Emerging contaminants

I. Metalloid As
II. Heavy metals
III. Pharmaceuticals
i. Endocrine disruptors
IV. Personal care products
V. Plastic microbeads
 Arsenic
• The common valence states in the groundwater are
As (III) (less soluble and immobile) and As (V)
(soluble and thus mobile).

• Over-exploitation of underground water causes the

geo-chemical leaching of arsenic from the arsenic-
bearing rocks into the groundwater used for
drinking purposes in many places in India

• It is by far one of the most toxic substances found in

groundwater.
 Arsenic
• Ingestion of arsenic at > 10 μg/L for a
prolonged time causes severe disorders.

• Pigmentation in the skin, soon followed by

skin lesions, keratosis, and damage to the
internal organs causing cancers and often
becomes fatal.

• In India, more than seven states have

dangerous levels of arsenic concentration in
public drinking water, often in the range of
100-500 μg/L (10 to 50 X the regulatory
limit). Currently, about 10 million people are
directly affected and many more are at risk.
ARSENIC POISONING
 Arsenic contamination

WHO recommended a maximum of 10 μg/L in drinking

water

EU and US EPA recommended level is 50 μg/L, which is

the level detectable by ICP - AES.

Up to 5000 μg/L in contaminated water

Groundwater contamination in India

Ganges Delta – Maximum: West Bengal, East U.P., Bihar etc.
Very costly equipment required for detection
Inductively coupled plasma atomic emission spectroscopy (ICP-
AES),
 Source of Arsenic
• As-rich sulphide deposits in the Himalayas erode
and As-rich sediment is being continuously
deposited in the Ganges Delta.

• Mobilization in the well water.

• Coal Combustion
Arsenic emissions (1.4-71 ppm in coal)
Hg emissions (o.1 ppm in coal)
Selenium emissions ( 3 ppm in coal)
 Heavy Metals
Important ones- Hg, Pb, Cd
 Toxic, carcinogenic, and non-degradable
 Cr, Cd in higher doses – nervous system / kidney
damage, creation of mutation, induction of
tumors
Exposure route depends upon a particular metal
and its form:
Ex. Liquid Hg- not very toxic
Hg Vapor- Highly Toxic (enters lungs, diffuses
into blood stream, may pass through blood and
damage the central nervous system
 Heavy Metals
• Kidney/complex filter/ eliminate toxic
substance from body.
• Kidney- Contains millions of excretory
units-nephrons
• Chemicals toxic to kidney- nephrotoxins
• Example of nephrotoxic metals - Cd, Pb,
Hg
• Bhasm  भस्म in India: Oxides of heavy
metals
Mercury Transport
Charleston, Rhode Island, USA
 Endocrine disruptors
Endocrine disruptors are chemicals that, at certain doses, can interfere
with the endocrine (or hormone) system in mammals. These disruptions
can cause cancerous tumors, birth defects, and other developmental
disorders. Any system in the body controlled by hormones can be
derailed by hormone disruptors.
 Endocrine Disruptors
• Pharmaceuticals, dioxin and dioxin-like compounds
• Polychlorinated biphenyls (carbonless paper,
dielectric and coolant fluids)
• DDT and other pesticides
• Plasticizers such as bisphenol A; plastic bombs
• May be found in many everyday products – plastic
bottles, metal food cans, detergents, flame
retardants, toys, cosmetics etc.
• Plastic tubing in medical profession- infants
• PVC pipes in summer vs in winter
 Endocrine Disruption
• Endocrine system secretes hormones into the
blood stream and works in conjunction with the
nervous system.

• Endocrine disrupting chemicals (EDCs) mimic

hormones and interfere with synthesis, secretion,
transport, binding action or elimination of natural
hormones.

• EDCs are bad for adults, worse for children and

worst for unborn children parents- mothers in
particular who are exposed to these chemicals.
 • EDCs mimic a natural
hormone, fooling the body
into over-responding to the
stimulus (e.g., a growth
hormone that results in
increased muscle mass), or
responding at inappropriate
times (e.g., producing insulin
when it is not needed).

• They block the effects of a

hormone from certain
receptors (e.g. growth
hormones required for normal
development).

• They directly stimulate or

inhibit the endocrine system
and cause overproduction or
underproduction of hormones
http://web.bryant.edu/~dlm1/sc372/
readings/toxicology/endocrinedisrupter.jpg
Waste flowing out of a treatment plant near Hyderabad in
India pollutes the region’s waters with some of the highest
levels of pharmaceuticals ever detected in the
environment. In a paper being released online this week,
researchers in Sweden report how this effluent has serious
adverse effects on the development of tadpoles and
zebrafish. The findings raise concerns for the health of
wildlife and ecosystems in the region, as well as
underscoring little-studied potential effects on human health.
“The volume of drug production in that valley is
overwhelming the system,” says Stan Cox, a researcher at
the Land Institute in Salina, Kansas. “Even though they
have good [environmental] laws on the books, they’re
being swamped by the production.”
Around 90 companies in the region that manufacture
active pharmaceutical ingredients, or assemble final
drug products, send their waste to PETL. With
permission, Larsson’s team sampled the waste exiting
the plant; they found drugs including the antibiotic
ciprofloxacin, at concentrations of up to 31,000
micrograms per litre, and the antihistamine
cetirizine, at up to 1,400 micrograms per litre. The
team estimated that the amount of ciprofloxacin
entering the river from the plant could amount to up to
45 kilograms a day — the equivalent of 45,000 daily
doses, says Larsson.
 3. Biochemical Water Quality
Parameters
Natural Sources and Human Activities (Anthropogenic)

CHNO

Biodegradable Non-Biodegradable
Can be utilized by naturally Resistant to biological
occurring microorganisms degradation: Exceptionally strong
bonds

Starch, fats, proteins, alcohols, Phenols, polysaccharides,

acids, aldehydes, esters etc. benzene, detergents, insecticides,
pesticides etc.
 Equivalence of Organics

• Oxygen Equivalent of Biodegradable

Organics: BOD: Aerobic and Anaerobic
• Oxygen Equivalent of Total Organics: COD
• Oxygen Equivalent of non-Biodegradable
Organics: COD-BOD
Biodegradable Organics: Oxygen Demanding

Biochemical Oxygen Demand

 Dissolved Oxygen Depletion

Waste With Biodegradable Organics

 Oxygen-Demanding Material
• Increased Biochemical Oxygen Demand
(BOD) can result in
– anaerobic conditions.
– Anaerobic conditions lead to killing of fish
and bad smell (H2S, NH3).
• High oxygen levels necessary for healthy stream
ecology
– trout require 5-8 mg/L dissolved oxygen (DO)
– carp require 3 mg/L DO
– aesthetic problem <1 mg/L
 Biodegradable organics
Oxygen-Demanding Material

• Measured in Terms of BOD

• BOD (Biochemical Oxygen Demand): amount of
oxygen (DO, Dissolved Oxygen) required for the
biological decomposition of organic matter. The
oxygen consumed is related to the amount of
biodegradable organics.
• When organic substances are broken down in
water and CO2, oxygen is consumed
organic C + O2 → CO2 Measure of BOD =
Initial oxygen-
Organic C : Protein, Carbohydrates, Final Oxygen after
Fats etc. and Human/animal Waste 3/5 days
 Biochemical Oxygen Demand

• Amount of oxygen required by bacteria

while stabilizing the decomposable
organic matter under aerobic conditions.
• It involves the measurement of oxygen
consumed by living organisms.
• NOT in anaerobic condition - CH4 and
CO2 are produced: Biogas production
Biochemical Oxygen Demand Measurement

• Take sample of wastewater, dilute if required with

oxygen saturated water and add nutrients and
microorganisms
• Measure dissolved oxygen (DO) levels over 5/3
day.
• Temperature 20/27° C.
• In dark, plastic bottle (prevents algae growth).
• Final DO concentration must be > 2 mg/L .
• Need at least 2 mg/L change in DO over 5/3 days.
 Simple BOD Measurement

Dilution and Putting at 20 oC in Measurement

seeding of the incubator for 5 days or of DO after 3
sample 27 oC for 3 days or 5 days
 Calculation of BOD
• If initial DO of a sample is 8 mg/L and final
DO after 5 days is 2 mg/L. What is the BOD
of the sample? 8-2=6 mg/L
• If initial DO of a another waste water sample
is 8 mg/L and final DO after 5 days is 0 mg/L.
What is the BOD of the sample ?
we can not say how much is BOD.
 Dilution
Anticipated Dilution Volume of sample Dilution Factor
range of BOD % in 300 ml of BOD P (sample vol./ 1/P
in mg/L bottle total vol.)

No
0-6 300 1 1
dilution

4-12 50 150 1/2 2

10-30 20 60 1/5 5
20-60 10 30 1/10 10
40-120 5 15 1/20 20
100-300 2 6 1/50 50
200-600 1 3 1/100 100
400-1200 0.5 1.5 1/200 200
1000-3000 0.2 0.6 1/500 500
2000-6000 0.1 0.3 1/1000 1000
 CALCULATION OF BOD
• Undiluted: Initial DO - Final DO = BOD
• Diluted
(DOi  DOf )
BOD 
P
P  dilution factor  volume sample/ total volume
DOi , DOf  initial and final DO concentrat ions of the
diluted wastewater sample
 Problem
• If initial DO of a another waste water sample is 8 mg/L and final DO after 5 days is 0 mg/L.
What is the BOD of the sample ?

• If the above sample is diluted 10 times, then final DO after 5 days was 5 mg/L, What is the
BOD5 ? Assuming initial BOD after dilution was 8 mg/L.
BOD= (8-5)*10=30 mg/L
 Example 1
• A BOD test was conducted in the
laboratory using wastewater being
dumped into River Yamuna. The samples
were prepared by adding 3.00 mL of
wastewater to the 300.0 mL BOD bottles.
The bottles were filled to capacity with
dilution water and the DO measured
values are given in table.
Example 1: Raw Data

Time Diluted Sample DO

(Days) (mg/L)
0 7.95
1 3.75
2 3.00
3 2.75
4 2.15
5 1.80
 Example 1: BOD Calculation

Time Diluted Sample DO BOD

(Days) (mg/L) mg/L
0 7.95 0
1 3.75 420
2 3.00 495
3 2.75 520
4 2.15 580
5 1.80 615
 Example1: Time-BOD trend

700
600
500
BOD, mg/L

400
300
200
100
0
0 1 2 3 4 5 6
Time, Days
 Organics (Oxygen eq.) Degradation

Oxygen
Equivalent
of Organics
remaining
 MODELING

Assuming rate of decomposition of organic waste (L) is

proportional to the waste that is left. First order reaction kinetics

dLt
 - kLt
dt
where Lt  amount of Oxygen Equivalent of Organics left after time t
k  the decay rate constant (time -1 )
Solving this equation yields :
Lt  Lo e  kt
where Lo is the total oxygen equivalent of organics at t  0
BOD: Amount of oxygen utilized

 kt
Oxygen
eq
Lt  Lo e
remaining

BOD: L0-Lt
Biochemical Oxygen Demand

Assuming that DO depletion is first order

BODt = Lo(1 - e-kt)
 Example 2
• If the BOD5 of a waste is 102 mg/L and the
BOD20 (corresponds to the ultimate BOD) is 158
mg/L, what is k ?

BOD t  L0 1  e  kt

BOD t  kt
1 e
L0

 BOD t 
ln 1    kt
 L0 
 Example 2 (cont)

 BOD t 
 ln 1  
 L0 
k
t
 102 mg/L 
 ln 1  
 158 mg/L 
k
5 day
-1
k  0.21 day
 Significance of k

700
600  k=0.6 day-1
500
BOD (mg/L)

400
300  k=0.2 day-1
200
100
0
0 1 2 3 4 5 6
Time (days)
Biochemical Oxygen Demand: Temperature
Dependence

• Temperature dependence of biochemical oxygen

demand
As temperature increases, metabolism increases, utilization of
DO also increases

kt = k20T-20

 = 1.135 if T is between 4 - 20 oC
 = 1.056 if T is between 20 - 30 oC
 Example 3

The BOD rate constant, k, was determined

empirically to be 0.20 days-1 at 20 oC.

– What is k if the temperature of the water

increases to 25 oC?
– What is k if the temperature of the water
decreases to 10 oC?
 Example 3

 -1

k 25  0.20 day (1.056) 25 20

-1
k 25  0.26 day

 -1
k10  0.20 day (1.135)  10 20

-1
k10  0.056 day
 Non-Biodegradable Organics
• Molecules with exceptionally strong bonds (some
polysaccharides) and ringed structures (benzene)
• Constituent of woody plants: tannic and lignin
acids, cellulose, phenols etc.
• Petroleum products, pesticides, industrial
chemicals: Toxic to microorganism.
• Total (Biodegradable + non Biodegradable) can be
measured in terms of Chemical Oxygen Demand
(COD).
• Individual Organics are Analyzed by GC &/or
HPLC and other sophisticated methods/equipment
COD (Chemical Oxygen Demand)
• Oxygen equivalent of the organic matter of
a sample susceptible to oxidation by a
strong chemical oxidant.
• Uses a strong chemical oxidant in an
acidic solution and heat to oxidize organic
carbon to CO2 and H2O.
• Oxygen demand is determined by
measuring the amount of oxidant
consumed using titrimetric or photometric
methods.
 Stochiometry of COD

2  3  a
Cn Ha Ob  Cr2 O  8H  nCO2  2 Cr   4    H2 O
7
 2
Organic Strong Sulphuric Carbon Chromic acid
Matter Oxidant Acid dioxide
Potassium
Dichromate

HEATING 2 HOURS 150 OC

Orange Green
Colored Colored

Where:  
2 n a b
 
3 6 3
 Relationship BOD and COD

800

(1)
600
COD, (2)
mg/L
400
(3)

200

0
0 100 200 300 400

BOD, mg/L
(1) LARGE INDUSTRIAL CITY, KANPUR
(2) RESIDENTIAL CAMPUS, IIT, KANPUR
(3) BIOLOGICALLY TREATED SEWAGE, OKHLA,
 Biodegradable Fraction

DOMESTIC DAIRY SUGAR

DISTILLERY

FRACTION TANNERY
BIODEGRADABLE
PULP & PAPER

10 100 1000 Waters

Natural 10,000 100,000
COD, mg/L
 TOC
 Total organic carbon (TOC) is the amount of carbon bound in an
organic compound and is often used as a non-specific indicator of
water quality
 TOC = Total Carbon (TC) – Inorganic Carbon (IC)
 TOC = All carbon atoms covalently bonded in organic molecules
 TC is a measure of all the carbon in the sample
 IC = carbonate, bicarbonate and dissolved carbon dioxide
 IC is analyzed in liquid samples by acidifying with an inorganic acid to pH
2 or lower, then sparging for a few minutes with a stream of a gas.

DOC = Dissolved Organic Carbon which passes through 0.45 micrometer

filter
COMPARISON: COD, BOD & TOC
Parameter COD BOD TOC
Oxidant Used K2Cr2O7 Oxidation by microbes O2, Heat

Suitable Use Rapid and frequent Effects of organic compounds Measures total organic
monitoring on the DO content of receiving carbon
waters

Time 1.5-3 hours 5/3 days (standard BOD test) Several min. to hour

Advantages Correlates with BOD Most closely models the natural Correlates with BOD on
on waste with constant environment when used with waste with constant
composition. proper “seed” composition, but not as
Toxic materials do not closely as COD
affect oxidant. Short analysis time
Short analysis time.

Disadvantages Interference from Toxic materials kill Requires expensive

chloride ions microorganisms. equipment.
Some organic Microorganisms do not oxidize Some organic compounds
compounds are not all material in waste. are not oxidized
oxidized completely Inaccuracies when used with completely.
improper seed. Measures Total Organic
Lengthy test period Carbon not oxygen
demand
 Oxygen Demand

If 1 mg/L Ethyl cyanoacetate is completely oxidized to CO2 Find :

1. Theoretical Oxygen Demand (ThOD)
2. Chemical Oxygen Demand (COD)
3. Biochemical Oxygen Demand (BOD)
4. BOD5
5. Total Organic Carbon (TOC)

C5H7NO2 + 5 O2 5CO2 +NH3 + 2 H2O

mw = 113 mw =160
– ThOD =160/113 = 1.42 mgO2/mg C5H7N O2
– COD = 1.42 mgO2/mg C5H7NO2
– BODult = COD
– BOD5 (5 days O2 Consumption) =0.68 BODult = 0.68 x 1.42 = 0.97 mg BOD5/
mg C5H7NO2
– TOC =5 x 12 / 113 = 0.53 mg TOC/ mg C5H7NO2
 Natural Organic Matter (NOM)
• Natural Organic Matter (NOM) is the organic material present
in surface or ground water.
• NOM includes both humic (humic and fulvic acids) and non-
humic (tannic acid) fractions.
• These substances are oxidized very slowly and their
solubility in water may vary with pH.
• The dissolved fraction of NOM may not be fully removed
using conventional water treatment practices and have been
shown to produce by-products such as trihalomethane during
chlorination.
• Dissolved organic carbon (DOC) is the most commonly used
parameter to quantify NOM.
 NOM
• UV absorbance at 254nm (UV254) is a useful surrogate measure
for DOC.
• This technique only requires very simple instrumentation and
can be performed by the operators in the treatment plant.
• NOM Can be removed by activated carbon adsorption
 4. Bacteriological Water Quality
Parameters

• Water Body Hosting Large number of

species with well balanced number of
individuals : Healthy System
• For Human Use and Consumption:
Pathogens: Capable of infecting or
transmitting disease to Humans
 Pathogens

• Bacteria, Virus, Protozoa, Helminths

• Cause Water-related diseases (e.g. gastro-intestinal,
typhoid, shigellosis, hepatitis and cholera)
• Main health concerns in the world.
• Often contamination through contact with water or via
food (e.g. via irrigated agriculture, or via fish/shellfish).
 Pathogenic Organisms
• Organisms colonize the intestinal tract but can live
for a period of time outside the body
• Carriers (who may or may not exhibit disease
symptoms) excrete these intestinal tract organism
in very large numbers.
• When water is contaminated by excreta, the
organisms can be transmitted to those who contact
the water.
Impacts on Human Health
Classification of Water Associated Diseases
Transmission Description Examples of diseases
mechanism

Water borne Oral ingestion of pathogens in Cholera, typhoid,

water contaminated by urine or bacillary, trachoma,
feces

Water-washed Disease spread enhanced by Trachoma, dysentery

scarcity of water making
cleanliness difficult

Water-based Water provides habitat for Schistosomiasis

intermediate organism,
transmission to human through
water contact

Water Related Insect vectors (mosquitoes) rely on Malaria, yellow fever,

water for habitat, human water dengue
contact not needed
 Pathogenic Organisms (Virus)
Virus (less than 1 micrometer, smallest Associated Disease
creature)
Poliovirus Poliomycetis
Hepatitis-A Virus Infectious Hepatitis
Adenovirus Respiratory, eye infections
Others Gastroenteritis, diarrhea

Nervous System disorders:

Immunization

Poliovirus

Bacteriophage
Pathogenic Organisms (Bacteria)
Bacteria (unicellular, <10 Associated Disease
micrometer)
Salmonella Typhi Typhoid fever
Shigella Bacillary dysentry
Vibrio Cholera Cholera
Yesina Enterocolitica Gastroenteritis

Gastrointestinal Infections

Salmonella typhi
Pathogenic Organisms (Protozoa)

Protozoa (10-50 micrometer, unicellular) Associated Disease

Entamoeba histolytica Amoebic dysentry
Giardia Lambia Diarrhea
Cryptosporidium Diarrhea

Milder Gastrointestinal Infections

Giardia Lambia
 Pathogenic Organisms (Helminths)

Helminths Associated Disease

Hookworm Hookworm
Roundworm Ascariasis
Whipworm Trichuriasis

Parasitic Worms
Infective
Stage of Infection
Eggs in Soil
 Water Washed (Trachoma)
• Trachoma is caused by Chlamydia trachomatis
(Pathogenic Bacteria) and it is spread by direct
contact such as towels and/or washcloths, that
have had similar contact with these secretions.
• Flies can also be a route of mechanical
transmission.
• Untreated, repeated trachoma infections result in
entropion—a painful form of permanent blindness
when the eyelids turn inward, causing the
eyelashes to scratch the cornea.
 Water based diseases

Trachoma is caused by
Chlamydia trachomatis
(Pathogenic Bacteria)
and it is spread by
direct contact such as
towels and/or
washcloths, that have
had similar contact with
these secretions.
 Water based diseases

                                                                                                   

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 Disease Rates and Risk

Disease Vector Morbidity Mortality Population at

Risk
Diarrheal Microorganism > 1.5 billion 4 million > 2 billion
Diseases s

Schistosomiasis Water snails 200 million 200,000 500-600

million
Malaria Mosquitoes 267 million 1-2 million 2.1 billion

Onchocerciasis Backflies 18 million 20-50,000 90 million

 Analysis of Pathogens
• Analysis of known pathogens time consuming. Test
for specific microorganisms (Shigella, Salmonella
etc.,) only when needed.
• Generally purity of water is checked by using
indicator microorganisms.
• Indicator microorganism should be:
– Always present when pathogens are present and always
absent when pathogens are absent
– Applicable to all types of water.
– Native to intestinal track of humans
– Safety of lab personnel: ?
 Indicator Organism

• Fecal Coliform groups: Principal strain is E

Coli.: Non pathogenic and longer survival time
outside the human body.
• Simple tests to determine the presence or
absence and enumeration.
• Membrane filter technique or multiple tube
tests.
 (River Bathing Standards)

PARAMETERS PERMISSIBLE LIMIT

 BOD 3 mg/L (MAXIMUM)

 DO 5 mg/L (MINIMUM)
 COLIFORM (FECAL) 500 (DESIRABLE)
MPN
2500 (MAX. PERMISSIBLE) 100 ml

BOD - BIOCHEMICAL OXYGEN DEMAND

DO - DISSOLVED OXYGEN
MPN - MOST PROBABLE NUMBER
Treated Water Quality Standards

INTO WATER BODY ON LAND

BOD (mg/l) 30 100

T S S (mg/l) 100 200

FECAL (MPN/100 ml) 1000 (Desirable)

COLIFORMS (Maximum)
10000

NRCP (National River Conservation Plan): BOD= 20 mg/L, TSS = 50 mg/L

Fecal coliforms: 1000 MPN/100 ml Desirable and 10000 MPN/100 ml as
maximum