Caffeine—The World’s Greatest Psychoactive Addiction

Continuing on through ground water and drinking water contaminants I decided to write a post about what is almost certainly the most interesting and ubiquitous human induced contaminant….caffeine. Most people probably never think of caffeine as a natural contaminant, however anytime a substance is introduced into the environment in new places it is going to have a reaction with the system that is already there. Caffeine is no exception. Although, it does seem to be an exception to almost everything else…

For instance, although caffeine is a psychoactive stimulant it is one of the only psychoactive substances that humans regularly consume that is unregulated. Almost everyone intakes caffeine right? Many of us can’t wake up in the morning without our cup. A recent study found that women consuming 200 mg or more per day are twice as likely to miscarriage¹. However, another study found no correlation¹.

Caffeine is a natural pesticide which protects plants from feeding insects. It acts to paralyze and kill certain insects. Its effects on humans are broad and not commonly understood. It is mainly a central nervous system stimulant which, as we all know, helps keep us awake and alert. Caffeine is also a diuretic…yep…it makes your body produce urine faster. It has a half life in most human adults of 3 to 4 hours². Caffeine is found in a variety of foods and drinks such as coffee, teas, mate, and soft drinks.

Caffeine is metabolized by your liver to³:

• Paraxanthine (84%)-Has similar effects to caffeine
• Theobromine (12%)-Used in the past as treatment for edema, syphilitic angina, hypertension, and vascular diseases⁴.
• Theophylline (4%)-Used in the past as a respiratory drug for asthma

Caffeine is nearly ubiquitous in natural waters. Several studies have measured the amount of caffeine and its metabolites in surface and ground waters across the world^5,6,7. It is an excellent method to track anthropomorphic effects on the environment because caffeine is almost always introduced into the environment in quantity by humanity.

Caffeine has multiple effects on wildlife and on the geochemistry of water systems. The total effects of caffeine are as yet unknown, but certainly it is one of the most pervasive geochemical pollutants on the planet.

 

1. Rubin, Rita (2008-01-20). New studies, different outcomes on caffeine, pregnancy (English). USA TODAY.

2. Meyer, FP; Canzler E, Giers H, Walther H. (1991). “Time course of inhibition of caffeine elimination in response to the oral depot contraceptive agent Deposiston. Hormonal contraceptives and caffeine elimination”. Zentralbl Gynakol 113 (6): 297-302. PMID 2058339

3. The Pharmacogenetics and Pharmacogenomics Knowledge Base. http://www.pharmgkb.org/do/serve?objId=464&objCls=DrugProperties#biotransformationData

4. Kelly, Caleb J (August 2005). “Effects of theobromine should be considered in future studies”. American Journal of Clinical Nutrition 82 (2).

5. Determination of pharmaceutical compounds in surface- and ground-water samples by solid-phase extraction and high-performance liquid chromatography-electrospray ionization mass spectrometry, J. D. Cahill, E. T. Furlong, M. R. Burkhardt, D. Kolpin and L. G. Anderson; Journal of Chromatography A, Volume 1041, Issues 1-2, 2 July 2004, Pages 171-180

6. Drugs and personal care products as ubiquitous pollutants: occurrence and distribution of clofibric acid, caffeine and DEET in the North Sea ;Stefan Weigel, Jan Kuhlmann and Heinrich Hühnerfuss; The Science of The Total Environment, Volume 295, Issues 1-3, 5 August 2002, Pages 131-141

7. Tracking persistent pharmaceutical residues from municipal sewage to drinking water; Thomas Heberer; Journal of Hydrology, Volume 266, Issues 3-4, 15 September 2002, Pages 175-189

8. Caffeine and Pharmaceuticals as Indicators of Waste Water Contamination in Wells; Ralph L. Seiler^aaU.S. Geological Survey, 333 W. Nye Lane, Carson City, NV 89706. (702) 887-7674 (voice); (702) 887-7629 (fax). E-mail: rseiler@usgs.gov., Steven D. Zaugg^bbU.S. Geological Survey National Water Quality Laboratory, Box 25046, MS-407, Denver Federal Center, Denver, CO 80225, James M. Thomas^aaU.S. Geological Survey, 333 W. Nye Lane, Carson City, NV 89706. (702) 887-7674 (voice); (702) 887-7629 (fax). E-mail: rseiler@usgs.gov., and Darcy L. Howcroft; Ground Water; Volume 37 Issue 3 Page 405-410, May 1999

9. Caffeine as an environmental indicator for assessing urban aquatic ecosystems; Cadernos de Saúde Pública; Print ISSN 0102-311X; Cad. Saúde Pública vol.21 no.6 Rio de Janeiro Nov./Dec. 2005

What is a chemical?

Ok, So I was encouraged the other day by a comment on my blog to stop being so negative about chemicals. I must admit that I was a little bit confused. My blog is primarily about contaminant remediation…which is what I study in school. I guess that sounds negative?

Anyway, the point is well taken. So, I started thinking about the word, ‘Chemical.’ What does the word, ‘chemical’ mean to most people? I realized that it has a somewhat negative connotation. At least I think it does. People seem to think that when something is called a chemical that means it is harmful. So, I looked up the definition on google (where else would I?). This is what I found:

1. A substance with a distinct molecular composition that is produced by or used in a chemical process.
2. A drug, especially an illicit or addictive one.
3. adj. relating to, involving, or denoting the use of poison gas or other chemicals as weapons of war: the manufacture of chemical weapons.

The third definition is from the U.S. Military dictionary (I didnt know we needed one). Besides being slightly weird and disturbing this didnt shed much light. Then I ran into a pop up (or maybe it ran into me) that had a picture of a cute dog and it said, “He has 35 chemicals inside him. How many do you have?” The chemist in me started thinking…well counting all the different organic species I would say….some millions.

Wait?!!?!? The dog only has 35 chemicals inside him? That must be like an amoeba dog or something. How can he live if he only has 35 chemicals? Then I realized that they meant the dog has 35 harmful chemical species.

Anyway, enough nerd stuff. I think I am starting to realize that the word chemical is synonymous with ‘harmful’ most of the time. I think part of my posts from now on should be devoted to explaining has chemical species can sometimes be good and sometimes be bad, but most of the time they are neither. They just are.

Mercury In Florescent Light Bulbs

Estimates are that as much as 25% of the average home energy budget is spent on electric lighting¹. Compact florescent lights have made a huge impact into the environmental scene in recent years because of their energy efficiency. They are extremely energy efficient. Some manufacturers claim things such as: compact florescent lamps are 4 times as efficient as regular light bulbs, they last 10 times as long as regular light bulbs, replacing a single light bulb with a compact florescent bulb will keep a half ton of CO₂ out of the atmosphere, and if everyone in the U.S. used energy-efficient lighting, we could retire 90 average size power plants. In truth, there is little reason to doubt these claims. They are certainly much more efficient. There has been much recent debate however on the actual environmental impact of compact florescent lights after the public became aware of the amount of mercury that was in the bulbs.

Of course, it should not come as a surprise that Mercury is found in compact florescent bulbs. Compact florescent bulbs are basically tiny versions of the full sized florescent bulbs we are more familiar with which contain mercury.

Mercury is a very harmful environmental contaminant. It is not beneficial to the body in any amount³, is a potent neurotoxin^{6, 7}, and has been linked to autism⁵. Recently, much news has been on mercury poisoning in fish especially sushi.

Manufacturers claim that there is very little mercury in the bulbs. Some sight that there is less mercury in some than in a common watch batteries. One article stated that there is more mercury in some tooth fillings than in the average compact florescent light bulb. Of course, the consumer should not be taken in by this last statement. The mercury in amalgam fillings is a different chemical species and is not toxic to the human body. For a more complete discussion of mercury in amalgam fillings see this post.

The real issue is the fragility of the light bulbs. If a florescent bulb breaks the mercury is released. This is a major problem because it is much easier for a watch battery to reach the landfill unharmed than it is for a glass bulb. Not only does this mercury get released to the environment (which can eventually find its way into fish believe it or not), but it also exposes city workers to high levels of a potent neurotoxin. Some cities have placed ordinances on putting compact florescent bulbs in the trash. Most major cities offer recycling options for florescent bulbs.

Therefore, the major question becomes: what is the actual environmental impact of compact florescent bulbs? Does the mercury pose a greater threat to the environment than the increased carbon emissions of less efficient traditional bulbs, or is the mercury of much smaller environmental impact?

In a recent paper entitled, “Release of mercury from broken fluorescent bulbs¹¹” Aucott, McLinden, and Winka develop a method for measuring mercury released from broken bulbs.  They found that between 17 and 40% of the mercury in broken low-mercury fluorescent bulbs is released to the air during a two-week period immediately following breakage which is approximately between 3 and 8 mg of elemental mercury vapor¹¹. Approximately 620 million fluorescent bulbs are discarded annually in the United States, and many are broken during disposal. Based on the estimated release rate of 3-8 mg per broken bulb developed in this study, discarded bulbs release approximately 2-4 tons of mercury per year in the United States^11.

That is certainly a significant amount of mercury being released to the environment every year in the United States. However, it should be recognized that our total carbon footprint is also reduced quite a bit from their use. My personal opinion is that use of compact florescent bulbs should be encouraged as long as recycling technologies are easily accessible and the public becomes aware of the proper disposal process.

 

1. http://www.eartheasy.com/live_energyeff_lighting.htm

2. Importance of wetlands as sources of methyl mercury to boreal forest ecosystems
St. Louis, VL; Rudd, JWM; Kelly, CA; Beaty, KG; Bloom, NS; Flett, RJ
Canadian Journal of Fisheries and Aquatic Sciences [CAN. J. FISH. AQUAT. SCI.]. Vol. 51, no. 5, pp. 1065-1076. 1994.

3. http://dcnutrition.com/minerals/minerals.cfm

4. Mercury methylation in aquatic systems affected by acid deposition; Gilmour CC, Henry EA, Environ Pollut. 1991; 71(2-4):131-69

5. Autism: a novel form of mercury poisoning; S. Bernard, A. Enayati, L. Redwood, H. Roger and T. Binstock; ARC Research, Cranford, New Jersey, USA

6. Methylmercury poisoning: long-term clinical, radiological, toxicological, and pathological studies of an affected family; Davis LE, Kornfeld M, Mooney HS, Fiedler KJ, Haaland KY, Orrison WW, Cernichiari E, Clarkson TW; Ann Neurol. 1994 Jun;35(6):680-8

7. Iatrogenic exposure to mercury after hepatitis B vaccination in preterm infants;

Stajich GV, Lopez GP, Harry SW, Sexson WR; J Pediatr. 2000 May;136(5):679-81

8. Personal Presentations in Biogeochemistry; Texas A&M University; Dr. McGuire

9. People with high mercury uptake from their own dental amalgam fillings; L Barregard, G Sallsten and B Jarvholm; Occupational and Environmental Medicine, Vol 52, 124-128

10. Regional differences in worldwide emissions of mercury to the atmosphere; Nicola Pirrone, Gerald J. Keeler and Jerome O. Nriagu; Atmospheric Environment Vol. 30, No. 17, pp. 2981 2987, 1996; Copyright © 1996 Published by Elsevier Science Ltd

11. Release of mercury from broken fluorescent bulbs; Aucott M, McLinden M, Winka M.; Journal of Air Waste Manag Assoc. 2003 Feb;53(2):143-51

12. The Materials Flow of Mercury in the Economies of the United States and the World; John L. Sznopek, Thomas G. Goonan; U.S. Geological Survey CIrcular 1197

13. Airborne Emission of Mercury from Municipal Solid Waste. I: New Measurements from Six Operating Landfills in Florida; Steven E. Lindberg, George R. Southworth, Mary Anna Bogle, T.J. Blasing, Jim Owens, and Kelly Roy; Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN

Arsenic Poisoning

Arsenic is a common natural and anthropogenic contaminant in sediments, surface waters, and ground waters. In Taiwan, Bangladesh, and the United States arsenic poisoning has been linked to disorders such as hyperpigmentation (Black-foot disease), Peripheral Vascular Disease, skin and bladder cancer, and gangrene ^2,3. Sporadic occurrences of Black-foot disease occurred in southwest Taiwan in the early twentieth century with a peak incidence in the late fifty’s ². The cause of this arsenic poisoning was due to resident’s use of contaminated artesian wells ². Arsenic poisoning incidents reduced significantly when residents began switching to tap water in the endemic villages ². Awareness of this outbreak caused the EPA cancer risk assessment to use the cancer data from Southwest Taiwan to predict the cancer risk assessment in the United States ^4,6. Recently changes in water quality standards in America along with greater understanding of arsenic toxicity have increased the necessity for methods of determining potentially bioavailable arsenic in field environments as well as characterization in natural environments.

Complex geochemical and biological mechanisms control the distribution of arsenic within repositories in the biosphere, hydrosphere, and lithosphere. Arsenic in water is primarily found in two oxidation states, As (III) and As (V) ¹. As (III) is considered more toxic than As (V), and is generally less mobile. Therefore, under many conditions As sequestion is undergone through reduction. This, however, is problematic because reducing environments release arsenic from arsenic bearing minerals such as oxyhydroxides. This is exactly what happened in Bangladesh when buried deposits of peat acted as electron donors for the reduction of arsenic bearing Goethite into the groundwaters^3. Controls on the distribution of arsenic include: redox conditions, pH, presence of Iron and Manganese Oxyhydroxides, and metabolic activities of microorganisms. Iron oxides, however, generally control arsenic speciation in near-surface environments ¹. Iron, when present, in the environment, controls the mobility, fate, and bioavailability of aqueous arsenic species by converting bioavailable arsenite (AsO₃^3-) and arsenate (AsO₄^3-) species to immobilized forms adsorbed or coprecipitated in iron oxides ¹. Chemical availability of As is an indirect measure of bioavailability. Bioavailability refers to the concentration of a target chemical that actually enters the systemic circulation of an organism from an administered dose⁵. (commonly considered the total concentration of the chemical present in the organism’s environment). It is generally assumed that dissolved phases are most bioavailable ⁵. Chemical availability of As is dependent on speciation. Therefore, when the speciation of arsenic in a soil system is known the chemical availability becomes a good indicator of bioavailability.

The World Health Organization estimates that 41 million people worldwide (some sources estimate 57 million) are drinking groundwater contaminated by arsenic at unsafe levels ¹⁰. In Taiwan alone approximately 2 million people are potentially exposed to polluted water ⁹. Arsenic, although rare in natural abundance in the lithosphere, is common in sulfides such as chalcopyrite, realgar, orpiment, galena, marcasite, arsenopyrite, enargite, and it has a strong affinity for pyrite, one of the world’s most common minerals ⁹. It is also common in other minerals through substitution. Arsenic in groundwater is often the result of dissolving weathered rock and soils or through reduction of iron oxides. In the case of the massive epidemic in Bangladesh the arsenic is released to the groundwater through goethite (FeOOH) reduction ⁴. Which is driven by microbial degradation of buried deposits of peat. The peat acts as an electron donor so that iron oxide reduction can take place.

Arsenic is often added to groundwater through anthropogenic sources such as use in alloying agents, wood preservatives, mineral extraction and processing wastes, poultry and swine feed additives, pesticides, and highly soluble arsenic trioxide stockpiles ^1,9. The most globally significant anthropomorphic source of arsenic is probably through combustion of fossil fuels ¹². The arsenic mainly appears as arsenite in the dust and travels through the atmosphere releasing arsenic throughout the globe. In 1988 Nriagu and Pacyna estimated that as much 70% of the global atmospheric As flux is anthropogenic. In the past arsenic acid was even used as a cotton defoliant in the southern part of the United States ¹¹.

Globally, millions of people are at risk for the adverse effects of arsenic exposure. Contaminated drinking water is usually contaminated through inorganic arsenic. Inorganic arsenic is more acutely toxic that organic arsenic species ^2,3. Other countries than Taiwan and Bangladesh that currently face arsenic exposure include: Argentina, Cambodia, Chile, China, Ghana, Hungary, India, Mexico, Vietnam, Tibet, Thailand, as well as the United States ^1,2,3,9. As the world population increases beyond 6 billion clean drinking water is quickly becoming one of globe’s most valuable resources. In order to protect our drinking water we must continue to study and understand contaminants of all varieties. This is a fundamental mission and goal of the applicant’s research group at Texas A&M University. This project will directly aid in this endeavor. Additionally, the international component to the proposed research will serve as a reminder to the scientific community of the importance in scientific collaboration and goodwill across global borders in solving the world’s environmental issues.

 This post is an excerpt from a copywritten article written by Clint Miller. All quotes must be cited to me.

Evaluating Arsenic Availability in Taiwanese Soils using DOWEX M4195, Fe³⁺ Substituted, Resin; Clint Miller; NSF EAPSI Grant Application; 2007

References

1. A review of the source, behaviour and distribution of arsenic in natural waters; P.L. Smedley*, D.G. Kinniburgh, Applied Geochemistry 17 (2002) 517-568

2. Long-term arsenic exposure and ischemic heart disease in arseniasis-hyperendemic villages in Taiwan, Chin-Hsiao Tseng, Choon-Khim Chong, Ching-Ping Tseng, Yu-Mei Hsueh, Hung-Yi Chiou, Ching-Chung Tseng, and Chien-Jen Chen; Toxicology Letters, Volume 137, Issues 1-2, 31 January 2003, Pages 15-21

3. Arsenic poisoning in groundwater: Health risk and geochemical sources in Bangladesh, H. M. Anawar, J. Akai, K. M. G. Mostofa, S. Safiullah, and S. M. Tareq; Environment International, Volume 27, Issue 7, February 2002, Pages 597-604

4. Significance of Exposure Assessment to Analysis of Cancer Risk from Inorganic Arsenic in Drinking Water in Taiwan; Kenneth G. Brown and Chien-Jen Chen; Risk Analysis, Volume 15 Issue 4 Page 475-484, August 1995

5. An In Vitro Gastrointestinal Method To Estimate Bioavailable Arsenic in Contaminated Soils and Solid Media; Rodriguez, R. R.; Basta, N. T.; Casteel, S.; S. W.; Pace, L. W.; Environmental Science & Technology, 1999, 33, 642-649

6. Inorganic arsenic: a need and an opportunity to improve risk assessment; W R Chappell, B D Beck, K G Brown, R Chaney, R Cothern, C R Cothern, K J Irgolic, D W North, I Thornton, and T A Tsongas; Environ Health Perspect. 1997 October; 105(10): 1060-1067.

7. Quantification of Potential Arsenic Bioavailability in Spatially Varying Geologic Environments at the Watershed Scale using Chelating Resins; Lake, G. E.; M.A. Thesis, Texas A&M University, 2002), 227 pp

8. Assessment of the phytotoxicity of chromium in soils using the selective ion exchange resin extraction method; Pei-Fang Yu, Kai-Wei Juang and Dar-Yuan Lee; Plant and Soil 258: 333-340, 2004.

9. Contamination of drinking-water by arsenic in Bangladesh: a public health emergency; Allan H. Smith; Elena O. Lingas; Mahfuzar Rahman; Bulletin of the World Health Organization; Print ISSN 0042-9686; Bull World Health Organ vol. 78 no. 9 Genebra 2000

10. Worldwide Occurrences of Arsenic in Ground Water; D. Kirk Nordstrom, SCIENCE VOL 296, 21 JUNE 2002; 2143-2145

11. Occurrence and Distribution of Arsenic in Soils and Plants; Leo M. Walsh; Malcolm E. Sumner; Dennis R. Keeney; Environmental Health Perspectives, Vol. 19. (Aug., 1977), pp. 67-71

12. Quantitative assessment of worldwide contamination of air, water, and soils by trace metals; Nriagu, J.O., Pacyna, J.M., Nature 333, 134-139; 1988

Public Enemy……Teflon?

Did you know that Teflon® (manufactured via DuPont) is made from a compound called PFOA (Perfluorooctanoic acid for all us chemistry nerds) which is almost certainly a human carcinogen? PFOA is a type of perfluorinated compound, and is currently under review by the EPA.

Here are a few facts about PFOA³:

1. It is very recalcitrant. This chemical seems to never break down in humans or in the environment⁴.
2. It is ubiquitous.
   • PFOA is in the blood of 95% of Americans.
   • PFOA is in the blood of people in four continents and in animals all over the world⁵.
3. It accumulates. It takes 4.4 years for humans to rid half of the volume of PFOA in their bodies⁶.
4. Artic animals double the amount of PFOA in their blood every four years⁷.
5. It is a health hazard.
   • PFOA has been linked to testicular, pancreatic, mammary, and liver tumors in male and female mice⁸. EPA considers PFOA an animal carcinogen at low levels.
   • It has been linked to ovarian and breast cancer⁹.
   • It has been linked to birth defects^8,9.

Perfluorinated compounds (PFC’s) are used in many industries for uses such as: keeping clothes wrinkle free, shedding water, repelling grease (from clothes and paper products such as microwave popcorn bags, pizza boxes, etc.), repelling stains, personal care products such as floss and nail polish, as well as flame retardant clothing. Stainmaster® uses a fluorinated telomere to keep stains off carpet and fabrics. Scotchgard uses a similar compound called PFOS or perfluorooctane sulfonate. As you may recall 3M recently pulled Scotchgard because of concerns over release of PFOS and PFOA into the environment after perfluorinated compounds were found in the blood of Alaskan polar bears.

 

In 2006 DuPont and seven other companies announced an agreement to reduce PFOA in emissions from manufacturing plants and in consumer products by 95% by the year 2010.

 

So, what can you do?

1. Stay away from packaged foods (this includes fast food restaurants). Packaging materials often contain PFC’s to keep the grease off the container. Plus, fast food is just gross. Vegetables people! When did this country stop eating fresh vegetables?
2. Stay away from stain resistant clothing and furniture. This one hits me (man I love my Gore-Tex lined hiking boots!) Generally clothes that say stain-resistant contain PFC’s but not always. Often schools with uniforms will choose wrinkle-free brands. PFC’s get into children dermally. If your school uses wrinkle-free uniforms lobby the school to choose new ones. Some children’s pajamas use PFC’s.  
3. Use personal care products that don’t contain words like, “”fluoro” or ”perfluoro” or “with Teflon.” These contain PFC’s.
4. Be very careful with Teflon® and other non-stick cookware. Do not ever let it get heated above 450°. If Teflon® pans are overheated PFOA is released. Throw away cookware when the non-stick surface has begun to degrade. Otherwise, you will begin to eat small bits in your food.
5. Lobby local, state, and national governments to phase out PFOA as well as chemicals that break down into PFOA.

   

1. Perfluorinated chemicals in relation to other persistent organic pollutants in human blood; Anna Kärrman, Bert van Bavel, Ulf Järnberg, Lennart Hardell and Gunilla Lindström; Chemosphere Volume 64, Issue 9, August 2006, Pages 1582-1591

2. Perfluorinated Chemicals and Fetal Growth: A Study within the Danish National Birth Cohort; Chunyuan Fei, Joseph K. McLaughlin, Robert E. Tarone, and Jørn Olsen; Environmental Health Perspectives Volume 115, Number 11, November 2007

 

 3. Fact Sheet on DuPont Zonyl; Paper, Allied-Industrial, Chemical and Energy Workers International Union

4. Environmental Protection Agency (EPA). 2003. Preliminary risk assessment of the developmental toxicity associated with exposure to perfluorooctanoic acid and its salts; April 10, 2003. EPA Docket: OPPT-2003-0012-0002.

5. Perfluorooctanesulfonate and related fluorochemicals in human blood from several countries; Kannan K, Corsolini S, Falandysz J, Fillmann G, Kumar KS, Loganathan BG, Mohd MA, Olivero J, Van Wouwe N, Yang JH, Aldoust KM. 2004. Environ Sci Technol 38(17): 4489-95.

6. Interim report: Determination of serum half-lives of several fluorochemicals; Burris JM, Lundberg JK, Olsen GW, Simpson D, Mandel JH. 2002.. AR226-1086. Washington, DC: U.S. Environmental Protection Agency.

7. Degradation of Fluorotelomer Alcohols: A Likely Atmospheric Source of Perfluorinated Carboxylic Acids; Ellis, D. A.; Martin, J. W.; De Silva, A. O.; Mabury, S. A.; Hurley, M. D.; Sulbaek Andersen, M. P.; Wallington, T. J. 2004.. Environ. Sci. Technol. 38(12): 3316-3321.

8. Evaluating human health risks from exposure to perfluorooctanoic acid (PFOA): Recommendations to the science advisory board’s PFOA review panel; Kropp, Tim and Jane Houlihan (Environmental Working Group). 2005.

 9. Environmental Working Group (EWG). 2003. PFCs: A chemical family that contaminates the planet. Available online at http://www.ewg.org/reports/pfcworld/