Appendix II. Detailed Contaminant Lists_2 by thevo

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									APPENDIX II Detailed Lists of Potential Contaminants at Foundry Sites

Appendix II

1. Potential Contaminants Deposited By Air Emissions from Ferrous Foundry Melting Processes
Metals & Metalloids: Sb As Ba Be Bi B Ca Cd Cr Co Cu Fe Pb Hg Mg Mn Mo Ni Se Ti V Zn OTHER: Cl & cmpds PCDD/F F & cmpds Na & cmpds PAH S & cmpds Emissions from Melting Fuels * Coal Coal Coke I Oil Gas gas L L L L L L L L L T T T P L L L L L L L L L L L L L L L C L L C C P L L L L L L T? L L L L L L L L C L L C C L L L L L L L L L L L L L L L L C L P? P P C
th

Emissions from Charge Materials Contaminants Ferrous Alloy Fluxes in Scrap Constituents T D/T P D/T

Metal Treatment Desulphurisation
I

NodularisationI

Bessemer Process/ Oxygen Lancing S

P

D/T D/T D/T D D D (may be T) C D D/T L D D

P

L

T T T T T

L

P L

C

C

C

P

P L

C L

L

T T P T T L P P

D/T D

P L T

P P C P

Key:

* where used. From late 19 century, electric melting methods were also in use in UK & are now the predominant technologies.
L: likely P: possible T: trace only D: dependant on alloys under production S: Steel foundries only

C: certain, i.e., always expected

Historic processes only, not used in ferrous foundries currently

I: Iron foundries only
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Appendix II

2. Potential Contaminants Deposited By Air Emissions from other Ferrous Foundry Processes
Mould & Coremaking* Resin Oilsand Shell Metals & Metalloids: Sb Bi Cr Co Cu Fe Mn Mo Ni V OTHER: SiO2 dust Zircon dust S # Chromite sand dust S Coaldust I Clay dust Phenolics on dust PAH on dust Sulphur & compounds Casting in Sand Moulds Greensand Phenolic bonded Silicate bonded Knockout from Sand Moulds Greensand Phenolic bonded Silicate bonded Fettling Shotblasting D/T D/T D D D/T C L D D D P P P P P P P C L P P L P P L D D D D P P Other D D D D D C D D D D P/T P/T P/T C L P P L Greensand Sand Reclaim Phenolic bonded Silicate bonded

P P L C C C C F P

C C C C

C C F

T

C C C C

C C F

Key:

* Oil-sand, loam & dry sand mould/core making processes involve drying in an oven, which may be gas or oil-fired. See list 1 for associated contaminants from the fuel use.
L: likely P: possible T: trace only D: dependant on process/alloy F: S-catalysed furans only

C: certain, i.e., always expected

I: Iron foundries only # Contains trace amounts of radioactive isotopes

S: Steel foundries only

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Appendix II

3. Potential Contaminants to Land from Foundry Raw Materials Storage, Handling & Use in Process
PROCESS AREA

RAW MATERIAL SOLID MATERIALS Wood & dust

FORM/CONTAINER

COMMENTS

L Tins, aerosols Tins Tins P: usually small amounts P: usually 0.5 – 200 l sizes P: usually small amounts P L: normally in bulk P: usually smaller amounts P: usually smaller amounts P P P L: usually small amounts L L: usually contains Zr L P: used for curing ovens P: for moulding equipment P: for pigging of metal C for cupola/blast furnaces P for crucible/reverberatory furnaces P C P: only present where malleable or ductile iron were/are made C L: may be contaminated with liquids L L L P: may contain RFC’s P: where used as melting fuel P: for hydraulic furnace controls L: PCB contamination possible P: may contain RFC’s P P: for degreasing P P

PATTERN SHOP

LIQUID MATERIALS Glues & adhesives Paints & Thinners Epoxy resins & hardeners Fibreglass resins SOLID MATERIALS Silica sand & dust Zircon sand, flour & dust # Chromite sand & dust S Resin shell sand Clay Coaldust I LIQUID MATERIALS Glues & adhesives Isopropyl alcohol IPA-based mould coatings Resins & Hardeners * Gas Oil Lubricating Oil SOLID MATERIALS Silica sand Coke I Coal Limestone/dolomite Refractory materials Calcium carbide I CaO/CaF I Sodium Carbonate I Metal returns Scrap ** Pig iron/ingot/bar Ferro-alloys Other additions Insulating wools LIQUID MATERIALS Gas Oil Lubricating Oil Transformer Oil SOLID MATERIALS Insulating wools LIQUID MATERIALS Quench oil Chlorinated solvents Bulk tanks (open) Drums, tanks Drums Powders in drums
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Silos, hoppers, 1-t bags, 50 kg sacks, open compounds (internal or extermal)

MOULD & COREMAKING

Tins, aerosols Tins, drums, IBC’s Drums, IBC’s, bulk tanks Drums, IBC’s, bulk tanks Bulk tanks Drums Bags or open compounds Internal or external storage compounds Solids & powders in bags Sealed drums Drums, bags Bins, compounds, piles (internal or external; on soil or hardstandings) Solids, pellets, etc. in drums or bags Blanket sheets Bulk tanks Drums Drums Blanket sheets

MELTING

HEAT TREATMENT

CASTING PAINTING

SOLID MATERIALS Zinc wire Other metals/coatings

Appendix II

PROCESS AREA CASTING PAINTING

RAW MATERIAL LIQUID MATERIALS Paints Thinners LIQUID MATERIALS Diesel Petrol Lubricating & hydraulic oils

FORM/CONTAINER

COMMENTS

Tins, drums, IBCs

P: most common solvents are xylene, white spirit, toluene, MEK L: for forklift trucks P: for vehicle refueling L: equipment & vehicle maintenance; foundry plant, machining operations L: capacitors in electric motors, fluorescent lights, hydraulic equipment & process heating plant P: used in non-destructive testing P: Machining operations L: for control of cooling systems P: use for control of machining fluids L: for control of cooling systems P: use on finished castings

Bulk tanks Bulk tanks Tins, drums In equipment Tins, aerosols, tanks Drums, IBCs, bulk tanks Drums, tanks Drums, tanks, tins

ANCILLARY OPERATIONS

PCB containing oils Solvent based products Coolants & cutting fluids Biocides Corrosion inhibitors

Key: C: certain L: likely P: possible RFCs: Refractory ceramic fibres

I: Iron foundries only * See detailed list 3(a) below

S: Steel foundries only ** See detailed list 3(b) below

# Contains trace amounts of radioactive isotopes A free flowing sand pre-coated with a phenol formaldehyde novolak resin, which contains a hexamine curing agent. Process first introduced in 1950’s. PCBs can also be found in large booster vacuum pumps installed between 1960 & 1970, as well as in some imported ring jet pumps May include chlorinated products

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Appendix II

3(a) Mould & Coremaking Resins, Hardeners & Catalysts
BINDER SYSTEM Alkaline phenolic * Alkyd urethane Ecolotec SO2 cured epoxy resin FIRST USE 1984/5 SETTING METHODS Self-set, gassed RESIN CONSTITUENTS Aqueous alkaline K or Na-based phenol formaldehyde resin; can contain methanol Part 1: drying oil modified alkyd (polyester) Part 2: polyisocyanate 1990’s Gassed Alkaline phenolic resin Modified epoxy resin mixed with an organic hydroperoxide; a furan version (from 1975) is also available Unsaturated urethane oligomers & acrylic monomers, with an organic peroxide Urea formaldehyde (UF), phenol formaldehyde (PF) & furfuryl alcohol (FA) resin mixtures Phenolic (PF) and urea furan (UF) resins Phenolic resin Esterfied or alkyd oil HARDENER/CATALYST CONSTITUENTS Self-set: organic esters Gassed: methyl formate or CO2 Cobalt naphthenate (commonly incorporated in Part 1) CO2 Sulphur dioxide gas

1960’s

Self-set

1983

Gassed

Free radical

1990’s

Gassed

Sulphur dioxide gas Para-toluene, xylene or benzene sulphonic acids, sulphuric acids & phosphoric acid, or mixtures. Ammonium chloride, urea & acid salts Methylal vapour with a toluene sulphonic acid catalyst Sodium perborate or polymeric isocyanate

Furan *

1958

Self-set

Hotbox Methylal cured phenolic resin No-bake oils Oil sand **

1960 mid1980’s 1950’s Pre1900 196870

Heat Gassed Self-set Heat

Modified vegetable oils & dextrin emulsions Part 1: phenol formaldehyde resin in ester/aromatic hydrocarbon solvents Part 2: Isocyanate, e.g., MDI Self-set: liquid tertiary amine, e.g., phenylpropylpyridine Gassed: dimethylethylamine or triethylamine Alkaline powder & CO2

Phenolic urethane *

Self-set, gassed Self-set, gassed Heat

Polidox

1980’s

Sodium polyacrylate Mostly supplied as dry coated sand, but phenol novolak resin liquid in methanol, shellacs, waxes (if sand coated at foundry) Sodium silicate solutions containing SiO2 and Na2O in varying proportions Furan resins

Resin shell *

1950

hexamine

Silicate *

1952

Self-set, gassed Heat

Self-set: organic esters Gassed: CO2 Copper salts or inorganic salts of sulphonic acid

Warm box

1978

* most common current systems

** commonly used historically for core making

Note: The term “self-set” is used to describe systems that cure at room temperature after the resin and liquid hardener are mixed together with the sand.

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Appendix II

3 (b) Contamination Potential of Pig Iron & Ferro Alloys
POTENTIAL ENVIRONMENTAL IMPACTS STORAGE ISSUES
Pig Iron – solid “pigs” Ferro Alloys – supplied as lumps, granules, or powders Ferro Boron Ferro Molybdenum Ferro Niobium Ferro Titanium Ferro Vanadium Ferro Silico Chrome Ferro Silicon Alloys Ferro Tungsten High Carbon Ferro Chrome Low Carbon Ferro Chrome Other Ferro Alloys – supplied as lumps, granules, or powders As above, with specific hazards listed below Exposure to air can result in formation of manganese carbide, which reacts with water to give explosive gases including hydrogen. Slightly soluble in water, some leaching into groundwater following spillage is possible. Contact with moisture can result in evolution of arsine, phosphine, or hydrogen. Forms corrosive solution on contact with acids. Contact with moisture can result in evolution of hydrogen, arsine or phosphine Soluble in acids, which can result in release of H2S gas. Slightly soluble in water, some leaching into groundwater following spillage is possible. Contact with moisture can result in evolution of hydrogen, arsine or phosphine Thermal decomposition produces SOx and H2S gases. Materials are stable, inert and insoluble in supplied form. Spillage, particularly of powders, could result in localised metals contamination of the ground surface, but leaching into groundwater is improbable. Spillages should be prevented from entering drains and watercourses. Will contribute small amounts to air emissions, depending on melting/boiling point properties, but is added to melt by methods that ensure maximum recovery in the metal being produced. None

MATERIAL/FORM

MELTING
Will contribute to Fe/Mn releases

Ferro Manganese

Ferro Silicon Zirconium

Ferro Phosphorus

Ferro Silicon

Ferro Sulphur

Magnesium Ferro Silicon

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Appendix II

4. Potential Contaminants to Land from Ferrous Foundry Wastes
A variety of wastes are generated during the foundry process. The quality of waste management also varies considerably around the modern industry and poor management was common in the past. Where sufficient space was available, waste may have been deposited directly on the property, in a company landfill, or left around on an ad hoc basis, inside or outside of buildings. Most companies now have some designated storage areas, although bunding of empty drums, etc. is still unusual. Note that the key for this table refers to whether the process will generate these wastes or not. Whether the wastes or associated residues may still be present at a site or not will depend entirely on waste management practices over the years. Any of the waste streams listed may also contain other materials, e.g., discarded gloves, packaging wastes, etc., depending on the extent of segregation practised/not practised at the site. Key to Whether Waste is Generated by the Process:
PROCESS AREA

C: certain

L: likely

P: possible

WASTE

CONTAMINANTS

COMMENTS

SOLID MATERIALS

Any form as received may be disposed of due to damage, spillage, etc. Dusts from processing & use of materials may also be present, e.g., sand dust, wood dust. Packaging wastes of all types are also found. Any materials arriving on site may eventually end up as waste. Full containers of resins, paints, oils, etc. may be discarded if the material becomes off spec, or is no longer required. Partially filled or “empty” containers will be generated as waste from many areas. Historically, there is a high potential that such wastes were poorly managed & spillage or leaks into soil may be expected.

ALL AREAS LIQUID MATERIALS

SOLID MATERIALS Waste mixed sand Mixer scrapings Floor sweepings Scrap moulds/cores Silo filter dust Cured resins Material dependant, e.g., SiO2 dust if silica sand Sand dust, residual binders, PAH, fine metallic drops from alloys C: where filtration used C: leachate levels considerably lower than for uncast sands due to burn out. pH varies (2.5-12) Uncured resins C: May or may not be segregated. Materials tend to be high in leachable phenolics, aromatics, etc. depending on the binder system.

(largest foundry waste by volume)
SAND SYSTEM WASTES ABATEMENT WASTES Dusts/sludge – knockout Greensand plants (in past, usually wet plants) Chemically bonded sand reclamation (usually dry) Thermal sand reclaim (dry) LIQUID WASTES Scrubber liquor

Cast/knocked out sand

SiO2 & binder residues (greensand or chemical) SiO2, clay & coal dusts SiO2 (or Zircon) & resin rich dusts SiO2 dusts (or Zircon)

C: plants can be wet or dry, which can affect likely spillage patterns & control issues (Dry bag filtration is now the predominant type) C

See comments under All Areas Amine, spent phosphoric or sulphuric acid and amine, sulphates/phosphates P: where gas-cured urethane systems are in use

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Appendix II

PROCESS AREA

WASTE SOLID MATERIALS Cupola Bottom Ash Clinker

CONTAMINANTS

COMMENTS

Coke dust, metals Sintered limestone with iron oxides

C: if cupola melting used C: if blast furnace used C: Variety of types (e.g., air-cooled, water granulated) & form differs according to the melting furnace. Physically unstable if oxides are not fully hydrated; S where present may be leachable. P: Physically & chemically unstable until oxide/carbide is fully hydrated/reacted. C P P L P: handling of wet slurries (e.g., dewatering) can result in considerable localised spillage P: dry dusts are prone to wind blowing if not properly contained & can be more widely distributed P: may be handled/treated in a settling pond or lagoon on site L L

Melting slag

CaO/ MgO, metals, sulphur

Desulphurisation slag Refractories from furnaces & ladles Refractories from nodularisation treatment ladles Cr-containing refractory waste Hot toppings/exothermics ABATEMENT WASTES Melting sludge (wet plant) Melting dusts (dry plant) LIQUID MATERIALS Melting Abatement Slurries SOLID MATERIALS Spent metallic blasting media Grinding wheels FETTLING ABATEMENT WASTES Shotblast dust Fettling sludge (wet plant) Fettling dusts (dry plant) Arc air (dry) SOLID MATERIALS Insulating materials/heat treatment furnace linings ANCILLARY OPERATIONS Asbestos LIQUID MATERIALS Waste oils Waste coolants

CaO / Ca carbide residues, high sulphur, v. alkaline – pH 12-13 Can be alkaline, although largely inert Mg nitride – v. reactive, produces ammonia in contact with water/moisture Cr – leachable Metals

MELTING

Metals - see Table 1; S & cmpds, PAH, dioxins, other organic residues also possible. Coke dust – only if used

As above

Fe Mainly alumino-silicate materials SiO2 dust, Fe & alloy constituents Mainly alloy constituents

L C: plants can be wet or dry, which can affect likely spillage patterns & control issues Dry plants now predominate

Refractory ceramic fibres Asbestos fibres

P L: Building waste, maintenance activities, protective gloves L C: if machining undertaken

Many contain PCBs/PAH Tramp oil, surfactants, etc.

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