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
The way it was
The smoke of chimneys
is the breath of Soviet
Russia
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
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)
Contaminant Hydrogeology
Physical Chemistry
Inorganic and Organic Chemistry
Physics
Calculus and Linear Algebra
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
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
Pollutant:
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.
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
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
Pollution
Introduction of harmful
substances [pollutants] into the
environment by human action
or natural processes (USGS)
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.
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.
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.
"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.
"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.
Pollutants
Secondary
Primary
Some heavy metals:
Hg, As, Pb
Nutrients:
P, N, Ca, K, Mg
Anthropogenic
sources
Point-sources
Non-pointsources
Chemical
Contaminants
Miscible
(hydrophilic)
Polar molecules
Immiscible
(hydrophobic)
Non-polar molecules
“Floaters”
“Sinkers”
Ground water contamination;
unlined sanitary landfill
Ground water contamination;
sinkers and floaters
Water – an ultimate solvent
Water – an ultimate solvent
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
Non–polar (hydrophobic)
molecules
Polar (hydrophilic)
molecules
Halite NaCl
Calcite CaCO3
Chloroform CHCl3
Trichloroethane H3CCCl3
Methanol CH3OH
Ethanol H3CCH2OH
Octanol CH3(CH2)7OH
Polar molecules
Strengths of polarity
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 pseudomallei
Cryptosporidium parvum
Giardia lamblia
Salmonella
Novovirus and other viruses
Parasitic worms (helminths)
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.
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.
Typical septic
tank system
Ground water biocontamination;
leaking septic tank
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.
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.
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.
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
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.
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.
Example of a detergent
Sodium
dodecylbenzenesulfonate
solubility in water: 20%
it is biodegradable
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).
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.
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.
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
(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
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.
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.
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.
Biologically generated VOCs
Methane CH4
Researchers were
surprised to find that
a single 550-kg cow
produces between
800 to 1,000 liters of
emissions each day.
Vasyugan Mire
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.
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).
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.
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.
Benzene C6H6 (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.
Chlorinated solvents (DNAPL
organochlorides)
(Dense Non-Aquesous Phase Liquid)
Dichloromethane (DCM) CH2Cl2
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.
Chlorinated solvents
(DNAPL organochlorides)
Tetrachloroethylene
Cl2C=CCl2
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.
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.
Chlorinated solvents
(DNAPL organochlorides)
Trichloroethylene C2HCl3
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.
MTBE (methyl tertiary butyl ether)
(CH3)3COOH3
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.
Formaldehyde CH2O
Formaldehyde
A gas at room temperature, formaldehyde is colorless and has a
characteristic pungent, irritating odor. In view of its widespread 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.
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.
Other types
of pollutants
 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
 Nurdles, small ubiquitous waterborne plastic pellets
 Shipwrecks, large derelict ships.
 Thermal pollution