Handbook of Pollution Prevention and Cleaner Production || Sources of air emissions from pulp and paper mills

6 Sources of air emissions from pulpand paper mills

6.1 Introduction

Most of the environmental impact from this industry sector is associated withthe manufacturing process (particularly with pulping), with the environmentalfate of the product representing a secondary, but still significant concern. Paperproducts constitute the largest single fraction of municipal solid waste. The USEnvironmental Protection Agency (EPA) Municipal Solid Waste Factbook(http://www.epa.gov/epawaste/index.htm) notes that paper constitutes about40% by weight of items discarded in municipal waste nationwide in 1995 beforerecycling, decreasing to about 32% after recycling. However, the effect of theproduct is due more to its quantity than to its characteristics, since paper isrelatively benign.

Manufacturing emissions, on the other hand, pose significant health risks tocommunities due to both the wide variety of hazardous air and water pollutantsand the quantities. Toxics Release Inventory (TRI) data for 1999 (Table 6.1)show the emissions of the paper sector as a whole (SIC code 26) as a percentageof all sectors.

The paper manufacturing sector was the third largest contributor of allindustry sectors to total reported (TRI) air releases in 1999, behind electricutilities (41%) and the chemicals industry (14%). It was the fourth largestcontributor to direct water releases, behind chemicals (30%), primary metals(24%), and food (19%). In terms of overall water use, the EPA Sector Notebookfor the sector indicates that ‘‘the pulp and paper industry is the largest industrialprocess water user in the USA’’.

Table 6.1 TRI data showing relative contributions of emissions from the paperindustry to all others

Releases to:

Air Water Land Off-site Total

Paper indus-try (lb)

185,968,357 19,118,393 15,268,270 5,201,498 225,556,518

All sectors(lb)

2,029,364,423 258,881,776 4,746,722,774 462,215,492 7,497,184,465

Paper indu-stry (%)

9.2 7.4 0.3 1.1 20.9

Handbook of Pollution Prevention and Cleaner Production Vol. 2

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180 Handbook of Pollution Prevention and Cleaner Production

According to the US Department of Energy, the pulp and paper sector wasresponsible for 198.8 Tg CO2 equivalent (1 Tg, or teragram ¼ 1 million metrictons). The industry is one of the top five sectors in terms of total greenhouse gasimpact (the others being electric power, petroleum refineries, chemicals, and ironand steel mills).

This chapter will assist the reader in understanding the major sources ofpollution, the chemicals of concern largely from an air pollution standpoint, andmethods to estimate some of the releases through the application of emissionfactors.

6.2 Manufacturing technologies

6.2.1 Wood to paper

The production and use of paper is an enormous industry. Each year, about 300million metric tons of paper and paperboard are produced worldwide, and theUSA alone produces nearly 87 million metric tons per year. Paper is mostcommonly produced from pulp, which is a dry fibrous material prepared bychemically or mechanically separating fibers from wood. Production of all thispulp and paper requires a large amount of wood. Each year, the world consumesapproximately 3.3 billion cubic feet of wood, and about 40% of this is used forpaper and paperboard. Paper production requires additional ingredients,including water, sulfur, lime, clay, coal, dye or bleach, and starch. These ingre-dients are used throughout the pulping process, which will be discussed in thissection.

6.2.2 Wood harvesting

To start the process, wood must be harvested from the forest or gathered byrecycling. Trees used for pulping are softwood trees (spruce, pine, fir, larch, andhemlock) and hardwoods (eucalyptus, aspen, and birch). Wood is harvestedthrough logging. Logging is the process of cutting down certain trees for timberor forest management purposes. Responsible logging and paper companies usesustainability techniques to ensure ample amounts of the raw materials (wood)needed for paper will be available. Illegal logging, such as clear cutting andtimber theft, is a common problem in the industry. Unsafe and irresponsibleforest harvesting can lead to the death of valuable and historic forests, a decreasein biodiversity, and legal and financial problems for the company in charge.Most companies, however, follow safe practices and use forests designated forlogging. Trees designated for pulp production account for 16% of world pulpproduction, old growth forests account for 9%, and second- and third- and moregeneration forests account for the rest (Martin, 2004).

Recycled sources of wood are also commonly used to produce pulp. Solidwastes from saw mills are a great source of wood chips and other scraps. Thesescraps are very cheap alternatives for two reasons: (1) they are waste and can be

Sources of air emissions from pulp and paper mills 181

obtained easily; (2) they are usually free of bark, which eliminates a later step ofthe process. Pulp mills also use recycled paper for raw materials. This is a veryecofriendly technique, but requires de-inking and other cleaning processes,which can add to production costs.

6.2.3 Cleaning and chipping

Once the wood is harvested, it must be shipped to the pulping plant. This isusually done on trucks (see Figures 6.1 and 6.2). The timber or pulpwood isbrought to the plant and stored in piles. Then the wood is sent through thebarking drum, where it is stripped of its bark and cleaned. Only sapwood andheartwood are used because bark contains relatively few useful fibers. Afterdebarking, the wood is sent through a chipper to break it into smaller pieces.These chips are screened to ensure consistent size and quality. After chipping, thewood is ready for the pulping process (IFPC, 2009).

6.2.4 Mechanical pulping

There are two main pulping processes: chemical and mechanical. Both processeshave the common goal of extracting cellulose from wood by dissolving the ligninthat binds the cellulose fibers together. Mechanical pulping is the process inwhich wood chips are broken down into fibers using mechanical means only.Mechanical pulp was first produced in the mid-nineteenth century by grindinglogs against a water-lubricated rotating stone-faced drum. The heat generated bygrinding softens the lignin, and the mechanical forces separate the fibers to formground wood. In the last two decades or so, new mechanical techniques using

Figure 6.1 Logging truck with crane.Source: Premier Alaska Inc., DBA Roland & Company; http://rolandandcompany.com/2005_projects/WES/index.html#n


refiners have been developed. In a refiner, wood chips are subjected to intensiveshearing forces between a rotating steel disk and a fixed plate. Wood chips canalso be steamed while being refined in a process called thermomechanicalpulping. Steam treatment significantly reduces the total energy needed to makethe pulp and decreases the cutting done to the cellulose fibers.

Mechanical pulping destroys more of the wood fibers than chemical pulping,which leads to slightly weaker products. Mechanical pulp is often used fornewsprint and paperboards. The main benefit of mechanical pulping is thatalmost all of the wood is used efficiently. Mechanical pulping yields 95% of thewood material used. This high yield efficiency helps keep manufacturing costslow. A negative side of mechanical pulping is that it is not self-sufficient inenergy. Mechanical pulping uses approximately 1000 kilowatts per ton of pulpproduced (EMT, 2008).

6.2.5 Chemical pulping

Chemical pulping is the other common pulping process. The four principalprocesses used in chemical pulping are kraft, sulfite, neutral sulfite semi-chemical(NSSC), and soda. The first three have great potential for causing air pollution.The kraft process alone accounts for over 80% of the chemical pulp produced inthe USA. The specific process selected for implementation is chosen based on thedesired product and wood species available, and by economic factors.

Figure 6.2 Logging Crane Positions Logs for Transport.


The main benefit of chemical pumping is that the pulp fibers produced are longand strong. These long fibers can be used to make much stiffer, stronger paperproducts. Chemical pulp is used for high-quality white paper and other qualitypaper products. Another reason why chemical pulping is sometimes preferred isits self-sustainability. The energy created from the combustion of its by-productscan generate enough energy to run the whole process. The drawback to chemicalpulping is that only 45% of the raw wood put in is returned as pulp. This lowefficiency tends to drive up the total cost of production. Table 6.2 shows thebenefits and statistics for each process.

6.2.6 Kraft pulping

Kraft pulping is the most common form of chemical pulping, at 80% of the totalchemical pulping industry. Kraft pulping involves the digesting of wood chips atelevated temperature and pressure in ‘‘white liquor’’. White liquor is a watersolution of sodium sulfide and sodium hydroxide. The lignin that binds thecellulose fibers together in the wood is chemically dissolved by this white liquor.

The physical pulping of the wood chips is done in digester systems. Twocommon types of digester systems are batch and continuous systems. Most kraftpulping is done in batch digesters, although recently, continuous digesters arebeing installed more commonly. In a batch digester, once cooking is complete,the contents of the digester are moved to an atmospheric tank, usually referred toas a blow tank. The entire contents of the blow tank are sent to pulp washers.The pulp washers separate the pulp from the spent cooking liquor. The pulp thenproceeds through various stages of washing and eventually bleaching, which willbe discussed later in this section.

A benefit of the kraft process is that it is designed to recover the cookingchemicals and heat. Spent cooking liquor and the pulp wash water are combinedto form a weak black liquor that is concentrated in a multiple-effect evaporatorsystem to about 55% solids. The black liquor is then further concentrated toabout 65% solids. This can be done in a direct-contact evaporator, by bringingthe liquor into contact with the flue gases from the recovery furnace, or in anindirect-contact condenser. The strong black liquor is then fired in a recovery

Table 6.2 Comparison of pulping processes

Mechanical pulp Chemical pulp

Energy consumption 1000 kW/ton of pulp Self-sufficient

Percent yield 95 45

Fiber length Short/broken Long/intact

Paper strength Lower High

Production costs Lower Higher than mechanical

Source: EMT (2008).


furnace. Combustion of the organics dissolved in the black liquor provides theenergy for the pulping process and for converting sodium sulfate to sodiumsulfide. Some mills require more energy than the recovery furnace can provide.These mills use conventional industrial boilers or wood boilers to provide thatnecessary power. Solid wood wastes are commonly used in these boilers, makingchemical pulping plants self-sufficient. Inorganic chemicals present in the blackliquor collect as a molten smelt at the bottom of the furnace.

This smelt is dissolved in water to form green liquor, which is transferred toa causticizing tank, where quicklime (calcium oxide) is added to convert thesolution back to white liquor for return to the digester system. A lime mudprecipitates from the tank and it is calcined in a lime kiln to regenerate quicklime.

Kraft pulping produces a large amount of pollution. Particulate emissionsfrom the kraft process occur largely from the recovery furnace, lime kiln, and thesmelt dissolving tank. These emissions are mainly sodium salts, with somecalcium salts from the lime kiln. They are caused mostly by carry-over of solidsand sublimation of condensation of the inorganic chemicals. Particulate controlis provided in a number of ways (see the sustainability/pollution control sectionfor various control techniques and devices).

The chemical emissions of the kraft process are what give pulp mills theirdistinctive odor. Reduced sulfur compounds, such as hydrogen sulfide, methylmercaptan, dimethyl sulfide, and dimethyl disulfide, are all constantly emitted bythe kraft process. These compounds have a very low odor threshold and canhave serious adverse health effects. The major source of hydrogen sulfide is thedirect-contact evaporator, in which the sodium sulfide in the black liquor reactswith the carbon dioxide in the furnace exhaust. Methyl mercaptan and dimethylsulfide are formed in reactions with the wood component, lignin. Thesecompounds are emitted from many points within a mill, but the main sources arethe digester/blow tank systems and the direct contact evaporator. Odor andchemical emission control is difficult and will be discussed in a later section (USEPA, 1995b).

6.2.7 Acid sulfite pulping

Acid sulfite pulp is produced similarly to kraft pulp, except different chemicalsare used in the cooking liquor. Instead of the caustic solution used to dissolve thelignin in the wood, sulfuric acid is employed. A bisulfate of sodium, magnesium,calcium, or ammonium is used to buffer the cooking solution.

The digestion process occurs under high pressure and high temperature, ineither batch mode or continuous digesters, and in the presence of a sulfurousacid/bisulfate cooking liquid. When cooking is completed, the contents of thedigester are either discharged at high pressure into a blow pit or pumped intoa dump tank at a lower pressure. The spent sulfite liquor (red liquor) is thendrained through the bottom of the tank. After that it is treated and then dis-carded, incinerated, or sent to a plant for recovery of heat and chemicals.


Due to the variety of cooking liquor bases used, there are numerous schemesfor heat and/or chemical recovery. Calcium-based systems, which are usuallyfound in older mills, do not have a practical chemical recovery system and thespent liquor is usually discharged or incinerated. In ammonium base operations,heat can be recovered by combusting the spent liquor, but the ammonium base isthereby consumed. In sodium or magnesium base operations, the heat, sulfur,and base can all feasibly be recovered.

If the spent red liquor is recovered, it is concentrated in a multiple-effectevaporator and a direct-contact evaporator to achieve 55–60% solids. Thisstrong liquor is added to a furnace and burned, producing steam to operate thedigesters, evaporators, etc. and to meet other power requirements.

When magnesium base liquor is burned, magnesium oxide can be recoveredfrom the flue gas combustion produces. This fine white powder, usually collectedby cyclones, is then water slaked and used as circulating liquid in a series ofventuri scrubbers. When sodium base liquor is burned, the inorganic compoundsare recovered as a molten smelt containing sodium sulfide and sodiumcarbonate. This smelt can be processed further to absorb sulfur dioxide from theflue gas and sulfur burner. Some sodium base mills sell this smelt to kraft mills inorder to produce green liquor.

Sulfur dioxide is considered the major pollutant of concern from sulfite pulpmills. A major SO2 source is the digester and the blow pit. Sulfur dioxide ispresent in the intermittent digester relief gases, as well as in the gases given off atthe end of the cook when the digester contents are discharged into the blow pit.The amount of sulfur dioxide emitted to the atmosphere from these streamsdepends on the pH of the cooking liquor, the pressure at which the digestercontents are discharged, and the effectiveness of the absorption systemsemployed for SO2 recovery. Additional sources of sulfur dioxide are the recoverysystem and the various pulp washing, screening, and cleaning operations (USEPA, 1995b).

6.2.8 Neutral sulfite semi-chemical (NSSC) pulping

During NSSC pulping, wood chips are cooked in a neutral solution of sodiumsulfite and sodium carbonate. Lignin in the wood reacts with sulfite ions, and thesodium bicarbonate acts as a buffer to maintain a neutral solution. The majordifference between all semi-chemical techniques and those of kraft and acidsulfite processes is that only a portion of the lignin is removed during the cook.The pulping process is completed by mechanical disintegration. This methodachieves pulp to wood returns as high as 60–80%, as opposed to 50–55% for allother chemical processes.

Some NSSC mills dispose of their spent liquor, some mills recover the cookingchemicals, and some, when operated in conjunction with kraft mills, mix theirspent liquor with the kraft liquor as a source of makeup chemicals. Whenrecovery is employed, the steps involved are similar to the sulfite process.


Particulate emissions from NSSC plants are only a concern when recoverysystems are involved. A potential gaseous pollutant is sulfur dioxide, andhydrogen sulfide can be produced by NSSC mills that use kraft-type recoveryfurnaces (US EPA, 1995b).

6.2.9 Soda pulping

Soda pulping was one of the first chemical pulping methods. The main differencebetween soda pulping and other chemical pulping processes is the makeup of thecooking liquor. Sodium hydroxide is used as the primary cooking chemical forsoda pulping. The soda process has limited use for easy pulped materials likestraws and some hardwoods, and generally is an outdated technique.

6.2.10 Bleaching

After exiting the digester, the pulp/liquor combination is sent through a series ofwashers and screeners. Eventually the liquor is separated and discharged orrecovered, and the pulp is ready for bleaching. Bleaching can be done ina number of different ways. Most methods are compromises between cost,quality, and environmental safety.

Mechanical pulps are bleached differently than chemical pulps. Bleaching isa process that reduces lignin, and mechanical pulp contains too much lignin to bepractically removed by bleaching. Therefore, the goal of bleaching mechanicalpulp (also referred to as brightening) is to remove only the color-causing groupsknown as chromophores. Alkaline hydrogen peroxide is the most commonlyused bleaching agent for mechanical pulp. The amount of base is less than thatused in bleaching chemical pulps, and the temperatures involved are lower.These conditions allow alkaline peroxide to selectively oxidize non-aromaticconjugated groups responsible for absorbing visible light. Sodium dithionite isthe other main reagent used to bleach mechanical pulps. The brightness gainedfrom bleaching mechanical pulps is temporary. Exposure to air and light canproduce new chromophores from residual lignin. This is why newspaper yellowsas it ages (Singh, 1979).

Chemical pulps contain far less lignin than mechanical pulps. Therefore, thegoal of chemical pulp bleaching is to remove essentially all of the residual lignin.Bleaching, or delignification, is rarely a single-step process, and is frequentlycomposed of four or more discrete steps. These steps are given a letter ofdesignation. These letters of designation and their meanings are described inTable 6.3.

Bleaching sequences are strings of stages put together. Three commonbleaching sequences are: (1) chlorinated – CEHEH; (2) elemental chlorine-free(ECF) – DEDED; or (3) ECF – OXZEPY.

In the past, chlorination was the most popular chemical pulp bleachingtechnique, but it created many environmental and health problems. Whenelemental chlorine is added to pulp, reactions occur between the chlorine atomsand the lignin. These reactions create chlorinated organic compounds. These


Table 6.3 Bleaching stages

Symbol Stage pH Temp. (8C) Description

A Acid wash Acid wash to remove metals

B Boron hydride,NaBH4

C Chlorination 2 20–25 Elemental chlorine (Cl2) is addedto the pulp. Cl2 is an effectivedelignifying agent. As it breakslignin bonds, it adds chlorineatoms to the lignin degradationproducts, thus producingsignificant amounts ofchlorinated organic material.This organic material can leadto serious environmentalhazards, which will bediscussed below

D Chlorinedioxide

3.5–4 60–80 Chlorine dioxide (ClO2) isa highly selective chemical thatcan both delignify and brightenpulp. It oxidizes lignin, but doesnot add chlorine atoms on tolignin fragments. This greatlyreduces the amount ofchlorinated organic materialproduced

E Alkalineextraction

12 45–95 The goal of this stage is to removecolored components frompartially bleached pulps thathave been rendered soluble indilute warm alkali solutions

F Formamidinesulfuric acid

H Sodiumhypochlorite

11–11.5 30–60 Sodium hypochlorite (NaOCl) isan inexpensive delignifyingagent formed by mixingelemental chlorine with alkaliat the mill

M Chlorinemonoxide

N Nitrogencompounds

Continued


Table 6.3 Bleaching stagesdcont’d

Symbol Stage pH Temp. (8C) Description

O Oxygen >7 85–95 In the oxygen delignification stagethe pulp is treated with oxygenin a pressurized vessel atelevated temperature in analkaline environment. Oxygenremoves lignin and modifiesother coloring components

P Peroxide 65–80 Hydrogen peroxide (H2O2) ismainly used to brightenmechanical and recycled pulpsin the final stages of bleaching.Peroxide is used to prevent pulpfrom losing its brightness overtime

Paa Peracetic acid

Q Chelatin Chelatin is added to control thebrightness-restricting andreversion effects of iron saltsand other heavy metals in thepulp

W Wash The pulp is washed to removereactants from the previousstage

X Xylanase(enzyme)

Xylanase-based enzymaticpretreatment results in easierbleaching and delignification ofthe pulp, causing a bleach-boosting effect. This is typicallyused in totally chlorine-free(TCF) pulp

Y Sodiumhydrosulfite

5.5 60–75 Reductive bleaching. Good forrecycled pulp

Z Ozone 2.5 <65 Ozone (O3) is an effectivedelignifying and brighteningagent. Ozone attacks thecellulose fibers as well as thelignin, however

Source: Paper on Web (PW), 2009.


compounds build up in the spent liquor, which is burned later in the process.Incomplete combustion of this liquor, and therefore these inorganic compounds,leads to the release of highly toxic and carcinogenic chemicals: dioxins andfurans.

Since dioxins and furans are toxic and carcinogenic, the use of elementalchlorine as a bleaching and delignifying agent has been regulated. Elementalchlorine-free (ECF) and totally chlorine-free (TCF) pulp production is morecommon now. ECF pulp uses chlorine dioxide as the bleaching agent. Chlo-rine dioxide is an effective delignifying agent, and it does not lead to theproduction of chlorinated organic chemicals. TCF pulp is what it sounds like:pulp created using no chlorine at all. Additional bleaching stages, such asa xylanase stage, are required but quality comparable to chlorinated pulp isproduced. Both techniques have shown great reduction in dioxin and furanproduction (PW, 2009).

6.2.11 Finishing

After the pulp has been successfully bleached and delignified, it is dried andready for shipment to the actual paper production plant. Once there, it iscombined with dyes, rosin, alum, clay, and possibly titanium dioxide. After thatthe pulp is pressed, dried, and turned into a number of different paper products.

6.2.12 Waste reduction/pollution control/sustainability

The paper industry is an energy-consuming giant. Worldwide, the paper industryis the fifth largest consumer of energy, accounting for 4% of total global energyuse. It also creates waste on a very large scale. It has been estimated that by 2020paper mills will produce 500 million tons of paper and paperboard per year.Great efforts are needed to ensure that the environment is protected during theproduction, use, and recycling/disposal of this enormous volume of material.Solid wastes are not the only pollutants that the paper industry must control.Pulp and paper is the third largest industrial polluter to air, water, and land inboth Canada and the USA. The industry as a whole releases well over 100million kg of toxic pollution each year. Both the public and the paper industryknow that a sustainable balance, where enough paper is produced and theenvironment remains unharmed, is necessary in order to keep our way of lifeintact.

In order to achieve sustainability, paper companies are implementing tech-niques to control waste and emissions. These techniques vary from reducing theoverall use of energy to using new technologies to help control emissions.The paper industry understands how important sustainability is. If they destroythe world’s forests then their wood supply will be cut off. Also, consumersdemand products that are produced responsibly. Many businesses and personalconsumers will not buy paper that is not certified by the Sustainable ForestryInitiative (SFI). The SFI is a nonprofit organization founded by the AmericanForest and Paper Association to provide a forest certification program.


Additional pressure to reduce waste and emissions comes from agencies such asthe EPA. The EPA will penalize a company if its emissions or waste exceedscertain limits. Different mills and plants have different restrictions, but all ofthem have some sort of regulation. In the future, these restrictions willundoubtedly become stricter.

There are many tasks and responsibilities that must be handled in order toachieve sustainability. One major goal of the paper industry today is tocompletely eliminate the use of elemental chlorine. Chlorine is often used forbleaching the wood pulp, but plants using elemental chlorine produce largeamounts of dioxins. Dioxins are some of the most toxic chemicals in theatmosphere, and the uncontrolled release of dioxins is prohibited. In order toreduce the amount of dioxins produced, many pulp mills have switched fromchlorine to chlorine dioxide. Plants that do not use elemental chlorine produceelemental chlorine-free (ECF) pulp. Plants that do not use any chlorine-basedbleaching techniques create totally chlorine-free (TCF) pulp. ECF and TCFplants release far fewer dioxins than the standard chlorine bleaching plants. Inaddition, using nonchlorine bleaching agents reduces water pollution in plants’effluent flows. Due to lack of regulations and consumer demand, only 6% ofkraft pulp is bleached without chlorine chemicals. Stricter laws and sanctionsneed to be implemented in order to convince paper mills to stop usingchlorine.

Due to the damage that chlorine bleaching inflicts on the environment andhuman health, the EPA ratified the ‘‘cluster rule’’. The final pulp and papercluster rule protects human health and the environment by reducing toxicreleases to the air and water from US pulp and paper mills. Since the cluster rulehas been in effect, all major pulp mills have switched to ECF pulping.

Another way paper companies are trying to reach sustainability is byreplanting trees. Paper companies devastate forests in order to get the woodsupply they need to produce all the necessary paper. In order to make sure thattheir wood supply does not run out, these companies plant millions of treesa year. Reforestation is not purely beneficial, however. Reforestation iscommonly criticized for creating a lack of biodiversity. Paper companies onlyreplant trees that they can use to produce paper, but the forests they destroyinvolve more than just trees. Shrubs, vines, and bushes are neglected when treesare artificially planted in forests. A careful eye must be kept on reforested areasto make sure that the diversity of the ecosystem is not being damaged byreforestation.

Due to the amount of water needed for paper production, a large aspect ofsustainability is water resources management. International Paper, a large papercorporation in the USA, used 148 million cubic meters of water in 2006. Paperproduction requires water for two purposes. Water is used directly in the paper-making process and it is used as a noncontact coolant. The water that is used inthe cooling towers is not altered in any way except for a small increase intemperature. The process water, however, will end up with all the waste andpollution from pulping. This water contains a number of different chemicals


depending on the specific pulping process. In order to maintain a clean, abun-dant water supply, effluent water must be treated and returned into the naturalwaterways. Most modern plants will recycle a lot of their wastewater within themills themselves. This is a great way to reduce the total water influent and wasteat the same time. In fact, International Paper saw a decrease of 2.4% in totalwater influent and a decrease of 7.1% in total water effluent from 2004 to 2006.Improvements like these are necessary steps towards a safe, sustainable paperindustry (International Paper, 2008).

Solid waste is another concern for the paper industry. Huge amounts ofsolid waste are produced every year. International Paper alone sent over onemillion tons to landfills in 2006. New recycling and reduction techniques areneeded in order to achieve a sustainable industry. One way the paper industryis reducing its solid waste is by beneficially applying the waste to the land.This is mainly done by producing fertilizer from the solid waste produced. Arapidly growing technique of solid waste reuse is incineration. Waste mate-rials can be burned to create necessary energy or heat for the paper-makingprocess. International Paper Company reused over 400,000 tons of solidwaste through incineration in 2006. This was a 39% increase in the amountburned compared to 2004. This also led to a 10% decrease in the amount ofsolid waste International Paper sent to the landfill. These improvements arehelpful, but landfills are still being filled at an alarming rate. The paperindustry has to continuously fight to reduce its solid waste in order to survivein the future (International Paper, 2008).

Reducing solid and water waste is important, but it won’t help controlchemical and particulate matter emissions. Particulate emissions from the kraftprocess occur largely from the recovery furnace, the lime kiln, and the smeltdissolving tank. These emissions are mainly sodium salt, with some calcium saltsfrom the lime kiln. They are caused mostly by carry-over of solids and subli-mation and condensation of the inorganic chemicals.

Particulate control is provided on recovery furnaces in a variety of ways. Inmills with either a cyclonic scrubber or cascade evaporator as the direct-contactevaporator, further control is necessary, as these devices are generally only 20–50% efficient. Most often in these cases, an electrostatic precipitator (ESP) isemployed after the direct-contact evaporator, for an overall particulate controlefficiency from 85% to >99%. Auxiliary scrubbers may be added at existingmills after a precipitator or venturi scrubber to supplement older and less effi-cient primary particulate control devices. The following is a discussion oncommonly used particulate control devices.

Cyclones

Cyclones (see Figure 6.3) are devices used for removing particles from a gasstream by vortex separation. A high-speed rotating flow is established withina cylindrical or conical container. Air flows in a spiral pattern, traveling thelength of the cylinder before exiting the cyclone via a straight stream flowing in


the center of the cyclone out of the top. Particles denser than air have too muchinertia to follow the tight curve of the stream and strike the side walls. Theparticles then fall down to the bottom of the cyclone, where they can beremoved. Increases in particle density, particle diameter, gas stream velocity, androtational passes all lead to increased removal efficiencies. The maximumremoval efficiency of cyclones is 90%. Limitations include low efficiency forsmall-diameter particles and high energy costs for volumetric flow requirements,and they are prone to internal corrosion/erosion (Hutter, 1997).

Incinerators

An incinerator is a furnace for burning waste. Many paper and pulp millsincorporate them into their pollution mitigation systems. Incineration involvesthe high-efficiency combustion of certain solid, liquid, or gaseous wastes. Thereactions may be self-sustaining based on the combustibility of the waste orrequire the addition of fuels. They may be batch operations or continuous aswith flares used to burn off methane from landfills, and they may incorporatesecondary control methods and operate at efficiency levels of 99.99%, as withhazardous waste incinerators. Volume of solid waste can be reduced by up to95%. Combustion temperatures, contact time, and mass transfer are the majorparameters affecting incineration performance. Limitations include high cost ofsupplementary fuel, high temperatures require good thermal loss control, and

PROCESS CYCLONE SCHEMATIC

CLEANGAS

DIRTYGAS

DUST

Figure 6.3 Simple cyclone.Source: Hutter, G.M., Meridian Engineering and Technology; http://www.meridianeng.com/airpolld.html


hot surfaces, flashback, and explosive conditions (Hutter, 1997). Figure 6.4shows a schematic of an incinerator.

Catalytic reactors

Catalytic reactors (Figure 6.5) can perform similar thermal destruction functionsas incinerators, but for selected gases only. They incorporate beds of solidcatalytic material that the unwanted gases pass through typically for oxidationor reduction purposes, and have the advantages of lowering the thermal energyrequirements and allow small, short-term fluctuations in stoichiometry. Effi-ciencies of 99.99% are possible with reduced energy costs. Limitations includepossible short-circuiting of flow through bed, excessive oxidation and thermalfailure, breakthrough of emissions as failure mode, abrasion and thermal shockof catalyst, poisoning of catalyst and drop in performance, and thick beds cancause high pressure drops and increased energy costs.

Wet scrubbers

Wet scrubbers are devices that remove pollutants from a gas stream. The goal inabsorption and wet scrubbing equipment is the removal of gases and particulatematter from an exhaust steam by causing the gaseous contamination to become

BURNER

CLEAN ODORLESSEFFLUENT

CATALYST

PREHEAT ZONE

FUMESFROMPROCESS

FAN

CONTROLPANEL

COMBUSTIONAIR BLOWER

INCINERATOR COMPONENTRY

Figure 6.4 Incinerator components.Source: Hutter, G.M., Meridian Engineering and Technology; http://www.meridianeng.com/airpolld.html


dissolved into the liquid stream and the solids to be entrained in the liquid. Therate of gas transfer into the liquid is dependent upon the solubility, masstransfer mechanism, and equilibrium concentration of the gas in solution. Gascollection efficiencies in the range of 99% are possible. Limitations include highpressure drops required, internal plugging and corrosion, increased need forinternal inspection, and gas and liquid chemistry control being necessary(Hutter, 1997).

One common type of wet scrubber is the venturi scrubber. Venturi scrubbersconsist of three sections: a converging section, a throat, and a diverging section.The inlet gas stream enters the converging section and, as the area decreases,gas velocity increases. Liquid is introduced either at the throat or at theentrance to the converging section. The inlet gas, forced to move at extremelyhigh velocities in the small throat section, shears the liquid from its walls,producing an enormous number of tiny droplets. Particle and gas removal occurin the throat section as the inlet gas stream mixes with the fog of tiny liquiddroplets. The inlet stream then exits through the diverging section, where it isforced to slow down (Brady and Legatski, 1977). Figure 6.6 shows a venturiscrubber.

Direct-contact evaporators

Direct-contact evaporators are devices in which the liquid phase is vaporized byinjection of a superheated gas. The superheated gas is injected into the liquid

CATALYST BED AND TEMPERATURE PROFILE

INLETCATALYST

BED OUTLET

X

TEMP

X

PRESSURE DROP

Figure 6.5 A catalytic reactor.


phase through submerged orifices of a distribution system. The gas formsbubbles that grow at the orifices until reaching a critical volume, at which pointthey detach (Kumar and Kuloor, 1970). After the formation stage, the bubblesascend in the liquid column. The vapor is then removed from the system by thebubbles that reach the top of the liquid column (see Figure 6.7). Drawbacksinclude high energy costs and relatively low removal efficiencies.

Baghouses

Baghouses (Figure 6.8), also known as fabric filters, use filtration to separatedust particulates from dusty gases. Dust-laden gases enter the baghouse andpass through fabric bags that act as filters. The bags can be of woven or feltedcotton, synthetic, or glass-fiber material in either a tube or envelope shape. Theyare one of the most efficient and cost-effective types of dust collectors availableand can achieve a collection efficiency of more than 99% for very fine particu-lates. This high efficiency is due to the dust cake formed on the surfaces of thebags. The filter cake is removed to hoppers by various shaking means. Limita-tions include plugging, short-circuiting, breakthrough, collection media fouling,

Liquid inlet

Liquidinlet

Throat

Figure 6.6 Venturi scrubber.Source: Wikipedia.org, ‘‘Venturi Scrubber’’, 2009; http://en.wikipedia.org/wiki/Venturi_scrubber


EXHAUST

SINGLE BAG SCHEMATIC

ΔP

REPRESSURINGVALVE

FILTERINGMODE

COLLECTIONHOPPER

COLLAPSING(BAG CLEANING MODE)

Figure 6.8 Baghouses.Source: Hutter, G.M., Meridian Engineering and Technology; http://www.meridianeng.com/airpolld.html

mg, xg mv+ mg, xv

Tg

Tv

Tvn

ms, Y, TL

me, Ye, Te

Qp

TgbTgd

mL, Y, TL

H

h

Qd

Tgn

dc

Qv

Qb

dt

Figure 6.7 Direct-contact evaporator.Source: Campos and Lage (2001).


accumulation of flammable gases and dusts, and unexpected bag failure due tochanges in operating procedures (Hutter, 1997).

Electrostatic precipitators

Electrostatic precipitators (ESPs; Figure 6.9), or electrostatic air cleaners, areparticulate collection devices that remove particles from a flowing gas (such asair) using the force of an induced electrostatic charge. To produce the free ionsand electric field, high internal voltages are required. ESPs are highly efficientfiltration devices that minimally impede the flow of gases through the device, andcan easily remove fine particles, such as dust and smoke, from the air stream. Incontrast to wet scrubbers, which apply energy directly to the flowing fluidmedium, an ESP applies energy only to the particulate matter being collected andis very efficient in its consumption of energy. Limitations include the largeinstallation space required, high potential for ignition sources, and susceptibilityto changes in moisture and resistivity (IUPAC, 2009).

Adsorption

The process of adsorption involves the molecular attraction of gas-phasematerials on to the surface of certain solids. This attraction may be chemical orphysical in nature and is predominantly a surface effect. Certain materials likeactivated carbon charcoal possess a large internal surface area and the presenceof physical attraction forces to adsorb large quantities of certain gases withintheir structure. The rate of adsorption is affected by the temperature,

Figure 6.9 Electrostatic precipitator.Source: Arizona State University, Electrical Engineering Department. ‘‘ElectricalEngineering for Pollution Control’’, January 2003; http://www.eas.asu.edu/~holbert/wise/electrostaticprecip.html


concentration, atmospheric pressure, and molecular structure of the gas. Limi-tations include the possible requirement of multiple units, flammable hydro-carbons, and chemical mixture problems (Hutter, 1997).

Odor control

The pulping process uses sulfur compounds to break wood down into pulp. Someof these sulfur compounds escape the process and are released into the atmo-sphere. Sulfur compounds, such as hydrogen sulfide, dimethyl sulfide, anddimethyl disulfide, are famous for their pungent odor and very low odorthresholds. Pulp and paper mills usually do not have odor control devices, butemitted sulfur compounds can be reduced by process modifications and improvedoperating conditions. For example, black liquor oxidation systems, whichoxidize sulfites into less reactive thiosulfates, can considerably reduce odoroussulfur emissions from the direct-contact evaporator, although the vent gases fromsuch systems become minor odor sources themselves. Also, noncondensableodorous gases vented from the digester/blow tank system and multiple effectevaporators can be destroyed by thermal oxidation, usually by passing themthrough the lime kiln. Efficient operation of the recovery furnace, by avoidingoverloading and maintaining sufficient oxygen, residence time, and turbulence,significantly reduces emissions of reduced sulfur compounds from this source aswell. The use of freshwater instead of contaminated condensates in the scrubbersand pulp washers further reduces odorous emissions (US EPA, 1995b).

Several new mills have incorporated recovery systems that eliminate conven-tional direct-contact evaporators. In one system, heated combustion air, ratherthan fuel gas, provides direct-contact evaporation. In another, the multiple-effectevaporator system is extended to replace the direct-contact evaporatoraltogether. In both systems, sulfur emissions from the recovery furnace/direct-contact evaporator can be reduced by more than 99% (US EPA, 1995b).

Controlling emissions is a vital part of a sustainable industry. Irresponsiblepollution, especially of odorous chemicals, can damage the environment and thepeople who live in it. The EPA does its part to ensure safe breathing environ-ments surrounding pulp and paper mills, but the leaders of the corporations haveto do their part too. Companies usually do what is best economically and notwhat is best morally or socially. If an emission control initiative will negativelyaffect a company’s stock market value, the initiative will probably not gothrough. Therefore, it is important that the EPA and other government agenciescontinue to put pressure on all manufacturing plants to keep lowering emissionsand waste every year. A good way to encourage ecoresponsibility is givingbonuses to plants that meet and exceed certain emission standards, and givingpenalties to plants that do not perform well. Without these incentives, corpo-rations will not go out of their way to improve emissions reduction, and theenvironment will continue to worsen (US EPA, 1995b).


6.3 Chemicals of concern and pollution sources

6.3.1 General information on pollution sources

The following provides a concise summary of the principal chemicals of concernand the sources of air emissions:

� Ammonia. Sources are digesters and the secondary treatment plant. This chemical isa concern because it is a precursor of fine particulate formation and it is an irritant.

� Carbon monoxide. Sources are the lime kiln and power boilers. This chemical isa concern because there is human visual impact at 50 ppm for 1 hour, death at morethan 750 ppm, and vegetation impact at higher levels.

� Carbon dioxide. Sources are the effluent treatment system and power boilers. Thischemical is a concern because it is a greenhouse gas.

� Carbonyl sulfide. The primary source is the recovery boiler. This chemical isa concern because it is a potential neurotoxin; acute (short-term) inhalation of highconcentrations of carbonyl sulfide may cause narcotic effects in humans. Carbonylsulfide may also irritate the eyes and skin in humans.

� Chlorine and chlorine dioxide. Sources are generation systems, extraction stagescrubbers, and bleach plant ‘‘upsets’’ such as explosions. Chlorine is present in almostall areas of a mill, including wood yards at facilities that rely on chlorine dioxidebleaching. Chlorine dioxide breaks down to release chlorine into the air and from thepulp. Chlorine and chlorine dioxide exposures can cause significant short-term peaksthat exceed regulatory limits, and pose a health risk. Chlorine is a severe short- andlong-term respiratory irritant at levels above 1 ppm (odor threshold 60–200 ppb);chlorine dioxide is a severe short- and long-term respiratory irritant at levels above0.1 ppm (odor threshold 100 ppb; NIOSH, 1987). Both compounds kill at highlevels. The characteristic response to short-term chlorine and chlorine dioxideexposure is reactive airway dysfunction syndrome (RADS), airway inflammation,and bronchial hyper-responsiveness, which may last for 3 years or more, and canresult from one acute exposure. Adverse effects on immune system, blood, heart, andrespiratory system have been reported from numerous reports in laboratory studies.

� Chloroform. Sources are the effluent treatment system and bleach plant. Thischemical is a recognized carcinogen, suspected respiratory, cardiovascular or blood,liver and kidney toxicant, and endocrine and neurological disruptor.

� Dioxins and furans. Sources are the recovery boiler and the power boiler if burning‘‘salty’’ hog fuel. Health effects associated with dioxins and the chemically similarpolychlorinated biphenyls (PCBs), probably through action on the chemicalmessengers of the body, and passed on through the generations, include: reproductiveeffects, from low sperm count to endometriosis; hyperactivity; allergies and immuneand endocrine system malfunctions; diabetes; low birth weight, poor motor coor-dination and lower IQ for children. Dioxins are classified as a human carcinogen bythe International Agency for Research on Cancer (IARC) and they are recognized astumor promoters, along with their other roles in modifying and disrupting growthfunctions. Adverse health effects include skin disease, immunosuppression, respira-tory effects, cardiovascular effects, liver effects, reproductive toxicity, and they havea Carcinogenicity 2B rating.


� Hydrogen chloride (part of particulate matter). The primary source is the recoveryboiler. This chemical is a concern because it is a suspected gastrointestinal or livertoxicant, and respiratory and skin or sense organ toxicant.

� Methanol. Sources are the recovery boiler, oxygen delignification systems, and theeffluent treatment system. Methanol has been accepted by the US EPA as a surrogatemonitoring measurement for a wide range of the hazardous air pollutants (chlori-nated compounds) that the USA requires polluters to report, and the US cluster rulesnow require mills to collect these gases and burn them in the fire zone of the recoveryboiler. Methanol is a concern because it is a suspected developmental toxicant,neurotoxin, gastrointestinal or liver toxicant.

� Nitrogen oxides (NOx). Sources are the lime kiln, recovery boiler, power boiler, gasturbines, and brown stock washers. NO2 is an acute respiratory irritant at 1 ppm for15 minutes. It is a harmful air contaminant, a precursor to smog, ground-level ozone,fine particulates, and acid rain. It is harmful to humans, vegetation growth, andhealth.

� Particulate matter (PM). Sources are the recovery boiler, lime kiln, smelt dissolvingtank, power boilers, wood chip yard, and dust from landfills. PM can be material,such as wood, lime, or road dust, or chemical compounds created with carbon,metallic oxides and salts, acids, oils, etc. The greatest health impact is felt fromparticles of the smallest size – designated PM10 (microns) or less, and especiallyPM2.5 – which penetrate the lungs and stay there, frequently delivering a toxic loadto the body. Fine particulates are linked to serious health impacts, including chronicbronchitis, asthma, and premature deaths. PM2.5 has been recognized to have thepotential for the greatest health impact on a larger segment of the general public.Secondary particles are formed through chemical reactions involving the precursorsNOx, volatile organic compounds (VOCs), sulfur oxides (SOx), and ammonia(NH3). The US Federal standard is 150 mg/m3; health impacts include children’sabsenteeism due to asthma at 50 mg/m3. British Columbia has set a new air-qualityobjective of 25 mg/m3 for PM2.5; the Canadian Council of Ministers of Environmenthave determined a Canada Wide Standard for PM, focused on the fine fraction ofPM, smaller than 2.5 microns, known as PM2.5, of 30 mg/m3 averaged over 24hours, on be achieved by 2010.

� Phenols. Sources are power boilers, brown stock washers, chip bins, and the effluenttreatment system. This chemical is a concern because it is a smog precursor, it killsfish, it is toxic on kidneys of humans, and it has a wide range of sensitive effects,including on blood, immune and nervous systems.

� Sulfur oxides (SO2, SO3, and solid sulfates). Sources are the recovery boiler, lime kiln,power boilers, brown stock washers, and chip bins. Anywhere sulfur-containingcompounds, including oil and gas, are burned, there will be sulfur oxide emissions.These chemicals are irritating to eyes and respiratory system at 5 ppm for 10 minutes.SOx is a precursor to fine PM formation. Sulfuric acid is implicated in bronchitis,emphysema, eye, nose, and stomach irritations, and possible lung cancer in exposedworkers.

� Total reduced sulfur compounds (including hydrogen sulfide, methyl mercaptan,dimethyl sulfide, and dimethyl disulfide). The primary source of these chemicals is therecovery boiler. These chemicals are associated with an extraordinary foul smell.They are toxic and heavier than air, thus traveling long distances to ground level. H2Sirritates eyes at 50 ppm and causes death at 100 ppm. The human nose detects H2S atabout 1 ppb.


� Miscellaneous. Miscellaneous chemicals that are emitted as air pollution includealcohols, terpenes, acetaldehyde, nitrates, fungi (Aspergillus fumigatus and A. ver-sicolor), bioaerosols (endotoxin), benzene and assorted substituted benzenes, chlo-rinated benzenes and phenolics, guaiacols, and various VOCs, many of themunquantified and unidentified, but including dichloroacetic acid methyl ester, 2,5-dichlorothiophane, styrene, toluene and xylenes, all varying from day to day,depending on feed stock and ‘‘upsets’’ anywhere in the mill. The EPA has noted underthe Clean Air Act that emissions from pulp and paper derive from chemicals used orby-products, and include alcohols, aldehydes, benzene, ketones, polyaromatichydrocarbons (PAHs), and phenolics. All of these chemicals are associated with heartdisease.

In addition to air emissions there are also solid wastes and significant liquideffluents, which include pulping liquors and bleaching effluents. Bleachingeffluents contain chlorinated dioxins and furans, chloroform, and various otherchlorinated compounds.

The impact of the pulp and paper sector on greenhouse gas emissions iscomplicated, as atmospheric carbon dioxide is the ultimate carbon source for thesector’s product. Arguments have been made that as long as the carbon issequestered in paper, it is not contributing to global warming. This viewpointallows us to subtract a portion of the total greenhouse gas emissions attributableto the sector (primarily due to its energy consumption) to account for the carbonremoved from the atmosphere. We actually like this argument within the contextof durable products like construction materials, which have an expected lifetimemeasurable in decades. We may make the same argument for products likecertain packaging materials made from plastics derived from renewable sourcesthat are used as an alternative to plastics derived from fossil fuels. But in the caseof paper products much of the output of the sector is returned to the atmosphereafter a relatively short period of time. The products are either burned ordeposited in landfills where they decompose biologically. Within the context ofa normal life-cycle assessment, we find this argument to be frivolous.

The National Emission Trends (NET) database reports air emissions data forcertain key criteria pollutants (ozone precursors). Hazardous air pollutantemissions data are available from the TRI. For the pulp and paper sector, thetotal emissions are, to say the least, impressive. For criteria pollutants, 1999reporting shows the following criteria pollutants:

� VOCs – 201,318 tons per year;� nitrogen oxides (NOx) – 325,958 tons per year;� fine particles, under 2.5 microns (PM2.5) – 65,237 tons per year;� hazardous air pollutants (HAPs) – 23,952 tons per year.

For VOCs, the pulp and paper sector is the second highest emitter of allmanufacturing sectors, second only to commodity chemicals. For NOx, pulp andpaper is the fourth highest, behind electric power, oil and gas extraction, andcommodity chemicals. For fine particles, it is second only to electric power. ForHAPs, it stands fifth, behind commodity chemicals, construction, petroleumrefining, and furniture.


As impressive as these figures are, they are dwarfed compared to those of twoto three decades earlier. We can get a sense of this from the the American Forestand Paper Association (AF&PA) Progress Report of December 2002 (http://www.afandpa.org/) in which the AF&PA lists a number of industry bench-marks, based on 1999 data from its members. Among the benchmarks listed forpulp and paper mills are:

� Water quality:� wastewater generation rate – 12,600 gallons per ton of production (a 44%

reduction since 1975);� biological oxygen demand (BOD) – 2.9 pounds per ton of production (an 84%

decrease since 1975);� total suspended solids (TSS) – 4.2 pounds per ton of production (a 68% decrease

since 1975);� adsorbable organic halides (AOX) – less than 0.4 kilograms per metric ton of

chemically bleached pulp (a 90% decrease since 1975).� Air quality:� sulfur dioxide (SO2) – 9 pounds per ton of production (a 65% decrease since

1980);� nitrogen oxides (NOx) – 6 pounds per ton of production (a 23% decrease since

1980);� total reduced sulfur (TRS) – 0.9 pounds per ton of kraft pulp production.

� Solid waste (nonhazardous) generation rate – 287 pounds per ton of product(excluding wood wastes that include a number of persistent and bioaccumulativetoxins (such as chlorinated dioxins and furans) that can impact the food chain, andcan collect in sediments).

6.3.2 Chemical exposure and toxicological profiles of chemicals

The paper and allied products industry (SIC 26) can be broken down into twocategories: pulp and paper mills that process raw wood fiber or recycled fiber tomake pulp and/or paper, and converting facilities that use these primary mate-rials to manufacture more specialized products such as paperboard boxes,writing paper, and sanitary paper. Pulp mills separate the fibers of wood or othermaterials, such as rags, linters, wastepaper, and straw, in order to create pulp.These mills commonly use chemical, semi-chemical, or mechanical processes inthe creation of pulp and may create toxic co-products such as turpentine and talloil. Paper mills primarily are engaged in manufacturing paper from wood pulpand pulp derived from other fibers.

Most of the chemical emissions of the paper industry come from chemicalwood pulping. Chemical wood pulping involves the extraction of cellulose fromwood by dissolving the lignin that binds the cellulose fibers together. The fourprocesses principally used in chemical pulping are kraft, sulfite, neutral sulfitesemi-chemical, and soda. The first three of these display the greatest potential forcausing air pollution. The kraft process alone accounts for over 80% of thechemical pulp produced in the USA. The choice of pulping process depends on


the desired product, wood species available, and economic considerations. Eachprocess has a specific set of emissions.

The kraft process is the digesting of wood chips at elevated temperature andpressure in ‘‘white liquor’’, which is an aqueous solution of sodium sulfideand sodium hydroxide. This process emits a wide variety of particulate matterand chemicals. Particulate emissions from the kraft process occur largely fromthe recovery furnace, lime kiln, and smelt dissolving tank. These emissions aremainly sodium salts, with some calcium salts. To control these particles a direct-contact evaporator and an electrostatic precipitator (ESP) are used for overallremoval efficiency between 85% and 99%.

Kraft pulping also releases a lot of chemical emissions. Since the process isdone in sodium sulfide solution, many of the chemicals released contain sulfur.Examples include hydrogen sulfide, sulfur dioxide, dimethyl sulfide, anddimethyl disulfide. These compounds are the major source of kraft mill odoremissions, and they can be detected easily due to their very low odor thresholds.Even though these kraft mills produce very odorous emissions, very few of themhave odor-controlling devices.

Not all kraft mill emissions are sulfur based. Some of the major chemicals thatare released are methanol, ammonia, carbon monoxide, formaldehyde, phenol,hydrochloric acid, and sulfuric acid. Many of these pollutants are produced byside processes including steam power production. Most of the chemicals emittedare on the EPA’s hazardous air pollutants list, and they need to be monitored andcontrolled at the highest level possible. The EPA pays attention to and regulatesthese chemicals due to their individual health and environmental effects. Thischapter describes each chemical, how they are produced and released, howhumans and animals can be exposed, and what effects exposure can lead to (USEPA 1995b).

The following chemicals are discussed:

� Acetaldehyde� Acrylonitrile� Ammonia� Benzene� Chlorine disulfide� Chlorine� Chloroform� Chromium(VI)� Dioxin� Ethylene glycol� Formaldehyde� Formic acid� Hydrochloric acid� Hydrogen fluoride� Hydrogen sulfide� Methanol� Methyl mercaptan� Pentachlorophenol


� Phenol� Sulfuric acid� Sulfur dioxide� Toluene.

Acetaldehyde

Acetaldehyde (CASRN 75-07-0) is a VOC with the formula CH3CHO. It isa flammable, colorless liquid with a pungent, fruity odor. Green plants produce itas they break down their food, and it is also found naturally in ripe fruit, coffee,and bread. It is produced in large amounts (740 million pounds in 1989) by twocompanies in the USA. Acetaldehyde is most commonly used as an intermediatein the chemical production of acetic acid and other chemicals.

Humans can be exposed to acetaldehyde in the workplace or in the environ-ment following a release into air, water, soil, or groundwater. Eating ripe fruit,drinking coffee, and smoking a cigarette can also expose humans or animals toacetaldehyde. Once released into air, acetaldehyde immediately evaporates anddisperses. It does not cause direct harm to the atmospheric environment by itself,but can contribute to the formation of photochemical smog in the presence ofother VOCs. Acetaldehyde does not bind well with soil, so most of the under-ground contamination occurs in groundwater.

The EPA has declared that acetaldehyde is a hazardous air pollutant (HAP).Health effects on humans and animals depend on the concentration and time ofexposure. The health of the person or animal exposed, as well as the conditionsof the environment, can also influence the effects of exposure. Acute inhalationexposure (25–200 ppm for 15–30 minutes) to humans can cause irritation ofthe eyes and respiratory tract, as well as altered respiratory function. Animalssuch as rats, exposed to acute inhalation of higher concentrations, showed skinand eye irritation and notable cellular alterations in the respiratory epitheliumand hyperkeratosis of the forestomach (Appleman et al., 1986). Also, acutetoxicity to aquatic life has been observed in concentrations in the range of 1–100 mg/l.

Human health effects associated with the chronic exposure to acetaldehydeare unknown. Evidence collected through animal studies show that exposure toacetaldehyde over long periods of time has numerous adverse effects. Ratsexposed to 2200 or 5000 ppm for 6 hours per day, 5 days per week for 4 weeksexperienced death, decreased organ weight, growth retardation, and severelydamaged respiratory tracts. Animal studies also showed that long-term exposureto acetaldehyde caused an increase in nasal tumors. These and similar studies ledthe EPA to declare that acetaldehyde is a class B2, probable human carcinogen.The EPA also determined the reference concentration (RfC), the lethal dose(LD50) and lethal concentration (LC50), the least-observed-adverse-effect level(LOAEL), the no-observed-adverse-effect level (NOAEL), and the permittedexposure limit (PEL) (US EPA, 1991a). The values for these properties can befound in Table 6.4.


The reference dose (Rfd) and reference concentration (RfC) are estimates(with uncertainty spanning perhaps an order of magnitude) of an applied doseor continuous inhalation exposure to the human population (including sensitivesubgroups) that is likely to be without an appreciable risk of deleterious effectsduring a lifetime. The LD50 and LC50 are the dose and concentration,respectively, required to kill at least 50% of the tested sample. The LC50

usually requires a given exposure time. The LOAED is the lowest concen-tration or dose that had an effect in a given trial, and the NOAEL is thehighest concentration or dose where no effect is observed in a given trial. Thepermitted exposure limit is a concentration ceiling that cannot be exceeded inany occupational workplace.

Acrylonitrile

Acrylonitrile (CASRN 107-13-1), also known as AN or vinyl cyanide, is a man-made VOC. It is a pungent smelling, colorless flammable liquid with thechemical formula CH2CHCN. Its vapors are highly flammable and can explodewhen exposed to an open flame. Five companies produce AN in the USA, andthey produced a total of 2.5 billion pounds in 1993. AN is most commonly usedto make acrylic and modacrylic fibers, but can also be used to produce high-impact plastics, packaging plastics, adiponitrile (a chemical involved in theproduction of nylon), dyes, drugs, and pesticides.

Exposure to AN may occur in the environment following releases to air, water,soil, and groundwater. Humans can also be exposed to AN in the workplace, bysmoking a cigarette, or by breathing automobile exhaust. AN can also beabsorbed through skin contact. It is not likely to be stored in plants and animals,however, due to easy breakdown and removal. AN evaporates when exposed toair and dissolves in water. Once dissolved in water, AN has relatively slowevaporation and biodegration rates. AN can stay dissolved in water for 6–20days. There is no evidence that AN directly harms the atmospheric environment,but it reacts with other VOCs to produce photochemical smog.

The EPA has declared AN an air toxic. Health effects on humans and animalsdepend on the concentration and time of exposure. The health of the person oranimal exposed, as well as the conditions of the environment, can also influencethe effects of exposure. The symptoms of acute toxicity for AN resemble those ofcyanide, which can adversely affect the nervous system, the blood, the kidneys,and the liver. There have been many instances of child mortality due to exposureto AN vapors, whereas adults experienced only mild symptoms when exposed to

Table 6.4 Toxicological characterization data for acetaldehyde

RfC LD50 (rats) LC50 (rats) LOAEL NOAEL PEL

0.009 mg/m3 1.93 g/kg 36 g/m3 (30 min) 720 mg/m3 702 mg/m3 360 mg/m3

Source: US EPA (1991a).


the same environment. Prior to death, these children experienced respiratorymalfunction, lip cyanosis, and tachycardia. Workers in a rubber manufacturingplant experienced irritation of the mucous membranes, nausea, headaches, andnervous irritability after being exposed to 15–100 ppm for 20–45 minutes. Thesesymptoms abated when exposure ceased (Wilson et al., 1948). AN is also toxicto most aquatic species exposed acutely. A study done on snails showed a 100%mortality rate in a concentration of 0.24 mg/l for 24 hours.

The results of studies in humans with long-term exposure to AN have beeneither negative or inconclusive for noncancer chronic effects. Studies on animals,however, have shown different results. Animals such as rats, rabbits, andmonkeys showed signs of toxicity when exposed to concentrations of 50–200ppm for 8 weeks. Their symptoms included irritation of the eyes and nose,gastrointestinal disturbances, and weakness of the hind legs. The animalsrecovered after exposure ceased. Cats and dogs showed even higher toxicity,including death, at the same concentration levels (Dudley et al., 1942). Also,exposure to pregnant animals orally or by inhalation showed signs of develop-mental toxicity, including malformations in fetuses. Table 6.5 shows values forsignificant properties of AN.

Exposure to AN has been associated with cancer in humans. The EPA clas-sifies AN as a B1, probable human carcinogen. This was based on a study thatfollowed 1345 textile workers who were exposed to 5–20 ppm acrylonitrile. In10 years of follow-up, there were 25 cases of cancer, and five of those cases wererespiratory cancer. The expected number of respiratory cancer cases for thatsample was 1.6 (O’Berg, 1980). This significant difference between expected andobserved instances proved to the EPA that AN was indeed a carcinogen. Furtherlaboratory experiments show that AN is also carcinogenic to animals (US EPA,1991b).

Ammonia

Ammonia (CASRN 7664-41-7) is another harmful chemical released by thepaper industry. Ammonia, a.k.a. anhydrous ammonia, has a pungent odor and isusually found in gas form due to its boiling point of �33�C. The most commonuse of ammonia is the production of fertilizer: 83% of all ammonia is used infertilizers. Ammonia is also commonly seen in household cleaning products inthe form of ammonium hydroxide, which is simply ammonia dissolved in water.Producing the necessary amount of ammonia for the modern world is not aneasy task, and it represents 1% of the world energy budget.

Table 6.5 Toxicological characterization data for acrylonitrile


0.002 mg/m3 93 mg/kg 470 mg/m3 (4 h) 43 mg/m3 10 mg/kg/day 4.3 mg/m3

Source: US EPA (1991b).


Ammonia can be released into the environment into air, water, soil, andgroundwater. The most common releases of ammonia are effluent dischargesfrom industrial processes and run-off from fertilized fields. Humans can beexposed to the hazards of ammonia through ingestion of contaminated food orwater, inhalation or skin contact.

The EPA has classified anhydrous ammonia as an extremely hazardoussubstance. Ammonia is very corrosive, a property that causes most of thenegative human health effects. Much like most toxic volatile liquids, ammoniavapor can cause chemical burns of the respiratory tract, skin, and eyes uponinhalation. Upon contact with the water present in skin, mucous membranes,and eyes, it forms ammonium hydroxide, which is a highly ionized weak basethat causes tissue necrosis. Specifically, ammonium hydroxide causes saponifi-cation of cell membrane lipids resulting in cell disruption and death. Addition-ally, it dehydrates cells, which initiates an inflammatory response, and furtherdamages the surrounding tissues. Direct contact with liquid ammonia results incryogenic injury in addition to the alkali burns. Airway blockage and respiratoryinsufficiency may be lethal outcomes of exposure to anhydrous ammonia vaporsor concentrated aerosols. Ingestion of concentrated ammonium solutions mayproduce severe burns and hemorrhage of the upper gastrointestinal (GI) tract.Hemorrhaging and open wounds of the GI tract can lead to infection andnecrosis. The negative effects that have been observed in humans exposed toammonia gas and ammonium salt aerosols have also been observed in animals.Hepatic and renal effects have been reported in animals and humans (US EPA,1991c). The US EPA (1991c) has released the toxicological properties forammonia given in Table 6.6.

Benzene

Benzene is another hazardous air pollutant that can result from the paper-making process. Benzene (CASRN 71-43-2) is an organic chemical compoundwith chemical formula C6H6. It is a colorless and highly flammable liquid, witha sweet smell. It is an important industrial solvent and precursor in theproduction of drugs, plastics, synthetic rubber, and dyes. It is a gasoline additive,but due to its health effects it is now highly controlled.

The EPA has classified benzene as a hazardous air pollutant. Regulations andlaws have been put into place since the 1970s in order to control and limit theamount of benzene released into the environment. Benzene can be absorbed intothe system through inhalation, oral ingestion, and skin contact. Dermal

Table 6.6 Toxicological characterization data for ammonia


0.1 mg/m3 350 mg/kg 5.4 g/m3 (1 h) 17.4 mg/m3 6.4 mg/m3 35.5 mg/m3


absorption is rare, however, due to benzene’s rapid evaporation from the skin.Distribution throughout the body occurs quickly after exposure by all routes,and accumulation in fatty tissues is also apparent.

Individual case reports of death from acute oral exposure to benzene haveappeared in the literature since the early 1900s. The benzene concentrationsingested by the victims often were not known. However, lethal oral doses forhumans have been estimated at approximately 125 mg/kg (Thienes and Haley,1972). Accidental ingestion and attempted suicide with lethal oral doses ofbenzene have produced the following signs and symptoms: staggering gait,vomiting, shallow and rapid pulse, somnolence, and loss of consciousness fol-lowed by delirium, pneumonitis, collapse, and then central nervous systemdepression, coma, and death (Thienes and Haley, 1972).

Human exposure to benzene occurs primarily via inhalation in the workplace,from gasoline vapors, tobacco smoke, and automotive emissions. Individualsexposed to benzene exhibit bone marrow depression, as evidenced by anemia(decreased red blood cell (RBC) count), leukopenia (decreased white blood cell(WBC) count), and/or thrombocytopenia (decreased platelet count). A depres-sion of all three elements is called pancytopenia, and the simultaneous depres-sion of RBCs, WBCs, and platelets, accompanied by necrosis of the bonemarrow, is diagnostic of aplastic anemia. Patients with aplastic anemia also haveexhibited bilirubinemia, changes in osmotic fragility of erythrocytes, shortenederythrocyte survival time, increased fecal urobilinogen, and mild reticulocytosis(Aksoy, 1991).

The human occupational inhalation study of Rothman et al. (1996) wasselected by the EPA as the principal study for determining the RfC and RfD ofbenzene. Table 6.7 summarizes the study’s findings.

Benzene is also classified as a known human carcinogen (category A) by theEPA and American Conference of Governmental Industrial Hygienists(ACGIH). Significantly increased risks of leukemia, chiefly acute myelogenousleukemia, have been reported in benzene-exposed workers in the chemicalindustry, shoemaking, and oil refineries. Aksoy et al. (1974) reported effects ofbenzene exposure among 28,500 Turkish workers employed in the shoeindustry; 26 cases of leukemia and a total of 34 leukemias or preleukemias wereobserved, corresponding to an incidence of 13/100,000 (by comparison with 6/100,000 for the general population). Numerous additional studies continue toshow that benzene is a dangerous human carcinogen. These studies show that

Table 6.7 Toxicological characterization data for benzene

RfD RfC LD50 (rats) LC50 (rats) LOAEL NOAEL PEL

0.004 mg/kg/day

0.03mg/m3

930mg/kg

32.4g/m3 (7 h)

24.6mg/m3

1.7mg/m3

3.24mg/m3

Source: Rothman et al. (1996).


the control of benzene emissions is a vital part of keeping the human populationsafe (US EPA, 2003a).

Chlorine dioxide

Chlorine dioxide (CASRN 10049-04-4; ClO2) is a yellow to reddish-yellow gasat room temperature that is stable in the dark but unstable in the light. It isa strong oxidizing agent that under oxidant demand conditions is likely toreduce to chlorite (CASRN 7758-19-2; ClO2

�), another strong oxidizing agent.This strong oxidizing ability makes it useful as a drinking water disinfectant.Other uses of chlorine dioxide include bleaching textiles and wood pulp. Thisbleaching process is what releases chlorine dioxide into the atmosphere andpaper mill effluents.

The EPA has classified chlorine dioxide as a regulated toxic substance.Exposure can occur via inhalation, ingestion, or skin contact. Since ClO2 isgaseous at room temperature, inhalation and dermal exposure are morecommon than ingestion, but there are reports of oral exposure. Two studies havebeen conducted to assess the short-term toxicity of chlorine dioxide. In the firststudy (Lubbers et al., 1981), a group of 10 healthy male adults drank 1000 ml(divided into two 500-ml portions, separated by 4 hours) of a 0 or 24 mg/lchlorine dioxide solution. In the second study (Lubbers et al., 1984), groups of10 adult males were given 500 ml distilled water containing 0 or 5 mg/l chlorinedioxide for 12 weeks. Neither study found any physiologically relevant alter-ations in general health.

Several case reports of accidental inhalation exposure to chlorine dioxide havebeen reported in the literature. Elkins (1959) described the case of a bleach tankworker who died after being exposed to 19 ppm chlorine dioxide (52 mg/m3) foran unspecified amount of time. A different worker exposed at the same timesurvived. Elkins also stated that 5 ppm was definitely irritating to humans. Ina case reported by Exner-Freisfeld et al. (1986), a woman experienced coughing,pharyngeal irritation, and headache after inhaling an unknown amount ofchlorine dioxide inadvertently generated while bleaching flowers. Seven hoursafter exposure, the woman was hospitalized with cough, dyspnea, tachypnea,tachycardia, rales on auscultation, marked leukocytosis and decreased lungfunction (US EPA, 2000). Using these and other studies, the EPA and Occupa-tional Safety and Health Administration (OSHA) have obtained the toxicologydata for chlorine dioxide given in Table 6.8.

Table 6.8 Toxicological characterization data for chlorine dioxide


0.03mg/kg/day

0.0002mg/m3

292mg/kg

2.07g/m3

193mg/m3

386mg/m3

0.3mg/m3

Source: US EPA (2000).


Chlorine

Chlorine (CASRN 7782-50-5; Cl2) is a highly toxic, greenish-yellow gas with thevery pungent odor that gives swimming pools their smell. Chlorine gas isa powerful oxidant and is used in bleaching and disinfectants. Due to itsbehavior and adverse effects on human health, chlorine has been classified asa hazardous air pollutant and a regulated toxic substance by the US EPA.

Humans are most likely to be exposed to chlorine through inhalation of thegas. Severe acute effects of chlorine exposure in humans have been well docu-mented since World War I, when chlorine gas was used in chemical warfare.Other severe exposures have resulted from the accidental rupture of chlorinetanks. These exposures have caused death, lung congestion, pulmonary edema,pneumonia, pleurisy, and bronchitis (Hathaway et al., 1991). Even concentra-tions as low as 5 ppm caused respiratory complaints, corrosion of the teeth,inflammation of the mucous membranes of the nose, and susceptibility totuberculosis among chronically exposed workers (ACGIH, 1991).

Molecular chlorine is rarely found in its liquid phase unless low tempera-tures and high pressures are involved. If, somehow, a person comes into contactwith this liquid, frostbite burns of the skin and eyes may occur (Genium, 1992).Table 6.9 shows the toxicology data for chlorine.

Chlorine is very toxic and can be lethal in relatively low concentrations.Storage and transfer of chlorine for our many modern processes must be donecarefully. Accidental leaks and releases cause serious human health problemsand damage to the environment and ozone layer. Therefore, the release andemissions of chlorine gas must be kept to a minimum (US EPA, 1994b).

Chloroform

Chloroform (CASRN 67-66-3), also called trichloromethane, is a colorless,volatile liquid with a distinct odor. It is a nonflammable substance with thechemical formula CHCl3. It is slightly soluble in water and is readily misciblewith most organic solvents. Because of chloroform’s volatility, it tends to escapefrom contaminated environmental media (e.g. water or soil) into the air, andmay also be released as vapor from some types of industrial or chemical oper-ations, including the paper production process. Therefore, humans may beexposed to chloroform by ingestion of contaminated drinking water, food, orsoil, by dermal contact with contaminated media (especially water), and byinhalation of vapor (especially in indoor air).

Table 6.9 Toxicological characterization data for chlorine

RfD LD50 (rats) LC50 (rats) LOAEL NOAEL PEL

0.1 mg/kg/day N/A 850 mg/m3 (1 h) N/A 14.4 mg/kg/day 3 mg/m3



The EPA has declared chloroform a hazardous air pollutant and a toxicsubstance due to its adverse effects on human health. The workplace, or otherindoor facilities, are the most common sites of exposure by inhalation. A numberof epidemiological studies have been performed to investigate the occurrence ofadverse effects in populations of workers exposed to chloroform vapors in theworkplace. These studies show that long-term exposure to concentrations of20–200 ppm (100–1000 mg/m3) of chloroform produces mainly neurologicaleffects. The symptoms observed are fatigue, nausea, vomiting, lassitude, drymouth, and anorexia (Phoon et al., 1983). Some studies have also observedeffects on the liver, including jaundice, increased serum enzyme levels, andincreased liver size (Bomski et al., 1967; Phoon et al., 1983).

Drinking water is often contaminated with chloroform, and this leads tohuman exposure by ingestion. There have been no studies of toxicity or cancerincidence in humans chronically exposed to chloroform alone, but there havebeen a number of studies on cancer risk in humans exposed to chlorinateddrinking water. Chlorinated drinking water typically contains chloroform. Itshould also be noted that humans exposed to chloroform in drinking water arelikely to be exposed both by direct ingestion and by inhalation of chloroform gasreleased from the water into indoor air. Some of the studies conducted detectedassociation between exposure to chlorinated water and cancer (mainly bladdercancer). The EPA has not declared chloroform a human carcinogen, however,because of the uncertainty of exactly what impurity in the water was actuallyincreasing cancer incidences (US EPA, 1994a, 1998a). Table 6.10 shows thetoxicological data for chloroform.

Although the EPA and other regulatory agencies have declared chloroformdangerous, there is not enough data and evidence to fully understand chlor-oform’s effect on human health. If cities and countries continue to use chlori-nation to purify drinking water, it is important that researchers continue to studychloroform. If studies are not conducted, the future could be filled withunforeseen problems caused by chlorinated drinking water (US EPA, 2001).

Chromium(VI)

Hexavalent chromium (CASRN 18540-29-9) is, and can react to form, manydifferent dangerous chemicals that are released by the paper industry. Chro-mium(VI) refers to chemical compounds that contain the element chromium inthe þ6 oxidation state. Chromium can exist as oxo species such as CrO3 and

Table 6.10 Toxicological characterization data for chloroform


0.01 mg/kg/day 1194 mg/kg 47 g/m3 (4 h) 12.9 mg/kg/day NA 240 mg/m3



CrO42�, which are strongly oxidizing. In solution, it exists as hydrochromate

(HCrO4�), chromate (CrO4

2�), and dichromate (Cr2O72�) ionic species (Cotton

and Wilkinson, 1980). Hexavalent chromium may exist in aquatic media aswater soluble complex anions and may persist in water (Callahan et al., 1979).

Humans can be exposed to chromium via inhalation, ingestion or skincontact. Cr(VI) is considerably more toxic than Cr(III). A cross-sectional studyof 155 villagers reported the effects of environmental contamination of wellwater adjacent to a chromium alloy plant. Cr(VI) concentrations were reportedas 20 mg/l, with an estimated dose rate of 0.57 mg/kg/day (Zhang and Li, 1987).Reported effects at this dose included oral ulcers, diarrhea, abdominal pain,indigestion, vomiting, leukocytosis, and presence of immature neutrophils.Other reports of toxic effects in humans are limited to case reports from acci-dental poisonings. Some Cr(VI) compounds (such as potassium tetrachromateand chromic acid) are potent oxidizing agents, and are thus strong irritants ofmucosal tissue. Effects included metabolic acidosis, acute tubular necrosis,kidney failure, and death (Saryan and Reedy, 1988).

Occupational exposure to chromium compounds has been studied in thechromate production, chrome-plating, chrome pigment, ferrochromiumproduction, gold mining, leather tanning, and chrome alloy production indus-tries. Mancuso and Hueper (1951) conducted a proportional mortality study ofa cohort of chromate workers (employed for longer than 1 year from 1931 to1949 in a Painesville, OH, chromate plant) in order to investigate lung cancerassociated with chromate production. Of the 2931 deaths of males in the countywhere the plant is located, 34 (1.2%) were due to respiratory cancer. Of the 33deaths among the chromate workers, however, 6 (18.2%) were due to respira-tory cancer. Within the limitations of the study design, this report stronglysuggested an increased incidence in cancer in the chromate production plant.Chronic or acute inhalation can also lead to metal fume fever, which is char-acterized by flu-like symptoms with metallic taste, fever, chills, cough, weakness,chest pain, muscle pain, and increased WBC count. Coughing, fever, weight loss,and pneumoconiosis are also common. Table 6.11 shows the toxicology data forchromium(VI).

Chromium(VI) and all the compounds it associates with are highly dangerous.Any employees or neighbors of a chromium plant should take notice andnecessary precautions to reduce their risk of cancer or other health effects (USEPA, 1998b).

Table 6.11 Toxicological characterization data for chromium(VI)


0.003mg/kg/day

8 � 106

mg/m352

mg/kg217

mg/m3 (4 h)0.002

mg/m32.5

mg/kg/day1

mg/m3



Dioxins

A dioxin is a heterocyclic, organic, anti-aromatic compound with the chemicalformula C4H4O2. The term ‘‘dioxins’’, however, is commonly used to describehazardous air pollutants known as polychlorinated dibenzodioxins (PCDDs).These PCDDs are created by the combination of chlorine and heat, along witha few other necessary components. The release of dioxins is very common incombustion, chlorine bleaching, and manufacturing processes. 2,3,7,8-Tetra-chlorodibenzo-p-dioxin (TCDD) is the best known and most toxic PCDD.

TCDD is one of the most, if not the most, toxic and carcinogenic substancesknown to man. TCDD has been given a 1 on the toxic equivalency factor (TEF),which is based on a scale from 0 to 1, 1 being the highest. Although it has thehighest TEF rating possible, TCDD’s toxicity varies greatly from species tospecies. For example, in guinea-pigs, an LD50 of 0.6 mg/kg was recorded, ascompared with an LD50 of greater than 5000 mg/kg in Syrian hamsters. Expla-nations for this variation include differences in the Ah receptor, such as size,transformation, and binding to the dioxin response element, pharmacokinetics(metabolic capacity, tissue distribution), and body fat content (Geyer et al.,1990; Pohjanvirta et al., 1998; van den Berg et al., 2000).

TCDD is very dangerous because it bioaccumulates in fatty tissues very well,and takes a very long time to metabolize and remove from the body. Exposure tosmall concentrations over time can lead to the buildup of dangerous levels.Humans are mostly exposed to TCDD through inhalation of polluted air oringestion of contaminated foods. The International Agency for Research onCancer (IARC) classified TCDD as a Group 1 carcinogen. High levels ofexposure have been shown by epidemiological studies to lead to an increasedrisk of tumors at all sites (Zambon et al., 2007). Noncancer effects on humanhealth include a severe form of persistent acne, called chloracne, developmentalabnormalities in the enamel of children’s teeth, central nervous systempathology, thyroid disorders, damage to immune systems, endometriosis, anddiabetes.

Studies performed on animals have shown even more adverse effects ofexposure to TCDD. One study performed by Kociba et al. (1976) exposed rats toTCDD concentrations of 0.001–1 mg/kg/day. More than half of the rats thatwere exposed to 1 mg died within the trial period of 13 weeks plus 49 days ofpost-trial observation. The rats exposed to the lesser doses showed signs ofincreased liver weight. Smits-van Prooije et al. (1993) conducted a study on30 pregnant rats. The rats were given a single dose of 0, 0.2, 0.6 or 1.8 mg/kg.Their pups were followed through to breeding about 1 year later. The high-dosepups had 2/16 successful pregnancies, compared to 15/17 and 11/17 at the 0.2and 0.6 mg/kg doses. This study provides strong evidence for the fact that TCDDhas adverse effects on mating behavior and fertility. There is not much toxico-logical data, such as LOAEL, NOAEL, RfC, and RfD for TCDD, but the knownLD50 for rats is 0.043 mg/kg (Stahl et al., 1992). This is lower than the value forthe previously discussed chemicals.


Dioxins are among the worst pollutants in the atmosphere today. They arevery toxic and carcinogenic, and it is very hard to rid them from the human body.Present and future emission standards need to pay close attention to them inorder to keep the public safe (Canady et al., 2001).

Ethylene glycol

Another pollutant involved in the paper industry is ethylene glycol (CASRN107-21-1). Ethylene glycol is an alcohol with two –OH groups (a diol), chemicalformula C2H4(OH)2. In its pure form, it’s an odorless, colorless, syrupy, sweettasting, toxic liquid with a melting point of �13�C. The major use of ethyleneglycol is as a medium for convective heat transfer. It can be used as a deicingagent for aircraft and windshields or in chilled water air-conditioning systems.

Exposure to ethylene glycol is usually through ingestion. Inhalation and skincontact can also occur, but since ethylene glycol’s boiling point is so high(197�C), it is rarely in gaseous form. Inhalation and skin contact may causeirritation, but there is low hazard for these types of exposure. Chronic exposurecan cause kidney problems.

Unlike the minor irritations experienced from inhalation and skin contact, theadverse effects of the ingestion of ethylene glycol are very harmful and can resultin death. Due to its sweet taste, children and animals will occasionally consumelarge quantities of ethylene glycol if given access to antifreeze. Upon ingestion,ethylene glycol is oxidized to glycolic acid, which is then oxidized to oxalic acid,which is highly toxic. These chemicals lead to ethylene glycol poisoning, which ischaracterized by three stages. Stage 1 (0.5–12 hours) consists of neurological andGI symptoms. People may appear to be intoxicated, exhibiting symptoms suchas dizziness, incoordination, nystagmus, headaches, slurred speech, and confu-sion. Irritation to the stomach may cause nausea and vomiting. Stage 2 (12–36hours) is a result of accumulation of the organic acids formed by the metabolismof ethylene glycol. Symptoms consist of increased heart rate, high blood pres-sure, hyperventilation, and metabolic acidosis. Additionally, low calcium levelsin the blood, overactive muscle reflexes, muscle spasms, and congestive heartfailure may occur. If untreated, death most commonly occurs during this stage.Stage 3 (24–72 hours) is the result of kidney injury. Symptoms consist of acutetubular necrosis, red blood and excess proteins in the urine, lower back pain,decreased production of urine, and acute kidney failure. Kidney failure can bereversed, but can take months of supportive care. Table 6.12 shows the toxi-cological data for ethylene glycol.

Table 6.12 Toxicological characterization data for ethylene glycol


2 mg/kg/day 4700 mg/kg – 1000 mg/kg/day 200 mg/kg/day 125 mg/m3



Ethylene glycol poisoning can also occur in aquatic life forms, but highconcentrations are needed for the effects to be fatal. Long-term effects on marinelife are not substantial due to ethylene glycol’s readiness to biodegrade in wateror on soil (US EPA, 1987).

Formaldehyde

Formaldehyde (CASRN 50-00-0) is another chemical that is emitted by pulp andpaper mills. It is the simplest aldehyde and has the formula CH2O. Formalde-hyde is an intermediate in the combustion of methane as well as other carboncompounds. In addition to paper mills, forest fires, car exhausts, and cigarettesmoke are all important sources of formaldehyde. Its boiling point is �19�C, soit is usually found in gaseous form, but both its liquid and vapor states are veryflammable. Due to its low boiling point, it is usually found in aqueous solutions,called formalin. Oral exposure is usually to formalin and not formaldehydeitself. A saturated formalin solution is 37% formaldehyde by weight.

The EPA has classified formaldehyde as a hazardous air pollutant anda controlled toxic substance due to its variety of adverse health effects. Exposurecan occur through inhalation, ingestion, and contact with the skin and eyes.Exposure to human eyes can lead to irritation, chemical conjunctivitis, andcorneal damage. Contact with the skin can cause irritation, skin sensitization,allergic reactions, and cyanosis of the extremities. Formaldehyde is toxic to bothterrestrial and aquatic animals. Animals tested showed symptoms similar tothose of humans.

Exposure by inhalation is also hazardous to human health. Adverse effects ofinhalation include nervous system effects, such as nausea, headache, dizziness,unconsciousness, and coma. Inhalation also leads to respiratory tract irritation.Severe asthma attacks can occur due to allergic sensitization of the respiratorytract. These attacks can lead to pulmonary edema. After inhalation occurs theexposed person or animal must be moved to fresh air to relieve the symptoms.Failure to do so can cause permanent damage or suffocation.

Ingestion of pure formaldehyde is rare due to the scarcity of its liquid phase.Ingestion of formalin is much more common. Even though formalin is an aqueoussolution, it is very harmful to humans and animals. Ingestion of formaldehyde maycause GI irritation with nausea, vomiting, and diarrhea. Large doses can causenervous system depression, characterized by excitement, followed by headache,dizziness, drowsiness, and nausea. Advanced stages may cause collapse, uncon-sciousness, and coma. Ingestion can also be fatal or cause permanent blindness.

Animals are also affected by the ingestion of formaldehyde. A study wasconducted where formaldehyde was administered daily in test rats’ drinkingwater. Chronic ingestion led to many adverse effects, including decreased bodyweight, decreased water intake, decreased organ weight, increased brain weight,and digestive system damage (Til et al., 1989). Exposure to pregnant rats lead toincreased numbers of resorption sites and decreased litter size. No effects onfetus size were reported (Marks et al., 1980).


Chronic exposure to formaldehyde is also dangerous. Repeated exposure maycause skin discoloration and thickening as well as nail decay. In addition, theOSHA and the ACGIH have labeled formaldehyde as a class A2 suspectedhuman carcinogen. Chronic inhalation of formaldehyde has been associatedwith nasal and nasopharyngeal cancer in humans. Consequences of inhalationexposure have also been studied in rats, mice, hamsters, and monkeys. Evidencesupporting formaldehyde as a carcinogen comes from positive studies in bothsexes of two strains of rats and males of one strain of mice, all of which showedsquamous cell carcinomas (Albert et al., 1982; Kerns et al., 1983; Tobe et al.,1985). These studies, as well as others, led to the toxicological data for form-aldehyde given in Table 6.13.

Formic acid

Formic acid (CASRN 64-18-6) is another pollutant released by the paperindustry. It is the simplest carboxylic acid and has the chemical formulaHCOOH. For humans, it functions as an important intermediate in chemicalsynthesis and a preservative and antibacterial agent in livestock feed. In nature itis used as venom by ants and bees. It is generally found in aqueous solution, butthe pure liquid and vapor are combustible and highly corrosive.

Exposure can occur through inhalation, ingestion, or skin contact. Theadverse effects of exposure are similar to those of acids such as HCl. Contactwith liquid is corrosive to the eyes and causes severe burns, an increase in tears,corneal edema, ulceration, and scarring. Skin contact may cause skin sensiti-zation, an allergic reaction, corrosive burns, and ulceration. Inhalation maycause asthmatic attacks due to allergic sensitization of the respiratory tract,chemical burns to the respiratory tract, dizziness, nausea, itching, burning, andswelling of the eyes. Ingestion may cause severe digestive tract burns withabdominal pain, vomiting, and possible death. Central nervous system depres-sion is also a common consequence. Ingestion may produce corrosive ulcerationand bleeding and necrosis of the GI tract accompanied by shock and circulatorycollapse.

The EPA has not labeled formic acid as a hazardous air pollutant or a toxicsubstance, but that does not mean formic acid is not harmful. The EPA has alsorecently withdrawn its assessment of the oral RfD value. Table 6.14 shows thetoxicological data for formic acid (US EPA, 1996).

Table 6.13 Toxicological characterization data for formaldehyde


0.2 mg/kg/day 100 mg/kg 203 mg/m3 83 mg/kg/day 15 mg/kg/day 0.92 mg/m3

Source: US EPA (1991d).


Hydrochloric acid

Hydrochloric acid (CASRN 7647-01-0) is used then released via effluentflows by the paper industry. It is a solution of hydrogen chloride (HCl) dis-solved in water. HCl is a highly corrosive, strong acid, and can be a clear/colorless or light yellow liquid. It is used in the chemical industry mainly asa chemical reagent in the large-scale production of vinyl chloride for poly-vinyl chloride plastic and methylene diphenyl diisocyanate/TDI for poly-urethane. Also, since HCl ionizes completely into H3Oþ and Cl�, it can easilybe used to produce salts like sodium chloride (NaCl). HCl is usuallyproduced with a concentration between 0% and 38% kg HCl/kg. If theconcentration of HCl is very low, approaching 0% HCl, the solution behavessimilarly to liquid water. If the concentration is high, above 30%, the boilingpoint decreases rapidly and evaporation rate increases. Forty percent HCl isknown as ‘‘fuming’’ hydrochloric acid because of its extremely high evapo-ration rate.

Due to its corrosive behavior, the EPA has classified HCl at concentrations of37% and higher as a toxic substance. Mucous membranes, skin, and eyes are allsusceptible to this corrosion. Acute inhalation may cause coughing, hoarseness,inflammation, and ulceration of the respiratory tract, chest pain, and pulmonaryedema in humans. Additionally, these symptoms are increased for humans whosuffer from asthma. Animals subjected to inhalation exposure suffered fromirritation and lesions of the upper respiratory tract and laryngeal and pulmonaryedema.

Acute oral exposure may cause corrosion of the mucous membranes, esoph-agus, and stomach, with nausea, vomiting, and diarrhea reported in humans.Dermal contact may produce severe burns, ulceration, and scarring. Animalsalso show signs of moderate to high toxicity from acute oral ingestion. Aquaticanimals are affected heavily by HCl due to the pH shift that occurs when HCl isadded to the water.

Chronic exposure to hydrochloric acid is also dangerous for humans andanimals. In humans, long-term exposure has been reported to cause gastritis,chronic bronchitis, dermatitis, and photosensitization. Prolonged exposure tolow concentrations may also cause dental discoloration and erosion. Rats sub-jected to chronic inhalation tests experienced hyperplasia of the nasal mucosa,larynx and trachea, and lesions in the nasal cavity (US EPA, 1995a). Table 6.15shows toxicity data for HCl obtained by the EPA.

Table 6.14 Toxicological characterization data for formic acid

LD50 (rats) LC50 (rats) LOAEL NOAEL PEL

1100 mg/kg 15 g/m3 (15 min) N/A 42 mg/m3 9 mg/m3

Source: EPA (1996).


Hydrogen fluoride

Hydrogen fluoride (CASRN 7664-39-3; HF) is a nonflammable, colorless gasthat is often expelled from the paper-making process. A solution of HF in wateris known as hydrofluoric acid. This acid is highly corrosive. HF is the principalindustrial source of fluorine and a precursor to many important compounds,including pharmaceuticals and polymers such as Teflon.

Hydrogen fluoride is on both the hazardous air pollutant and toxic substancelists released by the EPA. This is due to its highly corrosive behavior, which hasnumerous adverse effects on human health when ingested, inhaled, or contactedwith the skin or eyes. In humans, inhalation can cause immediate or delayed-onset pulmonary edema. Significant exposures via the dermal or inhalationroutes may cause hypocalcemia and hypomagnesemia, and cardiac arrhythmiasmay follow. Acute renal failure has also been documented after an ultimatelyfatal inhalation exposure. Repeated exposure to excessive concentrations of HFover a period of years results in increased bone density and eventually may causecrippling fluorosis, which is a form of osteosclerosis (Hathaway et al., 1991).

Ingestion of HF is also extremely dangerous. Consequences are similar tothose for other acids. Ingestion may cause burns and ulceration of the respiratorytract, damage to the GI tract, and permanent damage to any tissue that comes incontact with the solution. Ingestion of an estimated 1.5 g of hydrofluoric acidproduces sudden death. If the exposed person is lucky enough to survive the firstingestion, repeated ingestion of small amounts of HF may cause fluorideosteosclerosis (Gosselin et al., 1984).

The EPA does not have a reference dose or a reference concentration estab-lished. The only two pieces of toxicology data on HF are its 1-hour LC50 in ratsof 1.56 g/m3, and its OSHA permissible exposure limit (PEL) of 3.7 mg/m3

(OSHA, 2009).

Hydrogen sulfide

Hydrogen sulfide (CASRN 7783-06-4; H2S) is a major emission and the primarysource of odor of most paper mills. Most pulping processes use sulfur solutionsand compounds to break down the lignin that binds the cellulose fibers together.Many of these sulfuric compounds escape as emissions and cause the smellcharacteristic of rotten eggs or flatulence. Synonyms of H2S, such as sewer gasand stink damp, give even more detail to its pungent odor. In addition to itssmell, H2S is colorless, toxic, and flammable.

Table 6.15 Toxicological characterization data for hydrochloric acid


0.02 mg/m3 N/A 4.7 g/m3 (30 min) 15 mg/m3 N/A 7 mg/m3

Source: US EPA (1995a).


Exposure to humans mainly occurs due to inhalation and skin contact.Ingestion is highly unlikely because of its extremely low boiling point (�60�C).Eye and skin contact may cause inflammation, irritation, and ‘‘gas eyes’’,symptoms of which include soreness, scratchiness, irritation, tearing, andburning. Above 50 ppm, there is an intense tearing, blurring of vision, and painwhen looking at light. Exposed individuals may see rings around bright lights.Most symptoms disappear when exposure ceases; however, in serious cases, theeye can be permanently damaged.

Inhalation of high concentrations of H2S can cause dizziness, headache, andnausea. Exposure to even higher concentrations can result in respiratory arrest,coma, or unconsciousness. Exposures to 30 minutes at concentrations of greaterthan 600 ppm have been fatal. Severe exposures that do not result in death maycause long-term symptoms such as memory loss, paralysis of facial muscles, ornerve tissue damage.

A study by Burnett et al. (1977) showed hard evidence of these symptoms.A 19-year-old oil-rig worker had been exposed to unspecified concentrations ofH2S, rendering him unconscious for an indeterminate amount of time. Uponresuscitation, he exhibited malaise, anterior chest pain, dyspnea, headache,nausea and vomiting, tearing of the eyes and photophobia, and coughed upblood. Upon arrival at the hospital for further treatment, his vital signs werenormal and he was no longer in respiratory distress. He had severe photophobiaand blepharospasms, but no signs of conjunctivitis. He also possessed a coughand some motor weakness of his right arm and leg. A neurologic examinationand chest X-ray revealed no abnormalities. He was released from the hospitalafter a 3-day stay.

Hydrogen sulfide has never been associated with an increased risk of cancer, sothe EPA and similar agencies have declared it noncarcinogenic to humans.Additional toxicological data for H2S are shown in Table 6.16.

Due to its odor, H2S is very easy to detect and distinguish. Since paper millsemit a relatively large amount of H2S, they are very unpleasant to work in or liveby. There are sulfur control apparatuses in use today, but they can never keep thesmell contained completely. Odor has been linked to health issues such asolfactory fatigue and recurring nausea. The paper industry needs to realize theproblems that H2S causes, and hopefully they can invent a new process that doesnot require such ghastly chemicals (US EPA, 2003b).

Table 6.16 Toxicological characterization data for hydrogen sulfide


0.003 mg/kg/day

0.002 mg/m3

N/A 617 mg/m3

(5 min)41.7 mg/

m313.9 mg/

m327.8 mg/

m3



Methanol

Methanol (CASRN 67-56-1) is the primary chemical emitted by the paperindustry, and is ranked third among all chemicals for total releases into theenvironment (1992). Methanol, also known as methyl alcohol and woodalcohol, is a toxic chemical with the formula CH3OH. It is the simplest alcoholand is a light, colorless, volatile, flammable liquid with an odor similar toethanol. It occurs naturally in wood and volcanic gases, and it can also beproduced naturally by decaying organic material. Man-made production ofmethanol totalled 1.3 billion gallons a year (1992) in the USA alone. Its mainindustrial use is the production of methyl t-butyl ether, a gasoline additive, but itcan also be used to produce other chemicals and commercial products.

Humans can be exposed to methanol through air, water, soil, or groundwater.Methanol can enter the body by inhalation or consumption of contaminatedfood or water. It can also be absorbed through skin contact. Exposure can occurwhen using certain paint thinners, aerosol sprays, paints, windshield wiper fluid,or small engine fuel.

The EPA has declared methanol an HAP due to its adverse health effects onhumans. The nature and intensity of these effects depend on the concentrationand time of exposure. The health of the person or animal exposed as well asthe conditions of the environment can also influence the effects of exposure.Acute exposure to methanol is very dangerous and can be fatal. The ingestionof 80 ml is usually fatal for humans. Poisoning by nonlethal doses is commonand involves three stages: (1) narcotic stage similar to ethanol; (2) latentperiod of 10–15 hours; (3) visual disturbances and central nervous systemlesions, including headache, dizziness, nausea, and delirium that can lead tocoma. In fact, blindness has been caused by the ingestion of as little as 20 ml.Once methanol is consumed, it is oxidized by the human liver to formformaldehyde and formic acid. This formic acid is responsible for the toxiceffects of methanol. Table 6.17 describes important toxicity properties ofmethanol.

Human health effects associated with chronic exposure to methanol are notcompletely known. Workers exposed repeatedly over long periods of timeexperienced adverse effects, including headaches, sleep disorders, and GIproblems. In many cases, optic nerve damage was also apparent. Lab studiesshow that repeated exposure to large amounts of methanol in air or in drinkingwater cause similar adverse effects in animals (US EPA, 1988).

Table 6.17 Toxicological characterization data for methanol


0.5 mg/kg/day 6.2–13 g/kg 85.1 g/m3 (1 h) 2.5 g/kg/day 10 mg/kg/day 4.3 mg/m3



Methyl mercaptan

Methyl mercaptan (CASRN 74-93-1; CH4S), also known as methanethiol, isa toxic, extremely flammable, colorless gas with a smell similar to rottencabbage. It occurs naturally in the blood and brain, and in other animals andplant tissues. It is one of the main chemicals that cause bad breath and the odorof flatulence. Kraft pulp mills emit methyl mercaptan during the pulping process.An odorous plume that contains methyl mercaptan can be detected thousands offeet away from a kraft mill. The odor is so easily detected that methyl mercaptan,and other thiols, are added to otherwise odorless natural gas to aid in leakdetection. In addition, methyl mercaptan is a by-product of asparagus in roughly50% of humans, and it is responsible for the distinct change in odor of the urine(Richer et al., 1989).

The EPA has declared methyl mercaptan a regulated toxic substance due to itsadverse effects on human health. Exposure to humans can occur by eye/skincontact, inhalation, or ingestion, but ingestion is very unlikely due to methylmercaptan’s volatility. Ingestion can cause irritation of the mucous membranes,causing a burning feeling with excess salivation. Eye exposure to low concen-trations will generally cause irritation to the conjunctiva. Repeated exposure tolow concentrations is reported to cause conjunctivitis, photophobia, cornealbullae, tearing, pain, and blurred vision. Irritation can be caused by skin contactas well.

The most common form of human exposure to methanethiol is throughinhalation. Exposure may cause fever, cough, shortness of breath, a feeling oftightness and burning in the chest, pulmonary edema, respiratory failure andcollapse. Headache, loss of smell, dizziness, staggering gait, and heightenedemotions may occur. Memory loss, damage to the central and peripheral nervoussystem, tremor, convulsions, and coma may also result. Individuals exposed tohigh concentrations may develop acute hemolytic anemia and methemoglobi-nemia. Individuals with pre-existing conditions of the heart, lungs, blood, andnervous system may have increased susceptibility to the toxic effects of methylmercaptan.

Methyl mercaptan is on the EPA’s list of regulated toxic substances, but thereis a limited amount of toxicological data on methyl mercaptan; the LC50 for ratsby inhalation for 1 hour is 1.3 g/m3, and the OSHA PEL is 19.7 mg/m3 (BOC,1996).

Pentachlorophenol

Pentachlorophenol (CASRN 87-86-5; C6HCl5O; PCP) is a syntheticsubstance that is often emitted by wood treatment industries. The main usefor PCP is wood preservation, not the production of pulp and/or paper. PCPhas been detected in surface waters and sediments, rainwater, drinking water,aquatic organisms, soil, and food, as well as in human milk, adipose tissue,and urine.


As PCP is generally used for its properties as a biocidal agent, there isconsiderable concern about adverse ecosystem and health effects in areas of PCPcontamination. The EPA has placed PCP on the Clean Air Act of 1990 list ofhazardous air pollutants due to these adverse effects. Humans can be exposed toPCP by inhalation and skin contact, usually at the workplace, or by ingestion ofcontaminated drinking water and food. Short-term exposure by ingestion, tolarge amounts of PCP, can cause harmful effects on the liver, kidneys, blood,lungs, nervous system, immune system, and GI tract. Other consequencesinclude elevated temperature, profuse sweating, uncoordinated movement,muscle twitching, and possible coma. Inhalation of PCP vapor can producesimilar symptoms plus irritation of the skin and eyes.

Chronic exposure to low levels of PCP, such that can occur at the work-place, can cause damage to the liver, kidneys, blood, and nervous system.Also, PCP has been classified as a B2, probable human carcinogen. There isinadequate data to fully declare PCP a human carcinogen, but there werea couple of studies to examine its cancer-causing potential. Gilbert et al.(1990) attempted to study the effects of exposure to PCP among a cohort of182 men employed by the wood-treating industry in Hawaii. The workershad experienced a minimum of 3 months’ continuous employment treatingwood between 1960 and 1981. The study showed elevated levels of urinaryPCP among the wood treaters, but no morbidity or mortality endpoint wasachieved.

Studies in animals have provided the solid evidence on the cancerous effectsof exposure to PCP. In one of these studies, conducted by NTP (1989), twodifferent 90% pure preparations of PCP were tested in 2-year bioassays inmice. The incidences of hepatocellular adenomas and/or carcinomas weresignificantly increased in exposed test subjects compared to controls. Also, theincidences of benign and malignant pheochromocytomas of the adrenalmedulla were also significantly greater in dosed mice than in controls. TheEPA continues to study PCP and has released the toxicological data shown inTable 6.18.

The full effects of exposure to PCP are not known. Continued studiesconcerning the carcinogenic and noncancerous health effects on humans areneeded. Even though there is limited information and data concerning PCP,it is safe to say that it is harmful and needs strict regulation (US EPA,1991e).

Table 6.18 Toxicological data for pentachlorophenol


0.03 mg/kg/day 27 mg/kg 5.5 g/mg3 (4 h) 10 mg/kg/day 3 mg/kg/day 0.5 mg/m3

Source: US EPA (1991e).


Phenol

Another chemical commonly emitted by the paper industry is phenol. Phenol(CASRN 108-95-2), also known as carbolic acid, has the chemical formulaC6H5OH. It is a combustible, corrosive, toxic, white crystalline solid with a sweettarry odor, commonly referred to as a ‘‘hospital smell’’. Phenol is moderatelysoluble in water and commonly seen in aqueous solutions. Since it is toxic tobacteria and fungi, phenol used to be used as an antiseptic, but now it is mainlyused as an intermediate in the production of phenolic resins, which are used in theplywood, adhesive, construction, automotive, and appliance industries.

Phenol is readily absorbed by inhalation, oral, and dermal routes. Onceabsorbed, phenol is widely distributed throughout the body, but the levels in thelung, liver, and kidney are often reported as higher than average. Eliminationfrom the body is rapid, and phenol does not appear to accumulate significantly inthe body.

The EPA has established that phenol is a hazardous air pollutant due to itsadverse effects on human and animal health. Exposure can occur through skinand/or eye contact, inhalation, and ingestion. Adverse effects caused by eyecontact include severe burns, chemical conjunctivitis, corneal damage, andpossible irreversible eye damage. Skin contact may lead to wrinkled discolor-ation followed by severe burns. If not properly taken care of, phenol solutionsmay be rapidly absorbed through the skin, causing systematic poisoning andpossible death.

Ingestion of phenol is harmful and can be fatal. Its nonfatal effects includedepression of the central nervous system, characterized by excitement, followedby headache, dizziness, drowsiness, and nausea. Advanced stages may causecollapse, unconsciousness, and coma. Perforation and burning of the digestivetract are common consequences, as well as immediate pain and swelling in thethroat, convulsion, and possible coma. Studies of animals exposed to phenolhave shown further negative effects. Argus Research Laboratories (1997) helda large-scale oral toxicity study on rats. This study showed adverse effectssimilar to those in humans. Pregnant rats were also exposed to phenol, and theconsequences of that included an increase in abortions and still births, decreasedfetal weight, and an increase in litters with alterations.

Exposure to phenol through inhalation also leads to adverse health effects andpossibly death. Inhalation causes severe irritation of the respiratory tract withcoughing, burns, and breathing difficulty. Other nonfatal problems includepallor, loss of appetite, nausea, vomiting, diarrhea, weakness, darkened urine,headache, sweating, convulsions, cyanosis, unconsciousness, fatigue, pulmonaryedema, and coma. Inhalation of high concentrations may cause central nervoussystem depression, asphyxiation, and death.

Phenol is toxic to aquatic animals, but it biodegrades rapidly, so contamina-tion in water is usually short term. A common way phenol contaminates water israin absorbing it from the atmosphere (US EPA, 2002). Table 6.19 shows thetoxicological values for phenol.


Sulfuric acid

Sulfuric acid (CASRN 7664-93-9), also known as hydrogen sulfate, is a highlycorrosive, clear, colorless, odorless, strong mineral acid with the formula H2SO4.It is also one of the top 10 chemicals released (by weight) by the paper industry(US EPA, 2009). In modern industry, sulfuric acid is an important commoditychemical, and is used primarily for the production of phosphoric acid. It is alsogood for removing oxidation from iron and steel, so it is used in large quantitiesby metal manufacturers.

Sulfuric acid is a very dangerous chemical. It is extremely corrosive and toxic.Exposure can occur from inhalation, ingestion, and through skin contact.Inhalation of H2SO4 may cause irritation and/or chemical burns to the respira-tory tract, nose, and throat. Inhalation can also be fatal as a result of spasm,inflammation, edema of the larynx and bronchi, chemical pneumonitis, andpulmonary edema. Chronic inhalation is known to have caused kidney and lungdamage in addition to nosebleeds, erosion of the teeth, chest pain, and bronchitis.

The effects of ingesting sulfuric acid orally are just as bad as inhalation.Ingestion may cause systematic toxicity with acidosis, which can be fatal. It canalso cause severe permanent damage to the digestive and GI tracts. Prolonged orrepeated ingestion is not common because the first ingestion is usually the last.

Skin or eye contact with sulfuric acid can be devastating. The burns induced aresimilar, and often worse, than those caused by hydrochloric acid. What makessulfuric acid so dangerous is its exothermic reaction with water. When introducedto water or moisture, the solution reacts with the water to create hydronium ions.This reaction releases large amounts of heat to the environment. This reaction isso strong that concentrated sulfuric acid can char paper by itself (see Figure 6.10).Recurring contact with the skin is known to cause dermatitis, and repeatedcontact with the eyes can cause permanent visual problems.

Another deadly property of sulfuric acid is its carcinogenicity. The Interna-tional Agency for Research on Cancer (IARC) has classified ‘‘strong inorganicacid mists containing sulfuric acid’’ as a group 1 known human carcinogen. TheACGIH also classified sulfuric acid mists as a category A1 carcinogen. This onlyapplies to mists, and not to liquid sulfuric acid and its solutions (ISU, 2000).Table 6.20 shows toxicology values for sulfuric acid.

Sulfur dioxide

Sulfur dioxide (CASRN 7446-09-5; SO2) is another odorous pollutant releasedby the paper industry. Sulfur dioxide is a nonflammable, colorless, irritating gas.

Table 6.19 Toxicological characterization data for phenol


0.3 mg/kg/day 317 mg/kg 316 mg/kg 120 mg/kg/day 60 mg/kg/day 19 mg/m3



It has a suffocating odor, detectable at 3–5 ppm, and leaves an acidic taste in themouth. It is toxic and corrosive, and highly soluble in water. Most man-made/released SO2 is associated with the burning of fossil fuels. In nature, SO2 can beproduced by volcanic eruptions.

Much like hydrogen sulfide, SO2 is a primary reason paper mills smell the waythey do. This odor is not only unpleasant, but can be harmful as well. The EPAlists SO2 as a regulated toxic chemical due to its adverse effects on human health.Inhalation of SO2 can cause corrosive irritation to the respiratory tract andmucous membranes. Excess exposure to concentrations above exposure limitsmay result in chemical pneumonitis (inflammation), pulmonary hemorrhage,and edema fluid buildup. Inhalation exposure has also resulted in death. In onestudy, an SO2 level of 150 ppm was measured during the re-enactment of anincident in which a 76-year-old asthmatic woman died of an asthma attack afterinhaling vapors from a sulfite-based derusting agent used in her dishwasher(Huber and Loving, 1991). Actual SO2 levels were probably higher since thequantity of derusting agent used in the investigation was about 10% of theamount originally used by the woman. A concentration of 100 ppm is consideredimmediately dangerous to human life and health (HSDB, 1998).

Figure 6.10 Sulfuric acid (98%) on tissue paper.Source: Wikipedia; http://en.wikipedia.org/wiki/Sulfuric_acid

Table 6.20 Toxicological characterization data for sulfuric acid


0.001 mg/m3 2.14 g/kg 510 mg/m3 (2 h) 380 mg/m3 N/A 1 mg/m3

Source: ISU (2000).


Exposure by oral ingestion is nearly impossible due to sulfur dioxide’s lowboiling point (�10�C). Exposure to skin and eyes can cause irritation andburning. High concentrations or long-term exposure can lead to impaired visionor vision loss. Since ingestion is not plausible there are no data regarding theRfD, NOAEL, or LOAEL. The two pieces of available toxicological data are theLC50 for rats of 6.6 g/m3 for 1 hour, and the OSHA PEL of 13 mg/m3.

There is no definitive evidence for an increased cancer potential from SO2 inhumans, but some studies have shown increased cancer risk. Several epidemio-logical studies have been conducted on copper smelter workers and pulp andpaper workers who can be exposed to SO2 (IARC, 1992). A nested case–controlstudy of lung cancer among 308 workers in a large chemical facility revealedsignificantly elevated risks for workers with moderate and high potentialexposure (longer than 1 year) to SO2 (Bond et al., 1986). For workers who hadbeen exposed, the odds ratio for lung cancer was 1.40.

Although SO2 is not on the EPA’s hazardous air pollutants list, it is stilla dangerous chemical. The odor is painful and irritating, and inhaling thechemical can lead to serious adverse health effects. Perhaps it’s time SO2 madethe hazardous air pollutants list (US DHHS, 1998).

Toluene

Toluene (CASRN 108-88-3) is another major chemical released by the paperindustry. Toluene, a.k.a. methyl benzene, is a clear, flammable, water-insolubleliquid with the odor of paint thinner. It can be found naturally in petroleumcrude oil. Exposure to toluene can occur through air, water, soil, and ground-water, but almost all of the toluene released as emissions is dispersed into the air.Industrial emissions, car exhausts, and cigarette smoke (cigarettes contain about80 mg/cigarette) are three large sources of atmospheric toluene.

The EPA has labeled toluene as an HAP and a toxic substance. Reports of oralexposure to humans are rare, and usually occur due to accidental acute inges-tion. Ameno et al. (1989) reported 15 deaths by oral ingestion between 1977 and1986. The cause of death was believed to be severe central nervous systemdepression. Caravati and Bjerk (1997) discussed a case where a 46-year-old maningested nearly 1 quart of paint thinner containing toluene. The man experi-enced severe central nervous system depression, severe abdominal pain, diar-rhea, and hemorrhagic gastritis. He recovered after 36 hours of supportive care.Repeated exposure to toluene can cause permanent central nervous systemeffects, and can damage the liver, kidney, and upper respiratory system.

Exposure through inhalation is much more common. People ‘‘huff’’ or ‘‘sniff’’paint, paint thinner, or glue in order to feel the euphoric effects of a large dose oftoluene. Inhalation of toluene can lead to a variety of neurologic manifestations,including ataxia, tremor, anosmia, sensorineural hearing loss, dementia, corti-cospinal tract dysfunction, and epileptic seizures (Hormes et al., 1986).Hunnewell and Miller (1998) reported a case study where a 36-year-old chronictoluene abuser exhibited slurred speech, progressive ataxia, blurred vision, and


oscillopsia (jerky eye movement). High concentrations (10,000–30,000 ppm)can cause narcosis and death. A study in France on workers chronically exposedto toluene fumes reported leukopenia and neutropenia. Exposure levels were notgiven, but the average urinary excretion of hippuric acid, a metabolite oftoluene, was given at 4 g/l compared to the normal level of 0.6 g/l (Sandmeyer,1989). Table 6.21 shows toxicological data for toluene obtained by the EPA andOSHA.

Reports and studies have shown that toluene does not contribute to theformation of cancer in humans. Both the OSHA and ACGIH had labeled it asa noncarcinogen. Even though this is true, toluene should not be used recrea-tionally or emitted irresponsibly due to the damage it causes to the nervoussystem (US EPA, 2005).

6.4 Regulations

The sector is subject to the same environmental regulations as other industrysectors, but the most significant recent rulemaking activities affecting the pulpand paper sector are referred to collectively as the Cluster Rules (1998). Thisrefers to a set of air and water rules that were issued simultaneously. The rulesinclude:

� the Pulp and Paper NESHAP, specifying air emission standards for pulping andbleaching operations;

� the Effluent Limitations Guidelines and related water-quality standards for the pulp,paper, and paperboard category.

Estimates of the emissions reductions expected include:

� a 64% reduction in HAPs (by 153,000 tons per year, down from 240,000 tonsemitted during 1996);

� a 450,000 ton per year reduction in overall VOC emissions (as a consequence ofimplementing the technology needed to meet the HAP rules);

� an 87,000 ton per year reduction in emissions of odor-causing reduced sulfurcompounds (as a consequence of new source performance standards).

The water-quality standards specified under the Cluster Rules regulateconcentrations of dioxins and furans (specifically TCDD and TCDF), as well asadsorbable organic halogens (such as chloroform) and chemical oxygen demand(COD). The standards represent a compromise that allow the substitution of

Table 6.21 Toxicological characterization data for toluene


0.08 mg/kg/day 5 mg/m3 5.5 g/kg 17.4 g/m3

(6 h)446 mg/kg/

day128 mg/

m3753.7 mg/

m3



chlorine dioxide for elemental chlorine in the bleaching process. A stronger set ofstandards, which would have required technologies that avoided the use ofchlorine altogether, was not chosen.

The Regional NOx Transport Rule (1998) requires 22 eastern states to insti-tute measures to decrease their overall emissions of nitrogen oxides. The affectedstates were required to have controls on large industrial sources in place by2003, and to meet overall NOx limits by 2007. Since individual states haveconsiderable flexibility in devising their own specific implementation plans, theeffect on pulp and paper facilities has varied considerably, depending onlocation.

New standards for emissions of ozone precursors and fine particles affectsome pulp and paper mills, particularly those impacting on ozone non-attainment areas.

The Regional Haze Rule was finalized in 1999. This calls for states to establishgoals and develop long-term strategies for improving visibility, particularly innational parks and wilderness areas. Some pulp and paper mills located incertain regions (such as mills directly upwind of sensitive areas) have been calledupon to meet more stringent emissions limits for particulates and aerosolprecursors.

The Total Maximum Daily Load (TMDL) program defines the maximumamount of pollutants a given body of water can receive and still meet water-quality standards. Due to their high water use, pulp mills generally tend to beamong the most significant impactors of the water bodies on which they aresituated. State agencies are responsible for establishing effluent reduction levelsfor individual facilities.

The reader can obtain details of each of these rules from the EPA website athttp://www.epa.gov/owow/tmdl/index.html.

6.5 Emission factors

The pulp and paper sector relies on the application of AP-42 published emissionfactors to estimate reported emissions (see Chapter 4 for an explanation ofemission factors and the AP-42 publication).

In the AP-42 publication, emission factors are generally presented as a singlevalue that is the mean of the emissions data set, with nondetects included at one-half the method detection limit. A quality rating (A, B, C, D, or E) is assigned toeach factor. Statistical tests are not used to identify possible outliers.A description of how factors for the emission unit were developed is usuallyavailable in a background information document covering types of emissionunits found in an industrial source category or subcategory, e.g. chemical woodpulping. These documents may or may not contain summaries of emission testdata used to compute the average emission factor.

Section 10.2, Chemical Wood Pulping, is the AP-42 publication relied upon bythe sector for estimating emission sources. A problem with the information that


currently exists is that the data reported largely reflect emission testing done inthe 1970s. There are placeholders for sections on pulp bleaching and paper-making. A supplement to this resource is the EPA’s electronic WebFIRE (http://cfpub.epa.gov/oarweb/index.cfm?action¼fire.main) database, but this hasa very limited amount of newer test information for some pulp and paper millsources, with the most recent test reports being ca. 1990. Emission factors forindustrial boilers are in AP-42 Chapter 1, and are reasonably up to date.

Table 6.22 is a summary of the emission factors for the pulp and paperindustry downloaded from the EPA’s WebFIRE library. In applying the emissionfactors reported in the table the reader should note the following column entries:

� Source – identifies the emission source.� Pollutant – denotes the air pollutant.� Method of control – indicates whether the emission factor was measured from

a source that was uncontrolled or had a pollution control.� Value – emission factor value in scientific notation. For example, a value of 1.2Eþ01

is the same as 12.0.� Emission factor:� Unit – the unit that the emission factor is reported in.� Measure – the per-unit basis of the emission factor.� Material – the per-unit basis of material that the emission factor is reported for.� Action – the action under which the per-unit basis of the emission factor was

measured.As an example, the first entry in the table is for the emission source ‘‘Digester reliefand blow tank’’. The uncontrolled emission factor reported for methyl alcohol is1.70 lb of methyl alcohol per ton of pulp processed.� EF quality – the EPA’s rating of the reported emission factor. Refer to Chapter 4

for an explanation of the EPA rating system.

6.6 Case studies

The pulp and paper industry has previously and continues to contributea significant environmental footprint that impacts on communities. The industryhas struggled to control its environmental impacts on the whole to a greaterextent than the wood-preserving sector. Despite significant gains over the past30 years to reduce pollution, it continues to generate large emissions that placecommunities at risks. The following are brief case studies of environmentalimpacts and regulatory infractions.

6.6.1 International Paper Co., Jay, ME

International Paper Co. (IP) owns and operates the Androscoggin Mill in Jay, ME.In 1987, the workers of this mill went on strike for more than a year in order toprotest worker health issues and other pollution issues. In July 1991, five criminalindictments were brought against the mill. The allegations included misrepresen-tation in its wastewater license application and the burning of unlicensed waste.

Table 6.22 Emission factors for pulp and paper

on factorEFqualityMaterial Action

Pulp Processed U

Pulp Processed D

Pulp Processed DAir-dried

unbleachedpulp

Produced A

Air-driedunbleachedpulp

Produced U

Pulp Processed D


Produced U

s Black liquorsolids

Burned U


Burned U

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Source PollutantaMethod ofcontrol

Emissi

Value Unit Measure

Sulfate (kraft) pulping

Digester reliefand blow tank

Methyl alcohol Uncontrolled 1.70Eþ00 lb Tons

Methyl ethyl ketone Uncontrolled 1.40E�02 lb Tons

Washer/screens Methyl ethyl ketone Uncontrolled 2.70E�02 lb TonsSOx Uncontrolled 1.00E�02 lb Tons

VOC Uncontrolled 2.00E�01 lb Tons

Multi-effectevaporator


Recovery furnace/direct contactevaporator

Carbon monoxide Uncontrolled 1.10Eþ01 lb Tons

Chlorodibenzo-p-dioxin,chlorodibenzofurans,total

Electrostaticprecipitator –high efficiency

8.14E�02 mg Kilogram

Heptachlorodibenzo-p-dioxins, total


2.05E�03 mg Kilogram

lograms Black liquorsolids

Burned U

egagrams Air-driedunbleachedpulp

Produced U


Burned U

ns Pulp Processed Dns Air-dried

unbleachedpulp

Produced U


Burned U


Burned U

egagrams Air-driedunbleachedpulp

Produced U


Burned U

ns Air-driedunbleachedpulp

Produced U

Continued

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mills

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Heptachlorodibenzofurans,total


1.05E�03 mg Ki

Hexachlorodibenzo-p-dioxins, total

Electrostaticprecipitator

1.10E�03 mg M

Hexachlorodibenzofurans,total


1.17E�03 mg Ki

Methyl ethyl ketone Uncontrolled 1.50E�02 lb ToNOx Uncontrolled 2.00Eþ00 lb To

Octachlorodibenzo-p-dioxins, total


4.20E�03 mg Ki

Octachlorodibenzofurans,total


3.45E�04 mg Ki

Pentachlorodibenzo-p-dioxins, total

Miscellaneouscontrol devices

3.80E�04 mg M

Pentachlorodibenzofurans,total


< 9.900E�4 mg Ki

PM, filterable Uncontrolled 1.80Eþ02 lb To

Table 6.22 Emission factors for pulp and paperdcont’d

Emission factorEFqualityMeasure Material Action

Tons Air-driedunbleachedpulp

Produced A


Produced A


Produced A


Produced U


Produced C

Tons Black liquorsolids

Burned U


Produced U


Burned U

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Source PollutantaMethod ofcontrol Value Unit

PM, filterable Electrostaticprecipitator –mediumefficiency

2.00Eþ00 lb

PM, filterable Venturiscrubber

4.80Eþ01 lb

PM, filterable Scrubber 3.000E0–1.500E1

lb

PM10, filterable Uncontrolled 1.68Eþ02 lb

PM2.5, filterable Uncontrolled 1.50Eþ02 lb

Smelt dissolvingtank

Carbon monoxide Electrostaticprecipitator

1.91Eþ00 lb

NOx Uncontrolled 1.00Eþ00 lb

NOx Wet scrubber –mediumefficiency

2.09E�01 lb

NO Electrostatic 1.28Eþ00 lb Tons Black liquorsolids

Burned U

s Air-driedunbleachedpulp

Produced U


Burned U


Produced A


Produced A


Produced U


Produced C


Produced C


Produced C


Produced C

Continued

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x

precipitatorPM, filterable Uncontrolled 7.00Eþ00 lb Ton

PM, filterable Wet scrubber –mediumefficiency

1.84E�01 lb Ton


2.00E�01 lb Ton

PM, filterable Packedscrubber

1.00Eþ00 lb Ton

PM10, filterable Uncontrolled 6.20Eþ00 lb Ton

PM10, filterable Venturiscrubber

1.80E�01 lb Ton

PM10, filterable Packed scrubber 9.50E�01 lb Ton

PM2.5, filterable Uncontrolled 5.10Eþ00 lb Ton

PM2.5, filterable Venturiscrubber

1.60E�01 lb Ton

cont’d

Sourc

Emission factor

EFqualityMeasure Material Action


Produced C


Burned U


Burned U


Produced U


Burned U


Burned U


Produced U

Lime Tons Air-driedunbleachedpulp

Produced U

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Table 6.22 Emission factors for pulp and paperd

e PollutantaMethod ofcontrol Value Unit

PM2.5, filterable Packedscrubber

8.50E�01 lb

Sulfur dioxide Wet scrubber –mediumefficiency

8.04E�04 lb

Sulfur dioxide Electrostaticprecipitator

2.99E�03 lb

SOx Uncontrolled 2.00E�01 lb

TOCs Wet scrubber –mediumefficiency

1.14E�01 lb

TOCs Electrostaticprecipitator

1.38E�02 lb

VOCs Uncontrolled 1.60E�01 lb

kiln Acetaldehyde Uncontrolled 7.40E�05 lb

Arsenic Uncontrolled 4.68E�07 lb Tons Air-driedunbleachedpulp

Produced U


Produced U


Produced U


Produced U


Produced U


Produced U


Produced U


Produced U


Produced U


Produced U

Continued

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Beryllium Uncontrolled 7.80E�06 lb Tons

Cadmium Uncontrolled 2.02E�06 lb Tons

Carbon monoxide Uncontrolled 1.00E�01 lb Tons

Chromium Uncontrolled 4.66E�04 lb Tons

Copper Uncontrolled 2.80E�05 lb Tons

Fluoranthene Uncontrolled <3.480E�6 lb Tons

Heptachlorodi-benzofurans, total

Uncontrolled 1.66E�10 lb Tons

Hexachlorodi-benzofurans, total


Hydrogen chloride Uncontrolled 2.20E�06 lb Tons


Emission factor



Produced U


Produced U


Produced U


Produced U


Produced U


Produced U


Produced U


Produced U

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Lead Uncontrolled 1.09E�04 lb

Manganese Uncontrolled 3.50E�05 lb

Mercury Uncontrolled 2.90E�07 lb

Nickel Uncontrolled 1.29E�04 lb


Octachlorodibenzo-p-dioxins, total

Uncontrolled 1.75E�09 lb

Pentachlorodi-benzofurans, total

Uncontrolled 1.07E�10 lb

PM, filterable Uncontrolled 5.60Eþ01 lb


Produced A


Produced A


Produced U


Produced C


Produced C


Produced C


Produced C


Produced C

Continued

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5.00E�01 lb


5.00E�01 lb


PM10, filterable Electrostaticprecipitator –mediumefficiency

4.40E�01 lb

PM10, filterable Venturi scrubber 4.90E�01 lb


PM2.5, filterable Electrostaticprecipitator –mediumefficiency

4.20E�01 lb

PM2.5, filterable Venturiscrubber

4.80E�01 lb

So

on factorEF

qualityMaterial Action


Produced U


Produced U


Produced U


Produced A


Produced U


Produced U


Produced U

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urce PollutantaMethod of

control

Emissi

Value Unit Measure

Polychlorinated dibenzo-p-dioxins, total


Polychlorinateddibenzofurans, total


Selenium Uncontrolled 4.04E�07 lb Tons

SOx Uncontrolled 3.00E�01 lb Tons

2,3,7,8-Tetrachlorodibenzofuran

Uncontrolled < 0.000E0 lb Tons

Tetrachlorodibenzofurans,total


VOCs Uncontrolled 2.50E�01 lb Tons

Pulp Processed D


Produced U


Produced U


Produced U


Produced U


Produced U

Pulp Processed D


Produced U


Produced U


Produced U

Continued

Sources

of

air

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ns

from

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and

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Turpentinecondenser



Fluid-bed calciner NOx Uncontrolled 2.80Eþ00 lb Tons

PM10, filterable Uncontrolled 5.04Eþ01 lb Tons



Liquor oxidationtower




Recovery furnace/indirect contactevaporator

Carbon monoxide Uncontrolled 1.10Eþ01 lb Tons


Emission factor



Produced U


Produced U


Produced A


Produced U


Produced C


Produced C


Produced C

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PM, filterable Uncontrolled 2.30Eþ02 lb


2.00Eþ00 lb


PM10, filterable Electrostaticprecipitator –mediumefficiency

1.50Eþ00 lb


PM2.5, filterable Electrostaticprecipitator –mediumefficiency

1.30Eþ00 lb


Produced U

agrams Air-driedbleachedpulp

Produced U


Produced U


Produced U


Produced U


Produced U


Produced U


Produced U


Produced U


Produced U

Continued

Sources

of

air

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and

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Other notclassified

Acetaldehyde Uncontrolled 3.61E�04 kg Meg



Benzene Uncontrolled 9.12E�05 kg Meg

Carbon tetrachloride Uncontrolled 4.07E�04 kg Meg

Chlorine Uncontrolled 1.07E�06 kg Meg

Chloroform Uncontrolled 9.25E�03 kg Meg

Dichloromethane Uncontrolled 6.91E�05 kg Meg

Ethylene dibromide Uncontrolled <2.010E�04

kg Meg


mission factorEFqualityeasure Material Action

egagrams Air-driedbleachedpulp

Produced U


Produced U


Produced U


Produced U

ns Pulp Processed Degagrams Air-dried

bleachedpulp

Produced U


Produced U

ns Air-driedunbleachedpulp

Produced C

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Source PollutantaMethod ofcontrol

E

Value Unit M

Formaldehyde Uncontrolled 3.23E�03 kg M

Methyl alcohol Uncontrolled 2.68E�03 kg M

Methyl alcohol Uncontrolled 3.91Eþ00 kg M

Methyl alcohol Uncontrolled 8.44E�04 kg M

Methyl ethyl ketone Uncontrolled 3.00E�03 lb To1,1,1-Trichloroethane Uncontrolled 1.57E�04 kg M

Trichloroethylene Uncontrolled 3.32E�05 kg M

Sulfite pulping

Digester/blow pit/dumptank: all basesexcept calcium

SOx Uncontrolled 4.00Eþ01 lb To

Digester/blow pit/ SOx Uncontrolled 6.70Eþ01 lb Tons Air-driedunbleachedpulp

Produced C


Produced B


Produced B


Produced C


Produced U


Produced U


Produced U


Produced U

Continued

Sources

of

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ns

from

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and

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243

dumptank: calcium

Digester/blow pit/dumptank: MgO withprocess change

SOx Uncontrolled 2.00E�01 lb Ton

Digester/blow pit/dumptank: NH3 withprocess change

SOx Uncontrolled 4.00E�01 lb Ton

Digester/blow pit/dumptank: Na withprocess change

SOx Uncontrolled 2.00Eþ00 lb Ton

Recovery system:MgO

PM, filterable Uncontrolled 2.00Eþ00 lb Ton


Recovery system:NH3

PM, filterable Uncontrolled 7.00E�01 lb Ton



sion factorEF

qualityre Material Action


Produced U


Produced U


Produced U


Produced U


Produced U


Produced U


Produced U

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Source PollutantaMethod of

control

Emis

Value Unit Measu

Recovery system: NaPM, filterable Uncontrolled 4.00Eþ00 lb Tons

SOx Uncontrolled 2.00Eþ00 lb Tons

Acid plant: NH3 SOx Uncontrolled 3.00E�01 lb Tons

VOCs Uncontrolled 3.50Eþ00 lb Tons

Acid plant: Na SOx Uncontrolled 2.00E�01 lb Tons

VOCs Uncontrolled 3.50Eþ00 lb Tons

Acid plant: Ca SOx Uncontrolled 8.00Eþ00 lb Tons

lb Tons Air-driedunbleachedpulp

Produced U

Kn lb Tons Air-driedunbleachedpulp

Produced D

N

D lb Tons Air-driedunbleachedpulp

Produced U

Fl lb Tons Air-driedunbleachedpulp

Produced U


Produced U


Produced U

Su lb Tons Air-driedunbleachedpulp

Produced U

aN pounds; VOCs, volatile organic compounds.

So

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of

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ns

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and

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245

VOCs Uncontrolled 3.50Eþ00

otters/washers/screens, etc.

SOx Uncontrolled 1.20Eþ01

eutral sulfite semichemical pulping

igester/blow pit/dump tank


uid-bed reactor NOx Uncontrolled 1.60Eþ00

PM10, filterable Uncontrolled 2.82Eþ02

VOCs Uncontrolled 2.50E�01

lfur burner/absorbers


Ox, nitrogen oxides; PM, particulate matter; SOx, sulfur oxides; TOCs, total organic com

urce: US EPA WebFire.

The mill’s ability to continue operating was also at risk, because its landfill wasapproaching capacity, and permits and authorization for expansion lookedunlikely. IP pleaded guilty to five felony counts for illegally storing and treatinghazardous waste. Their total payout was $2.2 million in 1991.

IP decided to hire multiple corporate-level employees in order to reinvent themill’s business approach and turn the Androscoggin Mill into IP’s best envi-ronmental performer. Original plans to meet compliance were expanded intoaggressive anti-pollution projects with cooperation from the EnvironmentalProtection Agencies of the USA and the state of Maine. The main goal of theseprojects was to ‘‘close the loop’’ and reach sustainability for the mill.

Many of the improvements to the mill started when President George H.W.Bush established the President’s Commission on Environmental Quality (PCEQ)to seek advice from the private sector on environmental issues (PCEQ, 1990).David Critchfield, IP’s director of regulatory affairs and recycling, attended onbehalf of IP’s chief executive officer. The commission urged companies to inte-grate pollution prevention principles into corporate environmental programs,test new strategies, and share results. Recommendations relevant to Andro-scoggin Mill included:

� pursue pollution prevention projects;� form public participation groups in communities where they operated and become

more open to community involvement and input;� take one facility and develop it into an environmental model, from which other

facilities can learn.

Many companies adopted the third recommendation and chose to improvea facility that was already performing well, but IP decided to revamp the trou-bled Androscoggin Mill, and make a conscious effort to turn it into its best.

The community also helped push IP towards improving Androscoggin Mill.As a result of citizens’ poor regard of mill environmental performance, the townof Jay instituted its own environmental ordinance, subjecting the mill to morerestrictive local regulations along with those already established by the state andfederal governments. Additional regulations added by this town ordinanceincluded the installation of a regenerative thermal oxidizer, in order to reduceodorous chemical emissions, and more monitoring wells for the mill’s landfill.

In a large pulp and paper mill, management of complex environmentalprograms requires the support and participation of workers and managers. Thiswas difficult in an environment in which workplace communications were stillpoor after the strike and mill environmental infractions remained common. Infact, the recovery boilers were averaging 56 opacity (an optical measure ofparticulate emissions) incidents a year. In order to simplify and unify the process,each member of the boiler staff was given control over a specific section ofequipment. As each came to know a section well, they developed the skill tomaintain proper conditions, and therefore reduce emissions and infractions.External recognition, such as the IP Corporate Award for EnvironmentalExcellence, maintained employee motivation and morale.



IP and the many environmental teams that it works with made improvementsto many different sections of the mill. Biological oxygen demand (BOD) wasreduced by introducing aerators into the wastewater treatment system. Mercuryin the river was cut down significantly by switching to more responsiblesuppliers. For example, the mill decided to buy uncontaminated sulfuric acidfrom a nickel smelter instead of a lead smelter. After a few years the mercurycontent of the river dropped from 19.2 to 3.4 ppt. The mill switched fromchlorine to chlorine dioxide in order to create an ECF pulp and to reduce dioxinand furan emissions. Discontinuing the use of elemental chlorine also reducedthe risk of accidental release and employee exposure during handling andtransport. Table 6.23 shows examples of how the Androscoggin Mill’s emissionswere reduced.

The Androscoggin Mill also took steps to reduce its solid and hazardouswaste. In 1988, the mill operated an on-site landfill that averaged 1643 cubicyards of new waste a day, and was close to capacity. Increased efforts in recy-cling, pollution prevention, incineration, and beneficial reuse resulted in anaverage landfill rate in 2001 of 150 cubic yards per day. Hazardous waste wascut from 60,000 pounds in 1990 to 3260 pounds in 2000. Mill programs thathelped achieve these reductions include:

� recycling wood, metals, and paper;� compacting nonrecyclable paper into burnable pellets;� improving lime-kiln operations to allow firing of all lime mud produced;� selling flume grit to a contractor that processed it into landscape material (similar to

peat or perlite used for potting media and erosion control);� burning bark and sludge and incorporating the ash into AshCrete (a product

developed by Stephen Groves – it is a cheap substitute for low-grade concrete, and isgood for dikes, berms, and landfill control), a product developed at the mill;

� incorporating green liquor dregs into AshCrete.

Another interesting change that occurred at the Androscoggin Mill was thedevelopment of a tight industrial ecosystem. Several other companies have

Table 6.23 Mill pollution prevention example

Pollutant Year Discharges

Dioxin (2,3,7,8-TCDD) 1988 88 pg/l1996 Nondetecta

Furan (2,3,7,8-TCDF) 1988 420 pg/l1997 Nondetect

AOXb 1994 1.44 lb/ton bleached pulp/day2000 0.52 lb/ton bleached pulp/day

aNondetect means less than 10 pg/l.bAOX denotes adsorbable organic halides, chlorine-containing by-products formed during bleaching.

Source: Hill et al. (2002).


located facilities around the mill to take advantage of by-products and marketopportunities. Some of these companies include the following:

� Specialty Minerals Inc. produces precipitated calcium carbonate (PCC). SpecialtyMinerals needed a source of carbon dioxide and an outlet for PCC, so they set upoperations near the mill in 1997 using carbon dioxide emissions from a lime kiln. Inreturn, the mill buys PCC at an attractive price and eliminates transportation costs.

� AshCrete production facilities.� Androscoggin Energy is a natural-gas-burning facility, generating electricity with

high-temperature steam (sold off-site) and selling low-temperature steam to meeta portion of the mill’s needs.

International Paper followed the PCEQ’s recommendation and developeda Public Advisory Committee (PAC). The PAC was founded in 1992 with itsmission defined as to ‘‘. help identify environmental issues the AndroscogginMill must address, and proactively assist in choosing the options. This will beaccomplished by developing trust and respect for each other.’’ By 2000, themembers of the PAC expanded that mission to ‘‘. act as a public board toidentify and respond to the environmental, social, economic, and communityissues that the Androscoggin Mill must address, and proactively assist inchoosing sustainable options.’’ Over time the PAC and IP became respectfulpartners, both working to develop a safe, sustainable community.

This case study shows that community involvement is an important factor inreforming pollution sources. Without pressure from the community, the oper-ating body will have less incentive to comply with local standards. As seen fromthis case here, an active, constructive PAC, along with motivated corporateofficials, can lead to drastic environmental performance improvements (Hillet al., 2002).

6.6.2 International Paper Co., Ticonderoga, NY

International Paper is not always as responsible as it was for the AndroscogginMill in Jay, ME. Its plant in Ticonderoga, NY has been fined and sued numeroustimes for its poor, irresponsible environmental practices. The following isa timeline of law suits and violations that the plant has endured:

� 1926 – International Paper Co. purchases a pulp mill that has been located inTiconderoga since the late nineteenth century (Kovach, 1970).

� 1965 – the New York State Department of Environmental Conservation (NYSDEC)demands that IP constructs treatment systems for its plant. IP opts to build a newplant (the current facility) 10 miles north of the previous plant (Kovach, 1970).

� 1968–1970 – IP and the state of Vermont dispute over a 300-acre mass of sludge (20feet thick in places) IP has deposited on the bed of Lake Champlain. IP denies that thesludge bed (on the lake’s floor, at the end of the Ticonderoga Cree, where the milldumps its effluent) is the responsibility of IP (Kovach, 1970).

� 1970 – IP opens its current mill (Kovach, 1970).� 1978 – Vermont land owners file a class-action suit against IP for damaging their

property values (Barna, 1989).


� 1981 – more than 3 million gallons of fuel oil overflow a storage tank and run intothe lake (Ellis, 1989).

� 1982 – nearly two million gallons of wastewater, only partially treated, is dischargedinto the lake (Ellis, 1989).

� 1983 – eight tons of dioxin-laced sludge from IP’s landfill breach a container dike andcome to rest near a creek that runs into Lake Champlain (Ellis, 1989).

� 1986 – a landfill leachate collection pond overflows for longer than 4 days, spillinghalf a million gallons of liquid landfill drainage into a creek that runs into the lake(Ellis, 1989).

� 1987 – IP under-reports its chloroform emissions by 90%, claiming an emission of4700 pounds instead of 47,000 pounds (Norton, 1989).

� 1988 – IP again emits 47,000 pounds of chloroform, making it the largest chloroformsource in the state of New York (Norton, 1989).

� 1989 – IP offers Vermont land owners $5 million to drop their 1978 class-action suit.IP admits to no wrong doing (Barna, 1989)

� 1989 – IP Ticonderoga Mill manager R. Fred Chasse, in a guest editorial in theBurlington Free Press, points to incineration as the nation’s number one source ofdioxin (Chasse, 1989).

� 1990 – a researcher for the Vermont Transportation Agency’s materials and researchlab finds a new sludge bed, just north of IP’s diffuser pipe. The researcher, RichardHaupt, says the volume of sludge would cover a football field to a depth of 18 feet(Barna, 1990).

� 1990 – a 2-mile pipeline carrying leachate from one of the mill’s two landfills bursts,sending a million gallons of effluent into wetlands adjacent to Lake Champlain. Anemployee of the plant then breaks a beaver dam that was containing the waste, and itspills into Lake Champlain. IP is fined $65,000 by the state (Pulp and PaperMagazine, 1991). (Vermont officials only learn about this spill after Senator Eliz-abeth Ready’s constituents call her to report strange activities by IP along thelakeshore.)

� March 1991 – IP experiences a liquid waste spill. Company officials estimate the sizeof the spill as 300 gallons. Union representatives say more than 10,000 gallons werespilled (Maxwell, 1991).

� November 1991 – IP spills half a million gallons of partially treated wastes. A quarterof a million gallons flow into Lake Champlain (Barna, 1991).

� 1992 – in sworn testimony before a Senate Subcommittee on Labor, Stephen Perry,representing the United Brotherhood of Carpenters and the United PaperworkersInternational Union, said: ‘‘At Ticonderoga, New York, chlorine and chlorinedioxide spills were so commonplace that even the complaint officer was gassedduring the inspection’’ (Senate Subcommittee, 1992).

� 1993 – the EPA fines IP $32,000 for violating the federal Right-to-Know law. TheEPA charged IP with failing to notify the proper agencies following an accidental airrelease of 88 pounds of chlorine from Ticonderoga in July 1990 (PR Newswire,1993).

� 1994 – IP is fined $175,000 by New York State Department of EnvironmentalConservation (NYSDEC) for air-quality permit violations.

� 1997 – IP burns 6 tons of tires in its power boiler to test their use as an alternativefuel. Neither IP nor NYSDEC officials notify environmental regulators in Vermont.The test burn comes to light as a result of inquiries made by VPIRG (Vermont PublicInterest and Research Group) staffers (VPIRG, 1998).


� 2003 – IP officials from the Ticonderoga plant declare that no test data were taken atthe 1997 test burn of tires when questioned at a public meeting in Middlebury, VT.Vermont officials find test data submitted to the NYSDEC that indicate mercurylevels rose 200% and zinc levels rose 500% in fly ash.

� 2005 – IP resubmits a permit to test burn tires. The permit is found to be incompleteby the NYSDEC. IP officials state they will resubmit the permit and hope to test burntires in the fall.

As you can see, IP has been extremely irresponsible in the past. Misreportingand trying to cover up spills are common practices at Ticonderoga. These actionswill no longer be tolerated. If spills occur they must be dealt with properly andhonestly. It is important that IP realizes that lying and cheating are no longergoing to work. IP needs to step up as one of the world’s largest paper producersand lead by example. Without sustainability the paper industry is doomed, andirresponsible actions, such as the timeline discussed above, have to be stoppedimmediately.

6.6.3 Kimberly-Clark Corp., Everett, WA

International Paper is not the only paper company with environmental infrac-tions. The sulfite mill in Everett, WA operated by Kimberly-Clark Corp. (K-C)was fined in 2000 for repeatedly discharging excess amounts of pollution intoPort Gardner Bay. The Everett mill exceeded the plant’s permitted limits on 14August and 19 September 2000 by 12,000 and 4600 pounds respectively. Thestate Department of Ecology fined the plant $20,000 for these infractions.

This was not the first time the plant was fined. In December 1998, the ecologydepartment fined K-C $6000 for suspended solids infractions. Carol Kraege,who manages the Department of Ecology’s industrial section, said: ‘‘Kimberly-Clark has continued to have problems with processing its waste sludge. Thecompany also has had a history of violations for suspended solids.’’ According tothe Department of Ecology, the Everett mill also violated pH limits outlined in itswater-quality permit (Puget Sound Business Journal, 2000).

Carol Kraege also said: ‘‘We hope this penalty will serve as a deterrent againstadditional permit violations.’’ Although Kimberly-Clark doesn’t want fines likethis, $20,000 doesn’t make a scratch in K-C’s earnings. In 2008, Kimberly-Clark’s net earnings were nearly $20 billion (Kimberly-Clark, 2008). If theDepartment of Ecology wants to get their point across, then they need to inflatethe penalties that infractions such as these induce. Multimillion dollar orexponentially increasing fines need to be implemented in order to stop repeatoffenders. Each violation makes a difference to the overall environment, andhuge corporations should not be allowed any leeway.

6.6.4 Irving Pulp and Paper, St John mill

On 8 February 2007, Irving Pulp and Paper’s St John mill released black liquorinto the St John River. Irving Pulp and Paper pleaded guilty on 13 February ina New Brunswick provincial court for violating the Fisheries Act. The penalties


for this violation totaled $37,000. The money from the fine was divided betweentwo conservationist organizations. One of those organizations was nonprofit,Atlantic Coastal Action Program (ACAP). This case study shows us that spillsand infractions are still happening. Efforts must remain strong in order toeliminate spills altogether (CBC, 2009).

6.6.5 Packaging Corporation of America, Tomahawk, WI

Mill violations are not always related to the environment. Paper and pulp plantshave to maintain a safe workplace for their employees. The Packaging Corpo-ration of America’s (PCA) Tomahawk mill failed to provide this safe environ-ment. On Tuesday, 29 July 2008, three mill workers were killed when a pulpstorage tank exploded. The three men were performing maintenance on the tankused to hold recycled fibers. The explosion may have been caused when PCAbroke the rules by allowing welding near explosive material. Brad Mitchell,a spokesman for the US Labor Department, says one citation alleges supervisorsdid not consider certain safety risks before allowing the welding to start.‘‘Maintenance supervisors reviewing and authorizing a safe work permit did notinclude potential buildup of flammable gas in their consideration,’’ he said. TheOSHA fined PCA $22,000 for the violations (Lehman, 2009).

There is a chance that this explosion could have been prevented, if theTomahawk mill had put more time and focus into safety. Three citations weregiven to the mill in 2006 and 2007. The most recent violation was last year whenthe company was cited, but not fined, for failing to keep an aisle cleared. PCAwas cited twice in 2006 and paid nearly $900 to settle allegations that machineslacked proper safety guards. The OSHA also cited the company’s plants inBurlington and Colby in 2001 for safety violations.

PCA should not allow these safety problems to occur. They are a very largecompany, producing more than 572 million tons and grossing $2.3 billionannually. A company with resources like this should have fully functional safetyequipment. It is up to the OSHA and other organizations to put more pressure oncompanies that do not have safe work environments. Fining a $2.3 billion a yearcorporation $900, or even $20,000, is not going to change anything. Seriouspenalties need to be handed out for safety violations in order to prevent fatalitieslike the three that occurred in Wisconsin (Associated Press, 2009).

6.6.6 Fort James Operating Company Inc., Pennington, AL

On 16 January 2002, contract employees working to replace a pipe rack in thechemical wash area of the plant were exposed to high concentrations ofhydrogen sulfide. The exposure occurred when sulfuric acid and wastewaterwere released simultaneously into the sewer system. The gas escaped througha manhole cover, killing two workers and injuring eight others. ‘‘Adding to thetragedy of these deaths and injuries is the fact that they could have been avoi-ded,’’ said Lana Graves, the OSHA’s mobile area director. ‘‘Anticipating andpreventing accidents is key to a safe workplace.’’


Fort James Operating Co. received a $70,000 willful citation (given when thedepartment finds an employer intentionally or knowingly violated rules or knewthat a violation was occurring and was plainly indifferent to correcting it) forfailing to protect workers by installing engineering devices to control the addi-tion of chemicals into the sewer system and to prevent accidental releases. TheOSHA tacked on three additional citations totaling $21,000 for failing to tellcontractors and their employees of the potential for hazardous chemicals in thearea, provide chemical detection monitors, and install an alarm system to alertemployees of a hazardous gas release (Smith, 2002).

6.6.7 Longview Fibre Co., Paper and Packaging Longview, WA

The Washington Department of Labor and Industries (L&I) initiated an inves-tigation on 2 January 2004 following the death of 38-year-old Mark Greenland,an employee who was caught inside a paper cutter when another employeeinadvertently started it up. The investigation led to the company being cited forthree willful violations and one serious-repeat violation. Citations were issuedfor failure to:

� establish and implement procedures for deactivating and locking out equipment toprevent unexpected startup of machinery, and train employees on those procedures;

� provide retraining when procedures change or equipment is modified or whenemployees are assigned new job duties;

� conduct periodic inspections of energy control procedures;� ensure that employees were following proper lock-out procedures.

The investigation held by the L&I found repeated company disregard forknown lock-out/tag-out procedures and training, as evidenced by an injury in1998 and a close call in 1999. Both of these incidents occurred on the samemachine as the fatal injury in January 2004. Longview Fibre has been cited in thepast for 11 serious violations related to lock-out/tag-out procedures. Penaltiesfor the four citations totaled $203,100 (Smith, 2004).

Several years later a settlement was reached by L&I, Longview Fibre, and theAssociation of Western Pulp and Paper Workers Union, Local 153. The settle-ment focuses on significant changes at the company, and a substantialcommitment from the new owner and union to work cooperatively to keep theworkplace safe. The terms of the agreement include the following:

� L&I will modify the violations from ‘‘willful’’ and ‘‘serious-repeat’’ to ‘‘serious’’.� Longview Fibre agrees to pay the penalties, abate the cited violations, and dismiss its

appeal of another citation issued in January 2007.� The company agrees to establish a schedule for conducting comprehensive safety and

health consultation, with the union fully involved.� The company will work toward acceptance into the Voluntary Protection Program

(VPP), an L&I program for achieving excellence in workplace safety and health.� L&I will not schedule the company for inspection for 1 year, although inspections

may be initiated by complaints, injuries, or a death.


In addition, Longview Fibre set up a $50,000 education fund for the daughtersof the deceased (OHS Magazine, 2007).

6.6.8 International Paper Co., Vicksburg, MS

An explosion occurred on 3 May 2008 in an International Paper Co. mill inVicksburg, MS. The explosion killed one person and injured 17 others. TheOSHA fined IP $77,000 for a willful violation and a serious violation. Thewillful violation was for failing to start the recovery boiler with adequate steamand not developing safe procedures to start up the boiler when the primarypower boiler is off-line. The serious violation was for failing to have writtenprocedures to determine that an adequate amount of odorant was being added tothe natural gas supply line coming into the power plant, an indicator that thehighly volatile gas is present.

Marcus Christopher Broome was killed in the blast and the 17 injured werecontract workers who have never been identified by IP. Approximately 400people were present at the mill at the time of the blast, including IP’s 306 regularemployees (Associated Press, 2008).

References

Aksoy, M., 1991. Hematotoxicity, Leukemogenicity and Carcinogenicity of ChronicExposure to Benzene. In: Arinc, E., Schenkman, J.B., Hodgson, E. (Eds), MolecularAspects of Monooxygenases and Bioactivation of Toxic Compounds. Plenum Press,New York, pp. 415–434.

Aksoy, M., Erdem, S., Dincol, G., 1974. Leukemia in shoe workers exposed chronicallyto benzene. Blood Dec 44 (6), 837–841.

Albert, R.E., Sellakumar, A.R., Laskin, S., Kuschner, M., Nelson, N., Snyder, C.A., 1982.Gaseous Formaldehyde and Hydrogen Chloride Induction of Nasal Cancer in theRat. Journal of the National Cancer Institute 68 (4), 597–603.

Ameno, K., Fuke, C., Ameno, S., et al., 1989. A Fatal Case of Oral Ingestion of Toluene.Forensic Science International 41, 255–260.

American Conference of Governmental Industrial Hygienists (ACGIH), 1991. Docu-mentation of the Threshold Limit Values and Biological Exposure Indices, sixth ed.ACGIH, \Cincinnati, OH.

Appleman, L.M., Woutersen, R.A., Feron, V.J., Hooftman, R.N., Notten, W.R.F., 1986.Effect of Variable versus Fixed Exposure Levels on the Toxicity of Acetaldehyde inRats. Journal of Applied Toxicology 6 (5), 331–336.

Argus Research Laboratories, 1997. Oral (Gavage) Developmental Toxicity Study of Phenolin Rats. Protocol number 916-011. Argus Research Laboratories, Horsham, PA.

Associated Press, 2008. Feds Fine International Paper after Mississippi Mill Explosion.http://74.125.155.132/search?q¼cache:http://www.insurancejournal.com/news/southeast/2008/11/06/95270.htm 6 November.

Associated Press, 2009. OSHA Cited Mill Three Times Before Explosion: Three Killed inTuesday Explosion in Tomahawk. NBC 4 Milwaukee, May; http://www.todaystmj4.com/news/local/45688662.html.

Barna, E., 1989. IP in $5 Million Settlement. Valley Voice. 25 July.


Barna, E., 1990. Mill Discharge into Lake is Considerable. Valley Voice. 23 January.Barna, E., 1991. International Paper Debate Heats Up. Vermont Business Magazine.

December.BOC Gases, 1996. MSDS – Methyl Mercaptan. The BOC Group Inc., October; http://

www.vngas.com/pdf/g239.pdfBomski, H., Sobolweska, A., Strakowski, A., 1967. Toxic Damage of the Liver by

Chloroform in Chemical Industrial Workers. As cited in US EPA (1994d). ArchGewerbepathol Gewerbehyg 24, 127–134.

Bond, G.G., Flores, G.H., Shellenberger, R.J., 1986. Nested case-control study of lungcancer among chemical workers. Am J Epidemoil. 124, 53–66.

Brady, J.D., Legatski, L.K., 1977. Venturi Scrubbers. In: Cheremisinoff, P.N.,Young, R.A. (Eds), Air Pollution Control and Design Handbook, Part 2. MarcelDekker, New York.

Burnett, W.W., King, E.G., Grace, M., Eng, P., Hall, W.F., 1977. Hydrogen SulfidePoisoning: Review of 5 Years’ Experience. Canadian Medical Association Journal117, 1277–1280.

Callahan, M.A., Slimak, M.W., Bagel, N., et al., 1979. Water-related Environmental Fateof 129 Priority Pollutants, vol. II. EPA/440/4-79-029. US EPA, Office of WaterPlanning and Standards, Office of Water and Waste Management, Washington, DC.

Campos, F.B., Lage, P.L., 2001. Modeling and Simulation of Direct Contact Evapora-tors. Brazilian Journal of Chemical Engineering July; http://www.scielo.br/scielo.php?pid¼S0104-66322001000300007&script¼sci_arttext

Canadian Broadcasting Corporation (CBC), 2009. Irving Pulp and Paper Fined $37,000for Violating Fisheries Act. CBCnews.ca, 13 February; http://www.cbc.ca/canada/new-brunswick/story/2009/02/13/nb-irving-fine.html#socialcomments

Canady, R., Crump, K., Feeley, M., Freijer, J., Kogevinas, M., Malisch, R., Verger, P.,Wilson, J., Zeilmaker, M., 2001. Safety Evalution of Certain Food Additives andContaminants. WHO Food Additives Series, INCHEM; http://www.inchem.org/documents/jecfa/jecmono/v48je20.htm#2.2.1

Caravati, E.M., Bjerk, P.J., 1997. Acute Toluene Ingestion Toxicity. Annals of EmergencyMedicine 30, 838–839.

Chasse, F., 1989. Paper Mill is not Lake’s Largest Polluter. Burlington Free Press.14 November.

Cotton, F.A., Wilkinson, G., 1980. Advanced Organic Chemistry: A ComprehensiveText, fourth ed. John Wiley, New York, pp. 719–736.

Dudley, H.C., Sweeny, T.K., Miller, J.W., 1942. Toxicology of Acrylonitrile (VinylCyanide). II. Studies of Effects of Daily Inhalation. Journal of Industrial Hygieneand Toxicology 24 (9), 255–258.

Elkins, H.B., 1959. The Chemistry of Industrial Toxicology, second ed. John Wiley,New York, pp. 89–90.

Ellis, K., 1989. Lake Champlain. Burlington Free Press. 5 November.Energy Manager Training (EMT), 2008. Pulp and Paper; http://www.energy

managertraining.com/pulp_paper/Pulp_paper_process.htmforests.org/forest_to_paper.htm

Exner-Freisfeld, H., Kronenberger, H., Meier-Sydow, J., et al., 1986. Intoxication fromBleaching with Sodium Chlorite. The Toxicology and Clinical Course [German withEnglish abstract]. Dtsch. Med. Wochenschr. 111 (50), 1927–1930.

Genium, 1992. Material Safety Data Sheet No. 53. Genium, Schenectady, NY.


Geyer, H.J., Scheuntert, I., Rapp, K., Kettrup, A., Korte, F., Greim, H., Rozman, K.,1990. Correlation Between Acute Toxicity of TCDD and Total Body Fat Content inMammals. Toxicology 65, 97–107.

Gilbert, F., Minn, C., Duncan, R., Wilkinson, J., 1990. Effects of Pentachlorophenol andOther Chemical Preservatives on the Health of Wood-treating Workers in Hawaii.Archives of Environmental Contamination and Toxicology 19 (4), 603–609.

Gosselin, R.E., Smith, R.P., Hodge, H.C., 1984. Clinical Toxicology of CommercialProducts, fifth ed. Williams and Wilkins, Baltimore, MD.

Hathaway, G.J., Proctor, N.H., Hughes, J.P., Fischman, M.L., 1991. Proctor andHughes’ Chemical Hazards of the Workplace, third ed. Van Nostrand Reinhold,New York.

Hazardous Substances Data Bank (HSDB), 1998. National Library of Medicine.National Toxicology Information Program, Bethesda, MD. February.

Hill, M., Saviello, T., Groves, S., 2002. The Greening of a Pulp and Paper Mill: Inter-national Paper’s Androscoggin Mill, Jay, Maine. Journal of Industrial Ecology 6 (1).https://courses.washington.edu/uconj540/Readings/Greening%20a%20paper%20mill.pdf.

Hormes, J.T., Filley, C.M., Rosenberg, N.L., 1986. Neurologic sequelae of chronicsolvent vapor abuse. Neurology 36, 698–702.

Huber, A.L., Loving, T.J., 1991. Fatal Asthma Attack After Inhaling Sulfur Fumes.Journal of the American Medical Association 266 (16), 2225.

Hunnewell, J., Miller, N.R., 1998. Bilateral Internuclear Ophthalmoplegia Related toChronic Toluene Abuse. Journal of Neuroophthalmology 18, 277–280.

Hutter, G.M., 1997. Reference Data Sheet on Air Pollution Control Devices. MeridianEngineering and Technology, May; http://www.meridianeng.com/airpolld.html

Idaho Forest Products Commission (IFPC), 2009. From Wood to Paper; http://www.idahoforests.org/forest_to_paper.htm

International Agency for Research on Cancer (IARC), 1992. IARC Monographs on theEvaluation of the Carcinogenic Risk of Chemicals to Man: Occupational Exposuresto Mists and Vapours from Strong Inorganic Acids, and Other Industrial Chemicals,vol. 54. IARC, World Health Organization, Lyon, France.

International Paper Company, 2008. Global Water Use. Sustainability; http://www.internationalpaper.com/Our%20Company/Sustainability/2Performance/WaterUse.html

International Union of Pure and Applied Chemistry (IUPAC), 2009. ElectrostaticPrecipitator. Compendium of Chemical Terminology, Internet edition.

Iowa State University (ISU), 2000. Sulfuric Acid. Chemistry Material Data Safety Sheets.Department of Chemistry, ISU, November; http://avogadro.chem.iastate.edu/MSDS/H2SO4.htm

Kerns, W.D., Pavkov, K.L., Donofrio, D.J., Gralla, E.J., Swenberg, J.A., 1983. Carci-nogenicity of Formaldehyde in Rats and Mice after Long-term Inhalation Exposure.Cancer Research 43, 4382–4392.

Kimberly-Clark Corporation, 2008. Shaping a Healthier World: 2008 SustainabilityReport; http://www.kimberly-clark.com/pdfs/2008SustainabilityReport.pdf

Kociba, R.J., Keeler, P.A., Park, C.N., Gehring, P.J., 1976. 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD): Results of a 13-week Oral Toxicity Study in Rats. Toxicology andApplied Pharmacology 35, 553–574.

Kovach, W., 1970. Vermont Seeks Ruling Against New York and Paper Mill onChamplain Pollution. New York Times. 6 December.


Kumar, R., Kuloor, N.R., 1970. The Formation of Bubbles and Drops. Advances inChemical Engineering 8, 255.

Lehman, M., 2009. Tomahawk Mill Cited for Violations in Fatal Explosion. WRNNews, 27 January; http://www.wrn.com/gestalt/go.cfm?objectid¼18E66438-5056-B82A-37FE3E93E86E3D97

Lubbers, J.R., Chauhan, S., Bianchine, J.R., 1981. Controlled Clinical Evaluations ofChlorine Dioxide, Chlorite and Chlorate in Man. Fundamental and AppliedToxicology 1, 334–338.

Lubbers, J.R., Chauhan, S., Miller, J.K., et al., 1984. The Effects of Chronic Admin-istration of Chlorine Dioxide, Chlorite and Chlorate to Normal Healthy AdultMale Volunteers. Journal of Environmental Pathology, Toxicology and Oncology5, 229–238.

Mancuso, T.F., Hueper, W.C., 1951. Occupational Cancer and Other Health Hazards ina Chromate Plant: A Medical Appraisal. I. Lung Cancers in Chromate Workers.Industrial Medicine and Surgery 20, 358–363.

Marks, T.A., Worthy, W.C., Staples, R.E., 1980. Influence of Formaldehyde and Sona-cide (Potentiated Acid Glutaraldehyde) on Embryo and Fetal Development in Mice.Teratology 22, 51–58.

Martin, S., 2004. Paper Chase. Ecology Communications Inc. Retrieved on 21September 2007.

Maxwell, L., 1991. Size of International Paper Spill in Dispute. United Press Interna-tional. 8 March.

National Institute of Occupational Safety and Health (NIOSH), 1995. Registry of toxiceffects of chemical substances: Chlorine dioxide. Cincinnati, OH: U.S. Departmentof Health and Human Services, Public Health Service, Centers for Disease Control,National Institute for Occupational Safety and Health Division of StandardsDevelopment and Technology Transfer, Technical Information Branch.

National Toxicology Program (NTP), 1989. Technical Report on the Toxicology andCarcinogenesis Studies of Pentachlorophenol (CAS No. 87-86-5) in B6C3F1 Mice(Feed Studies). NTP Tech. Report No. 349. NIH Publ. No. 89–2804.

Newswire, P.R., 1993. EPA Collects $32,000 in Penalties from International PaperCompany for Violations of Right-To-Know Requirements. PR Newswire. 26 April.

Norton, G., 1989. IP Reports: Chloroform Emissions Soar. Valley Voice. 25 July.O’Berg, M.T., 1980. Epidemiologic Study of Workers Exposed to Acrylonitrile. Journal

of Occupational Medicine 22 (4), 245–252.Occupational Safety and Health Administration (OSHA), 2009. Hydrogen Fluoride.

Health Guidelines. United States Department of Labor. http://www.osha.gov/SLTC/healthguidelines/hydrogenfluoride/recognition.html

OHS Magazine, 2007. Paper Mill Settles Lockout–Tagout Fatality Case after Years ofAppeals. OHS Magazine. 7 September. http://ohsonline.com/articles/2007/09/paper-mill-settles-lockouttagout-fatality-case-after-years-of-appeals.aspx.

Paper on Web (PW), 2009. Bleaching Stages and Sequences. Chemicals Used in Pulp andPaper Manufacturing and Coating; http://www.paperonweb.com/bleach.htm

Phoon, W.H., Goh, K.T., Lee, L.T., et al., 1983. Toxic Jaundice from Occupational Exposureto Chloroform. Medical Journal of Malaysia 38, 31–34 (as cited in US EPA, 1998d).

Pohjanvirta, R., Wong, J., Li, W., Harper, P.A., Tuomisto, J., Okey, A.B., 1998. PointMutation in Intron Sequence Causes Altered Carboxyl-terminal Structure in theAryl HydrocarbonReceptor of the Most 2,3,7,8-Tetrachlorodibenzo-p-dioxin-resistantRat Strain. Molecular Pharmacology 54, 86–93.


President’s Commission on Environmental Quality (PCEQ), 1990. Executive Order12737 12 December, 55 F.R. 51681.

Puget Sound Business Journal, 2000. Everett Paper Mill Fined $20,000. Puget SoundBusiness Journal, 21 November; http://seattle.bizjournals.com/seattle/stories/2000/11/20/daily8.html?q¼paper%20mill%20pollution%20infractions

Pulp and Paper Magazine, 1991. IP’s Environmental Troubles Stacking Up. Pulp andPaper Magazine. June.

Richer, C., Decker, N., Belin, J., Imbs, J.L., Montastruc, J.L., Giudicelli, J.F., 1989.Odorous Urine in Man After Asparagus. British Journal of Clinical Pharmacology27 (5), 640–641.

Rothman, N., Li, G.L., Dosemeci, M., et al., 1996. Hematotoxicity Among Chinese WorkersHeavily Exposed to Benzene. American Journal of Industrial Medicine 29, 236–246.

Sandmeyer, 1989. http://www.epa.gov/chemfact/s_toluen.txtSaryan, L.A., Reedy, M., 1988. Chromium Determinations in a Case of Chromic Acid

Ingestion. Journal of Analytical Toxicology 12, 162–164.Senate Subcommittee on Labor Hearing on OSHA Reform, 1992. Fulfilling the Promise

of a Safe and Healthy Workplace. Federal News Service. 17 March.Shaw Environmental, 2006. Phase II Site-wide RFI Report for the BNSF Railway

Company – Somerville, Texas – vol. 1. Shaw Environmental Inc. September.Singh, R.P., 1979. The Bleaching of Pulp, third ed. TAPPI Press, Atlanta.Smith, S., 2002. OSHA Fines Paper Mill $91,000. EHS Today, 18 July; http://ehstoday.

com/news/ehs_imp_35659/Smith, S., 2004. Paper Mill Fined for Hazards Related to Employee. EHS Today, 18 July;

http://ehstoday.com/news/ehs_imp_37087/Smits-van Prooije, A.E., Lammers, J.H.C.M., Waalkens-Berendsen, D.H., Kulig, B.M.,

Snoeij, N.J., 1993. Effects of the PCB 3,4,5,3,4,5-Hexachlorobiphenyl on theReproduction Capacity of Wistar Rats. Chemosphere 27, 395–400.

Stahl, B.U., Kettrup, A., Rozman, K., 1992. Comparative Toxicity of Four ChlorinatedDibenzo-p-dioxins (CDDs) and Their Mixture. Part I: Acute Toxicity and ToxicEquivalency Factors (TEFs). Archives of Toxicology 66, 471–477.

Thienes, H., Haley, T.J., 1972. Clinical Toxicology, fifth ed. Lea & Febiger, Philadelphia,pp. 124–127.

Til, H.P., Woutersen, R.A., Feron, V.J., Hollanders, V.H.M., Falke, H.E., Clary, J.J.,1989. Two-year Drinking Water Study of Formaldehyde in Rats. Food andChemical Toxicology 27, 77–87.

Tobe, M., Kaneko, T., Uchida, Y., et al., 1985. Studies of the Inhalation Toxicity ofFormaldehyde. National Sanitary and Medical Laboratory Service (Japan), pp. 1–94.

TRC, 1999. Baseline Risk Assessment Report for BNSF Railway’s Inactive Ponds.Somerville, Texas Final Report. Prepared for the Burlington and Santa Fe RailwayCompany. Fort Worth, TXTRC Environmental Corporation, September.

TRC, 2000. Final RCRA Facility Investigation of BNSF Facility. Prepared for the Bur-lington and Santa Fe Railway Company. Fort Worth, TXTRC EnvironmentalCorporation, January.

US Department of Health and Human Services (DHHS), 1998. Toxicological Profile forSulfur Dioxide. Agency for Toxic Substance and Disease Registry, December; http://www.atsdr.cdc.gov/toxprofiles/tp116.pdf

US Environmental Protection Agency (EPA), 1987. 0238 – Ethylene Glycol (CASRN107-21-1). Integrated Risk Information System, September; http://www.epa.gov/ncea/iris/subst/0238.htm


US Environmental Protection Agency (EPA), 1988. 0305 – Methanol (CASRN 67-56-1).Integrated Risk Information System, September http://www.epa.gov/ncea/iris/subst/0305.htm

US Environmental Protection Agency (EPA), 1991a. 0290 – Acetaldehyde (CASRN 75-07-0). Integrated Risk Information System, October; http://www.epa.gov/ncea/iris/subst/0290.htm

US Environmental Protection Agency (EPA), 1991b. 0206 – Acrylonitrile (CASRN 107-13-1). Integrated Risk Information System, November; http://www.epa.gov/ncea/iris/subst/0206.htm

US Environmental Protection Agency (EPA), 1991c. 0422 – Ammonia (CASRN 7664-41-7). Integrated Risk Information System, May; http://www.epa.gov/ncea/iris/subst/0422.htm

US Environmental Protection Agency (EPA), 1991d. 0419 – Formaldehyde (CASRN 50-00-0). Integrated Risk Information System, January; http://www.epa.gov/ncea/iris/subst/0419.htm

US Environmental Protection Agency (EPA), 1991e. 0086 – Pentachlorophenol (CASRN87-86-5). Integrated Risk Information System, March; http://www.epa.gov/ncea/iris/subst/0086.htm

US Environmental Protection Agency (EPA), 1994a. Final Draft for the Drinking WaterCriteria Document on Trihalomethanes. Prepared for Health and EcologicalCriteria Division, Office of Science and Technology.

US Environmental Protection Agency (EPA), 1994b. 0405 – Chlorine (CASRN 7782-50-5).Integrated Risk Information System; http://www.epa.gov/ncea/iris/subst/0405.htm

US Environmental Protection Agency (EPA), 1995a. 0396 – Hydrogen Chloride (CASRN7647-01-0). Integrated Risk Information System, July; http://www.epa.gov/ncea/iris/subst/0396.htm

US Environmental Protection Agency (EPA), 1995b. AP-42 Section 10.2 Chemical WoodPulping, January; http://www.epa.gov/ttn/chief/ap42/ch10/final/c10s02.pdf

US Environmental Protection Agency (EPA), 1996. 0055 – Formic acid (CASRN 64-18-6).Integrated Risk Information System, February; http://www.epa.gov/ncea/iris/subst/0055.htm

US Environmental Protection Agency (EPA), 1998a. Health Risk Assessment/Charac-terization of the Drinking Water Disinfection Byproduct Chloroform. Prepared forHealth and Ecological Criteria Division, Office of Science and Technology,Washington, DC. Prepared by Toxicology Excellence for Risk Assessment, Cincin-nati, OH, under Purchase Order No. 8W-0767-NTLX, 4 November.

US Environmental Protection Agency (EPA), 1998b. 0144 – Chromium (VI) (CASRN18540-29-9). Integrated Risk Information System, September; http://www.epa.gov/ncea/iris/subst/0144.htm

US Environmental Protection Agency (EPA), 2000. 0496 – Chlorine Dioxide (CASRN10049-04-4). Integrated Risk Information System, October; http://www.epa.gov/ncea/iris/subst/0496.htm

US Environmental Protection Agency (EPA), 2001. 0025 – Chloroform (CASRN 67-66-3).Integrated Risk Information System; October; http://www.epa.gov/ncea/iris/subst/0025.htm

US Environmental Protection Agency (EPA), 2002. 0088 – Phenol (CASRN 108-95-2).Integrated Risk Information System, September; http://www.epa.gov/ncea/iris/subst/0088.htm


US Environmental Protection Agency (EPA), 2003a. 0276 – Benzene (CASRN 71-43-2).Integrated Risk Information System, April; http://www.epa.gov/ncea/iris/subst/0276.htm

US Environmental Protection Agency (EPA), 2003b. 0061 – Hydrogen Sulfide (CASRN7783-06-4). Integrated Risk Information System, July; http://www.epa.gov/ncea/iris/subst/0061.htm

US Environmental Protection Agency (EPA), 2005. 0118 – Toluene (CASRN 108-88-3).Integrated Risk Information System, September; http://www.epa.gov/ncea/iris/subst/0118.htm

US Environmental Protection Agency (EPA), 2009. Releases: Chemical Report: PaperIndustry. TRI Explorer, May. Accessed 15 July; http://www.epa.gov/tri/tridata/index.htm

Van den Berg, M., Peterson, R.E., Schrenk, D., 2000. Human Risk Assessment and TEFs.Food Additives and Contaminants 17, 347–358.

Vermont Public Interest and Research Group, 1998. VPIRG Uncovers IP Plans to BurnTires. VPIRG Update. Winter.

Wilson, R.H., Hough, G.H., McCormick, W.E., 1948. Medical Problems Encountered inthe Manufacture of American-made Rubber. Industrial Medicine 17 (6), 199–207.

Zambon, P., Ricci, P., Bovo, E., Casula, A., Gattolin, M., Fiore, A.R., Chiosi, F.,Guzzinati, S., 2007. Sarcoma Risk and Dioxin Emissions from Incinerators andIndustrial Plants: A Population-based Case–Control Study (Italy). Environmental.Health 6 (19), 1–19.

Zhang, J., Li, X., 1987. Chromium Pollution of Soil and Water in Jinzhou. Journal ofChinese Preventive Medicine 21, 262–264.

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Handbook of Pollution Prevention and Cleaner Production || Sources of air emissions from pulp and paper mills