Important chemical parameters:

Inorganics Organics
• pH • Total organic carbon (TOC)
• Hardness • Volatile organic compounds
• semi-Volatile organic
Non-Metallic

• Alkalinity (bicarbonate)
compounds
• Ammonia, nitrite, nitrate • Pesticides
• Chloride • Fats and oils
• Metals • Detergents
 Inorganics in groundwater
Dissolution: Example-Calcium carbonate dissolution to calcium ion and
bicarbonate ion

CaCO3(s) + H 2 0  Ca 2+ + HCO 3− + OH −
Oxidation-reduction: change in oxidation state.
Example-reduction of ferric iron in low oxygen water
3+ − 2+
Fe + e → Fe
Ion exchange: interaction between negatively charged clay particle in
sediment and cation in solution. Example: sodium ion exchange with
potassium to produce mineral Albite

KAlSi3O8 (s) + Na + → NaAlSi3O8 (s) + K +

Complexation: reaction of organic compound with waters in high ionic

concentration
 pH

• pH is a measure of the concentration

of hydrogen ions (H+) in water
• Negative log of hydrogen ion conc.
• pH ranges from 0 to 14
– 7 neutral
– 0 - 7 acidic
– 7 - 14 alkaline
• Standard range (between 6.5-8.5)

Acid release H+ ion in water

Bases accept H+ in ion water pH = -log10[H+]
 Hardness
• Hard water is water that contains cations with
a charge of +2, especially Ca2+ and Mg2+
• These ions leave insoluble mineral deposits
• To "soften" hard water; remove the calcium
and magnesium ions
• Units of mg/L as CaCO3
• Soft water 0-50 mg/L as CaCO3
• Hard water 100-150 mg/L as CaCO3
 Carbonate and non-carbonate
hardness

Hardness = (Ca 2+ ) + (Mg 2+ )

• Carbonate hardness causes the scale formation –

CaCO3 precipitation

• Non-carbonate hardness associated with other

anions, particularly Cl- and SO42-
 Carbon-dioxide gas
• Carbon-dioxide gas enters water from atmosphere and as a by-
product of respiration and microbial decay of natural organic
matter
CO 2 (atmosphere)  CO 2 (water)

(CO 2 ) aq + H 2 O  H 2 CO 3
− +
CO 2 + H 2 O  HCO + H 3
− 2− +
HCO  CO + H
3 3
 Alkalinity
• Alkalinity refers to the capability of water to neutralize
acid (accept H+ ions)
• Buffering capacity or ability of water to resist changes
in pH

• A buffer - a solution to which an acid can be added

without changing the concentration of available H+
ions (pH) appreciably.
• Primary source of alkalinity is the carbonate system
• For most waters, alkalinity includes the bicarbonate
ion (HCO3-)
 • Nitrogen is an essential
Nitrogen compounds component of proteins and
nucleic acids
• Atmosphere is 78% nitrogen
gas

© 2014 John Wiley & Sons,

8
Inc. All rights reserved.
 Nitrogen
• Most sources of nitrogen are biological origin and atmospheric nitrogen
• Most important forms are: ammonia (NH3, -III), ammonium (NH4+, -III),
nitrogen gas (N2, 0), nitrite ion (NO2-, +III), nitrate ion (NO3-, +V)
• Total nitrogen: organic nitrogen, ammonia, nitrite and nitrate
• Organic fraction is a mixture of compounds as amino acids, amino sugars,
and proteins, can be soluble or particulate
• Decomposition of bacteria changes organic form to ammonia
• In aerobic environment the ammonia is further oxidizes to nitrite and
nitrate

Total Kjeldahl
nitrogen (TKN) is
total of organic
nitrogen and
ammonia
 Nitrogen

• Nitrite is unstable easily oxidizes to nitrate

• Nitrate is fetal to infants and is regulated when
wastewater reclaimed for groundwater recharge (0-20
mg/L as N)
• Nitrate was present in shallow and deep aquifers
• High nitrate concentration show a clear impact of human
activity as use of pesticides and fertilizers and
wastewater contamination
 Chlorides
• Chlorides in natural waters result from chloride-containing rocks
which water comes in contact
• In addition agriculture, domestic and industrial WW are a source
• Human excreta contain 6 gr of chlorides per day
• Conventional WWTP do not remove chlorides significantly
• It impacts final reuse application of treated WW and surface
groundwater contamination with wastewater
• At the Mezquital Valley aquifer, average chloride of 162 mg/L
(Lesser, 2013), below permissible limits (250 mg/L)
 Metals
• A substance with high electrical conductivity, luster, which readily
loses electrons to form positive ions (cations).
• Metals are otherwise defined according to their position on the
Periodic Table, including groupings as alkali metals, alkaline earth
metals, transition metals, and rare earth metals.

academic.emporia.edu
 Metals

• Trace quantities of many metals such as nickel,

manganese, lead, chromium, copper, cadmium, zinc,
iron, and mercury are present in most waters
• The presence of any of these metals in excessive
quantities will interfere with the beneficial uses of the
water due to toxicity
 Metals
• High metal conc. suggest irrigation with excess
domestic and industrial wastewater
• In addition, low solubility of oxygen (negative redox)
and high temperatures, may facilitate metal oxide
mobilization (as iron and manganese) from the soil to
groundwater
• Arsenic is unique as it is found at typical groundwater
pH values and under both oxidizing and reducing
conditions.
• Arsenic may be of natural origin
and industrial pollution
 Important chemical parameters :
Inorganics Organics

• pH • Total organic carbon (TOC)

• Volatile organic compounds
• Hardness
Non-Metallic

• semi-Volatile organic
• Alkalinity (bicarbonate) compounds
• Ammonia, nitrite, nitrate • Pesticides
• Chloride • Fats and oils
• Metals • Detergents
 Organic chemical constituents
• Organic – a class of chemicals composed of carbon (C), hydrogen
(H) and in some cases oxygen (O) with nitrogen (N). Can also
contain sulfur (S), phosphorus (P), and halogens as chlorine (Cl),
bromine (Br) and Iodine (I)

• Carbon monoxide (CO), carbon dioxide (CO2), bicarbonate

(HCO3) are inorganic NOT organic

• Organic – strong C-C bond

• More difficult to dissolve because of size

Chemical Structure of Glucose

By heating or mixing the water sugar dissolution is

accelerated
• Oil cannot create enough “Van der-Waals”
bonds with water and will not be dissolved

Olive Oil Vegetable Oil

 Sources of organics in water
1. Natural organic matter (NOM) – chemical and
microbial degradation of vegetation and soil
material
2. Compounds from human activities –
wastewater contamination
3. Disinfection by-products
4. Formed/added during treatment
 Natural Organic Matter (NOM)
• Organic matter originating from plants and animals present in
natural (untreated or raw) waters, for example, in lakes, rivers
and reservoirs.
• In order to minimize water disinfectant byproducts, NOM
should be removed from waters to be treated with a
disinfectant.

• Measured by total organic carbon (TOC) as a surrogate

measure or by dissolved organic carbon (DOC).
 Organic matter in wastewater
• Proteins (40-60%)
• Carbohydrates (25-50%)
• Fats, oils, and grease (8-12%)
• Urea – major constituent of urine only in very
fresh WW
• Along with the above also small quantities of a
very large number of synthetic organic
compounds, with simple to complex structure
 Total organic carbon (TOC)
• TOC test is used to measure the organic matter present
in water
• The test is performed by injecting a known quantity of
sample into a high temp. furnace (and oxygen) or
chemically-oxidizing environment
• The carbon dioxide produced is measured quantitatively
• Dissolved organic carbon (DOC) is the fraction of TOC
that passes an 0.45m filter
• Relatively fast analysis
At the Mezquital Valley aquifer, average DOC
and TOC of 4.2 and 19.1 mg/L (Lesser, 2013),
no permissible limits
Nevertheless these are high conc.
 Individual organic compounds
• Requires sophisticated instruments for
measuring trace concentrations in the
range of 10-12-10-3 mg/L such as gas
chromatograph and liquid chromatographic
methods
Classification of Organic Pollutants
(adapted from WHO)
 Volatile Organic Compounds (VOCs)
• Very volatile: compounds that have low boiling points, usually
less than < 1000C, and therefore evaporate readily. Some are
gases at room temperature.
• Volatile: boiling points less than 2500C.
• VOCs are ground-water contaminants of concern because of very
large environmental releases, human toxicity, and a tendency for
some compounds to persist in and migrate with ground-water to
drinking-water supply well
• VOC’s include Methyl-tert-Butyl Ether (MTBE) , Tri-Halo-
Methanes (THMs), benzene, toluene, ethylbenzene xylen (BTEX)
and Tert-Butyl-Acetate (TBA)
 Sources of contamination
• Groundwater contamination with Volatile Organic
Compounds are due to leaking underground fuel or
solvent storage vessels, agriculture practices and
wastewater disposal

• Storage tanks
• Septic systems
• Landfills
• Chemicals
 Methyl tertiary-butyl ether (MTBE)
• MTBE is used as a fuel additive in motor gasoline and
produced in very large quantities.
• It is one of a group of chemicals known as
"oxygenates" because they raise the oxygen content of
gasoline.
• At room temperature, MTBE is a volatile, flammable
and colorless liquid
• MTBE is found in ground water; that may be sources of
drinking water.
• MTBE dissolves easily in water therefore rapidly
migrates in groundwater, and is persistent.
• Low levels of MTBE can make drinking water supplies
undrinkable due to its offensive taste and odor.
http://archive.epa.gov/mtbe/web/html/water.html
 Trihalomethanes (THM)
• Produced during chlorination of water containing
organics – may form compound that are potentially
human carcinogens
• Normally found THMs are chloroform (CHCl3),
bromodichloromethane (CHBrCl2),
dibromochloromethane (CHBr2Cl) and bromoform
(CHBr3)
 BTEX
• BTEX is the term used for benzene, toluene,
ethylbenzene, and xylene-volatile aromatic compounds
typically found in petroleum product, such as gasoline
and diesel fuel
• Present in coal tar, petroleum products, and various
organic chemical product formulations
• At the Mezquital Valley aquifer, toluene was detected at
an average conc. of 10.3 mg/L, higher than the
permissible limit of 0.7-1.0 mg/L (Lesser, 2013)
• These are the most soluble of the major gasoline
compounds and, therefore, are common indicators of
gasoline contamination of groundwater

http://toxics.usgs.gov/definitions/btex.html
 Semi-Volatile Organic Compounds
• Organic compound which has a boiling point higher
than water
• They may vaporize at temperatures above room
temperature
• Moderate tendency to volatilize
sVOC’s include:
• Diesel Range Origin C10-C28 (DRO)
• Gasoline Range Origin C4-C10 (GRO)
• Oil Range Origin C28-C40 (ORO)
• Polyaromatic Hydrocarbons (PAH), Phenols, Pesticides
Hydrocarbons, particularly alkylbenzenes may give rise to
a very unpleasant “diesel-like” odor (WHO, 2012)
http://www.epa.gov/reg3hwmd/bf-lr/regional/analytical/semi-volatile.htm
 Pesticides
• A pesticide is any substance or mixture of
substances intended for preventing, destroying,
repelling, or mitigating any pest
• Pests are living organisms that occur where they
are not wanted or cause damage to crops or
humans or other animals. Include: insects, mice,
unwanted plants (weeds), fungi and
microorganisms.
• Examples of pesticides: Alachlor, Aldicarb, Atrazine,
Diuron, Malathion, Methyl parathion, Metolachlor
• Pesticide contamination of groundwater especially
in agricultural areas
http://water.usgs.gov/edu/pesticidesgw.html

http://www.epa.gov/pesticides/regulating/index.htm#review
 Pesticide DDT (dichlorodiphen-
yltrichloroethane) A comparison of the number of successful bald eagle
• Banned in the US in 1972 offspring with the level of DDT residues in their eggs.

• Causes birds to lay eggs with thin

shells, break during incubation
• Persistence, bioaccumulation,
Biological magnification

32
Copyright © 2014 John Wiley & Sons, Inc. All rights reserved.
 Mobility of Pesticides in the
Environment
• Chemicals can move
through soil, water, air
• Agricultural pesticides
runoff into rivers and
streams, harming aquatic
life
– Adverse effects on
aquatic
plants and animals

33
Copyright © 2014 John Wiley & Sons, Inc. All rights reserved.
DDT

How do these DDT

blood levels
compare?
Why are Mexican
American blood
levels higher?

34
Copyright © 2014 John Wiley & Sons, Inc. All rights reserved.
Individual organic compounds -
others
• Emerging organic compounds – veterinary
and human antibiotics, human drugs,
industrial products, sex and steroidal
hormones
 Total Fat ,Oil and Grease (Grasas y
Aceites)
• For the determination of oil and grease, substances with
similar physical characteristics are determined by
substances soluble in a solvent. The extracted compounds
are hydrocarbons.
• Leaking underground storage tanks are the most frequent
causes in petroleum hydrocarbon problems.
• Soil contamination has been a growing concern, because it
can be a source of groundwater (drinking water)
contamination
• Petroleum products are complex mixtures of hundreds of
hydrocarbon compounds, ranging from light, volatile, short-
chained organic compounds to heavy, long-chained,
branched compounds.

http://www.atsdr.cdc.gov/toxprofiles/tp123-c3.pdf
 Total Fat ,Oil and Grease (Grasas y
Aceites)
• Specific contaminants that are components of Total
Petroleum Hydrocarbons, such as BTEX (benzene, toluene,
ethylbenzene, and xylene), n-hexane, jet fuels, automative
gasoline, fuel oils, and mineral oil including mineral-based
crankcase oil
• Automotive gasoline typically contains about 150
hydrocarbon compound
• The exact composition of petroleum products varies
depending upon (1) the source of the crude oil (crude oil is
derived from underground reservoirs which vary greatly in
their chemical composition) and (2) the refining practices
used to produce the product.
• During the refining process, crude oil is separated into
fractions having similar boiling points.
http://www.atsdr.cdc.gov/toxprofiles/tp123-c3.pdf
 Detergents
• Detergents include Anionic, Cationic and non-
anionic.
• Usually only anionic detergent is to be
determined in ground water.
• Anionic- extraction with chloroform, thereafter,
methylene blue is used for a color reaction
(MBAS method)
• At the Mezquital Valley aquifer, MBAS parameter
was detected at an average conc. of 0.7 mg/L
(max 20.50), higher than the permissible limit of
0.5 mg/L (Lesser, 2013)