Unit 4: Aquatic Chemistry

Introduction of aquatic chemistry;

C h e m i s t r y o f N a t u r a l Wa t e r
(Hydrogen bond and specific water
Aqua%c  
reactions); Complexation in
Chem  
Wa s t e wa t e r ( B a s i c f a c t o r s ,
hydrolysis, Transboundary
movement of heavy metals and
humic compound reactions);
Significances of Solubility of Gases
i n Wa t e r, M i c r o o r g a n i s m s a s
cat alys t of Aquatic Chemical
Reaction; Microbially mediated
e l e m e n t a l t r a n s i t i o n s c yc l e s
( S u l p h u r, c a r b o n , n i t r o g e n ,
phosphorous cycles and halogens
and organohalides).
 Unit 4.2: Aquatic Chemistry  

Due   to   water’s  
polar   molecular  
structure  and  its  
ability   to   form  
hydrogen   bonds  
 Unit 4.2: Aquatic Chemistry  
• Manhan: The branch of
environmental chemistry
that deals with chemical
phenomena in water.
• It addresses chemical
phenomena in so-called
“natural waters,”
c o n s i s t i n g o f wa te r i n
s tre am s, l ake s, o c e ans,
underground aquifers, and
other places where the
wa t e r i s r a t h e r f r e e ly
exposed to the atmosphere,
soil, rock, and living
systems.
 Unit 4.2: Aquatic Chemistry  
Water (H2O) is a clear, colorless,
nearly odorless and tasteless
liquid, essential for most plant and
animal life and the most widely
used as universal solvent. It has
melting point 0oC and boiling
point 100 o C with maximum
density (1) at 4oC. A molecular
weight of water is 18. Chemically,
it is dehydrate of oxygen. Unlike
other hydrides like hydrogen
sulfide (H2S), hydrogen selenide
(H 2 Se) & hydrogen telluride
(H2Te) of the same family, water
remains liquid at room
temperature.
 Unit 4.2: Aquatic Chemistry  
• Water has a very simple atomic structure. This structure consists of two
hydrogen atoms bonded to one oxygen atom. The nature of the atomic structure
of water causes its molecules to have unique electrochemical properties. The
hydrogen side of the water molecule has a slight positive charge. On the other
side of the molecule, a negative charge exists. This molecular polarity causes
water to be a powerful solvent and is responsible for its strong surface tension,
• The water molecule dipoles attract each other and form aggregates through
hydrogen bonds. In the dipole, the hydrogen atoms carry a positive charge
while the oxygen atom is negatively charged. The molecules consist of a central
oxygen atom with attached hydrogen atoms at the same plane forming a bond
angle of about 1050
Significances of Hydrogen Bonding
• Causes solvation of neutral molecules; Assists with solvation of molecules with
permanent dipoles; Stabilizes colloids
• Determines the tertiary shape of proteins and enzymes
• Stabilizes ionic double layers; Assists in solvation of charged ions
• Responsible for surface tension
Aquatic Chemical Processes
O2
Gas exchange with atmosphere
NO3-
2HCO3- + hγ Photo synthesis
CO2 Chelation { CH2O } + O2 (g) + CO32-
Acid-base
CO32- + H2O HCO3- + OH-
Cd2+
Precipitation
Ca2+ + CO32- CaCO3 (s)

2- +
Microbial
2{CH2O} + SO4 +2H H2S (g) + 2H2O + 2CO2 (g)
action

NH4+ leaching uptake

Sediment Ground water

Weathering  Reaction:
4KAlSi3O8+22H2O→Al4Si4O10(OH)8+8H4SiO4+4KOH  (kaolinite)  
Sequestration  Reaction:  CO2+Ca2++2X-­‐+H2O⇌CaCO3+2HX  
Solubilization  Reaction:  CO2+H2O⇌HCO3-­‐+H+⇌H2CO3  
Redox  Reactio𝑛:  2FeS2+15/2O2+4H2O⇌Fe2O3+2SO42-­‐+8H+  
Hydrolysis  Reaction:  Fe(H2O)63+    +H2O⇌Fe(H2O)5OH2++H3O+  
Complexation  Reaction:  Cu(H2O)4+    +4NH3⇌Cu(NH3)42++4H2O  
Acid  Base  Reaction:  2H2O⇌H3O++OH-­‐  
Carbon  Fixation  Reaction:  CO2+H2O+hυ→BiomassCH2O+O2  

Central Metal Ion + Ligand Complex

 Complexation
Molecular  or  addi%on  compounds  of  two  or  more  en%%es  
which   retain   their   iden%ty   even   in   solu%on   capable   of  
independent   existence   and   the   proper%es   of   which   are  
different  from  those  of  their  cons%tuents  are  coordina%on  
compounds.   The   process   of   forma%on   is   known   as  
complexa%on.  
 
These   complexes   consist   of   one   or   more   central   atoms   or  
ions  (usually  metals)  surrounded  with  a  number  of  ions  or  
molecules  (ligands)  
Fe(CN)2 + 4KCN K4Fe(CN)6
K4Fe(CN)6 4K+ + Fe(CN)64-
Water Complexation
 Water Complexation
• Water   is   itself   a   coordinated  ligand   in   solu3ons   of  
most   transi3on   metals.   The   forma3on   of   a  
complex  can  be  regarded  as  a  ligand  subs3tu3on  
reac3on   in   which   coordinated   water   molecules  
are  displaced  successively.    
Cu(H2O)42+  +  4NH3                              Cu(NH3)42+  +  4H2O  
• Some   chelates   are   built   up   in   a   stepwise   manner  
with   successive   addi3ons   of   ligand   bonds   and  
successive   stability   constants   that   generally  
decrease  in  stability  with  the  number  of  ligands.    
Cu2+,  Cu(NH3)2+,  Cu(NH3  )22+,  Cu(NH3)3  2+,  
Cu(NH3)42+  Cu(NH3)52+,  NH4+,  and  NH3.
 Wastewater Complexation
• In   various   environments   the   common   ligands   are  
sulfate,   chloride,   anions   of   organic   acids,   humic  
material.    
• These  ligands  are  libale  to  complex  with  metals.    
• The   common   complexing   agents   released   as  
effluents   into   water   bodies   (surface   and  
groundwater)   are   ammonia   (resul3ng   from   the  
decay   of   nitrogenous   organic   wastes)   ,   sulfide  
groups   (discharge   from   pulp   &   paper   mills),  
phosphate   (detergents   &   agro   -­‐   runoff),   cyanides  
(industrial  process),  EDTA  (cleaning,  photographic,  
tex3les   &   paper   industries)   and   nitrilotriacte3c  
acid,  NTA  (laundry  waste).  
 Wastewater Complexation
• The industries also utilize other strong
metal complexing agents like
ethylendiamine, glycine (amino acetic
acid), tartrate, citrate, malonate, oxalate.
• The organic constituents of the sewage
sludge bind the metals into a form that
renders them unavailable biologically
through chelation and outer sphere
complexation.
• The surface metal adsorption is affected by
soil pH, clay mineralogy, abundance of
o x i d e s a n d o r g a n i c m a t t e r, s o i l
composition and solution Ionic strength
 Complexation Reactions

Cr  (H20)6  Cl3à  Hexaquochromium  (III)  chloride.  

Complexation Reactions

CH2

NH2

CO
CO O

[CO (III) (gly)3]o , Triglycinato cobalt (III)]

Transboundary Movement of HM

.  
 Transboundary Movement of HM  
• Clay and silt components adsorb metal
ions much better than sediment
fractions of higher size.
• Manganese and iron contents in the
various fractions of the sediment
decrease with increasing particle size.
• The lead and zinc metal ions have more
affinity for the clay and silt fraction of
the sediment . in natural river systems,
salinity and pH highly affect the
speciation of the metal ions and greatly
interfere with their fixation on clay
minerals.
• Humic substances is their ability to form
water-soluble and water-insoluble
complexes with metal ions and hydrous
oxides and to interact with clay
minerals.
Transboundary Movement of HM  
Transboundary Movement of HM  

.  
Transboundary Movement of HM  
Transboundary Movement of HM  
Transboundary Movement of Hg  

 
Biogeochemical  cycling  
of  mercury  in  the   Copyright  (2013)  American  Associa3on  for  the  
environment   Advancement  of  Science  
Iron Band Formation  
Iron Band Formation  
 Microorganisms - The Catalyst of Aquatic
• The chemical reactions in aqueous
medium involving organic matter and
redox processes mediated through
microorganisms, bacteria, fungi and
algae.
• Microorganisms lead to the formation of
many sediment and mineral deposits.
• Bacteria are also known as reducers that
decompose chemical compounds to
simpler species and thereby drive the
energy requirements for their growth and
metabolism.  
 Microorganisms - The Catalyst of Aquatic

    bacteria
CH2O          O                      CO2  (aqua3c  system);             2

 
anaerobic
Chemicals                      bacteria
                       H2S,  CH4  
  bacteria
Dead  biomass                            Fungi
                                   Inorganic  +  Organic  (fulvic  acid)  
 
 
                                                                                                   

h‫ ע‬ 
                                                                                                                         

CO2                        algae                  Biomass  

     
 
86 KappIer & Straub
Iron Redox
Chemical or microbial Fe(ll) oxidation with °2 and microbial
Fe(ll) oxidation with C02 in the light or with N03- at neutral pH

/'
/ '"

Fe(lI) minerals
Dissolution
. F
(
2+
e
Microbial ~~OPhiliC

.
~
Fe(ll) oxidation
.- Fe3+
4
Precipitation
(pH increase)
. Fe(lII) minerals
\
+
Precipitation \ hemical or microbial Dissolution
Fe(lll) reduction (pH decrease)
at acidic pH
)
./
/

Chemical or microbial Fe(lll) reduction

at neutral pH

Figure 1. Microbial and chemical iron cycle.

 Microbial Transformation of Sulfur

• The   sulfate reduction & sulfide oxidation

are the major microbially mediated redox
reactions in the sulfur cycle. Desulfovibrio
bacteria utilizes sulfate as an electron
acceptor in the oxidation of organic matter
and reduces SO4 to H2S.
       SO42-­‐  +  2{CH2O}  +  2H+  à  H2S  +  2CO2  +  2H2O  
• The  oxida%on  of  sulfur  to  sulfate  ion  produces  sulfuric  
acid.   The   reac%on   is   mediated   by   acid   tolerant  
Thiobacillus  thiooxidans.  
           2H2S  +  4O2  à  4H+  +  2SO42-­‐
Microbial Oxidation & Reduction Processes

Nitrogen  Transforma%on  
•The   Microbially   medicated   conversion   of   ammonium   nitrogen   to  
nitrate   is   a   significant   nitrifica%on   process   during   biological   waste  
treatment.  The  ammonia  ion  is  first  bio  -­‐  degraded  by  nitrosomonas  and  
then  by  nitrobacter.  
•2NH4+  +  3O  à  4H+  +  2NO2-­‐  +  2H2O;  2NO2-­‐  +  O2  à  2NO3-­‐  
•In  anaerobic  condi%on,  the  nitrate  ion  is  reduced  to  lower  oxida%on  
states  nitrogen  by  microbial  ac%on.  
•2NO3-­‐  +  3{CH2O}  à  2NO2-­‐  +  H2O  +  CO2  
•Nitrifica%on  occurs  in  two  stages:    
Nitrosomonas:    NH4+  +  1  ½  O2  <=>  NO2-­‐  +  H2O  +  2H+    
Nitrobacter:    NO2-­‐  +  ½  O2  <=>  NO3-­‐  
•Denitrifica%on   is   almost   the   reverse   of   nitrifica%on   except   the   end  
products   are   N2O   and   N2.     Anaerobic   condi%ons,   Abundance   of  
decomposable  ma\er  ,  Presence  of  denitrify  bacteria  (many  species)  are  
the  factors  that  favor  denitrifica%on.              
2NO3-­‐  à    2NO2-­‐  à  2NO  à  N2O  àN2  
 
 Microbial Oxidation & Reduction Processes
Carbon Transformation
•The photosynthetic bacteria use light energy to reduce carbon
dioxide into the high energy organic compound.
                                                   h‫ע‬
CO2  +  H2O                                        {CH2O}  +  O2  
•The organic matter is then oxidized to carbon dioxide in presence
of molecular oxygen. {CH2O}  +  O2  à  CO2  +  H2O  
•Methane forming bacteria (methanobacterium) oxidizes the
organic matter to carbon dioxide in anoxic condition.
2{CH2O}  à  CH4  +  CO2  
•The biodegradation of organic matter in municipal wastewater
treatment produces carbon dioxide.
{CH2O}  +  O2  à  CO2  +  H2O  +  Biomass
Transforma%on  of  Iron  
Some   bacteria   like   Thiobacillus   thioxidans,   Thiobacillus   ferroxidans   &   ferroxidans  
are  able  to  catalyze  the  oxygena%on  of  ferrous  iron.  
 Fe2+    Fe3+  +  e-­‐  
4Fe(II)  +  4H+  +  O2  à  4Fe(III)  +  2H2O  
 
 Significances of Gas Solubility in water

• The  gas  transfer  or  retaining  proper%es  of  

water   body   is   dependent   upon   the  
temperature   and   pressure   status   of   the  
environment.    
• There   exists   the   correla%on   of   these  
parameters   directly   in   response   to   the  
broader  quality  of  the  water  masses.    
• The   well   known   Henry   Law   may   be  
deviated  due  to  the  effect  of  temperature  
and  pressure  too.  
 
 Carbon Dioxide Solubility
 
• Carbon  dioxide  gas  is  exchanged  across  the  air  -­‐  water  
interface  as  per  following  equilibria:  
CO2  (g)                            CO2  (aq)  
• The   equilibrium   process   obeys   Henry’s   law,   but   the  
dissolved   carbon   dioxide   reacts   rapidly   with   water   to  
become  hydrated  as    
CO2  (aq)  +  H2O                            H2CO3  
• Rela%ve   to   the   exchange   process,   the   hydra%on  
reac%on   forming   carbonic   acid   occurs   quite   quickly.  
This   signifies   that   the   concentra%on   of   dissolved  
carbon  dioxide  gas  is  extremely  low.  
 
Effect of Temperature & Pressure in Water System
Chemical & Microbiological Quality
Chemical & Microbiological Quality
Chemical & Microbiological Quality
Gas Transfer Mechanism