemical family referred to as perfluorinated alkyl substances (PFAS) PFOS denotes the form of the chemical as found in the environment; PFOS salts are the chemicals in commerce Precursors are compounds that contain the key PFOS chemical structure and are expected to degrade to PFOS in the environment Precursors were included in the assessment because PFOS is their likely final degradation product, they contribute to the distribution and loading of PFOS in the environment, and they may contribute jointly to the toxicity of PFOS in the environment C-F bond accounts for extreme stability and excellent properties of PFOS PFOS salts: potassium, ammonium lithium, diethanol-amine PFOS (salts and precursors) are used primarily in applications involving water, oil, soil and grease repellents for use on rugs, carpets, fabric and upholstery, and food packaging, and also specialized chemical applications (fire-fighting foams, hydraulic fluids, and metal finishing)

28 PFOS: Background PFOS (salts and precursors) belong to the fluorochemical family referred to as perfluorinated alkyl substances (PFAS) PFOS anion: C8F17SO3 - (K+, NH4+, Li+) Carbon bonds are saturated with Fluorine C-F bond accounts for the extreme stability and excellent properties of PFOS but also the environmental concerns Page 28

29 PFOS: Production, Import and Use PFOS (salts, precursors) are not manufactured in or exported from Canada PFOS is imported as raw chemicals, products, formulations and manufactured articles From 1997 – 2000, approx 600 T of PFAS was imported to Canada and PFOS was 43% of PFAS Primary US supplier of PFOS (salts, precursors) voluntarily phased out production in 2002 Since 2002 imports of PFOS (salts, precursors) have “essentially ceased” Potential for PFOS/PFOS containing products to be imported because PFOS production has been identified in other countries Page 29

30 PFOS: Why is Action Needed? The Stockholm Convention on Persistent Organic Pollutants (POPs) came into force in May 2004 This is an international legally binding agreement ratified by 128 countries (including Canada) under which the signatory countries are bound to take action to prohibit the manufacture and import of the chemicals listed in the convention In 2005 Sweden proposed PFOS and 96 PFOS-related substances as candidates for the POP list which would eliminate or restrict production and use PFOS is also on the Long - Range Transboundary Air Pollution (LRTAP) criteria for POPs LRTAP is an international legally binding agreement ratified by 51 countries to endeavour to limit and, as far as possible, gradually reduce and prevent air pollution, including long-range transboundary air pollution Page 30

31 PFOS: Canadian Action The Chemicals Management Plan (CMP) of Environment Canada was announced in December 2006 Mandate was to evaluate chemicals in commercial use that have not undergone scientific assessment for further action July 2006, proposal to add PFOS added to the List of Toxic Substances in Schedule 1 to the Canadian Environmental Protection Act (CEPA) 1999 “Screening assessment report concluded that PFOS (salts, precursors) are entering the environment in a quantity or concentration or under conditions that have or may have an immediate or long-term harmful effect on the environment” and which meets the criteria set out in paragraph of 64(a) of CEPA 1999 Because of this, PFOS was declared “toxic” to the environment The human health screening report, however, concluded that current levels of exposure for PFOS are below levels that might affect human health Page 31

32 PFOS Levels in Biota PFOS has been detected in vertebrate and invertebrate biota worldwide In Canada, PFOS detected in “higher trophic level biota”: fish, fish-eating birds, marine mammals PFOS is both hydrophobic and lipophobic and binds to proteins in the blood (serum) and liver Polar bear, Canadian Arctic (liver: pfos is 1700 – 4000 ng/g and exceeds all other individual organohalogens). Other species (ng/g): Arctic fox (liver – 1400) Mink (liver - 4870); Bald Eagle (plasma - 2570) Dolphin (liver - 1520) Seal (liver - 1100) PFOS is a persistent organic pollutant that accumulates in animals and magnifies in food chains Page 32

33 PFOS Exposure Sources Aqueous Film Forming Foams (AFFF) Surfactant Use in the Metal Finishing Industry (Fume Suppressants for control of surface tension) Industrial/Manufacturing Processes Material Disposal Long-Range Atmospheric Transport Material Use Page 33

34 PFOS and the Metal Finishing Industry Main use of PFOS is in Fume Suppressant (FS) formulations to reduce surface tension of plating solutions and control dragout Use of PFOS in FS formulations dates to about the late 1980’s early 1990’s PFOS content is from between 3 to 7 percent by weight of the FS formulation (from various MSDS information) Control of surface tension is a regulatory parameter in the US and in Canada for the control of emissions from chromium plating processes FS and control of surface tension is widely used in Canada by hard and decorative chromium platers Page 34

35 PFOS and the Metal Finishing Industry Fume Suppressants (FS) reduce the surface tension and PFOS retains stability in chromic acid Approx 3 Tonnes PFOS was imported in 2004 for FS use in Canada PFOS may enter the environment via treated rinse water discharged to municipal sewer systems Hard and Decorative chromium plating and Fume Suppressant use Rinse water treatment is (typically) by conventional hydroxide precipitation PFOS is not removed by conventional aerobic biological wastewater treatment (i.e. Activated Sludge) processes typically found at POTWs PFOS may also be contained in sludge from metal finishing treatment processes (from phys-chem treatment) which are sent for metal recovery Page 35

36 PFOS: Canadian Regulations The Perfluorooctane Sulfonate and its Salts and Certain Other Compounds Regulations came into force in June 2008 The regulations allow the use of PFOS in FS formulations for a period of 5 years from the day the regulations came into force (i.e. June 2008) for the following: Chromium electroplating, chromium anodizing and reverse etching Electroless nickel-polytetrafluoroethylene plating; and Etching of plastic substrates prior to their metalization Page 36

37 PFOS: Canadian Regulations The Chromium Electroplating, Chromium Anodizing and Reverse Etching Regulations came into force 4 th July 2009 This regulation allows three control options: Release limit (< 0.03 mg/dscm) Surface Tension Limits (<35 dynes/cm for a Tensiometer and <45 dynes/cm for a Stalagmometer) Closed Covers (“Zero Emission Devices”) For the control of surface tension (a regulatory parameter), fume suppressants with PFOS are allowed to be used until 2013 (which is due to the PFOS Regulations) Page 37

38 PFOS: Other Jurisdictions US: EPA adopted two SNUR (Significant New Use Rules) for 88 PFOS substances that apply to new producers and for new uses and a third SNUR (for 183 PFOS substances) posted for stakeholder review by 08/08/2006 SNUR requires manufacturers and importers to notify EPA 90 days before manufacture or import of these substances to provide EPA time to evaluate the intended new use and prohibit or limit the “new activity” The SNUR will essentially restrict all manufacture and importation. However, the SNUR identifies four uses as NOT new uses: aviation hydraulic fluids; photoresists in semiconductor production; surface tension; and intermediates in production of the preceding chemicals US EPA allows the use of FS containing PFOS indefinitely? Page 38

39 PFOS: Other Jurisdictions AUSTRALIA: PFOS in water, oil and grease repellents to be phased out by September 2002 PFOS in leather products phased out in March 2003 All other PFOS containing products phased out by December 2003 NORWAY: Reductions in PFOS emissions by 2010 SWEDEN: Proposed listing PFOS on the Convention of Persistent Organic Pollutants (POPs) in June 2005 UK: Proposed National Plan to restrict the use and marketing of PFOS and substances that degrade to it (see DEFRA report: August 204) Page 39

40 PFOS: Other Jurisdictions OECD Issued a hazard assessment in 2002 and is followed up on production phase out plans for manufacturers in Italy, Japan, Switzerland and UK

41 FUME SUPPRESSANTS Chromium plating is an electrochemical processes (efficiency ~20%) Anode and Cathode Reactions cause release of hydrogen (at cathode) and oxygen (at anode) Gas evolution entrains chromic acid forming mist above solution Options: Collect Mist; Reduce Mist; Contain Mist REDUCE MIST by Fume Suppressants / Wetting Agents FS reduce surface tension of plating bath to allow gases to escape with diminished “bursting” FS reduce bubble size First Generation and Second Generation Fume Suppressants: Plating Quality Concerns (Pit aggravation) Third Generation FS introduced early 1990’s are perfluorinated with higher solubility and lower foaming No adverse effects on plating quality U.S. EPA testing: Emissions significantly reduced at ST 30-40 FS used at low dosage to control dragout (and extend bath life) At ST 30-40 : CHROMIC ACID STACK concentration is less than MACT Reference: Hard Chrome Fume Suppressants and Control Technologies U.S. EPA Report EPA/625/R-98/002. December 1998 Page 41

42 FUME SUPPRESSANTS: BACKGROUND Defined as any chemical agent that reduces or suppresses fumes or mists at the surface of an electroplating solution  FUME SUPPRESSANTS: TEMPORARY OR PERMANENT Temporary: dissipated mainly by decomposition of the active chemical components Permanent: dissipated by drag-out of the solution FUME SUPPRESSANT: TYPES Foam Blanket: physically suppress mists Wetting Agents: lowers surface tension of solution ADVANTAGES OF FS: Minimization of solution evaporation loss Low cost for Cr6+ emission control Energy consumption very low No solid waste generation DISADVANTAGES OF FS: Possible aggravation of gas pitting and base metal defeats (especially for Hard) Entrapment of hydrogen gas (explosion) Constituents in permanent Fume Suppressants (PFOS) Page 42

43 FUME SUPPRESSANTS FOAM BLANKETS: Generates a layer of foam across the surface of the solution with current and agitation from hydrogen and oxygen Foam blankets trap chromic acid mist under the blanket Foam blanket is maintained from 0.5 to 1.0 inches thick and corners the entire solution surface Proper thickness is important Thin blanket: mist will not be contained Thick blanket: over 1 inch will cause build up of hydrogen (potential explosion) Issues with monitoring foam blanket thickness Visual monitoring Measurement WETTING AGENTS: Reduces the surface tension of the solution Gases escape with diminished “bursting” effect resulting in less mist formation Surface tension is due to imbalance between polar H 2 0 molecules at surface and polar H 2 0 molecules in bulk solution Molecular polarity refers to “dipoles” within molecules Page 43

44 FUME SUPPRESSANTS: EVOLUTION  1ST GENERATION (PRE 1954):  Hydrocarbon based (kerosene, paraffin oils)  Several disadvantages (layering of oil and carry over to rinse tanks)  Fire hazard and dermatitis  Oxidation of hydrocarbon to CO 2 and formation of Cr3+  Cr3+ is bath contaminant  2ND GENERATION (1954):  Fluorinated or perfluorinated carbon chain replaced HC chain  Stability in strong chromic acid and high oxidizing conditions at anodes  Active ingredients include  Potassium perfluoroalkyl sulfonate  Amine perfluoralkyl sulfonate  Potassium perfluoroethyl cyclohexyl sulfonate  Ammonium perfluorohexyethyl sulfonate  Low solubility and interaction with fluoride ions result in quality issues for hard chromium  3RD GENERATION (late 1980s/early 1990s):  Perfluorinated organic compounds  Higher solubility; lower foaming  Active ingredients  Organic fluorosulfunate  Tetraethylammonium-perfluoroctyl sulfonate  No adverse affect on hard chromium Page 44

45 PFOS: Summary PFOS is a widespread Persistent Organic Pollutant (POP) International recognition since 2000 Extremely stable molecule with properties which accounted for several industrial uses Many countries are controlling the use, manufacture and import of PFOS Environment Canada (EC) has declared PFOS to be “toxic” EC: “PFOS Regulations” came into force in June 2008 EC: “Chromium Regulations” came into force in July 2009 Canadian Regulations allow PFOS to be used in fume suppressant formulations for surface tension control until 2013 MFSA has replaced PFOS in commercial FS formulations MFI in Canada now adopting PFOS – free formulations but adoption is not as yet universal US EPA - Region 5 study on PFOS in wastewater from MFI (2009) Page 45

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47 Great presentation Peter. Want to go for a smoke now? Thanks Willie. Excellent idea. But I have to answer questions first. CHROME IS KING!! EVEN ON THE ROAD AGAIN!

48 Great presentation Peter. Want to go for a smoke now? Excellent idea Willie. Thanks but I have to answer questions first.

49


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