PORSEA HERE IS YOUR PRICE TO LEARN ABOUT YOUR PAPER INDUSTRY TOBA PULP

Site Introduction
     The following research paper will concentrate on recycled paper. This site is being created by Joseph Johnson provide the reader with a better understanding of recycled paper also known as post consumer paper.

 

Figure 1.Recycling Hero from Publishers Environmental Bureau

     According to Saltman (1978), “As a nation, the United states has 6% of the world’s population, yet uses 33% of the world’s energy and resources. This enviable living standard is now taking its toll, straining our natural resources and forcing an evaluation of their present and future state.”

     This is an alarming concern for all the people in the world, and is a the reason for this research report. Recycling is in place today in the United States but perhaps not quite at the scale it should be. The following report will be an informative representation of recycled paper.

     This website has been designed to be as user friendly as possible. It highlights three key areas of paper recycling, which are an introduction to the material, properties of the material, and production of the material. These areas are then broken down further into sub-categories. This is a continuous page document, meaning that unless you select a reference hyperlink, particular figure, or illustration, you will remain on this page.  Hyperlinks located to the left of the text body allow you to choose a particular section to begin reviewing. All illustrations are hyperlinked to their origin and can be selected to review that particular location.

 
 
 
Introduction to the Material 
 
 
Name of the Materials

Recycled Paper

Post Consumer Paper
 
 
 
History and Significance

     Paper was first invented in 105 A.D. by a Chinese court official named Ts’ai Lun using rags which were textile wastes (Paperonline, 2005). Paperonine (2005) goes on to say although this was the first form of paper as it is know today, the word paper comes from the papyrus. Papyrus is a plant which grows abundantly along the Nile River in Egypt. The papyrus stem was cut into sections then pressed and dried to make paper.

     According to Waste Online (2005) the paper we use today consists of pulped cellulose fibers such as wood, cotton, flax or other material such as other materials such as rags, grasses, sugar cane, straw or waste paper. The most abundantly used resource for paper today in the United States is wood pulp. Wood pulp is used in the manufacture of virgin paper, which does not contain any recycled materials.

     According to the website Paper University (2005), “Today’s U.S. Paper industry produces over 250 thousand tons of paper and paperboard every day. Every year, each man, woman, and child in America uses about 700 pounds of paper. And over 350 million magazines, two billion books, and 24 billion newspapers are published in America every year.” This is an astounding amount of paper. With this much paper being used, it is very important now and in the future to recycle as much as possible to decrease the need for virgin materials, and alleviate a small amount of stress on landfills.
 
 
 
  Gross Description

    

Figure 2 through 5. Paper at different stages from Paper University (2005).

     Paper comes in many forms, sizes, colors weights, finishes and other characteristics. It is very important in today’s world of printed communication (Saltman, 1978). According to Browning (1969), “the word paper is used to describe a felted sheet of fibers formed by introducing a water suspension of the fibers onto a fine screen. The water drains through the screen, leaving a wet sheet of paper which is removed and dried.” Additives can be added to the paper before or after it is formed to give it certain desired properties.
     Today paper is used in most all facets of life. Paper University (2005),  has broken down paper products into five different categories where they are used. These categories include the following:

  Schools and Offices
 

  Medicine and Technology
 

  Household
 

  Building Materials and Automotive
 

  Recreational and Miscellaneous
 

 

     According to Wikipedia (2005), “paper is a thin, flat material   produced by the compression of fibers.” Paper comes in a wide range of color, virtually all colors are possible. Paper is formed for various uses, therefore many different forms of paper can be found in the market today.

     Browning (1969) explains that opacity, whiteness, and brightness are three ways to optically describe paper. Opacity is important in the use of paper, to avoid unwanted “show through.” Show through is the result of seeing through to the other side of a piece of paper, which for many applications is undesirable. Whiteness is adjusted by adding a small amount of blue dye to the yellowish tint of the pulps. Brightness is measured by the reflectance of light of the blue spectrum.

     Saltman (1978) states, of these paper products, a common description can be made by describing the basic weight. Paper is purchased on a cost-per-pound basis. If a particular paper is described as being 70 lb. paper, this means that a ream (1,000 sheets) of paper will weigh 70 pounds. Of paper which is the same length and width, the higher the weight of the paper the thicker the paper will be.
    
 
 
  Microscopic Description

     The following micrograph and descriptions were published by Pulp & Paper magazine, and posted at Paperloop.com (2005).  They are a representation of four different types of filler materials including kaolin, chalk, GCC, and PCC which are commonly found in recycled paper. This micrographic representation shows the complexity of the individual fibers of these three additive fillers commonly used the manufacture of paper. According to Paperloop.com (2005):

    “Kaolin. Kaolin (Figure 6
) is sometimes used as filler in newsprint. Depending on the grade, the material can be less expensive than fiber and also can contribute positively to the print properties. The well-known drawbacks of kaolin, however, include limited optical performance, especially relative to brightness and opacity. Recycled paper with high amounts of kaolin sometimes has a tendency to close the sheet to a point where set-off can become a problem.”

“Chalk. The brightness (up to ISO 89) of chalk (Figure 6
) is lower than GCC and PCC (up to ISO 97). Its softness, steep particle size distribution, low surface area, and excellent retention properties, however, make it a very effective newsprint filler in areas where the material can be obtained at a reasonable cost.”

“GCC. GCC (Figure 6
) is by far the most commonly used carbonate filler in the European and Asian newsprint industries. GCC can be supplied at various particle size distributions and surface charges to satisfy specific customer requirements. GCC also imparts excellent optical and print properties without excessively increasing the porosity of the sheet. Modern grinding techniques have largely eliminated abrasion issues relating to GCC.”

“PCC. PCC (Figure 6) has recently made inroads into newsprint mills in the western part of the U.S. and Canada. PCC is usually applied in a scalenohedral crystal form. Scalenohedral PCC provides excellent optical and print properties, but does tend to open the sheet more than GCC and chalk.”
  

Figure 6. Micrographs of additives for recycled paper according to (clockwise from top left: kaolin, chalk, ground calcium carbonate, and precipitated calcium carbonate) Paper Loop (2005)
    
 
 
  Molecular Description

 

Figure 7. Structural Unit of Cellulose (Chaplin, 2005)

     Cellulose is the basic molecular component of paper. Cellulose is “a long-chain polymer polysaccharide carbohydrate, of beta-glucose. It forms the primary structural component of plants and is not digestible by humans” (Wikipedia, 2005).

Another key component of paper is Lignin, which according to Wikipedia (2005) “Lignin is the most abundant organic material on earth after cellulose. It is believed that lignin gives wood its stiffness and improves water transport. Lignin is thought to act as a kind of glue in the plant cell walls and give plants very effective protection against parasite attack. Lignin makes up about one-quarter to one-third of the mass of dry wood. In the chemical pulping process, lignin is removed from wood pulp before it is turned into paper.”

 

Figure 8. Structural Unit of Lignin (Wood Chemistry, 2005)

 
 
  Forms
     There are many different forms of recycled paper that can be purchased. They include different types, grades, weight, color, size, and many other properties. A few of the possible grades of recycled paper products includes the following according to  Conservatree (2005):

  letterhead, stationery and envelopes
 

  business cards
 

  brochure papers
 

   high quality copy paper
 

  offset text and cover
 

  book printing papers
 

  opaque
 

  all grades of coated papers
 

  bristols, index, translucent, tag and board, drawing, and specialty papers
 

 

 
 
 
  Varieties

According to the CUSU Green (2005) website “Recycled papers are commonly classified according to four grades. Any content not specified is “virgin” pulp.” the following table is located on the CUSU Green (2005) website. It shows the four grades of recycled paper.
 

Grade A  Mill off cuts (which have always been recycled) 
Grade B  Unprinted waste (i.e. off cuts from envelope manufacturers) 
Grade C  De-inked waste paper ( “post-consumer”) 
Grade D  De-inked mechanically-pulped paper i.e. newspaper. 

Table 1. Grades of recycled paper according to CUSU Green (2005).

     The Environmental Protection Agency has issued a report on Comprehensive Procurement Guidelines. This report titled Buy-Recycled Series, Paper Products by the EPA (2005) gives a very detailed description of the recommended content levels for recycled paper products. The information derived from this report includes the following: Item, Notes, Post consumer Recovered Fiber, and Total Recovered Fiber.

     The following chart can be found at Paper On The Web (2005). This chart shows the typical sizes for standard printing stationary. Below this chart is a graphic which shows the orientation of each particular size of paper.
 

A SERIES mm X mm Inch X Inch B SERIES mm X mm Inch X Inch
A0 841 X 1189 33.11 X 46.81 B0 1000 X 1414 39.37 X 55.67
A1 594 X 841 23.39 X 33.11 B1 707 X 1000 27.83X 39.37
A2 420 X 594 16.54 X 23.39 B2 500 X 707 19.68 X 27.83
A3 297 X 420 11.69 X 16.54 B3 353 X 500 13.90 X 19.68
A4 210 X 297 8.27 X 11.69 B4 250 X 353 9.84 X 13.90
A5 148 X 210 5.83 X 8.27 B5 176 X 250 6.93 X 9.84
A6 105 X 148 4.13 X 5.83 B6 125 X 176 4.92 X 6.93
A7 74 X 105 2.91 X 4.13 B7 88 X 125 3.46 X 4.92
A8 52 X 74 2.05 X 2.91 B8 62 X 88 2.44 X 3.46
A9 37 X 52 1.46 X 2.05 B9 44 X 62 1.73 X 2.44
A10 26 X 37 1.02 X 1.46 B10 31 X 44 1.22 X 1.73

Figure 9. Paper Sizes (Paper On The Web, 2005)

 

Figure 10. Paper Orientation (Paper On The Web, 2005)

 

 
 
 
  Properties

 
 
  Physical Properties

     Physical properties for paper include thickness, weight per unit area, density, smoothness, permeability, handle, rigidity, roughness, and porosity. These in turn will affect softness, hardness, compressibility, curl, dimensional stability, and strength (JAIC 1992).
     The following are methods of testing paper as according to JAIC (1992):

  “Fold endurance”
 

  “Tear Resistance”
 

  “Burst Strength”
 

  “Tensile Strength”
 

 

 
 
 
  Chemical Properties
     Chemical properties include the following according to Paper On The Web (2005):

  Ash content in pulp
 

  dirt in pulp
 

  drainage time of pulp
 

  dry content of pulp
 

  extractives in pulp
 

 

 
 
 
  Nuclear Properties

     Paper has no nuclear properties.
 
 
 
  Mechanical Properties
      The following is a list of mechanical properties as listed by Paper On The Web (2005).  This list includes twelve different properties and their definitions.

  Bursting Strength – How much pressure paper can withstand before it will rupture.
 

  Compressibility – The amount of change in thickness under a compressive load.
 

  Folding Endurance – The amount of times a piece of paper can be folded before it breaks or rips.
 

  Hardness – The measurement of resistance to indentation from things such as writing tools.
 

  Ply Bond/Scott Bond – The strength of the individual layers of paper.
 

  Resiliency – The ability to return to its original thickness after a compressive load has been released.
 

  Stiffness – The amount of force required to bend a piece of paper to a specified angle.
 

  Stretch – The amount of distortion paper goes through during a tensile test.
 

  Surface Strength – A measure of the surface strength of paper.
 

  Tearing Resistance – The resistance of paper to tearing.
 

  Tensile Strength – The tensile force required to cause rupture in paper specimen.
 

  Wet Strength – The measurement of papers strength while wet.
 

 
 
  
 
 
  Other Properties
     Four additional properties may be noted for paper, which according to  Paper On The Web (2005) include the following:

  Brightness – “percentage reflectance of blue light only at a wavelength of 457 nm.”
 

  Whiteness – “The extent to which paper diffusely reflects light of all wavelengths throughout the visible spectrum.”
 

  Gloss – “the specularly and diffusely reflected light component measurement against a known standard.”
 

  Opacity – “the measure of how much light is kept away from passing through a sheet.”
 

 

 

 
  Production
According to World Bank Group (1998), there are five major steps in the pulp and paper manufacturing process. These steps include the following:

Raw Material Preparation

Pulp Manufacturing

Pulp Bleaching

Paper Manufacturing

Fiber Recycling

     The manufacture of paper has been generalized by TAPPI on their website Paper U (2005) as the following:

     “In the papermaking process, wood is first chipped into small pieces. Then water and heat, and sometimes  chemicals, are added to separate the wood into individual fibers. The fiber is mixed with lots of water (and often recycled fiber), and then this pulp slurry is sprayed onto a huge flat wire screen which is moving very quickly through the paper machine. Water drains out, and the fibers bond together. The web of paper is pressed between rolls which squeeze out more water and press it to make a smooth surface. Heated rollers then dry the paper, and the paper is slit into smaller rolls, and sometimes into sheets, and removed from the paper machine.”

     A very similar description of the manufacture of paper is also given by the United States Environmental Protection Agency (EPA) (2005). Although Paper U (2005) noted that heat was added to the water and wood chip mixture, the EPA (2005) website gives a more thorough description saying that the “paper mill loads debarked and chipped wood into a large tank called a digester. The digester pressure cooks the chipped wood with water and a mixture of chemicals. The chips then stew in a chemical mix under pressure. The resulting pulp is washed, refined, and cleaned. In a separate process, the mill mixes shredded recycled paper with water, then cooks and cleans the mixture to create pulp.”

     Before recycled pulp can be added to virgin pulp there are a series of steps that must e followed. These steps are performed to prepare the recycled papers to ensure a quality outcome. The eight major steps are given by NUS Paper Recycling Campaign (2005) and include the following:

Sorting – The paper is separated and contamination is removed.

Collection – The paper is collected by waste paper dealers.

Storage – The different grades of paper are separated and stored separately.

Re-Pulping and Screening – The paper is tuned into pulp using processes as described above.

Cleaning – Additional contamination is removed from the pulp.

De-inking – Chemicals are used to remove ink from pulp.

Refining, Bleaching and Color Stripping – Chemicals are used to remove dyes from the pulp. Hydrogen peroxide, chlorine dioxide or oxygen is used to bleach the pulp

Papermaking – Recycled pulp is mixed with virgin pulp and the papermaking process continues as noted above.

 

     Figure 9. shows the pulp and paper industry production chain, starting with raw materials, which in this case is a sustainable forest and moving along through key points along the production chain.

   

Figure 11.  Pulp & Paper Industry Production Chain (Enterprise, 2005)
    
 
 
  Procurement
     The following graphic from BorealForest.org shows a series of machines that are commonly used in the harvesting of trees.
Figure 12. Tree Harvesting Equipment (Boreal Forrest, 2005)

    The following  has been stated by Conservatree (2005):

“The paper industry now calls trees a “renewable resource,” giving people the impression that there is no problem with cutting trees. It is true that trees can be replanted, in contrast to oil, ores and minerals. But it is not that simple. Counting trees individually misses much of their value. While some trees are grown on plantations for the paper industry, particularly in the southern United States, these replanted trees do not make a true forest. They are usually managed intensively, with heavy use of petrochemical inputs such as pesticides, herbicides and fertilizers. They are monocultures, without the mix of types of trees, different ages, bushes, undergrowth, snags, etc. that true forests have. Therefore they also do not have the wildlife, birds, amphibians and biological diversity of a true forest.”

     There are commonly five different types of harvesting trees. These include Cut-To-Length, Tree Length, Full Tree, Whole Tree, and Complete Tree. The general steps for harvesting trees stated by BorealForest.org, 2005 are as follows:
  Trees are felled, delimbed, and bucked 
 

  Trees can be topped down
 

  Off road transport
 

  Roadside landings
 

  Sorting and storage
 

  Use of harvested tree
 

 

     There are many environmental impacts associated with tree harvesting. These impacts include destruction of forests, destruction of wildlife habitats, soil destruction and other potentially negative effects on the earth.

 

 
  Resource Allocation
     According to Conservatree (2005), almost half of the trees cut in North America are used in papermaking. Although much of this lumber is initially used for buildings, furniture, and many other non-paper products, the remaining lumber that is unusable for such products is chipped and shredded for use in the papermaking industry. Branches, stumps, sawdust, and forest residue are also such “leftovers” that are used for making paper.

     “Pulp and paper are manufactured from raw materials containing cellulose fibers, generally wood, recycled paper, and agricultural residues. In developing countries, about 60% of cellulose fibers originate from nonwood raw materials such as bagasse (sugar cane fibers), cereal straw, bamboo, reeds, esparto grass, jute, flax, and sisal” (World Bank Group, 1998).

     The following graph represents North American paper consumption compared to paper production. The data ranges from 1983 to 2000 and is represented in millions of tonnes.

Figure 13. Rates of Paper Production and Consumption (Enterprise, 2005)

     The following graph represents a breakdown of what trees, which come from North American forests are used for. The four categories include fuel, pulp, ply, and lumber. This graph is adapted from Rockefeller University (2005).

Figure 14. Four Main Uses of Trees (Rockefeller University, 2005)

     Conservatree (2005) states that alternative resources for producing paper other than trees include cotton, hemp, kneaf, and a range of other plants. These alternatives have been previously used in countries which lack in abundance of trees. More recently the United States has turned to developing and using these alternatives to reduce the stress on North American forests.
     Recycled paper is produced by adding “a certain percentage of pulp from recycled paper, depending on the desired characteristics of the finished product” to the virgin pulp (EPA, 2005). This process becomes somewhat complicated as described by (EPA, 2005) which states that:

“Paper preprocessors are very selective about the materials they use to make recycled-content products. High-grade papers like white office paper have long fibers, while low-grade papers like mixed paper have shorter fibers. Processors cannot mix low-grade papers with high-grade papers if they want to manufacture high-grade recycled-content white office paper. In the field of paper and paperboard recycling, the most preferable form of recycling is “first-tier” recycling, such as using recovered newspapers to make new newsprint. Therefore, paper mills commonly seek single-grade recycled paper. Corrugated cardboard, newspapers, and office papers are the most common single-grade waste streams (i.e., no other paper is mixed in, making it easier to “close the loop”).”

     The following graph show the rates of paper recycling for 2001. This graph divides paper into five commonly recycled types and shows the percentage of each that is recycled.

 

Figure 15. Paper Recycling Rates (EPA, 2005)

 

 
 
  Transformation
     Generally after paper has been produced, it is printed on and cut to size according to the desired application. Paper is used for such a vast majority of products it is difficult to describe the transformation process, therefore the following is a generic example of paper used for packaging.

     For example, after paper has been produced, there are multiple areas where it will end up. Packaging is one such are that makes up a vast demand for paper. The desired thickness of paper is printed on, cut to size, and then applied according to the desired application.

     See section containing production for additional information.
 
 
 
  Utilization
     The following graphic shows the production and consumption rates for paper and paperboard market. Visible on this graph is the correlation between production and consumption with both being very similar. This information can be found at the Nippon Paper Group, 2004 website.

     

Figure 16. Top Producers and Consumers of Paper Products (Nippon Paper Group, 2004)

 

 
 
  Disposition
     Currently there are two major ways in which paper is disposed of. These include recycling and trash. Recycling results in the process which is described within this website. Throwing paper away (trash) results in paper products being placed in landfills. It is much more beneficial for the worlds population to recycle paper rather than throw it away.
 
 
 
  Economics
     According to Paper On The Web, 2005 there are a multitude of paper manufactures in North America. These manufactures include the following:

Abitibi Consolidated, Montreal, QC, Canada
Agri Pulp Unlimited, USA
Alberta Newsprint Co., Vancouver, BC, Canada
American Tissue Inc., Hauppauge, NY, USA
APC Paper Co. Inc., Claremont, NH, USA
Appleton Coated LLC (A division of Arjo wiggins), Kimberly, WI, USA
Appleton Papers Inc., Appleton, WI, USA
Arjo Wiggins USA, Stamford, CT, USA
Atlantic Packaging Products Ltd., Scarborough, ON, Canada
Atlas Paper Mills Ltd., FL, USA
Badger Paper Mills Inc., Pashtigo, WI, USA
Banner Fiberboard Co., Wellsburg, WV, USA
Beloit Box Board Co. Inc., Beloit, WI, USA
Blue Heron Paper Co., Oregon City, Oregon, USA
Boise Cascade Corp., Boise, ID, USA
Bowater Inc., Greenville, SC, USA
Brant-Allen Ind. Inc. (Bear Island Paper Co., F.F.Soucy Inc.), Greenwich, CT, USA
Brownville Specialty Paper Products Inc., Brownville, NY, USA
Buckeye Technology Inc., Memphis, TN, USA
Burrows Paper Corp., Little Falls, NY, USA
Canfor Corp., Vancouver, BC, Canada
Caraustar Industries, Inc., Austell, GA, USA
Cascade Corp., Montreal, QC, Canada
CDM Laminates Inc., Drummondville, QC, Canada
Cellu Tissue Holding Inc., east Hartford, CT, USA
Chespeake Corporation, Richmond, VA, USA
CityForest Corp., Ladysmith, WI, USA
Climax Manufacturing Co., Carthage, NY, USA
Concert Industries Corp., Gatineau, QC, Canada
Copamex, S.A. de C.V, Mexico
Corner Brook Pulp & Paper Ltd. (A Div. of Kruger), Corner Brook, NFld, Canada
Corporación Durango, S.A. de C.V.,Maxico (English & Spanish)
Costa Rica Natural (Ecopaper), Ventura, CA, USA
Cottrell Paper, Rock City Falls, NY, USA
Crane & Co. Inc., Dalton, MA, USA
Crescent Cardboard Co. LLC, Wheeling, IL, USA
Daishowa Inc., BC, Canada
Delta Paper Corp., Levittown, PA, USA
Dexter Corp., Windsor Locks, CT, USA (Acquired by Ahlstrom)
Document Security Consultants, Inc., Livonia, NY, USA
Domtar Inc., Montreal, QC, Canada
Esleeck Papers, Turners Falls, MA, USA
Fiber Mark Inc., Brattleboro, VT, USA
Finch, Pruyn & Co., Glens Falls, NY, USA
Flower City Tissue Mills Inc., Rochester, NY, USA
Fox River Paper Co., Appleton, WI, USA
Fraser Papers Inc. (Formerly Nexor), Toronto, ON<Canada
French Paper Co., USA
Georgia-Pacific Corp., Augusta, GA, USA
George A. Whiting Paper Co., Manesha, WI, USA
Glatelter, York, PA, USA
Grande Alberta Paper Ltd., Edmonton, AB, Canada
Graphic Paper New York, NY, USA
Green Bay Packaging Inc., Green Bay, WI, USA
Green Field Paper Co., San Diego, CA, USA
Greif Bros. Corp., Delaware, OH, USA
Gulf States Corp., Tuscaloosa, AL, USA
Hollingsworth & Vose Company, East Walpole, MA, USA
Howe Sound Pulp & Paper Ltd., Port Mellon, BC, Canada
Inland Empire Paper Co., Spokane, WA, USA
Inland Paperboard & Packaging Inc., Indianapolis, IN, USA
International Paper Inc., Stanford, CT, USA
Interstate Resources, Inc., Arlington, VA, USA
Interstate Paper LLC (IPC), Riceboro, GA
Irving Paper Ltd., St. John, NB, Canada
Kappa Graphic Board USA, Chesapeake, VA, USA
Kimberly-Clark Corp., Dallas, TX, USA
Knowlton Specialty Paper Inc., Watertown, NY, USA
Kruger Inc., Montreal, QC, Canada
Liberty Paper Inc., Becker, MN, USA
Little Rapid Corp., Green Bay, WI, USA
Mafcote Inc., Norwalk, CT, USA
Madison Paper Co., ME, USA
Manistique Papers Inc., Manistiques, MI, USA
Manufacturas 8-a S.A. de C.V. , Mexico (English & Spanish)
Marcal Paper Mills, Inc., Elmwood Park, NJ, USA
Martisco Paper Co. Inc, New York, USA
McKinley Paper Co., Albuquerque, NM, USA
MeadWestwaco (Formerly Mead) Corporation, Dayton, OH, USA
Membranas Estructuradas, Mexico (English & Spanish)
Menasha Corp., Neenah, WI, USA
Menominee Paper Co., Menominee, MI, USA
Merrimac Paper Co. Inc., (Pepperell Paper), Lawrence, MA, USA
Minas Basin Pulp & Power Co. Ltd., Hansport, NS, Canada
Mohawk Paper Mills, Inc., Cohoes, NY, USA
Monadnock Paper Mills Inc., Bennigton, NH, USA
New Leaf Paper, NY, USA
Newark Group Inc., Newark, NJ, USA
Norbord Inc.,Toronto, ON, Canada
Norske Skog Canada,Vancouver, BC, Canada
Packaging Corporation of America, Lake Forest, IL, USA
Papelera Istmena, Panama (Spanish only)
Paper Service Ltd., Hinsdale, NH, USA
Papier Masson Ltee, Masson-Angers, QC, Canada
Parson Paper Co., (NVF Inc.), Holyoke, MA, USA
Perkins Papers, ( Cascade Group) QC, Canada
P.H.Glatfelter, Spring Grove, PA, USA
Port Townsend Paper Corp., Port Townsend, WA, USA
Potlatch Corp., Potlatch, ID, USA
Procter & Gamble (P & G), USA
Putney Paper Co. Inc., Putney, VT, USA
Riverside Paper Corp., Appleton, WI, USA
Riverwood International Corp., USA
Rock-Tenn Co., Norcross, GA, USA
Schweitzer Mauduit International Inc., Alpharetta, GA, USA
Scott Paper (A Kruger Co.), Mississauga, ON, Canada
Seaman Paper Co., MA, USA
Simpson Tacoma Kraft Co, LLC, Tacoma, WA, USA
Smurfit Stone Container Corp., Chicago, IL, USA
Sonoco Products Co., Hartsville, SC, USA
Southworth Co., Agawam, MA, USA
Spexel Inc., Montreal, QC, Canada
Spruce Falls Inc. (A Tembec Co.), Kapuskasing, ON, Canada
SP Newsprint Co. Atlanta, GA, USA
Strathcona Papers, Napanee, ON, Canada
Stora Enso North America, Wisconsin Rapids, WI, USA
Tembec Inc., Montreal, QC, Canada
Tolko Industries Ltd., Vernon, BC, Canada
Uniforet Inc., QC, Canada
Vision Paper (KP Products Inc.), Albuquerque, NM, USA
Wausau Paper Mills Co., Wausau, WI, USA
West Fraser Timber Co. Ltd., Vancouver, BC, Canada
West Linn Paper Co., Oregon, USA
Weyerhaeuser Co., Tacoma, WA, USA
 

     Prices for paper and recycled paper may vary widely depending on a series of variables including: size, color, application, and many other.

 

 
 
  Safety
     According to MSDS Online (2005), keep paper away from open flames and other ignition sources to reduce the risk of combustion. Other recommended precautions include using gloves when handling paper to reduce the risk of paper cuts. Avoid contact of paper and wood dust with eyes and respiratory system.  Wash hands after handling paper and/or wood dust.
 
 
 
  MSDS
The following links are concerned with a variety of material safety data sheets (MSDS) and have been obtained from various locations as noted below.

Wood

http://msds.ehs.cornell.edu/msds/msdsdod/a266/m132560.htm (MSDS Search.com, 2002)

http://msds.ehs.cornell.edu/msds/msdsdod/a192/m95871.htm (MSDS Search.com, 2002)

Paper

http://msds.ehs.cornell.edu/msds/msdsdod/a212/m105824.htm (MSDS Search.com, 2002)

http://msds.ehs.cornell.edu/msds/msdsdod/a412/m205885.htm (MSDS Search.com, 2002)

http://msds.ehs.cornell.edu/msds/msdsdod/a20/m9875.htm (MSDS Search.com, 2002)

 

 
 
  Storage
     According to MSDS Online (2005) When storing or handling paper precautions taken to ensure safety include providing a  cool, moisture free storage area away from combustion sources. Keep paper away from open flames and other ignition sources to reduce the risk of combustion. Other recommended precautions include using gloves when handling paper to reduce the risk of paper cuts.
 
 
 
  Illustrations
Figure 17. Compacted Waste Paper For Recycling (http://www.poyry-nlk.com/img/en/linked/expertise/Recycled.jpg)

 

Figure 18. Compacted Waste Paper For Recycling (http://www.pulpandpaper-technology.com/projects/langerbrugge/images/i8_9705-40.jpg)

  

Figure 19-21. Varieties of Recycled Paper

(http://www.business-supply.com/product_images/image/EB043324_recycled-paper-plain-25-cotton-20-lb-8-1-2-x11-white.gif;

 http://www.bettymills.com/store/images/product/PHEW5035.JPG;

 http://graphics.samsclub.com/images/products/0003650008428_LG.jpg)

 

 
 
  Internet Reference
“Benefits of Waste Paper Recycling.” NUS Paper Recycling Campaign. Aug. 2000. 20 Nov. 2005 <http://www.comp.nus.edu.sg/~career/PRC/benefits.html>.

Blixt, Tony. “Newsprint Mill Cost Pressures Drive Reassessment of Filler Alternatives.” Paperloop. 2003. Paperloop INC. 20 Nov. 2005 <http://www.paperloop.com/db_area/archive/p_p_mag/2003/0004/wet_end2.html>.

“Building a Better Future with Recycled Paper.” 2005. Cardiff University. 1 Oct. 2005 <http://www.wwrrec.cf.ac.uk/projects/projects.asp?id=33>.

“Building a Better Future With Recycled Paper.” Wales Waste & Resource Centre. 20 Nov. 2005 <http://www.wwrrec.cf.ac.uk/projects/projects.asp?id=33>.

“Buy-Recycled Series.” 2004 CPG Comprehensive Procurement Guidelines. 2004. 20 Nov. 2005 <http://www.epa.gov/cpg/pdf/paper.pdf>.

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Oleh : Thorikul Huda
Pendahuluan

Seiring dengan pertumbuhan penduduk maka aktivitas manusia untuk menghasilkan sampah juga semakin meningkat. Sampah yang diproduksi oleh masyarakat berupa sampah organic maupun sampah anorganik. Data BPS pada tahun 2000 menunjukkan produksi sampah dari 380 kota di Indonesia sebesar 80.235,87 ton tiap harinya. Dari sampah yang dihasilkan tersebut 37,6 % atau sekitar 30.168,687 ton di tangani dengan cara di bakar.

Pembakaran sampah yang tidak menggunakan teknologi tinggi dapat berakibat pada pencemaran lingkungan. Sebab hal ini dapat menghasilkan senyawa kimia berbahaya dan beracun yang dikenal dengan nama dioksin. Senyawa ini dapat terbentuk pada pembakaran dengan temperature yang rendah. Bahkan menurut Sunardi (www.migas-indonesia) pembakaran dengan menggunakan incinerator pada temperatur 400 – 600 0 C merupakan kondisi yang optimum untuk pembentukan senyawa dioksin.

Apabila proses pembakaran sampah berlangsung sempurna maka tidak akan menghasilkan dioksin, seperti yang diperlihatkan pada persamaan reaksi (1)

CaHbOcNdSeClf + u (O2 + 3,76 N2) à sCO2 + tHCl + xH2O + ySO2 + zN2 (1)

Pada reaksi persamaan reaksi pembakaran (1) diatas memperlihatkan tidak terbentuk senyawa dioksin apabila reaksi berlangsung secara sempurna (dalam reaksi yang stabil). Namun dengan beragamnya komposisi yang terdapat pada sampah, maka ketika sampah dibakar maka dapat menghasilkan dioksin dan furan. Hal ini terjadi karena proses pembakaran tidak dapat dapat berlangsung secara stabil. Adapun proses pembentukan dioksin dan furan dapat ditunjukkan pada persamaan reaksi (2) dibawah ini.

C + H2 + Cl2 + O2 + N2 à CO2 + CO + HCl + N2 + O2 + PCDD + PCDF (2)

Dimana: PCDD adalah Polly Chlorinated Dibenzo-p-Dioxin

PCDF adalah Polly Chlorinated Dibenzo Furan

Adapun informasi yang mendasari pembentukan dioksin dari hasil pembakaran dapat ditunjukkan pada table 1 dibawah ini.

Tabel 1. Distribusi unsure pembentuk dioksin dan furan

Unsur
 Distribusi di dalam produk pembakaran
 
C
 CO2, CO, dioksin dan furan
 
H2
 HCl, H2O, dioksin dan furan (kecuali senyawa oktaklorida)
 
Cl2
 HCl, dioksin dan furan
 
O2
 CO2, CO, O2, dioksin dan furan
 

Sumber : Pirajan et.al, 2007

Dioksin sebenarnya tidak hanya dihasilkan dari pembakaran sampah, akan tetapi juga dapat dihasilkan dari gas emisi kendaraan, kebakaran hutan, asap rokok atau kegiatan lainnya. Disamping itu proses pada pemutihan bubur kertas juga dapat menghasilkan dioksin sebagai impurity pada produksi senyawa klorinat organic. Pada industry bubur kertas dioksin ditemukan pada air limbah (efluen). Pada proses pemutihan bubur kertas menggunakan bahan pemutih yang mengandung klorin dimana kemudian senyawa klorin tersebut bereaksi dengan senyawa organic membentuk dioksin.
Karakteristik senyawa Dioksin

Senyawa dioksin sendiri adalah senyawa yang tersusun oleh atom karbon, hydrogen, oksigen dan klor Dioksin sebenarnya istilah yang digunakan untuk menyebutkan sekelompok zat-zat kimia berbahaya yang termasuk kelompok atau golongan senyawa CDD (Chlorinated Dibenzo-p-Dioxin), CDF (Chlorinated Dibenzo Furan) atau PCB (Polly Chlorinated Biphenyl).

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Senyawa 2,3,7,8-TCDD murni telah disintesis sejak tahun 1967. Bentuk fisik dari senyawa murni ini adalah berbentuk serbuk kristal padat (seperti serbuk yang terdapat pada tablet), tidak larut di dalam air dan sedikit larut pada beberapa pelarut organic. (www.websorcerer.com).

Bahaya Keracunan Dioksin

Beberapa decade terakhir telah banyak dilakukan kajian dan riset tentang bahaya dioksin bagi mahluk hidup khususnya manusia. Adapun kasus-kasus yang terjadi sepanjang sejarah menyangkut efek bahaya dari senyawa dioksin misalnya kasus dari Monsanto plant di Nitro, West Virginia, tahun 1949. Akibat kecelakaan di pabrik herbisida 2,4,5-T itu, 250 pekerja terkena penyakit chloracne, penyakit kulit berupa gatal-gatal memerah. Baru tahun 1955, Karl Schultz (seorang dokter Jerman) mensinyalemen bahwa chloracne adalah akibat racun dioksin.

Yang paling terkenal adalah kasus meledaknya pabrik kimia Hoffman-LaRoche di Seveso, Italia, tahun 1976. Akibatnya, sejumlah besar TCDD terlepas sampai ke atmosfer. Di daerah sekitar pabrik, hewan-hewan mati, terjadi destruksi vegetasi, penduduk mengalami keracunan akut, kasus-kasus chloracne, abortus, dan kelainan kongenital. Bahkan penelitian yang dilakukan Bertozzi dkk. pada tahun 1993 menemukan adanya peningkatan kasus kanker.

Penggunaan herbisida Agent Orange dalam Perang Vietnam (1960 – 1970) ternyata juga menyemburkan dioksin. Agent Orange digunakan untuk merontokkan dedaunan agar hutan-hutan Vietnam tidak bisa digunakan untuk bersembunyi tentara Vietkong. Tahun 1983, kantor veteran Chicago mencatat ada 17 ribu lebih veteran yang mengklaim ganti rugi akibat dioksin sewaktu bertugas di Vietnam.

Terbakarnya kabel PVC di Beverly Hills Supper Club bahkan merenggut nyawa 161 orang. Kebakaran tahun 1977 itu menimbulkan asap putih. Menurut salah seorang pekerja di situ, asap pedas yang mengandung gas hidrogen klorida (HCl) itu bisa bereaksi dengan pewarna kuku. Bahkan hasil reaksi tersebut dapat memakan kuku. Ketika terhirup dan masuk ke dalam paru-paru bersama udara yang mengandung air, HCl akan berubah menjadi asam klorida yang korosif. Akibatnya, yang selamat pun mengalami luka parah pada saluran pernapasannya.

Biaya pemulihan daerah yang tercemar dioksin tidaklah sedikit. Kasus di Time Beach, Missouri, pada tahun 1971 bisa menjadi gambaran. Sebuah perusahaan herbisida sembarangan saja membuang sampah industri ke tempat pembuangan oli bekas. Lalu oli bekas tersebut terpakai untuk menyemprot lapangan pacuan kuda, jalanan, serta tempat-tempat berdebu. Selain gangguan berupa chloracne dan radang kandung kemih yang akut, penyemprotan itu juga menimbulkan kematian dan penyakit pada ternak. Daerah tersebut kemudian dibeli oleh EPA (Badan Perlindungan Lingkungan AS) dan biaya yang dikeluarkan untuk membersihkan dioksin mencapai AS $ 100 juta.

Dioksin bersifat ada terus menerus (persistent) dan terakumulasi secara biologi (bioaccumulated), dan tersebar didalam lingkungan dalam konsentrasi yang rendah. Tingkat konsentrasinya rendah, sampai parts per trillion (satu per 10 pangkat 12), terakumulasi sepanjang kehidupan dan ada terus bertahun tahun, walaupun tidak ada penambahan lagi kedalam lingkungan. Hal ini bisa meningkatkan risiko terkena kanker dan efek lainnya terhadap binatang dan manusia. (www1.bpkpenabur.or.id)

Jika dioksin berada diudara maka akan dapat terhirup oleh manusia dan masuk ke dalam sistem pernafasan. Risiko bagi manusia yang paling besar adalah jika dioksin diterima tetap, walaupun dalam satuan takaran kecil, dan selanjutnya mengendap dalam tubuh manusia. Dioksin menimbulkan kanker, bertindak sebagai pengacau hormon, diteruskan dari ibu ke bayi selama menyusui dan mempengaruhi sistem reproduksi. Selain mengakibatkan penyakit tersebut, dioksin dengan demikian juga mempengaruhi kemampuan belajar oleh anak yang sangat peka terhadap pencemaran udara. (Sinaga, 2006)

Dioksin dalam jumlah kecil juga terdapat dalam asap rokok. Belum banyak pula yang menyadari bahwa insinerator atau pembakaran sampah di rumah-rumah sakit merupakan penghasil dioksin yang sangat berbahaya. Dioksin mempunyai struktur kimia yang sangat stabil dan bersifat lipofilik, yaitu tidak mudah larut dalam air tetapi mudah larut di dalam lemak. Karena kestabilan strukturnya ini, maka dioksin sangat berbahaya, sebab tidak mudah rusak atau terurai. Dioksin dapat berada di dalam tanah dan terakumulasi sampai 10-12 tahun. Dioksin bersifat mudah larut dalam lemak sehingga dapat terakumulasi dalam pangan yang relatif tinggi kadar lemaknya.

Pencegahan Peningkatan Dioksin

Untuk dapat menahan laju pertumbuhan senyawa dioksin di udara, khususnya dari pembakaran sampah di perkotaan, maka perlu dilakukan pengendalian sampah secara terpadu. Pertama harus memberikan kesadaran pada masyarakat untuk dapat memisahkan sampah-sampah organic yang mudah terdegradasi oleh mikroorganisme dengan sampah yang susah terdegradasi seperti plastic. Sampah-sampah plastic yang susah terdegradasi harus dikumpulkan dan jangan dibakar begitu saja karena berpotensi untuk menghasilkan dioksin.

Pemerintah daerah, dimana daerahnya memproduksi sampah dalam jumlah yang sangat besar maka harus menyediakan incinerator yang mampu melakukan pembakaran sampah berkisar antara 800 – 1100 0C, sebab dengan incinerator yang mampu membakar sampah hingga temperature 1000 0C tidak akan menghasilkan dioksin. Terjadinya dioksin dalam pembakaran sampah, dapat dikendalikan dengan penguraian suhu tinggi dioksin atau prehormon melalui pembakaran sempurna yang stabil. Untuk itu, penting untuk mempertahankan suhu tinggi gas pembakaran dalam tungku pembakaran, menjaga waktu keberadaan yang cukup bagi gas pembakaran, serta pengadukan campuran antara gas yang belum terbakar dan udara dalam gas pembakaran. Kemudian terhadap pencegahan pembentukan senyawa de novo yang juga merupakan penyebab munculnya dioksin, pendinginan mendadak serta pengkondisian suhu rendah gas pembakaran akan efekti (Anonim, 2005) . Selain itu, terhadap debu terbang yang dikumpulkan dengan penghisap debu yang banyak mengandung dioksin, ada teknologi pemrosesan reduksi khlorinat dengan panas. Untuk udara atmosfir yang dikembalikan, karena menggunakan reaksi reduksi khlorinat dengan menukar khlor yang terkandung dalam dioksin dengan hidrogen, dengan terus memanaskan debu terbang pada suhu diatas 8000C dioksin dalam debu dari jumlah totalnya akan terurai. Ini digunakan sebagai teknologi yang dapat menguraikan dioksin dengan energi input lebih sedikit dibandingkan dengan peleburan.

DAFTAR PUSTAKA
Anonym, 2005, “Teknologi Pengolahan Sampah Jepang”, Bahan Seminar Teknologi Lingkungan, Kawasaki Juko Co. Ltd.
Pirajan, J.C.M., Ubaque, C.A.G., Fajardo, R., Giraldo, R., Sapag, K., 2007, “Evaluation of Dioxin and Furan Formation Thermodynamics in Combustion Proscesses of urban Solid Wate”s, Ecletice Quimica, Volume 32. Numero 1, Sao Paulo

General information Key Points Fire • Non flammable, but enhances combustion of other materials • Use fine water spray and liquid-tight protective clothing and breathing apparatus Health • Due to its gaseous nature inhalation and eye exposure are most likely • Toxic and irritant • Contact with liquefied gas can cause frostbite • Lung or eye irritation may occur following short-term exposure to chlorine• Long-term inhalation may cause lung damage Environment • Dangerous for the environment • Inform Environment Agency of substantial incidents Prepared by R P Chilcott CHAPD HQ, HPA 2007 Version 2
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General information: Page 4 of 21 BackgroundChlorine is a chemical element and has thesymbol ‘Cl’. It is part of the group of chemicals called ‘halogens’ which includefluorine, bromine and iodine. The word chlorine comes from the Greek word for ‘palegreen’, the colour of chlorine gas. Chlorine does not naturally exist as a gas as it is too reactive. Instead, it reacts with other earth elements to form halogen salts. Forexample, common salt (also known as seasalt or ‘halite’) is a combination of sodium and chlorine. Chlorine gas is produced on an industrial scale by passing electricity through water containing a chlorine salt. The process (known as electrolysis) can also produceother useful chemicals such as hydrogen gas and sodium hydroxide (caustic soda). Around 9½ million tonnes of chlorine was produced in the European Union in 2005, more than half of which was used in themanufacture of plastics, medicines,pesticides, bleaches and solvents. Clearly,chlorine is an important industrial chemical. Perhaps one of the most importantapplications of chlorine is in the disinfectionof public water supplies to prevent the transmission of waterborne diseases such as cholera and typhoid. The introduction of chlorinated water supplies has helped toeradicate such diseases from the developed world. Chlorine is a poisonous gas that may causedelayed, fatal lung damage at highconcentrations. At lower concentrations,chlorine may cause eye irritation and coughing. Chlorine was used as a chemical warfare agent during World War I. People who have been exposed to chlorinegas generally make a complete recovery,although a proportion may acquire acondition known as reactive airways dysfunction syndrome (RADS) in which the lungs become more sensitive to chemical irritants. CHLORINE – GENERAL INFORMATION
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General information: Page 5 of 21 Production and Uses Key Points • Chlorine and compounds are used in several consumer products such as in nickel-chlorine batteries and for electroplating other metals • Chlorine is also used in various industrial processes such as printing, textiles,photography, lasers and solar cells Approximately 45 million tons of chlorine is produced annually worldwide with around 1.6million tons produced within the UK. The majority of chlorine is used in the chemical synthesis of pharmaceutical agents, agrochemicals or plastics, although elemental chlorine or chlorine-liberating substances are still used for disinfection of municipal water supplies and public bathing pools. CHLORINE – GENERAL INFORMATION
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General information: Page 6 of 21 Frequently Asked Questions What is chlorine? Chlorine is a pale-green, reactive gas that is approximately three times as heavy as air. It has a characteristic odour similar to bleach. What is chlorine used for?The main use of chlorine is in the manufacture of plastics, medicines, pesticides and solvents. Chlorine has disinfectant properties and so is added at low concentrations to municipal water supplies to control the growth of micro-organisms such as viruses andbacteria. Chlorine has also been extensively in the pulp and paper industry as a bleachingagent and is also present in many domestic cleaning products. How does chlorine get into the environment? Chlorine is a reactive chemical and as such does not normally exist in its gaseous form in the environment. The most likely cause of chlorine in the environment is following accidental release from an industrial site or transport vehicle. How will I be exposed to chlorine? Chlorine is a gas and so the eyes and lungs are most likely to be exposed. Chlorine may also be transported in liquid form (in which case contact may cause frost-bite). Many swimmingpools may use chemicals that form chlorine, although the concentrations produced should berelatively low. If there is chlorine in the environment will I have any adverse health effects? The presence of chlorine in the environment does not always lead to exposure. Clearly, inorder for it to cause any adverse health effects you must come into contact with it. You may be exposed by breathing, eating, or drinking the substance or by skin contact. Following exposure to any chemical, the adverse health effects you may encounter depend on severalfactors, including the amount to which you are exposed (dose), the way you are exposed, the duration of exposure, the form of the chemical and if you were exposed to any other chemicals. Minor exposures may result in a burning sensation of the eyes and throat. More substantial exposure may cause coughing or breathing difficulties. Exposure to high concentrations ofchlorine may be potentially fatal due to leakage of fluid onto the lungs. Those with a chest condition such as asthma or emphysema may be more sensitive to the effects of chlorine.Most people who have developed symptoms of poisoning following exposure to chlorine will not suffer any long-term effects. However, a small proportion of individuals may acquire along-term sensitivity to inhaled chemicals known as ‘reactive airways dysfunction syndrome’or RADS. A one-off exposure (sufficient to cause mild lung or eye irritation) is unlikely toresult in long-term health effects. Can chlorine cause cancer? Exposure to chlorine has not been linked to the development of cancer. In other words, chlorine is not thought to be carcinogenic. CHLORINE – GENERAL INFORMATION
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General information: Page 7 of 21 Does chlorine affect or damage the unborn child?There is no evidence to suggest that chlorine can affect the health of the unborn child. What should I do if I am exposed to chlorine? You should remove yourself from the source of exposure. If you have inhaled chlorine seek medical advice.If you have got chlorine on your skin, remove soiled clothing, wash the affected area withlukewarm water for at least 10 – 15 minutes and seek medical advice. If you have got chlorine in your eyes, remove contact lenses, irrigate the affected eye withlukewarm water for at least 10 – 15 minutes and seek medical advice. CHLORINE – GENERAL INFORMATION
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Chlorine Incident management Key Points Fire • Non combustible, but enhances combustion of other materials • In the event of a fire involving chlorine, use fine water spray and liquid-tight protective clothing and breathing apparatus Health • Due to its gaseous nature inhalation and ocular exposure are most likely • Toxic and irritant • Contact with liquefied gas can cause frostbite • Irritating to eyes, respiratory system and skin Environment • Dangerous for the environment • Inform Environment Agency of substantial incidents Prepared by R P Chilcott CHAPD HQ, HPA 2007 Version 2
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Incident management: Page 9 of 21 Hazard IdentificationStandard (UK) Dangerous Goods Emergency Action Codes(a)UN1017 Chlorine EAC2XE Use fine water spray. Wear liquid-tight chemical protectiveclothing in combination with breathing apparatus*. Spillagesand decontamination run-off should be prevented from entering drains and watercourses. There may be a publicsafety hazard outside the immediate area of the incident**. APPA(c) Liquefied gas with boiling point below -20 °C. Gas-tight chemical protective suit with breathing apparatus***. Class 2.3 Toxic gas Hazards Sub risks 8 Corrosive substance HIN268 Toxic gas, corrosive UN – United Nations number; EAC – Emergency Action Code; APP – Additional Personal Protection; HIN – Hazard Identification Number * Liquid-tight chemical protective clothing (BS 8428) in combination with self-contained open circuitpositive pressure compressed air breathing apparatus (BS EN 137).** People should stay indoors with windows and doors closed, ignition sources should be eliminatedand ventilation stopped. Non-essential personnel should move at least 250 m away from the incident. *** Gas-tight chemical protective clothing (BS EN 943) in combination with self-contained open circuitpositive pressure compressed air breathing apparatus (BS EN 137).aDangerous Goods Emergency Action Code List, HM Fire Service Inspectorate, Publications Section,The Stationery Office, 2004. CHLORINE – INCIDENT MANAGEMENT
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Incident management: Page 10 of 21 Chemical Hazard Information and Packaging for Supply Classification(a)Chlorine T Toxic Xi Irritant Classification N Dangerous for the environment R23 Toxic by inhalation R36/37/38 Irritating to eyes, respiratory system and skin Risk phrases R50 Very toxic to aquatic organisms S(1/2) Danger of serious damage to health by prolonged exposure through inhalation S9 Avoid exposure – obtain special instructions before use S45 In case of accident or if you feel unwell seek medical advice immediately (show the label where possible)This material and its container must be disposed of as hazardous waste Safety phrases S61 Avoid release to the environment. Refer to special instructions / safety data sheet aEuropean Chemicals Bureau, Classification and Labelling, Annex I of Directive 67/548/EEC; http://ecb.jrc.it/classification-labelling/ (accessed 2/2007). CHLORINE – INCIDENT MANAGEMENT
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Incident management: Page 11 of 21 Physicochemical Properties References(a,b,c)aInternational Programme on Chemical Safety: International Chemical Safety Card Entry for Chlorine(00012623), 2001. bThe Dictionary of Substances and their Effects. Ed. S Gangolli. Second Edition, Volume 2, 1999. cThe Merck Index (14thEdition). Entry 2095: Chlorine, 2006. CAS number 7782-50-5 Atomic weight 35 Chemical symbol Cl Common synonyms – State at room temperature Gas VolatilityVapour pressure = 4,800 mm Hg at 20oC Vapour density2.5 at 21oC (air = 1) FlammabilityNon combustible but enhances combustion of other substances Lower explosive limitData not available Upper explosive limitData not available Water solubility0.65 g 100 mL-1 ReactivityReacts explosively with acetylene, ether, ammonia, fuel gas, hydrogen and finely divided metals Reaction or degradation products Reacts with hydrocarbons and Lewis acids to release HCl gas Odour Pungent odour of bleach CHLORINE – INCIDENT MANAGEMENT
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Incident management: Page 12 of 21 Threshold Toxicity ValuesEXPOSURE VIA INHALATIONppm mg m-3 SIGNS AND SYMPTOMS0.2 – 3.5 1 -10 Odour detection 1 – 3 3 – 9 Mild mucous membrane irritation, tolerable for upto one hour 5 14 Severe irritation of the eyes and respiratory tract 14 – 21 41 – 61 Dangerous if exposed for 30 – 60 minutes 35 – 50 101 – 145 Fatal in 60 – 90 minutes 430 1247 Fatal over 30 minutes 1000 2900 Fatal within minutes Reference(a)aChlorine (MEDITEXT® Medical Management). In: Klasco RK (Ed): TOMES® System. Thomson Micromedex, Greenwood Village, Colorado (accessed 02/2007). CHLORINE – INCIDENT MANAGEMENT
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Incident management: Page 13 of 21 Published Emergency Response Guidelines Emergency Response Planning Guideline (ERPG) Values(a)Listed value (ppm) Calculated value (mg m-3) ERPG-1*1 3 ERPG-2*3 9 ERPG-3*20 58 * Maximum airborne concentration below which it is believed that nearly all individuals could beexposed for up to 1 hr without experiencing other than mild transient adverse health effects or perceiving a clearly defined, objectionable odour. ** Maximum airborne concentration below which it is believed that nearly all individuals could beexposed for up to 1 hr without experiencing or developing irreversible or other serious health effects orsymptoms which could impair an individual’s ability to take protective action. *** Maximum airborne concentration below which it is believed that nearly all individuals could beexposed for up to 1 hr without experiencing or developing life-threatening health effects. Acute Exposure Guideline Levels (AEGLs)(b)ppm 10 min 30 min 60 min 4 hr 8 hr AEGL-1†0.5 0.5 0.5 0.5 0.5 AEGL-2††2.8 2.8 2.0 1.0 0.7 AEGL-3†††50 28 20 10 7.1 † The level of the chemical in air at or above which the general population could experience notablediscomfort. †† The level of the chemical in air at or above which there may be irreversible or other serious long-lasting effects or impaired ability to escape. ††† The level of the chemical in air at or above which the general population could experience life-threatening health effects or death. aAmerican Industrial Hygiene Association (AIHA). Emergency Response Planning Guideline Values and Workplace Environmental Exposure Level Guides Handbook, Fairfax, VA, 2005. bU.S. Environmental Protection Agency. Acute Exposure Guideline Levels, http://www.epa.gov/oppt/aegl/pubs/chemlist.htm (accessed 02/2007). CHLORINE – INCIDENT MANAGEMENT
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Incident management: Page 14 of 21 Exposure Standards, Guidelines or Regulations Occupational standards LTEL(8 hour reference period): 0.5 ppm (1.5 mg m-3) WEL(a)STEL(15 min reference period): 1 ppm (2.9 mg m-3) Public health guidelines DRINKING WATER QUALITY GUIDELINE(b)5 mg L-1250 mg L-1chloride ions AIR QUALITY GUIDELINENo guideline value specified SOIL GUIDELINE VALUE AND HEALTH CRITERIA VALUESNo guideline values specified WEL – Workplace exposure limit; LTEL – Long-term exposure limit; STEL – Short-term exposure limit aHealth & Safety Executive. EH40/2005 Workplace Exposure Limits 2005. The Stationery Office, London, 2005bWorld Health Organisation. Guidelines for Drinking-Water Quality. Third Edition, Geneva, 2004. CHLORINE – INCIDENT MANAGEMENT
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Incident management: Page 15 of 21 Health Effects Major routes of exposure(a)• Due to its gaseous nature inhalation and ocular exposure are most likely. • Dermal features usually occur only from exposure to concentrated chlorine gas or in the immediate vicinity of a release of pressurised liquid. • Significant ingestion is unlikely because chlorine is a gas at room temperature. Immediate Signs or Symptoms of Acute Exposure(a)• Inhalation: Symptoms usually occur immediately but, less commonly, may be delayedfor several hours. Irritation to the mucous membranes in the nose and throat may occur after exposure to low concentrations (10 ppm) of chlorine. A feeling ofsuffocation, breathlessness, rhinorrhoea, coughing with white or bloodstainedsputum, chest pain and tightness, abdominal pain, nausea, headache, dizziness andtachycardia may follow more substantial exposure (30 ppm) and worsen over several hours. Cardiorespiratory arrest may occur secondary to hypoxia. Hoarseness andstridor may develop due to laryngeal oedema. Severe bronchoconstriction and non-cardiogenic pulmonary oedema occur in severe cases. • Dermal exposure: Contact with concentrated chlorine may cause dermal burns andthe pressurised liquid can cause frostbite. • Ocular exposure: Chlorine causes immediate stinging and burning with lacrimationand blepharospasm. High concentrations will cause ocular burns. TOXBASE – http://www.toxbase.org aTOXBASE: Chlorine – medical briefing, 2000. CHLORINE – INCIDENT MANAGEMENT
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Incident management: Page 16 of 21 Decontamination and First Aid Important Notes • Ambulance staff, paramedics and emergency department staff treating chemically-contaminated casualties should be equipped with Department of Health approved, gas-tight (Respirex) decontamination suits based on EN466:1995, EN12941:1998and prEN943-1:2001, where appropriate. • Decontamination should be performed using local protocols in designated areas such as a decontamination cubicle with adequate ventilation. • Chlorine is a volatile gas and secondary contamination is unlikely, although chlorine gas can condense on the skin and contaminate others dermally, unless protected. Dermal exposure(a)• Remove patient from exposure. • The patient should remove all clothing and personal effects.• Double-bag soiled clothing and place in a sealed container clearly labelled as abiohazard. • Wash hair and all contaminated skin with copious amounts of water (preferably warm) and soap for at least 10-15 minutes. Decontaminate open wounds first and avoidcontamination of unexposed skin. • Pay special attention to skin folds, axillae, ears, fingernails, genital areas and feet. Ocular exposure(a)• Remove patient from exposure. • Remove contact lenses if necessary and immediately irrigate the affected eyethoroughly with water or 0.9% saline for at least 10-15 minutes. • Patients with corneal damage or those whose symptoms do not resolve rapidly should be referred for urgent ophthalmological assessment. Inhalation(a)• Remove patient from exposure. • Ensure a clear airway and adequate ventilation. • Give oxygen to patients with respiratory symptoms. • Apply other supportive measures as indicated by the patient’s clinical condition. • Exposed individuals who have not developed symptoms should be told to seek medical advice if they develop respiratory problems. Ingestion • Not applicable. TOXBASE – http://www.toxbase.org aTOXBASE: Chlorine – medical briefing, 2000. CHLORINE – INCIDENT MANAGEMENT
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Chlorine Toxicological overview Key Points Health effects of acute exposure • Due to its gaseous nature inhalation and ocular exposure are most likely, resulting inlung and eye irritation • Exposure to higher concentrations of chlorine may lead to coughing and breathing difficulties due to the development of pulmonary or laryngeal oedema Health effects of chronic exposure • Chronic inhalation exposure may result in impaired pulmonary function • Chlorine was found to be non-carcinogenic in animal studies, and hypochlorite salts were not classifiable as to their carcinogenicity in humans • Animal studies demonstrated no reproductive or teratogenic effects of chlorine Prepared by R P Chilcott CHAPD HQ, HPA 2007 Version 2
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Toxicological overview: Page 18 of 21 Toxicological Overview Summary of Health Effects Exposure of unprotected personnel to chlorine gas may initially result in eye and lungirritation, the severity of which will be dependent on the concentration and duration of contact. Relatively minor exposures may result in sensory irritation such as burning of the eyes and throat. These initial symptoms are caused by free-radicals, hypochlorous or hypochloric acidformed by the reaction of chlorine with water in lung or eye tissues. More significant exposures may lead to coughing and breathing difficulties due to the development of pulmonary and/or laryngeal oedema. Clearly, exposure to a large concentration of chlorine in an enclosed or poorly ventilated areamay cause asphyxiation as a result of decreased oxygen availability. There is some evidence to suggest that acute exposure may result in long-term pulmonary sequelae (reactive airways dysfunction; RADs) in a small proportion of individuals. Sources and route of human exposure Due to its gaseous nature, inhalation and ocular exposure are most likely. Dermal featuresusually occur only from exposure to concentrated chlorine gas or in the immediate vicinity ofa release of pressurised liquid. Significant ingestion is unlikely because chlorine is a gas atroom temperature. Deliberate release of chlorine occurred during World War I. Up to 2000 UK personnel diedand approximately 165,000 were injured [1]. A significant occupational setting for chlorine exposure has been within the pulp and paper industry, hence the term “bleachery disease” to describe the pulmonary effects of chronic chlorine exposure. Exposure of the general public to chlorine may arise through accidental release during roador rail transport. Globally, acute incidents have led to 73 deaths and 3,549 injuries since1974 [2]. A number of accidental domestic exposures to chlorine arise each year through the inappropriate mixing of domestic cleaning products or incorrect use of swimming pool disinfectants. CHLORINE – TOXICOLOGICAL OVERVIEW
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Toxicological overview: Page 19 of 21 Health Effects of Acute / Single Exposure Human Data InhalationImmediate symptoms following inhalation include a burning sensation in the eyes and pain orburning of the lungs during respiration. Sufficient exposure may induce reflex cholinergic bronchoconstriction with associated signs of coughing, wheezing and dyspnoea. Exposure to a sufficiently high dose may result in pulmonary oedema and respiratory failure, the onset ofwhich may be delayed by up to 36 hours. In extreme cases, pulmonary haemorrhage may also occur [3]. There is some evidence to suggest that exposure to chlorine may beassociated with long-term neuropsychological changes [4], although further studies are required to confirm this hypothesis. Table 1: Summary of acute toxic effects in relation to approximate (air) concentration of chlorine [5]. Concentration (mg m-3) are approximate conversions from the corresponding ppmvalue. Concentration ppm mg m-3Signs and symptoms 1 – 3 3 – 10 Mild mucous membrane irritation 5 – 15 15 – 45 Moderate irritation of upper respiratory tract 30 90 Immediate chest pain, vomiting and coughing 40 – 60 115 – 175 Toxic pneumonitis and pulmonary oedema 430 1250 Lethal after 30 minutes exposure 1000 2900 Lethal in minutes Delayed effects following an acute exposureMost studies of survivors of World War I gassing incidents have reported a high incidence of acute respiratory damage and a lower incidence of chronic sequelae following acute exposure [6]. Similar sequelae have also been reported for individuals following acuteexposure to the accidental release of chlorine gas, with the most consistently reported chronic effect being a reduction in the forced expiratory volume (FEV) [7]. A relatively recentreport relating to accidental exposure to chlorine gas suggests that chronic sequelae following acute exposure may be more frequent than previously anticipated: a follow-up study in July 1999 on twenty individuals (previously exposed in 1995) indicated that 75% had residual lung volumes below 80% of their predicted value and nearly half the subjects testedfor airway reactivity to methacholine had a greater than 15% decline in FEV [8]. There is some evidence to suggest that a single, acute exposure to chlorine gas may cause reactive airways dysfunction syndrome (RADS), also known as irritant-induced asthma [6, 9]. CHLORINE – TOXICOLOGICAL OVERVIEW
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Toxicological overview: Page 20 of 21 Health Effects of Chronic / Repeated Exposure Human Data InhalationThere is some evidence to suggest that chronic, occupational exposure to chlorine may result in impaired pulmonary function as demonstrated by a decrease in FEV1, FVC and FEF25-75[9].GenotoxicityNo data are available on the mutagenicity of chlorine gas per se, although the mutagenicity of solutions of chlorine in water (hypochlorite and its salts) has been investigated. Sodium hypochlorite has been shown to have some mutagenic activity in vitro (both bacterial andmammalian cells) that may be due to the generation of reactive oxygen species. However,there is no evidence for activity in vivo [7]. Negative results were obtained in bone marrow assays for clastogenicity (chromosome aberrations and micronuclei) in mice [10]. Thenegative results reported in the carcinogenicity bioassays also support the view that hypochlorite does not have any significant mutagenic potential in vivo. CarcinogenicityNegative results were obtained when chlorine (dissolved in drinking water) was investigatedin a National Toxicology Program (NTP) carcinogenicity bioassay in rats and mice;concentrations of up to 275 ppm chlorine were used [11]. Previously, the International Agency for Research on Cancer (IARC) had evaluated the carcinogenicity of hypochloritesalts [12] and concluded that there was no data available from human studies and that thedata from experimental studies in animals was inadequate. Therefore, hypochlorite salts were assigned to Group 3, i.e., compounds that are not classifiable as to their carcinogenicityin humans. Reproductive and developmental toxicityIn general, animal studies have demonstrated no reproductive or teratogenic effects ofchlorine [7]. The effects of water chlorinated to a level of 150 mg L-1were investigated in rats over 7 generations. No effects were observed on fertility, growth or survival [13]. CHLORINE – TOXICOLOGICAL OVERVIEW
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Toxicological overview: Page 21 of 21 References [1] Gilbert M (1995.) The first world war. Harper Collins Press, London [2] United Nations Environment Programme Transport Disasters. Division of echnology,Industry and Economics, Production and Transport Branch. [3] National Poisons Information Service (NPIS). Chlorine. TOXBASE®. [4] Dilks LS and Matzenbacher DL (2003). Residual neuropsychological sequelae of chlorine gas exposure. Neurotoxicol Teratolol 25, 391. [5] International Programme on Chemical Safety (IPCS) (1996). Chlorine. Poisons Information Monograph. PIM 947. [6] Ayres J and P, B. (2004). Irritant Induced Asthma and RADS. EPAQS short report. [7] World Health Organisation (WHO) (1999). Environmental Health Criteria 216. Disinfectants and disinfectant by-products. International programme on ChemicalSafety (IPCS) Monograph. [8] Schwartz DA, Smith DD and Lakshminarayan S (1990). The pulmonary sequelaeassociated with accidental inhalation of chlorine gas. Chest 97, 820-825. [9] Winder C (2001). The toxicology of chlorine. Environ Res 85, 105-114. [10] Meier JR, Bull RJ, Stober JA and Cimino MC (1985). Evaluation of chemicals usedfor drinking water disinfection for production of chromosomal damage and sperm-head abnormalities in mice. Environ Mutagen 7, 201-211. [11] National Toxicology Programme (NTP) (1992). Toxicology and Carcinogenesis Studies of Chlorinated Water (CAS Nos. 7782-50-5 and 7681-52-9) and Chloraminated Water (CAS No. 10599-90-3) (Deionized and Charcoal-Filtered) inF344/N Rats and B6C3F1 Mice (Drinking Water Studies). Technical Report 392. Department of Health and Human Services. [12] International Agency for Research on Cancer (IARC) (1986). Pulp and Paper Manufacture, Supplement 7. Lyon. [13] Druckrey H (1968). Chlorinated drinking water; toxicity tests involving 7 generations of rats. Food Cosmetic Toxicol 6, 147-154. This document will be reviewed not later than 3 years or sooner if substantive evidence becomes available. CHLORINE – TOXICOLOGICAL OVERVIEW