face of the water. Then, more soap wasadded, using a step-by-step procedure, untila permanent layer of suds remained on thesurface of the water. The total quantity ofsoap required to produce the stable suds layerwas proportional to the hardness of thewater. It was eventually realized that thehardness was due almost entirely to the pres-ence of calcium and magnesium ions in thewater, and as soon as analytical procedureswere developed that would analyze for theconcentrations of these ions directly, ratherthan indirectly, as with the shaking bottletest, the newer analytical procedures becamethe standard for the hardness test. In the con-text of use of water in industrial processes,however, and especially the reuse of treatedwastewaters in a recycle and reuse system, thesignificance of hardness is in the scale-form-ing properties of calcium and magnesiumsalts.

Iron and ManganeseIron and manganese are normally consideredtogether as problems in raw water suppliesfor industrial process use, as well as in proc-ess effluents. The reason is that these metalsare very often found together in groundwatersupplies and in some surface water supplies,under certain conditions. Iron and manga-nese are objectionable for two principal rea-sons. First, iron can be oxidized by oxygen inwater to insoluble ferric oxide, which precip-itates to form fine granules that can foul dis-tribution systems and cooling devices. Sec-ond, both iron and manganese react withchlorine to form highly colored chloridesthat stain many of the objects they come incontact with.

Characteristics of Discharges to theAir

There are three categories of air pollutantcharacterization: (1) stack discharge charac-terization, (2) fugitive emissions character-ization, and (3) ambient air quality charac-

terization. The three involve quite differentsampling procedures but similar, and in mostcases identical, analysis methods. Stack dis-charge and fugitive emission characterizationare done primarily to determine the state ofcompliance with one or more discharge per-mits. Ambient air quality characterization isdone primarily to determine the quality ofair in a given area.

Ambient air quality data are used formany purposes, including:

• Issuance of construction permits forindustrial projects

• Determination of state of compliancewith National Ambient Air Quality Stan-dards (NAAQS)

• Determination of the effectiveness ofameliorating activities

• Establishment of baseline informationprior to construction of a significantcontributor of substances to the atmos-phere

Stack SamplingThe most common reason for conducting astack sampling program is to determine thestate of compliance with regulatory require-ments. As such, the substances sampled forare usually dictated by the list of substancesincluded in the air discharge permits issuedto the facility.

The purpose of stack sampling is to deter-mine, with as much accuracy as is practicable,the quantity (magnitude) of the total gassource flow rate and the quality (types andamounts of air contaminants) of the totalsource gas discharge. The equipment includedin a typical stack sampling station includesdevices to measure characteristics from whichgas flow rate can be calculated, devices to mea-sure certain characteristics directly, and equip-ment to collect and store samples for subse-quent analyses in the laboratory.

In general, the equipment used to obtaindata from which to calculate gas flow rateincludes pitot tubes to measure gas velocity;a device to measure the static pressure of the

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stack gas; and devices to measure barometricpressure, moisture content, and temperature.Equipment used to characterize stack dis-charges in terms of specific substances is clas-sified in two broad categories: particulateand gaseous. The objective of this equipmentin both categories is to quantitatively removeair contaminants in the same condition asthey occur when they are discharged to theair. Many individual devices as well as inte-grated systems are commercially available toaccomplish this objective.

Sample CollectionSamples of ambient air or gas streams(including stack emissions and fugitive emis-sions) are sampled to determine the presenceof, and concentrations of, particulate andgaseous pollutants by use of the followingequipment and mechanisms:

• Use of a vacuum pump, hand operatedor automatic

• Vacuum release of an evacuated collec-tion container

• Tedlar bags• Adsorption on a solid• Condensation (freeze-out) in a trap

Vacuum PumpsVacuum pumps are the standard type ofequipment used to draw samples of ambientair of stack gas or other gas stream throughor into collection devices. Hand-operatedvacuum pumps are used extensively toobtain grab samples. Motor-driven vacuumpumps are the standard for continuous orintermittent monitoring. Vacuum pumpscan be fitted with, or connected in serieswith, gas flow meters to obtain data for cal-culation of concentrations.

Vacuum Release of an Evacuated CollectionContainerContainers (having appropriate linings) canbe evacuated by use of a vacuum pumpbefore traveling to sampling locations. Thecollection apparatus (soil gas sampling well,for instance) can be connected to the evacu-

ated container, the valve on the containeropened, and a sample of known volume willbe collected.

Tedlar BagsTedlar bags are made of a nonreactive, non-adsorbing (relatively) material, and are stan-dard equipment for sampling gaseous sub-stances in the air of a stack or other emission.They are purchased as a completely emptybag and are inflated with the collected sam-ple of air or other gas. Samples should beanalyzed as soon as possible after being col-lected in the Tedlar bag. Tedlar bags can bepurchased in different volume capacities,including 1-liter and 10-liter bags.

Adsorption on a SolidSolid adsorbents, such as activated carbon,can be used to collect certain airborne sub-stances, after which the substances can bedesorbed for further analysis or other work.Normally, a vacuum pump is used to draw avolume of air or other gas through a con-tainer of the adsorbent. In the case of certainsubstances (e.g., carbon monoxide), an indi-cator chemical can be incorporated with theadsorbent to directly indicate the presence ofthe substance.

Condensation (Freeze-Out) in a TrapCertain substances present in air or other gasstream as a result of volatilization can be col-lected by drawing a stream of the carrier airor other gas through a trap held at low tem-perature.

Equipment used to collect particulatematter and to determine the concentration,in ambient air as well as stack emission andother gas streams, uses one or more of thefollowing mechanisms:

• Filtration• Electrostatic impingement• Centrifugal force• Dry impingement• Wet impingement• Impaction

FiltrationThe standard method for determining theconcentration of particulate matter in emis-sions from stationary sources, as publishedin the Federal Register (40 CRR. Part 60, July1, 1998), is to withdraw, isokinetically, par-ticulate-laden air (or other gas) from thesource and collect it on a glass fiber filtermaintained at a temperature in the range of120 + 14°C (248 + 25°F), or such other tem-perature as specified by an applicable subpartof the published standards, or approved bythe Administrator, U.S. Environmental Pro-tection Agency for a particular application.The total quantity of particulates sampled isthen determined by weighing the dried filter.The standard sample train for this determi-nation, illustrated in Figure 5-7, includesequipment to measure gas flow rate as well astotal gas volume sampled. These data canthen be used to calculate particulate matterconcentration.

Electrostatic ImpingementFigure 5-8 shows a schematic of a typicalelectrostatic impingement device for collect-ing particulate matter from ambient air orother gas source. In order to determine theconcentration of particulate matter in the gassource sampled, additional equipment, dis-cussed above, must be used to determine therate of flow of the gas sampling system, or thetotal volume of source gas from which theparticulates were extracted. Then, the totalweight of particulate matter collected mustbe determined by weighing.

The principle of operation of the electro-static impingement apparatus is that of elec-trostatic attraction. The electrostaticimpingement surface is given an electrostaticcharge of polarity opposite to the polarity(positive or negative) of the particles in ques-tion.

Centrifugal ForceA typical particulate matter collector thatoperates on the principle of centrifugal forceis shown in Figure 5-9. This device acceptsthe sample of particulate-laden air, which

can be ambient air, stack gas, or another gasstream, and directs it through a circular pathon its way to the outlet. In traveling the cir-cular path, particulates are forced, by centrif-ugal action, to the collection device shown.As with other particulate collection devices,equipment to measure the rate of flow ofsample taken, or total volume from whichthe particulates were extracted, must be usedto enable calculation of particulate matterconcentration.

Dry ImpingementFigure 5-7 shows a "sample train" containingfour impingers. These impingers can be usedeither wet or dry and can be used to collectparticulates from ambient air of stack gasesor particulates from other gas streams.

Wet ImpingementWet impingement methods for collectingparticulate samples from ambient air, a stackemission, or other gas train operate by trap-ping the particulates in a liquid solution. Thetotal weight of particulate matter is thendetermined by filtering and weighing theentire volume of the liquid or by evaporatingthe liquid and weighing. A volume of freshliquid is also evaporated, and the residual (ifany) is weighed and compared with theweight of the dried sample to determine theactual weight of particulate matter. Again,equipment to measure the sample flow rateor the total volume sampled is necessary inorder to determine particulate concentra-tion.

ImpactionFigure 5-10 shows a schematic of a typicalimpaction particulate collector. The princi-ple upon which this collection device oper-ates is that of entrapment on a plate with afilm of sticky material on its surface. Collec-tion of pollen for pollen assay purposesmakes use of this type of equipment.

Particulates can be physically extractedfrom glass fiber filters or from the other col-lection devices for analysis as to individualconstituents, such as metals, radioactive ele-

Figure 5-7 Particulate sampling train.

TEMPERATURE SENSOR

PITOT TUBE

PROBE

PROBE

REVERSE-TYPEPITOT TUBE

PITOT MANOMETER

ORIFICE

TEMPERATURESENSOR

STACKWALL

HEATED AREA THERMOMETER

FILTER HOLDER

IMPINGEMENT TRAIN OPTIONAL, MAY BE REPLACEDBY AN EQUIVALENT CONDENSER

THERMOMETER

THERMOMETERS

DRY GAS METER AIR-TIGHTPUMP

MAINVALVE

VACUUMGAUGE

IMPINGERSBY-PASS VALVE

ICE BATH

VACUUMLINE

CHECKVALVE

Figure 5-10 Schematic of a typical impaction particle collector.

Pump and MeterFromSource

Figure 5-9 Schematic diagram of a centrifugal particlecollector.

merits or other materials. The analyst shouldconsult the appropriate Code of Federal Reg-ulations to determine acceptable procedures.

Figure 5-11 presents a schematic of anexample of a stack sampling system and illus-trates several of the methods employed fordata management.

Sample AnalysisAlthough it is realized that once a sample iscollected it is subject to change as a result ofchemical reaction, chemical degradation,absorption or adsorption onto the walls ofthe container or to other substances in thecontainer, or other phenomena. Not much ispresently known with certainty about howmuch change will take place in a sample onceit is collected. For this reason, it is extremelyimportant to perform the chemical or other

analyses as soon as possible after the samplesare collected.

Ambient Air SamplingDetermination of the quality of ambient airas it relates to the presence and concentrationof substances regarded as pollutants is theobjective of ambient air sampling. The spe-cialized devices and techniques for carryingout this task have been developed over half acentury. Here, again, obtaining representa-tive samples is a major objective of the workplan. Decisions about air sampling muststrike a balance between the cost of the char-acterization program and the value of thedata; these decisions include the duration ofthe sampling period, number of discretesamples taken, the size of each sample, andthe number of substances sampled for.

Particulate matter in ambient air is mea-sured by use of a "high-volume sampler,"which is an integrated filter holder/vacuumpump (high volume). A glass fiber filter isheld in the filter holder, and a high flow rateof ambient air is drawn through it over ameasured period of time. Calculations ofparticulate matter concentration in theambient air are carried out using the weightof particulate matter collected on the filter

Figure 5-8 Schematic of a typical electrostatic impingement collector.

Elect

Pump and MeterSourceFrom

AirOut

InAir Particles

Out

Storage andRemoval system

Punch Tape

Card File

Magnetic Tape

Off Line/On LineReal timeCostMaintenanceOperation

Data Analysisand Presentation

Video DisplayPlotterPrinterOff Line/On LineReal times

Computer

Manual

Other

Data Transmitted

Telemetry

Telephone

Manual

Other

CostOperationMaintenance

CostOperationMaintenanceOn site/Off site

Manual

Semi-continuous

Continuous

In-Situ Detector

Extraction Detector

Analyzer

Detector/Analyzer

ProbeStock

SampleConditioner(s)• Filters

CondensersHumidifiersPressureRegulators

• Temperature

Figure 5-11 Continuous monitoring system.

Data Recording

and the flow rate (or total volume) of airdrawn through the filter.

Air PollutantsThe following paragraphs present a brief dis-cussion of the major air pollutants that areregulated by the Clean Air Act, as amended.

Air Toxics. Control of the release of so-called "air toxics" took on a new impor-tance—in fact, a dominant importance—with promulgation of Title III of the 1990Clean Air Act Amendments (CAA). Previousto these amendments, the EPA had issuedstandards for only eight hazardous sub-stances over a 20-year period. The 1990 CAAlists 188 substances that must be controlled.

The designated air toxics are required tobe managed by use of "Maximum AchievableControl Technology" (MACT). In addition,residual risk after implementation of MACTmust be assessed. Industries are also subjectto a time schedule, by source category, forimplementation of MACT. All sources mustbe in compliance with the applicable stan-dard within a published time schedule. TheEPA published the initial list of source cate-gories in 1992 and since that time has issuedseveral revisions/updates to the list and pro-mulgation schedule.

There are significantly different require-ments for sources that qualify as a "majorsource" compared with those that do not. Amajor source is any stationary source thatemits in excess of 10 tons per year of any ofthe listed 188 hazardous substances or 25tons per year or more of any combination ofthose substances.

The list of 188 air toxics includes pesti-cides, metals, organic chemicals, coke ovenemissions, fine mineral fibers, and radionu-clides. The EPA is required to add to this listpollutants that may be shown to present,through inhalation or other routes of expo-sure, a threat of adverse effect on humanhealth or the environment. The EPA may alsoremove substances from the list if it can beshown that the reasons for placing them onthe list were in error.

There are also significantly elevated con-trol requirements for the sources that repre-sent 90% of the area sources that emit the 30hazardous air pollutants presenting thegreatest threat to public health in the largestnumber of urban areas.

Ozone. Ozone has the chemical formulaO3 and is a relatively strong oxidizing agent.Ozone is emitted directly by some sources,and is also a product of chemical and/or pho-tochemical reaction between other air pollut-ants in the atmosphere. Ozone is an irritantand can damage sensitive tissues in animals(including humans) as well as plant tissues.

Oxides of Sulfur (SOx). Sulfur dioxide isthe major sulfur oxide of concern in theatmosphere, although sulfur trioxide (SO3)and sulfate (SO4) are important. The pri-mary source of sulfur oxides in the nation'satmosphere is the burning of fossil fuels (oiland coal) to generate electrical power andheat. Since sulfur is an important componentof protein, and protein is an important com-ponent of virtually all plants and animals,sulfur is consequently a component of thefossil remains of these once-living entities.When oil or coal is burned, oxygen combineswith the sulfur and the resulting sulfur oxidesare emitted with the gaseous releases fromthe combustion process. The principal harm-ful effects of sulfur oxides are their eventualreaction with atmospheric moisture andreturn to the earth as acid rain, as well astheir participation in photochemical reac-tions in the atmosphere to produce smog.

Oxides of Nitrogen (NOx). Nitrogenoxides, principally nitrogen dioxide, NO2,and nitric oxide, NO, are produced duringthe combustion of all types of fuels. Thesegases are referred to together as NOx. Sinceair consists of nitrogen in the N2 gas form,and about 21% oxygen in the O2 gas form,there is an unlimited supply of both nitrogenand oxygen available to react with each other,which they will do at elevated temperatures.

The other source of nitrogen that resultsin the formation of significant amounts ofNOx is the nitrogen content of the fuel itself.For instance, Number 6 fuel oil typically con-

tains from 3% to 7% by weight of nitrogen. Ithas been observed that the NOx content ofstack gases increases linearly with a linearincrease in the nitrogen content of the fueloil. It is therefore to be concluded that: (1)the nitrogen content of fuel oil is convertedto NOx during the combustion process, and(2) a reasonable strategy for helping to com-ply with limits on NOx emissions is to obtainand burn fuel oil having a relatively lownitrogen content.

The source of nitrogen in fossil fuels issimilar to that of sulfur—namely, the livingtissue from which the fossil remains werederived. All living entities, since life began,have had deoxyribonucleic acid (DNA), ribo-nucleic acid (RNA), and protein materials askey components. Nitrogen has always been acomponent of these three substances, and thefossil remains contain nitrogen as well.

The principal harmful effect of the nitro-gen oxides is their reaction with atmospherichydrocarbons and other substances to formsmog.

Carbon Monoxide (CO). Carbon monox-ide is the product of incomplete combustionof organic matter, including fossil fuels.While complete combustion of materialcomposed of organic carbon produces car-bon dioxide, CO2, incomplete combustion,due to inadequate supply of oxygen, resultsin the production of some carbon monoxide,CO. Carbon monoxide is hazardous to thehealth of humans and other animals.

Carbon Dioxide (CO2). Carbon dioxide isa product of complete combustion. Theprincipal sources of carbon dioxide in theatmosphere are the respiration of plants, ani-mals, and microorganisms, which use oxygenas an electron acceptor, and the burning offossil and other fuels for generation of heatand power.

The principal harmful effect of carbondioxide in the atmosphere is its contribution,along with methane, to the promotion ofglobal warming due to the so-called "green-house effect."

Particulates. Particulates, known as "fineparticulate matter" or "PMlO," are very small

particles of any substance. The harmfuleffects of particulates are their tendency tolodge in the lungs and their objectionableeffect on visibility.

The sources of particulate matter in theatmosphere are many and varied. Every timesomething is burned, there is generation andrelease of particulate matter. Wind generatesparticulate matter by blowing dust and otherparticulates from places of deposition intothe ambient air. Automobiles and movingheavy equipment disturb land and generateairborne particulate matter.

Volatile Organic Carbon Compounds(VOCs). Volatile organic carbon compoundsare a class of chemicals that is emitteddirectly to the air as a result of evaporation orother type of volatilization. Sources includestored gasoline, stored solvents and otherindustrial chemicals, and certain industrialprocesses. Incomplete combustion of fuels ofmany types is also an important source ofVOC discharge to the ambient air.

The principal harmful effects of VOCs aretoxicity, possible contribution to smog viaphotochemical reactions in the atmosphere,and possible contribution to the greenhouseeffect and consequent global warming.

Malodorous Substances. There are manysubstances, including compounds of sulfurin the reduced state (such as hydrogen sul-fide, methyl and ethyl mercapatans, anddimethyl sulfide) and degradation productsof proteins (such as amines, amides, putri-cine, and cadaverine) that have extremelyobjectionable odors. Many of these com-pounds can be detected by the human olfac-tory apparatus in atmospheric concentra-tion ranges of only a few parts per billion byvolume. Although their common objection-able property is their bad smell, some ofthem are toxic.

Hydrogen Sulfide (H2S). Hydrogen sulfideis toxic as well as malodorous. Worse yet, ithas the characteristic of being able to desen-sitize the olfactory apparatus in a few min-utes' time if the concentration is higher thana few parts per billion by volume. Personswho have entered confined spaces containing

hydrogen sulfide gas have died because, soonafter entering the contaminated space, theywere unable to smell the H2S, did not realizethey were breathing H2S, and were overcomeby a fatal dose.

Other Reduced Sulfur Compounds. Areduced sulfur compound is a chemical sub-stance of low molecular weight that containsone or more sulfur atoms in the minus-two(sulfide) valence state. These substances,along with hydrogen sulfide, are referred toin the aggregate as TRS. Many air dischargepermits contain restrictions on TRS. SomeTRS compounds are toxic. All are objection-able because of their extremely strong, foulodors.

Common sources of hydrogen sulfide andother reduced sulfur compounds includetanneries, rendering plants, kraft pulp mills,and malfunctioning POTWs.

Organics. Several categories of organicmaterial are regulated through restrictionscontained in air discharge permits.

Hydrocarbons. Low molecular weightorganic compounds consisting of carbon andhydrogen are discharged to the air via evapo-ration and as a result of incomplete combus-tion of fossil fuels, including gasoline. Thesesubstances undergo photochemical reactionswith other substances in the atmosphere toform smog.

Methane. Methane, the lowest molecularweight hydrocarbon, enters the atmosphereas a result of natural gas extraction, coalextraction, management of solid waste,anaerobic degradation of organic material inthe natural environment, and the gaseousexpulsions of cattle and other animals associ-ated with agriculture.

The principal harmful effect of methanereleased to the atmosphere is its contribu-tion, along with carbon dioxide, to the causeof global warming, or the greenhouse effect.

Sampling Methods for Air Toxics. Compli-ance with the requirements of Title III of theCAA is based on the implementation of spec-ified (MACT) control technologies and/orachieving specific HAP limits. Ultimately,sampling and analysis work are required to

determine compliance with one or more ofthe 188 listed substances present in the dis-charge. This information is needed, in somecases, to determine whether or not a givencontrol technology must be installed.

Characteristics of Solid WasteStreams from Industries

The Resource Conservation and RecoveryAct (RCRA), as amended, is the primary lawgoverning the handling, transportation, anddisposal of solid and hazardous wastes. Thelaw is contained in its entirety, including theregulations that specifically regulate thesampling and analyses of hazardous andnonhazardous solid waste streams, in vol-ume 40 of the Code of Federal Regulations.Subtitles C and D are addressed to the man-agement of hazardous and nonhazardouswastes, respectively.

Hazardous WastesIn 40 CRR. 260, the EPA defines a genera-tor as "any person, by site, whose act or pro-cess produces hazardous waste identified orlisted in Part 261 or whose act first causes ahazardous waste to become subject to regu-lation." Further, the EPA has establishedthree categories of generator, depending onthe quantity of hazardous waste generatedper month. Table 5-5 provides a descriptionof generator categories. As the quantity ofwaste that is generated per month increases,the regulatory requirements also increase. Avery important first order of business,therefore, is to determine whether or not agiven industrial facility qualifies as a genera-tor, and, if so, which category of generatorthe facility is. This situation could change atany time, due to changes in raw materialsused, production chemicals and other mate-rials used, manufacturing processes, andeven changes in state or federal laws and/orregulations.

The generator categories described inTable 5-5 are based on EPA definitions. Moststates have been delegated the authority to

implement RCRA regulations and have theauthority to make more stringent regula-tions. It is important to check the regulationsfor the individual state where the facility islocated.

RCRA defines hazardous wastes in termsof specific properties. According to RCRA, asolid waste is hazardous if it meets one ofthree conditions and is not excluded fromregulation as a hazardous waste:

1. Exhibits, on analysis, any of the charac-teristics of a hazardous waste

2. Has been named a hazardous waste andappears on an appropriate list

3. Is a mixture containing a listed hazard-ous waste and any other solid wastematerial

RCRA has identified four characteristics,which, if exhibited by a solid waste, designateit as a hazardous waste:

• Ignitable• Corrosive• Reactive• Toxic

These four characteristics are described asfollows:

Ignitable• A liquid, except aqueous solutions con-

taining less than 24% alcohol, that has aflash point of less than 600C (1400F)

• A substance that is not a liquid and iscapable, under standard temperatureand pressure, of causing fire througheither friction, contact with moisture, orspontaneous chemical change

• A substance that is an ignitable com-pressed gas per Department of Transpor-tation (DOT) regulations

• An oxidizer per DOT regulations• Examples of ignitable substances are

waste solvents, paints, and some wasteoils

Corrosive• An aqueous material having a pH less

than or equal to 2.0 or greater than 12.5• A liquid that corrodes steel at a rate

greater than 1/4 inch per year at a tem-perature of 55°C (1300F)

• Examples of corrosive wastes are auto-mobile battery acid and waste pickleliquor from the manufacturing of steel

Reactive• Reacts violently with water• Normally unstable and reacts violently

without detonating

Table 5-5 Quantity Determines Which Regulations Apply

Generator

Large Quantity (LQG)

Small Quantity (SQG)

Conditionally Exempt

Small Quantity (CESQG)

Quantity

1,000 kg/month (approximately 2,200 Ib)

> 1 kg/month acute (approximately 2.2 Ib)

> 100-kg residue or contaminated soil fromcleanup of acute hazardous waste spill

Between 100 and 1,000 kg/month (approxi-mately 220 to 2,200 Ib)

100 kg/month

1 kg acute

100-kg residue or contaminated soil fromcleanup of acute hazardous waste spill

Regulation

All Part 262 Requirements

Part 262, Subparts A, B, C (§262.34[d] isspecific to SQGs); Subparts E, F, G, H if ap-plicable; and portions of Subpart D as speci-fied in §262.44

§261.5

• Generates toxic gases, vapors, or fumeson mixing with water

• Forms a potentially explosive mixturewith water

• Contains cyanide or sulfide and gener-ates toxic gases, vapors, or fumes at a pHof between 2.0 and 12.5

• Capable of detonation if heated underconfinement or subjected to a strongdetonating force

• Capable of detonation at standard tem-perature and pressure

• Listed as a Class A or B explosive by theDepartment of Transportation

ToxicA solid waste exhibits the characteristic oftoxicity if the extract from a sample obtainedfrom conducting the Toxicity CharacteristicLeaching Procedure (TCLP) contains any ofthe contaminants listed in Table 1 of 40 CRR.261.24 at concentrations equal to or greaterthan the respective value given in that table.

The Toxic Characteristic Leaching Proce-dure (TCLP) test was developed as a methodfor determining whether or not a wastematerial, after being placed in a landfill,would leach metals or other substances atrates greater than what was consideredacceptable. The TCLP test attempts to simu-late worst-case landfill leaching conditions,where low pH precipitation (acid rain)would percolate down through the landfilledwastes and cause metals to dissolve into solu-tion.

In performing the TCLP test, the materialto be landfilled is first pulverized to particlesizes no larger than one millimeter in diame-ter. Then, 5.0 grams of the solid phase of thewaste are placed in a 500-ml beaker or Erlen-meyer flask. Next, 96.5 ml of "reagent water"(deionized water) are added; then the beakeror flask is covered with a watchglass andstirred vigorously for five minutes. This pro-cedure is normally carried out in a beaker,with a magnetic stirrer keeping the granulesof waste material suspended and well mixedwith the reagent water.

It is very important that the instruction"cover with a watchglass" be followed. Afterthe five minutes of stirring, the pH of themixture is determined. If the pH is below 5.0,the mixture is subjected to the specifiedextraction procedure using extraction fluid#1, which is prepared by mixing 5.7 ml gla-cial acetic acid, 500 ml of reagent water, and64.3 ml IN sodium hydroxide. The pH ofthis mixture is 4.93 + 0.05. If the pH of themixture of pulverized waste and reagentwater (after mixing for five minutes) ishigher than 5.0, the mixture is subjected tothe specified extraction procedure usingextraction fluid #2, which is prepared bydiluting 5.7 ml glacial acetic acid to a volumeof 1 liter with reagent water. Extraction fluid#2 has a pH of 2.88 + 0.05, is thus a strongeracid solution than extraction fluid #1 (nosodium hydroxide is added during prepara-tion of extraction fluid #2), and will morestrongly dissolve metals from the waste mate-rial.

The reason it is important to keep the bea-ker covered with a watchglass during the stir-ring process is that carbon dioxide gas willeither escape from, or dissolve into, the mix-ture, causing the pH to change and possiblyresulting in the requirement to use the stron-ger extraction solution. Analysts sometimesdo not use the watchglass in order to enableleaving pH probes in the mixture during thestirring process.

After the extraction process has been car-ried out, the extract is analyzed for suspectedor possible substances. If the results of thisanalysis show that any of the substances arepresent in the extract in an amount exceed-ing the published limit, the waste is deemedto be "hazardous" and must be handled anddisposed of in accordance with all the appli-cable hazardous waste laws and regulations.See Table 5-5.

ExemptionsCertain materials under certain circum-stances have been specifically exempted fromhaving to be handled and disposed of as haz-

ardous waste. When applicable conditionsare met, these exempted materials can behandled and disposed of as ordinary solidwastes.

DelistingSome solid wastes can be removed from the"hazardous waste" category by goingthrough a process that enables the waste tobe delisted. Any generator or waste handlercan petition the EPA to exclude a listed wastefrom regulation under Subtitle C. The peti-tioner must prove to the EPA that, due tofacility-specific differences in raw materials,processing, or other factors, the waste is nothazardous and will therefore pose no risk topersons, animals, or the environment. If theEPA, upon examining all other factors inaddition to those cited by the petitioner,finds no reason for not delisting the waste,the waste may be handled and disposed of asordinary solid waste as regulated under 40CER., Subtitle D. It is noted here that thedelisting process can be time consuming andexpensive. Delisting is typically sought forhigh-volume waste streams.

Cradle to Grave ManifestingA significant requirement for all shipmentsof hazardous wastes subject to the regula-tions of Subtitle C is that they be accompa-nied by a written document called a mani-fest. Figure 5-12 shows an example of thestandard form, titled "Uniform HazardousWaste Manifest." At the time of this printing,the manifest was undergoing changes tomake it federally standardized. The manifestprovided in Figure 5-12 is intended to beillustrative of the type of information thatwould be required when filling out a mani-fest. It is the responsibility of the generator ofany hazardous waste to initiate the manifestby writing in the appropriate information. Ifthe waste is hauled away from the generator'sfacility by a second party, the hauler assumespossession of and responsibility for the man-ifest, although the generator retains a copy.Then, when the waste reaches the place ofultimate treatment, storage, or disposal (the

grave), the manifest again changes hands,with the hauler retaining a copy.

As shown on the example manifest pre-sented in Figure 5-12, information containedon the completed manifest may include, butis not limited to, the following:

• Name and EPA identification number ofthe generator, the hauler(s), and thefacility where the waste is to be treated,stored, or disposed ofU.S. EPA and U.S. DOT descriptions ofthe waste

• Quantities• Complete address of the treatment, stor-

age, or disposal facility

In addition, the manifest must certify thatthe generator has in place a program toreduce the volume and toxicity of hazardouswastes to the degree that is economicallypracticable, as determined by the generator,and that the treatment, storage, or disposalmethod chosen by the generator is a practi-cable method currently available that mini-mizes the risk to human health and the envi-ronment.

Once the waste is delivered to the finalplace of disposition (treatment, storage, ordisposal facility), the owner or operator ofthat facility must sign the manifest, retain acopy, and return a copy to the generator ofthat waste. If 35 days pass from the date onwhich the waste was signed for by the initialtransporter, and the generator has notreceived a copy of the manifest from the finalsite of disposition, the generator must con-tact the initial transporter to determine thefate of the waste. If 45 days pass and the gen-erator still has not received a copy of themanifest, the generator must submit anexception report.

Nonhazardous Solid Wastes from IndustriesSome industrial solid wastes can be disposedof in municipal solid wastes landfill facilities(MSWLF). The federal law that governs suchdisposal is contained in its entirety in 40CRR. Part 258. (Part 257 contains the provi-

Figure 5-12 Uniform Hazardous Waste Manifest.

sions for hazardous wastes). Within Part 257,"industrial solid waste" means any solidwaste generated by manufacturing or indus-

trial processes that is not a hazardous waste,regulated under Subtitle C of RCRA. Suchwaste may include, but is not limited to,

3lease print or type (Form designed for use on elite (12 - pitch) typewriter) Form Approved. OMB No. 2050 - 0039 Expires 9-30-91UNIFORM HAZARDOUSWASTE MANIFEST

3. Generator's Name and Mailing Address

4. Generator's Phone ( )5. Transporter 1 Company Name

7. Transporter 2 Company Name

9. Designated Facility Name and Site Address

1 Generator's US EPA ID No. ManifestDocument No.I I I I I I I I I I I I I I I I

6. US EPAID NumberI I I I I i I I I I I8. US EPA ID NumberI I I I I I I I10. US EPA ID Number

I I I I I I I I11. US DOT Description (Including Proper Shipping Name, Hazard Class, and ID Number)

b.

C.

d.

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2. Pageiof lnformstion in thtshaded areas

A. State Manifest Document Number

B. State Generator's ID

C. State Transporter's IDD. Transporter's PhoneE. State Transporter's IDF. Transporter's PhoneG. State Facility's ID

H. Facility's Phone

12. ContainersNo. Type

I I

I I

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I

I

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13.TotalQuantity

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14.UnitWt/Vol

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15. Special Handling Instructions and Additional Information

16. GENERATOR'S CERTIFICATION: I hereby declare that the contents of this consignment are fully and accurately described above byproper shipping name and are classified, packed, marked, and labeled, and are in all respects in proper condition for transport by highwayaccording to applicable international and national government regulations.economically practicable and that I have selected the practicable method of treatment, storage, or disposal currently available to me which minimizes the present andfuture threat to human health and the environment; OR, if I am a small quantity generator, I have made a good faith effort to minimize my waste generation and selectthe best waste management method that is available to me and that I can afford.

Printed/Typed Name Signature Month Day YearI I I I I I

17. Transporter 1 Acknowledgement of Receipt of MaterialsPrinted/Typed Name

Printed/Typed Name

Signature Month Day YearI I I l I I

Signature Month Day YearI I I I I I

19. Discrepancy Indication Space

20. Facility Owner or Operator: Certification of receipt of hazardous materials covered by this manifest except as noted in item 19.Printed/Typed Name

EPA Form 8700 - 22 (Rev. 9 - 88) Previous editions are obsolete.

Signature Month Day YearI I I I I I

waste resulting from electric power genera-tion; fertilizer/agricultural chemicals pro-duction; food and related products or by-products production; inorganic chemicalsmanufacturing; iron and steel manufactur-ing; leather and leather products production;nonferrous metals manufacturing; organicchemicals production; plastics and resinsmanufacturing; pulp and paper manufactur-ing; rubber and miscellaneous plastic prod-ucts manufacturing; the manufacture ofstone, glass, and concrete products; textilemanufacturing; transportation equipmentmanufacturing; and water treatment. Notincluded are wastes resulting from mining oroil and gas production.

MSWLF facilities are required by SubtitleD regulations to have, as a minimum, a linersystem composed of a single composite linerthat is part of a leachate collection andremoval system. A low-permeability covermust be installed when the landfill reachesmaximum capacity. In addition, a ground-water monitoring system must be used todetect liner failure during the 30-year man-dated postclosure care period.

States, of course, may promulgate lawsand regulations that are more restrictive thanthe federal laws and regulations. Again, it isthe responsibility of the owner of the facilityto determine which set of laws and regula-tions is the most restrictive, and this determi-nation should be used as the basis for designof discharge control equipment.

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