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Laboratory Safety, Waste Disposal, and Chemical

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1. remove person from contaminated area if it is safe to do so Get medical attention and do not leave person unattended Ingestion Exposures remove the person if possible from source of contamination Get medical attention Dermal Exposures remove person from source of contamination Remove clothing jewelry and shoes from the affected areas Flush the affected areas with water for at least 15 min and obtain medical attention Eye Contact remove person from source of contamination Flush the eyes with water for at least 15 min Obtain medical attention Personal Protective Equipment Always use a fume hood while working with flammable liquids Nitrile and neoprene gloves are effective against most flammables Wear a nonflammable lab coat to provide a barrier to your skin and goggles if splashing is likely to occur Oxidizers Oxidizers or oxidizing agents present fire and explosion hazards on contact with combustible materials Depending on the class an oxidizing material may increase the burning rate of combus tibles with which it comes in contact cause the spontaneous ignition of combustibles with which it comes in contact or undergo an explosive reaction when exposed to heat shock or friction Oxidizers are generally corrosive LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 751 Examples of Common Oxidizers Peroxides Nitrites Nitrates Chlorates Perchlorates Chlorites Hypochlorites Dichroma
2. Internet such as through the UAB Department of Occupational Health and Safety webpage at http www healthsafe uab edu In general the preferred source for the MSDS is the chemical manufacturer primarily because these files are actively updated to accurately reflect all that is known about the hazardous material in question MSDSs are the cornerstone of chemical hazard communication They provide most of the information you should know to work with chemicals safely The following sections describe the information normally contained in an MSDS 764 STORMWATER EFFECTS HANDBOOK Product Name and Identification Name of the chemical as it appears on the label Manufacturer s name and address Emergency telephone numbers for obtaining further information about a chemical in the event of an emergency Chemical name or synonym C A S the Chemical Abstract Service Registry number which identifies the chemical Date of preparation of the MSDS Hazardous Ingredients Identity Information Hazardous Ingredients Substances which in sufficient concentration can produce physical or acute or chronic health hazards to persons exposed to the product Physical hazards include fire explosion corrosion and projectiles Health hazards include any health effect even irritation or development of allergies Threshold Limit Value TLV A TLV is the highest airborne concentration of a substance to which nearly all adults can be repeatedly exposed
3. potassium K magnesium Mg calcium Ca Bromides sodium Na potassium K Carbonates sodium Na potassium K magnesium Mg calcium Ca Chlorides sodium Na potassium K magnesium Mg calcium Ca Fluorides calcium Ca Iodides sodium Na potassium K Oxides boron B magnesium Mg calcium Ca aluminum Al silicon Si iron Fe Phosphates sodium Na potassium K magnesium Mg calcium Ca ammonium NH Silicates sodium Na potassium K magnesium Mg and calcium Ca Sulfates sodium Na potassium K magnesium Mg calcium Ca ammonium NH Laboratory Materials Chromatographic adsorbents Filter paper without hazardous chemical residue Non contaminated glassware Rubber gloves Waste Disposal All laboratories are required to comply with federal and state regulations regarding the packing labeling and transport of hazardous materials Before contacting the Hazardous Materials Facility for waste removal the following procedures must be completed Improperly packed or labeled waste cannot be removed Step One Packing the Waste Containers Collect each chemical waste in a separate screw top container Do not mix wastes Use the smallest container size to match the amount of chemical waste generated The container the chemical was originally shipped in is an ideal waste collection container if it is an appropriate size All waste containers must be tightly capped Each cont
4. 3 If sparks are noticed while plugging in or unplugging equipment or if the cord feels hot do not use the equipment until it has been serviced 4 Do not run electrical cords along the floor where they will be a tripping hazard and subject to wear If a cord must be run along the floor protect it with a cord cover 5 Do notrun electrical cords along the floor where liquid spills may be a problem such as around sinks 6 Do not run electrical cords above the ceiling if possible The cord should be visible at all times to ensure that it is in good condition 7 Do not plug too many items into a single outlet Multistrip plugs can be used only if they are protected with a circuit breaker and if they are not overused 8 Do not use extension cords for permanent wiring USE AND STORAGE OF CHEMICALS IN THE LABORATORY Procurement of Chemicals Material Safety Data Sheets MSDS must accompany all initial incoming shipments of all chemicals MSDSs must be readily available to all personnel in the labs where the chemicals are stored and where they are used MSDSs shall be kept in three ring binders near the door so that personnel can familiarize themselves with new chemicals before getting them out and using them Before ordering a new chemical laboratory personnel should obtain information on proper handling storage and disposal methods for that chemical Consumer products used as they would be at home such as dishwashing detergent do not req
5. and special care needs to be taken Read and follow all precautions LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 785 e Select 9 Turbidity from the Calibrate menu and then 2 2 Point To begin the calibration immerse the sonde in approximately 300 mL of 0 NTU standard clear deionized water and press ENTER e Input the value 0 00 NTU at the prompt and press ENTER e After calibration of the mechanical wiper speed the screen will display real time readings which will allow you to determine when turbidity values have stabilized If the readings appear unusually high or low or are unstable there are probably bubbles on the optical surface Activate the mechanical wiper by pressing the 3 key to remove the bubbles e After stable readings are observed for approximately 40 s press ENTER to confirm the first calibration Press any key to continue e Dry the sonde and probes carefully and then place the sonde in approximately 300 mL of the second turbidity standard 100 NTU Input the value 100 0 NTU press ENTER and view the stabilization of the values on the screen e As described previously if the readings appear unusually high or low or are unstable activate the wiper to remove bubbles and be sure to wait 40 s before confirming the calibration e After the readings have stabilized press ENTER to confirm the calibration Press any key to return to the Calibrate menu Input 0 to return to the Main men
6. 7 buffer in a clean calibration cup Allow at least 1 min for temperature equilibrium before proceeding e Immerse probe into solution From the Calibrate menu select 6 pH to access the pH calibration choices and then 2 2 Point e Press ENTER and input the value of the buffer 7 00 at the prompt Press ENTER and observe the values under pH until the readings are stable for 30 s e Press ENTER The display will indicate that the calibration is accepted If an error message is received repeat with fresh buffer e Press any key to continue e Rinse the sonde in water and dry before proceeding e Place approximately 400 mL of a second pH buffer solution in a clean calibration cup The second buffer might be pH 4 01 if the monitored water is expected to be acidic or pH 10 01 if the monitored water is expected to be basic Allow at least 1 min for temperature equilibrium before proceeding e Press ENTER and input the value of the second buffer 4 01 or 10 01 at the prompt Press ENTER and observe the values under pH until the readings are stable for 30 s e Press ENTER After the second value calibration is complete press any key to return to the Calibrate menu e Rinse the sonde in water and dry before proceeding Turbidity Probe Calibration e Prepare 100 NTU solution Dilute 4000 NTU formazin solution 1 40 with diH O pipette 25 mL of 4000 NTU formazin solution into 1 L volumetric flask and qs to 1 L Formazin is a hazardous material
7. 741 Fumie OOS soos siisctscesacsss is cessscstisesecsbstagessecedianacensesisadasaesssandasedoaseatesesaunestavacsugessandaapscsssetieess 741 Choice of Chemicals isiingie renie na dbevies ovaia ste E EE E ETE N 742 Equipment and Glassware iscss sssivscceesiecessiecasedesskecscbasdecsodves EEEE E a 742 Labels and Signs cccccsc 53 cscssveetesdeettuadesshacetadesaganeds suadi avies igeWicdksveenscsebeseuedssabsssuedes costs euseedd bass 742 Unattended Operations s ss csccses iscsseiescageesicetiavass uyesisasssaasasncasess chsh cadessesescdpassegesscnassystesietueess 743 Electrical Satetys sci cise sh octes bee cease uate a isked oa eats e iA tle A EA E 743 Use and Storage of Chemicals in the Laboratory 0 ees eee ceceessceeeseeeseceeceseceeeeaessaeeseeeneeaees 743 Procurement of Chemicals sisicisc c tecsscsscsveaes cesuesisceed sviek spetasedeveteds tbe cetedeans soa Eni EEEa iien s 743 Working with Allergens ics ccccicsssescctesagcessoasiaraseneedicadasaesssandasssvasesti seasesestagsscugessancaayscdisesioess 743 Working with EMmbryotoxins esient riin ae E E E Ea EEE aa GEEAE 744 Working with Chemicals of Moderate or High Acute Toxicity or High Chronic Toxicity 744 Chemical Stora ges sec icscecgcsessancteceseteusds aen eaa E easier sbetertesbabetdedes costa susensgevesss 747 WranSpOrtaton ss css25sspsetescdevtesecgek riaa aei ae EA roas aE aE ap Saa Eo E Eaa piraso ae 748 Procedures for Specific Classes of Hazardous Materials
8. If someone is seriously injured the most important step is to contact emergency responders as quickly as possible Explain the situation and describe the location clearly and accurately If someone is bleeding severely apply a sterile dressing clean cloth or handkerchief to the wound Then put protective gloves on and place the palm of your hand directly over the wound and apply pressure and keep the person calm Continue to apply pressure until help arrives If a person s clothes are on fire he or she should drop immediately to the floor and roll If a fire blanket is available put it over the individual An emergency shower if one is immediately available can also be used to douse the flames If a person goes into shock have the individual lie down on his her back if safe to do so and raise the feet about 1 ft above the floor Personal Protective Equipment Wear appropriate personal protective clothing while working with highly reactive materials This might include impact resistant safety glasses or goggles a face shield gloves a lab coat to minimize injuries from flying glass or an explosive flash and a shield Conduct work within a chemical fume hood as much as possible and pull down the sash as far as is practical When the experiment does not require you to reach into the fume hood keep the sash closed Barriers can offer protection of personnel against explosion and should be used Many safety catalogs offer commercial shie
9. Sharps and poor recovery not very repeatable Extra time required to dissolve reagent not very repeatable Sharps Sharps chloroform extraction very small volume and well contained Large amounts of benzene required require laboratory hood waste disposal problem SCGOHLSW SSSATVNV IWOINSHO ANY YSOdSIA SLSVM ALSSVS AYOLVYHOSV1 692 Table E 2 Summary of All Field Test Kits Evaluated continued Expendable Time Problems with Test Manufacturer Capital Cost Reqd Precision Recovery safety hazards expertise Method and Kit Name Cost per sample min Useful Range COV RO runoff required etc Fluoride lon selective Cole Parmer Fluoride 600 for 0 25 5 10 0 1 20 mg L 0 22 0 97 0 96 Requires frequent and time electrode Tester electrode consuming calibration too meter and fragile for field use calib kit Spectrophotometric HACH Fluoride 1495 for 0 37 10 0 3 2 na 1 10 1 07 Should use automatic pipettes determination of SPADNS Reagent DR 2000 hard to use in field SPADNS bleaching by Reagent is hazardous fluoride Spectrophotometric HACH Fluoride 1495 for 1 17 5 0 1 2 0 05 0 97 0 94 Sharps SPADNS Reagent is determination of SPADNS Reagent DR 2000 hazardous bleaching by Using AccuVac fluoride Ampoules Hardness EDTA titration CHEMetrics Hardness 0 00 2 25 5 10 na 0 01 na Sharps Total 20 200 ppm EDTA titration HACH Total Hardness 94 for Varies with Varies na na na Using Digital Titrator digital sample with t
10. and holes If the gloves are not in good condition replace them 740 STORMWATER EFFECTS HANDBOOK Table E 1 Chemical Resistance of Glove Materials E Excellent G Good F Fair P Poor Chemical Natural Rubber Neoprene Nitrile Vinyl Acetaldehyde G G E G Acetic acid E E E E Acetone G G G F Acrylonitrile P G N A F Ammonium hydroxide G E E E Aniline F G E G Benzaldehyde F F E G Benzene P F G F Benzyl chloride F P G P Bromine G G N A G Butane P E N A P Butyraldehyde P G N A G Calcium hypochlorite P G G G Carbon disulfide P P G F Carbon tetrachloride P F G F Chlorine G G N A G Chloroacetone F E N A P Chloroform P F G P Chromic acid P F F E Cyclohexane F E N A P Dibenzyl ether F G N A P Dibutyl phthalate F G N A P Diethanolamine F E N A E Diethyl ether F G E P Dimethyl sulfoxide N A N A N A N A Ethyl acetate F G G F Ethylene dichloride P F G P Ethylene glycol G G E E Ethylene trichloride P P N A P Fluorine G G N A G Formaldehyde G E E E Formic acid G E E E Glycerol G G E E Hexane P E N A P Hydrobromic acid 40 G E N A E Hydrochloric acid G G G E Hydrofluoric acid 30 G G G E Hydrogen peroxide G G G E lodine G G N A G Methylamine G G E E Methyl cellosolve E E N A P Methyl chloride P E N A P Methyl ethyl ketone F G G P Methylene chloride F F G F Monoethaloamine F E N A E Morpholine F E N A E Naphthalene G G E G Nitric acid P P P G Perchloric acid F G F E Phosphoric acid G E N A E Potas
11. by mixing the ether with 10 w w aqueous potassium iodide solution a yellow color change due to oxidation of iodide to iodine confirms the presence of peroxides Small amounts of peroxides can be removed from contaminated ethers via distillation from lithium aluminum hydride LiAIH which both reduces the peroxide and removes contaminating water and alcohols However if you suspect that peroxides may be present it is wise to dispose of the material If you notice crystal formation in the container or around the cap do not attempt to open or move the container 11 Never distill an ether unless it is known to be free of peroxides 12 Store shock sensitive materials separately from other chemicals and in a clearly labeled cabinet 13 Never allow picric acid to dry out as it is extremely explosive Always store picric acid in a wetted state Health Hazards Associated with Reactives Reactive chemicals are grouped as a category primarily because of the safety hazards associated with their use and storage and not because of similar acute or chronic health effects For health hazard information on specific reactive materials consult the MSDS or the manufacturer However LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 757 there are some hazards common to the use of reactive materials Injuries can occur due to heat or flames inhalation of fumes vapors and reaction products and flying debris First Aid for Reactives
12. electrode cell with 0 100 mS cm 0 5 of reading 0 01 autoranging 0 001 mS cm mS cm Temperature Thermistor 5 45 C 0 15 C 0 01 C pH Glass combination electrode 2 14 units 0 2 units 0 01 units ORP Platinum ring 999 999 mV 20 mV 0 1 mV Turbidity Optical 90 scatter 0 1000 NTU 5 0 1 NTU mechanical cleaning Depth Medium Stainless steel strain gauge 0 61 m 0 12 m 0 001 m Depth Shallow Stainless steel strain gauge 0 9 1 m 0 06 m 0 001 m a Report outputs of specific conductance conductivity corrected to 25 C e Volumetric flasks graduated cylinders pipette and pipette tips for preparation of calibration solutions e Barometer NOTE Remember that barometer readings which appear in meteorological reports are generally corrected to sea level and are not useful for your calibration procedure unless they are uncorrected and at the elevation and location of the sonde e Dissolved oxygen probe maintenance kit contains O rings DO membranes pencil eraser or very fine sandpaper electrode filling solution e Several clean absorbent paper towels or cotton cloths for drying the sonde between rinses and calibration solutions e Computer with Ecowatch software connection cable for interfacing computer with sonde AC power supply and eight C size alkaline batteries e Allen wrench for removing sonde guard and battery compartment cover Reagents e Deionized water diH O e pH buffers 7 00 4 01 and or 10 01 either 4
13. emergency telephone numbers vendor s catalog number date of the MSDS and version of the MSDS Product Information Product name Chemical Abstract Services CAS number Chemical name Chemical formula where appropriate Chemical family to which the material belongs Ingredients lists all components PCT Percent by weight of each component in product unless trade secret CAS NO Chemical Abstract Services CAS registry number for component SARA If component is listed in SARA 313 and more is used than amount listed must notify EPA TLV Threshold Limit Value Maximum airborne concentration for 8 hour exposure that is recom mended by the American Conference for Governmental Industrial Hygienists ACGIH PEL Permissible Exposure Limit Maximum airborne concentration for 8 hour exposure that is regulated by the Occupational Health and Safety Administration OSHA HAZARD Physical and health hazards of component explained Physical Data Physical state color odor solubility boiling point melting point specific gravity pH vapor density evaporation rate corrosivity stability and storage precautions Fire Explosion Hazard and Reactivity Data Flashpoint Temperature at which liquid will give off enough vapor to ignite Used to define flammability and ignitability Lower Flammable Limit LFL or LEL Lowest concentration that will produce flash or fire when ignition source is present LABORATORY SAFETY WASTE DIS
14. eseeseeesseessseesrsesresreresresrsresrseresesrees 748 Flammable Solvent icvscsiecsscvisesesssoesaty nuana a i gecceveyecdevaaecasess 749 ORIGIZELS orines oeir E EA E S WA toe G Aeas eas aE E A N eas 750 COMOSIVES iieo pasea aa A E E OE E EE EEEE a EEN EE aa EREE iTe 752 735 736 STORMWATER EFFECTS HANDBOOK REACIIVES E E dea ietiteet alee Mun eae Lied E ee ead aide 754 Compressed Gas Cylinders secen neie a n a E sats E E TR ERIKA 757 Emergency Procedures aa eooo Sentai i ok eu a a ee lee Ee ae ails 758 Chemical Waste Disposal Program vursa eniri arinou ieren e aa aoee dno iit kedri 760 Chemical Waste Containers aniisi ia a N E A dati tah ied 760 Waste Minimization oense ree ie E E E EE EE TE E 760 Disposal of Chemicals down the Sink or Sanitary Sewer System eeeseeeseeerseeseeerrerereees 761 Chemical SUbStrtutroms ices aea ea r a eor EEE PEATE SE IEA E 761 Neutralization and Deactivation 0 0 eee ceeesecseceeesseeseceeeesecsseeseeesecsesesecseesaesseeeaeseaeeaees 761 Elimination of Nonhazardous Waste from Hazardous Waste eseeseeeeseeeseeeeseesrrerssrereees 761 Waste Disposals a ink di tener a eee A A E A E E 762 Material Safety Data Sheets MSDS Jt enro isere renine ana ece adi 763 Product Name and Identification eee eeeeseeecceseceeeeseceeeeseeesecaeseseceeeaesseseseseeeeaees 764 Hazardous Ingredients Identity Information 0 0 0 eee cece ceeeneceseeeeeeseceeeeseseeeeseenaetaees 764 Physical Chemical Characteristics
15. gloves available on the market should serve general laboratory purposes Personal Protection Other Protective Clothing 1 The primary purpose of a lab coat is to protect against splashes and spills A lab coat should be nonflammable where necessary and easily removed 2 Rubber coated aprons can be worn to protect against chemical splashes and may be worn over a lab coat for additional protection 3 Face shields can protect the face eyes and throat against impact dust particulates and chemical splashes However always wear protective eyewear underneath a face shield Always wear a face shield when handling large quantities of hazardous chemicals such as when preparing an acid bath 4 Shoes that fully cover the feet should always be worn in a lab If work is going to be performed that includes moving large and heavy objects steel toed shoes must be worn Avoidance of Routine Exposure Develop and encourage safe habits Avoid unnecessary exposure to chemicals by any route Do not smell or taste chemicals Vent apparatus that may discharge toxic chemicals e g vacuum pumps microwaves into local exhaust devices Inspect gloves before use Do not allow release of toxic substances in cold rooms or warm rooms since these have contained recirculated atmospheres Fume Hoods 1 Use the fume hood for all procedures that might result in the release of hazardous chemical vapors or dust Confirm that the hood is working by holding a Ki
16. lower limits of quantification The lower limits of the flame AAS optimal concentration ranges are generally about the same as for the plasma AES while the electrothermal AAS lower limits are 10 to 1000 times lower However the plasma AES instrument has a much greater dynamic range than either AAS instrument The plasma AES also has fewer interferences and can analyze many elements simultaneously Because of these differences many laboratories use a plasma AES for general 776 STORMWATER EFFECTS HANDBOOK Table E 4 Optimal Concentration Ranges of Metals in Samples Flame AAS Electrothermal Inductively Coupled mg L AAS mg L Plasma AES mg L Aluminum 5 100 0 02 0 2 0 6 100 Antimony 1 40 0 02 0 3 0 45 100 Arsenic 0 005 0 1 0 75 100 Barium 1 20 0 01 0 2 0 030 50 Beryllium 0 05 2 0 001 0 03 0 005 10 Bismuth 1 5 Cadmium 0 05 2 0 0005 0 01 0 06 50 Calcium 0 2 20 0 15 100 Cesium 0 5 15 Chromium 0 2 10 0 005 0 1 0 1 50 Cobalt 0 5 10 0 005 0 1 0 1 50 Copper 0 2 10 0 005 0 1 0 1 50 Gold 0 5 20 Iron 0 3 10 0 005 0 1 0 1 100 Lead 1 20 0 005 0 1 0 6 100 Lithium 0 1 2 0 06 100 Magnesium 0 02 2 0 45 100 Manganese 0 1 10 0 001 0 03 0 06 50 Molybdenum 1 20 0 003 0 06 0 12 100 Nickel 0 3 10 0 005 0 1 0 2 50 Platinum 5 75 Potassium 0 1 2 1 5 100 Selenium 0 005 0 1 1 0 100 Silver 0 1 4 0 001 0 025 0 1 50 Sodium 0 03 1 Strontium 0 3 5 0 03 50 Thallium 0 6 100 Tin 10 200 0 02 0 3 Titanium 5 100 Vanadium 2 100 0 1 50 Zinc 0 05
17. nonleaking screw on caps e Must be filled to a safe level not beyond the bottom of the neck of the container or a 2 in headspace for a 55 gallon drum NOTE Do not use RED BAGS or SHARPS CONTAINERS Biohazard for hazardous waste collection Labeling Containers Before chemicals can be disposed of a waste tag is required It should be filled out by the waste generator and attached to each container The information on the tag is used to categorize and treat the waste A manifest is also required Fill out all paperwork legibly accurately and completely Waste Minimization Avoid purchasing and using large quantities when it is not necessary Implement microscale techniques whenever possible Flammable Organic Solvents Collection for Reuse Many flammable organics can be reused for fuel unless they are extremely toxic or give off toxic products of combustion Do not combine any other chemicals with the flammable organic solvents listed below Halogenated solvents solvents containing chlorine fluorine or bromine acutely toxic flammables acids bases heavy metals oxidizers and pesticides should be collected LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 761 in separate containers The following is a list of the most frequently encountered compounds that are suitable for heat recovery Acetone Methyl alcohol 2 Butanol Methyl cellosolve Butyl alcohol Pentane Cyclohexane Petroleum ether Diethyl ether 2 Pro
18. other solvent processes 3 Detergent and enzymatic cleaners can be substituted for sulfuric acid potassium dichromate chromerge cleaning solutions and ethanol potassium hydroxide cleaning solutions Neutralization and Deactivation Certain hazardous chemical wastes can be rendered nonhazardous by specific neutralization or deactivation laboratory procedures Contact the Chemical Safety Officer to see if the waste you generate is suitable for neutralization Elimination of Nonhazardous Waste from Hazardous Waste The following items are not considered to be hazardous They should be collected in disposable containers or plastic bags clearly labeled as nonhazardous waste and put in the wastebasket All compounds identified by the two letter code NH are nonhazardous and should not be disposed of via the chemical waste program unless they are components of a mixture with hazardous materials or are suitable for chemical recycling 762 STORMWATER EFFECTS HANDBOOK Nonhazardous Waste Organic Chemicals Acetates calcium Ca sodium Na ammonium NH and potassium K Amino acids and their salts Citric acid and salts of sodium Na potassium K magnesium Mg calcium Ca and ammonium NH Lactic acid and salts of sodium Na potassium K magnesium Mg calcium Ca and ammonium NH Sugars glucose lactose fructose sucrose maltose Inorganic Chemicals Bicarbonates sodium Na potassium K Borates sodium Na
19. safe to reach them Use safety showers and eye washes as appropriate In the case of eye contact promptly flush eyes with water for a minimum of 15 minutes and seek immediate medical attention For ingestion cases contact the Poison Control Center at 1 800 POISON1 In the case of skin contact promptly flush the affected area with water and remove any contaminated clothing or jewelry If symptoms persist after washing seek medical attention Notify persons in the immediate area about the spill evacuating all nonessential personnel from the spill area and adjoining areas that may be impacted by vapors or a potential fire If the spilled material is flammable turn off all potential ignition sources Avoid breathing vapors of the spilled materials Be aware that some materials either have no odor or create olfactory fatigue so that you stop smelling the odor very quickly LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 759 7 Leave on or establish exhaust ventilation if it is safe to do so Close doors to slow the spread of odors 8 Notify the appropriate authorities Laboratory Supervisor Principal Investigator Chemical Health and Safety about the spill and the required documentation 9 IF THERE IS AN IMMEDIATE THREAT TO LIFE OR HEALTH call Emergency Services at 911 Building Evacuation Procedures 1 Building evacuation may be necessary if there is a chemical release fire explosion natural disaster or medical emer
20. to an emergency shower or source of water Remove clothing shoes socks and jewelry from affected areas as quickly as possible cutting them off if necessary Be careful to not get any chemical on your skin or to inhale the vapors Flush the affected area with water for a minimum of 15 minutes Get medical attention Eye Contact remove person from source of contamination if safe to do so and take immediately to an eyewash or source of water Rinse the eyes for a minimum of 15 minutes Have the person look up and down and from side to side Get medical attention Do not let the person rub the eyes or keep them tightly shut Personal Protective Equipment Always wear proper gloves when working with acids Neoprene and nitrile gloves are effective against most acids and bases Polyvinyl chloride PVC is also effective for most acids A rubber coated apron and goggles should also be worn If splashing is likely to occur wear a face shield over the gloves Always use corrosives in a chemical fume hood Reactives General Characteristics Polymerization Reactions Polymerization is a chemical reaction in which two or more molecules of a substance combine to form repeating structural units of the original molecule This can result in an extremely high or uncontrolled release of heat An example of a chemical that can undergo a polymerization reaction is styrene LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 755 Water Reacti
21. water for at least 15 minutes remove clothing and then promptly seek medical attention If hydrogen fluoride vapors are inhaled move the person immediately to an uncontaminated atmosphere if safe to do so keep the person warm and seek prompt medical attention 6 NEVER STORE HYDROFLUORIC ACID IN A GLASS CONTAINER BECAUSE IT IS INCOMPATIBLE WITH GLASS 7 Store hydrofluoric acid separately in an acid storage cabinet and keep only the amount necessary in the lab 8 Creams for treatment of hydrofluoric acid exposure are commercially available and should be kept on site Health Effects Associated with Corrosives All corrosives are severely damaging to living tissues and also attack other materials such as metal Skin contact with alkali metal hydroxides e g sodium hydroxide and potassium hydroxide is more dangerous than with strong acids Contact with alkali metal hydroxides normally causes deeper tissue damage because there is less pain than with an acid exposure The exposed person may not wash it off thoroughly enough or seek prompt medical attention All hydrogen halides are acids that are serious respiratory irritants and also cause severe burns Hydrofluoric acid is particularly dangerous At low concentrations hydrofluoric acids do not immediately show any signs or symptoms upon contact with skin It may take several hours for the hydrofluoric acid to penetrate the skin before you would notice a burning sensation However by thi
22. 0 ccccesceessesseceseesseeseceeeesecseeeseessecseeeseceeesessaseseeneeeaees 764 Fire and Explosion Hazard Data cies ecceceseeecceseeeeeesececeeaecseeeseeesecsesesececesesseeeseeeaeeaees 765 Reactivity Date ence arora E NARA E eee age NEN S 765 Health Hazard Data miror a e a E E dus A E S dhe ERIE 765 Specific HACH MSDS Information eseesseeeeeeereseeseresrrsesresrssestestsresresteresresrsestesrsrrsresrse 766 Summary Of Field Test Kats miaire a bess e Ea ea Ea pa E E e A E 767 Special Comments Pertaining to Heavy Metal Analyses sssessssesseessesreresesrsreserersesresrsresrsee 774 Stormwater Sample Extractions for EPA Methods 608 and 625 ooo eee eeeeseeeeeeneeneeeaeeee 779 Calibration and Deployment Setup Procedure for YSI 6000upg Water Quality Monitoring SOnde PAPAE MEE EE EEA EEEE EEEE EEEE 782 References eaters sake oana an a RA ie hea R ete N A R A 785 INTRODUCTION The laboratory safety discussion included in this appendix is summarized from the Laboratory Safety and Standard Operating Procedures manual prepared for use in the Water Quality Labora tories of the Department of Civil and Environmental Engineering at the University of Alabama at Birmingham It was prepared by Shirley Clark and Robert Pitt to ensure safe laboratory practices during our research The manual and the excerpted information in this appendix include information concerning safe laboratory practices the use of personal protective equipment emer
23. 01 or 10 01 in addition to the 7 00 solution is suitable for two point calibration e Conductivity standard e g NaCl solution at 16 640 uS cm 25 C Turbidity standard e g Formazin solution at 4000 NTU Initial Calibration Procedure e Remove sonde guard e Check to see if DO electrode is bright silver if not clean by gently rubbing with the pencil eraser Clean eraser particles off probe completely Fill probe well with filling solution and replace membrane Put probe guard back onto sonde e Connect computer to sonde and connect sonde to external AC power supply Conductivity Probe Calibration e Prepare conductivity standard Use a 1 mS cm 1000 uS cm standard if the sonde is to be deployed in fresh water For example dilute typically available 16 640 mS cm standard solution 1 16 64 with diH O to prepare 500 mL add 30 mL of 16 640 mS cm standard and QS to 500 mL with diH O e Decant 1 mS cm solution into calibration cup and immerse sonde into cup e Launch Ecowatch software Open communications with sonde and type menu From the sonde main menu select 2 Calibrate From the calibrate menu select 1 Conductivity to access the conductivity calibration procedure and then 1 SpCond to access the specific conductance calibration procedure Enter the calibration value of the standard you are using 1 000 mS cm at 25 C and press ENTER e The current values of all enabled sensors will appear on the screen and will change with
24. 2 0 03 100 Data from Standard Methods for the Examination of Water and Wastewater 19th edition Water Environment Federation Washington D C 1995 analytical work and an electrothermal AAS for individual samples for single elements at very low concentrations Table E 5 lists various operational and cost attributes of these metal analysis methods Pitt et al 1997 The trade offs between the various types of equipment are obvious The instruments with greater sensitivity cost more Only an electrothermal AAS instrument can analyze many samples quickly with an autosampler with good sensitivity but with only a few metals being analyzed at a time at the most The instruments that can analyze many metals at a time include the ICP units However only the ICP MS units are capable of similar low sensitivities as the electrothermal AAS units These units are mostly still being used in research environments and are not typically used in production laboratories as they require well trained specialized operators and are the most costly alternative shown In flame AAS a sample is aspirated directly into a flame typically air acetylene and is atomized A light beam from a hollow cathode lamp designed for a specific wave length is directed through the flame and into a monochromator and finally into a detector The detector measures the amount of light absorbed by the atomized element The lamp operating at the specific wavelength of the metal mak
25. 9 10 Dimethyl 1 2 benzanthracene DMBA Erionite Germane Hexaethyltetraphosphate Hydrogen cyanide Hydrogen selenide Melphalan N Methyl N benzylnitrosamine N Methyl N nitrosourea STORMWATER EFFECTS HANDBOOK LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 747 Mustard gas 2 Naphthylamine Nitric oxide Nitrogen dioxide Nitrogen tetroxide Parathion Phosgene Phosphine 2 3 7 8 Tetrachlorodibenzo p dioxin Thorium dioxide Some examples of compounds normally classified as strong carcinogens include the following 2 Acetylaminofluorene Benzo a pyrene 7 12 Dimethylbenz a anthracene Dimethylcarbamoy chloride Hexamethylphosphoramide 3 Methylcholanthrene 2 Nitronaphthalene Propane sultone Various N nitrosamides The above substances in both lists must be used and stored in areas with restricted access Special warning signs must be posted in these areas Containers should be stored in chemical resistant trays and work must be performed within or above these trays Cover surfaces where these substances are used with absorbent plastic backed paper Performance certified hood or other containment devices must be used when generation of toxic vapor gases dusts or aerosols might occur Chemical Storage The chemical storage area should be posted with an appropriate sign Chemicals must be stored in appropriate containers and correctly labeled Chemical compatibility must be determined to reduce the likelihood
26. APPENDIX E Laboratory Safety Waste Disposal and Chemical Analyses Methods CONTENTS Mtr MUCHON msee a iE ir REEE AAA E REE E E E A RER R E 736 Fundamentals of Laboratory Safety 00 eee ceecsecseeeseesseeseceeeeaecnsesseceaececeseseceaeseaeeseeeneeaees 737 Procurement Of Chemicalls c scscssessacestssessssdassscoacevsscasesesedbes sides tesussscedbansyinsasisasstastasieoases gt 737 Distribution of Chemicals sisri enoe vases e E ehacteadvess E EEEa 737 Laboratory Chemical Storage cs cc e csce cscceessgecaseseseuessssesdsescavessigesnepesedavseensbensasvaceabascsuvedaenss 737 Storage Cabinets iios e ieie aisan iari Eaa E Wana Mel aed doe Re ees 738 Basic Rules and Procedures for Working with Chemicals 0 cee eceecceseesseeseseeeeeeseseeseeeneesees 738 Laboratory Protocol cies 0 231 hesteeseeutes ano RE EEE aE R EEE NA 738 Personal Safety Practices ias 3sccecsssssiessescssscessgecdsesesstees leas A E E E R E 738 Housekeeping orein aaa ccoendundeesbaceed esagandds svat E E E e cespesvseedd bans 739 Personal Protection Protective Eyewear 0 eceseesceseeseeseceseeseceseeseeeseceeceseseeeeeeeaeesees 739 Personal Protection Protective Gloves cece eeseeseceeeeseceeeeseeesecseeeseceenseseeseseenseeaees 739 Personal Protection Other Protective Clothing ec eeeeseeseeeeceeeeseseeeeseeeseesees 741 Avoidance of Routine Exposure 0 cccceeeescceseeceseeeseeeececeaeeesceceaeeesaeceaeeeseeceaeeeeessaeeeseeeeas
27. Fire and Explosion Hazard Data Flashpoint refers to the lowest temperature at which a liquid gives off enough vapor to form an ignitable mixture with air Flammable or Explosive Limits the range of concentrations over which a flammable vapor mixed with air will flash or explode if an ignition source is present Extinguishing Media the fire fighting substance that is suitable for use on the substance which is burning Unusual Fire and Explosive Hazards hazards that might occur as the result of overheating or burning of the specific material Reactivity Data Stability indicates whether the material is stable or unstable under normal conditions of storage handling and use Incompatibility lists any materials that would upon contact with the chemical cause the release of large amounts of energy flammable gas or vapor or toxic vapor or gas Hazardous Decomposition Products any materials that may be produced in dangerous amounts if the specific material is exposed to burning oxidation heating or allowed to react with other chemicals Hazardous Polymerization a reaction with an extremely high or uncontrolled release of energy caused by the material reacting with itself Health Hazard Data Routes of Entry Inhalation breathing in of a gas vapor fume mist or dust Skin Absorption a possible significant contribution to overall chemical exposure by way of absorption through the skin muco
28. HEAVY METAL ANALYSES The above discussion on field test kits points out the obvious shortcomings of trying to obtain meaningful heavy metal data using simple procedures There are a number of methods available for heavy metals with the traditional methods restricted to the laboratory The following discussion summarizes these available methods especially their sensitivities Table E 3 lists the metals and associated methods included in the 1995 version of Standard Methods for the Examination of Water and Wastewater Other listings of environmental analytical methods are published by ASTM American Society of Testing Materials and by the U S Environmental Protection Agency in the Code of Federal Regulations especially 40 CFR 136 Guidelines Establishing Test Procedures for the Analysis of Pollutants Methods listed in these references are generally taken as approved for many purposes Table E 3 lists about 40 different metals and 12 different basic analytical methods Most all of the metals can be analyzed using atomic absorption spectrometry AAS and inductively coupled plasma emission spectrometry ICP In addition many of the metals have specific chemical tests that use spectrophotometric or titration methods For most stormwater investigations only a relatively few of these metals are routinely evaluated including arsenic cadmium chromium copper lead mercury nickel selenium and zinc LABORATORY SAFETY WASTE DISPOSAL AND CHEM
29. ICAL ANALYSES METHODS 775 Table E 3 Metal Methods Included in the 1995 19th Edition of Standard Methods for the Examination of Water and Wastewater Color AAS Flame C V AAS ETAAS Hydride ICP ASV Other Aluminum x x Antimony Arsenic x x Barium Beryllium x Bismuth Cadmium x Calcium x Cesium Chromium x Cobalt Copper x Gold Iridium Iron x Lead x Lithium Magnesium Manganese x Mercury x x Molybdenum Nickel Osmium Palladium Platinum Potassium Rhenium Rhodium Ruthenium Selenium x x x Silver x Sodium Strontium Thallium Thorium Tin Titanium Vanadium x Zinc x x xX X X XK X x x x x grav xX X X X X KX KX KX KX KX KX K KX XK XK X x x X X XK X x x x ISE xX X X X X X X XK X fluro x xX X X X X x x xX X X X X KX XK XK X Note Color Specific chemical colorimetric methods AAS Atomic absorption spectrometry Flame Flame emission photometry ASV Anodic stripping voltammetry C V AAS Cold vapor AAS ET AAS Electrothermal AAS ICP Inductively coupled plasma emission spectrometry Hydride Hydride generation AAS Other IC ion chromatography grav gravimetric ISE ion selective electrode and fluro fluorometric Table E 4 compares the optimal metal concentration ranges for AAS and ICP the most commonly used instrumentation Standard Methods 1995 Instrument detection limits are about 15 times less than the lower values shown on this table which represent the
30. L of methylene chloride is placed in the concentration vial for rinsing This rinse solvent is then used to adjust the volume of extract to 2 0 mL Extract is then poured into a labeled Teflon sealed screw cap vial and freezer stored until analysis Figure E 22 unless the sample matrix creates excessive background interference When sediments are being analyzed for organic compounds we use a semiautomated method in place of the traditional Soxlet extraction method A Dionex ASE accelerated solvent extractor Figure E 23 is used to extract organic compounds from the sediment while an OI gel permeation chromatograph Figure E 24 is used to clean up the extracts Figure E 19 Drying columns containing anhydrous Figure E 18 Extract placed in centrifuge sodium sulfate Figure E 20 Automatic vacuum centrifuge concen trator Savant AS 160 centration method 781 Figure E 21 Alternative micro Kuderna Danish con 782 Figure E 22 GC MSD used for organic analyses hi l _ 7 Figure E 23 Dionex ASE for automatic extractions of organics from sediment samples Figure E 24 Ol GPC used to clean sed iment extracts STORMWATER EFFECTS HANDBOOK CALIBRATION AND DEPLOYMENT SETUP PROCEDURE FOR YSI 6000UPG WATER QUALITY MONITORING SONDE This discussion on calibration and deployment setup procedures for the YSI 6000 is presented here due to the reliance on this water quality monitoring sonde for many diff
31. POSAL AND CHEMICAL ANALYSES METHODS 767 Upper Flammable Limit UFL or UEL Vapor concentration in air above which the vapor concentration is too great to burn NFPA Codes The National Fire Protection Association NFPA has a system to rate the degree of hazard presented by a chemical Codes usually found in colored diamond and range from 0 minimal hazard to 4 extreme hazard They are grouped into the following hazards health blue flamma bility red reactivity yellow and special hazards white Health Hazard Data Describes how a chemical can enter body ingestion inhalation skin contact its acute and chronic effects and lists if a component is a carcinogen mutagen or teratogen Precautionary Measures Special storage instructions Handling instructions Conditions to avoid Protective equipment needed First Aid Spill and disposal procedures Transportation Data Shipping name hazard class and ID number of the product References Supporting references are also included in the HACH MSDS sheets SUMMARY OF FIELD TEST KITS Field test kits can be important analytical tools during receiving water investigations Chapter 6 among others described how they can be used to obtain rapid and cost effective data However the careful selection of the test kits to be used is critical It is important to consider several factors specifically the sensitivity of the procedure safety hazards associated with the method the co
32. TORMWATER EFFECTS HANDBOOK Compressed gas cylinders must be stored in well ventilated areas where the temperature does not exceed 125 F Cylinders must be stored in an upright position Cylinders not in use should have the valve protection caps in place Cylinders must be chained down to a fixed structure using the appropriate brackets and chains Never mix chemicals unless such mixing is part of a documented and approved procedure Transportation 1 All chemicals should be labeled before being transported 2 When chemicals are hand carried they should be placed in an outside container or acid carrying bucket to protect against breakage and spillage 3 When chemicals are transported by wheeled cart the cart should be stable under the load and have wheels large enough to negotiate uneven surfaces such as expansion joints and floor drain depressions without tipping or stopping suddenly Incompatible chemicals should never be trans ported on the same cart 4 Laboratory moves and transfers of large amounts of chemicals should be coordinated through the Hazardous Materials Facility 5 Secondary containment should always be used to contain substances if there is a break in the primary container The following are conditions for chemical transport in elevators Chemicals should be labeled and carried in secure break resistant containers with tight fitting caps The packing systems supplied by manufacturers are excellent at preventing bre
33. Wash exposed skin before leaving the laboratory Keep the work area clean and uncluttered Do not smell or taste chemicals No horseplay in laboratories Do not engage in behavior that may distract another worker Always make sure that the exits from the laboratory are free of obstruction Do not allow children or pets in the lab Never pipette anything by mouth Be aware of dangling jewelry loose clothing or long hair that might get caught in the equipment DSO 08ST SON vec LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 739 11 Store food and drinks in refrigerators that are designated for that use only Food and drinks shall not be carried into the work areas in the lab Do not consume food or drinks using glassware or utensils that are used for laboratory procedures 12 Never work alone in the lab if it is avoidable If you must work alone make someone aware of your location and have him or her call or check on you periodically If you must work alone do not use large containers of any dangerous chemical such as acids or solvents 13 Wash your hands frequently throughout the day and before leaving the lab for the day 14 Do not wear contact lenses in the lab because chemicals or particulates may get caught behind them and cause severe damage to the eye Housekeeping 1 Work areas must be kept clean and free of unnecessary chemicals Clean your work area throughout the day and before you leave at the end o
34. ainer must be labeled as to chemical content For mixtures give approximate percentages of each chemical compound Milk jugs are not accept able for chemical storage If using a container that originally contained another chemical com pletely remove the original label prior to relabeling Completely fill chemical waste collection containers Shock Sensitive and Water Reactive Compounds and Lecture Bottles Shock sensitive and water reactive compounds and lecture bottles require special handling These materials should always be packed separately from other chemicals LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 763 Packing Filled Containers in Boxes Chemicals that have the potential to react with each other should not be packed in the same box Determine the packing hazard class for each chemical waste When determining the class for a mixture of chemicals reactivity has priority over toxicity If you have difficulty determining the packing class of a mixture call the Hazardous Materials Manager Segregate the wastes according to the hazard class and pack them into cardboard boxes Do not pack different classes in the same box Place dividers and shock absorbing materials newspapers vermiculite between the containers Step Two Completing the Manifest The label for the chemical waste is called a packing manifest A manifest must be completed and attached to each box Laboratory personnel should complete the manife
35. akage during transport and may be reused for this purpose The individual transporting the hazardous chemicals should operate the elevator alone whenever possible The safe transport of small quantities of flammable liquids should include provisions that include the use of rugged pressure resistant nonventing containers storage during transport in a well ventilated vehicle and elimination of potential ignition sources If there is a spill or accident contact the University Chemical Safety Director and state your name telephone number location of incident name and quantity of material involved and the extent of injuries if any Take all necessary emergency measures such as removing contaminated clothing washing any chemicals from the skin with soap and water and seeking prompt medical attention If it is necessary for the individual transporting the chemicals to leave the scene of an accident or spill he she should delegate someone to remain at the scene until emergency personnel arrive The responsible party should return as soon as possible Cylinders that contain compressed gases are primarily shipping containers and should not be subjected to rough handling or abuse Such misuse can seriously weaken the cylinder and render it unfit for further use or transform it into a missile with sufficient energy to propel it through masonry walls To protect the valve during transport the cover cap should be left screwed on hand tight until the cyli
36. and quantified Only metals that form an amalgam can be determined such as cadmium copper lead and zinc metals of great interest in most environmental investigations Because the instrument is so sensitive great care must be taken to avoid contamination Interferences may be caused by complexes that form between metals in the sample such as between high concentrations of copper and zinc ASV is especially well suited for analyzing heavy metals in saline waters such as snowmelt where graphite furnace procedures are subject to many interferences from the high salt concentrations X ray fluorescence Figure E 12 can also be used to detect heavy metals in solid samples such as sediments and soils including particulates trapped on filters from water or air samples The sample is irradiated with low intensity X rays causing the elements in the sample to fluoresce The emitted X rays from the irradiated sample are sorted by their energy level and are used to identify and quantify the metals of interest Relatively little sample preparation is needed especially for homogeneous samples The technique is commonly used as a screening tool in the field to guide sampling for more accurate and sensitive laboratory analyses Its relatively poor sensitivity limits its use for most environmental investigations except for evaluating heavily contaminated sites Sample preparation is very critical for all of these metal analysis procedures Typical sample pre
37. ated part of the lab and in clearly marked cabinets Be sure to routinely check the integrity of the container and dispose of materials in corroded or damaged containers 5 Do not open the chemical container if peroxide formation is suspected The act of opening the container could be sufficient to cause a severe explosion Visually inspect liquid peroxide forming materials for crystals or unusual viscosity before opening Pay special attention to the area around the cap Peroxides usually form upon evaporation so they will most likely be formed on the threads under the cap 6 Date all peroxide forming materials with the date received and the expected shelf life Chemicals such as diisopropyl ether divinyl acetylene sodium amide and vinylidene chloride should be discarded after 3 months Chemicals such as dioxane diethyl ether and tetrahydrofuran should be discarded after 1 year 7 Store all peroxide forming chemicals away from heat sunlight and sources of ignition Sunlight accelerates the formation of peroxides 8 Secure the lids and caps on these containers to discourage the evaporation and concentration of these chemicals 9 Never store peroxide forming chemicals in glass containers with screw cap lids or glass stoppers Friction and grinding must be avoided Also never store these chemicals in a clear glass bottle where they would be exposed to light 10 Contamination of an ether by peroxides or hydroperoxides can be detected simply
38. ater 19th edition Water Environment Federation Washington D C 1995
39. azardous chemicals are required by law to be labeled by the manufacturer The chemical hygiene officer must ensure that each existing container and any incoming containers are properly labeled The label must provide the following information The identity of the chemical e Any warnings The manufacturer s name and address Temporary or transfer containers intended for immediate use by the person who transferred the chemical need not be labeled However if the chemical is left unattended such as premade standards the container must be labeled Temporary labels must include The identity of the chemical e Any warnings The target organs affected if applicable LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 743 Signs are intended to warn employees of chemical and physical dangers such as designated areas where carcinogens or highly toxic chemicals are used or stored All high hazard areas or hazardous chemical storage should be posted with the proper signs Unattended Operations If an experiment operation is left unattended place an appropriate sign on the door and provide for containment of toxic substances in the event of equipment or utility service Electrical Safety 1 Examine all electrical cords periodically for signs of wear and damage If damaged electrical cords are discovered unplug the equipment and repair or send the equipment out for repair 2 Properly ground all electrical equipment
40. ce that can draw contaminants out of the hood and into the room Choice of Chemicals Use only those chemicals for which the quality of the available ventilation system is appropriate Do not begin any experiment that requires a fume hood if the hood is not working If the hood is not working call Maintenance immediately Equipment and Glassware 1 Inspect all glassware before use Repair or discard any broken cracked or chipped glassware 2 Transport all glass chemical containers in rubber or polyethylene bottle carriers 3 Inspect laboratory apparatus before use Use only equipment that is free from cracks chips or other defects 4 If possible place a pan under a reaction vessel or other container to contain the liquid if the glassware breaks Do not allow burners or any other ignition source nearby when working with flammable liquids Properly support and secure laboratory apparatus before use 7 Either work in the fume hood or ensure that the apparatus is venting to the fume hood if there is a possibility of hazardous vapors being evolved 8 Always work in a fume hood if there is a possibility of an implosion or explosion 9 If possible vent vacuum pump exhaust into a fume hood 10 When using a vacuum pump place a trap between the pump and the apparatus 11 Lubricate pump regularly if possible Check belt condition and do not operate in a fume hood cabinet that is used for storage of flammables NN Labels and Signs All h
41. ck shelves and support for corrosion Nitric acid should always be stored by itself or in a separate cabinet compartment BASIC RULES AND PROCEDURES FOR WORKING WITH CHEMICALS Laboratory Protocol Everyone in the lab is responsible for his or her own safety and for the safety of others Before starting any work in the lab make it a point to become familiar with the procedures and equipment that are to be used Work only with chemical products when you know their flammability reactivity toxicity safe handling storage and emergency procedures If you do not understand or are unclear about something ASK Personal Safety Practices 1 Lab coats and safety glasses are required of all persons in laboratories where chemicals are used This includes visitors as well as all laboratory personnel Safety glasses can be found in a case just inside the door to each laboratory Safety equipment must be donned before a person crosses the tape line separating the entryway to the lab from the working area Personal protective equipment is only required in the areas designated 2 Never wear shorts short skirts sandals or open toed or perforated shoes in the lab 3 Minimize skin contact Disposable gloves are available in all labs Their use is recommended especially when handling dangerous chemicals or samples whose properties are unknown This is especially important since we often work with stormwater samples that may be contaminated by raw sewage
42. compatible with the residual gas remaining in the cylinder or may be incompatible with the cylinder material 7 Never completely empty cylinders during lab operations rather leave approximately 25 PSI of pressure This will prevent any residual gas in the cylinder from becoming contaminated 758 10 11 12 13 14 15 16 17 18 All accidents hazardous materials spills or other dangerous incidents should be reported A list of telephone numbers must be posted on the door to each laboratory and must be kept up to date Telephone numbers shall also be posted beside every telephone in the laboratories The list of STORMWATER EFFECTS HANDBOOK Place all cylinders so the main valve is accessible Close the main cylinder valve whenever the cylinder is not in use Remove regulators from unused cylinder and always put the safety cap in place to protect the valve Always secure cylinder whether empty or full to prevent it from falling over and damaging the valve or falling on your foot Secure cylinders by chaining or strapping them to a wall lab bench or other fixed support Oxygen should be stored in an area that is at least 20 feet away from any flammable or combustible materials or separated from them by a noncombustible barrier at least 5 ft high and having a fire resistant rating of at least 2 hour To transport a cylinder put on the safety cap and strap the cylinder to a hand truck in an upright position Never
43. day after day without experiencing adverse effects These are usually based on an 8 hour time weighted average Permissible Exposure Limit PEL The PEL is an exposure limit established by OSHA Short Term Exposure Limit STEL The STEL is a 15 min time weighted average exposure which should not be exceeded at any time during a workday A STEL exposure should not occur more than four times per day and there should be at least 60 min between exposures Lethal Dose 50 LD50 Lethal single dose usually oral in mg kg milligrams of chemical per kilogram of animal body weight of a chemical that results in the death of 50 of a test animal population Lethal Concentration 50 LC50 Concentration dose expressed in ppm for gases or micrograms per liter of air for dusts or mists that results in the death of 50 of a test animal population administered in one exposure Physical Chemical Characteristics Boiling point vapor pressure vapor density specific gravity melting point appearance and odor are given in this section and all provide useful information about the chemical Boiling point and vapor pressure provide a good indication of the volatility of the material Vapor density indicates whether vapors will sink rise or disperse throughout the area The farther the values are from 1 the value assigned to atmospheric air the faster the vapors will sink or rise LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 765
44. e 20 na 30 ol PAH 30 60 pH na 0 8 3 mg L 4 9 1 7 500 na 2 8 16 0 5 22 na 0 14 0 12 0 14 na na 0 97 na na na na na 0 01 lt 0 01 lt 0 01 na 0 81 1 06 0 90 0 70 1 00 1 61 na 0 93 1 06 1 06 1 02 na na na na Not sensitive enough Designed for high concentrations poor recoveries and precision at lower concentrations Reagents must be refrigerated more scatter than most other tests Sharps too sensitive of a test Sharps Sharps Reagents expire in 1 to 2 months and require refrigeration requires 30 60 min to conduct test requires extensive expertise 25 per test Daily calibration fragile meter Daily calibration Expensive but rugged instrument 595 SCGOHLSW SSSATVNV IVOINSHO ANY IWSOdSIG SLSVM ALSSAVS AYOLVYOSV1 LZZ Table E 2 Summary of All Field Test Kits Evaluated continued Expendable Time Problems with Test Manufacturer Capital Cost Reqd Precision Recovery safety hazards expertise Method and Kit Name Cost per sample min Useful Range COV RO runoff required etc Test paper EM Science 500 for 0 89 2 4 9 0 08 na Optics of expensive instrument ReflectoQuant pH Reflecto 500 are difficult to keep Quant clean Meter Spectrophotometric La Motte pH 895 for 0 22 5 5 9 5 na na Smart Color Test paper Fisher Scientific 0 00 1 0 12 0 07 na Only readable to within 1 pH Alkacid Te
45. ed briefly INSTRUMENT IS IN UNATTENDED MODE e Continue to press zero until the Ecowatch software breaks communication with the sonde after exit from the Main menu e Remove the communication cable from the sonde and screw on the waterproof connector cap The sonde is now ready for deployment REFERENCES Day J Selection of Appropriate Analytical Procedures for Volunteer Field Monitoring of Water Quality MSCE thesis Department of Civil and Environmental Engineering University of Alabama at Birmingham 1996 Pitt R E R I Field M M Lalor D D Adrian and D Barbe Investigation of Inappropriate Pollutant Entries into Storm Drainage Systems A User s Guide Rep No EPA 600 R 92 238 NITS Rep No PB93 131472 AS U S EPA Storm and Combined Sewer Pollution Control Program Edison NJ Risk Reduction Engineering Lab Cincinnati OH 1993 Pitt R S Mirov K Parmer and A Dergachev Laser applications for water quality analyses in ALT 96 International Symposium on Laser Methods for Biomedical Applications Edited by V Pustovoy SPIE The International Society for Optical Engineering Vol 2965 pp 70 82 1997 786 STORMWATER EFFECTS HANDBOOK Pitt R and S Clark Communication Manhole Water Study Characteristics of Water Found in Communica tions Manholes Final Draft Office of Water U S Environmental Protection Agency Washington D C July 1999 Standard Methods for the Examination of Water and Wastew
46. erchloric acid is on a metal shelf or in a metal cabinet away from organic or flammable materials A bottle of perchloric acid should also be stored in a glass secondary container to contain leakage 5 Do not allow perchloric acid to come in contact with any strong dehydrating agents such as sulfuric acid The dehydration of perchloric acid is a severe fire and explosion hazard 6 Do not order or use anhydrous perchloric acid It is unstable at room temperature and can decompose spontaneously with a severe explosion Anhydrous perchloric acid will explode upon contact with wood Health Effects Associated with Oxidizers Oxidizers are covered here primarily due to their potential to add to the severity of a fire or to initiate a fire But there are some generalizations that can be made regarding the health hazards of an oxidizing material In general oxidizers are corrosive and many are highly toxic Acute Health Effects Some oxidizers such as nitric and sulfuric acid vapors chlorine and hydrogen peroxide act as irritant gases All irritant gases can cause inflammation in the surface layer of tissues when in direct contact They can also cause irritation of the upper airways conjunctiva and throat Some oxidizers such as fluorine can cause severe burns of the skin and mucous membranes Chlorine trifluoride is extremely toxic and can cause severe burns to tissue 752 STORMWATER EFFECTS HANDBOOK Nitrogen trioxide is very damaging to ti
47. erent applications presented in this book This discussion was prepared by John Easton Ph D candidate University of Alabama at Birmingham who has used this equipment extensively during his research These procedures are there fore a compilation of the instructions given by YSI in addi tion to his field and lab experience with this equipment The YSI 6000upg Environmental Monitoring System is a multiparameter water quality measurement and data logging system It is intended for use in research assessment and regulatory compliance applications This instrument or sonde is ideal for profiling and monitoring water conditions in lakes rivers wetlands estuaries coastal waters and mon itoring wells It can be left unattended for weeks at a time with measurement parameters sampled at a user defined setup interval and data saved securely in the unit s internal memory The Model 6000upg is designed to house four field replaceable probes six sensors and a depth sensor module in the sonde body The 6000upg communicates with a com puter with a terminal emulation program or via the Ecowatch for Windows software The data is easily exported to any spreadsheet program for sophisticated data analysis The unit operates on eight C size alkaline batteries Depending upon the activated sensor configuration and frequency of data col lection the unit can provide up to 90 days of battery life The Environmental Research Area at UAB has four 6000
48. es the method relatively free from spectral and radiation interferences However different schemes continuum source Zeeman or Smith Hieftje to correct for molecular absorption and light scattering interferences are typically used LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 777 Table E 5 Attributes of Metal Analysis Methods Anodic Electrothermal Stripping X Ray Flame AAS AAS Plasma ICP Plasma ICP MS Voltammetry Fluorescence Capital cost 10 000 25 000 40 000 150 000 8000 25 000 US 30 000 80 000 80 000 250 000 25 000 60 000 Operational cost Low Moderate Moderate High Low to Low high moderate Sensitivity Good Very good Poor good Very good Excellent Poor solid matrices only Operation Single Single few Many Many Few Few number of metals at a time Sample High High High Low Moderate Moderate throughput Ease of use Good Moderate Good Poor Moderate Moderate moderate poor External sample Acid Acid Acid Acid Filtration Possibly grind preparation digestion digestion digestion digestion and sieve to obtain uniform particles a Approximate operational costs including expendable supplies gases acids filters graphite tubes etc but not labor sample low 3 10 moderate 10 25 high gt 25 From Pitt R S Mirov K Parmer and A Dergachev Laser applications for water quality analyses in ALT 96 International Symposium on Laser Methods for Biomedical Applications Edited by V Pu
49. f the day 2 If necessary clean equipment after use to avoid the possibility of harming the next person who uses it or of contaminating his her samples Keep all aisles and walkways in the lab clear to provide a safe walking surface and an unobstructed exit 4 Do not block access to emergency equipment and utility controls 9 Personal Protection Protective Eyewear 1 Goggles provide the best all around protection against chemical splashes vapors dusts and mists 2 Goggles that have indirect vents or are not vented provide the most protection but an anti fog agent might be needed 3 Standard safety glasses provide protection against impact 4 If using a laser or strong UV light sources such as photodegradation equipment wear safety glasses or goggles that provide protection against the specific wavelengths involved 5 Prescription glasses are generally not appropriate in a laboratory setting If you wear prescription glasses either get and wear a pair of prescription safety glasses from your optician or wear the over the glasses safety glasses when working in the laboratory 6 Contact lenses should not be worn in a laboratory because they can trap contaminants behind them and reduce or eliminate the effectiveness of flushing with water from an eyewash Contact lenses may also increase the amount of chemicals trapped on the surface of the eye and decrease removal of the chemical by tearing If it is necessary to wear c
50. gency 2 Be aware of the marked exits from your area and building 3 To activate the building alarm system pull the handle on one of the red boxes located in the hallway 4 Call the appropriate authorities 5 Walk quickly to the nearest marked exit and ask others to do the same 6 Outside proceed to a clear reassembly area that is at least 150 ft from the affected building and that does not interfere with the work of emergency personnel 7 DO NOT RETURN TO THE BUILDING UNTIL YOU ARE TOLD THAT IT IS SAFE TO DO SO Minor Spills 1 Trained personnel should use the spill control kit appropriate to the material spilled to clean up the spill 2 Ifthe spill is minor and of known limited danger clean it up immediately Determine the appropriate cleaning method by referring to the material s MSDS During cleanup wear the appropriate protective gear 3 Cover liquid spills with compatible adsorbent material such as spill pillows or a kitty litter vermiculite mix if it is compatible If appropriate materials are available corrosives should be neutralized prior to adsorption Clean spills from the outer area first cleaning toward the center 4 Place the spilled material into an appropriate impervious container and seal Schedule its disposal 5 If appropriate wash the affected surface with soap and water Mop up the residues and place them in an appropriate container for disposal 6 If the spilled material is not water soluble a s
51. gency proce dures use and storage of chemicals and the proper method of waste disposal This manual also covers hazard communication and incident response This information is intended to help those in the laboratory to minimize hazards to themselves and their colleagues In view of the wide variety of chemical products handled in laboratories it should not be assumed that the precautions and requirements stated here are all inclusive This information should be updated as needed with supplementary information to better protect the health and safety of anyone working in or visiting the laboratories Also included in this appendix is a summary of analytical test kits that have been reviewed as to their ability to be used in the field by a variety of users These kits were reviewed during projects funded by the EPA Pitt et al 1993 and by the telecommunications industry Day 1996 Pitt and Clark 1999 In addition comments pertaining to needed stormwater extraction methods for organic analyses are also presented along with information pertaining to the various methods available for analyzing heavy metals The appendix concludes with a detailed description of calibration and setup procedures for the YSI 6000 water quality sonde that is frequently referenced in the text LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 737 FUNDAMENTALS OF LABORATORY SAFETY Procurement of Chemicals Before a chemical is received information on pr
52. han TNT Just the friction from unscrewing the cap of a container of ether that has peroxides in it can provide enough energy to cause a severe explosion Examples of peroxide forming materials Diisopropyl ether Sodium amide Dioxane Tetrahydrofuran Butadiene Acrylonitrile Divinylacetylene Potassium amide Diethyl ether Vinyl ethers Vinylpyridine Styrene 756 STORMWATER EFFECTS HANDBOOK Other Shock Sensitive Materials These materials are explosive and sensitive to heat and shock Examples of shock sensitive materials Chemicals containing nitro groups Fulminates Hydrogen peroxide 30 Ammonium perchlorate Benzoyl peroxide when dry Compounds containing the functional groups acetylide azide diazo halamine nitroso and ozonide Use and Storage of Reactives 1 A good way to reduce the potential risks is to minimize the amount of material used in the experiment Use only the amount of material necessary to achieve the desired results 2 Always substitute a less hazardous chemical for a highly reactive chemical whenever possible If it is necessary to use a highly reactive chemical order only the amount that is necessary for the work 3 Store water reactive materials in an isolated part of the lab A cabinet far removed from any water sources such as sinks emergency showers and chillers is an appropriate location Clearly label the cabinet Water Reactive Chemicals No Water 4 Store pyrophorics in an isol
53. he ICP is the extremely wide dynamic range of the instrument as shown in Table E 4 An emission light emitted from the sample and plasma combination is focused in a monochromator and is detected using a series of photomulti pliers set at specific wavelengths for the elements of interest The ICP MS uses a mass spectrophotometer to separate the analyte ions emitted by the plasma and sample mixture according to their mass to charge ratios This results in a much more sensitive unit comparable to the electrothermal AAS and it can detect multiple elements simultaneously Anodic stripping voltammetry is rarely used in a production laboratory but it is a relatively common research instrument Figure E 11 ASV is one of the most sensitive metal analysis techniques even more sensitive than electrothermal AAS Cyclic ASV is also capable of identifying 778 STORMWATER EFFECTS HANDBOOK Figure E 10 Graphite furnace AAS used for storm Figure E 11 Anodic stripping voltammeter Outo water analyses at the University of kompku for heavy metal analyses Alabama at Birmingham different characteristics of the metals in the sample The analyzer uses a three step process The first step typically plates a mercury film on a glossy carbon electrode The second step plates the metals on the mercury film and the third step strips the metals from the film as a function of increasing oxidizing potential This last step allows the individual metals to be identified
54. ith 2 Goggles must be worn if the potential for splashing exists or if exposure to vapor or gas is likely 3 Always use these materials in a chemical fume hood as most pose a hazard via inhalation Corrosives General Characteristics 1 Corrosives are most commonly acids or alkalis but many other materials can be severely damaging to living tissue 2 Corrosives can cause visible destruction or irreversible alterations at the site of contact Inhalation of the vapor or mist can cause severe bronchial irritation Corrosives are particularly damaging to the skin and eyes 3 Certain substances considered noncorrosive in their natural dry state are corrosive when wet such as when in contact with moist skin or mucous membranes Examples of these materials are lithium chloride halogen fluorides and allyl iodide 4 Sulfuric acid is a very strong dehydrating agent and nitric acid is a strong oxidizing agent Dehydrating agents can cause severe burns to the eyes due to their affinity for water Examples of Corrosives Sulfuric acid Chromic acid Stannic chloride Ammonium bifluoride Bromine Ammonium hydroxide LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 753 Use and Storage of Corrosives 1 Always store acids separately from bases Also store acids in acid storage cabinets away from flammables since many acids are also strong oxidizers 2 Do not work with corrosives unless an emergency shower and continuous flo
55. itrator strength sample strength Lead Solid phase HACH LeadTrak 395 for 4 61 45 0 005 0 15 na 0 84 0 87 Requires extensive expertise extraction System DR 100 kit complex kit time consuming colorimeter or 1495 45 min but only kit with for useful sensitivity DR 2000 Sulfide staining Innovative Synthesis 3 00 5 na na na Poor sensitivity Corporation The Lead Detective HybriVet Systems 3 00 5 na na na Poor sensitivity Lead Check Swabs Carolina Environment 3 00 5 na na na Poor sensitivity Company KnowLead OLZ MOOSANVH S193443 YHSALVMAYOLS Test strips Colorimeter ISE Test strips Spectrophotometric Spectrophotometric Colorimeter EM Science Lead La Motte Nitrate Horiba CARDY EM Science Nitrate Quant Test Strips HACH Nitrate LR HACH Nitrate MR CHEMetrics Nitrate Nitrogen 500 for Reflecto Quant Meter 895 for Smart Color 235 for kit 500 for Reflecto Quant Meter 1495 for DR 2000 1495 for DR 2000 48 for 1st 30 tests and standards 1 11 1 22 60 sensor per 6 months 0 49 0 56 0 73 Nitrite and nitrate tests have a Cd based reagent that is hazardous Immunoassay Electrode Electrode Electrode EM Science Dtech PAH Test Kit Cole Parmer pH Wand Horiba Twin pH Sentron pH Probe 500 155 for kit 235 for kit 595 for meter and electrode 25 92 electro 70 for sensor 25 for stand None 10 Nitrat
56. lds that are commonly polycarbonate and are weighted at the bottom for stability It may be necessary to secure the shields firmly to the work surface Compressed Gas Cylinders Cylinders of compressed gas can pose a chemical as well as a physical hazard If the valve were to break off a cylinder the amount of force present could propel the cylinder through a block wall For example a small cylinder of compressed breathing air used by SCUBA divers has the explosive force of 1 5 lb of TNT Use and Storage of Compressed Gas Cylinders 1 Whenever possible use flammable and reactive gases in a fume hood or other well ventilated enclosure Certain categories of toxic gases must always be stored and used in well ventilated enclosures 2 Always use the appropriate regulator on a cylinder If a regulator will not fit a cylinder s valve do not attempt to adapt or modify it to fit a cylinder it was not designed for Regulators are designed to fit only specific cylinders to avoid improper use 3 Inspect regulators pressure relief valves cylinder connections and hose lines frequently for damage 4 Never use a cylinder that cannot be positively identified Color coding is not a reliable way to identify cylinders since the color can vary from supplier to supplier 5 Do not use oil or grease on any cylinder component of an oxidizing gas because a fire or explosion can result 6 Never transfer gases from one cylinder to another The gas may be in
57. lectronic probe Electronic probe Colorimeter Colorimeter Colorimeter Colorimeter Colorimetric Colorimetric HACH silver nitrate titration YSI Model 33 SCT Horiba Twin Horiba U 10 Cond temp DO turb pH CHEMetrics Copper 1 DCR Photometer Kit La Motte Copper Diethyldithio carbamate La Motte Copper Bicinchoninic Acid HACH Bicinchonate Copper Method Using AccuVac Ampoules CHEMetrics Detergents Anionic Surfactants HACH Surfactants Anionic Crystal Violet Method 94 for digital titrator 600 for kit 250 for kit 2800 for kit 435 for kit 895 for Smart Color 895 for Smart Color 1495 for DR 2000 60 for 1st 30 tests and standards 1495 for DR 2000 0 66 0 00 0 00 0 00 0 63 0 41 0 23 0 28 2 38 1 10 Chlorides not evalu ated Conductivity Copper 15 10 20 20 Detergents 10 30 na 98 uS cm 75 50 000 uS cm 87 uS cm 0 3 3 5 mg L 0 1 3 5 0 6 3 5 0 5 5 0 0 15 3 mg L na na na 0 04 na na na na na na na na 0 90 0 93 1 08 1 02 0 95 0 96 0 64 0 52 1 11 0 93 0 94 0 93 0 97 0 96 1 66 1 82 na Unclear titration endpoint no useful data obtainable recommended that conductivity analyses be used as a better indicator of chlorides in a sample Replace sensor every 6 months for 60 Expensive instrument but multiparameter
58. ly collected extract in the Erlenmeyer flask For persistent emulsions those with emulsion interface between layers more than one third the volume of the solvent layer the extract including the emulsion is poured into a 50 mL centrifuge vial capped and centrifuged at 2000 rpm for 2 min to break the emulsion Figures E 17 and E 18 Water phase separated by the centrifuge is collected from the vial and returned to the separatory funnel using a disposable pipette The centrifuge vial with the extract is recapped before performing the extraction of the acid portion 5 The pH of the remaining sample in the separatory funnel is adjusted to pH lt 2 using sulfuric acid The acidified aqueous phase is serially extracted twice with 10 mL aliquots of methylene chloride as in the previous base neutral extraction procedure Extract and any emulsions are again collected in the 125 mL Erlenmeyer flask 6 The base neutral extract is poured from the centrifuge vial though a drying column of at least 10 cm of anhydrous sodium sulfate and is collected in a 50 mL beaker Figure E 19 The Erlenmeyer flask is rinsed with 5 mL of methylene chloride which is then used to rinse the centrifuge vial and then to rinse the drying column and complete the quantitative transfer Figure E 14 Initial hand shaking the separatory Figure E 15 Separation of organic solvent extract funnel and venting gas from water sample Figure E 16 Collecting solvent extract and emulsio
59. mwipe or other lightweight paper up to the opening of the hood The paper should be pulled inward Leave the hood on when it is not in active use if toxic substances are stored inside or if it is uncertain whether adequate general laboratory ventilation will be maintained when it is off 2 Equipment and other materials should be placed at least 6 in behind the sash This will reduce the exposure of personnel to chemical vapors that may escape into the lab due to air turbulence 3 When the hood is not in use pull the sash all the way down 742 STORMWATER EFFECTS HANDBOOK 4 While personnel are working in the hood pull the sash down as far as is practical The sash is protection against fires explosions chemical splashes and projectiles Never put the sash above the line marked as the maximum allowable height for safe use 5 Do not keep loose papers paper towels or tissues in the hood These material can be drawn into the blower and adversely affect the performance of the hood 6 Do not use a fume hood as a storage cabinet for chemicals Excessive storage of chemicals and other items will disrupt the designed airflow in the hood In particular do not store chemicals against the baffle at the back of the hood because this will interfere with the laminar air flow 7 Do not place objects directly in front of a fume hood 8 Minimize the amount of foot traffic immediately in front of a hood Walking past hoods causes turbulen
60. n after separation Figure E 17 Extract in centrifuge vial LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS Te 10 Notes for method 608 under the alkaline conditions of the extraction step BHC y BHC endosulfan I and II and endrin are subject to partial decomposition Florisil cleanup is not utilized The base neutral extract is transferred into a 50 mL concentration vial and is placed in an automatic vacuum centrifuge concentrator from Savant Figure E 20 Vacuum concentration is used in place of the Kuderna Danish method Figure E 21 Extract is concentrated to approximately 0 5 mL The acid extract collected in the 125 mL Erlenmeyer flask is placed in the 50 mL centrifuge vial Again if emulsions persist the extract is centrifuged at 2000 rpm for 2 min Water is drawn from the extract and discarded Extract is poured through the 10 cm anhydrous sodium sulfate drying column and collected in the 50 mL beaker as before The Erlenmeyer flask is then rinsed with 5 mL of methylene chloride which is then poured into the centrifuge vial and finally through the drying column The acid extract is then poured into the 50 mL concentration vial combining it with the evaporated base neutral extract The combined extract is then concentrated to approximately 0 5 mL in the automatic vacuum centrifuge concentrator Using a disposable pipette extract is transferred to a graduated Kuderna Danish concentrator Approximately 1 5 m
61. nce using appropriate protective apparel to prevent skin contact If you are pregnant notify your supervisor and consult your physician before working with these materials LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 745 In addition to the safety protocols discussed earlier the following three steps must be followed when working with one or more of these substances 1 Label containers of substances having high chronic toxicity as follows WARNING HIGH ACUTE OR CHRONIC TOXICITY OR CANCER SUSPECT AGENT 2 Protect the hands and forearms by wearing either gloves and a laboratory coat or suitable long gloves to avoid contact of the toxic material with the skin 3 Procedures involving volatile toxic substances and those involving solid or liquid toxic substances that may result in the generation of aerosols should be conducted in a fume hood or other suitable containment device 4 After working with toxic materials wash the hands and arms immediately Never eat drink chew gum apply cosmetics take medicine or store foods in areas where toxic substances are being used These standard precautions will provide laboratory workers with good protection from most toxic substances In addition records that include amounts of material used and names of workers involved should be kept as part of the laboratory notebook record of the experiment For strong carcinogens an accurate record of such substances being stored and the amo
62. nd Kit Name Cost per sample min Useful Range COV RO runoff required etc Ammonia Colorimetric CHEMetrics Ammonia 435 for kit 0 63 5 0 03 2 5 mg L 0 15 0 85 1 27 6 month shelf life with determination of 1 DCR Photometer refrigeration sharps and ammonia using mercury in waste Nessler s reaction Colorimetric HACH Nitrogen 1495 for 2 88 20 0 10 0 7 0 17 1 15 1 10 determination of Ammonia Salicylate DR 2000 ammonia using Method without salicylate Distillation Colorimetric La Motte Ammonia 895 for 0 33 10 0 38 3 na 1 22 1 21 Waste contains a mercury determination of Nitrogen High Range Smart compound high detection ammonia using Color limit 0 4 mg L Nessler s reaction Colorimetric La Motte Ammonia 895 for 0 76 20 0 17 1 5 na 1 04 0 96 determination of Nitrogen Low Range Smart ammonia using Color salicylate Bacteria Colorimetric IDEXX Colilert 24 hr na na na 24 hour test period required Colorimetric Industrial Municipal 0 00 4 00 30minto na na na Not a selective test but Equipment Inc IME 13 hr sensitive to a mixed microbial Test KoolKount population Assayer BTEX Immunoassay Dtech EM Science 500 25 30 60 na na na Reagents expire in 1 to 2 BTEX Test Kit months and require refrigeration requires 30 60 min to conduct test requires extensive expertise 25 per test PetroSense 6900 5 na na na Expensive instrument 6900 892 MOOSANVH S193443 YHSALVMAYOLS Silver nitrate titration Electronic probe E
63. nder is in place and ready for actual use The preferred transport method even for short distances is by suitable hand truck with the cylinder strapped into place Only one cylinder should be handled at a time After a cylinder has been relocated straps chains or a suitable stand to keep it from falling must restrain it PROCEDURES FOR SPECIFIC CLASSES OF HAZARDOUS MATERIALS This section will address the rules and procedures for handling chemicals that fall into one or more of five fundamental classes of laboratory chemicals flammables corrosives oxidizers reac tives and compressed gases LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 749 Flammable Solvents Flammable liquids are the most common chemicals found in a laboratory The primary hazard associated with flammable liquids is their ability to readily ignite and burn One should note that it is the vapor of a flammable liquid not the liquid itself which ignites and causes a fire The rate at which a liquid vaporizes is a function of its vapor pressure In general liquids with a high vapor pressure evaporate at a higher rate compared to liquids of lower vapor pressure It should be noted that vapor pressure increases rapidly as the temperature rises as does the evapo ration rate A reduced pressure environment also accelerates the rate of evaporation The flash point of a liquid is the lowest temperature at which a liquid gives off a vapor at a rate sufficien
64. nner such as the following EMBRYOTOXIN READ SPECIFIC PROCEDURES FOR USE If the storage container is breakable it should be kept in an impermeable unbreakable secondary container having sufficient capacity to retain the material should the primary container fail Working with Chemicals of Moderate or High Acute Toxicity or High Chronic Toxicity Before beginning a laboratory operation each worker is strongly advised to consult the standard compilations that list toxic properties of known substances and learn what is known about the substance to be used The precautions and procedures described in this section should be followed if any of the substances to be used in significant quantities is known to be moderately or highly toxic If any of the substances being used is known to be highly toxic it is desirable to have two people present in the area at all times These procedures should be followed if the toxicological properties of any of the substances being used or prepared are UNKNOWN If any of the substances to be used or prepared are known to have high chronic toxicity e g compounds of heavy metals and other potent carcinogens then the precautions and procedures described in this section should be supplemented with additional precautions to aid in containing and ultimately destroying the substances having high chronic toxicity If you are considering pregnancy handle these substances only in a hood with a confirmed satisfactory performa
65. ns are necessary because of the large amount of particulates in the samples and the large particulate fraction of the organics of greatest interest These particulates interfere with solid phase extraction procedures for example resulting in very little recovery of organic toxicants using that method 1 Samples are extracted using a liquid liquid separatory funnel technique This has been found to give the most reliable results especially compared to solid phase extraction or critical fluid extraction methods for stormwater samples and most surface water samples The problem with stormwater organics is that a substantial fraction of many of the organic compounds of interest are associated with particulates This particulate fraction needs to be quantified as stormwater has been shown to have significant effects on receiving water sediments If emulsions prevent achieving acceptable solvent recovery with separatory funnel extraction continuous extraction is used The separatory funnel extraction scheme described below assumes a sample volume of 250 mL Serial extraction of the base neutrals uses 10 mL additions of methylene chloride as does the serial extraction of the acids Prior to the extraction all glassware is oven baked at 300 C for 24 hours 2 A sample volume of 250 mL is collected in a 400 mL beaker and poured into a 500 mL glass separation funnel For every 12 samples extracted an additional four samples are extracted for quality cont
66. of hazardous reactions The following steps should be followed when assessing chemical compatibility 1 Identify the chemical 2 Determine the hazard class of the chemical toxic flammable reactive corrosive oxidizer low hazard 3 Segregate the chemicals according to the above classifications If there is a potential for hazardous interactions within a specific class further separation is warranted Label the area for each class of chemical 4 General rules for compatibility a Highly toxic or carcinogenic chemicals should be ordered and stored in the smallest practical amount b Flammable or combustible liquids must be stored in approved containers flammable material storage cabinets or in properly designed under hood storage areas No more than 10 gallons of flammable liquids may be stored outside an approved flammable material storage cabinet No more than 60 gallons of flammable liquids may be stored in a laboratory c Water reactive chemicals should be located in a cool dry area away from potential sources of water d Corrosives should be separated into acid and base subclasses Large containers of corrosives should be stored on the lowest shelf or in special cabinets Acids and bases should be separated from active metals and substances that can generate toxic gases upon contact NITRIC ACID MUST BE STORED SEPARATELY e Oxidizers must be separated from combustible and flammable chemicals as well as reducing agents 748 S
67. olvent such as xylene may be necessary to clean the surface s Check the solubility of the spilled material in various solvents and use the least toxic effective solvent available Wear appropriate personal protective equipment 7 Notify the Laboratory Supervisor about the need to replace the used items from the spill control kit Mercury Spills Mercury is commonly used in many technical procedures When contained properly it is of little threat to our health Immediate attention to mercury spills is important because spilled mercury can accumulate over time resulting in exposure to mercury vapor When a spill occurs use the following procedure 1 Restrict the area Allow no one to enter the room except for trained personnel to help with containment of the spill 2 Contact the Chemical Safety Director 3 Broken thermometers that contain small amounts of mercury may be safely collected by trained laboratory personnel in a container that can be sealed Always wear disposable gloves when cleaning up mercury and dispose of all mercury and mercury contaminated waste through the chemical waste program Anyone handling mercury or cleaning up mercury spills should wash hands thoroughly using soap and water when finished Report all mercury spills to the Chemical Safety Director 760 STORMWATER EFFECTS HANDBOOK CHEMICAL WASTE DISPOSAL PROGRAM Chemical Waste Containers Containers used for the accumulation of hazardous waste must be in good c
68. ondition free of leaks and compatible with the waste being stored in them A waste accumulation container should be opened only when it is necessary to add waste and should otherwise be capped Hazardous waste must not be placed in unwashed containers that previously held incompatible materials If a hazardous waste container is not in good condition i e it leaks either transfer the waste from the bad container into a good container pack the container in a larger and nonleaking container or manage the waste in some other way that prevents the potential for a release of contamination A storage container holding a hazardous waste that is incompatible with any waste or other materials stored nearby in other containers must be separated from the other materials or protected from them by means of a wall partition or other secondary containment device Guidelines for Waste Containers e Must be marked with the words waste or spent and its contents indicated NO container should be marked with the words hazardous or nonhazardous Paint over or remove old labels from waste containers e Must be kept at or near immediate vicinity the site of generation and under control of the generator e Must be compatible with the contents i e acid should not be stored in metal cans e Must be closed at all times except when actively receiving waste e Must be properly identified before disposal e Must be safe to transport with
69. ontact lenses in a lab wear protective goggles at all times Personal Protection Protective Gloves 1 Chemicals can permeate any glove The vapor form of the liquid chemical will break through to the skin side of the glove in most cases within a matter of minutes The rate at which this occurs depends on the composition of the glove the chemicals present and their concentration and the exposure time While for most chemicals this vapor exposure will not be particularly harmful for some of the more toxic chemicals it can be In addition once chemicals reach the skin the glove then acts as a barrier which aids in the penetration of the chemicals through the skin Effectively a process called occlusion can occur by which the chemical penetrates the skin more easily when trapped between the glove and the skin than if the skin were exposed without a glove Consult glove and chemical compatibility charts such as Table E 1 to ensure that you are using the most appropriate glove Be sure to check the most up to date recommendations from the glove vendors 2 If direct chemical contact occurs replace gloves regularly throughout the day Wash hands regularly and remove gloves before answering the telephone or opening doors Make sure that hands are clean before using gloves If chemicals have contaminated the skin prior to the glove being put on the glove will then speed up the process of skin penetration 3 Check gloves for cracks tears
70. oper handling storage and disposal must be known to those involved Refer to the appropriate MSDS for further information No container may be accepted into a laboratory without an adequate identifying label This label cannot be removed defaced or damaged in any way All substances should be received in a central location The date of receipt should be noted on all chemicals Receipt of all chemicals must be noted in the chemical inventory as well as the laboratory in which the chemical shall be located Distribution of Chemicals When chemicals are hand carried between laboratories place the chemical in an outside sec ondary container or bucket These secondary containers provide protection to the bottle and help keep it from breaking They also help minimize spillage if the bottle does break It is recommended that transport of chemicals inside a building be done using a cart where feasible Laboratory Chemical Storage a Read the label carefully before storing a chemical All chemicals must be stored according to the Chemical Storage Segregation Scheme Note that this is a simplified scheme and that in some instances chemicals in the same category may be incompatible b Store all chemicals by their hazard class Only within segregation groups can chemicals be stored in alphabetical order If a chemical exhibits more than one hazard segregate by using the charac teristic that exhibits the primary hazard c Do not store chemicals nea
71. panol Ethyl acetate Sec butyl alcohol Ethyl alcohol Tert butyl alcohol Heptane Tetrahydrofuran Hexane Xylene Disposal of Chemicals down the Sink or Sanitary Sewer System Very few chemical wastes produced in laboratories are acceptable for disposal down the sink or sanitary sewer system The local Sewer Use Pretreatment Ordinance establishes uniform require ments for all users of the wastewater treatment system Many chemicals can interfere with the proper function of the treatment facility and can render them unable to comply with state and federal regulations under the Clean Water Act of 1977 Generators of laboratory waste are advised to exercise caution with respect to sink disposal of chemical wastes In general small scale research activities 100 mL or less of certain types of water soluble nontoxic and nonflammable chemicals may be poured if they have been approved by the Chemical Safety Director It is recommended that such materials be disposed of through the Department of Occupational Health and Safety even in small quantities Chemical Substitution Whenever possible it is desirable to substitute nonhazardous biodegradable chemicals for hazardous chemicals Use of these chemicals will reduce the volume of hazardous waste generated Examples of acceptable substitutes include 1 Citric acid based cleaning solutions for xylene benzene and toluene containing cleaning solutions 2 Nonhalogenated solvents in parts washers or
72. paration requires acid digestion using a combination of acids to reduce interferences by organic matter and to convert the metal associated with particulates and colloids to the free metal forms that can be detected Nitric acid digestion with heat is adequate for most samples However hydrofluoric acid is also needed if the digestion is to completely release metals that may be tied up in a silica matrix Unfortunately hydrofluoric acid forms volatile compounds with some metals resulting in their partial loss upon storage if not analyzed immediately Almost all of the stormwater heavy metals can be released from the particulates using just nitric acid especially considering metal losses from using a hydrofluoric acid digestion A nitric acid and perchloric acid mixture may be needed to digest organic material in the samples Microwave assisted digestion Figure E 13 has become more common recently because of improved metal recovery much faster digestion and better repeatability LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 779 lt Figure E 12 X ray fluorescence unit for analyses of Figure E 13 Microwave digestion of stormwater sam heavy metals in solids ples for heavy metal analyses STORMWATER SAMPLE EXTRACTIONS FOR EPA METHODS 608 AND 625 The following paragraphs outline the modified organic extraction methods that have been used by UAB for the analysis of wet weather flows Pitt and Clark 1999 These modificatio
73. per test kit against color standards Figure E 5 CHEMetrics color reader Figure E 6 HACH AccuVac kit for fluoride 774 STORMWATER EFFECTS HANDBOOK CHEMets Pi ap aii 4 D Figure E 7 Reading AccuVac absor Figure E 8 CHEMetrics nitrate test kit Figure E 9 Cole Parmer bance ORP probe kits to automatically draw a sample into an evacuated ampoule that contains a specific amount of reagent Figures E 4 through E 8 are different examples of these types of kits Figure E 9 is an example of a simple probe used to directly measure ORP of a water sample a necessary field analysis because of changes occurring after sample collection and transport to the laboratory Many of other types of test kits are more complex and require several steps for the analyses Some of the most complex procedures may require as many as 10 steps and more than 30 min for analyses While many of the simple methods are quite useful for field monitoring the more complex and expensive procedures must be more carefully weighed against traditional and more accurate laboratory methods In general we found that the field test kits were more accurate than we had originally expected However the sensitivities of many of the field test kits were much poorer than expected making them much less useful In addition numerous safety hazards can exist with these kits sharps and hazardous reagents and wastes being the most serious SPECIAL COMMENTS PERTAINING TO
74. pt in lab safe refrigerators Lab safe refrigerators freezers must be used for cold storage of flammables k Do not store chemicals above eye level If the container breaks the contents can easily fall on the face and body 1 Do not store excessive amounts of chemicals in the lab 738 STORMWATER EFFECTS HANDBOOK Storage Cabinets Flammable Material Storage Cabinets Flammables not in active use must be stored in safe containers inside fire resistant storage cabinets specifically designed to hold them Flammable material storage cabinets must be specified for all labs that use flammable chemicals The cabinets must meet NFPA 30 and OSHA 1910 106 standards Flammable material storage cabinets are designed to protect the contents of the cabinet from the heat and flames of external fire rather than to confine burning liquids within They can perform their protective function only if used and maintained properly Cabinets are generally designed with double walled construction and doors that are 2 in above the base the cabinet is liquid proof up to that point Acid Storage Cabinets Acids should be kept in acid storage cabinets specifically designed to hold them Such cabinets have the same construction features as flammable materials storage cabinets but are coated with epoxy enamel to guard against chemical attack and use polyethylene trays to collect small spills and provide additional protection from corrosion for the shelves Periodically che
75. r heat sources such as ovens or steam pipes Also do not store chemicals in direct sunlight d Date chemicals when received and first opened This will ensure that the oldest chemicals are used first which will decrease the amount of chemicals for disposal If a particular chemical can become unsafe while in storage an expiration date should also be included Keep in mind that expiration dates set by the manufacturer do not necessarily imply that the chemical is safe to use up to that date e Do not use lab benches as permanent storage for chemicals In these locations the chemicals can easily be knocked over incompatible chemicals can be stored alongside one another and the chemicals are unprotected in the event of a fire Each chemical must have a proper designated storage location and be returned to it after use f Inspect chemicals and their containers for any signs of deterioration and for the integrity of the label g Do not store any chemicals in glass containers on the floor h Do not use fume hoods as a permanent storage location for chemicals with the exception of particularly odorous chemicals that may require ventilation The more containers boxes equipment and other items that are stored in a fume hood the greater likelihood of having chemical vapors drawn back into the room i Promptly dispose of any old outdated or unused chemicals j Chemicals that require refrigeration must be sealed with tight fitting caps and ke
76. rol and quality assurance These include three 250 mL composite samples made of equal amounts of the 12 samples and one 250 mL sample of reverse osmosis water Standard solution additions consisting of 25 uL of 1000 ug mL base neutral spiking solution 25 uL of 1000 ug mL base neutral surrogates 12 5 uL of 2000 ug mL acid spiking solution and 12 5 uL of 2000 pg mL acid surrogates are made to the separation funnels of two of the three composite samples and mixed well Sample pH is measured with wide range pH paper and adjusted to pH gt 11 with sodium hydroxide solution 3 A 10 mL volume of methylene chloride is added to the separatory funnel and sealed by capping The separatory funnel is gently shaken by hand for 15 s and vented to release pressure Figure E 14 The cap is removed from the separatory funnel and replaced with a vented snorkel stopper The separatory funnel is then placed on a mechanical shaker and shaken for 2 min After returning the separatory funnel to its stand and replacing the snorkel stopper with the cap the organic layer is allowed to separate from the water phase for a minimum of 10 min longer if an emulsion develops 780 STORMWATER EFFECTS HANDBOOK Figure E 15 The extract and any emulsion present is then collected into a 125 mL Erlenmeyer flask Figure E 16 4 A second 10 mL volume of methylene chloride is added to the separatory funnel and the extraction method is repeated combining the extract with the previous
77. roll a cylinder Always clearly mark empty cylinders and store them separately using chalk to write MT on a cylinder in big letters is satisfactory for noting an empty cylinder Open cylinder valves slowly Only compatible gases should be stored together in a gas cylinder cabinet Flammable gases must be stored in properly labeled secured areas away from possible ignition sources and kept separate from oxidizing gases Do not store compressed gas cylinders in areas where the temperature can exceed 125 F EMERGENCY PROCEDURES telephone numbers must include 24 hour numbers for the following personnel Laboratory Supervisor Principal Investigator s Emergency Medical Services Police Department Maintenance Chemical Response Unit Callers should explain any emergency situation clearly calmly and in detail Primary Emergency Procedures for Fires Spills and Accidents 2 In the event of a fire pull the nearest fire alarm If you are in the laboratory and a fire alarm sounds quickly secure your work cap bottles etc so that it is not dangerous to a passer by lock the laboratory and evacuate the building per the fire evacuation instructions If the emergency is not in the laboratory where you are located the last person to leave should turn off the lights If you are unable to control or extinguish a fire follow the building evacuation procedure Attend to any person who may have been contaminated and or injured if it is
78. s time permanent damage such as second and third degree burns with scarring can result 754 STORMWATER EFFECTS HANDBOOK Acute Health Effects Inhalation irritation of mucous membranes difficulty in breathing fits of coughing pulmonary edema Ingestion irritation and burning sensation of lips mouth and throat pain in swallowing swelling of the throat painful abdominal cramps vomiting shock risk of perforation of stomach Skin Contact burning redness and swelling painful blisters profound damage to tissues and with alkalis a slippery soapy feeling Eye Contact stinging watery eyes swelling of eyelids intense pain ulceration of eyes loss of eyes or eyesight Chronic Health Effects Symptoms associated with a chronic exposure vary greatly depending on the chemical The chronic effect of hydrochloric acid is damage to the teeth the chronic effects of hydrofluoric acid are decreased bone density fluorosis and anemia the chronic effects of sodium hydroxide are unknown First Aid for Corrosives Inhalation remove person from source of contamination if safe to do so Get medical attention Keep person warm and quiet and do not leave unattended Ingestion remove person from source of contamination if safe to do so Get medical attention and inform emergency responders of the name of the chemical swallowed Skin Contact remove person from source of contamination if safe to do so and take immediately
79. screen will display the percent saturation value which corresponds to your local barometric pressure input For example if your local barometer reads 742 mm Hg the screen will display 97 6 742 760 at this point If an error message is received proceed to the diagnostics step otherwise press any key to return to the Calibrate menu and skip the following diagnostic step e If an error message was received conduct a diagnostics test From the Main menu chose 8 Diagnostics Check the DO charge This value should read between 25 and 75 during calibra tion If out of this range then the probe needs to be cleaned pencil eraser or replaced After cleaning repeat the above DO calibration procedure Following the DO calibration leave the sonde in water saturated air From the Calibrate menu select 3 Depth to access the depth calibration procedure e Input 0 00 or some known sensor offset in feet The depth sensor is about 0 46 ft above the bottom of the probe compartment and this offset value could be used if installing the unit vertically and depth in relation to the sonde bottom was desired Press ENTER and monitor the stabilization of the depth readings with time e When no significant change occurs for approximately 30 s press ENTER to confirm the calibration and zero the sensor with regard to the current barometric pressure e Press any key to return to the Calibrate menu pH Probe Calibration e Place approximately 400 mL of pH
80. se flammables only in areas free of ignition sources 4 Never heat flammables with an open flame Instead use steam baths water baths oil baths hot air baths sand baths or heating mantles 5 Never store flammable chemicals in a standard household refrigerator There are several ignition sources located inside a standard refrigerator that can set off a fire or violent explosion Flammables can only be stored cold in a lab safe or explosion proof refrigerator Another alternative is to use an ice bath to chill the chemicals Remember there is no safety benefit in storing a flammable chemical in a refrigerator if the flash point of that chemical is below the temperature of that refrigerator 6 The transfer of material to or from a metal container is generally accompanied by an accumulation of static charge on the container This fact must be kept in mind when transferring flammable liquids since the discharge of this static charge could generate a spark thereby igniting the liquid To make these transfers safer flammable liquid dispensing and receiving containers must be bonded together before pouring Large containers such as drums must also be grounded when used as dispensing or receiving vessels All grounding and bonding connections must be metal to metal 750 STORMWATER EFFECTS HANDBOOK Health Effects Associated with Flammables In general the vapors of many flammables are irritating to mucous membranes of the respiratory system and e
81. sium hydroxide G G G E Propylene dichloride P F N A P Sodium hydroxide G G G E Sodium hypochlorite G P F G Sulfuric acid G G F G Toluene P F G F Trichloroethylene P F G F LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 741 Table E 1 Chemical Resistance of Glove Materials continued E Excellent G Good F Fair P Poor Chemical Natural Rubber Neoprene Nitrile Vinyl Tricresyl phosphate P F N A F Triethanolamine F E E E Trinitrotoluene P E N A P Aromatic halogenated hydrocarbons attack all types of glove Should glove swelling occur change to fresh gloves No data available regarding resistance to DMSO by natural rubber neoprene nitrile or vinyl use butyl rubber gloves 4 Butyl neoprene and nitrile gloves are resistant to most chemicals e g alcohols aldehydes ketones most inorganic acids and most caustics 5 Disposable latex and vinyl gloves protect against some chemicals most aqueous solutions and microorganisms and reduce the risk of product contamination DO NOT WEAR LATEX GLOVES IF YOU SHOW SIGNS OF A LATEX ALLERGY 6 Leather and some knit gloves will protect against cuts abrasions and scratches but not against chemicals 7 Temperature resistant gloves protect against cryogenic liquids flames and high temperatures 8 Ifthe above guidelines are followed and gloves are changed frequently particularly when liquid comes in contact with the glove then any of the thin rubber
82. ssue especially the respiratory tract The symptoms from an exposure to nitrogen trioxide may be delayed for hours but fatal pulmonary edema may result Osmium tetroxide another oxidant commonly employed in the laboratory is also dangerous due to its high degree of acute toxicity It is a severe irritant of both the eyes and the respiratory tract Inhalation can cause headache coughing dizziness lung damage difficulty breathing and may be fatal Chronic Health Effects Nitrobenzene and chromium compounds can cause hematological and neurological changes Compounds of chromium and manganese can cause liver and kidney disease Chromium VI compounds have been associated with lung cancer First Aid for Oxidizers In general if a person has inhaled ingested or come into direct contact with these materials the person must be removed from the source of contamination as quickly as possible when it is safe to do so Medical help must be summoned In the case of an exposure directly to the skin or eyes it is imperative that the exposed person be taken to an emergency shower or eyewash immediately Flush the affected areas for a minimum of 15 minutes and then get medical attention Personal Protective Equipment 1 In many cases the glove of choice will be neoprene polyvinyl chloride PVC or nitrile Be sure to consult a glove compatibility chart to ensure that the glove material is appropriate for the particular chemical you are working w
83. st both capital and expendables to conduct the analyses and the time and expertise needed to conduct the test Table E 2 summarizes these attributes including results of conducting sensitivity tests using ultra clean water and stormwater Pitt and Clark 1999 The useful range is the minimum detection limit found during our tests to the upper limit that does not require dilution The precision is the coefficient of variation based on replicate analyses and the recovery is the slope of the regression line comparing analyses of spiked samples using these procedures and standard methods The recovery tests were conducted using both ultra clean water prepared using reverse osmosis RO and stormwater to identify any matrix interference problems Any problems noted during the tests are also indicated especially safety concerns unusual amounts of expertise needed and storage requirements These tests represent several classes of analytical procedures The following sets of photos illustrate some of the simpler test kit methods Figure E 1 illustrates the basic colorimetric procedure with a color wheel to analyze basic water color using a HACH test kit while Figures E 2 and E 3 show simple color indicator paper strips for alkalinity Vacuum vials are also used in several test Table E 2 Summary of All Field Test Kits Evaluated Expendable Time Problems with Test Manufacturer Capital Cost Reqd Precision Recovery safety hazards expertise Method a
84. st Strips unit poor comparison to pH meters for actual samples Potassium Spectrophotometric HACH Potassium 1495 for 3 30 0 5 7 mg L na 0 81 0 90 Tetraphenylborate DR 2000 ISE Horiba CARDY 235 for kit 60 sensor 5 2 0 0 04 0 53 0 46 Method designed for much per 6 higher concentrations more months scatter than other tests Colorimeter La Motte Potassium 895 for 0 29 15 3 3 10 na 1 35 1 05 Smart Color Spectrophotometric La Motte Potassium 895 for 0 29 15 1 3 7 0 06 2 0 90 Reagent Set Smart Color Zinc Spectrophotometric La Motte Zinc 895 for 0 59 5 0 14 3 mg L na 0 88 0 85 Dilute indicator expires in a Smart month uses dilute cyanide Color Spectrophotometric HACH Zinc Zincon 1495 for 0 37 10 na na na Uses granular cyanide and is Method DR 2000 unacceptable for field use Test strips EM Science 500 for 0 56 5 na na na Reflectoquant requires ReflectoQuant Zinc Reflecto frequent cleaning and test has Quant high detection limit Meter From Day J Selection of Appropriate Analytical Procedures for Volunteer Field Monitoring of Water Quality MSCE thesis Department of Civil and Environmental Engineering University of Alabama at Birmingham 1996 With permission oll MOOSANVH S193443 YHSALVMAYOLS LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 773 alinity Figure E 1 HACH color test kit Figure E 2 Quantistrip method for alkalinity Figure E 3 Comparing Quantistrip Figure E 4 CHEMetrics cop
85. st following the direc tions below 1 Laboratory Information Fill in the generator s name i e principal investigator lab director telephone number department building room number and the date 2 Waste Information The contents of each container must be identified on the manifest Nonspecified chemical waste items are extremely difficult for hazardous materials personnel to handle Good laboratory record keeping and labeling of all chemicals and chemical wastes prevents unknown waste items Any chemical material that is potentially recyclable should not be contaminated with other chemicals for disposal Where appropriate note on the manifest if material is unopened 3 The generator should check the information on the manifest sign his or her name and attach it to the corresponding box Step Three Chemical Waste Removal Attach one copy to the box and retain a copy for laboratory records Specify where the waste is to be picked up If your waste is not picked up in a reasonable period of time call to inquire Any incomplete or improperly completed manifest will be returned to the generator with an explanation for its return MATERIAL SAFETY DATA SHEETS MSDS Since Material Safety Data Sheets MSDS are centrally related to the safe handling of haz ardous substances it is imperative that laboratory workers have easy access to them There are three basic means of obtaining an MSDS Chemical manufacturer Chemical supplier
86. stovoy SPIE The International Society for Optical Engineering Volume 2965 pp 70 82 1997 Cold vapor AAS is used for very sensitive determinations of mercury In this scheme the sample modified with H SO HNO KMnO and SnCl to volatilize the mercury is purged with air which is then directed into an absorption cell placed in the light pathway where the flame unit is normally located Electrothermal graphite furnace AAS is much more sensitive than flame AAS because it can place a much greater density of atoms in the light pathway Contamination is therefore much more critical than with flame units Electrothermal AAS is subject to more interferences than flame AAS and is only recommended for very low concentrations of metals However because of the relatively low concentrations of many heavy metals found in stormwater especially the dissolved fraction graphite furnace AAS Figure E 10 is the preferred method in this area of research using a suitable background corrector to minimize most interferences Inductively coupled plasma atomic emission spectroscopy uses a controlled plasma from argon gas ionized by an applied radio frequency A sample aerosol is directed into the plasma which is at an extremely high temperature 6000 to 8000 K This results in almost complete dissociation of the metal molecules and significantly reduced chemical interferences compared to most other metal analyses techniques Another important advantage of t
87. t to form an air vapor mixture that will ignite but will not sustain ignition Many common flammable solvents have flash points significantly lower than room temperature The limits of flammability or explosivity define the range of fuel air mixtures that will sustain combustion The lower limit of this range is called the lower explosive limit LEL and the higher limit of this range is called the upper explosive limit UEL Materials with very broad flammability ranges are particularly treacherous due to the fact that virtually any fuel air combination may form an explosive atmosphere The vapor density of a flammable material is the density of the corresponding vapor relative to air under specific temperature and pressure conditions Flammable vapors with densities greater than one and thus heavier than air are potentially lethal because they will accumulate at floor level and flow with remarkable ease in much the same manner that a liquid would The obvious threat is that these mobile vapors may eventually reach an ignition source such as an electrical outlet or a lit Bunsen burner Examples of Flammable Liquids Acetone Ethyl ether Toluene Methyl formate Use and Storage of Flammables 1 Flammable liquids that are not in active use must be stored in safe containers inside fire resistant storage cabinets designed for flammables or inside storage rooms 2 Minimize the amount of flammable liquids stored in the lab 3 U
88. tes Use and Storage of Oxidizers 1 In general store oxidizers away from flammables organic compounds and combustible materials Strong oxidizing agents like chromic acid should be stored in glass or some other inert container preferably unbreakable Corks and rubber stoppers should not be used 3 Reaction vessels containing appreciable amounts of oxidizing materials should never be heated in oil baths but rather on a heating mantle or sand bath Use and Storage of Perchloric Acid 1 Perchloric acid is an oxidizing agent of particular concern The oxidizing power of perchloric acid increases as concentration and temperature increase Cold 70 perchloric acid is a strong nonoxidizing corrosive A 72 perchloric acid solution at elevated temperatures is a strong oxidizing agent An 85 perchloric acid solution is a strong oxidizer at room temperature 2 Do not attempt to heat perchloric acid if you do not have access to a properly functioning perchloric acid fume hood Perchloric acid can only be heated in a hood specially equipped with a wash down system to remove any perchloric acid residue The hood should be washed down after each use and it is preferred to dedicate the hood to perchloric acid use only 3 Whenever possible substitute a less hazardous chemical for perchloric acid 4 Perchloric acid can be stored in a perchloric acid fume hood Keep only the minimum amount necessary for your work Another acceptable storage site for p
89. time as they stabilize Observe the readings under SpCond and when they show no significant change for approximately 30 s press ENTER e The screen will indicate that the calibration has been accepted and prompt you to HIT ANY KEY to return to the Calibrate menu 784 STORMWATER EFFECTS HANDBOOK e If you receive an error message indicating that the calibration is out of range assure yourself that the calibration solution was prepared correctly If it was remove sonde guard and using small brush located in pocket in user s manual clean out the channel on the conductivity probe BE GENTLE Replace sonde guard and repeat calibration steps e Rinse the sonde in tap or purified water and dry DO Probe and depth Calibration e Place approximately s in 3 mm of water or a saturated sponge in the bottom of the calibration cup Make sure the DO and temperature probes are not immersed in the water Wait approximately 10 minutes for the air in the cup to become water saturated NOTE if the transport cup is used make certain that the cup is vented to the atmosphere by loosening the vent screw e From the Calibrate menu select 2 DO to access the DO calibration procedure Enter the current barometric pressure in mm Hg inches of Hg x 25 4 mm Hg e Press ENTER and the computer will indicate that the calibration procedure is in progress e After approximately 1 min the calibration will be complete Press any key as instructed and the
90. tive equipment Some examples of potent carcinogens substances known to have high chronic toxicity along with their corresponding chemical class are Alkylating Agents a Halo ethers Bis chloromethyl ether and chloromethyl ether Methyl chloromethyl ether Aziridines Ethylene imine 2 Methylaziridine Diazo azo and azoxy compounds 4 Dimethylaminobenzene Electrophilic alkenes and alkynes Acrylonitrile Acrolein Ethyl acrylate Epoxides Ethylene oxide Diepoxybutane Epichlorohydrin 746 Propylene oxide Styrene oxide Acylating Agents B Propiolactone Dimethylcarbamoyl chloride B Butyrolactone Organohalogen compounds 1 2 Dibromo 3 chloropropane Vinyl chloride Chloroform Methyl iodide 2 4 6 Trichlorophenol Bis 2 chloroethy sulfide Carbon tetrachloride Hexachlorobenzene 1 4 Dichlorobenzene Natural products Adriamycin Bleomycin Progesterone Aflatoxins Reserpine Safrole Inorganic compounds Cisplatin Aromatic amines 4 Aminobipheny Aniline o Anisidine Benzidine and derivatives 1 1 Bis p chlorophenyl 2 2 2 trichloroethane DDT o Toluidine Other Extremely Hazardous Chemicals Arsenic organic arsenic and derivatives Arsine and gaseous derivatives Asbestos Azathioprine Bromodeoxyuridine 1 4 Butanediol dimethylsulfonate Myleran N Butyl N 4 hydroxybutyl nitrosamine OH BBN Chlorambucil Chloropicrin in gas mixtures Cyanogen Cyanogen chloride Cyclophosphamide Diborane Diisopropylfluorophosphate
91. u e Proceed to the deployment setup procedure Deployment Setup Procedure for unattended monitoring Unplug the AC power source and continue this procedure using the sonde s internal battery power e Select 1 Run from the sonde Main menu The Run menu will be displayed e Select 3 Unattended sample from the Run menu The current time and date all active sensors battery voltage and free flash disk space will be displayed e Note if the current time and date are not correct your unattended sampling study will not begin or end when you desire To correct the time and date see Section 2 5 in the instruction manual e You will be asked to enter the starting date Use the following format XX XX XX For example to start on 1 January 1999 enter 01 01 99 Enter the starting time Use the following format XX XX XX You must include not only hours and minutes but seconds For example if you want to start a study at 8 AM you must enter 08 00 00 e Enter the study duration in days For example for a 2 week study enter 14 Enter interval in minutes For example to collect data every 15 minutes enter 15 e Enter the site description e You will be asked if all start up information is correct Check the information carefully especially the estimated battery life and if you want to change something press N If all information is correct press Y The following message will be display
92. uire an MSDS Sources of MSDSs include e Chemical supplier e Chemical manufacturer e Internet resources such as the UAB Department of Occupational Health and Safety webpage http www healthsafe uab edu Working with Allergens A wide variety of substances can elicit skin and lung hypersensitivity Examples include common substances such as diazomethane chromium nickel bichromates formaldehyde isocyanates and certain phenols Because of this variety and the varying responses of individuals suitable gloves should be used whenever there is a potential for contact with chemicals that may cause skin irritation 744 STORMWATER EFFECTS HANDBOOK Working with Embryotoxins Embryotoxins are substances that cause adverse effects on a developing fetus These effects may include embryolethality malformations retarded growth and postnatal function deficits A few substances have been demonstrated to be embryotoxic in humans These include Acrylic acid Aniline Benzene Cadmium Carbon sulfide N N dimethylacetamide Dimethylformamide Dimethyl sulfoxide Diphenylamine Estradiol Formaldehyde Formamide Hexachlorobenzene Iodoacetic acid Lead compounds Mercury compounds Nitrobenzene Nitrous oxide Phenol Thalidomide Toluene Vinyl chloride Xylene Polychlorinated and polybrominated biphenyls Embryotoxins requiring special controls should be stored in an adequately ventilated area The container should be labeled in a clear ma
93. unts used dates of use and names of users must be maintained To minimize hazards from accidental breakage of apparatus or spills of toxic substances in the hood containers of such substances should be stored in pans or trays made of polyethylene or other chemical resistant material and the apparatus should be mounted above trays of the same material Alternatively the working surface of the hood can be fitted with a removable liner of adsorbent plastic backed paper Such procedures will make clean up of accidental spills easier Areas where toxic substances are being used and stored must have restricted access and warning signs should be posted if a special toxicity hazard exists If the substance is suspected of having a high chronic toxicity the storage area must be maintained under negative pressure with respect to its surroundings In general the waste materials and solvents containing toxic substances should be stored in closed impervious containers so that personnel handling the containers will not be exposed to their contents The laboratory worker must be prepared for potential accidents or spills involving toxic sub stances If a toxic substance contacts the skin the area should be washed with water If there is a major spill outside the hood the room or appropriate area should be evacuated and necessary measures should be taken to prevent exposures to other workers Spills must be cleaned by personnel wearing suitable personal protec
94. upgs configured to collect the following measurement parameters dissolved oxygen conductivity specific con ductance salinity total dissolved solids resistivity temper ature pH ORP depth level and turbidity Table E 6 gives the reported performance specifications for each sensor This method details how to calibrate the sonde for the following measurement parameters specific conductivity dissolved oxygen depth pH and turbidity for freshwater monitoring plus routine maintenance of the DO and conduc tivity probes The temperature and ORP probes require no calibration but should be checked against known standards This method also describes how to configure the sonde for unattended deployment or sampling All calibration standards should be prepared fresh and this procedure should be done at approximately 25 C The following lists the materials and supplies needed for calibrations Materials e One or more containers to hold calibration standards YSI calibration cup or 800 mL beaker e Large 5 gallon bucket filled with tap water for rinsing the sonde between calibration solutions LABORATORY SAFETY WASTE DISPOSAL AND CHEMICAL ANALYSES METHODS 783 Table E 6 Performance Specifications and Sensor Types in the YSI 6000 Sonde Parameter Sensor Type Range Accuracy Resolution Dissolved oxygen Rapid Pulse Clark type 0 200 air 2 air saturation 0 1 air saturation polarographic saturation saturation Conductivity 4
95. us membranes and eyes by direct or airborne contact Ingestion the taking up of the substance through the mouth Injection having the material penetrate the skin through a cut or by mechanical means Health Hazards Acute and Chronic Acute an adverse effect with symptoms developing rapidly Chronic an adverse effect that can be the same as an acute effect except that the symptoms develop slowly over a long period of time or with recurrent exposures Carcinogen A substance that is determined to be cancer producing or potentially cancer producing 766 STORMWATER EFFECTS HANDBOOK Signs and Symptoms of Overexposure The most common symptoms or sensations a person could expect to experience from over exposure to a specific material It is important to remember that only some symptoms will occur with exposures in most people Emergency and First Aid Procedures Instructions for treatment of a victim of acute inhalation ingestion and skin or eye contact with a specific hazardous substance The victim should be examined by a physician as soon as possible Specific HACH MSDS Information This information is presented here because of the large number of specialized HACH Co reagents and procedures used in environmental laboratories HACH MSDSs describe the hazards of their chemical products Each of their MSDSs has 10 sections Header Information Typically provides the vendor name company address and telephone number
96. ve Molecules When water reactive materials come in contact with water one or more of the following can occur e Liberation of heat which may cause ignition of the chemical itself if it is flammable or ignition of flammables that are stored nearby e Release of a flammable toxic or strong oxidizing gas release of metal oxide fumes e Formation of corrosive acids Water reactive chemicals can be particularly hazardous to firefighting personnel responding to a fire in a lab because water is the most commonly used fire extinguishing medium Examples of water reactive materials Alkali metals lithium sodium potassium Magnesium Silanes Alkylaluminums Zinc Aluminum Pyrophoric material can ignite spontaneously in the presence of air Examples of pyrophoric materials Diethylzinc Triethylaluminum Many organometallic compounds Peroxide Forming Materials Peroxides are very unstable and some chemicals that can form them are commonly used in laboratories This makes peroxide forming materials some of the most hazardous substances found in a lab Peroxide forming materials are chemicals that react with air moisture or impurities to form peroxides The tendency to form peroxides by most of these materials is greatly increased by evaporation or distillation Organic peroxides are extremely sensitive to shock sparks heat friction impact and light Many peroxides formed from materials used in laboratories are more shock sensitive t
97. w eyewash are available 3 Add acid to water but never water to acid This is to prevent splashing from the acid due to the generation of excessive heat as the two substances mix 4 Never store corrosives above eye level Store on a low shelf or cabinet 5 It is a good practice to store corrosives in a tray or bucket to contain any leakage 6 When possible purchase corrosives in containers that are coated with a protective plastic film that will minimize the danger to personnel if the container is dropped 7 Store corrosives in a wood cabinet or one that has a corrosion resistant lining Corrosives stored in an ordinary metal cabinet will quickly damage it If the supports that hold up the shelves become corroded the result could be serious Acids should be stored in acid storage cabinets specially designed to hold them and nitric acid should be stored in a separate cabinet or compartment Use and Storage of Hydrofluoric Acid 1 Hydrofluoric acid is extremely hazardous Hydrofluoric acid can cause severe burns and inhalation of anhydrous hydrogen fluoride can be fatal 2 Initial skin contact with hydrofluoric acid may not produce any symptoms 3 Only persons fully trained in the hazards of hydrofluoric acid should use it 4 Always use hydrofluoric acid in a properly functioning fume hood Be sure to wear personal protective clothing 5 If you suspect that you have come in direct contact with hydrofluoric acid wash the area with
98. yes and in high concentrations are narcotic The following symptoms are typical for the respective routes of entry Acute Health Effects Inhalation headache fatigue dizziness drowsiness narcosis stupor and unresponsiveness Ingestion slight gastrointestinal irritation dizziness fatigue Skin Contact dry cracked and chapped skin Eye Contact stinging watery eyes inflammation of the eyelids Chronic Health Effects The chronic health effects will vary depending on the specific chemical the duration of the expo sure and the extent of the exposure However damage to the lungs liver kidneys heart and or central nervous system may occur Cancer and reproductive effects are also possible Flammable Groups Exhibiting These Health Effects Hydrocarbons aliphatic hydrocarbons are narcotic but their systemic toxicity is relatively low Aromatic hydrocarbons are all potential narcotic agents and overexposure to the vapors can lead to loss of muscular coordination collapse and unconsciousness Benzene is toxic to bone mar row and can cause leukemia Alcohols vapors are only moderately narcotic Ethers exhibit strong narcotic properties but for the most part are only moderately toxic Esters vapors may result in irritation to the eyes nose and upper respiratory tract Ketones systemic toxicity is generally not high First Aid Procedures for Exposures to Flammable Materials Inhalation Exposure

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