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BAPPG CYANIDE PRESENTATION Team Cyanide Fact Sheet:Sarah Scheidt, City of Sunnyvale Presentation:Norm Domingo, SBSA Michael Dunning, USD.

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Presentation on theme: "BAPPG CYANIDE PRESENTATION Team Cyanide Fact Sheet:Sarah Scheidt, City of Sunnyvale Presentation:Norm Domingo, SBSA Michael Dunning, USD."— Presentation transcript:

1 BAPPG CYANIDE PRESENTATION Team Cyanide Fact Sheet:Sarah Scheidt, City of Sunnyvale Presentation:Norm Domingo, SBSA Michael Dunning, USD

2 BAPPG PRESENTATION OUTLINE: CYANIDE INTRODUCTION: The goal of this presentation will be to: Identify industrial sources of Cyanide to the influent of San Francisco Bay Area Wastewater Treatment Plants. Explain how Cyanide is used in these industrial sources. Explain treatment methodologies Explain analysis methods Identify industrial Cyanide discharge regulatory requirements Identify RWQCB Cyanide discharge requirements for POTWs PRESENTATION OULTINE I) Define Cyanide II) Identify Industrial Users III) Treatment methodologies IV) Analytical Methods VI) Identify RWQCB discharge requirements for POTWs

3 CYANIDE CN -, (C≡N), –C≡N

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5 Chemical Structure A cyanide is any chemical compound that contains the cyano group (C≡N), which consists of a carbon atom triple-bonded to a nitrogen atom. Inorganic cyanides are generally salts of the anion CN −. Organic compounds that have a –C≡N functional group are called nitriles. Of the many kinds of cyanide compounds, some are gases; others are solids or liquids. Those that can release the cyanide ion CN − are highly toxic to animals.chemical compoundcyano groupcarbonatomtriple-bonded nitrogenanionOrganic compoundsfunctional groupnitrilesion

6 INORGANIC FORMS Two basic forms Simple Cyanides represented by the formula: A(CN) X where A is an alkali (sodium, potassium, ammonium) and X is the valence of A. Complex Cyanides represented by the formula: A Y M(CN) X where A represents the alkali present Y times, M the heavy metal (iron, cadmium, copper) and X the number of cyanide groups.

7 ORGANIC FORMS Organic compounds that have a cyanide functional group are called NITRILES An example of a nitrile is CH 3 CN, acetonitrile (ethanenitrile per IUPAC), also known as methyl cyanide.acetonitrileIUPACmethyl Nitriles do not release cyanide ions. A functional group with a hydroxyl and cyanide bonded to the same carbon is called cyanohydrin, and cyanohydridins are hydrolyzed into hydrogen cyanide and a carbonyl compound (ketone or aldehyde).cyanohydrinhydrogen cyanide

8 FUN FACTS Cyanides are produced by certain bacteria, fungi, and algae and are found in a number of foods and plants. Cyanides are found, although in small amounts, in certain seeds and stones, e.g. those of apple, mango, peach, and bitter almonds. [5] In plants, cyanides are usually bound to sugar molecules in the form of cyanogenic glycosides and defend the plant against herbivores. Cassava roots (also called manioc), an important potato-like food grown in tropical countries (and the base from which tapioca is made), also contain cyanogenic glycosides. [6][7]bacteriafungialgaeapple mangopeachbitter almonds [5]sugarglycosidesherbivoresCassavapotatotapioca [6][7] The cyanide radical CN· has been identified in interstellar space. [8]cyanide radical [8] Hydrogen cyanide is produced by the combustion or pyrolysis of certain materials under oxygen-deficient conditions. For example it can be detected in the exhaust of internal combustion engines and tobacco smoke. Certain plastics, especially those derived from acrylonitrile, release hydrogen cyanide when heated or burnt. [9]pyrolysisexhaustinternal combustion engines tobaccoplastics acrylonitrile [9]

9 TOXICITY Cyanide is a rapidly acting, potentially deadly chemical that can exist in various forms. Cyanide can be a colorless gas, such as hydrogen cyanide (HCN) or cyanogen chloride (CNCl), or a crystal form such as sodium cyanide (NaCN) or potassium cyanide (KCN). Cyanide sometimes is described as having a “bitter almond” smell, but it does not always give off an odor, and not everyone can detect this odor.

10 TOXICITY Many forms of cyanide are toxic to humans. Toxicity can be attributed to interactions with low pH (acidic) solutions and some biological systems to produce hydrogen cyanide. Most of the inorganic salts have exposure limits of a few parts per million. Exposure can occur by absorption through the skin, by inhalation of dusts or gas, or by ingestion. Exposure to minor amounts of cyanide on the skin can result in dermatitis. Certain species of fish are extremely sensitive and can be killed by low levels of cyanide (US EPA, 1979). Bluegill, salmon and trout are killed by levels slightly over 0.1 ppm cyanide. Compound levels below 0.1 ppm can functionally effect metabolic and reproductive cycles. Cyanide levels that kill fish often do not adversely impact lower aquatic organisms like crustaceans and mussels. Toxicity may extend to microorganisms that digest sewage and sludge.

11 Table 3. Toxicity of Cyanide Compounds Sources: (Sax, Merck) TLV threshold limit value is the time time-weighted average concentration for an 8-hour workday and 40-hour workweek to which a worker may be repeatedly exposed without adverse effect. LD50 lethal dose to 50% of a specified population. NAME/FORMULAPHYSICAL FORMTLVLD50 HYDROGEN CYANIDE (HCN) GAS5mg/m 3 1mg/kg human POTASSIUM CYANIDE (KCN) SOLID5mg/m mg/kg human SODIUM CYANIDE (NaCN) SOLID5mg/m mg/kg human

12 SAFETY The most dangerous cyanides are hydrogen cyanide (HCN) and salts derived from it, such as potassium cyanide (KCN) and sodium cyanide (NaCN), among others.hydrogen cyanide If accidentally ingested (swallowed), chemicals found in acetonitrile based products that are used to remove artificial nails can produce cyanide.

13 SAFETY The hazards associated with cyanide use cannot be minimized; however, the risks can be reduced through safe handling practices. Cyanide safety procedures should include instructions for: chemical storage Containment piping, transportation handling, use protective equipment personal hygiene monitoring and emergency contingencies All personnel who are exposed to cyanide, including contractors and visitors, should receive appropriate training.

14 SAFETY GUIDELINES Managing cyanide safely requires effective segregation of cyanide solutions. The accidental mixing of acids with cyanide causes a reaction that can quickly release dangerous amounts of hydrogen cyanide gas. Handling of solids should be limited to trained personnel, and solutions should be prepared in areas with adequate ventilation to prevent exposure to dust. Use of dust masks is recommended. Safe cyanide handling requires careful attention to personal hygiene. Workers must avoid skin and eye contact through the use of protective clothing and equipment. Ideally, workers should shower and change clothes at the end of the work shift and workers should always wash up before handling food or other items. Exposure to small amounts of cyanide over a period of time can result in dermatitis.

15 SAFETY Air agitation of cyanide solutions should be avoided because it causes misting and carbon dioxide in the air is acidic enough to liberate hydrogen cyanide. Alkaline chlorination treats cyanide wastewater. A residual concentration of free chlorine will be present after treatment, and it is important that the residual be reduced. If chlorine gas is used an excessive concentration of chlorine can result in the release of chlorine gas during pH adjustment. Other sources of Cl2, such as sodium hypochlorite, may be safer.

16 USES Cyanide has many industrial and commercial uses. It is used in industry for mining, metal finishing, medical applications and pharmaceutical manufacturing. Commercial businesses such as printers have it as a component of their inks. Pest companies use it as a pesticide and algaecide. It is used by fishing poachers to capture tropical fish near live coral reefs for the aquarium and seafood markets. Jewelers may have small quantities on site.

17 MEDICAL USE The cyanide compound sodium nitroprusside is occasionally used in emergency medical situations to produce a rapid decrease in blood pressure in humans; it is also used as a vasodilator in vascular research. The cobalt in artificial Vitamin B12 contains a cyanide ligand as an artifact of the purification process. During World War I, a copper cyanide compound was briefly used by Japanese physicians for the treatment of tuberculosis and leprosy. [12]sodium nitroprussideblood pressure vasodilator Vitamin B12World War IJapanesetuberculosisleprosy [12] It is used in pharmaceuticals such as the anti cancer drug laetrile. Also in surgical dressings that foster healing and reduce scarring.

18 SOURCES There are three main wastewater sources of Cyanide. They are industrial, commercial and residential. Cyanide is naturally present in some foods and in certain plants such as cassava. Cyanide is contained in cigarette smoke and the combustion products of synthetic materials such as plastics. Combustion products are substances given off when things burn. In manufacturing, cyanide is used to make pharmaceuticals, paper, textiles, and plastics. It is present in the chemicals used to develop photographs. Cyanide salts are used in metallurgy for electroplating, metal cleaning, and removing gold from its ore. Cyanide gas is used to exterminate pests and vermin in ships and buildings.

19 INDUSTRIAL SOURCES The biggest source of Cyanide in the SBSA service area, as is for other POTWs, is from Metal Finishers. Industrial use of Cyanide is also regulated at Centralized Waste Treatment and Pharmaceutical facilities.

20 CENTRALIZED WASTE TREATMENT

21 METAL FINISHERS

22 Electroplating

23 PLATING SHOP TANK LAYOUT

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25 PROCESS SCHEMATICS

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34 TREATMENT

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36 TREATMENT AREA

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39 SEGREGATED PLATING AREA

40 TREATMENT BY CHLORINATION

41 HCN MONITORING

42 ALARM SET POINTS 2 PPM HCN SETS OFF ROOM ALARM 10 PPM BUILDING EVACUATION ALARM AND ALARM TO FIRE DEPARTMENT

43 AREAS MONITORED 3 AREAS MONITORED PLATING ROOM BY CONTROL PANEL LOCATED OUTSIDE THE PLATING ROM ROOF VENT FROM THE PLATING ROOM

44 METAL FINISHING BEST MANAGEMENT PRACTICES Develop a cyanide management plan, and integrate it with the facility environmental and safety management plan. Establish initial and refresher cyanide management training for managers, workers and contractors. Establish well-defined personnel responsibilities and clear chains of command for cyanide use and management. Develop safe procedures for handling cyanide, i.e., storage, transportation, containment, spill management, production processes, raw material additions, solution sampling and analysis, solution maintenance, waste treatment, waste disposal and equipment maintenance. Develop rinsewater quality standards for all cyanide processes and pre-cyanide processes. Generally 5 ppm is a reasonable rinsewater standard for a final cyanide process rinse. Develop and implement an integrated pollution prevention strategy encompassing point source waste minimization, recovery, and recycling, waste treatment and off-site disposal. Conduct regular cyanide audits, with corrective action, and update the cyanide management plan on a regular basis. Maintain primary containment tanks, drums, piping, valves, pumps and other equipment to prevent leaks and spills. Segregate cyanide processes, pretreatment, storage and other operations from non-cyanide operations in a separate secondary containment system.

45 BMPs Store cyanide-based raw materials in a secure, dry and ventilated storage area. Monitor work areas for hydrogen cyanide and wastewater treatment areas for hydrogen cyanide and cyanogen chloride Ventilate all cyanide process, wastewater treatment and storage areas Provide workers and visitors with proper protective equipment including gloves, aprons, face shields, goggles, safety glasses, respirators and other protective clothing. Provide workers and visitors with access to lavatories and showers to maintain appropriate personal hygiene. Dispense and weigh raw materials in a ventilated area. Develop and practice emergency procedures for cyanide spills. Develop and practice emergency procedures for human exposure (skin, eye, ingestion) to cyanide mists and fumes. Use the minimum amount of cyanide required for adequate process or operation. Avoid air agitation of cyanide solutions as carbon dioxide can liberate hydrogen cyanide.

46 Alternatives to Cyanide Non-cyanide Plating Processes Metal Cyanide Non-cyanide Brass Proven No Bronze Proven No Cadmium Proven Yes Copper Proven Proven* Gold Proven Developing Indium Proven Yes Silver Proven Developing Zinc Proven Proven * New alternatives in development for specific cyanide processes.

47 Alternatives Non-cyanide process alternatives provide surface finishing facilities with significant advantages in specific circumstances. However, non-cyanide processes are often more difficult to treat in conventional wastewater treatment systems, more difficult to recover or recycle and are, generally, more difficult to control.

48 Analysis All wastewater sampling and analysis is required to be performed in accordance 40 CFR 136. Sampling : Grab, dark amber glass/plastic, NaOH Analysis: Total Cyanide Cyanide Amenable to Chlorination

49 Regulated by Federal, State and Local Regulations. _Treatment_for_Aqueous_Waste_Containing_Cyanide Permit by Rule: Treatment for Aqueous Waste Containing Cyanide The following are highlights of the new regulations for Permit by Rule for Aqueous Waste Containing Cyanide. Please refer to the Permit by Rule fact sheet or the regulations for more details. New Permit by Rule Eligible Treatment Methods for Aqueous Waste Streams Containing Cyanide 1. oxidation by addition of hypochlorite; 2. oxidation by addition of peroxide or ozone, with or without the use of ultraviolet light; 3. alkaline chlorination; 4. electrochemical oxidation; 5. ion exchange; orion exchange 6. reverse osmosis.reverse osmosis

50 RWQCB REQUIREMENTS Cyanide Site Specific Objectives and Cyanide Action Plan Fact Sheet Resolution R – To amend the Water Quality Control Plan (Basin Plan) for the San Francisco Bay Region to adopt Site-Specific Objectives for Cyanide for San Francisco Bay and an Implementation Plan. The Basin Plan requires cyanide source control programs, or “Cyanide Action Plans”, as incorporated into municipal NPDES Permit provisions. Dischargers shall implement monitoring and surveillance, pretreatment, source control and pollution prevention for cyanide in accordance with the following tasks: Cyanide Action Plan Task Additional Resource / Reference Task (1) Review Potential Cyanide Contributors - The Discharger shall submit an inventory of potential contributors of cyanide to the wastewater treatment facility (e.g., metal plating operations, hazardous waste recycling, etc.). If no contributors of cyanide are identified, Tasks 2 and 3 are not required, unless the Discharger receives a request to discharge detectable levels of cyanide to the sanitary sewer. If so, the Discharger shall notify the Executive Officer and implement Tasks (2) and (3). Compliance Date December 1, 2009 Task (2) Implement Cyanide Control Program The Discharger shall submit a plan for, and begin implementation of, a program to minimize cyanide discharges to the sanitary sewer system consisting, at a minimum, of the following elements: Compliance Date February 28, 2010 with 2009 annual P2 report i. Inspect each potential contributor to assess the need to include that contributing source in the control program. ii. Inspect contributing sources included in the control program annually. Inspection elements may be based on USEPA guidance, such as Industrial User Inspection and Sampling Manual for POTWs (EPA 831-B ).

51 Cyanide Control Plan Review POTW Influent Data Review Pretreatment Program Significant and Categorical Industrial User, and Commercial / Industrial User Inventories Pretreatment Inspections and regulations cover Action Plan requirements for inspections. Review sanitary sewer trunk line monitoring data for commercial, industrial, and residential service areas. BAPPG P2 and the Cyanide SSO Presentation August 2008 by Betsy Elzufon BAPPG Factsheet on Approaches to Pollution Prevention for Cyanide – August 2008 City of San Jose Cyanide Fact Sheet BAPPG Presentation Cyanide; 6/2/2010 iii. Develop and distribute educational materials to contributing sources and potential contributing sources regarding the need to prevent cyanide discharges. Wastewater Discharge Permits DTSC Fact Sheets January 2002, 1) Jewelry Manufacturing Pollution Prevention Recommendations; and 2) Cyanide Waste Produced in Jewelry Manufacturing iv. Prepare an emergency monitoring and response plan to be implemented if a significant cyanide discharge occurs. v. If ambient monitoring shows cyanide concentrations of 1.0 μg/L or higher in the main body of San Francisco Bay, undertake actions to identify and abate cyanide sources responsible for the elevated ambient concentrations. BAPPG Cyanide SSO / Action Plan Fact Sheet with ERP Fact Sheet 6/2/2010. Regional Monitoring Program (RMP) through BACWA Task (3) Report Status of Cyanide Control Program Submit a report to the Regional Water Board documenting implementation of the cyanide control program. Compliance Date Annually with P2 reports due February 28. POTW Annual Pollution Prevention Reports:

52 Cyanide Monitoring and Emergency Response Plan Fact Sheet The Basin Plan Cyanide Site Specific Objectives require POTWs to prepare an emergency monitoring and response plan that will be implemented if a significant cyanide discharge occurs. Purpose is to respond to illicit discharges

53 Potential Monitoring and Emergency Response Plan Contents POTW influent monitoring, typically per NPDES Permit influent and effluent monitoring requirements. Agency should define what a “significant discharge” of cyanide means as it pertains to influent or effluent monitoring data. This could be done by creating performance based limit for cyanide using existing cyanide data. When significant discharge occurs take another effluent sample and an influent sample. Sanitary sewer surveillance monitoring at a specified frequency for a number of trunkline, commercial, and residential area sites. One example would be monitoring quarterly at seven sewer trunkline locations, three commercial area locations and three residential area locations. The seven trunkline locations are the same every quarter. The commercial and residential sampling locations change every quarter. If any of the sampling results for cyanide are detectable, the POTW will sample the same location the next quarter. In addition when cyanide is detected from trunkline, commercial or residential surveillance, the Pretreatment Inspectors will audit the area to determine if there are any potential sources of cyanide. If there are any potential industrial or commercial sources in the area they will be inspected. Contact all potential cyanide sources and discuss any recent activities that could have caused high value. Investigate suspected cyanide dischargers that may have contributed to high value include review of delivery, use, and shipment of cyanide. Develop procedures for follow-up sampling and enforcement response if an IU discharges above the appropriate Federal categorical limits or local limits. Ensure procedures are in the Pretreatment Program Enforcement Response Plan and the Pretreatment Sampling Standard Operating Procedure (SOP). Report all findings in SMR, or in a letter to Regional Board. Follow up actions, and summarized program results will be reported in the Annual Pollution Prevention Report.

54 Ambient San Francisco Bay Monitoring Cyanide SSO resulted in NPDES Permit language stating: “If ambient monitoring shows cyanide concentrations of 1.0 ug/L or higher in the main body of San Francisco Bay, undertake actions to identify and abate cyanide sources responsible for the elevated ambient concentrations.” Most agencies are participating in the Regional Monitoring Program (RMP) through BACWA. The RMP has been tasked with sampling the San Francisco Bay for cyanide and compiling the data for BACWA. If the RMP ambient monitoring cyanide concentrations are equal to or greater than 1.0 ug/L, agencies will compile and review their effluent cyanide data to determine if the POTW could potentially be a source responsible for the elevated ambient concentrations. Agencies will also work through BACWA to undertake actions on a regional level to identify and abate cyanide sources responsible for the elevated ambient concentrations.

55 References Capsule Report, Managing Cyanide in Metal Finishing, EPA 625/R- 99/009December 2000 Pollution Prevention for the Metals Finishing Industry - A Manual for Pollution Prevention Technical Assistance Providers Permit By Rule - Management of Aqueous Waste Containing Cyanide WIKIPEDIA THANKS TO: INDUSTRIAL PLATING CO. IN SAN CARLOS, CA SLAC, NATIONAL ACCELERATOR LABORATORY IN MENLO PARK, CA


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