Groundwater Quality Analysis
Groundwater Quality Analysis
Groundwater Quality Analysis
Introduction
Indian Ground Water Scenario and Brief Management
Groundwater Quality
– Sampling Plan
– Field Measured Parameters
• pH
• Alkalinity
• Conductance
• Salinity
• Dissolved Oxygen
• Turbidity
– Chemical Equivalence
– Laboratory QA/QC
– Diagrams
• Piper
• Stiff
– Water Quality Classification
– Ground water Quality & Associated Problems
– Irrigation Water
• Sodium
•
– Arsenic
Salinity
– Fluoride
– Iron
– Nitrates
Recent Advancements & Remedial Measures
• Water is the most important in shaping the
land and regulating the climate. It is one of
the most important compounds that
profoundly influence life.
• In the last few decades, there has been a
tremendous increase in the demand for fresh
water due to rapid growth of population and
the accelerated pace of industrialization.
• Groundwater is used for domestic and
industrial water supply and also for irrigation
purposes in all over the world.
• According to WHO organization, about 80% of
all the diseases in human beings are caused by
water.
• Once the groundwater is contaminated, its
quality cannot be restored back easily and to
device ways and means to protect it.
Groundwater Quality
• Helps us understand the hydrogeologic
system
• Indicates comingling of groundwater and
surface water
• Helps us interpret groundwater flow
dynamics
• Delineates groundwater contamination
• Water quality index is one of the most
effective tools to communicate information
on the quality of water to the concerned
citizens and policy makers.
• It, thus, becomes an important parameter for
the assessment and management of
groundwater.
• The more soluble constituents
include
common calcium, sodium, bicarbonate and
sulphate ions.
WQI Status Possible Usage
150
Unfit for Drinking Proper Treatment Required
• Another common constituent is chloride ion
derived from intruded sea water, connate
water, and evapotranspiration concentrating
salts, and sewage wastes, for example Nitrate
can be a natural constituent but
concentrations high suggest a
often pollution. source of
• Water quality standards are needed to
determine whether ground water of a certain
quality is suitable for its intended use.
• Due to increasing urbanization, surface water
is getting over contaminated and more
stringent treatments would be required to
make surface water potable. Therefore, it is
required to additional sources for fulfil the
requirement of water. Because the ground
water sources are safe and potable for
drinking and other useful purposes of human
being. Hence studies of physic-chemical
characteristics of underground water to find
out whether it is fit for drinking or some other
beneficial uses.
DYNAMIC GROUND WATER
RESOURCES OF INDIA
Annual Replenishable Ground Water
• Resources 433 BCM.
• Annual Ground Water Draft for Irrigation, Domestic & Industrial uses 245
BCM.
Safe 4530
Semi-Critical 697
Critical 217
Over-Exploited 1071
Saline 92
Precipitation map of India
Annual Recharge & Withdrawal of
Ground Water
Ground Water Quality & Depth in
Various Parts of Our Country
Ground Water Stage in India
Sampling and Analysis Plan
• Document written in advance of sampling that
defines:
– Sampling locations and frequency
– How field parameters are measured
– How samples are collected
– Quality control and assurance measures
• Do NOT go to the field without a plan!
Groundwater Sampling
• Important Points
– Be sure to take a representative sample
– Make sure sample bottles are properly rinsed
– Filter and preserve samples in the field
– Take field measurements with proper equipment
– Store on ice
– Send to a certified water chemistry laboratory within
24 hours of sampling
– Have a quality control program with duplicates,
blanks, field blanks, or spiked samples
Groundwater Sampling Methods
Sampling is the process of obtaining, containerizing, and preserving (if required) a
ground water sample after the purging process is complete.
There are few technical methods, which can be adopted for collection of
representative samples are-
Sampling Wells With In-Place Plumbing
Samples should be collected following purging from a valve or cold water tap as
near to the well as possible, preferably prior to any storage/pressure tanks or
physical/chemical treatment system that might be present.
Sampling Wells Without Plumbing, Within the Limit of Suction
The pump of choice for sampling ground water within the limit of suction is the
variable- speed peristaltic pump. Its use is described in the following sections.
Other acceptable alternatives that may be used under these conditions are the
RediFlo2® electric submersible pump (with Teflon® tubing) and a closed-top
Teflon® bailer.
(variable speed peristaltic pump/ Peristaltic Pump/ Vacuum jug/ RediFlo2
Electric Submersible Pump/ Bailers)
Sampling Wells without Plumbing, Exceeding the Limit of Suction
RediFlo2® Electric Submersible Pumps, and Bailers, are suitable sample methods where
the water table is too deep to consider the use of a peristaltic pump for sampling.
–Mg
–Na
–Cl
–Si
–SO4 - sulfate
2- -
–Fe
–CO32-- carbonate
Abundance of Dissolved Constituents
in Surface and Ground Water
• Trace Constituents
(< 0.1 mg/l) – Pb
– Mn
–Al
– Ni
–As – Se
–Ba – Ag
– Zn
–Br
– others
–Cd
–Co
–Cu
Water Classification
• How?
– Compare ions with ions using chemical equivalence
– Making sure anions and cations balance
– Use of diagrams and models
• Why?
– Helps define origin of the water
– Indicates residence time in the aquifer
– Aids in defining the hydrogeology
– Defines suitability
What is Chemical Equivalence?
• Chemical analysis of groundwater samples
– Concentrations of ions are reported by
• weight (mg/L)
• chemical equivalence (meq/L)
• Takes into account ionic charge
• Equivalent Concentration
Periodic Table of the Elements
1A http://chemistry.about.com 8A
1 © 2012 Todd Helmenstine 2
H About Chemistry He
1.00794 4.002602
Hydrogen 2A 3A 4A 6A 7A Helium
5A
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.941 9.012182 10.811 12.0107 14.0067 15.9994 18.9984032 20.1797
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
22.989769 24.3050 26.9815386 28.0855 30.973762 32.065 35.453 39.948
Sodium Magnesium 3B 4B 5B 6B 7B ┌───── 8B ─────┐ 1B 2B Aluminum Silicon Phosphorus Sulfur Chlorine Argon
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.0983 40.078 44.955912 47.867 50.9415 51.9961 54.938045 55.845 58.933195 58.6934 63.546 65.38 69.723 72.64 74.92160 78.96 79.904 83.798
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.4678 87.62 88.90585 91.224 92.90638 95.96 [98] 101.07 102.90550 106.42 107.8682 112.411 114.818 118.710 121.760 127.60 126.90447 131.293
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
55 56 57-71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9054519 137.327 178.49 180.94788 183.84 186.207 190.23 192.217 195.084 196.966569 200.59 204.3833 207.2 208.98040 [209] [210] [222]
Cesium Barium Lanthanides Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
87 88 89-103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Uuo
[223] [226] [267] [268] [271] [272] [270] [276] [281] [280] [285] [284] [289] [288] [293] [294] [294]
Francium Radium Actinides Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roent genium Copernicium Ununtrium Flerovium Ununpent ium Livermorium Ununseptium Ununoctium
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Lanthanides La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
138.90547 140.116 140.90765 144.242 [145] 150.36 151.964 157.25 158.92535 162.500 164.93032 167.259 168.93421 173.054 174.9668
Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Actinides [227] 232.03806 231.03588 238.02891 [237] [244] [243] [247] [247] [251] [252] [257] [258] [259] [262]
Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium
Alkaline Transition
Alkali Metals Basic Metal Semi Metal Non Metal Halogen Noble Gas Lanthanides Actinides
Earth Metal
Formula weight
• Formula weight
– Multiply atomic weight by # of atoms and add together
• E.g.,
– Formula weight of water
H2O = 2*(Atomic Wt of H) + 1*(Atomic Wt of O)
2*(1.008) + 1*(16) = 18.01
Atomic Weight (Relative atomic mass) is a dimensionless physical quantity, the ratio
of the average mass of atoms of an element to 1/12 of the mass of an atom of
carbon-12
Ion Balance
• If all ions are correctly determined by a lab
sum of cations should equal sum of anions (all in
meq/L)
• Errors in analysis and chemical reactions in
samples
5 % difference is considered acceptable
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Pie Diagrams
Igneous Volcanic
Sandstone Aquifer
Na
Na
Ca
Ca
Mg
Cl
Mg
SO4
Cl
HCO3
SO4
NO3
HCO3
NO3
tteerr
Na
Na Ca
Ca Mg
Mg Cl
Cl SO4
SO4 HCO3
HCO3 NO3
NO3
Na 10,500 20
Cl 19,000 24
C
SO4 2,700 51 l
Ca 410 38
Mg 390 10 Mississippi River water (mg/
HCO3 142 113 L)
Na
Cl
HCO3
SO4
Ca
Ground Water Quality in Different Aquifers
Igneous/
Sandstone Limestone Shale with Alluvium
Parameter
Aquifer Aquifer Salts (Farmland)
Aquifer
Volcanic
pH 7.5 7.8 6.5 7.1 7.4
Cl 13 53 6 1980 30
SO4 7 60 7 1000 74
Ca 88 144 34 353 64
pH 6.5-9.5
pH 6.5-8.5 Aesthetic
Health
Barium 2 mg/L
Total Dissolved
500 mg/L Taste
Solids
Basic Water Quality Parameters
• pH
• Specific conductance (EC)
• Salinity
• Total dissolved solids (TDS)
• Turbidity
• Dissolved oxygen (DO)
• Biochemical oxygen demand (BOD)
• Temperature
• Total Hardness
• Magnesium • C.O.D.
• Sulphate • Iron & Manganese
• Nitrate • Cadmium
• M.P.N. • Chromium
• Total alkalinity • Nickel
• Chloride • Zinc
• Fluoride • Sodium
• Boron
• Phosphates
pH
• Measures hydrogen ion
concentration
• Negative log of hydrogen ion
concentration
• Ranges from 0 to 14 std. units
• pH
– 7 neutral
– 0 - 7 acidic
– 7 - 14 alkaline
HF Scientific MicroTPI
– Turbidity Meter YSI 556 MPS
Thanks to Phil Brown
Total Dissolved Solids
• One measure of the quality of the water in
lakes, rivers, and streams is the total amount
of solids dissolved in the water. High amounts
of dissolved solids can indicate poor water
quality. The same is true for drinking water.
Methods:
• Gravimetric method.
• Electrical Conductivity.
Gravimetric method.
• Gravimetric means weighing". Balances
"by
require gravity to weigh something. You will
weigh the total dissolved solids after water
water sample. is
boiled away. This will be done using just one
Procedure:
• To measure TDS using this method, the water
sample is first passed through a filter that blocks
anything bigger than 2 microns ( 2 micrometers
or 2 millionths of a meter).
• This ensures the test measures dissolved solids not solids
suspended in the water. Such things as sediment or specks of
plant material are filtered out and therefore not counted in
the "total dissolved solids“
• A certain amount of the filtered water is then weighed out
and the water is boiled away leaving the dissolved solids
behind as a solid residue. This residue is weighed. This is
called the gravimetric method because a balance is used.
Balances need gravity to find the mass. So that's why it's
called a gravimetric method.
Nitrate
Sources:
• Fertilizers and manure
• Decayed vegetable
• Animal feedlots
• Municipal wastewater and sludge disposal to
land
• Industrial discharges
• Leachates from refuse
• dumps Septic systems
Methods for Nitrate Estimation
Ultraviolet Spectrophotometric Method
• Filter the sample.
• Add 1 ml of 1N HCl per 50 ml of sample.
• Read absorbance or transmittance at 220 nm
and 275 nm.
• Set 0 absorbance or 100% transmittance with
distilled water.
Nitrate Electrode Method
• Useful for Nitrate concentration range of 0.14
to 1400 mg/L
• NO -N
3
• Interferences
• Chloride and bicarbonate with weight ratios to
NO3-N >10 or >5 respectively
bleaching is a function of
• fluoride ions, it is directly proportional to the
concentration of fluoride.
• It obeys Beer’s law in a reverse manner.
Ion Selective Electrode Method
Principle:
• The fluoride sensitive electrode is of the solid
state type, consisting of a lanthanum fluoride
crystal; in use it forms a cell in combination
with a reference electrode, normally the
calomel electrode.
• The crystal contacts the sample solution at
one face and an internal reference solution at
the other.
• A potential is established by the presence of
fluoride ions across the crystal which is
measured by a device called ion meter or by
any modern pH meter having an expanded
milli volt scale.
• Calculate mg F- / L present in the sample using
standard curve.
Presence of Fluoride
85 % of rural population of the country uses ground water for drinking and
domestic purposes, which contains a high concentration of fluorides (> 1.5 mg
/litre).
Sulphate
Significance:
• Occurs in natural water
• High concentration of Sulphate laxative effect
• (enhances when sulphate consumed with
magnesium)
• Problem of scaling in industrial water supplies
• Problem of odour and corrosion in wastewater
treatment due to its reduction to H2S
Spectorphotometric Method
Principle:
• Sulfate ions are precipitated as in acidic
BaSO 4media (HCl) with Barium Chloride.
• The absorption of light by this
precipitated suspension is measured by
• Spectrophotometer at 420 nm or scattering
of light by Nephelometer
Calculate:
• mg / L SO = mg SO x 1000
4 4
• ml sample
Ammonia
• Ammonia is present naturally in surface and
wastewaters. Its concentration is generally
low in ground waters because it adsorbs in soil
particles and clays and is not leached readily
from soils.
• It is produced largely by de-amination of
organic nitrogen containing compounds and
by hydrolysis of urea.
• The graduated yellow to brown colors produced
by nessler-ammonia reaction absorb strongly
over wide wavelength range
• Low ammonia concentration of 0.4 to 5 mg/L can
be measured with acceptable sensitivity in
wavelength region from 400 to 425 nm with
1cms light path
• A light path of 5 cm extends measurements of
ammonia concentrationsrange of 5 to 60 μg/L
• In the chlorination of water, chlorine reacts
with ammonia to form mono and
dichloramines (combined residual chlorine)
• Ammonia concentration in water vary from
less than 10μg in some natural surface and
ground waters to more than 30 mg/L in some
wastewaters.
Methods for Ammonia Estimation
Nesslerization Method:
• Direct method is useful for
nesslerization
purified natural water and highly purified
wastewater effluents with very light color and
having NH3-N concentrations more than 20
μg/L.
• Applicable to domestic wastewater only when
errors of 1 to 2 mg/L are acceptable.
Ammonia Selective Electrode Method
• The ammonia selective electrode uses a hydro-
phobic gas permeable membrane to separate the
sample solution from an electrode internal
solution of ammonium chloride
• Dissolved ammonia is converted to NH aq) by
3( raising
pH to above 11 with a strong base, which
diffuses through membrane changes the
and internal solution pH sensed by a pH
that
electrodeis
• The fixed level of chloride in the internal
solution is sensed by a chloride ion-selective
electrode that serves as the reference
electrode.
• Applicable to the measurement of 0.03 to
1400 mg NH3-N/L in potable and surface
waters and domestic and industrial wastes.
• High concentrations of dissolved ions affect
the measurements but color and turbidity do
not.
Titrimetric Method
T07_04_02
ANALYSIS OF WATER SAMPLES
• Field:
– pH, specific conductance, temperature,
dissolved oxygen, and alkalinity
• Laboratory:
– Cations: sodium, calcium
magnesium, potassium, and iron
– Anions: bicarbonate, carbonate,
sulfate, and chloride
– Trace Metals, Radioactivity
Ground water Quality &
Associated Problems
Indian Sub- Continent is endowed with diverse geological formations from
oldest Achaeans to Recent alluviums and characterized by varying climatic
conditions in different parts of the country.
The main ground water quality problems in India are as follows-
Inland Salinity (Rajasthan, Haryana, Gujarat, Andhra Pradesh, Maharashtra,
Tamil Nadu etc.)
Coastal Salinity (The Indian subcontinent has a dynamic coastline of about
7500 km length, which stretches from Rann of Kutch in Gujarat to Konkan
and Malabar coast to Kanyakumari)
3 probable cases of coastal salinity
Saline water overlying fresh water aquifer
Fresh water overlying saline water
Alternating sequence of fresh water and saline water aquifers
Sodium and Irrigation
• Sodium reacts with soil to reduce permeability.
• Alkali soils - High sodium with carbonate
• Saline soils – High sodium with chloride or sulphate
• Neither support plant growth
• Sodium Adsorption Ratio (SAR) is a measure of the suitability of water
for use in agricultural irrigation, as determined by the concentrations of solids dissolved in the
water. It is also a measure of the sodicity of soil, as determined from analysis of water
extracted from the soil.
Sodium and Irrigation
• Low-sodium water
– Used on all soils with little danger of harmful levels of
exchangeable sodium.
• Medium-sodium water
– appreciable sodium hazard in certain fine-textured
• soils
High-sodium water
– harmful levels of exchangeable sodium in most soils
– require special soil management such as good drainage,
• leaching, and additions of organic matter.
Very high sodium water
– unsatisfactory for irrigation unless special action is taken,
such as addition of gypsum to the soil
Salinity and irrigation
• Low salinity water
– used for most crops
• Medium salinity water
– used with moderate amount of leaching (potatoes,
corn, wheat, oats, and alfalfa)
• High salinity water
– Cannot be used on soils having restricted drainage.
• Very high salinity water
– Can be used only on certain crops and then only if
special practices are followed
Arsenic in Groundwater
• Long-term exposure to arsenic from drinking
water is directly linked to:
– Cancer of the skin, lungs, urinary bladder and kidneys.
– Acute gastrointestinal and cardiac damage as well as
vascular disorders such as Blackfoot disease.
– Sub-lethal effects include diabetes, keratosis, heart
disease and high blood pressure.
• Toxicity is dependent on diet and health, but is
cumulative. Arsenic is excreted very slowly by the
body through deposition in the hair and nails.
BACKGROUND
• Arsenic (As)
– toxic metal widespread in groundwater
• Occurs widely in aquifers
– deltaic sediments near mountain uplift zones
– deep sandy aquifer layers originating as riverine, lake
or coastal deposits.
– Ganges, Mekong and Red River deltas, sandy alluvial
deposits in South Asia, South East Asia, South
America, and in many parts of North America and
Europe.
Chemistry
• Arsenic has the ability to switch between two
valency forms,
– As3+and As5+.
• As3+
– more soluble and more likely to be absorbed than
As5+
– This switching property makes detection and
measurement difficult and frequently unreliable
Arsenic Contamination
• Associated with fluctuating water tables and
flooding cycles particularly in
– Acidic sulfate soils or
– Iron and/or manganese-enriched layers,
– saline-layered aquifers
• Levels in water supplies can vary through a
year adding to the difficulties of identification
and monitoring.
Drinking Water Standards
• Worldwide 50 ppb limit (1942)
• US EPA
– Acceptable mortality = 1 death per 1,000 people
for carcinogens
– Lifetime risk from exposure to 50 ppb As
• 13 cancer-related deaths per year per 1000 people
(1992)
– Current standard = 10 ppb standard
Arsenic in the United States
• USGS analyzed US water quality data
• 10 ppb level exceeded by 8% of public ground
waters tested
• EPA estimates that the 10 ppb rule affects
about 4,000 water systems
• "Hotspots" of high concentration
– Central New England
– Midwest
– Western states.
Arsenic in the United States
Presence of Arsenic India
Arsenic occurs naturally in the environment as an element of the
earth’s crust with an abundance of 1.8 ppm by weight.
Determination of Metals
Inductively Coupled Plasma-Atomic
Emission Spectrometer
Instrument set up
Heliborne Survey
Aquifer
Mapping
Participatory Ground Water Management
Artificial Ground Water Recharge etc.
Heliborne Survey