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

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  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)  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.

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 Philippus Aureolus Bombastus 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 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 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: A substance or condition that contaminates air, water, or soil in harmful concentrations. Pollutants can be: 1.substances, artificial - such as pesticides and PCBs, or naturally occurring, such as oil or carbon dioxide in harmful concentrations ; or 2.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 Philippus Aureolus Bombastus 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.  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. "Contamination" also has more specific meanings in some sciences:

17.  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. "Contamination" also has more specific meanings in some sciences:

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

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

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

22. Ground water contamination; unlined sanitary landfill

23. Ground water contamination; sinkers and floaters

24. Water – an ultimate solvent

26. Non–polar (hydrophobic) molecules Carbon dioxide CO 2 Oxygen O 2 Ammonium NH 4 Benzene C 6 H 6 Methane CH 4 Ethane H 3 CCH 3 Propane H 3 CCH 2 CH 3 Naphthalene C 10 H 8 Anthracene C 14 H 10 Carbon tetrachloride CCl 4

27. Non–polar (hydrophobic) molecules

28. Polar (hydrophilic) molecules Halite NaClCalcite CaCO 3 Chloroform CHCl 3 Trichloroethane H 3 CCCl 3 Methanol CH 3 OH Ethanol H 3 CCH 2 OH Octanol CH 3 (CH 2 ) 7 OH

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: Burkholderia pseudomalleiSalmonella Cryptosporidium parvumNovovirus and other viruses Giardia lambliaParasitic 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 Burkholderia pseudomallei 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.  Pyrethroid 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).  Biopesticides are 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  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.  Herbicides, also commonly known as weedkillers, are pesticides used to kill unwanted plants.

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 stormwater runoff.  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 (NH 4 ClO 4 ), perchloric acid (HClO 4 ), potassium perchlorate (KClO 4 ), and sodium perchlorate (NaClO 4 ). 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 CH 4 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  Methane CH 4 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. Vasyugan Mire

51. Anthropogenic sources of VOCs  Paints and coatings Typical components are aliphatic hydrocarbons, ethyl acetate, glycol ethers, and acetone. Motivated by cost, environmental concerns, and regulation, the paint and coating industries are increasingly shifting toward aqueous solvents.  Chlorofluorocarbons and chlorocarbons Chlorofluorocarbons, which are banned or highly regulated, were widely used cleaning products and refrigerants. Tetrachloroethene is used widely in dry cleaning and by industry. Industrial use of fossil fuels produces VOCs either directly as products (e.g., gasoline) or indirectly as byproducts (e.g., automobile exhaust).

52. LNAPLs (“floaters”)  A Light Non-Aqueous Phase Liquid (LNAPL) is a groundwater contaminant that is not soluble and has a lower density than water, which is the opposite of DNAPL. Once LNAPL infiltrates through the soil, it will stop at the height of the water table since LNAPL is less dense than water. The effort to locate and remove LNAPL is relatively cheaper and easier than DNAPL because LNAPL will float on top of the water in the underground water table.  Examples of LNAPLs are gasoline, benzene, toluene, xylene, and other hydrocarbons.

53. DNAPLs (“sinkers”)  A dense non-aqueous phase liquid or DNAPL is a liquid that is both denser than water and is immiscible in or does not dissolve in water.  DNAPLs tends to sink below the water table when spilled in significant quantities and only stop when they reach impermeable bedrock. Their penetration into an aquifer makes them difficult to locate and remediate.  Examples of materials that are DNAPLs when spilled include: chlorinated solvents, coal tar, creosote, polychlorinated biphenyl (PCBs), mercury, extra heavy crude oil, etc.

54. Benzene C 6 H 6 (LNAPL) (Light Non-Aqueous Phase Liquid)  Benzene is a known human carcinogen, which is a chemical found in environmental tobacco smoke, stored fuels, and exhaust from cars. Benzene also has natural sources such as volcanoes and forest fires. It is frequently used to make other chemicals in the production of plastics, resins, and synthetic fibers. Benzene evaporates into the air quickly and the vapor of benzene is heavier than air allowing the compound to sink into low-lying areas. Benzene has also been known to contaminate food and water and if digested can lead to vomiting, dizziness, sleepiness, rapid heartbeat, and at high levels, even death may occur.

55. Chlorinated solvents (DNAPL organochlorides)  Dichloromethane (DCM) CH 2 Cl 2 DMCs volatility and ability to dissolve a wide range of organic compounds makes it a useful solvent for many chemical processes. It is widely used as a paint stripper and a degreaser. In the food industry, it has been used to decaffeinate coffee and tea as well as to prepare extracts of hops and other flavorings. Its volatility has led to its use as an aerosol spray propellant and as a blowing agent for polyurethane foams. DCM is the least toxic of the simple chlorohydrocarbons, but it is not without health risks, as its high volatility makes it an acute inhalation hazard. (Dense Non-Aquesous Phase Liquid)

56. Chlorinated solvents (DNAPL organochlorides)  Tetrachloroethylene It is a colorless liquid widely used for dry cleaning of fabrics, hence it is sometimes called "dry-cleaning fluid." It has a sweet odor detectable by most people at a concentration of 1 part per million (1 ppm). Usually as a mixture with other chlorocarbons, it is also used to degrease metal parts in the automotive and other metalworking industries. It appears in a few consumer products including paint strippers and spot removers. Tetrachloroethene, suspect carcinogen, is a central nervous system depressant and can enter the body through respiratory or dermal exposure. Tetrachloroethene dissolves fats from the skin, potentially resulting in skin irritation. Cl 2 C=CCl 2

57. Chlorinated solvents ( DNAPL organochlorides)  Polychlorinated biphenyl (PCBs) Polychlorinated biphenyls (PCBs) were widely used as dielectric and coolant fluids, for example in transformers, capacitors, and electric motors. Due to PCBs' environmental toxicity and classification as a persistent organic pollutant, PCB production was banned by the United States Congress in 1979 and by the Stockholm Convention on Persistent Organic Pollutants in 2001. According to the U.S. Environmental Protection Agency (EPA), PCBs have been shown to cause cancer in animals, and there is also evidence that they can cause cancer in humans.

58. Chlorinated solvents ( DNAPL organochlorides)  Trichloroethylene C 2 HCl 3 Commonly used as an industrial solvent. Under the trade names Trimar and Trilene, trichloroethylene was used as a volatile anesthetic and as an inhaled obstetrical analgesic in millions of patients. However, due to concerns about its toxicity, the use of trichloroethylene in the food and pharmaceutical industries has been banned in much of the world since the 1970s. It is characterized s a human carcinogen and a non-carcinogenic health hazard. Groundwater contamination by TCE has become an important environmental concern for human exposure.

59. MTBE (methyl tertiary butyl ether) (CH 3 ) 3 COOH 3  MTBE MTBE is a gasoline additive, used as an oxygenating agent to raise the octane number. Its use is controversial in the US and declining in use in part because of its occurrence in groundwater and legislation favoring ethanol. However, worldwide production of MTBE has been constant at about 18 million tons/y (2005) owing to growth in Asian markets which are less subject to ethanol subsidies. MTBE gives water an unpleasant taste at very low concentrations, and thus can render large quantities of groundwater non-potable. MTBE can be tasted in water at concentrations of 5 – 15 µg/l.

60. Formaldehyde CH 2 O  Formaldehyde A gas at room temperature, formaldehyde is colorless and has a characteristic pungent, irritating odor. In view of its wide- spread use, toxicity and volatility, exposure to formaldehyde is a significant consideration for human health. Because formaldehyde resins are used in many construction materials it is one of the more common indoor air pollutants. Processes in the upper atmosphere contribute up to 90 percent of the total formaldehyde in the environment. Formaldehyde is an intermediate in the oxidation (or combustion) of methane as well as other carbon compounds, e.g. forest fires, in automobile exhaust, and in tobacco smoke. When produced in the atmosphere by the action of sunlight and oxygen on atmospheric methane and other hydrocarbons, it becomes part of smog.

61. Inorganic pollutants  Acidity caused by industrial discharges (especially sulfur dioxide from power plants)  Ammonia from food processing waste  Chemical waste as industrial by-products  Fertilizers containing nutrients--nitrates and phosphates—which are found in stormwater runoff from agriculture, as well as commercial and residential use  Heavy metals from motor vehicles (via urban stormwater runoff) and acid mine drainage  Silt (sediment) in runoff from construction sites, logging, slash and burn practices or land clearing sites.

62. Other types of pollutants  Nurdles, small ubiquitous waterborne plastic pellets  Shipwrecks, large derelict ships.  Thermal pollution  Trash or garbage (e.g. paper, plastic, or food waste) discarded by people on the ground, along with accidental or intentional dumping of rubbish, that are washed by rainfall into storm drains and eventually discharged into surface waters