Hexavalent Chromium -
Chromium exists primarily in trivalent (Cr(III)) or hexavalent (Cr(VI)) oxidation states. Cr(VI) is a notorious environmental pollutant because it is a strong oxidant and much more toxic than Cr(III) and carcinogenic. Cr(VI) exists as the chromate ion in basic solutions and as dichromate in acidic solutions.[1]
One of the traditional methods for determining Cr(VI) uses diphenylcarbohydrazide (DPC) to form an intensely colored complex with Cr(VI). The complex is measured quantitatively by its visible absorption at 520 nm. However, as in any colorimetric analysis, this test is subject to positive interferences from other colored materials in the sample as well as from other elements that form colored complexes with DPC. [1]
Hexavalent chromium is used for the production of stainless steel, textile dyes, wood preservation, leather tanning, and as anti-corrosion and conversion coatings as well as a variety of niche uses. [2]
Hexavalent chromium is recognized as a human carcinogen via inhalation. [3] Workers in many different occupations are exposed to hexavalent chromium. Problematic exposure is known to occur among workers who handle chromate-containing products as well as those who arc weld stainless steel.[3] Within the European Union, the use of hexavalent chromium in electronic equipment is largely prohibited by the Restriction of Hazardous Substances Directive
Chemical name: Ammonium Dichromate Chromium[VI]
Synonyms: Chromic acid, diamonium salt
Chemical Formula: (NH4)2Cr2O7
CAS registry: 7789-09-05
Chromium VI New Field Detection Method for Ground Water Sampling -
Hexavalent chromium (Cr VI) is very toxic and a carcinogen compound found in groundwater all over. Testing for such a toxic has become increasingly important. Previously, field sampling for hexavalent chromium has been somewhat difficult. Several interested parties, including the USGS (United States Geological Survey) have been working on developing new field methods for collecting and analyzing ground water for the presence of chromium VI. The most popular method used since 2003, developed in part by USGS, enables the field distinguishment between Cr VI and its less toxic form, chromium III. The advantages of the new field method include lower detection limits, down to 0.05 micrograms per liter; small cation exchange cartridge that allows Cr VI to be stabilized in the field; storage of field samples for up to several weeks; as well as the use of common lab equipment to reduce analytical cost. Time stability of preserved samples is a great advantage over the 24 hour time constraint specified for EPA method 218.6. Prior to 2003, Cr VI field analysis was not very reliable and very expensive. The newer method is comparable with standard laboratory based methods. Since the toxicity of Cr VI is widely known, quicker more accurate field sampling is of great benefit to communities. (Ball, James. 2003. A New Cation-Exchange Method for Accurate Field Speciation of Hexavalent Chromium).
Health Effects –
“The respiratory tract is the major target organ for chromium (VI) toxicity, for acute (short-term) and chronic (long-term) inhalation exposures. Shortness of breath, coughing, and wheezing were reported from a case of acute exposure to chromium (VI), while perforations and ulcerations of the septum, bronchitis, decreased pulmonary function, pneumonia, and other respiratory effects have been noted from chronic exposure. Human studies have clearly established that inhaled chromium (VI) is a human carcinogen, resulting in an increased risk of lung cancer. Animal studies have shown chromium (VI) to cause lung tumors via inhalation exposure.“ (EPA, 2000)
Short term Effects of Cr VI
- Bronchial effects such as shortness of breath, coughing, wheezing
- Gastrointestinal and neurological effects
- Skin burns
Long Term Effects of Cr VI
- Perforations of the septum
- Bronchial effects such as bronchitis, decreased pulmonary functions, asthma and pneumonia
- Effects on the liver, kidney and immune system
- Upper respiratory tract, reproductive and renal effects
Other Effects of Cr VI
- Complications during pregnancy
- Complications during childbirth
Cancer Risks from Cr VI
- Classified as a human carcinogen
Case Study 1 -
A relatively recent industrial source of concern for CrVI is Portland Cement. Concrete, a very common building material is a mixture of portland cement, aggregate (sand and rock), and water. Raw materials used in the manufacture of portland cement, such as limestone, clay, and silica contain naturally occurring sources of chromium. During the cement manufacturing process, raw materials, are mixed and heated in a large kiln to produce an intermediate pebble-sized material called clinker. Fugitive dust emissions from stored piles of clinker are alleged to be a significant source of CrVI contamination to air, soil, and potentially groundwater in the area surrounding a cement plant operated by TXI International near Riverside, California. (Insurance Journal, 2008)
Cr VI Case Study 2 -
Erin Brockovich, who was depicted by Julia Roberts in a Hollywood motion picture, has played a large roll in the world of Hexavalent Chromium in drinking water. Her first major case was in Henkley, California where she won over 330 million dollars for a town whose drinking water was nearly 6 times the Maximum Contaminant Level (0.10 PPM) set by the EPA (Brockovich, Famous Trials, Chapter 1 Preface." Enemy at the Gates, Thirteen Days, Erin Brockovich, Stories Behind The Movies. 15 Sep. 2009 ).
Later, in 2007, at a site in Oinofyta, Greece, Brockovich became involved at a similar case involving the Asopos River (Brockovich, Erin. " Pollution Flows in Asopos :: The Brockovich Report ." The Brockovich Report :: Published by Los Angeles Area Consumer Advocate Erin Brockovich. 25 Aug. 2007. 15 Sep. 2009 )
Most recently Brockovich has been invovled in a major drinking water case in Midland, Texas where well water has been reported to have hexavalent chromium levels 10 times higher than those at the Henkley California site ("The Real News Network - Erin Brockovich Is Back." The Real News. 15 Sep. 2009 ).
Though Brockovich has a many opponents that say her work is a sham, I believe she has done great things to bring areas back into federal or local regulatory Cr VI levels. She has prospered greatly from her work but more so have so many others who had been, or could have been affected by the contamination.
Case Study 3 -
An example of an airborne Cr VI case study comes from Davenport California where a local Cemex cement plant was the source of levels of contamination above those set by local standards, however the recorded levels were below those set by the EPA. The significance of this case is that it bring to light Cr VI as a harmful by product possible in the production of cement (McCord, Shanna. "Chromium 6 testing continues in Davenport, Cemex changes business practices - October 9th,2008 by Shanna McCord." Home - Santa Cruz Sentinel. 9 Oct. 2008. 15 Sep. 2009 ).
The results of air sampling at the Cemex plant in Davenport had shown to be within regulatory limits by the 1st of the year, however, later in January 2009 the plant laid off most off it's 125 employees due to the recession ("Davenport's Cemex Plant Stops Production: More than 100 Employees Laid Off - KION - Monterey, Salinas, Santa Cruz - News Weather-." KION - Monterey, Salinas, Santa Cruz - News Weather- - Home. 19 Jan. 2009. 29 Sep. 2009 ).
References
"5. Potential for Human Exposure." Department of Health and Human Services. www.atsdr.cdc.gov/toxprofiles/tp7-c5.pdf (accessed September 15, 2009).
Agency for Toxic Substances and Disease Registry (ATSDR). 2008. Toxicological profile for Chromium (Draft for Public Comment). Atlanta, GA: U.S. Department of Health and Human Services, Public Health Service.
"Air Toxics Hotspots Program Risk Management Guidelines, Part II: Technical Support Document for Describing Available Cancer Potency Factors ." Office of Environmental Health Hazard Assessment. www.oehha.ca.gov/pdf/HSCA2.pdf (accessed September 15, 2009).
Australian Centre for International Agricultural Research (ACIAR) Media Release (2003). Cleaning Up Tannery Waste. Retrieved September 17, 2009 from the World Wide Web: http://www.aciar.gov.au/node/10365
Brockovich, Erin. " Pollution Flows in Asopos :: The Brockovich Report ." The Brockovich Report :: Published by Los Angeles Area Consumer Advocate Erin Brockovich. 25 Aug. 2007. 15 Sep. 2009
California AG sues cement plant for hexavalent chromium exposure. (2008). Retrieved September 18, 2009, from http://www.insurancejournal.com/news/west/2008/07/08/91677.htm
"Chromium Compounds | Technology Transfer Network Air Toxics Web site | US EPA." U.S. Environmental Protection Agency. http://www.epa.gov/ttn/atw/hlthef/chromium.html (accessed September 15, 2009).
Chromium (VI) (CASRN 18540-29-9) | IRIS | US EPA." U.S. Environmental Protection Agency. 22 Sep. 2009
"Davenport's Cemex Plant Stops Production: More than 100 Employees Laid Off - KION - Monterey, Salinas, Santa Cruz - News Weather-." KION - Monterey, Salinas, Santa Cruz - News Weather- - Home. 19 Jan. 2009. 29 Sep. 2009.
Gerd Anger, Jost Halstenberg, Klaus Hochgeschwender, Christoph Scherhag, Ulrich Korallus, Herbert Knopf, Peter Schmidt, Manfred Ohlinger, "Chromium Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005.
Gonzalez, Juan. "Indiana Guardsmen Sue KBR Over Chemical Exposure in Iraq." Democracy Now! | Radio and TV News. 4 Dec. 2008. 15 Sep. 2009
Hexavalent Chromium, Cr(VI), Analysis. (n.d.). Retrieved September 16, 2009, from http://www.wcaslab.com/tech/HEXCHROM
"Hexavalent chromium - Wikipedia, the free encyclopedia." Wikipedia, the free encyclopedia. 20 Sep. 2009
IARC (1999-11-05) [1990] (PDF). Volume 49: Chromium, Nickel, and Welding. Lyon: International Agency for Research on Cancer. ISBN 92-832-1249-5. http://monographs.iarc.fr/ENG/Monographs/vol49/volume49.pdf. Retrieved 2006-07-16.
Mandate, Congressional, the Agency for Toxic Substances, Toxicity, and Potential for Human Exposure. Toxicological profiles are developed from a priority list of 275 substances. ATSDR also prepares toxicological profiles for the Department of Defense (DOD). "ATSDR - Toxicological Profile Information Sheet." ATSDR Home. http://www.atsdr.cdc.gov/toxpro2.html#bookmarkset19 (accessed September 15, 2009).
"KBR - Featured Articles." KBR, Inc.: A Leading Global Engineering, Construction and Services Company.. 29 Sep. 2009. 29 Sep. 2009 .
McCord, Shanna. "Chromium 6 testing continues in Davenport, Cemex changes business practices - October 9th,2008 by Shanna McCord." Home - Santa Cruz Sentinel. 9 Oct. 2008. 15 Sep. 2009
Mineral tolerance of animals . washington: National Research Council Committee on Minerals and Toxic Substances. , 2005. Pg 116-120
NIOSH Topic: Hexavalent Chromium | CDC/NIOSH." Centers for Disease Control and Prevention. 18 Sep. 2009
Photo of concrete pouring retrieved 18 Sep 2009 from http://www.speciation.net/Public/News/2007/04/12/2796.html
Srinath, T., Verma, T., Ramteke, P.W., Garg, S.K. (2002). Chromium (VI) biosorption and bioaccumulation by chromate resistant bacteria Chemosphere, 48 427-435.
THE ASSOCIATED PRESS. "National Briefing - Northwest - Oregon - Possible Chemical Exposure - NYTimes.com." The New York Times - Breaking News, World News & Multimedia. 12 Feb. 2009. 15 Sep. 2009
"The Real News Network - Erin Brockovich Is Back." The Real News. 15 Sep. 2009
"There is sufficient evidence in humans for the carcinogenicity of chromium[VI] compounds as encountered in the chromate production, chromate pigment production and chromium plating industries."
Toxicological profile for chromium(2008). (ATSDR Toxicological Profile. Atlanta, GA: U.S. Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry. Retrieved from http://www.atsdr.cdc.gov/toxprofiles/tp7.html
U.S. Environmental Protection Agency. (2000). Chromium compounds hazard summary. Retrieved September 18, 2009, from http://www.epa.gov/ttn/atw/hlthef/chromium.html
Wednesday, September 30, 2009
Tuesday, September 22, 2009
Hexavalent Chromium CrVI - Team Beta
Hexavalent Chromium (CrVI) – Team Beta
Hexavalent chromium is used for the production of stainless steel, textile dyes, wood preservation, leather tanning, and as anti-corrosion and conversion coatings as well as a variety of niche uses.
CrVI Facts and Figures -
The 2007 CERCLA NPL (National Priority List) of Hazardous Substances lists Hexavalent Chromium as number 18 of 275 hazardous materials. The levels of contamination may also violate the Clean Water Act of 1972 and the California Drinking Water Standards of 50 ppb total chromium. The California Air Resources Board has identified CrVI as a Toxic Air Contaminant, CAS 18540-29-9.
The Department of Health and Human Services’ Agency for Toxic Substances & Disease Registry estimates that 2,700–2,900 tons of chromium is emitted into the air annually by anthropogenic sources. 35% of these emissions are expected to be hexavalent chromium. (ATSDR “5. Potential for Human Exposure”, retrieved September 15, 2009). The ATSDR also calculates the mean daily dietary intake of chromium from air <0.2-0.4μg, from water 2.0μg, and food 60μg.
Sources of hexavalent chromium (CrVI) –
Chromium is a chemical element that occurs naturally in minerals and soils. It is also found in volcanic dust and gases. The most predominant industrial sources of chromium are from the metallurgical, refractory and chemicals industries. Metallurgical industry use includes mining/refining of chromite ore, and manufacture of ferrochromiums, such as stainless steel and other ferrous and non-ferrous alloys. Chromium is contained in refractory bricks and other refractory materials used for linings of high temperature industrial furnaces. Predominant chemical industry uses of chromium are in the manufacture of pigments, metal finishing (such as chrome plating), leather tanning, and wood preservatives. (ATSDR, 2008)
CrVI Chemistry -
Chromium exists primarily in trivalent (Cr(III)) or hexavalent (Cr(VI)) oxidation states. Cr(VI) is a notorious environmental pollutant because it is a strong oxidant and much more toxic than Cr(III) and carcinogenic. Cr(VI) exists as the chromate ion in basic solutions and as dichromate in acidic solutions.
Hexavalent chromium is recognized as a human carcinogen via inhalation. Workers in many different occupations are exposed to hexavalent chromium. Problematic exposure is known to occur among workers who handle chromate-containing products as well as those who arc weld stainless steel. Within the European Union, the use of hexavalent chromium in electronic equipment is largely prohibited by the Restriction of Hazardous Substances Directive
Chemical name: Ammonium Dichromate Chromium[VI]
Synonyms: Chromic acid, diamonium salt
Chemical Formula: (NH4)2Cr2O7
CAS registry: 7789-09-05
Chromium VI is a hazardous chemical due to its toxicity. Chromium exposure can be by breathing, contaminated air, or drinking water, or eating tainted food. Contaminated well water presents the most potential for ingestion, since chromium will stay longer at it´s hexavalent state. The potential impact is strictly to human health, since hexavalent chromium has been shown to cause cancer in lab animals. Toxic effects may include liver and heart failure, reproductive and respiratory failure. (ATSDR, 2009)
CrVI Health Effects -
Inhalation risks are assessed in different ways (LC 50, TLV, etc). The main reason is that CrVI is a carcinogen. Cancer risk or the incremental cancer risk caused by an emission is better assessed when concentrations are compared to OEHHA’s (Office of Environmental Health and Hazard Assessment) reference level of 0.002 μg Cr(VI)/m3 (OEHHA, 2009).
“The respiratory tract is the major target organ for chromium (VI) toxicity, for acute (short-term) and chronic (long-term) inhalation exposures. Shortness of breath, coughing, and wheezing were reported from a case of acute exposure to chromium (VI), while perforations and ulcerations of the septum, bronchitis, decreased pulmonary function, pneumonia, and other respiratory effects have been noted from chronic exposure. Human studies have clearly established that inhaled chromium (VI) is a human carcinogen, resulting in an increased risk of lung cancer. Animal studies have shown chromium (VI) to cause lung tumors via inhalation exposure. “ (EPA, 2000)
Acute Effects of Cr VI
- Shortness of breath, coughing, wheezing
- Gastrointestinal and neurological effects
- Skin burns
Chronic (Noncancer) Effects of Cr VI
- Perforations and ulcerations of the septum, bronchitis, decreased pulmonary function, pneumonia and asthma
- Effects on the liver, kidney, gastrointestinal and immune systems and possibly the blood
- Particulates effects include upper respiratory tract, reproductive and renal effects
Reproductive and Developmental Effects of Cr VI
- Possible complications during pregnancy and childbirth
Cancer Risks from Cr VI
- Inhaled chromium is a human carcinogen, causing an increased risk of lung cancer
(From EPA website http://www.epa.gov/ttn/atw/hlthef/chromium.html)
Toxicity and Metabolism of CrVI –
Hexavalent chromium is absorbed to a greater extent than the trivalent Chromium and readily enters cells through nonspecific anoin carriers. In significant amounts of hexavalent chromium are likely to be consumed orally because chromium(+6) is reduced in the environment to Chromium (+3) , the more stable oxidation state. chromium(+6) consumed is totally or partly reduced to Chromium (+3) in the acid environment of the stomach. Hexavalent chromium also doesn’t generally occur naturally and is produced almost totally from human activities as discussed above.
Chromium is transported in the blood primarily bound to transferring. Plasma or serum chromium conc. In humans are less than 0.30ug/L. Blood chromium concentrations are not in equilibrium with tissue chromium concentrations and do not reflect body stores. Tissue concentrations are low with kidney, liver, spleen and bone containing the highest concentrations.
Hexavalent chromium is transported into cells via the sulfate transport mechanisms, taking advantage of the similarity of sulfate and chromate with respect to their structure and charge. Trivalent chromium, which is the more common variety of chromium compounds, is not transported into cells.
Inside the cell, Cr(VI) is reduced first to metastable pentavalent chromium (Cr(V)), then to trivalent chromium. Trivalent chromium binds to proteins and creates haptens that trigger immune response. Once developed, chrome sensitivity can be persistent. In such cases, contact with chromate-dyed textiles or wearing of chromate-tanned leather shoes can cause or exacerbate contact dermatitis. Vitamin C and other reducing agents combine with chromate to give Cr(III) products inside the cell.
It appears that the mechanism of genotoxicity relies on pentavalent or trivalent chromium. According to some researchers, the damage is caused by hydroxyl radicals, produced during reoxidation of pentavalent chromium by hydrogen peroxide molecules present in the cell. Strontium chromate is the strongest carcinogen of the chromates used in industry. Soluble forms of Chromium (+6) are several fold more toxic than soluble forms of Chromium (+3)
Ground Water Field Sampling –
The USGS (United States Geological Survey) developed a new field method for collecting and analyzing ground water for the presence of chromium VI, widely used since 2003. Hexavalent chromium (Cr VI) is very toxic and a carcinogen. The new method, developed by USGS, enables the field distinguishment between Cr VI and its less toxic form, chromium III. The advantages of the new field method include lower detection limits, down to 0.05 micrograms per liter; a small, disposable cation exchange cartridge that allows Cr VI to be separated and stabilized in the field; storage of field samples for up to several weeks; as well as the use of common lab equipment to reduce analytical cost. Time stability of preserved samples is a great advantage over the 24 hour time constraint specified for EPA method 218.6. Prior to 2003, Cr VI field analysis was not very reliable and very expensive. The newer method is comparable with standard laboratory based methods. Since the toxicity of Cr VI is widely known, quicker more accurate field sampling is of great benefit to communities. (Ball, James. 2003. A New Cation-Exchange Method for Accurate Field Speciation of Hexavalent Chromium).
One of the traditional methods for determining Cr(VI) uses diphenylcarbohydrazide (DPC) to form an intensely colored complex with Cr(VI). The complex is measured quantitatively by its visible absorption at 520 nm. However, as in any colorimetric analysis, this test is subject to positive interferences from other colored materials in the sample as well as from other elements that form colored complexes with DPC.
Cr VI Case Study 1 –
Erin Brockovich, who was depicted by Julia Roberts in a Hollywood motion picture, has played a large roll in the world of Hexavalent Chromium in drinking water. Her first major case was in Henkley, California where she won over 330 million dollars for a town whose drinking water was nearly 6 times the Maximum Contaminant Level (0.10 PPM) set by the EPA (Brockovich, Famous Trials, Chapter 1 Preface." Enemy at the Gates, Thirteen Days, Erin Brockovich, Stories Behind The Movies. 15 Sep. 2009 ).
Later, in 2007, at a site in Oinofyta, Greece, Brockovich became involved at a similar case involving the Asopos River.
Most recently Brockovich has been invovled in a major drinking water case in Midland, Texas where well water has been reported to have hexavalent chromium levels 10 times higher than those at the Henkley California site
Case Study 3 -
A relatively recent industrial source of concern for CrVI is Portland Cement. Concrete, a very common building material is a mixture of portland cement, aggregate (sand and rock), and water. Raw materials used in the manufacture of portland cement, such as limestone, clay, and silica contain naturally occurring sources of chromium. During the cement manufacturing process, raw materials, are mixed and heated in a large kiln to produce an intermediate pebble-sized material called clinker. Fugitive dust emissions from stored piles of clinker are alleged to be a significant source of CrVI contamination to air, soil, and potentially groundwater in the area surrounding a cement plant operated by TXI International near Riverside, California. (Insurance Journal, 2008)
CrVI Case Study 2 -
An example of an airborne Cr VI case study comes from Davenport California where a local Cemex cement plant was the source of levels of contamination above those set by local standards, however the recorded levels were below those set by the EPA. The significance of this case is that it bring to light CrVI as a harmful by product possible in the production of cement
Case Study General –
A general case study are Cr(VI) in discharge from tanneries, this is regulated and can be treated at the source. However in India, reguation hasn't happened until recently and studies have conducted to remediate contamination sites.
As part of the tanning process hexavalent chromium compounds are often a byproduct of the chemicals used to alter the rawhide material into leather. In areas with little to no regulation hexavalent chromium compounds are discharged in effluent into the environment (Sirnath, et al 2002). Tanneries in India discharge effluent containing hexavalent chromium compounds into the environment which in turn contaminates agricultural land and ground water (ACIAR, 2003). Effluent discharge from tanneries can be treated to reduce hexavalent chromium compounds; however these processes may is seen as not economically feasible (Sirnath et al, 2002). Studies, using microbial remediation and phytoremediation at contaminated sites in India have proven insightful. Microbes that can bioaccumulate hexavalent chromium compounds can be added to tannery sludge which will in turn reduce chromium compounds in sludge to acceptable levels (Sirnath et al, 2002). Other techniques are being used to remove chromium compounds from tannery sludge, by planting crops that are more tolerant to chromium or by planting crops that will absorb chromium and reduce it from contaminate sites (ACIAR, 2003). To curb the environmental contamination from tannery discharge India has enacted regulations (ACIAR, 2003). These remediation techniques will help to met these regulations in addition to better treatment at discharge source.
References
"5. Potential for Human Exposure." Department of Health and Human Services. www.atsdr.cdc.gov/toxprofiles/tp7-c5.pdf (accessed September 15, 2009).
Agency for Toxic Substances and Disease Registry (ATSDR). 2008. Toxicological profile for Chromium (Draft for Public Comment). Atlanta, GA: U.S. Department of Health and Human Services, Public Health Service.
"Air Toxics Hotspots Program Risk Management Guidelines, Part II: Technical Support Document for Describing Available Cancer Potency Factors ." Office of Environmental Health Hazard Assessment. www.oehha.ca.gov/pdf/HSCA2.pdf (accessed September 15, 2009).
Australian Centre for International Agricultural Research (ACIAR) Media Release (2003). Cleaning Up Tannery Waste. Retrieved September 17, 2009 from the World Wide Web: http://www.aciar.gov.au/node/10365
Brockovich, Erin. " Pollution Flows in Asopos :: The Brockovich Report ." The Brockovich Report :: Published by Los Angeles Area Consumer Advocate Erin Brockovich. 25 Aug. 2007. 15 Sep. 2009
California AG sues cement plant for hexavalent chromium exposure. (2008). Retrieved September 18, 2009, from http://www.insurancejournal.com/news/west/2008/07/08/91677.htm
"Chromium Compounds | Technology Transfer Network Air Toxics Web site | US EPA." U.S. Environmental Protection Agency. http://www.epa.gov/ttn/atw/hlthef/chromium.html (accessed September 15, 2009).
Chromium (VI) (CASRN 18540-29-9) | IRIS | US EPA." U.S. Environmental Protection Agency. 22 Sep. 2009
Gerd Anger, Jost Halstenberg, Klaus Hochgeschwender, Christoph Scherhag, Ulrich Korallus, Herbert Knopf, Peter Schmidt, Manfred Ohlinger, "Chromium Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005.
Gonzalez, Juan. "Indiana Guardsmen Sue KBR Over Chemical Exposure in Iraq." Democracy Now! | Radio and TV News. 4 Dec. 2008. 15 Sep. 2009
Hexavalent Chromium, Cr(VI), Analysis. (n.d.). Retrieved September 16, 2009, from http://www.wcaslab.com/tech/HEXCHROM
"Hexavalent chromium - Wikipedia, the free encyclopedia." Wikipedia, the free encyclopedia. 20 Sep. 2009
IARC (1999-11-05) [1990] (PDF). Volume 49: Chromium, Nickel, and Welding. Lyon: International Agency for Research on Cancer. ISBN 92-832-1249-5. http://monographs.iarc.fr/ENG/Monographs/vol49/volume49.pdf. Retrieved 2006-07-16.
Mandate, Congressional, the Agency for Toxic Substances, Toxicity, and Potential for Human Exposure. Toxicological profiles are developed from a priority list of 275 substances. ATSDR also prepares toxicological profiles for the Department of Defense (DOD). "ATSDR - Toxicological Profile Information Sheet." ATSDR Home. http://www.atsdr.cdc.gov/toxpro2.html#bookmarkset19 (accessed September 15, 2009).
McCord, Shanna. "Chromium 6 testing continues in Davenport, Cemex changes business practices - October 9th,2008 by Shanna McCord." Home - Santa Cruz Sentinel. 9 Oct. 2008. 15 Sep. 2009
Mineral tolerance of animals . washington: National Research Council Committee on Minerals and Toxic Substances. , 2005. Pg 116-120
NIOSH Topic: Hexavalent Chromium | CDC/NIOSH." Centers for Disease Control and Prevention. 18 Sep. 2009
Photo of concrete pouring retrieved 18 Sep 2009 from http://www.speciation.net/Public/News/2007/04/12/2796.html
Srinath, T., Verma, T., Ramteke, P.W., Garg, S.K. (2002). Chromium (VI) biosorption and bioaccumulation by chromate resistant bacteria Chemosphere, 48 427-435.
THE ASSOCIATED PRESS. "National Briefing - Northwest - Oregon - Possible Chemical Exposure - NYTimes.com." The New York Times - Breaking News, World News & Multimedia. 12 Feb. 2009. 15 Sep. 2009
"The Real News Network - Erin Brockovich Is Back." The Real News. 15 Sep. 2009
"There is sufficient evidence in humans for the carcinogenicity of chromium[VI] compounds as encountered in the chromate production, chromate pigment production and chromium plating industries."
Toxicological profile for chromium(2008). (ATSDR Toxicological Profile. Atlanta, GA: U.S. Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry. Retrieved from http://www.atsdr.cdc.gov/toxprofiles/tp7.html
U.S. Environmental Protection Agency. (2000). Chromium compounds hazard summary. Retrieved September 18, 2009, from http://www.epa.gov/ttn/atw/hlthef/chromium.html
Hexavalent chromium is used for the production of stainless steel, textile dyes, wood preservation, leather tanning, and as anti-corrosion and conversion coatings as well as a variety of niche uses.
CrVI Facts and Figures -
The 2007 CERCLA NPL (National Priority List) of Hazardous Substances lists Hexavalent Chromium as number 18 of 275 hazardous materials. The levels of contamination may also violate the Clean Water Act of 1972 and the California Drinking Water Standards of 50 ppb total chromium. The California Air Resources Board has identified CrVI as a Toxic Air Contaminant, CAS 18540-29-9.
The Department of Health and Human Services’ Agency for Toxic Substances & Disease Registry estimates that 2,700–2,900 tons of chromium is emitted into the air annually by anthropogenic sources. 35% of these emissions are expected to be hexavalent chromium. (ATSDR “5. Potential for Human Exposure”, retrieved September 15, 2009). The ATSDR also calculates the mean daily dietary intake of chromium from air <0.2-0.4μg, from water 2.0μg, and food 60μg.
Sources of hexavalent chromium (CrVI) –
Chromium is a chemical element that occurs naturally in minerals and soils. It is also found in volcanic dust and gases. The most predominant industrial sources of chromium are from the metallurgical, refractory and chemicals industries. Metallurgical industry use includes mining/refining of chromite ore, and manufacture of ferrochromiums, such as stainless steel and other ferrous and non-ferrous alloys. Chromium is contained in refractory bricks and other refractory materials used for linings of high temperature industrial furnaces. Predominant chemical industry uses of chromium are in the manufacture of pigments, metal finishing (such as chrome plating), leather tanning, and wood preservatives. (ATSDR, 2008)
CrVI Chemistry -
Chromium exists primarily in trivalent (Cr(III)) or hexavalent (Cr(VI)) oxidation states. Cr(VI) is a notorious environmental pollutant because it is a strong oxidant and much more toxic than Cr(III) and carcinogenic. Cr(VI) exists as the chromate ion in basic solutions and as dichromate in acidic solutions.
Hexavalent chromium is recognized as a human carcinogen via inhalation. Workers in many different occupations are exposed to hexavalent chromium. Problematic exposure is known to occur among workers who handle chromate-containing products as well as those who arc weld stainless steel. Within the European Union, the use of hexavalent chromium in electronic equipment is largely prohibited by the Restriction of Hazardous Substances Directive
Chemical name: Ammonium Dichromate Chromium[VI]
Synonyms: Chromic acid, diamonium salt
Chemical Formula: (NH4)2Cr2O7
CAS registry: 7789-09-05
Chromium VI is a hazardous chemical due to its toxicity. Chromium exposure can be by breathing, contaminated air, or drinking water, or eating tainted food. Contaminated well water presents the most potential for ingestion, since chromium will stay longer at it´s hexavalent state. The potential impact is strictly to human health, since hexavalent chromium has been shown to cause cancer in lab animals. Toxic effects may include liver and heart failure, reproductive and respiratory failure. (ATSDR, 2009)
CrVI Health Effects -
Inhalation risks are assessed in different ways (LC 50, TLV, etc). The main reason is that CrVI is a carcinogen. Cancer risk or the incremental cancer risk caused by an emission is better assessed when concentrations are compared to OEHHA’s (Office of Environmental Health and Hazard Assessment) reference level of 0.002 μg Cr(VI)/m3 (OEHHA, 2009).
“The respiratory tract is the major target organ for chromium (VI) toxicity, for acute (short-term) and chronic (long-term) inhalation exposures. Shortness of breath, coughing, and wheezing were reported from a case of acute exposure to chromium (VI), while perforations and ulcerations of the septum, bronchitis, decreased pulmonary function, pneumonia, and other respiratory effects have been noted from chronic exposure. Human studies have clearly established that inhaled chromium (VI) is a human carcinogen, resulting in an increased risk of lung cancer. Animal studies have shown chromium (VI) to cause lung tumors via inhalation exposure. “ (EPA, 2000)
Acute Effects of Cr VI
- Shortness of breath, coughing, wheezing
- Gastrointestinal and neurological effects
- Skin burns
Chronic (Noncancer) Effects of Cr VI
- Perforations and ulcerations of the septum, bronchitis, decreased pulmonary function, pneumonia and asthma
- Effects on the liver, kidney, gastrointestinal and immune systems and possibly the blood
- Particulates effects include upper respiratory tract, reproductive and renal effects
Reproductive and Developmental Effects of Cr VI
- Possible complications during pregnancy and childbirth
Cancer Risks from Cr VI
- Inhaled chromium is a human carcinogen, causing an increased risk of lung cancer
(From EPA website http://www.epa.gov/ttn/atw/hlthef/chromium.html)
Toxicity and Metabolism of CrVI –
Hexavalent chromium is absorbed to a greater extent than the trivalent Chromium and readily enters cells through nonspecific anoin carriers. In significant amounts of hexavalent chromium are likely to be consumed orally because chromium(+6) is reduced in the environment to Chromium (+3) , the more stable oxidation state. chromium(+6) consumed is totally or partly reduced to Chromium (+3) in the acid environment of the stomach. Hexavalent chromium also doesn’t generally occur naturally and is produced almost totally from human activities as discussed above.
Chromium is transported in the blood primarily bound to transferring. Plasma or serum chromium conc. In humans are less than 0.30ug/L. Blood chromium concentrations are not in equilibrium with tissue chromium concentrations and do not reflect body stores. Tissue concentrations are low with kidney, liver, spleen and bone containing the highest concentrations.
Hexavalent chromium is transported into cells via the sulfate transport mechanisms, taking advantage of the similarity of sulfate and chromate with respect to their structure and charge. Trivalent chromium, which is the more common variety of chromium compounds, is not transported into cells.
Inside the cell, Cr(VI) is reduced first to metastable pentavalent chromium (Cr(V)), then to trivalent chromium. Trivalent chromium binds to proteins and creates haptens that trigger immune response. Once developed, chrome sensitivity can be persistent. In such cases, contact with chromate-dyed textiles or wearing of chromate-tanned leather shoes can cause or exacerbate contact dermatitis. Vitamin C and other reducing agents combine with chromate to give Cr(III) products inside the cell.
It appears that the mechanism of genotoxicity relies on pentavalent or trivalent chromium. According to some researchers, the damage is caused by hydroxyl radicals, produced during reoxidation of pentavalent chromium by hydrogen peroxide molecules present in the cell. Strontium chromate is the strongest carcinogen of the chromates used in industry. Soluble forms of Chromium (+6) are several fold more toxic than soluble forms of Chromium (+3)
Ground Water Field Sampling –
The USGS (United States Geological Survey) developed a new field method for collecting and analyzing ground water for the presence of chromium VI, widely used since 2003. Hexavalent chromium (Cr VI) is very toxic and a carcinogen. The new method, developed by USGS, enables the field distinguishment between Cr VI and its less toxic form, chromium III. The advantages of the new field method include lower detection limits, down to 0.05 micrograms per liter; a small, disposable cation exchange cartridge that allows Cr VI to be separated and stabilized in the field; storage of field samples for up to several weeks; as well as the use of common lab equipment to reduce analytical cost. Time stability of preserved samples is a great advantage over the 24 hour time constraint specified for EPA method 218.6. Prior to 2003, Cr VI field analysis was not very reliable and very expensive. The newer method is comparable with standard laboratory based methods. Since the toxicity of Cr VI is widely known, quicker more accurate field sampling is of great benefit to communities. (Ball, James. 2003. A New Cation-Exchange Method for Accurate Field Speciation of Hexavalent Chromium).
One of the traditional methods for determining Cr(VI) uses diphenylcarbohydrazide (DPC) to form an intensely colored complex with Cr(VI). The complex is measured quantitatively by its visible absorption at 520 nm. However, as in any colorimetric analysis, this test is subject to positive interferences from other colored materials in the sample as well as from other elements that form colored complexes with DPC.
Cr VI Case Study 1 –
Erin Brockovich, who was depicted by Julia Roberts in a Hollywood motion picture, has played a large roll in the world of Hexavalent Chromium in drinking water. Her first major case was in Henkley, California where she won over 330 million dollars for a town whose drinking water was nearly 6 times the Maximum Contaminant Level (0.10 PPM) set by the EPA (Brockovich, Famous Trials, Chapter 1 Preface." Enemy at the Gates, Thirteen Days, Erin Brockovich, Stories Behind The Movies. 15 Sep. 2009 ).
Later, in 2007, at a site in Oinofyta, Greece, Brockovich became involved at a similar case involving the Asopos River.
Most recently Brockovich has been invovled in a major drinking water case in Midland, Texas where well water has been reported to have hexavalent chromium levels 10 times higher than those at the Henkley California site
Case Study 3 -
A relatively recent industrial source of concern for CrVI is Portland Cement. Concrete, a very common building material is a mixture of portland cement, aggregate (sand and rock), and water. Raw materials used in the manufacture of portland cement, such as limestone, clay, and silica contain naturally occurring sources of chromium. During the cement manufacturing process, raw materials, are mixed and heated in a large kiln to produce an intermediate pebble-sized material called clinker. Fugitive dust emissions from stored piles of clinker are alleged to be a significant source of CrVI contamination to air, soil, and potentially groundwater in the area surrounding a cement plant operated by TXI International near Riverside, California. (Insurance Journal, 2008)
CrVI Case Study 2 -
An example of an airborne Cr VI case study comes from Davenport California where a local Cemex cement plant was the source of levels of contamination above those set by local standards, however the recorded levels were below those set by the EPA. The significance of this case is that it bring to light CrVI as a harmful by product possible in the production of cement
Case Study General –
A general case study are Cr(VI) in discharge from tanneries, this is regulated and can be treated at the source. However in India, reguation hasn't happened until recently and studies have conducted to remediate contamination sites.
As part of the tanning process hexavalent chromium compounds are often a byproduct of the chemicals used to alter the rawhide material into leather. In areas with little to no regulation hexavalent chromium compounds are discharged in effluent into the environment (Sirnath, et al 2002). Tanneries in India discharge effluent containing hexavalent chromium compounds into the environment which in turn contaminates agricultural land and ground water (ACIAR, 2003). Effluent discharge from tanneries can be treated to reduce hexavalent chromium compounds; however these processes may is seen as not economically feasible (Sirnath et al, 2002). Studies, using microbial remediation and phytoremediation at contaminated sites in India have proven insightful. Microbes that can bioaccumulate hexavalent chromium compounds can be added to tannery sludge which will in turn reduce chromium compounds in sludge to acceptable levels (Sirnath et al, 2002). Other techniques are being used to remove chromium compounds from tannery sludge, by planting crops that are more tolerant to chromium or by planting crops that will absorb chromium and reduce it from contaminate sites (ACIAR, 2003). To curb the environmental contamination from tannery discharge India has enacted regulations (ACIAR, 2003). These remediation techniques will help to met these regulations in addition to better treatment at discharge source.
References
"5. Potential for Human Exposure." Department of Health and Human Services. www.atsdr.cdc.gov/toxprofiles/tp7-c5.pdf (accessed September 15, 2009).
Agency for Toxic Substances and Disease Registry (ATSDR). 2008. Toxicological profile for Chromium (Draft for Public Comment). Atlanta, GA: U.S. Department of Health and Human Services, Public Health Service.
"Air Toxics Hotspots Program Risk Management Guidelines, Part II: Technical Support Document for Describing Available Cancer Potency Factors ." Office of Environmental Health Hazard Assessment. www.oehha.ca.gov/pdf/HSCA2.pdf (accessed September 15, 2009).
Australian Centre for International Agricultural Research (ACIAR) Media Release (2003). Cleaning Up Tannery Waste. Retrieved September 17, 2009 from the World Wide Web: http://www.aciar.gov.au/node/10365
Brockovich, Erin. " Pollution Flows in Asopos :: The Brockovich Report ." The Brockovich Report :: Published by Los Angeles Area Consumer Advocate Erin Brockovich. 25 Aug. 2007. 15 Sep. 2009
California AG sues cement plant for hexavalent chromium exposure. (2008). Retrieved September 18, 2009, from http://www.insurancejournal.com/news/west/2008/07/08/91677.htm
"Chromium Compounds | Technology Transfer Network Air Toxics Web site | US EPA." U.S. Environmental Protection Agency. http://www.epa.gov/ttn/atw/hlthef/chromium.html (accessed September 15, 2009).
Chromium (VI) (CASRN 18540-29-9) | IRIS | US EPA." U.S. Environmental Protection Agency. 22 Sep. 2009
Gerd Anger, Jost Halstenberg, Klaus Hochgeschwender, Christoph Scherhag, Ulrich Korallus, Herbert Knopf, Peter Schmidt, Manfred Ohlinger, "Chromium Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005.
Gonzalez, Juan. "Indiana Guardsmen Sue KBR Over Chemical Exposure in Iraq." Democracy Now! | Radio and TV News. 4 Dec. 2008. 15 Sep. 2009
Hexavalent Chromium, Cr(VI), Analysis. (n.d.). Retrieved September 16, 2009, from http://www.wcaslab.com/tech/HEXCHROM
"Hexavalent chromium - Wikipedia, the free encyclopedia." Wikipedia, the free encyclopedia. 20 Sep. 2009
IARC (1999-11-05) [1990] (PDF). Volume 49: Chromium, Nickel, and Welding. Lyon: International Agency for Research on Cancer. ISBN 92-832-1249-5. http://monographs.iarc.fr/ENG/Monographs/vol49/volume49.pdf. Retrieved 2006-07-16.
Mandate, Congressional, the Agency for Toxic Substances, Toxicity, and Potential for Human Exposure. Toxicological profiles are developed from a priority list of 275 substances. ATSDR also prepares toxicological profiles for the Department of Defense (DOD). "ATSDR - Toxicological Profile Information Sheet." ATSDR Home. http://www.atsdr.cdc.gov/toxpro2.html#bookmarkset19 (accessed September 15, 2009).
McCord, Shanna. "Chromium 6 testing continues in Davenport, Cemex changes business practices - October 9th,2008 by Shanna McCord." Home - Santa Cruz Sentinel. 9 Oct. 2008. 15 Sep. 2009
Mineral tolerance of animals . washington: National Research Council Committee on Minerals and Toxic Substances. , 2005. Pg 116-120
NIOSH Topic: Hexavalent Chromium | CDC/NIOSH." Centers for Disease Control and Prevention. 18 Sep. 2009
Photo of concrete pouring retrieved 18 Sep 2009 from http://www.speciation.net/Public/News/2007/04/12/2796.html
Srinath, T., Verma, T., Ramteke, P.W., Garg, S.K. (2002). Chromium (VI) biosorption and bioaccumulation by chromate resistant bacteria Chemosphere, 48 427-435.
THE ASSOCIATED PRESS. "National Briefing - Northwest - Oregon - Possible Chemical Exposure - NYTimes.com." The New York Times - Breaking News, World News & Multimedia. 12 Feb. 2009. 15 Sep. 2009
"The Real News Network - Erin Brockovich Is Back." The Real News. 15 Sep. 2009
"There is sufficient evidence in humans for the carcinogenicity of chromium[VI] compounds as encountered in the chromate production, chromate pigment production and chromium plating industries."
Toxicological profile for chromium(2008). (ATSDR Toxicological Profile. Atlanta, GA: U.S. Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry. Retrieved from http://www.atsdr.cdc.gov/toxprofiles/tp7.html
U.S. Environmental Protection Agency. (2000). Chromium compounds hazard summary. Retrieved September 18, 2009, from http://www.epa.gov/ttn/atw/hlthef/chromium.html
Team Delta Project One: Vinyl Chloride
Vinyl Chloride – A Brief Introduction to a Dangerous Chemical
By Team Delta
David Seidel Andrew Smith Daniel South Doug Sposito
Mary Steffen-Deaton Stacey Stephenson Kandy VanMeeteren
Robin Walker Andrew Watson Damien Watt
General Chemistry and Use
by Damien Watt
Vinyl chloride is the organic compound with the formula CH2:CHCl. It burns easily and it is not stable at high temperatures. It is a manufactured substance that does not occur naturally. It can be formed when other substances such as trichloroethane, trichloroethylene, and tetrachloroethylene are broken down. This colorless compound is an important industrial chemical chiefly used to produce the polymer polyvinyl chloride (PVC). Vinyl chloride was first produced in 1835 by Justus von Liebig and his student Henri Victor Regnault. They obtained it by treating ethylene dichloride with a solution of potassium hydroxide in ethanol (Vinyl Chloride, 2006).
Vinyl chloride, also known as chloroethene, is a halogenated aliphatic hydrocarbon with an empirical formula of C2H3Cl and a molecular weight of 62.5. It is a colorless gas with a mild sweetish odor, a melting point of -153.71 °C, a boiling point of -13.8°C, a specific gravity of 0.9121 g/mL, and a vapor pressure of 2580 torr. The odor threshold for vinyl chloride is 3,000 ppm. Vinyl chloride is slightly soluble in water and is quite flammable. The vapor pressure for vinyl chloride is 2,600 mm Hg at 25 °C, and it has a log octanol/water partition coefficient (log Kow) of 1.36 (Vinyl Chloride, 2006).
Production
Two methods that are used in the commercial production of vinyl chloride are the
hydrochlorination of acetylene and the dehydrochlorination of dichloroethylene processes.
Production from Ethylene dichloride
The production of vinyl chloride from ethylene dichloride (EDC) consists of a series of welldefined steps. Ethylene dichloride (EDC) is prepared by reacting ethylene and chlorine (About Vinyl and PVC, 2008). In the presence of iron (III) chloride as a catalyst, these compounds react exothermically:
CH2=CH2 + Cl2 → ClCH2CH2Cl
When heated to 500 °C at 15–30 atm (1.5 to 3 MPa) pressure, EDC decomposes to produce vinyl chloride and HCl:
ClCH2CH2Cl → CH2=CHCl + HCl
A refrigerant is then used to chill the outlet stream prior to a series of distillation towers (About Vinyl and PVC, 2008). The last distillation tower has pure HCl going from the top and product vinyl chloride coming out of the bottom. The recycled HCl is used to produce more EDC. The recycling process involves a copper (II) chloride-catalyzed oxychlorination of ethylene. Oxychlorination entails the combined action of oxygen and hydrogen chloride to produce chlorine in situ:
CH2=CH2 + 2 HCl + ½ O2 → ClCH2CH2Cl + H2O
Due to the economical advantages of this recycling as well as the low cost of ethylene, most vinyl chloride has been produced via this technique since the late 1950s. (David Allen, 2009)
Production from Acetylene
Acetylene, produced by the hydrolysis of calcium carbide, is treated with hydrogen chloride to give vinyl chloride:
C2H2 + HCl → CH2=CHCl
The method is not widely practiced in the west due to the cost of the acetylene and the associated environmental impact of its production. (David Allen, 2009)
References:
David Allen. (2009, April 3). Industrial Ecology. [Green Engineering]. Retrieved April 3, 2009, from
http://www.epa.gov/opptintr/greenengineering/pubs/ch14_summary.html: Allen, David, Environmental Protection
Agency
Vinyl Chloride. (2006, July). Retrieved April 3, 2009, from http://www.atsdr.cdc.gov/toxprofiles/tp20-c2.pdf: Center for Disease Control
___________________________________________________________________________
Vinyl Chloride Toxic Effects
by Mary Steffen-Deaton
Vinyl chloride is a sweet smelling, colorless gas at room temperature. It is used commonly in our society in the production of PVC (polyvinyl chloride). The emissions of vinyl chloride are mostly into the air. A smaller percentage of the emissions enter into the water supply and contaminate wells. Studies have shown us that vinyl chloride is a toxic chemical for humans and the environment. Vinyl chloride is not a naturally occurring chemical but seeps into the environment through several sources like from the chemical industry, plastics industry, wastes in landfills, and treated wastewater. The EPA classifies vinyl chloride as a carcinogen. It is recommended to avoid human exposure to vinyl chloride. Some of the major potential health effects of vinyl chloride exposure are cancer, liver disease, lymphoma, Acroosteolysis, Raynaud's syndrome and leukemia.
How do you get exposed to Vinyl Chloride?
A person can get exposed to vinyl chloride through inhalation, touching or ingestion. Most ingestion exposure generally occurs through drinking or cooking with water from a contaminated well. Inhalation exposure can come from several sources. Breathing vinyl chloride at a contaminated work place or breathing air from a leaking landfill or the plastics industry are some examples. Also cigarettes with tobacco contain low levels of vinyl chloride so avoid breathing second hand smoke is recommended. Touching or skin exposure can occur in industry.
Toxic Effects from Exposure to Vinyl Chloride:
What toxic effects occur depends on several factors:
- the length of exposure to the vinyl chloride
- the amount of exposure
- how the vinyl chloride entered into the body (inhaled, touched, or eaten).
Acute exposure to high levels of vinyl chloride by inhalation has effects on the Central Nervous System (CNS), such as sleepiness, dizziness, drowsiness, and headaches. Vinyl chloride is slightly irritating to the eyes and respiratory tract in humans also.
Chronic effects of exposure to vinyl chloride can result in liver damage, immune reactions, nerve damage, and liver cancer. The long term effects to exposure to high levels of vinyl chloride result in decrease in bone strength in fingers, arms, and joints as well as blood flow problems.
References:
Air toxics and indoor air quality in Australia. State of knowledge reportEnvironment Australia, 2001 ISBN 0 6425 4739 4 from: http://www.environment.gov.au/atmosphere/airquality/publications/sok/vinyl.html
EPA Hazard Summary-Vinyl Chloride: Created in April 1992; Revised in January 2000 from: http://www.epa.gov/ttn/atw/hlthef/vinylchl.html
Agency for Toxic Substances and Disease Registry (ATSDR). 2006. Toxicological Profile for Vinyl Chloride. Atlanta, GA: U.S. Department of Health and Human Services, Public Health Service. From: http://www.atsdr.cdc.gov/tfacts20.html#bookmark05
Ohio Department of Health: Health Assessment Section Vinyl Chloride From:
http://www.odh.ohio.gov/ASSETS/B5689E862EAB4FD89846F63EB9ACBE04/vinlchl.pdf
__________________________________________________________________________
Health Hazard Information
By Kandy VanMeeteren
There has been many years of studies done that have proven workers who had inhalation exposure to high levels of vinyl chloride toxin had a higher risk of cancer, such as liver, brain or lung cancer. Workers have also been diagnosed with cancers of the blood. Breathing in high levels of this highly toxic substance increases the chances a person will develop drowsiness, headaches, and giddiness conditions.
Vinyl chloride is a vascular toxin and can lead to a tumor that grows very quickly called angiosarcoma. Workers who inhaled the toxin for chronic effects (many years) possibly changed the structure of their liver. When it arrives at the liver, the liver breaks down the vinyl chloride substance. These new substances journey throughout your blood, to your kidneys and they leave through your urine. The new substances that are in your liver do not leave as quickly. These new substances do more damage than the original toxin does. The reason for the delay is that the respond with the new chemical within your body will interrupts how your body would usually react to those chemicals.
Being exposed to high levels of vinyl chloride in the air can cause a set of symptoms termed "vinyl chloride disease," known as Raynaud's phenomenon that effects the flow of blood in your hands. Raynaud's is a deterioration of the bone that causes a lack of feeling in the tips of your fingers with discomfort to cold exposure and following ulcers that will deformity in the ends of the fingers.
The inhalation of air containing this carcinogen can cause ocular irritation and respiratory weakness. The central nervous system can be effected with dizziness, fatigue, visual, memory loss, and sleep disturbances.
Figure 1 The Normal Liver and a Liver Exposed to Vinyl Chloride
Figure 1 was in medical article www.beliefnet.com
references:
http://www.epa.gov/ttn/atw/hlthef/vinylchl.html
____________________________________________________________________
Federal Regulations of Vinyl Chloride
By Stacy Stephenson
According to the International Agency for Research on Cancer (IARC), vinyl chloride is classified as a Group 1 carcinogen mostly affecting the liver. (http://www.inchem.org/documents/iarc/suppl7/vinylchloride.html) and there is no level of exposure at which there are no possible health effects (http://www.articlecbase.com/health-articles/vinylchloride-classified-as-carcinogen-508930.html). These findings support the federal regulation of vinyl chloride in such everyday things as food, water and air.
In 1974, Congress passed the Safe Drinking Water Act (SDWA) which required the Environmental Protection Agency (EPA) to set safe levels of contaminants in water. The result was the Maximum Contaminant Level Goals (MCLG) which the EPA set at zero for vinyl chloride. Since these are non-enforceable limits they were tasks with developing the Maximum Contaminant Level (MCL) which are enforceable by law. The MCL for vinyl chloride is 2ppbm and should not be exceeded at any time. The EPA set this limit because it is the lowest level that is possible to reasonably reach based on the technology and the resources that are available today. The National Primary Drinking Water Regulations is the body of legislation responsible for ensuring that the MCLs are met in all public water supplies
(http://www.epa.gov/OGWDW/contaminants/dw_contamfs/vinylchl.html).
The Food and Drug Administration (FDA) regulates the content of vinyl chloride in plastic containers that are used to house and/or transport foods. These limits vary depending on the nature of the plastic used but are monitored by the FDA for acceptable levels- Toxicological Profile for Vinyl Chloride (http://www.atsdr.cdc.gov/lfacts20.html#bookmark10). Aerosol drug products containing vinyl chloride have been pulled from the market and its use is now banned in the production of aerosol (cosmetic) products (http://ntp.niehs.nih.gov/ntp/roc/eleventh/profiles/s186viny.pdf).
Given that vinyl chloride is a Hazardous Air Pollutant (HAP) it also regulated by the Clean Air Act (CAA) under NESHAPS (National Emission Standard for Hazardous Air Pollutants) and NSPS (New Source Performance Standards). These are standards adopted by the EPA to regulate air emissions from industries (http://www.cdphe.state.co.us/ap/nsps.html#nspsoverview).
In addition to the above mentioned regulations, vinyl chloride is also regulated under RCRA as a hazardous constituent and hazardous waste, Superfund as a hazardous substance, Clean Water Act as a priority pollutant, under the Toxic Release Inventory as a reportable chemical (http://www.scorecard.org/chemical-profiles/regulation) and under The Emergency Planning and Community Right-to-know Act of 1986. The release of more than 1 pound into the air, water or land must be reported to the EPA. It is also regulated under the Department of Transportation (DOT) as a hazardous material (http://ntp.niehs.nih.gov/ntp/roc/eleventh/profiles/s186viny.pdf).
As far as the workplace is concerned, vinyl chloride is regulated by OSHA under 1910.1200- Hazard Communication Standard. They place a PEL (permissible exposure limit) on vinyl chloride which is the regulatory limits of the concentration of a substance in air and is based on an 8 hour time weighted average (TWA) work shift unless otherwise stated. Another standard if measurement is the action level which is the regulatory limit set at one half the PEL but can vary. The PEL for vinyl chloride is 1ppm TW and 0.5ppm action level. Vinyl chloride also has an Threshold Limit Value (TLV) that is set forth by the American Conference of Governmental Industrial hygienists (ACGIH) which is not a standards but an opinion of a safe worker level. It is 1ppm TWA (http://www.mathesongas.com/pdfs.msds). This happens to agree with OSHA’s level but this isn’t always the case.
____________________________________________________________________
Transportation of Vinyl Chloride
By Andrew Watson
The handling and transportation of Vinyl Chloride is important to ensure the safety of the general public and property along its route is protected. Vinyl Chloride is an extremely flammable gas and exposure to it can cause serious harm to those who encounter it unprotected. Although, Vinyl Chloride is a hazardous chemical or a hazardous waste byproduct, it can be safely transported throughout the world as long as the generator, shipper, and transporter follow rules created by national governmental agencies. In the United States, the transportation of hazardous chemicals is regulated by the Pipeline and Hazardous Materials Safety Administration (PHMSA) and the United States Department of Transportation (DOT).
Classification
Before any chemical can be transported, it must first be classified to determine if it is deemed a hazardous chemical/waste or if it is non-hazardous. This can be accomplished by looking in the Code of Federal Regulation (49 CFR) book under the proper shipping name of the chemical. Vinyl Chloride is listed as hazardous chemical (Class 2.1 flammable Gas) and to ensure safe transport, special handling and shipping requirements must be followed.
Mode of Transportation
Now that Vinyl Chloride has been determined to be a Class 2.1 flammable Gas material and needs to have special handling, a safe mode of transportation needs to be determined. The only approved modes of transportation for Vinyl Chloride are:
· Truck transport
· Cargo air craft
Forbidden modes of transportation are:
· Passenger aircraft
· Rail car
Placards
Placarding is a form of hazard communication and is the backbone of emergency response. The primary mission of DOT hazard communication is to alert the public and transportation workers of the presence of hazardous materials. Also, placarding provides visual indication to responders to a hazardous material incident. The United States Department of Transportation (US DOT) has specific requirements for placarding. Transporters, shippers, and generators must have placards that must meet the size, color, and placement required by the US DOT when shipping any hazardous chemical material or waste. An example of a placard for Vinyl Chloride is below:
Shipping papers
To become a shipper of hazardous chemicals or hazardous waste, special training and certification must be attained through agencies approved by US DOT. Shipping papers (manifest or bill of lading) are typically created and completed by the generator/shipper of hazardous chemicals/wastes and they will always be responsible for the accuracy and completeness of any manifest or documents they sign. Failure to review or falsify shipping documents can result in heavy fines AND jail time to the company and generator/shipper. So, it is imperative that the shipper/generator knows what the shipping papers requirements are and understand what the consequences are if they are not followed.
References:
PHEMSA Webpage:
http://www.phmsa.dot.gov/hazmat/regs
Matheson Tri Gas Webpage:
http://www.mathesongas.com/pdfs/msds/MAT24940.pdf
___________________________________________________________________________
A Selected List of Vinyl Chloride Contaminated Sites
By David Seidel
SOURCE: http://www.epa.gov/superfund/sites/npl/nar1787.html
National Priorities List (NPL)
Top of Form
NEW CARLISLE LANDFILL
New Carlisle, Ohio
Clark County
Site Location: New Carlisle Landfill is an inactive landfill located at 715 North Dayton-Lakeview Road, New Carlisle, Clark County, Ohio.
Site History: New Carlisle Landfill served as a general refuse and solid waste landfill from the mid-1950s until the early 1970s. During its operation, it received industrial, commercial and residential waste. The landfill was officially closed in 1977, after several years of inactivity. It was covered with two to four feet of clay. Since 1993, Ohio EPA has been sampling a nearby public well that serves a nursery and landscape business. In 1997, Ohio EPA discovered vinyl chloride above the safe drinking water standard in this well.
Site Contamination/Contaminants: New Carlisle Landfill is an unlined landfill that encompasses between approximately 12 to 21 acres. Ground water contaminated with volatile organic compounds including trichloroethene (TCE), tetrachloroethene and vinyl chloride have been detected beneath the landfill and in a plume south of the landfill.
Potential Impacts on Surrounding Community/Environment: Vinyl chloride contaminated two public wells and two residential wells above the safe drinking water level. The vinyl chloride ground water contamination could potentially migrate and affect approximately 15 residential wells within ½ mile radius of New Carlisle Landfill.
Response Activities (to date): In 2002, Ohio EPA required the nearby nursery and landscape business to cease public use of the well and limited future use to irrigation. In 2003, the nursery and landscape business installed a new public well. In 2005, at the request of the state, EPA extended the water line from the New Carlisle public water system to two residences and the nursery and landscape business.
Need for NPL Listing: The State of Ohio referred the site to EPA because vinyl chloride was detected at levels above the safe drinking water standard in three wells, and because of the potential threat the site poses to other residents who live in the area. Other federal and state cleanup programs were evaluated, but are not viable at this time because there are insufficient state funds to address the cleanup of this site. EPA received a letter of support for placing this site on the NPL from the state.
[The description of the site (release) is based on information available at the time the site was evaluated with the HRS. The description may change as additional information is gathered on the sources and extent of contamination. See 56 FR 5600, February 11, 1991, or subsequent FR notices.]
For more information about the hazardous substances identified in this narrative summary, including general information regarding the effects of exposure to these substances on human health, please see the Agency for Toxic Substances and Disease Registry (ATSDR) ToxFAQs. ATSDR ToxFAQs can be found on the Internet at ATSDR - ToxFAQs (http://www.atsdr.cdc.gov/toxfaq.html) or by telephone at 1-888-42-ATSDR or 1-888-422-8737.
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NPL Site Narrative for Operating Industries, Inc., Landfill
OPERATING INDUSTRIES, INC., LANDFILLMonterey Park, California
Federal Register Notice: June 10, 1986
Conditions at proposal (October 15, 1984): Operating Industries, Inc., operated a landfill on 190 acres in the City of Monterey Park, Los Angeles County, California. The 45-acre northern section was separated in the 1960s from the southern 145-acre section by the Pomona Freeway. EPA has evidence that the original landfill included at least a portion of both sections. From 1948 to 1983, solid and liquid wastes, some hazardous, were disposed of at the site.
Leachate generated by the landfill contains vinyl chloride, benzene-type compounds, tetrachloroethylene, heavy metals, and other contaminants, according to testing by the Los Angeles County Sanitation District (LACSD), the California Department of Health Services (CDHS), and the company. In July 1983, the South Coast Air Quality Management District (SCAQMD) detected vinyl chloride above ambient standards in air at and around the landfill, which is adjacent to a large residential area. SCAQMD, CDHS, and the Los Angeles County Department of Health Services have taken enforcement actions against the facility.
About 23,000 people use wells within 3 miles of the site as a source of drinking water.
The company acquired Interim Status when it filed Part A of a permit application under Subtitle C of the Resource Conservation and Recovery Act (RCRA). The company submitted a draft plan for closing the landfill under RCRA, but CDHS, in conjunction with other State agencies and EPA, determined that the plan had numerous deficiencies, most notably the failure to (1) provide financial assurance requirements for closure and (2) develop an adequate plan for monitoring ground water and for collecting and disposing of leachate. The company has not submitted complete and adequate closure and postclosure documents.
Status (February 1986): EPA collected gas samples in November 1984 from 16 subsurface probes in an adjacent housing development. Some samples confirmed the presence of methane and vinyl chloride in subsurface soils. Interior home samples collected in November 1984 had low levels of methane and nondetectable levels of vinyl chloride. Elevated levels of methane and vinyl chloride were also detected in a home adjacent to the landfill in October 1985.
EPA installed six monitoring wells around the landfill in 1984-85. Quarterly samples collected since March 1985 contain organic chemicals and trace metals.
In July 1985, EPA started planning for a comprehensive remedial investigation to determine the nature and extent of the problems associated with the landfill. When the investigation is complete, various alternatives to remedy the problems will be evaluated in a feasibility study. Interim measures are planned to stabilize and control the landfill, including slope stabilization and upgrading of existing gas leachate collection systems. EPA trucked leachate to an off-site treatment facility from October 1985 to February 1986, when the State took over.
Status (June 10, 1986): This site is placed on the NPL because the potentially responsible party declined to initiate work, and CERCLA-funded remedial activities are underway. Thus, the site meets one of the requirements of EPA's policy for placing RCRA-related sites on the NPL.
For more information about the hazardous substances identified in this narrative summary, including general information regarding the effects of exposure to these substances on human health, please see the Agency for Toxic Substances and Disease Registry (ATSDR) ToxFAQs. ATSDR ToxFAQs can be found on the Internet at http://www.atsdr.cdc.gov/toxfaq.html or by telephone at 1-888-42-ATSDR or 1-888-422-8737. This page was generated on Friday, September 18, 2009
View the graphical version of this page at: http://www.epa.gov/superfund/sites/npl/nar932.htm
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SOURCE: http://www.epa.gov/cgi-bin/epaprintonly.cgi
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NPL Site Narrative for Cayuga County Ground Water Contamination
CAYUGA COUNTY GROUND WATER CONTAMINATIONCayuga County, New York
Federal Register Notice: September 5, 2002Conditions at Proposal (September 13, 2001): The Cayuga County Ground Water Contamination site consists of a plume of contaminated ground water from an unknown source(s). The site is located west of Syracuse in a rural area of Cayuga County, between the Village of Union Springs to the west and the City of Auburn to the northeast. The site is in an area consisting of residential properties intermingled with extensive farmland and patches of woodlands. The homes in the area use private wells for potable water supply and septic systems for sanitary waste water disposal. The affected area is not serviced by a public water supply.
Routine testing of the Village of Union Springs' municipal drinking water supply revealed low levels of cis-1,2, DCE, and prompted referral to the U.S. Environmental Protection Agency (EPA) for a CERCLA/SARA response action on December 4, 2000. Through investigations conducted by the New York Departments of Health and Environmental Conservation and by the EPA, over 300 drinking water supplies have been sampled as of April 2001. As a result of these sampling events, EPA determined that 51 residential wells are contaminated with volatile organic compounds (VOCs), primarily vinyl chloride, trichloroethylene (TCE) and cis-1,2,dichloroethylene (cis-1,2,DCE), in concentrations above the Federal maximum contaminant levels (MCLs). Twenty-four of these drinking water supply wells are contaminated above EPA's Removal Action Levels (RALs) for vinyl chloride and/or cis-1,1,DCE of two parts per billion (ppb) and 400 ppb, respectively.
As of July 2001, EPA has installed 55 treatment systems to treat contaminated water from 52 wells as part of a time critical Removal Action. Two large dairy farms in the impacted area have had air-stripper treatment systems installed; at these farms water is used for both residential drinking water and for livestock (approximately 1,500 dairy cows). A treatment system installed on a well at a child day care facility exhibited partial breakthrough of contaminants in May 2001; however, contamination was contained due to built-in redundancy in the treatment system.
The suspected extent of the plume covers an area of approximately 3,050 acres or 4.8 square miles and falls within three townships, Aurelius, Fleming and Springport. The plume extends from the Village of Union Springs to the Auburn City limits, a distance of seven miles, and has approximately 120 homes within its boundaries.
The ground water flow system consists of three hydrological units: the overburden, shallow bedrock (Onondaga, Oriskany, and Manlius Formations) and the deep bedrock (Rondout, Cobleskill and Bertie Formations). Downward hydraulic gradients exist throughout, but are particularly strong between the shallow and deep bedrock units, with water-level differences in excess of 40 feet observed during dry periods of the year.
An observed release of vinyl chloride, TCE and cis-1,2 DCE has been documented by chemical analysis of ground water samples collected from private wells during an April 2001, sampling event. Actual contamination was documented for 49 wells during an April 2001 EPA sampling event. According to information provided by NYSDEC and preliminary information gathered by EPA, the source of the ground water contamination at the site has not been determined. Due to these conditions, the State of New York requested on June 7, 2001 that EPA place the site on the NPL.
Status (September 2002): EPA is considering various alternatives for this site.
For more information about the hazardous substances identified in this narrative summary, including general information regarding the effects of exposure to these substances on human health, please see the Agency for Toxic Substances and Disease Registry (ATSDR) ToxFAQs. ATSDR ToxFAQs can be found on the Internet at http://www.atsdr.cdc.gov/toxfaq.html or by telephone at 1-888-42-ATSDR or 1-888-422-8737.
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This page was generated on Saturday, September 19, 2009
View the graphical version of this page at: http://www.epa.gov/superfund/sites/npl/nar1650.htm
Brio/Dixie Refining NPL Site
SOURCE:
http://www.fws.gov/southwest/es/contaminants/NRDAR/SiteInformation/Texas/BrioDixie.pdf
Case History: The Brio and Dixie Oil Refining Site is located near the city of Friendswood, in southern Harris County, Texas. Between 1957 and 1982, site operations included by-product recycling, copper catalyst regeneration, petrochemical recovery, and jet fuel processing. Contaminants include styrene tars, vinyl chloride, chlorinated solvent residues, metallic catalyst, and fuel oil residues. The site occupies about 58 acres, and drains to a tributary feeding Clear Creek. Large numbers of birds were assumed killed over time in the open pits located on the site. The adjacent South Bend Subdivision was bought out due to a class action suit, and demolition of the homes has been completed. The Trustees and the Responsible Parties agreed upon the creation of 6 acres of freshwater riparian wetland habitat adjacent to Mud Gully in Harris County and the preservation of 100 acres of mature mixed forest with a 19 acre pasture buffer zone. This habitat creation and acquisition compensates the public for injuries to natural resources. The total settlement value at this site is worth over $1.2 million.
Responsible Parties: Dixie Oil, Intercoastal Chemical Co., Dow Chemical Co., Merichem Co., Monsanto Co., Lowenco, Inc., Mobil Chemical Co., Petro-Tex Chemical Co., Rohm & Haas Co., and Tex-Tin Co.
Trustees:
Texas Parks and Wildlife Department (TPWD)
Texas Commission on Environmental Quality (TCEQ)
Texas General Land Office (TXGLO)
Created Marsh on Lavaca Bay
NOAA
DOI-FWS
Current Status: The Restoration Plan/ Environmental Assessment was completed in December 2003 and a Consent Decree was signed on January 2006. The 6 acre wetland habitat has been constructed and planted. The entire restoration site is protected in perpetuity through a Conservation Easement held by the Legacy Land Trust.
U.S. EPA Adds East Troy Site to Superfund List, Proposes Two Ohio and One Indiana Site for List
SOURCE: http://www.redorbit.com/news/science/1542250/us_epa_adds_east_troy_site_to_superfund_list_proposes/#
Posted on: Wednesday, 3 September 2008, 12:00 CDT
CHICAGO, Sept. 3 /PRNewswire-USNewswire/ -- U.S. Environmental Protection Agency has added the East Troy Contaminated Aquifer site in Troy, Ohio, to the Superfund National Priorities List. Three other sites in EPA Region 5 -- the Behr Dayton Thermal System VOC Plume site in Dayton, the New Carlisle Landfill in New Carlisle, Ohio, and the U.S. Smelter and Lead Refinery in East Chicago, Ind. -- were proposed for addition to the NPL. Sites on the list are eligible for additional study and resources under EPA's Superfund program.
Nationally, six new sites were added to the NPL, bringing the total to 1,258, and 11 sites were proposed for addition to the list. Under the NPL process, sites are first proposed and public comments considered before a determination is made to formally add a site to the list. The NPL is updated twice each year.
The East Troy site is an area where volatile organic compounds, including the common industrial chemicals PCE and TCE, have contaminated ground water, soil and the indoor air in basements. EPA addressed the indoor air health risk by installing vapor abatement systems in 16 homes and St. Patrick Elementary School in the summer of 2007. EPA and Ohio EPA data also shows that VOCs have contaminated ground water below the city of Troy, as well as a local drinking water well field. To address this, Ohio EPA and Troy have taken steps to contain one potential source of the contamination, and are treating contaminated ground water prior to use. Adding the site to the NPL enables EPA to study site conditions further, identify possible sources of the contamination, and develop a comprehensive strategy to address all locations and sources of the VOC contamination.
The proposed Behr Dayton site also involves TCE contamination in ground water. In 2003 and 2006, volatile organic compounds were detected in ground water beneath the Behr Dayton Thermal System auto parts manufacturing facility at 1600 Webster St. To address potential health risks associated with the pollution, EPA has installed vapor mitigation systems in 180 homes in the neighborhood south of the plant since late 2006. EPA will soon announce an October open house session to discuss the project.
The New Carlisle Landfill, at 715 N. Dayton-Lakeview Road in New Carlisle, operated from the mid-1950s until the early 1970s. It is now covered with two to four feet of clay, but was not designed with a protective liner in the manner of modern landfills. Ohio EPA data indicates that water from two public wells and two residential wells in the nearby area contain vinyl chloride above the safe drinking water level. In 2005, EPA extended the water line from the New Carlisle public water system to two homes and a plant nursery business. EPA remains concerned about potential migration of the vinyl chloride toward residential wells within one-half mile of the site.
The U.S. Smelter and Lead Refinery site, 5300 Kennedy Ave., East Chicago, Ind., was also proposed for addition to the NPL today. The company operated from 1920 to 1985. Lead, most likely dispersed from long-removed smokestacks, has been detected in residential soil north of the property. The company also discharged process water to wetlands on the property that flow toward the Grand Calumet River Corridor. In July 2008, EPA began removing lead-contaminated soil from 15 nearby homes. Adding the site to the NPL will enable EPA and the Indiana Department of Environmental Management to complete a comprehensive approach to address the contamination.
A 60-day comment period on all three newly proposed NPL sites is under way. Links to the Federal Register notice, information on submitting comments, background on the NPL process and summaries of the sites newly added or proposed are at http://www.epa.gov/superfund/sites/npl/current.htm.
U.S. Environmental Protection Agency Region 5
CONTACT: Mick Hans of U.S. Environmental Protection Agency Region 5,+1-312-353-5050, hans.mick@epa.gov; Heather Lauer or Dina Pierce,+1-614-644-2160, both of Ohio EPA; Barry Sneed of IDEM, +1-317-232-8596
Web Site: http://www.epa.gov/
Berks Landfill
SOURCE: http://www.epa.gov/reg3hscd/npl/PAD000651810.htm
Current Site Information EPA Region 3 (Mid-Atlantic)
PennsylvaniaBerks CountySinking Springs
EPA ID# PAD000651810
6th Congressional District
Last Update: March 2009
Other Names
Stabatrol Berks County Landfill
Current Site Status
EPA prepared a final close-out report (FCOR) in March 2008 that documents the cleanup was fully implemented and the cleanup objectives have been met. EPA recommended removing the site from the National Priorties List (NPL) in the fall of 2008. The Berks Landfill site was removed or deleted from the National Priorties List in November 2008.
EPA will continue to oversee the operation and maintenance at the site. EPA will perform another five-year review in 2010.
Site Description
The Berks Landfill Superfund Site is located in Spring Township, Berks County, Pennsylvania. It is approximately seven miles southwest of the City of Reading. The site consists of two closed landfills: a 49-acre eastern landfill and a 19-acre western landfill.
The property historically was used as an iron ore mine. Later from the 1950s to the 1980s, the Berks Landfill operated as a municipal landfill. In 1975, the landfill was granted a permit by the state to discharge leachate from its collection system into an adjacent stream. Also, in 1975, the eastern landfill was granted a solid waste permit to accept municipal refuse and demolition refuse. In 1986 landfill operations ended and the landfills were closed with a soil cap. Later on a fence was erected around the eastern landfill, the existing cap was repaired, and a pumping station was constructed to convey the leachate to the local wastewater treatment plant.
Site Responsibility
Cleanup of this site is the responsibility of Federal and State governments and parties potentially responsible for site contamination.
NPL Listing History
Our country's most serious, uncontrolled, or abandoned hazardous waste sites can be cleaned using federal money. To be eligible for federal cleanup money, a site must be put on the National Priorities List. This site was proposed to the list on June 24, 1988 and formally added to the list October 4, 1989.
Threats and Contaminants
Sampling of on-site monitoring wells in the 1980's discovered the groundwater was contaminated with volatile organic compounds (VOCs) and metals. VOCs include vinyl chloride, trichloroethene, and cis-1,2-dichloroethene and metals include aluminum, iron, and manganese. The groundwater on-site can pose a threat to human health if consumed.Contaminant descriptions and associated risk factors are available at: (ATSDR web site).
Cleanup Progress
In July 1997, EPA selected a remedy to repair the eastern landfill cap; to repair and to continue operating of the existing leachate collection system; to perform long-term sampling and monitoring of a sentinel well, residential wells, on-site wells, landfill gas, and the creek; and to implement institutional controls to prevent future consumption of on-site groundwater and to restrict development on-site.
EPA gave the parties potentially responsible for the pollution (PRPs) the opportunity to provide good faith offers to do the cleanup work. None were recieved, so EPA ordered them to perform the work. In accordance with the order, a subgroup of the PRPs developed a remedial design that outlined how the landfill cap and leachate collection system would be repaired. EPA conditionally approved this final design on September 30, 1999. Following approval of the design, EPA approved a plan for implementing the design on January 13, 2000. The PRPs selected a construction firm to build the remedy in March 2000.
Construction Activities:
The PRPs submitted a plan detailing the management of construction and EPA approved the plan in May 2000. Construction started in June 2000 and continued until November 2000 with regular oversight from EPA. During the construction the eastern landfill was cleared of vegetation, covered by soil, and seeded and on the western landfill 7,000 feet of inspection trails were laid. The leachate collection lines and manholes were cleaned, inspected, and repaired and the three leachate collection ponds were re-shaped and re-lined for an approximate volume of 1.5 million gallons. The leachate is then pumped to the local wastewater treatment plant. To monitor the site gas monitoring probes and a groundwater monitoring well were installed. A total of 300 trees were planted to improve a wetland area on-site.
After construction was completed, EPA conducted two inspections: one in October 31, 2000 and a second on November 14, 2000. On December 22, 2000 EPA documented in a Preliminary Close-Out Report (PCOR) that the remedy was constructed.
Long-term monitoring of the site will continue to evaluate the groundwater, on-site wells and gas probes, residential wells, and the sentinel well. EPA prepared a final close-out report on the clean-up activities in March 2008 that documents the cleanup objectives have been met. EPA will recommend removing the site from the Superfund list in 2008.
Five-Year Review:
EPA completed a Five-Year Review of the Berks Landfill Superfund Site in August 2005. As part of the five-year review, EPA inspected the landfills and reviewed the monitoring data. The remedy currently protects human health and the environment because on-site and residential groundwater is being monitored; the leachate is collected and then discharged to the wastewater treatment plant; the eastern landfill cap was repaired; and there is regular monitoring and maintenance. EPA also recommended that institutional controls, or legal restrictions, be implemented in order for the remedy to maintain protective in the long-term. In follow-up to the five-year review, institutional controls were fully implemented. EPA will also perform another five-year review in 2010.
Site Deletion:
EPA prepared a final close-out report (FCOR) in March 2008 that documents the cleanup was fully implemented and the cleanup objectives have been met. EPA recommended removing the site from the National Priorties List (NPL) in the fall of 2008 and received no comment. The Berks Landfill site was removed or deleted from the National Priorties List in November 2008.
__________________________________________________________________________
PVC in the Third World the Hidden Cost
By Rob Walker
In Ghana Africa a child laborer “… hoists a tangle of copper wire off the old tire he's using for fuel and douses the hissing mass in a puddle. With the flame retardant insulation burned away—a process that has released a bouquet of carcinogens and other toxics.” (http://ngm.nationalgeographic.com/2008/01/high-tech-trash/carroll-text/1 ; September 19 2009)
Others buy computers or TVs. Salvage useable parts then they rip out wiring and burn the plastic. Scenes like this are typical in the growing trade in e-waste. http://www.youtube.com/watch?v=-j_Zohgg4S8
Scenes like these are repeated from India to Africa and China. The burning of e-waste produces toxic that damage health and have long turn health consequences.
E-waste trade is a growing problem in many third world countries. But what does e-waste have to do with PVC? PVC makes up a large constituency of the plastics casings and wire insulation that cover copper wire. Plastic casings PVC make up to 6.3 Kg of an average computer. Over a ¼ of all the Plastic used by computer and electronics industry are PVC based plastics (everything2.com/title/e-waste , September 19 2009). In Africa and Third World countries the common practice of copper recover is to burn wire/cords to remove the protective casing. Often the casing are PVC based. Most developed countries and some companies have laws and policy that prohibit E-waste from being shipped to developing countries. Some company and shady recycles often conceal e-waste as second hand goods (useable goods) and ship them to developing nations. Once the “second hand goods” reached the developing world it is sold as scrap and is scraped out for its useable part and copper content. (http://ngm.nationalgeographic.com/2008/01/high-tech-trash/carroll-text/1 ; September 19 2009)
References:
ngm.nationalgeographic.com/2008/01/high-tech-trash/carroll-text/1
(everything2.com/title/e-waste
http://ewasteguide.info/e-waste-campaign-gra
http://abcnews.go.com/WN/
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Remediation of Vinyl Chloride Contamination
By Daniel South
Groundwater:
Groundwater contaminated by vinyl chloride can be treated in two ways: ex-situ and in-situ. Either method has its positive and negative points.
Ex-Situ Remediation
For ex-situ (meaning “out of place”), the water is pumped out of the ground and sent to a treatment plant. The water is then treated by running it through activated carbon that causes the pollutants to adsorb onto the carbon. Frequently there is an air stripper as well. An air stripper usually is a column filled with plastic or steel balls so that there is a large amount of surface area. The contaminated water trickles down the balls, exposing it to the atmosphere. Volatile organic compounds, like vinyl chloride leave the water and go into a gaseous phase where they can react with oxygen and break down or be sucked into the carbon filter. Water leaving the treatment plant should have no contaminants and the water is either pumped back into the ground, usually upgradient, or it is discharged into surface drainage under a National Pollutant Discharge Elimination System (better known as NPDES) permit.
In-Situ Remediation
For in-situ (meaning “in place”) remediation, the primary method of remediation is to oxidize the contaminant and chemically change it to an end result of carbon dioxide. The oxidation breaks the carbon-carbon double bond and replaces it with a carbon-oxygen double bond. The chlorine is removed to form hydrochloric acid as an intermediate compound before reacting to form other compounds.
Vinyl Chloride
Molecular Formula C2H3Cl
Source of diagram: http://z.about.com/d/chemistry/1/0/5/1/ethylene.gif
Source of diagram: http://chemistry.about.com/od/factsstructures/ig/Chemical-Structures---C/Carbon-Dioxide.htm
This is done in three ways: direct chemical oxidation, bioremediation using aerobic micro-organisms, and bioremediation using anaerobic micro-organisms.
Direct Chemical Oxidation
Direct chemical oxidation is performed by injecting a strong oxidizer such as concentrated hydrogen peroxide, ozone, or one of the other commercially available products. This method uses direct chemistry to destroy the vinyl chloride by reacting directly with it. One problem associated with this method is that the oxidizer reacts with other compounds as well as the intended contaminant. Enough oxidizer must be injected into the groundwater such that there is sufficient amount to cover the mass of contaminant in the water as well as enough to cover that lost to reactions with unintended materials such as organic roots, debris, and peat. Also, these reactions generate significant amounts of heat and pressure and can damage well casings and other buried objects. On the positive side, this treatment is quick and the vinyl chloride can be destroyed in a matter of days.
Injection of remediation agent into the subsurface using direct-push technology
http://www.regenesis.com/library/Regenesis_Corp_Brochure_0607_L.pdf
Bioremediation Using Aerobic Micro-organisms
Micro-organism using enzymes are able to carry out chemical reactions without the heat generated by direct chemical reaction. As such, there is less likelihood of damaging subsurface materials and it is a very effective method of remediation. It can be a much slower process than direct oxidation. The main goal is to create conditions that will promote the growth of colonies of the desired organisms. These organisms use the vinyl chloride as food and use the oxygen for respiration. Most environments already contain these organisms to some degree unless the environment is severely reducing or too harsh in other ways. This method injects a product that releases oxygen slowly into the groundwater. This can be a commercial product such as Oxygen Release Compound (ORC®) produced by Regenesis, or simply dilute hydrogen peroxide (5-10% concentration). Depending on the size of the area to be remediated and the nature of the subsurface environment, it may take several injections over time to create the conditions you desire. Evidence that you are creating an aerobic environment would include an increase in dissolved oxygen content in the groundwater and an increase in levels of oxidation-reduction potential (ORP) which measures the relative reducing or oxidizing ability of the groundwater. These measurements are easily made at wells using commercially available meters. Analysis of groundwater samples should show a decrease in vinyl chloride and an increase in ethene or ethane.
Bioremediation Using Anaerobic Micro-organisms
There can exist environments where it may be too difficult to create oxidizing conditions. Luckily, there are some microbes that can de-chlorinate the vinyl chloride under reducing conditions. The goal of dechlorination is to convert the vinyl chloride into ethene (also known as ethylene) by removing the chlorine. The chlorine is converted into a chloride ion and usually forms a non-hazardous compound such as sodium chloride. For chlorinated solvents it is relatively easy to remove a chlorine atom from tetrachlorethene (C2Cl4) under reducing conditions. It is a bit harder to remove a chlorine atom from trichloroethene (C2HCl3) and harder still from cis-1,2-dichloroethene (C2H2Cl2) under these conditions. With each step you need slightly stronger reducing conditions. With vinyl chloride it is hardest of all under reducing conditions, but it can be done. Again, the process is not complicated. A compound is injected into the area to be cleaned by direct-push applications. This time though, the object is to create strongly reducing conditions so compounds that put hydrogen into the groundwater such as Hydrogen Release Compound (HRC®) again by Regenesis, or some similar compound are used. For this method, the concentration of dissolved oxygen in groundwater should decrease and the ORP readings should become strongly negative. The time it takes for remediation is very site-dependent and groundwater will need to be sampled several times to monitor concentrations of vinyl chloride to see if the process is working.
Source of diagram: http://z.about.com/d/chemistry/1/0/5/1/ethylene.gif
Injection into the subsurface,
Source: www.teamzebra.com
Soil:
Vinyl chloride does not tend to adsorb onto soil. It may occur in the pres between soils and in groundwater that may have sorbed onto soil. Treating soil contaminated by vinyl chloride would include excavation or by injecting the same compounds described above with enough water to temporarily saturate the soil. Systems can be developed to recirculate water through an area that is being treated and keeping the water table elevated in the area of remediation.
This brief summary has described a few methods of remediation for sites affected by vinyl chloride. There are more methods available, but this has introduced some of the more popular methods.
Sources
http://www.epa.gov/ttn/atw/hlthef/vinylchl.html, accessed 9/20/09.
http://z.about.com/d/chemistry/1/0/5/1/ethylene.gif%20accessed%209/17/09.
http://chemistry.about.com/od/factsstructures/ig/Chemical-Structures---C/Carbon-Dioxide.htm accessed 9/22/09.
http://www.regenesis.com/library/Regenesis_Corp_Brochure_0607_L.pdf accessed 9/20/09.
http://toxics.usgs.gov/sites/solvents/oxidation_VC.html accessed 9/18/09.
http://wvlc.uwaterloo.ca/biology447/Assignments/assignment1/vinyl_chloride/vinyl_chloride1.htm%20accessed%209/18/09.
http://www.teamzebra.com/ accessed 9/20/09.
By Team Delta
David Seidel Andrew Smith Daniel South Doug Sposito
Mary Steffen-Deaton Stacey Stephenson Kandy VanMeeteren
Robin Walker Andrew Watson Damien Watt
General Chemistry and Use
by Damien Watt
Vinyl chloride is the organic compound with the formula CH2:CHCl. It burns easily and it is not stable at high temperatures. It is a manufactured substance that does not occur naturally. It can be formed when other substances such as trichloroethane, trichloroethylene, and tetrachloroethylene are broken down. This colorless compound is an important industrial chemical chiefly used to produce the polymer polyvinyl chloride (PVC). Vinyl chloride was first produced in 1835 by Justus von Liebig and his student Henri Victor Regnault. They obtained it by treating ethylene dichloride with a solution of potassium hydroxide in ethanol (Vinyl Chloride, 2006).
Vinyl chloride, also known as chloroethene, is a halogenated aliphatic hydrocarbon with an empirical formula of C2H3Cl and a molecular weight of 62.5. It is a colorless gas with a mild sweetish odor, a melting point of -153.71 °C, a boiling point of -13.8°C, a specific gravity of 0.9121 g/mL, and a vapor pressure of 2580 torr. The odor threshold for vinyl chloride is 3,000 ppm. Vinyl chloride is slightly soluble in water and is quite flammable. The vapor pressure for vinyl chloride is 2,600 mm Hg at 25 °C, and it has a log octanol/water partition coefficient (log Kow) of 1.36 (Vinyl Chloride, 2006).
Production
Two methods that are used in the commercial production of vinyl chloride are the
hydrochlorination of acetylene and the dehydrochlorination of dichloroethylene processes.
Production from Ethylene dichloride
The production of vinyl chloride from ethylene dichloride (EDC) consists of a series of welldefined steps. Ethylene dichloride (EDC) is prepared by reacting ethylene and chlorine (About Vinyl and PVC, 2008). In the presence of iron (III) chloride as a catalyst, these compounds react exothermically:
CH2=CH2 + Cl2 → ClCH2CH2Cl
When heated to 500 °C at 15–30 atm (1.5 to 3 MPa) pressure, EDC decomposes to produce vinyl chloride and HCl:
ClCH2CH2Cl → CH2=CHCl + HCl
A refrigerant is then used to chill the outlet stream prior to a series of distillation towers (About Vinyl and PVC, 2008). The last distillation tower has pure HCl going from the top and product vinyl chloride coming out of the bottom. The recycled HCl is used to produce more EDC. The recycling process involves a copper (II) chloride-catalyzed oxychlorination of ethylene. Oxychlorination entails the combined action of oxygen and hydrogen chloride to produce chlorine in situ:
CH2=CH2 + 2 HCl + ½ O2 → ClCH2CH2Cl + H2O
Due to the economical advantages of this recycling as well as the low cost of ethylene, most vinyl chloride has been produced via this technique since the late 1950s. (David Allen, 2009)
Production from Acetylene
Acetylene, produced by the hydrolysis of calcium carbide, is treated with hydrogen chloride to give vinyl chloride:
C2H2 + HCl → CH2=CHCl
The method is not widely practiced in the west due to the cost of the acetylene and the associated environmental impact of its production. (David Allen, 2009)
References:
David Allen. (2009, April 3). Industrial Ecology. [Green Engineering]. Retrieved April 3, 2009, from
http://www.epa.gov/opptintr/greenengineering/pubs/ch14_summary.html: Allen, David, Environmental Protection
Agency
Vinyl Chloride. (2006, July). Retrieved April 3, 2009, from http://www.atsdr.cdc.gov/toxprofiles/tp20-c2.pdf: Center for Disease Control
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Vinyl Chloride Toxic Effects
by Mary Steffen-Deaton
Vinyl chloride is a sweet smelling, colorless gas at room temperature. It is used commonly in our society in the production of PVC (polyvinyl chloride). The emissions of vinyl chloride are mostly into the air. A smaller percentage of the emissions enter into the water supply and contaminate wells. Studies have shown us that vinyl chloride is a toxic chemical for humans and the environment. Vinyl chloride is not a naturally occurring chemical but seeps into the environment through several sources like from the chemical industry, plastics industry, wastes in landfills, and treated wastewater. The EPA classifies vinyl chloride as a carcinogen. It is recommended to avoid human exposure to vinyl chloride. Some of the major potential health effects of vinyl chloride exposure are cancer, liver disease, lymphoma, Acroosteolysis, Raynaud's syndrome and leukemia.
How do you get exposed to Vinyl Chloride?
A person can get exposed to vinyl chloride through inhalation, touching or ingestion. Most ingestion exposure generally occurs through drinking or cooking with water from a contaminated well. Inhalation exposure can come from several sources. Breathing vinyl chloride at a contaminated work place or breathing air from a leaking landfill or the plastics industry are some examples. Also cigarettes with tobacco contain low levels of vinyl chloride so avoid breathing second hand smoke is recommended. Touching or skin exposure can occur in industry.
Toxic Effects from Exposure to Vinyl Chloride:
What toxic effects occur depends on several factors:
- the length of exposure to the vinyl chloride
- the amount of exposure
- how the vinyl chloride entered into the body (inhaled, touched, or eaten).
Acute exposure to high levels of vinyl chloride by inhalation has effects on the Central Nervous System (CNS), such as sleepiness, dizziness, drowsiness, and headaches. Vinyl chloride is slightly irritating to the eyes and respiratory tract in humans also.
Chronic effects of exposure to vinyl chloride can result in liver damage, immune reactions, nerve damage, and liver cancer. The long term effects to exposure to high levels of vinyl chloride result in decrease in bone strength in fingers, arms, and joints as well as blood flow problems.
References:
Air toxics and indoor air quality in Australia. State of knowledge reportEnvironment Australia, 2001 ISBN 0 6425 4739 4 from: http://www.environment.gov.au/atmosphere/airquality/publications/sok/vinyl.html
EPA Hazard Summary-Vinyl Chloride: Created in April 1992; Revised in January 2000 from: http://www.epa.gov/ttn/atw/hlthef/vinylchl.html
Agency for Toxic Substances and Disease Registry (ATSDR). 2006. Toxicological Profile for Vinyl Chloride. Atlanta, GA: U.S. Department of Health and Human Services, Public Health Service. From: http://www.atsdr.cdc.gov/tfacts20.html#bookmark05
Ohio Department of Health: Health Assessment Section Vinyl Chloride From:
http://www.odh.ohio.gov/ASSETS/B5689E862EAB4FD89846F63EB9ACBE04/vinlchl.pdf
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Health Hazard Information
By Kandy VanMeeteren
There has been many years of studies done that have proven workers who had inhalation exposure to high levels of vinyl chloride toxin had a higher risk of cancer, such as liver, brain or lung cancer. Workers have also been diagnosed with cancers of the blood. Breathing in high levels of this highly toxic substance increases the chances a person will develop drowsiness, headaches, and giddiness conditions.
Vinyl chloride is a vascular toxin and can lead to a tumor that grows very quickly called angiosarcoma. Workers who inhaled the toxin for chronic effects (many years) possibly changed the structure of their liver. When it arrives at the liver, the liver breaks down the vinyl chloride substance. These new substances journey throughout your blood, to your kidneys and they leave through your urine. The new substances that are in your liver do not leave as quickly. These new substances do more damage than the original toxin does. The reason for the delay is that the respond with the new chemical within your body will interrupts how your body would usually react to those chemicals.
Being exposed to high levels of vinyl chloride in the air can cause a set of symptoms termed "vinyl chloride disease," known as Raynaud's phenomenon that effects the flow of blood in your hands. Raynaud's is a deterioration of the bone that causes a lack of feeling in the tips of your fingers with discomfort to cold exposure and following ulcers that will deformity in the ends of the fingers.
The inhalation of air containing this carcinogen can cause ocular irritation and respiratory weakness. The central nervous system can be effected with dizziness, fatigue, visual, memory loss, and sleep disturbances.
Figure 1 The Normal Liver and a Liver Exposed to Vinyl Chloride
Figure 1 was in medical article www.beliefnet.com
references:
http://www.epa.gov/ttn/atw/hlthef/vinylchl.html
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Federal Regulations of Vinyl Chloride
By Stacy Stephenson
According to the International Agency for Research on Cancer (IARC), vinyl chloride is classified as a Group 1 carcinogen mostly affecting the liver. (http://www.inchem.org/documents/iarc/suppl7/vinylchloride.html) and there is no level of exposure at which there are no possible health effects (http://www.articlecbase.com/health-articles/vinylchloride-classified-as-carcinogen-508930.html). These findings support the federal regulation of vinyl chloride in such everyday things as food, water and air.
In 1974, Congress passed the Safe Drinking Water Act (SDWA) which required the Environmental Protection Agency (EPA) to set safe levels of contaminants in water. The result was the Maximum Contaminant Level Goals (MCLG) which the EPA set at zero for vinyl chloride. Since these are non-enforceable limits they were tasks with developing the Maximum Contaminant Level (MCL) which are enforceable by law. The MCL for vinyl chloride is 2ppbm and should not be exceeded at any time. The EPA set this limit because it is the lowest level that is possible to reasonably reach based on the technology and the resources that are available today. The National Primary Drinking Water Regulations is the body of legislation responsible for ensuring that the MCLs are met in all public water supplies
(http://www.epa.gov/OGWDW/contaminants/dw_contamfs/vinylchl.html).
The Food and Drug Administration (FDA) regulates the content of vinyl chloride in plastic containers that are used to house and/or transport foods. These limits vary depending on the nature of the plastic used but are monitored by the FDA for acceptable levels- Toxicological Profile for Vinyl Chloride (http://www.atsdr.cdc.gov/lfacts20.html#bookmark10). Aerosol drug products containing vinyl chloride have been pulled from the market and its use is now banned in the production of aerosol (cosmetic) products (http://ntp.niehs.nih.gov/ntp/roc/eleventh/profiles/s186viny.pdf).
Given that vinyl chloride is a Hazardous Air Pollutant (HAP) it also regulated by the Clean Air Act (CAA) under NESHAPS (National Emission Standard for Hazardous Air Pollutants) and NSPS (New Source Performance Standards). These are standards adopted by the EPA to regulate air emissions from industries (http://www.cdphe.state.co.us/ap/nsps.html#nspsoverview).
In addition to the above mentioned regulations, vinyl chloride is also regulated under RCRA as a hazardous constituent and hazardous waste, Superfund as a hazardous substance, Clean Water Act as a priority pollutant, under the Toxic Release Inventory as a reportable chemical (http://www.scorecard.org/chemical-profiles/regulation) and under The Emergency Planning and Community Right-to-know Act of 1986. The release of more than 1 pound into the air, water or land must be reported to the EPA. It is also regulated under the Department of Transportation (DOT) as a hazardous material (http://ntp.niehs.nih.gov/ntp/roc/eleventh/profiles/s186viny.pdf).
As far as the workplace is concerned, vinyl chloride is regulated by OSHA under 1910.1200- Hazard Communication Standard. They place a PEL (permissible exposure limit) on vinyl chloride which is the regulatory limits of the concentration of a substance in air and is based on an 8 hour time weighted average (TWA) work shift unless otherwise stated. Another standard if measurement is the action level which is the regulatory limit set at one half the PEL but can vary. The PEL for vinyl chloride is 1ppm TW and 0.5ppm action level. Vinyl chloride also has an Threshold Limit Value (TLV) that is set forth by the American Conference of Governmental Industrial hygienists (ACGIH) which is not a standards but an opinion of a safe worker level. It is 1ppm TWA (http://www.mathesongas.com/pdfs.msds). This happens to agree with OSHA’s level but this isn’t always the case.
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Transportation of Vinyl Chloride
By Andrew Watson
The handling and transportation of Vinyl Chloride is important to ensure the safety of the general public and property along its route is protected. Vinyl Chloride is an extremely flammable gas and exposure to it can cause serious harm to those who encounter it unprotected. Although, Vinyl Chloride is a hazardous chemical or a hazardous waste byproduct, it can be safely transported throughout the world as long as the generator, shipper, and transporter follow rules created by national governmental agencies. In the United States, the transportation of hazardous chemicals is regulated by the Pipeline and Hazardous Materials Safety Administration (PHMSA) and the United States Department of Transportation (DOT).
Classification
Before any chemical can be transported, it must first be classified to determine if it is deemed a hazardous chemical/waste or if it is non-hazardous. This can be accomplished by looking in the Code of Federal Regulation (49 CFR) book under the proper shipping name of the chemical. Vinyl Chloride is listed as hazardous chemical (Class 2.1 flammable Gas) and to ensure safe transport, special handling and shipping requirements must be followed.
Mode of Transportation
Now that Vinyl Chloride has been determined to be a Class 2.1 flammable Gas material and needs to have special handling, a safe mode of transportation needs to be determined. The only approved modes of transportation for Vinyl Chloride are:
· Truck transport
· Cargo air craft
Forbidden modes of transportation are:
· Passenger aircraft
· Rail car
Placards
Placarding is a form of hazard communication and is the backbone of emergency response. The primary mission of DOT hazard communication is to alert the public and transportation workers of the presence of hazardous materials. Also, placarding provides visual indication to responders to a hazardous material incident. The United States Department of Transportation (US DOT) has specific requirements for placarding. Transporters, shippers, and generators must have placards that must meet the size, color, and placement required by the US DOT when shipping any hazardous chemical material or waste. An example of a placard for Vinyl Chloride is below:
Shipping papers
To become a shipper of hazardous chemicals or hazardous waste, special training and certification must be attained through agencies approved by US DOT. Shipping papers (manifest or bill of lading) are typically created and completed by the generator/shipper of hazardous chemicals/wastes and they will always be responsible for the accuracy and completeness of any manifest or documents they sign. Failure to review or falsify shipping documents can result in heavy fines AND jail time to the company and generator/shipper. So, it is imperative that the shipper/generator knows what the shipping papers requirements are and understand what the consequences are if they are not followed.
References:
PHEMSA Webpage:
http://www.phmsa.dot.gov/hazmat/regs
Matheson Tri Gas Webpage:
http://www.mathesongas.com/pdfs/msds/MAT24940.pdf
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A Selected List of Vinyl Chloride Contaminated Sites
By David Seidel
SOURCE: http://www.epa.gov/superfund/sites/npl/nar1787.html
National Priorities List (NPL)
Top of Form
NEW CARLISLE LANDFILL
New Carlisle, Ohio
Clark County
Site Location: New Carlisle Landfill is an inactive landfill located at 715 North Dayton-Lakeview Road, New Carlisle, Clark County, Ohio.
Site History: New Carlisle Landfill served as a general refuse and solid waste landfill from the mid-1950s until the early 1970s. During its operation, it received industrial, commercial and residential waste. The landfill was officially closed in 1977, after several years of inactivity. It was covered with two to four feet of clay. Since 1993, Ohio EPA has been sampling a nearby public well that serves a nursery and landscape business. In 1997, Ohio EPA discovered vinyl chloride above the safe drinking water standard in this well.
Site Contamination/Contaminants: New Carlisle Landfill is an unlined landfill that encompasses between approximately 12 to 21 acres. Ground water contaminated with volatile organic compounds including trichloroethene (TCE), tetrachloroethene and vinyl chloride have been detected beneath the landfill and in a plume south of the landfill.
Potential Impacts on Surrounding Community/Environment: Vinyl chloride contaminated two public wells and two residential wells above the safe drinking water level. The vinyl chloride ground water contamination could potentially migrate and affect approximately 15 residential wells within ½ mile radius of New Carlisle Landfill.
Response Activities (to date): In 2002, Ohio EPA required the nearby nursery and landscape business to cease public use of the well and limited future use to irrigation. In 2003, the nursery and landscape business installed a new public well. In 2005, at the request of the state, EPA extended the water line from the New Carlisle public water system to two residences and the nursery and landscape business.
Need for NPL Listing: The State of Ohio referred the site to EPA because vinyl chloride was detected at levels above the safe drinking water standard in three wells, and because of the potential threat the site poses to other residents who live in the area. Other federal and state cleanup programs were evaluated, but are not viable at this time because there are insufficient state funds to address the cleanup of this site. EPA received a letter of support for placing this site on the NPL from the state.
[The description of the site (release) is based on information available at the time the site was evaluated with the HRS. The description may change as additional information is gathered on the sources and extent of contamination. See 56 FR 5600, February 11, 1991, or subsequent FR notices.]
For more information about the hazardous substances identified in this narrative summary, including general information regarding the effects of exposure to these substances on human health, please see the Agency for Toxic Substances and Disease Registry (ATSDR) ToxFAQs. ATSDR ToxFAQs can be found on the Internet at ATSDR - ToxFAQs (http://www.atsdr.cdc.gov/toxfaq.html) or by telephone at 1-888-42-ATSDR or 1-888-422-8737.
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NPL Site Narrative for Operating Industries, Inc., Landfill
OPERATING INDUSTRIES, INC., LANDFILLMonterey Park, California
Federal Register Notice: June 10, 1986
Conditions at proposal (October 15, 1984): Operating Industries, Inc., operated a landfill on 190 acres in the City of Monterey Park, Los Angeles County, California. The 45-acre northern section was separated in the 1960s from the southern 145-acre section by the Pomona Freeway. EPA has evidence that the original landfill included at least a portion of both sections. From 1948 to 1983, solid and liquid wastes, some hazardous, were disposed of at the site.
Leachate generated by the landfill contains vinyl chloride, benzene-type compounds, tetrachloroethylene, heavy metals, and other contaminants, according to testing by the Los Angeles County Sanitation District (LACSD), the California Department of Health Services (CDHS), and the company. In July 1983, the South Coast Air Quality Management District (SCAQMD) detected vinyl chloride above ambient standards in air at and around the landfill, which is adjacent to a large residential area. SCAQMD, CDHS, and the Los Angeles County Department of Health Services have taken enforcement actions against the facility.
About 23,000 people use wells within 3 miles of the site as a source of drinking water.
The company acquired Interim Status when it filed Part A of a permit application under Subtitle C of the Resource Conservation and Recovery Act (RCRA). The company submitted a draft plan for closing the landfill under RCRA, but CDHS, in conjunction with other State agencies and EPA, determined that the plan had numerous deficiencies, most notably the failure to (1) provide financial assurance requirements for closure and (2) develop an adequate plan for monitoring ground water and for collecting and disposing of leachate. The company has not submitted complete and adequate closure and postclosure documents.
Status (February 1986): EPA collected gas samples in November 1984 from 16 subsurface probes in an adjacent housing development. Some samples confirmed the presence of methane and vinyl chloride in subsurface soils. Interior home samples collected in November 1984 had low levels of methane and nondetectable levels of vinyl chloride. Elevated levels of methane and vinyl chloride were also detected in a home adjacent to the landfill in October 1985.
EPA installed six monitoring wells around the landfill in 1984-85. Quarterly samples collected since March 1985 contain organic chemicals and trace metals.
In July 1985, EPA started planning for a comprehensive remedial investigation to determine the nature and extent of the problems associated with the landfill. When the investigation is complete, various alternatives to remedy the problems will be evaluated in a feasibility study. Interim measures are planned to stabilize and control the landfill, including slope stabilization and upgrading of existing gas leachate collection systems. EPA trucked leachate to an off-site treatment facility from October 1985 to February 1986, when the State took over.
Status (June 10, 1986): This site is placed on the NPL because the potentially responsible party declined to initiate work, and CERCLA-funded remedial activities are underway. Thus, the site meets one of the requirements of EPA's policy for placing RCRA-related sites on the NPL.
For more information about the hazardous substances identified in this narrative summary, including general information regarding the effects of exposure to these substances on human health, please see the Agency for Toxic Substances and Disease Registry (ATSDR) ToxFAQs. ATSDR ToxFAQs can be found on the Internet at http://www.atsdr.cdc.gov/toxfaq.html or by telephone at 1-888-42-ATSDR or 1-888-422-8737. This page was generated on Friday, September 18, 2009
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NPL Site Narrative for Cayuga County Ground Water Contamination
CAYUGA COUNTY GROUND WATER CONTAMINATIONCayuga County, New York
Federal Register Notice: September 5, 2002Conditions at Proposal (September 13, 2001): The Cayuga County Ground Water Contamination site consists of a plume of contaminated ground water from an unknown source(s). The site is located west of Syracuse in a rural area of Cayuga County, between the Village of Union Springs to the west and the City of Auburn to the northeast. The site is in an area consisting of residential properties intermingled with extensive farmland and patches of woodlands. The homes in the area use private wells for potable water supply and septic systems for sanitary waste water disposal. The affected area is not serviced by a public water supply.
Routine testing of the Village of Union Springs' municipal drinking water supply revealed low levels of cis-1,2, DCE, and prompted referral to the U.S. Environmental Protection Agency (EPA) for a CERCLA/SARA response action on December 4, 2000. Through investigations conducted by the New York Departments of Health and Environmental Conservation and by the EPA, over 300 drinking water supplies have been sampled as of April 2001. As a result of these sampling events, EPA determined that 51 residential wells are contaminated with volatile organic compounds (VOCs), primarily vinyl chloride, trichloroethylene (TCE) and cis-1,2,dichloroethylene (cis-1,2,DCE), in concentrations above the Federal maximum contaminant levels (MCLs). Twenty-four of these drinking water supply wells are contaminated above EPA's Removal Action Levels (RALs) for vinyl chloride and/or cis-1,1,DCE of two parts per billion (ppb) and 400 ppb, respectively.
As of July 2001, EPA has installed 55 treatment systems to treat contaminated water from 52 wells as part of a time critical Removal Action. Two large dairy farms in the impacted area have had air-stripper treatment systems installed; at these farms water is used for both residential drinking water and for livestock (approximately 1,500 dairy cows). A treatment system installed on a well at a child day care facility exhibited partial breakthrough of contaminants in May 2001; however, contamination was contained due to built-in redundancy in the treatment system.
The suspected extent of the plume covers an area of approximately 3,050 acres or 4.8 square miles and falls within three townships, Aurelius, Fleming and Springport. The plume extends from the Village of Union Springs to the Auburn City limits, a distance of seven miles, and has approximately 120 homes within its boundaries.
The ground water flow system consists of three hydrological units: the overburden, shallow bedrock (Onondaga, Oriskany, and Manlius Formations) and the deep bedrock (Rondout, Cobleskill and Bertie Formations). Downward hydraulic gradients exist throughout, but are particularly strong between the shallow and deep bedrock units, with water-level differences in excess of 40 feet observed during dry periods of the year.
An observed release of vinyl chloride, TCE and cis-1,2 DCE has been documented by chemical analysis of ground water samples collected from private wells during an April 2001, sampling event. Actual contamination was documented for 49 wells during an April 2001 EPA sampling event. According to information provided by NYSDEC and preliminary information gathered by EPA, the source of the ground water contamination at the site has not been determined. Due to these conditions, the State of New York requested on June 7, 2001 that EPA place the site on the NPL.
Status (September 2002): EPA is considering various alternatives for this site.
For more information about the hazardous substances identified in this narrative summary, including general information regarding the effects of exposure to these substances on human health, please see the Agency for Toxic Substances and Disease Registry (ATSDR) ToxFAQs. ATSDR ToxFAQs can be found on the Internet at http://www.atsdr.cdc.gov/toxfaq.html or by telephone at 1-888-42-ATSDR or 1-888-422-8737.
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Brio/Dixie Refining NPL Site
SOURCE:
http://www.fws.gov/southwest/es/contaminants/NRDAR/SiteInformation/Texas/BrioDixie.pdf
Case History: The Brio and Dixie Oil Refining Site is located near the city of Friendswood, in southern Harris County, Texas. Between 1957 and 1982, site operations included by-product recycling, copper catalyst regeneration, petrochemical recovery, and jet fuel processing. Contaminants include styrene tars, vinyl chloride, chlorinated solvent residues, metallic catalyst, and fuel oil residues. The site occupies about 58 acres, and drains to a tributary feeding Clear Creek. Large numbers of birds were assumed killed over time in the open pits located on the site. The adjacent South Bend Subdivision was bought out due to a class action suit, and demolition of the homes has been completed. The Trustees and the Responsible Parties agreed upon the creation of 6 acres of freshwater riparian wetland habitat adjacent to Mud Gully in Harris County and the preservation of 100 acres of mature mixed forest with a 19 acre pasture buffer zone. This habitat creation and acquisition compensates the public for injuries to natural resources. The total settlement value at this site is worth over $1.2 million.
Responsible Parties: Dixie Oil, Intercoastal Chemical Co., Dow Chemical Co., Merichem Co., Monsanto Co., Lowenco, Inc., Mobil Chemical Co., Petro-Tex Chemical Co., Rohm & Haas Co., and Tex-Tin Co.
Trustees:
Texas Parks and Wildlife Department (TPWD)
Texas Commission on Environmental Quality (TCEQ)
Texas General Land Office (TXGLO)
Created Marsh on Lavaca Bay
NOAA
DOI-FWS
Current Status: The Restoration Plan/ Environmental Assessment was completed in December 2003 and a Consent Decree was signed on January 2006. The 6 acre wetland habitat has been constructed and planted. The entire restoration site is protected in perpetuity through a Conservation Easement held by the Legacy Land Trust.
U.S. EPA Adds East Troy Site to Superfund List, Proposes Two Ohio and One Indiana Site for List
SOURCE: http://www.redorbit.com/news/science/1542250/us_epa_adds_east_troy_site_to_superfund_list_proposes/#
Posted on: Wednesday, 3 September 2008, 12:00 CDT
CHICAGO, Sept. 3 /PRNewswire-USNewswire/ -- U.S. Environmental Protection Agency has added the East Troy Contaminated Aquifer site in Troy, Ohio, to the Superfund National Priorities List. Three other sites in EPA Region 5 -- the Behr Dayton Thermal System VOC Plume site in Dayton, the New Carlisle Landfill in New Carlisle, Ohio, and the U.S. Smelter and Lead Refinery in East Chicago, Ind. -- were proposed for addition to the NPL. Sites on the list are eligible for additional study and resources under EPA's Superfund program.
Nationally, six new sites were added to the NPL, bringing the total to 1,258, and 11 sites were proposed for addition to the list. Under the NPL process, sites are first proposed and public comments considered before a determination is made to formally add a site to the list. The NPL is updated twice each year.
The East Troy site is an area where volatile organic compounds, including the common industrial chemicals PCE and TCE, have contaminated ground water, soil and the indoor air in basements. EPA addressed the indoor air health risk by installing vapor abatement systems in 16 homes and St. Patrick Elementary School in the summer of 2007. EPA and Ohio EPA data also shows that VOCs have contaminated ground water below the city of Troy, as well as a local drinking water well field. To address this, Ohio EPA and Troy have taken steps to contain one potential source of the contamination, and are treating contaminated ground water prior to use. Adding the site to the NPL enables EPA to study site conditions further, identify possible sources of the contamination, and develop a comprehensive strategy to address all locations and sources of the VOC contamination.
The proposed Behr Dayton site also involves TCE contamination in ground water. In 2003 and 2006, volatile organic compounds were detected in ground water beneath the Behr Dayton Thermal System auto parts manufacturing facility at 1600 Webster St. To address potential health risks associated with the pollution, EPA has installed vapor mitigation systems in 180 homes in the neighborhood south of the plant since late 2006. EPA will soon announce an October open house session to discuss the project.
The New Carlisle Landfill, at 715 N. Dayton-Lakeview Road in New Carlisle, operated from the mid-1950s until the early 1970s. It is now covered with two to four feet of clay, but was not designed with a protective liner in the manner of modern landfills. Ohio EPA data indicates that water from two public wells and two residential wells in the nearby area contain vinyl chloride above the safe drinking water level. In 2005, EPA extended the water line from the New Carlisle public water system to two homes and a plant nursery business. EPA remains concerned about potential migration of the vinyl chloride toward residential wells within one-half mile of the site.
The U.S. Smelter and Lead Refinery site, 5300 Kennedy Ave., East Chicago, Ind., was also proposed for addition to the NPL today. The company operated from 1920 to 1985. Lead, most likely dispersed from long-removed smokestacks, has been detected in residential soil north of the property. The company also discharged process water to wetlands on the property that flow toward the Grand Calumet River Corridor. In July 2008, EPA began removing lead-contaminated soil from 15 nearby homes. Adding the site to the NPL will enable EPA and the Indiana Department of Environmental Management to complete a comprehensive approach to address the contamination.
A 60-day comment period on all three newly proposed NPL sites is under way. Links to the Federal Register notice, information on submitting comments, background on the NPL process and summaries of the sites newly added or proposed are at http://www.epa.gov/superfund/sites/npl/current.htm.
U.S. Environmental Protection Agency Region 5
CONTACT: Mick Hans of U.S. Environmental Protection Agency Region 5,+1-312-353-5050, hans.mick@epa.gov; Heather Lauer or Dina Pierce,+1-614-644-2160, both of Ohio EPA; Barry Sneed of IDEM, +1-317-232-8596
Web Site: http://www.epa.gov/
Berks Landfill
SOURCE: http://www.epa.gov/reg3hscd/npl/PAD000651810.htm
Current Site Information EPA Region 3 (Mid-Atlantic)
PennsylvaniaBerks CountySinking Springs
EPA ID# PAD000651810
6th Congressional District
Last Update: March 2009
Other Names
Stabatrol Berks County Landfill
Current Site Status
EPA prepared a final close-out report (FCOR) in March 2008 that documents the cleanup was fully implemented and the cleanup objectives have been met. EPA recommended removing the site from the National Priorties List (NPL) in the fall of 2008. The Berks Landfill site was removed or deleted from the National Priorties List in November 2008.
EPA will continue to oversee the operation and maintenance at the site. EPA will perform another five-year review in 2010.
Site Description
The Berks Landfill Superfund Site is located in Spring Township, Berks County, Pennsylvania. It is approximately seven miles southwest of the City of Reading. The site consists of two closed landfills: a 49-acre eastern landfill and a 19-acre western landfill.
The property historically was used as an iron ore mine. Later from the 1950s to the 1980s, the Berks Landfill operated as a municipal landfill. In 1975, the landfill was granted a permit by the state to discharge leachate from its collection system into an adjacent stream. Also, in 1975, the eastern landfill was granted a solid waste permit to accept municipal refuse and demolition refuse. In 1986 landfill operations ended and the landfills were closed with a soil cap. Later on a fence was erected around the eastern landfill, the existing cap was repaired, and a pumping station was constructed to convey the leachate to the local wastewater treatment plant.
Site Responsibility
Cleanup of this site is the responsibility of Federal and State governments and parties potentially responsible for site contamination.
NPL Listing History
Our country's most serious, uncontrolled, or abandoned hazardous waste sites can be cleaned using federal money. To be eligible for federal cleanup money, a site must be put on the National Priorities List. This site was proposed to the list on June 24, 1988 and formally added to the list October 4, 1989.
Threats and Contaminants
Sampling of on-site monitoring wells in the 1980's discovered the groundwater was contaminated with volatile organic compounds (VOCs) and metals. VOCs include vinyl chloride, trichloroethene, and cis-1,2-dichloroethene and metals include aluminum, iron, and manganese. The groundwater on-site can pose a threat to human health if consumed.Contaminant descriptions and associated risk factors are available at: (ATSDR web site).
Cleanup Progress
In July 1997, EPA selected a remedy to repair the eastern landfill cap; to repair and to continue operating of the existing leachate collection system; to perform long-term sampling and monitoring of a sentinel well, residential wells, on-site wells, landfill gas, and the creek; and to implement institutional controls to prevent future consumption of on-site groundwater and to restrict development on-site.
EPA gave the parties potentially responsible for the pollution (PRPs) the opportunity to provide good faith offers to do the cleanup work. None were recieved, so EPA ordered them to perform the work. In accordance with the order, a subgroup of the PRPs developed a remedial design that outlined how the landfill cap and leachate collection system would be repaired. EPA conditionally approved this final design on September 30, 1999. Following approval of the design, EPA approved a plan for implementing the design on January 13, 2000. The PRPs selected a construction firm to build the remedy in March 2000.
Construction Activities:
The PRPs submitted a plan detailing the management of construction and EPA approved the plan in May 2000. Construction started in June 2000 and continued until November 2000 with regular oversight from EPA. During the construction the eastern landfill was cleared of vegetation, covered by soil, and seeded and on the western landfill 7,000 feet of inspection trails were laid. The leachate collection lines and manholes were cleaned, inspected, and repaired and the three leachate collection ponds were re-shaped and re-lined for an approximate volume of 1.5 million gallons. The leachate is then pumped to the local wastewater treatment plant. To monitor the site gas monitoring probes and a groundwater monitoring well were installed. A total of 300 trees were planted to improve a wetland area on-site.
After construction was completed, EPA conducted two inspections: one in October 31, 2000 and a second on November 14, 2000. On December 22, 2000 EPA documented in a Preliminary Close-Out Report (PCOR) that the remedy was constructed.
Long-term monitoring of the site will continue to evaluate the groundwater, on-site wells and gas probes, residential wells, and the sentinel well. EPA prepared a final close-out report on the clean-up activities in March 2008 that documents the cleanup objectives have been met. EPA will recommend removing the site from the Superfund list in 2008.
Five-Year Review:
EPA completed a Five-Year Review of the Berks Landfill Superfund Site in August 2005. As part of the five-year review, EPA inspected the landfills and reviewed the monitoring data. The remedy currently protects human health and the environment because on-site and residential groundwater is being monitored; the leachate is collected and then discharged to the wastewater treatment plant; the eastern landfill cap was repaired; and there is regular monitoring and maintenance. EPA also recommended that institutional controls, or legal restrictions, be implemented in order for the remedy to maintain protective in the long-term. In follow-up to the five-year review, institutional controls were fully implemented. EPA will also perform another five-year review in 2010.
Site Deletion:
EPA prepared a final close-out report (FCOR) in March 2008 that documents the cleanup was fully implemented and the cleanup objectives have been met. EPA recommended removing the site from the National Priorties List (NPL) in the fall of 2008 and received no comment. The Berks Landfill site was removed or deleted from the National Priorties List in November 2008.
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PVC in the Third World the Hidden Cost
By Rob Walker
In Ghana Africa a child laborer “… hoists a tangle of copper wire off the old tire he's using for fuel and douses the hissing mass in a puddle. With the flame retardant insulation burned away—a process that has released a bouquet of carcinogens and other toxics.” (http://ngm.nationalgeographic.com/2008/01/high-tech-trash/carroll-text/1 ; September 19 2009)
Others buy computers or TVs. Salvage useable parts then they rip out wiring and burn the plastic. Scenes like this are typical in the growing trade in e-waste. http://www.youtube.com/watch?v=-j_Zohgg4S8
Scenes like these are repeated from India to Africa and China. The burning of e-waste produces toxic that damage health and have long turn health consequences.
E-waste trade is a growing problem in many third world countries. But what does e-waste have to do with PVC? PVC makes up a large constituency of the plastics casings and wire insulation that cover copper wire. Plastic casings PVC make up to 6.3 Kg of an average computer. Over a ¼ of all the Plastic used by computer and electronics industry are PVC based plastics (everything2.com/title/e-waste , September 19 2009). In Africa and Third World countries the common practice of copper recover is to burn wire/cords to remove the protective casing. Often the casing are PVC based. Most developed countries and some companies have laws and policy that prohibit E-waste from being shipped to developing countries. Some company and shady recycles often conceal e-waste as second hand goods (useable goods) and ship them to developing nations. Once the “second hand goods” reached the developing world it is sold as scrap and is scraped out for its useable part and copper content. (http://ngm.nationalgeographic.com/2008/01/high-tech-trash/carroll-text/1 ; September 19 2009)
References:
ngm.nationalgeographic.com/2008/01/high-tech-trash/carroll-text/1
(everything2.com/title/e-waste
http://ewasteguide.info/e-waste-campaign-gra
http://abcnews.go.com/WN/
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Remediation of Vinyl Chloride Contamination
By Daniel South
Groundwater:
Groundwater contaminated by vinyl chloride can be treated in two ways: ex-situ and in-situ. Either method has its positive and negative points.
Ex-Situ Remediation
For ex-situ (meaning “out of place”), the water is pumped out of the ground and sent to a treatment plant. The water is then treated by running it through activated carbon that causes the pollutants to adsorb onto the carbon. Frequently there is an air stripper as well. An air stripper usually is a column filled with plastic or steel balls so that there is a large amount of surface area. The contaminated water trickles down the balls, exposing it to the atmosphere. Volatile organic compounds, like vinyl chloride leave the water and go into a gaseous phase where they can react with oxygen and break down or be sucked into the carbon filter. Water leaving the treatment plant should have no contaminants and the water is either pumped back into the ground, usually upgradient, or it is discharged into surface drainage under a National Pollutant Discharge Elimination System (better known as NPDES) permit.
In-Situ Remediation
For in-situ (meaning “in place”) remediation, the primary method of remediation is to oxidize the contaminant and chemically change it to an end result of carbon dioxide. The oxidation breaks the carbon-carbon double bond and replaces it with a carbon-oxygen double bond. The chlorine is removed to form hydrochloric acid as an intermediate compound before reacting to form other compounds.
Vinyl Chloride
Molecular Formula C2H3Cl
Source of diagram: http://z.about.com/d/chemistry/1/0/5/1/ethylene.gif
Source of diagram: http://chemistry.about.com/od/factsstructures/ig/Chemical-Structures---C/Carbon-Dioxide.htm
This is done in three ways: direct chemical oxidation, bioremediation using aerobic micro-organisms, and bioremediation using anaerobic micro-organisms.
Direct Chemical Oxidation
Direct chemical oxidation is performed by injecting a strong oxidizer such as concentrated hydrogen peroxide, ozone, or one of the other commercially available products. This method uses direct chemistry to destroy the vinyl chloride by reacting directly with it. One problem associated with this method is that the oxidizer reacts with other compounds as well as the intended contaminant. Enough oxidizer must be injected into the groundwater such that there is sufficient amount to cover the mass of contaminant in the water as well as enough to cover that lost to reactions with unintended materials such as organic roots, debris, and peat. Also, these reactions generate significant amounts of heat and pressure and can damage well casings and other buried objects. On the positive side, this treatment is quick and the vinyl chloride can be destroyed in a matter of days.
Injection of remediation agent into the subsurface using direct-push technology
http://www.regenesis.com/library/Regenesis_Corp_Brochure_0607_L.pdf
Bioremediation Using Aerobic Micro-organisms
Micro-organism using enzymes are able to carry out chemical reactions without the heat generated by direct chemical reaction. As such, there is less likelihood of damaging subsurface materials and it is a very effective method of remediation. It can be a much slower process than direct oxidation. The main goal is to create conditions that will promote the growth of colonies of the desired organisms. These organisms use the vinyl chloride as food and use the oxygen for respiration. Most environments already contain these organisms to some degree unless the environment is severely reducing or too harsh in other ways. This method injects a product that releases oxygen slowly into the groundwater. This can be a commercial product such as Oxygen Release Compound (ORC®) produced by Regenesis, or simply dilute hydrogen peroxide (5-10% concentration). Depending on the size of the area to be remediated and the nature of the subsurface environment, it may take several injections over time to create the conditions you desire. Evidence that you are creating an aerobic environment would include an increase in dissolved oxygen content in the groundwater and an increase in levels of oxidation-reduction potential (ORP) which measures the relative reducing or oxidizing ability of the groundwater. These measurements are easily made at wells using commercially available meters. Analysis of groundwater samples should show a decrease in vinyl chloride and an increase in ethene or ethane.
Bioremediation Using Anaerobic Micro-organisms
There can exist environments where it may be too difficult to create oxidizing conditions. Luckily, there are some microbes that can de-chlorinate the vinyl chloride under reducing conditions. The goal of dechlorination is to convert the vinyl chloride into ethene (also known as ethylene) by removing the chlorine. The chlorine is converted into a chloride ion and usually forms a non-hazardous compound such as sodium chloride. For chlorinated solvents it is relatively easy to remove a chlorine atom from tetrachlorethene (C2Cl4) under reducing conditions. It is a bit harder to remove a chlorine atom from trichloroethene (C2HCl3) and harder still from cis-1,2-dichloroethene (C2H2Cl2) under these conditions. With each step you need slightly stronger reducing conditions. With vinyl chloride it is hardest of all under reducing conditions, but it can be done. Again, the process is not complicated. A compound is injected into the area to be cleaned by direct-push applications. This time though, the object is to create strongly reducing conditions so compounds that put hydrogen into the groundwater such as Hydrogen Release Compound (HRC®) again by Regenesis, or some similar compound are used. For this method, the concentration of dissolved oxygen in groundwater should decrease and the ORP readings should become strongly negative. The time it takes for remediation is very site-dependent and groundwater will need to be sampled several times to monitor concentrations of vinyl chloride to see if the process is working.
Source of diagram: http://z.about.com/d/chemistry/1/0/5/1/ethylene.gif
Injection into the subsurface,
Source: www.teamzebra.com
Soil:
Vinyl chloride does not tend to adsorb onto soil. It may occur in the pres between soils and in groundwater that may have sorbed onto soil. Treating soil contaminated by vinyl chloride would include excavation or by injecting the same compounds described above with enough water to temporarily saturate the soil. Systems can be developed to recirculate water through an area that is being treated and keeping the water table elevated in the area of remediation.
This brief summary has described a few methods of remediation for sites affected by vinyl chloride. There are more methods available, but this has introduced some of the more popular methods.
Sources
http://www.epa.gov/ttn/atw/hlthef/vinylchl.html, accessed 9/20/09.
http://z.about.com/d/chemistry/1/0/5/1/ethylene.gif%20accessed%209/17/09.
http://chemistry.about.com/od/factsstructures/ig/Chemical-Structures---C/Carbon-Dioxide.htm accessed 9/22/09.
http://www.regenesis.com/library/Regenesis_Corp_Brochure_0607_L.pdf accessed 9/20/09.
http://toxics.usgs.gov/sites/solvents/oxidation_VC.html accessed 9/18/09.
http://wvlc.uwaterloo.ca/biology447/Assignments/assignment1/vinyl_chloride/vinyl_chloride1.htm%20accessed%209/18/09.
http://www.teamzebra.com/ accessed 9/20/09.
Monday, September 21, 2009
Team Alpha - Project 1 - Chromium
BASIC CHEMISTRY OF CHROMIUM
Chromium is an odorless, tasteless element occurring both naturally and as a product of industrial processes. The Chemical Abstract Services identification number for elemental chromium is 7440-47-3. It exists in the environment primarily as Cr (III), but also exists as Cr (VI) and Cr (0), the latter two resulting from industry. In the periodic table of elements, chromium is a primordial transition metal with the atomic number 24. The term ‘primordial’ refers to elements that have been found on earth and existed in their current state prior to the existence of the earth, based on the best accepted theories of geochemistry. The half-life of these atoms is approximately greater than 108 years. Cr (III) is a naturally occurring element found in rocks, animals, plants, soils, volcanic gases, and it is an essential nutrient. There are reactions, as in the case of in-situ oxidation with permanganate, producing MnO2, which can convert Cr (III) to Cr (VI), the more toxic form found in 1,127 of the 1,699 current or former National Priorities List sites.
The densities of the most common compounds containing chromium vary from 2-3 times that of water (with some variances in temperature). Chromium compounds are primarily soluble in water. The densities of compounds that are greater than 3 times the density of water are slightly soluble to insoluble. Oxidation states range from -2 to +6, with the most common being +2, +3, and +6. The +2 can be readily oxidized to +3 due to its relative instability. The pH of water causes the solubility of Cr (VI) to be very high while Cr (III) compounds tend not to be very soluble.
SOURCES AND TYPES OF CONTAMINATION
People love to chrome-plate anything and everything. Take a look at this beauty:
It is also what makes rubies RED, especially the lab-grown synthetic ones!
But let’s face it – despite the (usually truthful) claims of increased durability and decreased corrosion, we like it for one reason: it is *shiny*. We can see our own reflection in it and it is a bling-ready status symbol. Rarely do we take a minute to think about what went into the chrome-plating, and how it affects the environment.
In The Environment
Chromium can be found in the environment as trivalent chromium (Cr III) and as hexavalent chromium (Cr VI); metal chromium (Cr 0) is rarely found in the environment. Trivalent chromium is an essential human nutrient, found in contaminated and non-contaminated (natural) sites. Hexavalent chromium is the dangerous form, with known toxicity and carcinogenicity issues.Controllable sources of this contaminant include the following:
• Airborne emissions (chemical plants, incinerators, stationary power plant)
• Contaminated landfills
• Water-borne emissions (chemical plants)
• Cement production and dust
• Chrome alloy production and use
• Electroplating
• Welding
• Acid mine drainage
• Combustion activities at utilities
• Fugitive emissions from road dust, and former (pre 1993) industrial cooling towers
• Drilling wells
Industrial / Occupational Sources
There are 3 industries that use/discard the majority of chromium. It is used in metallurgy as a vital component of stainless steel, as well as other metal alloys. The chemical industry uses it for chrome-plating, leather tanning, paint pigmentation, corrosion inhibition, magnetic tape, catalytic manufacture, electroplating cleaning agents, wood preservation, and water treatment. The refractory industry uses it in heat-resistant materials like firebrick for furnaces.
Air Contamination
Chromium released into the air only accounts for 2.2% of environmental releases. These emissions are mostly from stationary fuel combustion and the metal industry. These emissions are mostly Cr (III), not the more dangerous Cr (VI) form. The chrome-plating industry, however, it estimated to release ONLY Cr (VI) into the atmosphere.
Water Contamination
Chromium released into the water accounts for just 0.3% of the contamination into the environment. These releases are mostly from electroplating and leather tanning.
Soil Contamination
Chromium released into the soil accounts for a whopping 94.1% of the contamination. Chromium waste slag found a secondary use as fill material in construction sites (residential, commercial, recreational, and industrial). When the soil is contaminated, it affects the air and water as well, via wind erosion and rainwater leaching into aquifers/surface waters.Hexavalent chromium is very soluble in soils and groundwater, making it a very mobile pollutant. In contrast, trivalent chromium is immobile, forming tight complexes with the soil minerals.
CHROMIUM TOXICOLOGY AND HEALTH EFFECTS
The three main forms of chromium include elemental or metallic chromium, trivalent chromium (Cr3+) and hexavalent chromium (Cr6+). The trivalent and hexavalent forms of chromium however, are the most prevalent forms found in soil.
Trivalent chromium is of lesser concern than hexavalent chromium and is actually an essential nutrient. Trivalent chromium is also found to be less mobile and reactive in soil, therefore it is generally not found in ground water concentrations above water quality standards.
Hexavalent chromium is found to cause a wide range of health problems once ingested. These health problems include ulcers in the stomach and small intestine, as well as anemia and cancer. Once ingested, chromium rapidly distributes itself to almost all tissues. The highest concentrations of chromium, however, will be found in the kidneys and liver.
A person can experience what is called allergic contact dermatitis when coming into contact with hexavalent chromium. The symptoms are an itchy red rash with swelling. Also, an individual can experience what is called chrome ulcers which are small crusted sores with round borders.
Respiratory exposure is the most dangerous way to be exposed to hexavalent chromium. Symptoms of exposure may include irritation in the nose, throat and lungs. If an individual is repeatedly exposed, damage to the mucous membranes may result. Under severe cases, exposure can cause perforations of the septum (the wall separating the nasal passages).
The Occupational Safety and Health Administration (OSHA) has established an 8-hour time-weighted average (TWA) exposure limit of 5 micrograms of Cr(VI) per cubic meter of air (5 µg/m³). This is a considerable reduction from the previous permissible exposure limit (PEL) of 52 µg/m³.
For Cr(II) and Cr(III) compounds, the PEL is an 8-hour TWA of 500 µg Cr/m³. For chromium metal and for insoluble compounds, the PEL is 1,000 µg Cr/m³.
Since hexavalent chromium is unstable in the body, it is reduced within the liver to form the stable trivalent chromium species. Although the reduction of hexavalent chromium to trivalent chromium can produce a number of reactive intermediates, it is actually the reduction to trivalent chromium that may cause cancer in individuals. Once formed during metabolism, trivalent chromium is inserted within a cell nucleus where it can cross link DNA to the protein actin.
REMEDIATION
Chromium poses a significant threat to both the environment and human health. The main goal of chromium remediation is to take the more harmful form (hexavalent chromium) and reduce it to the less harmful form. That being trivalent chromium. There are numerous methods that can be used to remediate a site contaminated with chromium, though they can be broken up in to either above ground treatment or treatment of the subsurface (groundwater).
The two methods for above ground treatment include excavation of the contaminated soil, as well as pumping contaminated groundwater to the surface where it can be treated and re-injected back into the aquifer.
Subsurface treatment may include pumping different chemicals into the groundwater that can reduce the hexavalent chromium to the trivalent form. Sulfur compounds are generally used. A permeable barrier can be placed in the path of a chromium plume. When chromium contacts this barrier, it is essentially immobilized. Another possible chromium remediation method includes “inoculating” groundwater with nutrients suitable for microbial growth. The microbial growth decreases oxygen levels in the groundwater which in turn can reduce hexavalent chromium to trivalent chromium. Finally, phytoremediation may be an option, albeit a slower one. With phyotoremediation, certain plant species are used to take up the chromium both in the soil as well as in shallow aquifers. The plants are chosen based on how favorably they can take up the chromium and store it.
Several technologies exist when searching for ways to remediate water or wastewater contaminated with chromium. (Mohen and Pittman Jr., 2006) Although found naturally in the environment in several different forms, Chromium, produced by industries, can be harmful to the environment. (ASTDR 2008) Among various chromium species, trivalent Cr(III) and hexavalent chromium Cr(VI), are the most stable in the environment. Cr(VI) is more toxic than Cr(III). (Zhao et al, 2006) Chemical Precipitation, among several precipitation removal processes, is the most commonly used method to remediate chromium contaminated waters, despite sludge production. (Mohen and Pittman Jr., 2006)
References:
Basic Chemistry of Chromium:
Agency for Toxic Substances and Disease Registry. (ATSDR, 2000). Public Health Statement: Chromium. Retrieved September 17, 2009 from http://www.atsdr.cdc.gov/toxprofiles/tp7-c1-b.pdf.
United States Environmental Protection Agency. (2008). CLU-IN Contaminant Focus: Chromium VI. Retrieved September 16, 2009 from http://www.clu-in.org/contaminantfocus/ default. focus/sec/chromium_VI/cat/Toxicology/.
Sources and Types of Chromium Contamination:
Agency for Toxic Substances & Disease Registry. (2008). Case Studies in Environmental Medicine (CSEM) Chromium Toxicity Where Is Chromium Found? Retrieved September 18, 2009, from http://www.atsdr.cdc.gov/csem/chromium/cr_where-found.html
United State of Environmental Protection Agency.(2009). Chromium VI Environmental Occurrence. Retrieved September 18, 2009, from http://www.clu-in.org/contaminantfocus/default.focus/sec/chromium_VI/cat/Environmental_Occurrence/United States Environmental Protection Agency (2009). Technology Transfer Network – Air Toxics Website. Chromium Compounds Hazard Summary. Retrieved September 17, 2009, from http://www.epa.gov/ttn/atw/hlthef/chromium.html
Hansel, C.M., Weilinga, B.W, Fendorf, S. (2003). Stanford Synchrotron Radiation Laboratory. Investigating Chromium-Contamination and Remediation. Abstract retrieved September 17, 2009, from http://ssrl.slac.stanford.edu/research/chromium_summary.html
Chromium Toxicology and Health Effects:
Pichtel, John. (2007). Fundamentals of Site Remediation, Second Edition. Lanham, Maryland: Government Institutes.
Agency for Toxic Substances & Disease Registry (2008). ToxFaqs for Chromium. Retrieved September 14, 2009 from http://www.atsdr.cdc.gov/tfacts7.html#bookmark05
Agency for Toxic Substances & Disease Registry. Health Effects of Chromium. Retrieved September 14, 2009 from http://www.atsdr.cdc.gov/toxprofiles/tp7-c3.pdf
Environmental Health Perspectives Supplements Volume 110, Number 5, October 2002. Metabolic Pathways of Carcinogenic Chromium. Retrieved September 14, 2009. http://www.ehponline.org/realfiles/members/2002/suppl-5/733-738gaggelli/gaggelli-full.html Agency for Toxic Substances & Disease Registry (2008). Case Studies in Environmental Medicine (CSEM) Chromium Toxicity. What are the Standards and Regulations for Chromium Exposure? Retrieved September 18, 2009. http://www.atsdr.cdc.gov/csem/chromium/cr_standards-regulations.html
Occupational Safety & Health Administration (2008). Hexavalent Chromium. Hazard Recognition. Retrieved September 18, 2009. http://www.osha.gov/SLTC/hexavalentchromium/recognition.html
Remediation:
In Situ Treatment of Soil and Groundwater Contaminated with Chromium, Environmental Protection Agency, October 2000, from: http://www.epa.gov/nrmrl/pubs/625r00005/625r00005.pdf
Mohan, Dinesh, and Charles U. Pittman Jr.. "Activated carbons and low cost adsorbents for remediation of tri- and hexavalent chromium from water ." Journal of Hazardous Materials 137.2 (2006): 762-811.
Zhao, Wei, Yu-Ming Zheng, Shuai-Wen Zou, Yen Peng Ting, and J. Paul Chen. "Effect of Hexavalent Chromium on Performance of Membrane Bioreactor in Wastewater Treatment."
JOURNAL OF ENVIRONMENTAL ENGINEERING 135.9 (2009): 796-805.
"Potential for Human Exposure." Agency for Toxic Substances and Disease Registry. 5 Oct. 2009
Photos:
Photo of chromium metal: http://www.goldbamboo.com/pictures-t6412.html
Photo of car: http://www.nu-chrome.com/
Figure of chromium speciation: http://www.hgcinc.com/summer99_news/chromium.htm
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