Contaminant Hydrogeology I

1. Contaminant Hydrogeology I Гидрогеология Загрязнений и их Транспорт в Окружающей Среде Yoram Eckstein, Ph.D. Fulbright Professor 2013/2014 Tomsk Polytechnic University Tomsk, Russian Federation Fall Semester 2013

2. The way it was The smoke of chimneys is the breath of Soviet Russia

3. The problem: “By sensible definition any by-product of a chemical operation for which there is no profitable use is a waste. The most convenient, least expensive way of disposing said waste – up the chimney or down the river – is the best” Haynes, W. (1954) American Chemical Industry – A History, vol. I-VI Van Nostrand, New York

5. The River That Caught Fire • At least 13 fires have been reported on the Cuyahoga River, the first occurring in 1868. The largest river fire in 1952 caused over $1 million in damage to boats and a riverfront office building. Fires erupted on the river several times between the 1952 fire and June 22, 1969. • The 1969 Cuyahoga River fire helped spur an avalanche of water pollution control activities, resulting in the Clean Water Act, Great Lakes Water Quality Agreement, and the creation of the federal Environmental Protection Agency and the Ohio Environmental Protection Agency (OEPA)

6. Contaminant Hydrogeology • Physical Chemistry • Inorganic and Organic Chemistry • Physics • Calculus and Linear Algebra

7. Pollution or Contamination? “No substance is a poison by itself … all substances can be poisonous. It is the dose that makes a substance a poison … and the right dose differentiates a poison and a remedy.” Theophrastus PhilippusAureolusBombastus von Hohenheim (1493-1541) – aka Paracelsus

8. Contaminant: 1. a: substance soiling, staining, corrupting, or infecting by contact or association e.g., bacteria contaminating the wound b:  substance making inferior or impure by admixture e.g., iron contaminated with phosphorus 2.  substance making unfit for use by the introduction of unwholesome or undesirable elements

9. Pollutant: A substance or condition that contaminates air, water, or soil in harmful concentrations. Pollutants can be: • substances, artificial - such as pesticides and PCBs, or naturally occurring, such as oil or carbon dioxide in harmful concentrations ; or • conditions, e.g. heat transmitted to natural waterways through warm-water discharge from power plants or uncontained radioactivity from nuclear wastes in harmful quantities.

10. Pollution or Contamination? “No substance is a poison by itself … all substances can be poisonous. It is the dose that makes a substance a poison … and the right dose differentiates a poison and a remedy.” Theophrastus PhilippusAureolusBombastus von Hohenheim (1493-1541) – aka Paracelsus

11. Contaminant ≠ Pollutant Contamination ≠ Pollution but Pollution = CONTAMINATION Implication: contamination is a broader concept, involving introduction into a substance of some foreign, but not necessarily polluting components

12. Pollution Introduction of harmful substances [pollutants] into the environment by human action or natural processes (USGS)

13. What are Contaminants? • Contamination is the presence of a minor constituent [contaminant] in another chemical or mixture, often at the trace level. In chemistry, the term usually describes a single chemical, but in specialized fields the term can also mean chemical mixtures, even up to the level of cellular materials.

14. What are Contaminants? • All chemicals contain some level of contamination. Contamination may be recognized or not and may become an issue if the contaminated chemical is mixed with other chemicals or mixtures and causes additional chemical reactions. The additional chemical reactions can sometimes be beneficial, in which case the label ‘contaminant’ is replaced with reactant or catalyst. If the additional reactions are detrimental, other terms are often applied such as toxin, or pollutant depending on the chemistry involved.

15. What are Contaminants? • The term "environmental contaminant" is another name for pollution. A contaminant is any potentially undesirable substance (physical, chemical or biological). It usually refers to the introduction of harmful human-made substances. • However, some substances that may have harmful effects at high levels, like cadmium, occur naturally in ecosystems and may also be introduced through human activities.

16. "Contamination" also has more specific meanings in some sciences: • In food and medicinal chemistry, the term "contamination" is used to describe harmful intrusions, such as the presence of toxins or pathogens in food or medicinal drugs. • In forensic science, a contaminant can be complex materials such as hair or skin particles arising from sources not related to the ongoing investigation.

17. "Contamination" also has more specific meanings in some sciences: • In the biological sciences accidental introduction of "foreign" material ('contaminantion') can seriously distort the results of experiments where small samples are used. In cases where the contaminant is a living microorganism, it can often multiply and take over the experiment, especially cultures, and render them useless. The term "contamination" is sometimes used to describe accidental transfers of organisms from one natural environment to another. • In geology and especially geochemistry, it can have similar effects where even a few grains of "modern" dust can distort results of sophisticated experiments.

18. BasicsofPollutants

19. Pollutants Secondary Nutrients: P, N, Ca, K, Mg Primary Some heavy metals: Hg, As, Pb

20. Anthropogenic sources Point-sources Non-point- sources

21. Chemical Contaminants Immiscible Miscible (hydrophobic) (hydrophilic) Non-polar molecules Polar molecules “Floaters” “Sinkers”

22. Ground water contamination; unlined sanitary landfill

23. Ground water contamination; sinkers and floaters

24. Water – an ultimate solvent

25. Water – an ultimate solvent

26. Non–polar (hydrophobic) molecules Carbon dioxide CO2 Oxygen O2 Ammonium NH4 Benzene C6H6 Methane CH4 Ethane H3CCH3 Propane H3CCH2CH3 Naphthalene C10H8 Anthracene C14H10 Carbon tetrachloride CCl4

27. Non–polar (hydrophobic) molecules

28. Polar (hydrophilic) molecules Halite NaCl Calcite CaCO3 Chloroform CHCl3 Trichloroethane H3CCCl3 Methanol CH3OH Ethanol H3CCH2OH Octanol CH3(CH2)7OH

29. Polar molecules

30. Strengths of polarity

31. Bio-pollutants Pathogens • Coliform bacteria are a commonly used bacterial indicator of water pollution, although not an actual cause of disease. • Other microorganisms sometimes found in waters which have caused human health problems include: Burkholderiapseudomallei Salmonella Cryptosporidium parvumNovovirus and other viruses Giardia lamblia Parasitic worms (helminths)

32. Bio-pollutants Pathogens Cryptosporidium parvum It is one of several protozoal species that cause cryptosporidiosis, a parasitic disease of the mammalian intestinal tract. C. parvum is considered to be the most important waterborne pathogen in developed countries. The protozoa also caused the largest waterborne-disease outbreak ever documented in the United States, making 403,000 people ill in Milwaukee, Wisconsin in 1993. It is resistant to all practical levels of chlorination, surviving for 24hrs at 1000 mg/L free chlorine.

33. Bio-pollutants Pathogens Giardia lambilia Giardia lamblia is a flagellated protozoan parasite that colonizes and reproduces in the small intestine, causing giardiasis. Chief pathways of human infection include ingestion of untreated sewage, a phenomenon particularly common in many developing countries; contamination of natural waters also occurs in watersheds where intensive grazing occurs.

34. Typical septic tank system

35. Ground water biocontamination; leaking septic tank

36. Bio-pollutants Pathogens Burkholderiapseudomallei is the soil saprophyte, straight or slightly curved rods measuring 2-5 × 0,4-0,8 mm. Lives in the soil and groundwater throughout. The causative agent of melioidosis, a disease occurs almost exclusively in the South-East Asian Nations (endemic in the region), northern Australia and other tropical regions.

37. Bio-pollutants Pathogens Salmonella Salmonella is enterobacteria with diameters around 0.7 to 1.5 µm and are found worldwide in cold- and warm-blooded animals (including humans), and in the environment. Most infections are due to ingestion of contaminated food. They cause illnesses such as typhoid fever, paratyphoid fever, and foodborne illness.

38. Bio-pollutants Pathogens • High levels of pathogens may result from inadequately treated sewage discharges. This can be caused by a sewage plant designed with less than secondary treatment (more typical in less-developed countries). In developed countries, older cities with aging infrastructure may have leaky sewage collection systems (pipes, pumps, valves), which can cause sanitary sewer overflows. Some cities also have combined sewers, which may discharge untreated sewage during rain storms. • Pathogen discharges may also be caused by poorly managed livestock operations.

39. Disinfection by-products • Disinfection by-products (DBPs) result from reactions between organic and inorganic matter in water with chemical treatment agents during the water disinfection process. • Chlorinated disinfection agents such as chlorine, chlorine dioxide, and chloramine are strong oxidizing agents introduced into water in order to destroy pathogenic microbes, to oxidize taste/odor-forming compounds, and to form a disinfectant residual so water can reach the consumer tap safe from microbial contamination. • These disinfectants may react with naturally present fulvic and humic acids, amino acids, and other natural organic matter, as well as iodide and bromide ions, to produce a range of DBPs such as the trihalomethanes (THMs), haloacetic acids (HAAs), and chlorite (which are regulated in the US), and so-called "emerging" DBPs such as halonitromethanes, haloacetonitriles, haloamides, halofuranones, iodo-acids, iodo-THMs, nitrosamines, and others

40. Disinfection by-products By-products from non-chlorinated disinfectants Several powerful oxidizing agents are used in disinfecting and treating drinking water, and many of these also cause the formation of DBPs. Ozone, for example, produces ketones, carboxylic acids, and aldehydes, including formaldehyde. Bromide in source waters can be converted by ozone into bromate, a potent carcinogen that is regulated in the United States, as well as other brominated DBPs As regulations are tightened on established DBPs such as THMs and HAAs, drinking water treatment plant may switch to alternative disinfection methods. This change will alter the distribution of classes of DBP's.

41. Types of chemical pollutants: organics Detergents • A detergent is a surfactant or a mixture of surfactants with cleaning properties in dilute solutions. • Detergents, like soaps, are amphiphilic: partly hydrophilic (polar) and partly hydrophobic (non-polar). • They are usually alkylbenzenesulfonates, or soaps (hydrolyzed triglyceride fats combined with sodium hydroxide.

42. Example of a detergent Sodium dodecylbenzenesulfonate solubility in water: 20% it is biodegradable

43. Insecticides and pesticides • Organophosphates affect the nervous system by disrupting the enzyme that regulates acetylcholine, a neurotransmitter. Most organophosphates are insecticides. They were developed during the early 19th century, but their effects on insects, which are similar to their effects on humans, were discovered in 1932. Some are very poisonous (they were used in World War II as nerve agents). However, they usually are not persistent in the environment. • Organochlorine insecticides were commonly used in the past, but many have been removed from the market due to their health and environmental effects and their persistence (e.g. DDT and chlordane).

44. Insecticides and pesticides • Carbamate pesticides affect the nervous system by disrupting an enzyme that regulates acetylcholine, a neurotransmitter. The enzyme effects are usually reversible. There are several subgroups within the carbamates. • Pyrethroidinsecticides were commonly used in the past, but many have been removed from the market due to their health and environmental effects and their persistence (e.g. DDT and chlordane). • Biopesticidesare certain types of pesticides derived from such natural materials as animals, plants, bacteria, and certain minerals. For example, canola oil and baking soda have pesticidal applications and are considered biopesticides.

45. Herbicides • Herbicides, also commonly known as weedkillers, are pesticides used to kill unwanted plants. • Selective herbicides kill specific targets, while leaving the desired crop relatively unharmed. Some of these act by interfering with the growth of the weed and are often synthetic mimics of natural plant hormones. • Herbicides used to clear waste ground, industrial sites, railways and railway embankments are not selective and kill all plant material with which they come into contact. • Herbicides are widely used in agriculture and landscape turf management. In the US, they account for about 70% of all agricultural pesticide use.

46. Fuels and lubricants • Petroleum hydrocarbons, including fuels (gasoline, diesel fuel, jet fuels, and fuel oil) and lubricants (motor oil), and fuel combustion byproducts, from stormwaterrunoff. • Perchlorate salts are produced industrially by the oxidation of solutions of sodium chlorate by electrolysis. This method is used to prepare sodium perchlorate. Four perchlorates are of primary commercial interest: ammonium perchlorate (NH4ClO4), perchloric acid (HClO4), potassium perchlorate (KClO4), and sodium perchlorate (NaClO4). The main application is for rocket fuel. • In some places, perchlorate is detected because of contamination from industrial sites that use or manufacture it. In other places, there is no clear source of perchlorate. In those areas it may be naturally occurring. Natural perchlorate on Earth was first identified in terrestrial nitrate deposits of the Atacama Desert in Chile as early as in the 1880s

47. Volatile organic compounds (VOCs) • Volatile organic compounds (VOCs) are organic chemicals that have a high vapor pressure at ordinary, room-temperature conditions. Their high vapor pressure results from a low boiling point, which causes large numbers of molecules to evaporate or sublimate from the liquid or solid form of the compound and enter the surrounding air. An example is formaldehyde, with a boiling point of –19 °C (–2 °F), slowly exiting paint and getting into the air.

48. Volatile organic compounds (VOCs) • VOCs are numerous, varied, and ubiquitous. They include both human-made and naturally occurring chemical compounds. Most scents or odors are of VOCs. VOCs play an important role in communication between plants. Some VOCs are dangerous to human health or cause harm to the environment. Anthropogenic VOCs are regulated by law, especially indoors, where concentrations are the highest. Harmful VOCs are typically not acutely toxic, but instead have compounding long-term health effects. Because the concentrations are usually low and the symptoms slow to develop, research into VOCs and their effects is difficult.

49. Biologically generated VOCs • Methane CH4 Methane is the simplest alkane and the main component of natural gas. The relative abundance of methane makes it an attractive fuel. However, because it is a gas at normal onditions, methane is difficult to transport from its source. Atmospheric methane is a potent greenhouse gas (per unit, more so than carbon dioxide. The concentration of methane in Earth's atmosphere in 1998, expressed as a mole fraction, was 1745 nmol/mol (parts per billion, ppb). By 2008, however, global methane levels, which had stayed mostly flat since 1998, had risen to 1800 nmol/mol.

50. Biologically generated VOCs Vasyugan Mire • Methane CH4 Researchers were surprised to find that a single 550-kg cow produces between 800 to 1,000 liters of emissions each day. Current estimates of global methane emission from wetlands range between 100-250 million tons of methane per year, equivalent to around a quarter of total global methane emissions.