Abstract:
Water is an essential natural resource for sustaining existence of humans and their
surroundings that are perceived to be free and unlimited gift given to us. As regards the
chemical composition of surface or subsurface, it can easily be seen as one of the most
significant factors having a great effect on the usefulness of water for all kinds of life as well
as industrial or agricultural purposes. Freshwater is found as surface as well as groundwater.
On one hand groundwater constitutes barely 0.6% from the overall water available on this
planet; on the other hand it is the most reliable and the most recommended source of water
for domestic purposes everywhere. This is more so especially in countries with sufficient
potential to achieve the status of developed nations, such as India, as processing of this
groundwater, with disinfection, is generally not needed. Groundwater covers 80% of the total
requirement of water for domestic use and 50% of in rural India for agrarian purposes. In the
present age of economic and industrial development, groundwater is becoming more and
more polluted because of industrialization and urbanization. During the last few decades, the
continually-increasing population, urbanization and industrialization, as well as exploitation
of available resources have yielded a kind of decline in the quality level of water and also
decrease in the amount of water available per capital in various developing countries.
When it comes to considering health detriments due to fluoride, it can be seen as a grave
concern related to our environment everywhere in the world. These detriments can happen
owing to changes in nature as well as due to human activities. Drinking water containing
fluoride may be beneficial or detrimental depending upon its concentration and total amount
consumed. Fluoride concentrations between 0.5-1.5 mg/L are beneficial, especially to infants
for the prevention of dental caries or tooth decay, but concentrations above 1.5 mg/L cause
mottling of teeth in mild cases but fluorosis (dental or skeletal) and several neurological
disorders in severe cases. Defluoridation is usually done through absorption, chemical as well
as electrochemical processes, and dialysis or the ion-exchange process. When it comes to
choosing the most effective, eco-friendly and cost-effective process, absorption can be found
as the best one.
Among various treatment procedure used for defluoridation, batch adsorption process gives
satisfactory results to an extent. In this study, we have studied fluoride removal using citrus
iv
limetta peel, Java Plum Seed (Syzygium cumini), banana peel, groundnut shell, Neem leaves
(Azadirachta indica) as it serves as a low cost, easily available and a highly effective
adsorbent. These adsorbents were collected from local market of Roorkee, Haridwar,
Uttarakhand, India. It was washed with distilled water several times, crushed and sieved to
get a particle size range of 0.5 – 2.0 mm. The adsorbents so developed were used for removal
of fluoride and further the batch process is optimized by varying the adsorbent dose, pH,
fluoride concentration and time of contact. The detailed characterization pertaining to physiochemical,
structural and morphological properties of agricultural waste were also carried out.
The adsorption capacity of all adsorbents was compared to that of GAC. GAC was chosen as
the control since a considerable work has been reported in the literature. On the basis of result
obtained, we can conclude that java plum (Syzygium cumini) seed is the best adsorbent in the
present list of adsorbents for defluoridation process for same biological conditions.
Equilibrium and kinetics and modeling of adsorption and SAB process were also done. To
study the mechanism of adsorbate transfer from the solution to the surface of the adsorption
particles Weber-Morris’s equation was applied. It was observed that macropore diffusion rate
is greater than micropore diffusion rate. The kinetic of the process has been studied using
pseudo first order, pseudo second order and Elovich model. The isotherm equation including
the conventional Freundlich, Langmuir and Temkin isotherm have been fitted with the
equilibrium adsorption and SAB data. The fitness of the isotherm towards the prediction of
specific uptake was analyzed by computing standard deviation to calculate squared sum of
errors (SSE) function.
Column and continuous studies are done so as to study the defluoridation capacity of the
adsorbent in continuous mode. The effect of flow rate, fluoride concentration and bed height
is studied. The Empty Bed Residence Time, Thomas model and bed Depth Service Time
design model were used to inspect the effect of the different operating variables such as bed
depth; flow rate and initial concentration. The performances of the column were tested on
these simple fixed bed design models. To evaluate the possibilities of regeneration and reuse
of the adsorbents, desorption experiments were conducted. We also examined the effects of
co-existing ions on the adsorption capacity in batch mode.
Bioaccumulation studies have been carried out for studying the effectiveness of single
microorganisms. The single cultures of nitrogen fixing bacteria Acinetobacter baumannii
v
(MTCC No.-11451) were used for fluoride bioaccumulation from water and soil. Initially the
microorganism acclimatized to grow at higher fluoride concentration and their ability to
accumulate fluoride was measured. The effect of initial fluoride concentration and sucrose (as
second carbon source) concentration on the removal efficiency was studied for single
microorganism. It was found to have maximum efficiency at about 20 mg/L of fluoride
concentration. Acinetobacter baumannii (MTCC No.-11451) was found to be most efficient
bacterial strain on the basis of fluoride removal capacity.
Simultaneous adsorption and bioaccumulation studies were conducted in SBB reactor using
Acinetobacter baumannii (MTCC No.-11451) immobilized on java plum seed (Syzygium
cumini). Optimum condition, estimated by adsorption and bioaccumulation studies was
maintained in SAB process. SAB process was used for removal of fluoride at higher
concentration than 20 mg/l from synthetic simulated waste water and real industrial effluent,
both in batch and continuous reactor. To overcome the drawbacks and adsorption and
bioaccumulation integration of adsorption in the form of immobilized cell technology and
bioremediation is carried out in the present study. The recent development, commonly known
as, simultaneously adsorption and bioaccumulation (SAB) has been used by a few researchers
and results was found to be better than individual adsorption or bioaccumulation. Due to the
biolayer formation on the adsorbent bed simultaneous adsorption and bioaccumulation occurs
simultaneously. Adsorption and bioaccumulation have successfully supplemented to each
other here microbial mass bio accumulate toxic substance into simpler product as well as
biosorbes some of them on the other hand. Adsorption of toxic substances on to a adsorbent
reduces the inhibitory effect of the substance on the microbial growth. Accordingly,
simultaneous adsorption and bioaccumulation (SAB) is expected to be more efficient as
compared to adsorption and bioaccumulation alone.
Granular/powdered activated carbon is most widely used adsorbent for fluoride removal. The
surface chemistry of activated carbon on the chemical characteristic of adsorbate such as
functional group, ionic nature, polarity and solubility determine the nature of binding
mechanism as well as the extent and strength of adsorption. GAC has good adsorption
capacity and biolayer formation capacity. In the search of more effective and economical
adsorbents agriculture byproducts e.g. citrus lemetta peel, banana peel, groundnut shell, neem
leaves, turmeric, GAC and java plum seed, etc. were used in present work for the removal of
fluoride compounds. These adsorbents have been successfully used for the adsorptive
vi
removal of many other toxic substances. However SAB process along with this agriculture
waste based adsorbent for fluoride removal has not been reported yet.
Continuous studies were carried out using packed column along with Acinetobacter
baumannii (MTCC No.-11451). The effect of bed height and flow rate on fluoride removal
capacity of the column was studied. The continuous processes were found to be feasible and
effective for removal of higher concentrations of fluoride pointing towards development of
new and efficient technology for fluoride removal.
We had taken two aquatic plant species which were selected for the studies were Ipomoea
aquatica [Water spinach] and Eichhornia crassipes [Water Hyacinth] in the
phytoremedation of fluoride study. These were very common aquatic plants which can easily
found in water bodies like pond, lake, river etc. They were grown in plant growth chamber
and studied for 10 days exposure period to fluoride of different concentrations and pH. The
removal efficiency of Ipomoea aquatica [Water spinach] was found 40.988 % and for
Eichhornia crassipes [Water Hyacinth] it was found 58.894 %. Results show that water
hyacinth had better removal efficiency to remediate fluoride. In pH study for both the plants
shows negative results, as we increase or decrees the pH of the solution the removal
efficiency was decreased for both the plants. Accumulation of fluoride was found mainly in
the roots for both plants. It was found 872.866 μg/g Dw for Ipomoea aquatica and 1148.479
μg/g Dw for Eichhornia crassipes. Both the plants show the biomass degradation due to the
fluoride exposure.