cwe journal volume 7 number 2

INTRODUCTION

The air around us contains aromaticcompounds originated from citizens’ daily activityin residential, trade and industrial areas whichcreate the modern societies. Daily exposure to odorpollution is a part of modern life1. Odor is generallydefined as the feeling caused by chemicalcompounds which are called odorants while beingperceived by stimulating the sensory receptors ofsmell2. Odor is a combination of one or more volatilechemical compound that humans perceive bythe sense of olfaction3. According to the EPAdefinition odorous compounds are pollutants whileannoying the human or affect his health or welfare4.

Current World Environment Vol. 7(2), 191-200 (2012)

Assessment of Odor Annoying Impacts on Tradeand Serving Centers Close to a Vegetable Oil

Manufacturing Plant

MOHAMMAD REZA MONAZZAM1*, M. AVISHAN2,M.ASGHARI1 and M. BOUBEHREJH2

1Department of Occupational Hygiene, School of Public Health and Center for AirPollution Research (CAPR), Institute for Environmental Research (IER),

Tehran University of Medical Sciences, Tehran, Iran.2Air Pollution Bureau, Iran Department of the Environment, Tehran, Iran.

(Received: July 12, 2012; Accepted: September 17, 2012)

ABSTRACT

The environmental odor pollution emitted from different sources has undesirable impactson communities’ health and welfare in a way that caused increasing public worry and complainsaround the world. Pars Vegetable Oil Processing Plant (PVOPP) is located near populated residentialareas in Tehran; hence, many people are exposed to the plant process annoying odor daily. Inorder to assess the odor annoying impacts on its nearby business centers a social survey hasbeen applied. In the field area 200 questionnaires were intended to be filled out but 180 of themhave been completed by the respondents (90%). Almost 98% of the respondents have perceivedthe odor from the outdoor source in their working places which is known as the industry by 78%of them. Among the respondents 42% of them have defined the odor as intolerable. Consideringthat industry has been recognized as the most important external parameter which affect thequality of working environments, the impact of this industrial unit on decreasing the quality level ofworking conditions is more obvious. The duration of presence in the working place and record ofservice are related to disorders in working activity and emotion and thus confirm the odor pollutionimpacts on the employees’ efficiency.

Key words: Odor pollution, questionnaire, annoyance, Vegetable Oil Manufacturing.

Researches show that environmental irritants likenoise and odor can have considerable impacts onthe physical and moral condition of the people andtheir quality of life5-6. If this exposure is long orintensive the unpleasantness would be convertedto annoyance gradually. Annoyance is describedas an unpleasant feeling about a defined factor orcondition which adversely affects the individualsor groups9. The human perception of odor is theresult of a set of physiological and mental reactionswhich identify the odor quality7. Hence, thecompatibility of odor perception is widely personalamong individuals which their reaction is differentdue to their age and health status8. The unpleasantimpacts of odor emitted from different sources have

192 MONAZZAM et al., Curr. World Environ., Vol. 7(2), 191-200 (2012)

increased the public complaints and worry allaround the world, more people are sensitive to theissue and request for more control and moreeffective measures to decrease the odor emissionby authorities9. Odorous compounds impress thehealth and welfare of communities11. Since WorldHealth Organization (WHO) defines health as “astate of complete physical, mental and social well-being and not merely the absence of disease orinfirmity”11, in recent years health and environmentalorganizations have paid more attention to the odorpollution issue because of its negative impacts onthe neighborhoods. Researches about odorpollution effects on human health concluded thatthey could be categorized to physiological andmental impacts12.

The most common odor-related symptomsare reported burning eyes, soar throat, noseirritation, headache, nausea, cough, nosecongestion and short breath13-18. Mental effects aredepression18,20, fatigue and sleepiness21-25 mooddisturbance26-30 and also decrease in the individualsworking efficiency31, 32.

Environmental odor can impress theevaluation of indoor and outdoor air quality andworks as a warning sign. Nowadays, publicawareness about the association of indoor airquality (home and office) with their health haveincreased which could be due to more amount oftime spent indoors, aging population, decreasingair conditioning to reduce the energy consumption,increased usage of chemical compound in workingand living environment and also outdoor airpollution. Millions of Americans spend two thousandhours or more per year in closed spaces and sogradually become prone to ailments related toindoor pollutant exposure such as odorousmaterials33. Therefore, identifying the surroundingair combination is very significant which lead tovarious investigations implemented about odorpollution annoyance impact assessment on nearbyresidents and/or the employees working in odorousindustries and facilities and odor related mentaland physical health effects34.

On the basis of the wide reviews, noinvestigation about odor annoyance effects on non-industrial workers which work in areas affected by

odor has been done yet. So, it is the first time in Iranthat the nuisance impact of emitted odor from an oilprocessing plant on the trade and serviceemployees around has been implemented.

MATERIAL AND METHODS

This study has been done in a crowdedarea in southern part of Tehran. The currentpopulation of Tehran as the capital of Iran is7,975,679[34]. In spite of the measures taken toorganize the industries settlement out of the city’sarea, there are still some old industries working.One of these active units is Pars Vegetable OilProcessing Plant (PVOPP) which has been selectedas the odor source in the area. Figure 1 illustratesthe plant location and study area. It should also bementioned that the same level of impressibility hasbeen determined for both trade and serving centersconsidering their approximately equal distribution.

A questionnaire method has been appliedto examine the odor annoyance for workers in thestudy area. The questionnaires were filled out indirect interview in summer 2011. In order toimplement the research, 200 workers wereselected stochastically in trade and serving areaand were directly interviewed by trainedquestioners.

While designing the questionnaireGerman VDI Guideline (VDI3883 -Part II) publishedin 1993 and researches about CommunityResponse to Odorous Emissions in other countrieshave been considered35. It is necessary to mentionthat the guideline is used in various researches tostudy the community response to odor annoyancein neighborhoods. So, in this study it has been triedto design an appropriate questionnaire consideringthe necessary parameters for odor annoyancesurvey in non-industrial working environmentaround the odor source by keeping the generalstructure of the guideline recommendedquestionnaire or in some cases adding or changingthe related questions. Questions could becategorized in four sections including a) personalcharacteristics (age, gender, type of job, length ofworking time, working place conditions, record ofservice,… ) b) environmental issues and personalhealth conditions ( environmental problems,

193MONAZZAM et al., Curr. World Environ., Vol. 7(2), 191-200 (2012)

Table 1: Socio-statistical Data

N=180 Mean Standard Deviation Range

Age (year) 35.8 13 17-75Duration of presence at work (hour) 9.8 3 1-17Workspace area (m) 26 23 1-120Record of service ( year) 9.6 10.3 1-48

Table 2: Workers’ common health problems

Health problem Percentage

Irritation symptoms 21Not getting enough sleep 21Headache 19Breathing difficulties 14Difficulties falling asleep 17Cough 14Waking up during the night 12Stomach disorders 9Difficulties falling asleep after Waking up 8

Table 3: Odor intensity perceived by workers

Odor intensity Percentage

Unbearably strong 14Very strong 9Strong 27Distinct 23Weak 19Very weak 6Not perceptible 2

Table 4: Odor hedonic tone perceived by workers

Hedonic tone Percent

Very pleasant 3PleasantModerately pleasantMildly pleasantNeutral odor / No odorMildly unpleasant 14Moderately unpleasant 5Unpleasant 36Offensive 42

personal health problems,… ) c) odor nuisancevariables ( type of source, intensity, frequency,quality, level of disturbance and annoyance,hedonic tone, acceptability,… ) and the final part d)which is focused on individuals’ daily activity andemotion. The related scales for the variables wouldbe presented in the result chapter comprehensively.

In order to decrease the residents’sensitivity to the odor source and also minimizingthe error percentage in results, other environmental

aspects of the region have been also scripted inthe questionnaire. Data analysis has been doneusing SPSS (Version 18).

RESULT

Part 1: Social and Statistical variables DataAmong 200 questionnaires predicted for

the study area, 180 have been completed by therespondents; the response rate is 90%. Accordingto the questionnaires 174 (96.7%) of the

respondents were male with the mean age of 35.8(with the range of 17 to 75 years). Considering thevery few number of women participated in answeringthe questionnaires the related data have beenremoved. 64% of respondents were working intrade and 36% in serving centers.

The mean area of studied work places isabout 26 2m and the average duration of presenceat work is calculated to 9.8 ± 2.9 hr/day. Data relatedto socio-statistical variables are summarized inTable1.

Data related to environmental issues


Table 5: Relationship between odor-related variableswith odor source and mutual comparison of variables

Test Variable Odor source Post Hoc (ααααα=.05) (ααααα=.033)

Odor intensity .010 Vehicle < IndustryP=.006

negative impacts of .001 Waste water < Industryactivity and emotion P<.001

Vehicle < IndustryUnpleasantness .032 P=.009Odor disturbance >.001 * Waste water < Industry

P<.001Annoyance .004 Waste water < Industry

P=.001

Table 6: Relationship between odor-related variableswith odor quality and Mutual comparison of variables

Test Variable Odor source Post Hoc (ααααα=.05) (ααααα=.033)

Odor intensity .072 -negative impacts .001 Waste water < Burningon activity and P<.001 emotion Waste water < Sulfur

P=.001Unpleasantness .017 Burning < Sulfur

P=.006Odor disturbance .001 > Burning < Sulfur P<.013

Waste water < SulfurP<.001

Annoyance .001 Waste water < BurningP=.013Waste water < SulfurP<.001

showed that almost 87.7% of participants havechosen odor as the most considerable problem intheir working environment while 42.2% havementioned air pollution and 55.5% have impliednoise pollution.

Part 2: Personal Health Status DataIn this part data illustrated that eye irritation

(21%) and not getting enough sleep (21%) wereequally more common in respondents comparing

with other health problems. Data related to this partare briefed in Table2.

Generally 69% of the respondents had atleast on of the problems mentioned in the abovetable. 69% showed no allergy symptoms. 39% ofthe allergic people had to take medicine. Only 19%of the participants were regular smokers.

Part 3: Odor characteristics


Fig. 1: Map of Pars Vegetable Oil Processing Plant Location and Study Area

Sensitivity to odorData resulted from this item showed that

98% of the individuals have perceived the odorfrom the outdoor source in their working placeswhich is known as the industry (Vegetable OilManufacturing plant) by 78% of them. Figures 1and 2 illustrate the odor source and quality. Sulfuric,burning, sweet and wastewater are the options fordetermining odor quality.

Odor frequency

6 categories from 1 for once or lessmonthly to 6 for frequently in a day have beenoffered for this variable, the last item frequently in aday has been chosen by 91% of the respondents.

Odor intensity7 classes from 0 for not perceptible to 6 for

unbearably strong have been chosen fordetermining the intensity of odor, 23% of the workershave mentioned it as distinct and totally 73% have

Fig. 3: Proportion of odor quality

Fig. 2: Proportion of odor sources


Fig. 4: Odor annoyance perceived by workers

Fig. 5: Odor disturbance perceived by workers

Fig. 6: Odor negative impact on workers’ activity and emotion

chosen distinct to unbearable options. Results areshown in Table3.

Hedonic tone

This variable has been divided to 9 classesfrom -4 for offensive to +4 for very pleasant.

Annoyance


7 scales have been offered in thequestionnaire for this variable from 0 for noannoyance to 6 for maximum annoyance, 41% ofthe respondents have chosen the maximumannoyance item. Nearly 66.6% of the people haveanswered 4 to 6. The sample annoyance mean hasbeen 4.64 ( ± 1.58). The confidence interval forodor annoyance level which has been calculatedby non-parametric percentile bootstrapping was 4.6and 4.2. Figure 3 illustrates the related results.

DisturbanceIn order to determine the disturbance level

it has been divided to 11 categories from 0 for nodisturbance to 10 for maximum disturbance. 37.2%of the respondents have selected number 10 whichmeans maximum disturbance. The mean odordisturbance degree was 7.4 ( ± 4.6). Theconfidence interval for odor disturbance has beencalculated by non-parametric percentilebootstrapping which was 7.0 and 7.8. Figure 4shows the related results.

Odor acceptability2 scales have been defined in this part (0

for acceptable and 1 for unacceptable). The resultsshow that 82% of the respondents have known theodor unacceptable, 33% of which have complainedto the related authorities.

The statistical relationship between therespondents’ adaptability to odor and complainingto the local governors has been calculated byFisher’s Exact 2-sided Test which was significant(p<0.002).Part 4: Odor negative impacts on workers’activity and emotion

Results related to this topic showed that10% of the respondents have always felt the odornegative effects on their activity and emotion. Figure5 illustrates the result of this section.

There is a significant relationship betweenthe duration of time spent at work with theevidences these effects. (Spearman r=+0.26p<0.001). The relationship between record ofservice and showing these impacts is significantadditionally. (Spearman r= +0.34 p< 0.001). Recordof service has also significant relationship with odor

disturbance and annoyance but no relationshipwere found with odor intensity.

Spearman correlation coefficientsbetween odor perception intensity, negativeimpacts on activity and emotion, hedonic tone,disturbance and annoyance show significantrelationship among them (p<0.001). The coefficientvalues are +0.40 to +0.83.

The effect of odor source on its intensity,negative impacts on activity and emotion,unpleasantness, disturbance and annoyance havebeen studied by Kruskal-Wallis test at first, thendifferent sources have been compared by repeatingMann-Whitney U test and applying Bonferronicorrection in order to adjust type 1 error whilecomparing multiple variables.

According to the results, this industrialsource odor and its unpleasantness are significantlymore than other sources which were defined in thisstudy.

The role of odor type on the relatedproperties including negative impacts on activityand emotion, unpleasantness, disturbance andannoyance have been also investigated by Kruskal-Wallis test at first, then different sources have beencompared by repeating Mann-Whitney U test andapplying Bonferroni correction in order to adjusttype 1 error while comparing multiple variables.

Odor intensity is not significantly differentin defined odor types but sulfur type is moreunpleasant, annoying and disturbing than others.

DISCUSSION

The main objective of this research hasbeen assessment of industrial source odor relatedparameters on non-industrial workers in the region.In many countries investigations about odorpollution have been considered and the impacts ofthis environmental problem on nearby residents orthe employees working in the place which is knownas odor source have been studied. Unfortunatelythere is no research about odor related effects onother workers close by. This group of people is notexposed to odor as long as near residents and also


is not intensely in contact with odorous materialslike industrial workers, but the result of this studyshows that odor pollution is unbearable for 82% ofthe respondents.

Considering that industry has beenrecognized as the most important externalparameter which affect the quality of workingenvironments, the impact of this plant on decreasingthe quality level of working conditions is moreobvious.

The duration of presence in the workingplace and record of service are related to disordersin working activity and emotion and thus confirmthe odor pollution impacts on the employees’efficiency. The results achieved by Ludvigson et al.(1989) and Wilkinson (2002) have also mentionedthis.

According to Winneke and Steinheider in1993 38 and also Thuerauf et al. in 2009 39 genderaffects the intensity of odor perception and femalesfeel more level of annoyance. In this study, alsoaverage values women have given to annoyanceand disturbance levels are more than men(Although due to the insufficient number of womenthe test is not strong enough).

In this research there is an adverserelationship between age increase with annoyance,the level of which is less in older workers thanyounger ones. This conclusion is confirmed by theresults from Konstantinidis et al (2006), Larsson etal (2009) ,Pierre M. Cavalini and RAJESH KUMARSINGH researches38- 41.

On the basis of results of this study, morecomprehensive investigations about odor pollutionmanagement in different fields is recommended.Moreover, effective measures to decrease andcontrol the odor related impacts and providing thecitizens’ health is emphasized. It should also bementioned that compliance with the regulationsrelated to industrial positioning and keeping thepossible maximum distance from residential areaare effective ways of reducing air pollution such asodor and increasing the residents’ quality of life.

Considering the lack of comprehensivemanagement systems to decrease the odorpollution and also absence of necessary relatedregulations in Iran, it is expected that the results ofsuch researches would be an effective factor inmaking the authorities more sensitive and amotivation to develop comprehensive studies aboutodor pollution management plan.

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INTRODUCTION

Cadmium is a trace heavy metal of greatimportance in environmental protection since it is ahighly toxic element. 1 Determination of cadmiumin environment samples is so important as thiselement exist in environment samples as acontaminant originating from industrial or urbanwaste pollution. As a result of high toxicity even atlow concentrations, and various matrixinterferences in real samples, developing anaccurate, precise and selective method for cadmiumdetermination is necessary.

Different instrumental methods such asflame atomic absorption spectrometry (FAAS),2

graphite furnace atomic absorption spectrometry(GFAAS),3 inductively coupled plasma atomicemission spectrometric (ICP-AES),4 andelectrochemical methods5 have been used forcadmium determination. Among these methods,potentiometric methods using ion sensors arecommon due to their accuracy, high rate, low costand also being non-destructive6. Potentiometriccarbon paste electrodes, in comparison to polymeric


Determination of Cadmium (II) Ions in EnvironmentalSamples : A Potentiometric Sensor

MOHAMMAD KARIMI, FOROUZAN ABOUFAZELI, HAMID REZA LOTFI ZADEH ZHAD,OMID SADEGHI and EZZATOLLAH NAJAFI1

Department of Chemistry, Shahr-e-Rey Branch, Islamic Azad University,P. O. Box 18735-334, Tehran, Iran.


ABSTRACT

A sensor electrode was modified by multi-walled carbon nanotubes functionalized bydithizone. The electrode was used for determination of trace amounts of cadmium (II) ions. Theelectrode composition was 67% graphite powder, paraffin 23%, 10% modified MWCNTs (W/W).The linear range for lead (II) was 1.8×10-7 to 1.0×10-4 mol L”1 and the limit of detection was obtained1.0×10-7 mol L”1. The lifetime of the electrode was 12 weeks and a fast response time was observed.The electrode was used for determination of trace amounts of Cd(II) ions in standard referencematerials of water and soil.

Key words: Sensor, Cadmium; Modified MWCNTs, Potentiometry, dithizone.

membrane electrodes, posses very attractiveproperties such as ease of preparation, renewablesurface, stability of their response, low ohmicresistance and no need of internal solution7.

In this technique, a chemical modifier isintroduced to carbon paste electrode to increasethe methods sensitivity8. In carbon paste methods,carbon nano-tubes have attract lots of attentionas a modifier due to having high electricalconductivity, high mechanical and thermalstability9. These nano-tubes can be easily modifiedwith a ligand in order to change their selectivitytoward a specific ion.

In this work, multi-walled carbonnanotubes were functionalized by dithizone. Thematerial was characterized by FT-IR, SEM andelemental analysis. A carbon paste sensor wasmodified by this material and used for determinationcadmium content in environmental samples. Theeffective parameters on response of the electrodewere investigated and good selectivity towardcadmium ion was observed. This electrode can beused as fast simple method for determination of

202 KARIMI et al., Curr. World Environ., Vol. 7(2), 201-206 (2012)

cadmium content in environmental samples withlow concentrations.

MATERIALS AND METHODS

Regents and solutionsAll reagents were of analytical grade and

used without any further purification. Paraffin oil andCadmium nitrate were purchased from Sigma-Aldrich Company. Carboxyl modified multiwalledcarbon nanotube (COOH-MWCNT) was purchasedfrom Neutrino Company (Tehran-Iran). Multiwalledcarbon nanotubes were 30 µm length and 5-10 nmin diameter. The other chemicals such as Oxalylchloride and dithizone were from Merck Company.All solutions were made using deionized water. Thedeionized water was provided from a Milli-Q(Millipore, Bedford, MA, USA) purification system.

Preparation of dithizone functionalizedmultiwalled carbon nanotube

For synthesis of dithizone functionalizedmultiwalled carbon nanotube, 1.0 g of COOH-MWCNT was suspended in 50 mL of dried CH2Cl2under nitrogen atmosphere. Then 5 mL of oxalylchloride was slowly added to mixture from adropping funnel. After stirring for 24 h, CH2Cl2 wasremoved under reduced pressure, and the residuewas suspended again in 50 mL of dried methanol.Then 5 mL triethylamine and excess amount ofdithizone (2 g) were added to reaction mixture. Afterrefluxing the mixture for 24 h, methanol was removedunder reduced pressure and the sorbent was driedat 80 °C under vacuum. The formation of dithizonefunctionalized multiwalled carbon nanotube wasconfirmed by IR spectroscopy, elemental analysisand SEM micrograph. A schematic diagram of thissynthesis is represented in Fig. 1.

ApparatusThe reference electrode was a glass cell,

consisted of an R684 model Analion Ag/AgCldouble junction. A Corning ion analyzer 250pH/mV meter was used for the potential measurements.The pH meter was a digital WTW Metrohm 827 Ionanalyzer (Switzerland) equipped with a combinedglass-calomel electrode. The pH adjustments weremade at 25±1°C. The elemental analyses (CHNS)were performed on a Thermo Finnigan Flash-2000microanalyzer (Italy). IR spectra were recorded on

a Bruker IFS-66 FT-IR Spectrophotometer. The SEMmicrograph was recorded by a Vega-TeScanscanning electron microscope.

Preparation of modified carbon paste electrodeBy thoroughly mixing an accurate of

amount of graphite 67% graphite powder, paraffin23%, 10% modified MWCNTs (W/W) the carbonpaste electrode was prepared. The electrode bodywas fabricated from a glass tube of i.d. 5 mm and aheight of 3 cm. To avoid possible air gaps, the pastewas packed carefully into the tube tip, oftenenhancing the electrode resistance. A copper wirewas inserted into the opposite end to establishelectrical contact. The external electrode surfacewas smoothed on a soft paper. A new surface wasproduced by scraping out the old surface andreplacing the carbon paste.

Electrode conditioning and Emf measurementsThe electrode surfaces were conditioned

in a solution of 1.0×10"4 mol L-1 Cd(NO3)2 and1.0×10"3 mol L-1 NaNO3 for 24 hours. The electrodeswere rinsed by deionized and polished beforepotentiometric measurements. In all solutions thepotential was measured versus Ag, AgCl(s)reference electrode.

The electrochemical cell can berepresented as follows:

Ag, AgCl (s), KCl (3 mol L-1) || analyte solution |carbon paste electrode

Sample preparation

The soil standard reference material wasdigested in an 8 mL mixture of 5% aqua regia withthe assistance of a microwave digestion system.Digestion was carried out for 2 min at 250 W, 2 minat 0 W, 6 min at 250 W, 5 min at 400 W and 8 min at550 W, and the mixture was then vented for 8 minand the residue from this digestion was then dilutedwith deionized water 10.

RESULTS AND DISCUSSION

Dithizone functionalized multiwalled carbonnanotube characterization

The reaction of chlorine group in acylchloride with amine group in dithizone group leads

203KARIMI et al., Curr. World Environ., Vol. 7(2), 201-206 (2012)

Table 1: Optimization of the electrode composition

Electro Graphite Paraffin Modified Slope Linear range R2

de No. powder (%) MWCNTs (mV) (mol L-1)(%) (%)

1 75 25 0 15.3±6.4 - -2 72 25 3 22.7±2.8 5.0×10-5 to 5.0×10-2 0.9323 70 25 5 25.1±2.4 7.5×10-6 to 1.0×10-3 0.9414 68 25 7 26.3±2.1 1.0×10-6 to 3.5×10-4 0.9525 66 25 9 27.9±1.7 5.5×10-7 to 1.0×10-4 0.9616 64 25 11 27.7±1.8 6.5×10-7 to 1.0×10-4 0.9667 65 25 10 28.9±1.5 2.7×10-7 to 1.0×10-4 0.9738 67 23 10 29.4±1.3 1.8×10-7 to 1.0×10-4 0.983

Table 2: Matched potential selectivitycoefficient for interfering cations

interfering ions (X)MPMHg,Xk

Na+ 3.5×10-4

K+ 5.8×10-4

Cs+ 4.3×10-4

Ca2+ 6.8×10-4

Mg2+ 2.5×10-4

Pb2+ 5.3×10-3

Ni2+ 4.6×10-3

Cu2+ 5.7×10-3

Cr3+ 2.4×10-3

Fe3+ 6.8×10-3

Ag+ 2.5×10-3

Zn2+ 3.6×10-3

Table 3: Recovery of determination of Cd(II) ions in certified reference materials

Sample Unit Concentration Recovery

Certified Found (%)

NIST 1640 (Drinking water) µg L-1 22.79 22.27 97.7SRM 2709 (San Joaquin Soil) mg kg-1 0.371 0.35 94.3

to formation of this composite. A schematic diagramof this synthesis is represented in Fig. 1. Theformation of dithizone functionalized multiwalledcarbon nanotube was confirmed by IRspectroscopy, elemental analysis and SEMmicrograph. IR spectrum of this composite is asfollow; IR (KBr, cm-1): 3400 (NH), 3017 (CH,

aromatic), 2964 (CH, aliphatic), 1563 (C=C,aromatic), 1318 (C=S), 1237 (N=N) and 890(MWCNT). In order to investigate the amount ofgrafted dithizone, elemental analysis wasperformed on this composite. According toelemental analysis results (%C=18.12, %H=1.81,%N=5.27, %S= 2.99), the dithizone concentration

on the surface of this composite is approximately0.94 mmol g-1. Finally, in order to investigate themorphology and size of this composite, SEMmicrograph was performed on this modifiedMWCNT. According to the SEM micrograph, thenano-structure of MWCNT remained unchangedafter functionalization and the multiwalled carbonnanotubes have approximately 20 nm diameter(Fig. 2).

Electrode compositionThe electrode composition is the most

important factor in the responses and selectivity ofthe electrode. Different amounts of graphite powder,paraffin oil and modified MWCNTs were thoroughlymixed and the responses are listed in Table 1. Inthe first study no modifier was added to the electrode


Fig. 1: A schematic model for modification of MWCNTs by dithizone

Fig. 2: SEM micrograph of modified MWCNTs

and only graphite powder, paraffin oil were used(electrode no. 1). In the next electrodes differentamounts of modified MWCNTs were added to theelectrode (electrode no. 2-7). It was observed thatthe electrode performance can improve by addingmodified MWCNTs. This should be result of twofactors: 1) improving the conductivity of the electrodewhich is the result of high conductivity of MWCNTs;2) complexation of cadmium ion with dithizonewhich increases the analyte concentration on thesurface of the electrode. The response of theelectrode was increased with adding modifiedMWCNTs up to 10% (electrode no. 7) and in higher

values the Nernstian slope was decreased(electrode no. 6). By changing the composition ratioto 67% graphite powder, paraffin 23%, 10%modified MWCNTs in electrode no. 8 the best resultswere ontained. A Nerstian solpe of 29.4 mV in alinear range of 1.8×10-7 to 1.0×10-4 mol L-1 wasobtained. The standard deviation for ten replicateswas 1.3 mV

Calibration curveQuantitative determination of cadmium (II)

ions was done by a calibration curve in the linearrange of 1.8×10-7 to 1.0×10-4 mol L-1 versus Emf

measurements. The calibration curve is shown inFig. 3. The detection limit of the electrode wascalculated by extrapolating the linear parts of theion selective calibration curve11,12. The limit ofdetection of the electrode was 1.0×10-7 mol L-1.

Influences of pHThe effect of pH of the test solution on the

sensor potential was investigated by following thepotential variation of the sensor over the pH rangeof 2.0 to 9.0. The pH of a sample solution of 1×10-5

mol L-1 of cadmium (II) ion was adjusted byintroducing small drops of hydrochloric acid solution(0.10 mol L-1) and/or sodium hydroxide solution(0.10 mol L-1). The result of this study is shown inFig. 4. The results show that the potentials of thesensor remain constant from pH of 3.0 to 7.0. Under


Fig. 3: The calibration curve for Cd (II) ion

Fig. 4: Influence of pH on electrode response to Cd(II)

more acidic conditions, the ligand may beprotonated and thereby lose its capacity to form acomplex with the metal ions, whereas for the higherpH values , the hydroxyl ions in the solution reactwith Cd(II) to make Cd(OH)2.

Study of Response timeThe average static response time was

defined as the required time for the sensors to reacha potential of 90% of the final equilibrium values,after successive immersions in a series of solutions,each having a 10-fold concentration difference11,12.To investigate this parameter, The Cd(II)concentration was changed in the liner range andthe results were studied. The results showed thatthe response time for the proposed electrode is 37seconds.

Influence of interference ionsThe selectivity behavior is obviously one

of the important characteristics of membranesensors in which the possibility of reliablemeasurement of the target sample is determined.Matched potential method (MPM) is therecommended method for studying Influence ofinterferences ions in ion selective electrodes byIUPAC13. The method is base on measuring thespecific activity of the primary ion which is added toa reference solution. In this study the interferingions were successively added to an identicalreference solution with concentration of 1.0×10-6

mol L-1, until the measured potential matched toobtained value before adding the primary ions. Then

matched potential selectivity coefficient, MPMPb,Xk is

calculated from the resulting primary ion to the


interfering ion activity ratio, HgMPM

Pb,Xx

ak

a= Δ .14 The

interference of Na+, K+, Cs+, Ca2+, Mg2+, Pb2+, Ni2+,Cu2+, Cr3+, Fe3+, Ag+ and Zn2+ was investigated andshowed that they have no significant effect on the

response to Cd2+. The MPMPb,Xk values for the

interferences are shown in Table 2. The electrodeshowed a good selectivity toward Cadmium (II) ions.

LifetimeThe lifetime of an electrode is the period

of time that the electrode shows no changes in theefficiency of the measurements. The electrode wascalibrated periodically with standard cadmiumsolutions. The next time the electrode was calibratedin the next week. It was observed that within 12weeks no changes in the electrode response occur.After 12 weeks the sole was changed and lingerrange became more limited.

Method validation

Different type of standard referencematerials (water and soil) was used for validationof this method. The samples were digested bymentioned method and the Cd(II) contents wereanalysed by this method. As it can be seen in Table3, the results have good compatibility with certifiedones and this method can be consider as anaccurate and reliable method for cadmiumdetermination in environmental samples.

CONCLUSION

A paste electrode was developed fordetermination of cadmium ions. . The electrodecomposition was 67% graphite powder, paraffin23%, 10% modified MWCNTs (W/W). Effects ofelectrode composition, and pH on the electroderesponse were studied. The electrode has a longlifetime and a response time. A good selectivity tocadmium ion was observed which makes theelectrode a good candidate for determination ofcadmium content in environmental samples.Method validation was done by analysis of standardreference materials with a matrix of water and soil.

REFERENCES

1. Bowen H. J. M., Environmental chemistry ofthe elements, Academic Press, London,(1979).

2. Xiang G., Wen S., Wu X., Jiang X., He L. andLiu Y., Food Chem., 132: 532 (2012).

3. Maranhão T. A., Martendal E., Borges D. L.G., Carasek E., Welz B. and Curtius A. J.,Spectrochim. Acta B, 62: 1019 (2007).

4. Boevski I., Daskalova N. and Havezov I.,Spectrochim. Acta B, 55: 1643 (2000).

5. Wu K., Hu S., Fei J. and Bai W., Anal. Chim.Acta, 489: 215 (2003).

6. Khan A. A. and Paquiza L., Desalination, 272:278 (2011).

7. Zhang T., Chai Y., Yuan R. and Guo J., Anal.Methods, 4: 454 (2012).

8. Mashhadizadeh M. H., Khani H., Foroumadi

A. and Sagharichi P., Anal. Chim. Acta, 665:208 (2010).

9. Faridbod F., Ganjali M.R., Larijani B. andNorouzi P., Electrochim. Acta, 55: 234 (2009).

10. Sayar O., Lotfi Zadeh Zhad H.R., SadeghiO., Amani V., Najafi E., Tavassoli N., Biol. TraceElem. Res. DOI: 10.1007/s12011-012-9467-9

11. Gupta V. K., Singh A. K. and Gupta B., Anal.Chim. Acta, 575: 198 (2006).

12. Ganjali M. R., Norouzi P., Faridbod F., YousefiM., Naji L., Salavati-Niasari M., SensorActuat. B-Chem., 120: 494 (2007).

13. Buck P. R. and Lindner E., Pure Appl. Chem.,66: 2527 (1994).

14. Umezawa Y., Umezawa K., Hamada N., AokiH., Nakanishi J. U. N., Sato M., Ping Xiao K.and Nishimura Y., Pure Appl. Chem., 48: 127(1976).

INTRODUCTION

In recent years, the demands for energyhave grown very quickly due to the rapiddevelopment of certain growing economies,especially in Asia and the Middle East. Biofuelssuch as alcohols and biodiesel have beenproposed as alternatives for diesel engines1,2,3.Especially, the environmental issues concernedwith the exhaust gases emission by the usage offossil fuels also encourage the usage of biodiesel,which has proved to be ecofriendly far more thanfossil fuels. In particular, biodiesel has receivedwide attention as a replacement for diesel fuelbecause it is biodegradable, nontoxic and cansignificantly reduce toxic emissions and overall lifecycle emission of CO2 from the engine when burnedas a fuel4,5.

Biodiesel is known as a carbon neutralfuel because the carbon present in the exhaust was


Effects of Biodiesel and Engine Load on Some EmissionCharacteristics of a Direct Injection Diesel Engine

ALIREZA SHIRNESHAN1*, MORTEZA ALMASSI2, BARAT GHOBADIAN3,ALI MOHAMMAD BORGHEI1 and GHOLAM HASSAN NAJAFI3

1Department of Agricultural Machinery Engineering, Science and Research Branch,Islamic Azad University, P.O.Box 14515-755, Tehran, Iran.

2Department of Agricultural Mechanization, Science and Research Branch,Islamic Azad University, P.O.Box 14515-755, Tehran, Iran.

3 Department of Mechanics of Agricultural Machinery, Tarbiat Modares University,P.O.Box, 14115-111,Tehran, Iran.


ABSTRACT

In this research, experiments were conducted on a 4-cylinder direct-injection diesel engineusing biodiesel as an alternative fuel and their blends to investigate the emission characteristics ofthe engine under four engine loads (25%, 40%, 65% and 80%) at an engine speed of 1800 rev/min.A test was applied in which an engine was fueled with diesel and four different blends of diesel/biodiesel (B20, B40, B60 and B80) made from waste frying oil and the results were analyzed. Theuse of biodiesel resulted in lower emissions of hydrocarbon (HC) and CO and increased emissionsof CO2 and NOx. This study showed that the exhaust emissions of diesel/biodiesel blends werelower than those of the diesel fuels.

Key words: Emission, Biodiesel, Waste fraying oil, Diesel.

originally fixed from the atmosphere6-7. This supplydeficit will have serious implications for many non-oil producing countries which are dependent on oilimports. Furthermore, the extensive use of fossilfuels has increased the production of greenhousegases, especially carbon dioxide (CO2), thusexacerbating the greenhouse effect. The potentialto both reduce fossil fuel reliance and the releaseof CO2 to the atmosphere.

Biodiesel from waste cooking oil is a moreeconomical source of the fuel. Kulkarni and Dalai8

concluded that the engine performance of biodieselobtained from waste frying oil is better than that ofdiesel fuel while the emissions produced by theuse of biodiesel are less than those using dieselfuels except that there is an increase in NOx.

Lapuerta et al.,9 tested two differentbiodiesel fuels obtained from waste cooking oilswith different previous uses on diesel particulate

208 SHIRNESHAN et al., Curr. World Environ., Vol. 7(2), 207-212 (2012)

emissions. They found no important differences inemissions between the two tested biodiesel fuels.

Based on exhaustive engine tests, it canbe concluded that bio-diesel can be adopted as analternative fuel for existing conventional dieselengines without requiring any major modificationsin the mechanical system of the engines. Bio-dieselemissions in a conventional diesel engine containsubstantially less unburned HC, CO, sulfates,polycyclic aromatic hydrocarbons, nitratedpolycyclic aromatic hydrocarbons and PM thanconventional diesel emissions10-11. The NOxemissions from bio-diesel blends of various originsare slightly lower than those of conventional diesel,and the difference is greater for blends with higherpercentages of bio-diesel12. Other researchers haveobserved the same behavior for all vegetable oilblends of various origins13-15. Various studies haveshown that biodiesel made from waste cooking oilcan be used in different types of diesel engineswith no loss of efficiency16 and significant reductionsin PM emissions17-21, Co emissions17,20 and totalhydrocarbon (THC) emissions20-22 when comparedwith emissions from conventional fossil diesel fuel.The performance and smoke results obtained froman engine used for generating electricity, whenfueled with biodiesels of waste cooking oil origin,showed that the smoke reduction was about 60%for B100 and approximately 25% for B20 12. Doradoet al.,23 used waste olive oil in a four-stroke, three-cylinder, and 2.5 L direct injection engine with apower rating of 34 kW through an eight mode test.They achieved 58.9% reduction in CO, 8.6%reduction in CO2 and 57.7% reduction in SO2

emissions. On the other hand, increases of 32 and8.5% in the NOx emissions and specific fuelconsumption were observed in the B100 and B20mixtures, respectively. Murillo et al., (2007)24 testeda four-stroke diesel outboard engine running onconventional diesel, conventional diesel blendedwith certain amounts of waste cooking oil biodiesel(10, 30 and 50%), and pure bio-diesel and provedthat the bio-diesel blends are environmentallyfriendly alternatives to conventional diesel. Theyfound some reduction in power of approximately5% with B10 and B30, and 8% with B50 and B100with respect to the power obtained fromconventional diesel.

The biodiesel from waste cooking oil wastested by Meng et al.,24-25 on an unmodified dieselengine, and the results showed that under allconditions, the dynamical performance remainednormal. Moreover, B20 and B50 blend fuels createdunsatisfactory emissions, while the B20 blend fuelreduced PM, HC and CO emissions significantly. Inanother study, wasted cooking oil from restaurantswas used to produce neat biodiesel throughtransesterification, and this converted biodiesel wasthen used to prepare biodiesel/diesel blends. Theauthors of the study concluded that B20 and B50are the optimum fuel blends in terms of emissions26.

In this research, the performance of wastefrying oil methyl ester blended with diesel fuel inratios of 20% (B20), 40% (B40), 60% (B60) and80% (B80) was investigated and compared withthat of regular diesel in terms of emissions in dieselengine under four engine loads at an engine speedof 1800 rev/min.


The experiments were conducted on a fourcylinders, four-stroke, turbocharged direct injectiondiesel engine. The engine specifications are givenin Table 1.

The test engine was coupled to a hydraulicdynamometer providing a maximum engine powerof 110 KW with a ±0.1 KW of uncertainty to controlengine speed and load. The test engine wasoperated at different torques when different fuelswere tested. The load on the dynamometer wasmeasured by using a strain gauge load sensor thatwas calibrated by using standard weights justbefore the experiments. An inductive pickup speedsensor was used to measure the speed of theengine, and it was also calibrated by an opticaltachometer. An AVL DICOM4000 gas analyzer wasused to measure CO, CO2, NOx and HC emissions.

In the experiments, diesel fuel no. 2 andfour diesel fuel/biodiesel blends were tested. Wastefrying oil methyl ester was blended with diesel fuelin 0%, 20%, 40%, 60% and 80% proportions byvolume. The blends were prepared just before theexperiments. In the tests, wasted frying oil wassupplied from Modares university biodiesel institute.

209SHIRNESHAN et al., Curr. World Environ., Vol. 7(2), 207-212 (2012)

The specifications of the waste frying oil methylester are shown in Table 2.

All fuels were tested at 1800 rpm and fourengine partial loads (25%, 40%, 65% and 80%).The general testing procedure can be summarizedas follows. The engine was run with the diesel fuel.After completion of standard warm-up duration, theengine speed was increased to 3000 rpm. The testsand data collection were performed at four differentengine loads. The engine was kept running to flushout the diesel/biodiesel blend from the fuel lines,injection pump and the injectors for a while beforeshutting down.

RESULTS

Experiments were performed at the ratedtorque speed of 1800 rev/min, and at 25%, 40%,65% and 80% engine loads.

At each engine load, experiments werecarried out for diesel and each blended fuel. In thispaper, the effects of engine load and biodiesel onemissions included HC, CO, CO2 and NOx wereinvestigated.

As shown in Fig. 1, for Diesel, the HCemission decreases with increase of engine load,due to the increase in combustion temperatureassociated with higher engine load. For biodieselblended fuel, the HC emission is lower than that ofdiesel and decreases with increase of biodiesel inthe fuel. However, for the biodiesel blended fuel,the HC emission, instead of decreasing straightlywith engine load, has a peak value at the 40%engine load. The reduced HC emission with

biodiesel blended diesel can be accounted for byseveral reasons as stated in Lapuerta et al.(2008)[8]. However, the lower volatility of biodieselcompared with diesel contributes to the largerdifference in HC emission at low engine loads. Themaximum concentrations of HC are 35 ppm, 29ppm, 27 ppm, 26 ppm and 25 ppm, respectively, fordiesel, B20, B40, B60, B80, indicating that themaximum HC emission declines with the additionof biodiesel.

The characteristics of CO emission areshown in Fig. 2. For each fuel, there is a decreaseof Co emission on increase of the engine load. Thepeak concentrations at the 25% engine load are0.04%, 0.037%, 0.036%, 0.035% and 0.035%,respectively, for diesel, B20, B40, B60, B80. Thehigher combustion temperature at higher engineload contributes to the general decreasing trend.With the addition of biodiesel, CO emission alsodecreases. It is possible that the oxygen containedin the fuel enhances complete combustion in thecylinder and reduces CO emission27-29. Fig.3compares the CO2 emissions of various fuels usedin the diesel engine. The CO2 emission increaseswith increases in load, as expected. The lowerpercentage of biodiesel blends emits very low

Table 1: Specifications of the test engine

Cylinder number 4Displacement(Lit) 3.9Compression ratio 17:1Power (kW/rpm) 85:2800Torque (Nm/rpm) 340:1800Cooling system Water cooled

Table 2: Specifications of diesel and biodiesel fuels

Property Method Biodiesel Property

Flash point, closed cup D 93 64 ° C 182 ° CPour point D 97 0 ° C -3 ° CKinematical viscosity D 445 4.03 mm²/s 4.15 mm²/sSulfated ash D 874 - 0 wt.%Total Sulfur D 5453 0.05 wt.% 0.0018 wt.%Copper strip corrosion D 130 1a 1aCloud point D 2500 2 ° C 0 ° C


Fig. 1: Effect of biodiesel and engine load on hydrocarbon emission

Fig. 2: Effect of biodiesel and engine load on CO emission

Fig. 3: Effect of biodiesel and engine load on CO2 emission

amount of CO2 in comparison with diesel. B20 emitsvery low level of CO2 emissions. Using higherconcentration biodiesel blends as the fuel, CO2

emission is found to increase. But, its emission level

is lower than that of the diesel mode. B80 emitsmore amount of CO2, as compared to that ofbiodiesel blends. More amount of CO2 in exhaustemission is an indication of the complete

211SHIRNESHAN et al., Curr. World Environ., Vol. 7(2), 207-212 (2012)

combustion of fuel. This supports the higher valueof exhaust gas temperature.

Fig.4 shows the variation of NOx emissionwith engine load. The NOx concentration increaseswith increase of engine load for all the fuels.Compared with diesel, NOx emission of the

biodiesel blended fuel increases slightly at all testedengine loads and the increase is more obvious athigher engine loads. From diesel to B80, the NOx

emission increases. The peak concentrations at the80% engine load are 670 ppm, 640 ppm, 640 ppm,620 ppm and 600 ppm respectively, for diesel, B20,B40, B60, B80.

Fig. 4: Effect of biodiesel and engine load on NOx emission

CONCLUSION

Experiments have been conducted on adiesel engine using diesel, diesel-biodieselblended fuels. Biodiesel used in the present studywas manufactured from waste frying oil. Blendedfuels containing 20%, 40%, 60% and 80% byvolume of biodiesel, were used in the tests. Theeffect of engine load and fuel mix on emissionswas investigated. The use of diesel blended withbiodiesel, compared with diesel on the emissions;in general, HC and CO emissions are higher at

low engine loads and lower at high engine loadswhile NOx increase with engine loads. Also theCO2 emission increases with increases in load, asexpected. The lower percentage of biodieselblends emits very low amount of CO2 incomparison with diesel. After the addition ofbiodiesel in the blended fuel, HC and COemissions decrease due to improved combustionwith oxygen enrichment of the fuel. However, NOx

emissions increase due to the higher combustiontemperature and the increased oxygen level inthe combustible mixtures.

REFERENCES

1. Agarwal AK., Biofuels (alcohols andbiodiesel) applications as fuels for internalcombustion engines. Prog Energy CombustSci 33: 233-71 (2007).

2. Demirbas A., Biodiesel impacts oncompression ignition engine (CIE): Analysisof air pollution issues relating to exhaustemissions. Energy Sources, 27(6): 549-558(2005).

3. Ribeiro NM, Pinto AC, Quintella CM, RochaGOD, Teixeira LSG, Guarieiro LLN, et al., Therole of additives for diesel and diesel blended(ethanol or biodiesel) fuels: a review. Energ

Fuel, 21: 2433-45 (2007).4. Cvengroš J, Pova•anec F., Production and

treatment of rapeseed oil methyl esters asalternative fuels for diesel engines. BioresourTechnol 55: 145-52 (1996).

5. USEPA., A comprehensive analysis ofbiodiesel impacts on exhaust emissions;EPA. 420-P-02-001 (2002).

6. Srivathsan VR, Srinivasan LN, Karuppan M.,An overview of enzymatic production ofbiodiesel. Bioresour Technol, 99(10): 3975-81 (2008).

7. Manish Kumar Mishra and D.P. Pandey,


Orient J. Chem., 27(1): 305-311 (2011).8. Kulkarni MG, Dalai AK., Waste cooking oil-

an economical source for biodiesel: a review.Ind Eng Chem Res; 45: 2901-13 (2006).

9. Lapuerta M, Rodriguez-Fernandez J,Agudelo JR., Diesel particulate emissionsfrom used cooking oil biodiesel. BioresourTechnol 99: 731-740 (2008).

10. Cherng-Yuan L, Lin H-A., Engineperformance and emission characteristics ofa three-phase emulsion of biodieselproduced by peroxidation. Fuel ProcessingTechnol. 88(1): 35-41 (2007).

11. Demirbas A., Progress and recent trends inbiofuels. Prog Energy Combust Sci, 33: 1-18(2007).

12. Rakopoulos CD, Antonopoulos KA,Rakopoulos DC., Comparative performanceand emissions study of a direct injectiondiesel engine using blends of diesel fuel withvegetable oils or biodiesels of variousorigins. Energy Conver. Manage. 47(18-19):3272-3287 (2006).

13. Ulusoy Y, Tekin Y, Çetinkaya M,Karaosmano_lu F., The engine tests ofbiodiesel from used frying oil. EnergySources, 26: 27-932 (2004).

14. Kaplan C, Arslan R, Sürmen A, PerformanceCharecteristics of Sunflower Methyl estersas Biodiesel. Energy Sources, 28: 751-755(2006).

15. Çetinkaya M, Karaosmano_lu F., A newapplication area for used cooking oiloriginated biodiesel: Generators. EnergyFuels, 19(2): 645-652 (2005).

16. Hamasaki K, Kinoshita E, Tajima H, TakasakiK, Morita D., Combustion characteristics ofdiesel engines with waste vegetable oilmethyl ster. The fifth InternationalSymposium on Diagnostics and Modelingof Combustion in Internal CombustionEngines (COMODIA 2001). Nagoya, Japan(2001).

17. Lapuerta M, Armas O, Jose RF., Effect ofbiodiesel fuels on diesel engine emissions.Prog Energ Combust, 34:198-223 (2008).

18. Tat ME., Investigation of oxides of nitrogenemissions from biodiesel-fueled engines.PhD thesis. Iowa State University.http://www3.me.iastate.edu/biodiesel/Technical

Papers/Dissertati on_link.htm (2003).19. Çanakçi M, VanGerpen JH., Comparison of

engine performance and emissions forpetroleum diesel fuel, yellow greasebiodiesel, and soybean oil biodiesel. Trans.ASAE, 46(4): 937-944 (2003).

20. Mittelbach M, Tritthart P., Diesel fuel derivedfrom vegetable oils, III. Emission tests usingmethyl esters of used frying oil. J AmericanOil Chemists’ Soc. 65(7): 1185-1187 (1988).

21. Payri F, Macián V, Arregle J, Tormos B,Martínez JL, Heavy-duty diesel engineperformance and emission measurementsfor biodiesel (from cooking oil) blends usedin the ECOBUS project. SAE paper. 2005-01-2205 (2005).

22. Aakko P, Nylund NO, Westerholm M,Marjamäki M, Moisio M, Hillamo R.,Emissions from heavy-duty engine with andwithout after treatment using selectedbiodiesels. FISITA 2002 World AutomotiveCongress Proceedings; F02E195 (2002).

23. Dorado M, Ballesteros E., Arnal J, Gomez J,Lopez F., Exhaust Emissions from a DieselEngine Fueled with Transesterified WasteOlive Oil. Fuel, 82: 1311-1315 (2003).

24. Murillo S, Mý´guez JL, Porteiro J, GranadaE, Mora´n JC., Performance and exhaustemissions in the use of biodiesel in outboarddiesel engines. Fuel, 86: 1765-1771 (2007).

25. Meng X, Chen G, Wang Y., Biodieselproduction from waste cooking oil via alkalicatalyst and its engine test. Fuel ProcessingTechnol. 89: 851-857 (2008).

26. Preeti Jain and Sucheta Khowal, Orient J.Chem., 26(2): 509-516 (2010).

27. Lin Y, Wu YG, Chang CT., Combustioncharacteristics of waste oil producedbiodiesel/diesel fuel blends. Fuel, 86: 1772-1780 (2007).

28. Ullman, T.L., Spreen, K.B., Mason, R.L.,Effects of cetane number, cetane improver,aromatics and oxygenates on 1994 heavy-duty diesel engine emissions. SAE Tec PapSer; No. 941020 (1994).

29. Ramadhas AS, Muraleedharan C, JayarajS., Performance and emission evaluation ofa diesel engine fueled with methyl esters ofrubber seed oil. Renew Energy; 30: 1789-800 (2005).

INTRODUCTION

Over the last few decades, there has beengrowing interest in determining heavy metal levelsin the marine environment and attention was drawnto the measurement of contamination levels inpublic food supplied, particularly fish1-3. Althoughheavy metal is a loosely defined term4, it is widelyrecognized and usually applied to the wide spreadcontaminants of terrestrial and fresh waterecosystems. Some examples of heavy metalinclude lead, zinc, cadmium, copper andmanganese. Many of these heavy metals are toxicto organisms at low concentration5-6.


Assessment of Heavy Metals in Water, Fish and Sedimentsfrom UKE Stream, Nasarawa State, Nigeria

O.D. OPALUWA1*, M. O. AREMU1, L. O. OGBO2, J. I. MAGAJI2,I.E. ODIBA3 and E.R. EKPO1

1Department of Chemistry, Nasarawa State University, Keffi, Nigeria.2Department of Geography, Nasarawa State University, keffi, Nigeria.

3Department of Geology and Mining, Nasarawa State University, Keffi, Nigeria.


ABSTRACT

The levels of lead, zinc, copper, iron, manganese, cadmium and mercury were determinedin various body parts of two species of catfish; Clarias gariepinus and Synodontis schall, waterand sediment samples from Uke stream using atomic absorption spectrophotometer (AAS)method. The results obtained showed that iron (Fe) had the highest concentration with average of8.78 mg/g and 7.51 mg/l in sediment and water respectively followed by Zn with 4.79 mg/g(sediment) and 3.19 mg/l (water) while Cd had the lowest concentration of 0.035 mg/g and 0.023mg/l in the sediment and water respectively. In the two fish species, zinc (0.17 – 3.25 mg/g) wasthe most highly concentrated in the various matrices while lead (0.011 – 0.031mg/g) was thelowest. Metal levels in the various body parts of the two species of fish studied were found to bemore concentrated in either, the head, gills or the intestine. In both species zinc had the widestvariability while lead was the least. The metal levels determined in water and sediment are all abovethe tolerable limits recommended by regulatory bodies which is an indication that this ecosystemis contaminated with heavy metals which would eventually end up in the food chain. The metalsdetermined in various body parts of two species of catfish were below deleterious level; howeverthere is the need for regular monitoring of the heavy metal load in this water body and the aquaticorganisms in there because of the long term effects.

Key words: Clarias gariepinu, Synodontis schall, water, sediments, heavy metals, AAS.

The concentration of metals in bio-available form is not necessarily proportional to thetotal concentration of the metal. The concentrationof various elements in the air, water and land maybe increased beyond their natural level due to theagricultural, domestic and industrial effluents. Thesesubstances are described as “contaminants” whendischarged to the environment7. In water, insolubleheavy metals may be bound to small silt particles.Metals and other fluvial contaminants in suspensionor solution, do simply flow down the stream, theyform complexes with other compounds settle to thebottom and ingested by plants and animals oradsorbed to sediments8. Consequently, aquaticorganisms may acquire heavy metals in body

214 OPALUWA et al., Curr. World Environ., Vol. 7(2), 213-220 (2012)

directly from the water via gills or food chainmechanisms9.

Work has been presented on heavy metalconcentrations in water, sediments and fishes fromNasarawa and Antau streams in Nasarawa Stateto ascertain the extent of heavy metal pollution inthese aquatic ecosystems and their eventual uptakeby aquatic organisms. Different parts of fish (head,gills, intestine and flesh) were used and by dryingthese parts of fish and the sediment samples andemploying the method of wet digestion and AAS,the level of metals in these parts of fish and thesediment were determined. The level of metals inwater was also determined using AAS afterpretreatment. The results showed the presence ofmetals determined in all the samples but were belowthe deleterious level5,10.

Water and sediments are commonly usedas indicators for the state of pollution of aquaticecosystem11. Uke stream runs through the centre ofthe town and the water from this stream servesdomestic purposes as well as irrigation farming andaquatic organisms (fish) from this water body is onethe major sources of protein for the populace of thislocation. However, the stream also serves as pointsof discharge for domestic wastes in some areasalong the length of the stream and runoffs fromagricultural lands always flow into the stream atdifferent points.

Aquatic animals (including fish) bio-accumulate heavy metals in considerable amountin tissues over a long time and the dependence ofthe populace in this area on this water body fordomestic water supply and its aquatic organisms(fish) as source of protein makes it imperative toassess the level of heavy metals in this aquaticecosystem in view of the health implications thatcut across the food strata.

This research reports the level of Pb, Zn,Fe, Cd, Cu and Mn in parts of fish caught from Ukestream as well as the stream water and sedimentsin order to ascertain the relationship betweenbioaccumulation of these metals in the aquaticorganisms (fish) with the distribution andconcentrations of these metals in the stream waterand sediments. This is aimed at ensuring the safety

of this ecosystem for the benefits of the residents ofUke and its environs.


Collection of samplesWater samples were collected using

plastic containers to fetch water below the surfaceat designated points, mixed properly and stored ina plastic container rinsed with 0.01N nitric acid andkept in deep freezer prior to the time of analysis11.The sediment samples were collected by scoopingwith a plastic spoon from the points where the watersamples were taken, air dried and kept awaitinganalysis. The samples of available fish species(Clarias gariepinus and Synodontis schall) in thestream were purchased from fishermen at thestream site. They were properly and carefullywashed and stored at 40C pending analysis. Thesesamples were all collected at7.00 local time whilethe temperature (28ºC) of the water was taken atthe point of collection.

Sample treatmentFive (5.0) cm3 of concentrated hydrochloric

acid were added to 250.0 cm3 of water sample andevaporated to 25.0 cm3. The concentrate wastransferred to a 50.0 cm3 standard flask and dilutedto the mark with de-ionized water11. 5.0 g of preparedsediment sample was digested with 15.0 cm3 nitricacid, 20.0 cm3 perchloric acid and 15.0 cm3

hydrofluoric acid and placed on a hot plate for 3h.On cooling, the digest was filtered into a 100.0 cm3

volumetric flask and made up to the mark withdistilled water12. Different body parts of the fish(Head, gills, intestine and flesh) were dried in theoven at 1050C until constant weight is obtained andblended. 2.0 g of the blended fish parts wereweighed and digested using the approvedmethod14.

Mineral analysisLead, zinc, copper, iron, manganese,

cadmium and mercury were determined in samplesof fish body parts of Clarias gariepinus andSynodontis schall, water and sediment usingcomputer controlled Atomic AbsorptionSpectrophotometer (AAS VGB 210 System). Theinstrument setting and operational conditions weredone in accordance with the manufacturers’

215OPALUWA et al., Curr. World Environ., Vol. 7(2), 213-220 (2012)

specifications. All determinations were in triplicates.

Statistical analysisThe results obtained were subjected to

statistical evaluation. Parameters evaluated weregrand mean, standard deviation (SD) and coefficientof variation (CV %).


Table 1 shows the mean metalconcentrations, grand mean, standard deviationand coefficient of variation percent of water andsediments. The mean concentration of metalsdetermined in the water samples ranged from 0.023– 7.51 mg/L and for sediments the range was 0.095– 8.78 mg/g. The metals determined were Pb, Zn,Fe, Cd, Cu, Mn and Hg with mean concentrationsof 0.040, 3.19, 7.51, 0.023, 0.95, 0.51 (mg/l) in waterand 0.095, 4.79, 8.78, 0.035, 1.34, 0.24, and (mg/g) in sediment respectively with Hg not detected inboth water and sediment samples. Theconcentrations of Fe, Zn, in both samples and Cuin sediment were high (> 1.0 mg/L). Theconcentration of Fe being highest in sediment

agrees with the result of the report of heavy metalsin sediments of Rafin Mallam stream10 but its valuein water, also highest is high than the value recordedin the report of heavy metals in water and fish fromRiver Antau5. However, the concentration of Fe insediments and water to an extent is determined bythe nature of soil along the stream banks15 fromwhere it is leached into the water body andsediments. The values of Zn recorded are lowerthan the ones obtained from the results of the reportof heavy metals in water, sediments and fish fromRiver Nasarawa and for Cu, its concentration is thesame for water and higher for sediment than thatobtained for River Nasarawa10. Zinc is widely usedfor making paints, dyes, rubber, wood preservativesand through wares and tears; zinc from this sourcesis discharged into the environment. Although zincis required by plants and animals for normal growth,higher concentration of it is toxic16.

The concentrations of Cd and Pb obtainedare lower for water and higher for sediments fromthe work on a water body used for irrigation in Keffi10.The concentration of Mn in sediment is lower andhigher in water than those obtained from the work

Table 1: Mean metal concentrations in water (mg/L) and sediment (mg/g)

Parameter Pb Zn Fe Cd Cu Mn Hg

Water 0.040 3.19 7.51 0.023 0.95 0.51 NDSediment 0.095 4.79 8.78 0.035 1.34 0.24 NDGrand mean 0.068 3.99 8.15 0.029 1.15 0.38 -SD 0.039 1.13 0.90 0.008 0.28 0.19 -CV% 57.35 28.35 11.04 2.76 24.35 50.00 -

standard deviation, SD; coefficient of variation percent, CV%.

Table 2:National and International Standards

Metals Water (mg/L) Fish (mg/g)

FDA WHO EPA WHO

Pb 0.005 0.01 0.05 1.5Zn - 3.0 5.0 150Cu 1.0 1-2 1.0 -Fe - 0.3 0.1 -Mn - 0.1-0.5 0.05 2.5Cd 0.005 0.003 - 0.2

carried out on River Tammah12. Cu, Pb and Mn aresome of the metals that get into aquatic ecosystemfrom runoffs from agricultural lands as a result ofthe use of agrochemicals containing heavy metalssuch as Cu, Mg, Mn, Pb and Zn17. The probablesources of Cd in surface water includes leachingfrom Ni – Cd batteries, run off from agricultural soilswhere phosphate fertilizers are used and otherwastes18-19.


Table 3: Mean metal concentrations in the body parts of African catfish (Clarias garipienus), mg/g


Head 0.031 0.17 0.13 0.005 0.05 0.22 NDGills 0.022 2.35 1.63 0.016 1.31 0.12 NDIntestine 0.012 0.26 0.26 0.025 0.31 0.21 NDFlesh 0.013 0.18 0.13 0.001 0.15 0.11 NDGrand mean 0.020 0.73 0.54 0.012 0.46 0.37 -S.D 0.009 1.08 0.73 0.011 0.58 0.27 -CV (%) 45.00 147.94 135.18 91.67 126.08 72.97 -

SD standard deviation; CV% coefficient of variation percent; ND not detected

Table 4: Mean metal concentrations (mg/g) in the body parts of African catfish (Synodontis schall)


Head 0.021 0.19 0.12 0.005 0.06 0.24 NDGills 0.014 3.25 1.52 0.015 1.35 0.11 NDIntestine 0.011 0.21 0.31 0.026 0.25 0.18 NDFlesh 0.012 0.17 0.16 0.001 0.15 0.11 NDGrand mean 0.015 0.96 0.53 0.118 0.45 0.39 -S.D 0.005 1.53 0.67 0.111 0.60 0.26 -CV (%) 33.33 159.38 126.41 94.06 133.33 66.67 -

SD standard deviation; CV% coefficient of variation percent; ND not detected

All the metals determined were above theWorld Health Organization (WHO) safety standards,Food and Drugs Administration (FDA) Table-2, andthe United States Environment Protection Agency(USEPA) maxima20 except for copper in water whichis within the range recommended by W.H.O higherthan the ranges recommended by other regulatorybodies. The level of zinc in sediment is howeverwithin the range recommended by EPA20. Ironthough high above WHO safety standard, it is stillsafe because it has benefits to organism though invery high concentration leads to conjunctivitis,chroiditis and retinitis if it is in contact and remainsin the tissue but Cd is a toxic metal and has nometabolic benefits to human and aquatic biota21. Itspresence in any compartment of the aquaticecosystem indicates contamination.

The high level of these metals in both thewater and sediment samples are as a result of therunoffs during the rainy season from agricultural

fields and the dumping of domestic wastes in thewater body at different points along the length ofthe stream as they are known to contain heavymetals such as As, Cd, Co, Cu, Fe, Hg, Mn, Pb, Niand Zn which will eventually end up in this aquaticecosystem23.

Among all these metals determined ironhas the highest concentration with average of 8.78mg/g and 7.51 mg/l in sediment and water,respectively followed by Zn with 4.79 mg/g(Sediment) and 3.19 mg/l (Water) while Cd has thelowest concentration of 0.035 mg/g and 0.023 mg/l in the sediment and water respectively. Theseresults are in agreement with the result of in whichCd was found to have the lowest concentration inboth sediment and water. Going by the calculatedcoefficient of variation percent (CV %) when thelevels of metals in water and sediment werecompared the variability was highest in lead whilecadmium was the least varied.


Table 6: Bioconcentration factors of the various metals in the body parts of Synodontis schall


Head 0.53 0.06 0.02 0.22 0.06 0.47 -Gills 0.35 1.01 0.20 0.65 1.42 0.22 -Intestine 0.28 0.07 0.04 1.13 0.26 0.35 -Flesh 0.30 0.05 0.02 0.04 0.16 0.22 -Grand mean 0.37 0.30 0.07 0.51 0.48 0.32 -S.D 0.12 0.47 0.08 0.49 0.64 0.12 -CV (%) 32.43 156.67 114.29 96.08 133.33 37.50 -

SD standard deviation; CV% coefficient of variation percent

Table-3 and Table-4 show mean metalconcentrations in the body parts (head, gills,intestine and the flesh) of African catfish, Clariasgaripienus and Synodontis schall respectively. Thepresence of these metals analysed in the body partsof fish serves as an indicator for the extent of heavymetal pollution of the water body from where theseaquatic organisms (fish) are obtained10. Also thepresence of most of the metals determined in thefish parts agrees with the results of the report of thelevel of heavy metals in aquatic organism fromdifferent water bodies24-25 which showed that aquaticanimals, fish, inclusive bio-accumulate heavymetals in considerably amount, and because thesemetals are not bio-degradable, the metal tend tostay in the fish tissues for a very long time whichupon consumption of these fish, the heavy metalsget transferred to man, leading to heavy metalpoisoning in man especially if present in higherconcentrations. In both species of the fish zincpresented the highest concentrations followed by

iron in the various parts studied and this is relativeto the concentrations of these metals observed inboth water and sediment samples.

Copper was the next metal after zinc andiron with concentration range of 0.05 – 1.35 mg/gin the various parts of both species of the fishstudied. Lead, cadmium and manganese showeddifferent distribution among the various parts of fish.Mercury was not detected in any part of both speciesjust as it was neither detected in water nor sedimentsamples. Zinc showed the highest variability of147.94 and 159.38 % in Clarias garipienus andSynodontis schall respectively with lead having theleast in both cases. This results agrees with thatobtained for the analysis of the levels of metals inorgans of Clarias lazera from river Nasarawa10.

Most of the metals had highestconcentrations either in the head part (lead andmanganese) or the gills part (zinc, iron and copper).

Table 5: Bioconcetration factors of the various metals in the body parts of Clarias garipienus


Head 0.78 0.05 0.02 0.22 0.05 0.43 -Gills 0.55 0.74 0.28 0.70 1.38 0.24 -Intestine 0.30 0.08 0.04 1.09 0.33 0.41 -Flesh 0.33 0.06 0.02 0.04 0.16 0.22 -Grand mean 0.49 0.23 0.09 0.51 0.48 0.33 -S.D 0.22 0.34 0.13 0.48 0.61 0.11 -CV (%) 44.90 147.82 144.44 94.12 127.08 33.33 -

SD standard deviation; CV% coefficient of variation percent


This is as result of the fact that the gills helps inrespiration and filtration of water24. Relatively highconcentrations of some of the metals were found inthe intestine since the intestine is part of the visceralmuscles which concentrates toxic metals25. Zinc andcopper are mineral elements which are essentialmetals and play vital role in enzyme activity andiron is very important in heamoglobin formation.Lead and cadmium are toxic at very lowconcentration and have no known functions inbiochemical processes. Sources of cadmiuminclude wastes from cadmium- based batteries,incinerators and runoff from agricultural soils wherephosphate fertilizers are used since cadmium is acommon impurity in phosphate fertilizers18. Lead ismainly from storage batteries, type metal and anti-knock compound in petrol27. The levels of all themetals determined were however below theconcentrations recommended by regulatorybodies21.

Table-5 and Tables-6 show thebioconcentration factors for Clarias garipienus andSynodontis schall, respectively. Most of the valuesobtained for the various fish parts were relativelylow (< 1) which showed there was no biologicalmagnification of metal concentration in fish samplesexcept for cadmium (in the intestine) and copper(in gills) for Clarias garipienus and zinc (in gills),cadmium (in the intestine) and copper (in gills) forSynodontis schall. Order of bioconcentration in thevarious body parts of Clarias garipienus is Zn > Fe

> Cu > Cd > Pb > Mn while that of Synodontis schallis Zn > Cu > Fe > Cd > Mn > Pb. Zn showed thewidest variation in both species of fish while theleast variations were recorded in Mn and Pb forClarias garipienus and Synodontis schall,respectively. The levels of metals in the body partsof the two species of catfish were lower than that ofthe water or sediment. However the presence ofmetals in the two fishes biochemically showed thatfish is relatively dependent on the levels of metalsavailable in aquatic ecosystem.

CONCLUSION

This research has presented data on thelevels of heavy metals in sediments, water andvarious body parts of two species of catfish fromUke stream in Uke town, Nasarawa State. Althoughthe results obtained does not show any form ofdanger posed to consumers of sea foods and waterfrom this stream but the possibility of deleteriouseffects after long period cannot be ruled out. This isas a result of the fact that this water body serves asthe receptor for domestic wastes as well as runofffrom agricultural lands where phosphate fertilizersand other agrochemicals are frequently used. Thereis therefore the need for continual assessment ofthe level of pollution of this stream with metals fromthe mentioned sources with a view to reducing thelevel of pollution via education and publicenlightenment.

REFERENCES

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2. Rose, J., Hutcheson, M.S., West, C.R .andPancorbo, O., “Fish Mercury Distribution inMassachusetts, USA Lakes”, Environ.Toxicology and Chem., 18(7): 1370-1379(1999).

3. Tariq, J., Jaffa, M. and Ashraf, M., “HeavyMetal concentrations in fish, shrimp,seaweed, sediment and water from Arabian

Sea, Pakistan”, Marine Pollution Bulletin,26(11): 644-647 (1993).

4. Duffus, J. H., “Heavy Metal” - A meaninglessterm. Pure and Applied chemistry, 74: 793-807 (2002).

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7. Madu, P.C., Tagwoi, J.T. and Babalola, F., A


study of heavy metal pollution of River Antau,Keffi, Nasarawa State, Nigeria, India J. ofMulti. Res., 4(1): 8-18 (2008).

8. Odiete, W.O., Environmental Physiology ofAnimals and Pollution, 1st ed. DiversifiedResources Limited, Lagos.1-end (1999).

9. Collison, C. and Shrimp, N.F., Trace elementsin bottom sediments from Upper Peria Lake.Middle Illinois River. Illinois Geo. Survey andEnviron. Geology Note, 56: 21 (1972).

10. Huckabee, J.W and Blaylock, B.G., Transferof mercury and cadmium from terrestrial toaquatic ecosystem. Environmental sciencesDivision, Oak Ridge National LaboratoryOak Ridge, Tennesse, 55 (1972).

11. Aremu, M.O., Atolaiye, B.O., Shagye, D., andMoumouni, A., Determination of trace metalsin Tilapia zilli and Clarias lazera fishesassociated with water and soil sediment fromRiver Nasarawa in Nasarawa State, Nigeria,India J. Multi. Res., 3(1): 159-168 (2007).

12. Opaluwa, O.D. and Umar, M.A., Level ofheavy metals in vegetables grown onirrigated farmland, Bull. of Pure and AppliedSci., 29C (1): 39-55 (2010).

13. Atolaye, B. O, Aremu, M.O., Shagye, D. andPennap, G.R. I., Distr ibution andconcentration of some mineral elements insoil sediment, ambient water and body partsof Claria gariepinus and Tilapia queneensisfishes in stream Tammah, Nasarawa StateNigeria, Curr World Environ., 1(2): 95-100(2006).

14. Adekenya B., Variation of metal pollutantswith depths, Techforum, An Interdisci., J. 2(3):82-97 (1998).

15. Ibok, U.J; Udosen, E.D and Udoidiong, O.M.,Heavy Metals in Fishes from Streams in IkotEkpene Area of Nigeria, Nigeria J. Tech.Res., 1: 61-68 (1989).

16. Osakwe, S. A. and Peretiemo-Clarke, B.O.,Evaluation of heavy metals in sediments fromRiver Ethiope, Delta State, Nigeria. 31st CSNConference paper, 611-613 (2008).

17. Umar, M.A. and Opaluwa, O.D., Evaluationof heavy metals in sediments of Rafin Mallamstream in Keffi, Nasarawa State, Intl. J.Chem., 20(2): 99-103 (2010).

18. Pate, K.P., Pandy, R.M. and George, L.,Heavy metal content of different effluentswater around major industrial cities ofGuryurat, J. of Indian Society of Soil Sci.,59(1): 89-94 (2001).

19. Hutton, M. and Symon, C., The quantities ofcadmium, lead, mercury and arsenicentering the U.K environment from humanactivities, Science of the total environment,59: 129-150 (1986).

20. Stoeppler, M., Cadmium. In: Merian E (ed)Metals and their compounds in theenvironment: Occurrence, analysis andbiological relevance. VCH. New York, 803-851 (1999).

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22. Environmental Protection Agency EPA,(1976): “Quality Criteria for Water”.Washington, 440 (9): 76-123 (1986a).

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24. Oluyemi, E.A.; Fenyuit, G.J; Oyekunle, J.A.O.and Ogunfowokan, A.O., Seasonalvariations in heavy metal concentrations insoil and some selected crops at a landfill inNigeria, African J. of Sci. and Tech., 2(5): 89-96 (2008).

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Food. A Review. Analyst, 102: 225-268(1997).

INTRODUCTION

Organic halogen alkane compounds orhalocarbon compounds are chemicals in which oneor more carbon atoms are linked by covalent bondswith one or more halogen atoms (fluorine, chlorine,bromine or iodine - group 17) resulting in theformation of organofluorine compounds,organochlorine compounds, organobrominecompounds, and organoiodine compounds.Chlorine halocarbons are the most common andare called organochlorides. Many synthetic organiccompounds such as plastic polymers, and a fewnatural ones, contain halogen atoms; they areknown as halogenated compounds ororganohalogens. Organochlorides are the mostcommon industrially used organohalides, althoughthe other organohalides are used commonly inorganic synthesis. Except for extremely rare cases,organohalides are not produced biologically, butmany pharmaceuticals are organohalides. Organichalogen compounds have many uses in theoreticaland industrial1-5. Common uses for halocarbonshave been as solvents, pesticides, refrigerants, fire-resistant oils, ingredients of elastomers, adhesives


Structural Properties, Natural Bond Orbital, TheoryFunctional Calculations (DFT), and Energies

for the ααααα Halorganic Compounds

NAJLA SEIDY and SHAHRIAR GHAMMAMY

Department of Chemistry, Faculty of Science, Imam Khomeini International University, Qazvin, Iran.


ABSTRACT

In this paper, the optimized geometries and frequencies of the stationary point and theminimum-energy paths of C3H2F4Br2 are calculated by using the DFT (B3LYP) methods withLANL2DZ basis sets. B3LYP/ LANL2DZ calculation results indicated that some selected bondlength and bond angles values for the C3H2F4Br2.

Key words: Halo fluoroalkane, C3H2F4Br2, Electronic structure, Calculations,Vibrational analysis, B3LYP level.

and sealants, electrically insulating coatings,plasticizers, and plastics. Many halocarbons havespecialized uses in industry. One halocarbon,sucralose, is a sweetener. Many different data havebeen found about the structural properties of halocompounds, but they are insufficient and opposingin somewhere. The investigation of the structuresand properties of the compound and similaritiesare interested. The structure has been confirmedby neutron diffraction studies and is justified byVSEPR theory5-8. During this study we report theoptimized geometries, assignments and electronicstructure calculations for the compound. Thestructure of the compound has been optimized byusing the DFT (B3LYP) method with the LANL2DZbasis sets, using the Gaussian 09 program [9]. Thecomparison between theory and experiment ismade. Density functional theory methods wereemployed to determine the optimized structures ofC3H2F4Br2 and Initial calculations were performedat the DFT level and split- valence plus polarizationLANL2DZ basis sets were used. Local minima wereobtained by full geometrical optimization have allpositive frequencies10.

222 SEIDY & GHAMMAMY, Curr. World Environ., Vol. 7(2), 221-226 (2012)

METHODS

All computational are carried out usingGaussian 09 program [11]. The optimized structuralparameters were used in the vibrational frequencycalculations at the HF and DFT levels to characterizeall stationary points as minima. Harmonic vibrationalfrequencies (í) in cm-1 and infrared intensities (int)in Kilometer per mole of all compounds wereperformed at the same level on the respective fullyoptimized geometries. Energy minimum moleculargeometries were located by minimizing energy, withrespect to all geometrical coordinates withoutimposing any symmetrical constraints.


Molecular propertiesThe structures of compounds are shown

in Figure 1.

All calculations were carried out using thecomputer program GAUSSIAN 09.

Theoretical calculation of bond and anglefor the compound was determined by optimizingthe geometry (Table 1).

NBO Analysis in Table1 and The NBOCalculated Hybridizations are reported in Table2.We could not compare the calculation results given

in bond lengths and bond angle values with theexperimental data. Because the crystal structure ofthe title compound is not available till now. B3LYP/LANL2DZ calculation results showed that the (C1-F6) bond length values for the C3H2F4Br2 and incompounds 1-2 are 1.3909 Å and 1.3765 Årespectively. And (C-Br-) bond length values for theC3H2F4Br2 compounds 1-2 are 1.8031Å and1.7727Å respectively. Alkyl halide compounds aremostly dense liquids and solids that are insolublein water. The halogens are all more electronegativethan carbon and this makes the carbon-halogenbond a polar bond with a slight positive charge (d+) residing on the carbon end of the bond and aslight negative charge (d-) on the halogen end.

Table 1: Geometrical parameters optimized for C3H2F4Br2

some selected bond lengths (Å) and angles (°C)

B3LYP/6-311 MethodC3H2F4Br2 C3H2F4Br2

Bond lengths (Å) angles (°) Bond lengths (Å) angles (°C)

C1-C3 2.41 C1-C2 3.15C3-F6 1.86 C3-F4 0.75C1-F7 1.56 C2-H9 0.53C3-F5 1.97 C-2Br11 0.80C1-Br8 3.86 C2-H10 0.53Bond angles (°) Bond angles (°)C1-C3-F4 123.258 C2-C1-F4 123.255C1-C3-F5 123.258 C2-C1-F5 123.253C1-C3-F4 113.483 F4-C1-F5 113.491

The carbon-halogen bond strengthdecreases in the order C-F > C-Cl > C-Br > C-I

Alkyl fluorides tend to be less reactive thanother alkyl halides, mainly due to the higher strengthof the C-F bond.

223SEIDY & GHAMMAMY, Curr. World Environ., Vol. 7(2), 221-226 (2012)

Table 2: The NBO Calculated Hybridizations for (C3H2F4Br2, B3LYP/LANL2DZ)

(1)C3H2F4Br2 (2)C3H2F4Br2

Bond Atom B3LYP Bond Atom B3LYP

C-C C1-C2 S1P2.56, S1P2.91 C-C C1-C3 S1P2.00, S1P1.61

C-F C1-F7 S1P4.22, S1P2.57 C-Br C1-Br8 S1P4.16, S1P7.90

C-C C1-C2 S1P2.56, S1P2.91 C-C C1-C3 S1P2.00, S1P1.61

C-H C2-H9 S1P2.51, S1P0 C-H C1-H10 S1P2.63, S1

C-Br C2-Br11 S1P4.44, S1P7.37 C-F C3-F4 S1P3.92, S1P2.64

C-F C3-F5 S1P3.84, S1P2.62 C-F C3-F6 S1P3.85, S1P2.52

C C1 S1P0.00 C C2 S1P0.00

C C3 S1P0.00 F F4 S1P0.00

F F5 S1P0.00 F F6 S1P0.00

F F7 S1P0.00 Br Br8 S1

Br Br11 S1

Table 3: Second order perturbation theory analysis of Fock matrix in NBO basis for (1) C3H2F4Br2 (2))a

means energy of hyper conjugative interaction (stabilization energy); b Energy differencebetween donor and acceptor i and j NBO orbital’s; c F(i, j) is the Fock matrix element between i and j NBO

Donor (i) Type ED/e Acceptor Type ED/e E(2) E(j) E(i) F(i,j)c

(j) a(KJ/mol) b(a.u) (a.u)

C3F4H2Br2

C1F4 σ 1.98934 C1F5 σ* 1.98934 0.92 1.00 0.027C1F5 σ 1.98934 C1F4 σ* 1.98934 0.92 1.00 0.027Br(2) n 1.97731 C1F4 σ* 1.98934 2.75 0.58 0.036F (4) n 1.97731 C1F4 σ* 1.98934 2.75 0.58 0.036F (5) n 1.97731 C1F4 σ* 1.98934 2.75 0.58 0.036C3H2F4Br2

C1F4 σ 1.97477 C1F5 σ* 1.97477 2.39 0.64 0.036C1F5 σ 1.97477 C1F4 σ* 1.97477 2.39 0.64 0.036Br (2) n 1.95128 C1F4 σ* 1.97477 1.94 0.40 0.025F (4) n 1.95128 C1F4 σ* 1.97477 1.94 0.40 0.025F (5) n 1.95128 C1F4 σ* 1.97477 1.94 0.40 0.025

NBO study on structuresNatural Bond Orbital’s (NBOs) are

localized few-center orbital’s that describe theLewis-like molecular bonding pattern of electronpairs in optimally compact form. More precisely,NBOs are an orthonormal set of localized “maximumoccupancy” orbital’s whose leading N/2 members(or N members in the open-shell case) give themost accurate possible Lewis-like description ofthe total N-electron density. This analysis is carriedout by examining all possible interactions between

“filled” (donor) Lewis-type NBOs and “empty”(acceptor) non-Lewis NBOs, and estimating theirenergetic importance by 2nd-order perturbationtheory. Since these interactions lead to donation ofoccupancy from the localized NBOs of the idealizedLewis structure into the empty non-Lewis orbitals(and thus, to departures from the idealized Lewisstructure description), they are referred to as“delocalization” corrections to the zeroth-ordernatural Lewis structure. Natural charges have beencomputed using natural bond orbital (NBO) module


Fig. 1: The schematic structure of the C3H2F4Br2

E LUMO = -0.08718 a.u

ΔE=0.21634

E HOMO = -0.30352 a.u

Fig. 2: The atomic orbital of the frontier molecular orbital for C3H2F4Br2 B3LYP/6-311 level of theory

225SEIDY & GHAMMAMY, Curr. World Environ., Vol. 7(2), 221-226 (2012)

implemented in Gaussian09. The NBO CalculatedHybridizations are significant parameters for ourinvestigation. These quantities are derived from theNBO population analysis. The former provides anorbital picture that is closer to the classical Lewisstructure. The NBO analysis involving hybridizationsof selected bonds are calculated at B3LYP methodsand LANL2DZ level of theory (Table 2).

These data shows the hyper conjugationof electrons between ligand atoms with centralmetal atom. These conjugations stand on the baseof p-d σ-bonding.

The NBO calculated hybridization forC3H2F4Br2 shows that all of complexes have SPX

hybridization and non planar configurations. Thetotal hybridization of these molecules are SPX thatconfirmed by structural. The amount of bondhybridization showed the in equality betweencentral atoms angles (Table 2) Shown distortionfrom octahedral and VSEPR structural andconfirmed deviation from VSEPR structures.

In C3H2F4Br2 the lone pair located onbromin atoms and significantly delocalized hybridorbital’s of C-F bonds. Indeed, in the interactionenergy from the charge transfers C3H2F4Br2

complex confirms the above point and in theaverage for C3H2F4Br2 the maximum interactionenergy is predicted (Table 3).

Frontier molecular orbitalBoth the highest occupied molecular

orbital (HOMO) and lowest unoccupied molecularorbital (LUMO) are the main orbital take part inchemical stability. The HOMO represents the abilityto donate an electron, LUMO as an electron

acceptor represents the ability to obtain an electron.The HOMO and LUMO energy were calculated byB3LYP/ LANL2DZ method12. This electronicabsorption corresponds to the transition from theground to the first excited state and is mainlydescribed by one electron excitation from thehighest occupied molecular or orbital (LUMO).Therefore, while the energy of the HOMO is directlyrelated to the ionization potential, LUMO energy isdirectly related to the electron affinity. Energydifference between HOMO and LUMO orbital iscalled as energy gap that is an important stabilityfor structures. In addition, 3D plots of highestoccupied molecular orbitals (HOMOs) and lowestunoccupied molecular orbitals (LUMOs) are shownin Figure 2. The HOMO–LUMO energies were alsocalculated at the LANL2DZ and the values are listedin Figure 2, respectively.

CONCLUSION

In this research we are interested instudying on two Halo Organic Compounds waschosen to theoretical studies. In this paper, theoptimized geometries and frequencies of thestationary point and the minimum-energy paths arecalculated by using the DFT (B3LYP) methods withLANL2DZ basis sets. B3LYP/ LANL2DZ calculationresults indicated that some selected bond lengthand bond angles values for the C

3H2F4Br2.

ACKNOWLEDGMENTS

We gratefully acknowledge the financialsupport from the Research Council of ImamKhoemieni International University by Grant No,751387-91.

REFERENCES

1. Ghammamy, Sh., Z. Anvarnia, M. Jafari, K.Mehrani, H. Tavakol, Z. Javanshir, and G.Rezaeibehbahani, Synthesis andcharacterization of two new halo complexesof Iodine (C4H9)4N[I2Br]- and (C4H9)4N[I2Br]-

and theoretical calculations of theirstructures. Main Group Chemistry, 8: 299-306(2009).

2. Becke, A. D., Density-FunctionalThermochemistry. III. The Role of ExactExchange. J. Chem. Phys., 98: 5648-5652(1993).

3. Sundaraganesan, N. and S. Ilakiamani,Dominic Joshua B Vibrational spectroscopyinvestigation using ab initio and densityfunctional theory analysis on the structure of


3, 4-dimethylbenzaldehyde. SpectrochimicaActa Part A., 68: 680-687 (2007).

4. Lewis, D. F. V., C. Ioannides, and D. V. Parke,Interaction of a series of nitriles with thealcohol-inducible isoform of P450: computeranalysis of structure-activity relationships.Xenobiotica, 24: 401-408 (1994).

5. R. Soleymani, R.D. Dijvejin, A.G.A. Hesar andE. Sobhanie, Orient J. Chem., 28(3): 1291-1304 (2012).

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8. Zhang, W., D.P. Curran, Synthetic Applicationof Fluorous. Tetrahedron 62: 11837-11865(2006).

9. Smith, M. C., Y. Ciao, H. Wang and S. J.George, Coucouvanis D, Koutmos M,

Sturhahn W, Alp EA, Zhao J, Kramer SPNormal-Mode Analysis of FeCl4- andFe2S2Cl42- via Vibrational Mossbauer,Resonance Raman, and FT-IRSpectroscopies. Inorg. Chem., 44: 5562-5570 (2005).

10. Vrajmasu, V. V., E. Mu¨nck, and E. L. Bominaar,Theoretical Analysis of the Jahn”TellerDistor tions in Tetrathiolato Iron(II)Complexes. Inorg. Chem., 43: 4862-4866(2004).

11. Ghammamy, Sh., K. Mehrani, S.Rostamzadehmansor, and H.Sahebalzamani, Density functional theorystudies on the structure, vibrational spectraof three new tetrahalogenoferrate (III)complexes. Natural Science, 3: 683-688(2011).

12. Frisch, M. J. Trucks, G. W., GASSIAN 98(Revision A. 3) Gaussian Inc., (1998).

INTRODUCTION

Increasing demand for noble metals,particularly platinum group metals (PGM), such aspalladium(II), platinum(IV), ruthenium(III),rhodium(III) has been recently observed becauseof their wide range of industrial applications, e.g.as catalysts in organic processes, value addedcomponents in metal alloys and vehicle catalyticconverter systems, in chemical, pharmaceutical,petroleum and electronic industries and also injewellery making.

These applications of PGMs haveincreased the demand for these metals, whereasthe natural resources are limited1-3.

Flame atomic absorption spectrometry(FAAS) is one of the most popular techniques fordetermination of metal ions because of its high


Pyridine-Functionalized TiO2 Nanoparticles as aSorbent for Preconcentration and Determination

of Ultra-Trace Palladium Ions

MOHAMMAD KARIMI1, MONA FEIZ BAKHSH BAZARGANI2, FOROUZAN ABOUFAZELI1,HAMID REZA LOTFI ZADEH ZHAD1, OMID SADEGHI1 and EZZATOLLAH NAJAFI1

1Department of Chemistry, Shahr-e-Rey Branch, Islamic Azad University, Tehran, Iran.2Department of Chemistry, Islamic Azad University, Karaj Branch, Tehran, Iran.


ABSTRACT

In this work, TiO2 nano-particles were modified by pyridine group and characterized byscanning electron microscopy (SEM), X-Ray diffraction (XRD), FT-IR and elemental analysis(CHN). This sorbent was applied for pre-concentration of ultra-trace amount of palladium prior toits determination by flame atomic adsorption spectroscopy (FAAS). Through this study, differentfactors such as sample pH, sample flow rate, eluent parameters (type, concentration and volume),and elunet flow rate were optimized. Also effects of the selectivity of sorbent toward Pd(II) wasinvestigated by palladium determination in presence of various interfering ions. The limit of detectionwas 3.8 ng mL”1 and recovery was 99.1 % with a relative standard deviation of 2.5%. Finally themethod was validated using standard reference material which their paladium concentrations arecertified.

Key words: Palladium determination; Pyridine-functionalized TiO2 nanoparticles;solid phase extraction; Flame atomic absorption spectrometry.

specificity and low cost. However its sensitivity isusually insufficient for determination of trace metalions in environmental samples. In order to overcomethis problem and prevent interference effects, thosewho use this method usually include an efficientpreconcentration step4-5.

Solid-phase extraction (SPE) is one of themost common methods for preconcentration ofnoble metals. It has the advantages of flexibility,economical and environmental-friendly, simplicity,and being fast and safe. 5 Since the key point inSPE is choosing adsorbent, several SPE methodsbased on sorbents such as different polymers7,silica8 and Fe3O4

9 have been developed. Comparedto the other sorbents TiO2 has attracted moreattention due to its high surface area10-12.

In this work, a novel sorbent based onfunctionalization of TiO2 nano-particles by pyridine


group is constructed. This sorbent was applied forpreconcentration of Pd(II) ions in aqueous samplesafter characterization by FT-IR, XRD pattern,elemental analysis and SEM micrograph.

EXPERIMENTAL

Reagents and MaterialsThe standard solution of Pd(II), 1000 mg

L-1, was purchased from Aldrich Company(Milwaukee, Wi, USA). TiO2 nano-particles with 10-15 nm in diameter were purchased from NeunanoCompany (Tehran, Iran). All reagents includessolvents, acids, 3-aminopropyltriethoxysilane,triethylamine, dichloromethane, oxalyl chloride and4-pyridine carboxylic acid were of analytical gradeand purchased from Merck Company (Darmstadt,Germany). The standard reference material (NISTSRM 2557) was purchased from National Instituteof Standards.

ApparatusThe atomic absorption spectrometer (AAS)

used in this experiment was a Shimadzu AA-680equipped with a single element hollow cathodelamp (6.0 mA for palladium). Burner head was 50mm and air acetylene burner head was used duringthe experiment. Resonance line for palladium is244.8 nm, so the wavelength was set at this value.The spectral band width was set at 0.5 nm and theratio of air-acetylene was set at 4.7. The pH wasmeasured at 25 ±1 ºC with a digital WTW Metrohm827 Ion analyzer (Herisau, Switzerland) equippedwith a combined glass-calomel electrode. TheFourier Transform Infrared (FT-IR) spectrum wasrecorded on a BOMEM MB-Series FT-IRspectrometer in the form of KBr pellets. Theelemental analyses (CHNS) were performed on aThermo Finnigan Flash-2000 microanalyzer (Italy).The SEM micrograph was recorded by a Vega-TeScan scanning electron microscope.

Preparation of Pyridine functionalizing agentPyridine functionalizing agent was

synthesized according to earlier report 12 andcharacterized by 1H NMR. Briefly, 1.0 g of 4-pyridinecarboxylic acid was suspended in 100 mL of driedCH2Cl2 under nitrogen atmosphere and 10 mL ofoxalyl chloride was slowly added to the mixtureand was stirred for 12 h. Then CH2Cl2 was removed

under reduced pressure, and the residue wassuspended again in 100 mL of dried CH2Cl2. Afteraddition of 17 mL triethylamine to reaction mixture,4.0 g 3-aminopropyltrimethoxysilane was slowlyadded. The reaction mixture was stirred at roomtemperature for further 4 h. Then the solvent wasremoved under reduced pressure to obtainbrownish viscose oil.

Preparation of pyridine functionalized TiO2 nano-particles

In a typical reaction, 1.0 g TiO2 nano-particles were suspended in 50 mL toluene, and 2mL pyridine functionalization agent was added andthe mixture was refluxed for 24 h under nitrogenatmosphere. Then the solid was collected byfiltration and washed with methanol and acetoneand then dried at room temperature. Formation ofpyridine functionalized TiO2 nano-particles (Py-TiO2

NPs) was confirmed by FT-IR spectroscopy, XRDpattern, elemental analyses and SEM micrograph.

Column preparationA glass column, 120 mm in length and 20

mm in diameter, was blocked by polypropylenefilters at the ends, filled with 200 mg of the Py-TiO2

nano-particles, and then used for the experiments.Before extraction, the column was treated with 5mL hydrochloric acid (1 M), 5 mL nitric acid (1 M), 5mL toluene, 5 mL ethanol and 20 mL distilled waterto remove organic and inorganic contaminants.

Preconcentration procedureA solution containing 1 µg mL-1 of

palladium with pH=7.0 was prepared. The pH wasadjusted with Na2HPO4/ NaH2PO4 buffer solutionand then 50 mL of solution was passed through thecolumn at a flow rate of 8 mL min-1. The column waseluted by 12 mL of 1 mol L-1 thiourea in 0.1 mol L-1

HCl solution, then the eluent was analyzed by FAAS.

Standard reference materials pretreatmentAuto-catalyst NIST SRM 2557 of 0.1000 g

were mixed with about 5.0 mL aqua regia and 1.0mL HF (48–51%, v/v) in a Teflon vessel, and heateduntil the sample was completely decomposed.Then the solutions were evaporated in a water bath.The residues were dissolved with 0.05 mol l-1 HCland diluted to the appropriate volume with distilledwater13.



Sorbent CharacterizationModification of TiO2 nano-particles have

been performed according to previous report14.Reaction of pyridine functionalizing agent withactive hydroxyl group on the surface of TiO2 leadsto formation of this sorbent (Fig. 1). Formation ofthis sorbent was confirmed by FT-IR spectroscopy,XRD pattern, elemental analyses and SEMmicrograph. The presence of peaks at 3027 (CH,aromatic), 2953 (CH, aliphatic), 1561&1470 (C=C,aromatic) and 1402 (C=N) in IR spectrum confirmpresence of pyridine in this sorbent. Also the amountof grafted pyridine was calculated by elementalanalysis. According to the elemental analysisresults (%C= 6.74, %H= 0.69, %N= 1.73),approximately 0.61 mmol pyridine is grafted oneach gram of TiO2 nano-particles. In order to confirmremaining TiO2 nano-particles unchanged afterfunctionalization (no decomposition or convertingto the other oxides), XRD pattern of final productwas recorded. Comparing to reference pattern(JCPDS file, No. 86–0147), the results show theTiO2 nanoparticles structure has not been changedafter functionalization (Fig. 2). Finally in order to

investigate the size and morphology of this sorbent,SEM micrograph of Py-TiO2 nano-particles wasrecorded. As it can be seen in Fig. 3, sphericalnanoparticles with approximately 15-20 nm indiameter were obtained.

Optimization studiesInfluence of pH

In order to study the effect of pH on thePd(II) extraction, the pH of 50 mL of different samplesolutions containing 1 mg L-1 palladium wereadjusted in the range of 2-9. The samples werepassed through the column at a flow rate of 8 mLmin-1. Then the column was eluted by 12 mL of 1 molL-1 thiourea in 0.1 mol L-1 HCl solution and the Pd(II)content in eluent was analyzed by FAAS. As theresults in Fig. 4 show, the highest palladium recoveryis at pH=7.0. The best recovery at neutral pH may beattributed to the presence of free lone pair of electronson the nitrogen atoms which are suitable donors forcoordination to the palladium ions.

Effect of type, concentration and volume ofeluent

Different eluent solutions includingdifferent HCl solutions and their mixture with

Table 1: The effect of diverse ions on recovery ofpalladium(II) on Py-TiO2 nano-particles

Interfering ion Concentration(µg mL-1) Recovery(%)

Na+ 1000 98.3K+ 1000 98.9Cs+ 1000 98.6Ca2+ 1000 98.1Mg2+ 1000 98.3Fe2+ 250 96.4Pb2+ 100 91.8Mn2+ 250 95.7Cd2+ 100 92.3Cr3+ 250 96.1

Table 2: The analysis of standard reference materials (NIST SRM 2557)

Sample Certified value Obtained value Recovery (%) RSD (%)Name (ng g-1) (ng g-1) (n=10)

NIST SRM 2557 239.8 235.9 98.3 3.2


Fig. 1: A schematic diagram for synthesis of pyridine functionalized TiO2 nanoparticles

Fig. 2: The XRD pattern of pyridine functionalized TiO2 nanoparticles

Fig. 3: SEM micrograph of pyridinefunctionalized TiO2 nanoparticles

thiourea with different concentrations were usedfor desorption of palladium from Py-TiO2 nano-particles. In this approach, a solution containing 1µg mL-1 of palladium with pH=7.0 was passedthrough the column at a flow rate of 8 mL min-1.Then the adsorbed ions were desorbed by 20 mLof each eluent. Then the palladium content in eacheluent was analyzed by FAAS. According to theseresults the best eluent is a solution of 1 mol L-1

thiourea in 0.1 mol L-1 HCl. Moreover in order tostudy the effect of elunet volume, different volumeof 1 mol L-1 thiourea in 0.1 mol L-1 HCl solution (2 ,4, 6, 8, 10, 12, 14, 16 and 18 mL) was used forpalladium desorption. The results show that at least12 mL of this eluent is needed for completepalladium desorption from the column.


Sample and eluent flow ratesIn order to study sample and eluent flow

rates, the pH of 100 mL of 1 µg mL-1 palladium (II)solution was adjusted to 7 and the solution waspassed through the column with different flow ratesin the range of 1-10 mL min-1 using a peristalticpump. As Fig. 5 show, the maximum flow rate forcomplete adsorption is 8 mL min-1. Also sameexperiments were performed by different eluent

flow rates. As it is shown in Fig. 5, at the flow ratesmore than 2 mL min-1, the Pd(II) desorption will bedecrease. So in the further experiments, 8 and 2mL min-1 were choosed as optimum sample andeluent flow rates, respectively.

Influence of interference ionsTo investigate the selectivity of the sorbent,

the effect of different cations such as Na+, K+, Cs+,

Fig. 4: The effect of pH on adsorbtion of palladium on pyridine functionalized TiO2 nanoparticles

Fig. 5: Investigation of adsorption and desorption time ofpalladium on pyridine functionalized TiO2 nanoparticles


Mg2+, Ca2+, Fe2+, Pb2+, Mn2+, Cd2+ and Cr3+ in thePd(II) determination was studied. The cations of astheir chloride salts with various concentrations wereadded to a 100 mL of single solution containing1 µg mL-1 palladium (II) and the extraction procedurewas followed. As can be seen from Table 1, a goodselectivity for palladium extraction was observedin pH=7.0 and this sorbent could be used as aselective Pd(II) extractor in natural samples withdiverse interfere ions.

Maximum adsorption capacityIn order to determine the maximum

adsorption capacity of this sorbent, 500 mL of asolution containing 100 mg palladium was treatedwith the extraction procedure and the maximumcapacity was calculated by analyzing the adsorbedpalladium in eluent. The maximum adsorptioncapacity for three replicates was found to be 61 mgg-1 (0.57 mmol g-1).

Analytical performanceIn order to determine the detection limit

(DL) of the presented method, 500 mL of ten blanksolutions were passed through the column underthe optimal conditions. The LOD values of 3.8 ng

mL”1 was obtained for palladium with Py-TiO2 nano-particles from CLOD= KbSb/m using a numerical factorof kb=3.The analytical values of the proposedmethod were calculated from the data obtainedunder the optimum conditions. The recovery of theextraction of palladium ion on Py-TiO2 wasdetermined to be 99.1 % with a relative standarddeviation of 2.5 % for ten replicated analysis.

Method validationThe method validation was done by

analyzing a standard reference material. NIST SRM2557 was analyzed by this method and the resultsof this study are presented in Table 2. The obtainedresults were in a good agreement with the certifiedvalue of the standard reference material.

CONCLUSION

The proposed solid phase extractionprocedure based on TiO2 functionalized withpyridine group shows a good selectivity forpreconcentration and determination of palladiumions in trace levels. The low detection limit,palladium at trace level can be determined by thisrapid and selective proposed method.

REFERENCES

1. Matthey J., Platinum 2008: 1 (2008).2. C. Hagelüken, Metall. 1-2: 31 (2006).3. Mehran Raizian, Naser Montazeri and

Esmaeil Biazar, Orient J. Chem., 27(3): 203-219 (2012).

4. Spivakov B. Y., Malofeeva G. I. and PetrukhinO. M., Anal. Sci., 22: 503 (2006).

5. Bulut V. N., Gundogdu A., Duran C., SenturkH. B., and Soylak M., J. Hazard. Mater., 146:155 (2007).

6. Thurman E.M., and Mills M.S. Solid-PhaseExtraction: Principles and Practice, Wiley,New York (1998).

7. Kiyoyama S., Yonemura S., Yoshida M.,Shiomori K., Yoshizawa H., Kawano Y. andHatate Y., React. Funct. Polym., 67: 522(2007).

8. Ghaedi M., Rezakhani M., Khodadoust S.,Niknam K. and Soylak M., Scientific World

Journal. doi:10.1100/2012/764195 (2012).9. Lotfi Zadeh Zhad H. R., Aboufazeli F.,

Sadeghi O., Amani V., Najafi E. and TavassoliN., http://dx.doi.org/10.1155/2013/482793,(2013).

10. Zhaoa X. N., Shia Q. Z., Xieb G. H., Zhoua Q.X., Chin. Chem. Lett., 19: 865 (2008).

11. Ali Moghini and Mohamad JavadPoursharifi, Orient J. Chem., 28(1): 203-219(2012).

12. Hoogboom J., Garcia P. M. L., Otten M. B.,Elemans J. A. A. W., Sly J., Lazarenko S. V.,Rasing T., Rowan A. E., Nolte R. J. M., J. Am.Chem. Soc. 127: 11047 (2005).

13. Fan Z., Jiang Z., Yang F., Hu B., Anal. Chim.Acta 510: 45 (2004).

14. Tasviri M., Rafiee-Pour H. A., Ghourchian H.,Gholami M. R., functionalized A., Appl.Nanoscience 1: 189 (2011).

INTRODUCTION

The rule of water quality on human healthis well known and recently attracted a great deal ofinterest. Many water quality problems have beenidentified and addressed in the past from severalparts of the world1. According to Nature (2010) about80% of the world’s population (4.8 billion in 2000)lives in areas with threats to water security2. Mostcases of waterborne diseases and related deathsoccur in developing nations are directly due tounsafe water, unsanitary conditions and insufficienthygiene3, 4.

Shallow groundwater provides drinkingwater for human in most parts of the world includingIran. But, the water table of shallow groundwater isoften quite near the surface. Therefore, there are alot of risks for this groundwater both on its quantity


Assessment of Arsenic, Nitrate and PhosphorusPollutions in Shallow Groundwater of the

Rural Area in Kurdistan Province (Iran)

ZAHED SHARIFI* and ALI AKBAR SAFARI SINEGANI

Department of Soil Science, College of Agriculture, Bu-Ali Sina University,Postal Code - 6517833131, Hamedan, Iran.


ABSTRACT

Quality of water resources in the rural area of Qorveh Plain (Kurdistan Iran) is facing aserious challenge due to arsenic (As) pollution and agricultural development. Therefore, 25 shallowgroundwater samples (from 14 households and 11 farms) were collected from this area with aimof evaluating their quality as drinking purposes. The water samples were analyzed for pH, waterelectrical conductivity (Ecw), As, Mn, Fe, Ca, Mg, Na, K, NO3, P, Cl, HCO3, SO4, Si, total hardness(TH), and total dissolved solids (TDS) by using standard methods. Results showed that thetoxicity of arsenic (on average, 51.8 ppb), nitrate (on average, 116.7 ppm) and phosphorus (onaverage, 0.32 ppm) are in an alarming state in this area. Furthermore, all of the wells under test inthis study fail to meet at least one safe drinking water standards, particularly with regard toarsenic, nitrate, TDS and pH. Among the appeared pollutions arsenic has a geologic origin andnitrate and phosphorus can affect by human activities such as agriculture, household chemicals,run-off and failing septic systems in this area. Based on the results of this assessment, the qualityof the groundwaters is not suitable for drinking purpose without appropriate remediation.

Key words: Water quality, Arsenic, Nitrate, Phosphorus, Pollution, Iran.

and quality. In some areas groundwater resourcesare at risk from the results of point and non-pointsource pollutants such as agricultural fertilizerapplication, irrigation return flows, industrial andwastewater discharges, animal waste andhousehold chemicals run-off, failing septic systems,etc5-7.

Kurdistan, a western province of Iran, isfacing the problem of As con-tamination withgeologic or igin. The discovery of As in thegroundwater of Kurdistan is a major concern topeople’s livelihood in the province. Exposure to highdoses of As can cause organ cancers, organdamage, weakness, neural disorders anddecreased appetite1, 8. Qorveh Plain is one of themost important agriculture areas in the Kurdistanprovince. However, the water and fertilizers in thisarea are not used effectively and economically.

234 SHARIFI & SINEGANI, Curr. World Environ., Vol. 7(2), 233-241 (2012)

Thus, arsenic pollution along with agricultural drainwaters from the heavy fertilizer lands is a greatchallenge to water recourses in this area. Nosci-entific and systematic studies have beenconducted in the region. However, several studieshave documented that contamination (e.g. nitrate)of household and farm wells can occur fromagricultural activities around the wells7, 9-11. In orderto improvement in water supplies and sanitation,the monitor and assessment of water quality onregular basis is very important. Hence, the presentwork is undertaken with the objective to assessshallow groundwater quality for drinking purposein the rural area of Kurdistan province (Iran).


Study areaSeven villages of Qorveh plain located

around the Sari Gunay Gold Mine were selectedfor this study. These villages confined betweenlongitudes 47° 57× 40' and 48° 8× 34' E and latitudes35° 7× 2' and 35' 12× 47° N (Figures, 1a, 1b and1c) in the northern-east region of Qorveh city inKurdistan province, western Iran. The climate in thisarea is semi-arid and the average annual rainfalland temperature is 339 mm and 11.4 oC,respectively. Twenty-five shallow groundwatersamples were collected from the area duringSeptember 2009. Of all these samples, 14 werecollected from household wells (depth on average,11 m) including Babashydolah (B1), Dashkasan(D1 to D6), Dosar (S), Jodaqye (G1 to G3), Narenjak(N) and Nayband (A1 to A3), the other 11 (depth onaverage, 26 m) were collected nearly from allshallow farm wells in this area includingBabashydolah (B2 and B3), Dashkasan (D7 to D9)and Zang Abad (Z1 to Z5) (Table 1).

Sampling methodTo collect the water samples, 300 ml (for

assessment of cations) and 1000 ml (for assessmentof anions plus pH and electrical conductivity (EC)clean polyethylene containers were washed bydetergent, rinsed first with hot water, then once with0.1 N HCl and twice with distilled water. Thencontainers were left to dry, and then they werecapped. The containers were then ready to be usedto collect the water samples from the wells. Watersamples were collected from wells, taps or other

points used by local residents. The samples werecollected after at least 10 min of pumps and tapsoperation. To keep the cations as solution andprevent adsorption or deposition on the walls ofthe sample containers, pH of the smaller containerswas reduced to below 2 using ultra pure HNO

3

immediately after filtering. After the sampling, thesamples were immediately transferred to laboratoryand refrigerated (at 4 °C) until their analysis.

Sample analysisSamples were analyzed in the laboratory

for the major physio-chemical properties accordingto the Standard Methods for the Examination ofWater and Wastewater (volume 1) described inAndrew et al. (2005) [12]. The pH and water electricalconductivity (ECw) were measured on pH andelectrical conductivity meters, respectively. Calcium(Ca2+) and magnesium (Mg2+) were determined bycomplexometric method. Chloride (Cl–) wasmeasured by AgNO3 titration method. Bicarbonate(HCO3

–) was determined by titration with H2SO4.Sodium (Na+) and potassium (K+) were measuredby flame emission photometric method. Sulphate(SO4

2–) was determined by turbidimetic method.Silicon (Si) was measured by thespectrophotometric molybdosilicate method. Nitrate(NO3

–) and phosphorus (P) were measured byspectrophotometric method. Total arsenic (Astotal)was determined by the graphite furnace atomicabsorption spectrophotometry (GF-AAS) (Varian220, Mulgrave, Victoria, Australia) and the total iron(Fetotal) and total manganese (Mntotal) were alsodetermined using atomic absorptionspectrophotometry (AAS). Total hardness (TH) wascalculated as CaCO3. Total dissolved solids (TDS)were calculated by using the following equation:

TDS (ppm) = 640 × ECw (dSm–1).


The physicochemical analyses of thehousehold and farm wells were statisticallyanalyzed and the results are presented in Tables 2and 3 respectively. In this study, assessment of thesuitability of collected samples for humanconsumption was evaluated by comparing thephysicochemical parameters with standard set ofthe World Health Organization (WHO 2011a) [4].

235SHARIFI & SINEGANI, Curr. World Environ., Vol. 7(2), 233-241 (2012)

The results have been discussed by the followingbasic criteria (Tables 2 and 3):

pHThe pH values of the water samples

ranged between 6.0 to 7.7 at household and 5.9 to7.4 at farm wells. On average, water sampled fromhousehold wells (7.2, weakly alkaline) hadcomparatively higher pH contents than thosesampled from farm wells (6.5, acidic). Lower pHvalues in the farm wells may be attributed by largerquantities of dissolved minerals15 and acidic ionssuch as SO4

2– due to the cropping activity (use offertilizers, pesticides, etc) 14. It confirm by the higheramounts of SO4

2– and TDS at the farm wells thanthe household wells (Tables 2 and 3). In the currentstudy because of acidic pH values of farm wells54% of the samples go beyond the normalpermissible range of pH (6.5-8.5) for drinking usage.

However, 14% of household wells did not fall inthis desirable range. Waters with a low pH arecorrosive, which can damage to metal pipes andother fixture of the plumbing system. The problemis more acute when the waters contact toxic metalpiping systems where these metals such as copper,lead, zinc, etc, can dissolve into the human’sdrinking water.

ArsenicThe deleterious effect of heavy metals in

the environment is well known15. Total Asconcentrations ranged from 15.6 to 60.5 ppb inhousehold wells, 47.4 to 102.4 ppb in farm wells. Itis a major concerning that all water samples fromhousehold and farm wells showed Asconcentrations of above the WHO guideline valuein potable water (10 ppb) 4, while 91% of farm wellsand 21% of household wells exceeded the

Table 1: Identification of sampling wells

No Code Village and type of water Depth (m)

1 B1 Babashydolah, source of drinking water of village 82 B2 Babashydolah, farm well 63 B3 Babashydolah, farm well 154 D1 Dashkasan, source of drinking water of village 65 D2 Dashkasan, household well 126 D3 Dashkasan, household well 107 D4 Dashkasan, household Well 158 D5 Dashkasan, household well 109 D6 Dashkasan, household well 1210 D7 Dashkasan, farm well 1411 D8 Dashkasan, farm well 612 D9 Dashkasan, farm well 1213 S Dosar, farm well 4014 G1 Jodaqye, household well 1215 G2 Jodaqye, household well 1216 G3 Jodaqye, household well 2517 N Narenjak, source of drinking water of village 718 A1 Nayband, household well 719 A2 Nayband, household well 1220 A3 Nayband, household well 721 Z1 Zang Abad, farm well 2222 Z2 Zang Abad, farm well 4023 Z3 Zang Abad, farm well 5024 Z4 Zang Abad, farm well 5025 Z5 Zang Abad, farm well 30


maximum acceptable level in potable water in Iran(50 ppb) [16]. High concentration of As in the drinkingwater can have detrimental effects on health. It isworth to note that some multi-chronic arsenicalpoisoning symptoms, such as skin lesions(including, keratosis and pigmentation), and evenamputation due to gangrene, have been reportedamong residents in west of Iran1, 8. In this area, as inmany part of the world, naturally-occur-ring As isresponsible for groundwater contamination. It is wellknown that natural enrichment of groundwater byAs is governed by the geophysical, chemical andbiological processes, such as oxidation–reduction,dissolution–precipitation and sorption–desorption177An important observation in this studyis that As contamination was increased with depthof wells (r = 0.71; P<0.01) and its concentration infarm wells (on average, 70.8 ppb) was nearly 2times higher than household wells (on average,36.8 ppb). In fact, in household wells, Asconcentrations in 79% of water samples stay below

50 ppb because As in the oxic shallow groundwater,and in recharging water, is sorbed to aquifersediments18.

Iron and manganeseTotal iron and Mntotal concentration varied

from 0 to 0.23 and 0 to 0.33 ppm in householdwells, and 0.03 to 1.86 and 0 to 0.12 ppm in farmwells, respectively. Out of all wells sampled, D7 andD9 (from farm wells) contain Fetotal higher thanallowable limit (0.3 ppm) for drinking purpose [4].Eight percent of water samples i.e. D5 (fromhousehold wells) and D9 (from farm wells) showedMntotal concentrations above the allowable limit (0.1ppm) for drinking usage4.

Nitrate and phosphorusThe concentrations of NO3

– varied from23.2 to 916.9 ppm at household wells, 1.8 to 79.0at farm wells with a mean of 178.3 and 38.2 ppm,respectively. In compared to the WHO’s drinking

Table 2: Summary statistics of physicochemical analysis and wise suitabilitycategorization of them for drinking in household wells collected in the rural

area of Qorveh plain (unit as ppm except As (ppb) and Ecw (dSm-1)

Parameter Min Mean Max Std. MPL1 (WHO, SEMPL2

dev. 2011a)

pH 6.0 7.2 7.7 0.5 6.5-8.5 14% (D3&D5)AsTotal 15.6 36.8 60.5 14.2 10 100%NO3

- 23.2 178.3 916.9 234.4 50 71% (N,D1,D3-D6,G1,G3,A1&A3)

Cl - 34.5 139.9 469.0 122.4 250 14% (A13&D3)HCO3

- 201.0 333.5 461.5 86.1 N.G –SO4

2- 37.8 133.0 309.7 95.1 250 14% (D4&G3)P 0.02 0.09 0.19 0.05 N.G –Na+ 41.0 91.4 169.6 32.2 200 0K+ 1.0 5.9 30.4 7.9 N.G –Ca2+ 52.75 152.0 468.9 108.3 200 14% (D3&D4)Mg2+ 7.3 38.1 125.4 33.1 150 0FeTotal N.D 0.09 0.23 0.07 0.3 0MnTotal N.D 0.03 0.33 0.08 0.1 7% (D5)SiO2 16.2 23.8 37.5 6.6 N.G –Ecw

5 0.44 1.30 3.50 0.78 N.G –T.D.S6 279.2 826.5 2217.3 501.7 1000 28% (A1,G1,D3&D4)TH7 162.0 536.5 1687.1 401.8 1000 0

1Maximum Permissible Limits, 2Samples Exceeding the Maximum 3Not Detected Permissible Limits, 4No Guideline,5Water Electrical Conductivity, 6Total Dissolved Solid, 7Total Hardness


water guideline of 50 ppm for NO3", 71% of

household wells and 45% of farm wells showedhigher concentrations4. The high concentration ofnitrate in the surveyed groundwaters is toxic andcan cause methemoglobimia or blue-babysyndrome in infant and also can increase the riskof gastric cancer19. In compared to farms wells,concentrations of nitrate at household wells wereunusually high (on average 178.3 ppm). It can beas a result of closeness of septic tank to thewells20, 21, lower depth and higher pH of the wells15

and abandoned livestock yards in the rural area. Inaddition to all the aforementioned, most of thehousehold wells often left open that exposes thewells to contamination by runoff during heavyprecipitation.

The concentration of phosphorus wasbetween 0.02 to 0.19 ppm at household wells,0.05 to 0.17 ppm at farm wells. There is no guideline for phosphorous in dr inking water, butphosphorus concentrations in all of the watersamples were considerably higher than the

normal limit of phosphorus (0.02 ppm) in shallowgroundwater24.

It is possible that the high concentration ofnitrate and phosphorous in these groundwatersresult from excessive application of manure andinorganic fertilizer at a rate greater than agronomicrate in this area. Farmer inquiries indicate that inaddition to chemical fertilizer – used often up to 2–3 times the recommended rate – the use of organicmanure, especially poultry manure, the type mostfrequently used (for potato fields about 10 ton ha-

1year-1 is used). Nitrate and phosphorus from suchsources coupled with widespread irrigation can beincreased groundwater contamination via runoffand infiltration in this area as previously shown byJeyaruba and Thushyanthy (2009) [23] and Jalali(2005 and 2009) 10, 11.

ChlorideThe concentrations of Cl– ion lie in

between the ranges of 34.5 to 469.0 and 51.5 to202.7 with a mean of 139.9 and 112.0 ppm, at

Table 3: Summary statistics of physicochemical analysis and wise suitabilitycategorization of them for drinking in farm wells collected in the rural area of

Qorveh plain (unit as ppm except As (ppb) and Ecw (dSm-1)

Parameter Min Mean Max Std. dev. MPL1 (WHO, 2011a) SEMPL2

pH 5.9 6.5 7.4 0.6 6.5-8.5 54% (D9&Z1-Z5)AsTotal 47.4 70.8 102.4 19.0 10 100%NO3

- 1.8 38.2 79.0 27.3 50 45% (B2,S&Z2-Z4)Cl - 51.5 112.0 202.7 38.7 250 0HCO3

- 397.4 600.0 958.3 187.7 N.G –SO4

2- 85.3 187.6 331.1 65.9 250 9% (S)P 0.05 0.1 0.17 0.04 N.G –Na+ 91.2 122.2 151.8 19.8 200 0K+ 7.7 11.7 28.2 5.7 N.G –Ca2+ 117.2 185.0 253.2 50.3 200 45% (S,Z1&Z3-Z5)Mg2+ 7.3 33.0 64.2 14.4 150 0FeTotal 0.03 0.3 1.9 0.04 0.3 18% (D7&D9)MnTotal N.D 0.02 0.12 0.04 0.1 9% (D9)SiO2 19.2 26.0 35.4 4.8 N.G –Ecw

5 1.02 1.47 1.91 0.28 N.G –T.D.S6 652.2 944.4 1223.4 179.1 1000 45% (S,Z1&Z3-Z5)TH7 448.8 597.8 756.2 102.7 1000 9% (D9)

1Maximum Permissible Limits, 2Samples Exceeding the Maximum 3Not Detected Permissible Limits, 4No Guideline,5Water Electrical Conductivity, 6Total Dissolved Solid, 7Total Hardness


household and farm wells, respectively. Theconcentration of Cl– at all of farm wells were wellwithin the acceptable drinking limit values for Cl–

(250 ppm) [4], however, 14% of household wellsi.e. A1 and D3 exceeded the recommended level.

Bicarbonate and sulphateThe concentrations of HCO3

– and SO42–

varied from 201.0 to 461.5 and 37.8 to 309.7 ppmat household, 397.4 to 958.3 and 85.3 to 331.1ppm at farm wells, respectively. Fourteen percentof household wells and 9% of farm wells werebeyond the permissible limit (250 ppm) for SO4

2–

[4]. Although the amount of this ion at Z2 (176.7ppm), Z3 (192.3 ppm) and Z4 (213.8 ppm) wasconsiderable.

Sodium, Calcium and magnesiumThe concentrations of the Na+, Ca2+ and

Mg2+ ranged from 41.0 to 169.6, 52.7 to 468.9 and7.3 to 125.4 ppm, with the respective averagevalues 91.4, 152.0 and 38.1 ppm at householdwells, 91.2 to 151.8, 117.2 to 253.2 and 7.3 to 64.2ppm with the respective average values 122.2,185.0 and 33.0 ppm, at farm wells. As shown inTables 2 and 3 all of water samples under test arewell within the acceptable drinking limit values forNa+ (200 ppm) and Mg2+ (150 ppm) [4]. However,14% of household wells i.e. D3 and D4 and 45% offarm wells i.e. S, Z1 and Z3 to Z5 are exciding themaximum permissible level for Ca2+ (200 ppm) indrinking water4.

Fig. 1: The Sanandaj-Sirjan zone in Iran (a), Kurdistan province mapand location of study area (b), Location of farm wells sampled (c)


Silica and potassiumThe Si and K+ concentrations varied from

16.2 to 37.5 and 1.0 to 30.4 ppm, with the respectivemean values of 23.8 and 5.9 ppm at householdwells, 19.2 to 35.4 and 7.7 to 28.2 ppm, with therespective mean values 26.0 and 11.7 ppm at farmwells. Permissible limit for silica in drinking waterhave not been prescribed not only by the WHO butalso by similar agencies. However, in view of thehigh concentration of Si in the Earth’s crust (28%by weight); life would have been real precarious ifexcessive ingestion of Si is really harmful. Furtherresearch is required in this direction. In the case ofpotassium, although potassium may cause somehealth effects in susceptible individuals, potassiumintake from drinking-water is well below the level atwhich adverse health effects may occur24. Thus,there is no guideline for potassium.

SalinitySalinity is the total amount of inorganic solid

material dissolved in any natural water, and watersalinization refers to an increase in total dissolvedsolids (TDS) and the overall chemical content of thewater25. Salinity of groundwater is a useful indicatorof the land area and drinking water at risk fromsalinity. Electrical conductivity and TDS are used astools for salinity assessment; their amounts rangedfrom 0.4 to 3.5 dSm–1 and 279.2 to 2217.3 ppm athousehold wells, 1.0 to 1.9 dSm–1 and 652.2 to1223.4 ppm at farm wells, respectively. As shown inTables 2 and 3, on average, the TDS at farms wells(944.4 ppm) was higher than household wells (826.5ppm), it can be attributed to the grater effects ofhuman activities such as application of fertilizers andirrigation practice on salinity of farm wells than thehousehold wells in this area. Previous studies haveshown that salinity is usually affected mainly bytopography, lithology of aquifer, recharge, runoff anddischarge conditions of groundwater26. Thepalatability of water with a TDS level of less thanabout 600 ppm is generally considered to be good;all of farm wells and 71% of household wells wereexceeded this desirable limit. However, Drinking-water becomes significantly and increasinglyunpalatable at TDS levels greater than about 1000ppm; 28% of household wells and 45% of farm wellsexhibit TDS values outside the maximum permissiblelimit. The presence of high levels of TDS in thesegroundwaters can have an objectionable to

consumers, owing to excessive scaling in waterpipes, heaters, boilers and household appliances4.

Total Hardness (TH)Water hardness is primarily due to the

amount of calcium and magnesium and, to a lesserextent, iron. The TH value ranged from 162.0 to1687.1 and 448.8 to 756.2 with an average of 536.5and 597.8 ppm as-CaCO3, in household and farmwells, respectively. According to the gradingstandards of TH, all of farm wells and 71% ofhousehold wells fall in the very hard waters category(TH>300 ppm as-CaCO3). The recommended valueof TH for potable water is 1000 mg as CaCO3. TheTH of all water samples except one sample (D9)was well within the permissible limit. But previousstudies have shown that consumption of waters withhigh TH cause numerous human diseases such asheart disease and kidney stone27.

CONCLUSIONS

The shallow groundwater sources in therural area of Kurdistan province have beenevaluated for their physicochemical composition andsuitability for drinking purpose. Results showed thatAs, NO3

– and P pollution are in an alarming state inthis area. The observed As in these groundwatershas a geologic origin and the high NO3

– and P couldoccur from human activities such as agriculture,household chemicals run-off and failing septicsystems. All wells under test failed at least one safedrinking water standard. So that, based on Astotal,NO3

–, TDS, pH, Ca2+, SO42– and Mntotal, 100%, 71%,

28%, 14%, 14%, 14%, and 7% of analyzed samplesat household wells and 100%, 45%, 45%, 54%, 45%,9%, and 9% of analyzed samples at farm wells wereunsuitable for human consumption, respectively.Other parameters that exceeded WHO guidelinevalues in this assessment were Fetotal (18% of farmwells) and Cl– (14% of household wells). Inconclusion, in order to improve public health, theusers of the groundwaters must be awareness onthe dangers of consumption of the waters.

ACKNOWLEDGMENTS

We acknowledge our gratefulness to theresidents of all the villages we visited for theircontribution to the research.


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2. Nature online Balancing water supply andwildlife, 29 September, http://www.nature.com/news /2010/10 /100929 /full /news. 2010.505. html (2010).

3. Olajire A. A. and Imeokparia F. E., Waterquality assessment of Osun river: studies oninorganic nutrients. Environ. MonitoringAssess, 69(1): 17-28 (2001).

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16. Liu A. Ming J. and Ankumah R. O., Nitratecontamination in private wells in ruralAlabama United States, Sci. Total. Environ.,346(1-3): 112-120 (2005).

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INTRODUCTION

Among different ecosystems, wetlandsconstitute one of the most important ecosystemsfor man offering numerous regulating services.Water quality assessment of small water bodies ofthe wetlands are of immense importance in themanagement of fisheries, water supply, andirrigation. Pollution status of water bodies are usuallyexpressed as biological and physico-chemicalparameters1. Several authors have extensivelydocumented the responses of macro-invertebratesto organic and inorganic pollution 2,3. Chatlafloodplain (24042/697// N and 92046/264//E) situatedin the south of Silchar town, Barak Valley, Assamhas 1500 fishery ponds and 12 seasonal lakes.(Fig.1). Although the wetland is resourceful withvariety of macrophytes, trees and fishes it is in aderelict or near derelict state due to high rates ofsiltation, infestation of weeds, unscientific fishingactivities, and use of pesticides in the surroundingtea gardens and agricultural fields 4 which led to aloss of 73% wetland area of Chatla floodplain 5. Allthese factors can affect the communities of aquaticorganisms leading to loss of diversity and species


Insect Diversity and Water Quality Parameters of TwoPonds of Chatla Wetland, Barak Valley, Assam

PINKI PURKAYASTHA and SUSMITA GUPTA*

Department of Ecology and Environmental Science, Assam University, Silchar - 788 011, India.


ABSTRACT

An investigation was carried out on two ponds of Chatla floodplain, Barak valley, Assamwith special reference to aquatic insects. Pond 1 is purely a fish pond where as pond 2 is acommunity pond too. Present study revealed the status of water quality and in turn diversity,density, dominance and abundance of aquatic insects in both the ponds. Almost all the physicochemical parameters of both the ponds were found within permissible range for aquatic life.However in pond 2 level of phosphate was found little higher than pond 1 due to release of soapsand detergents by human influence. In both the ponds order Hemiptera showed maximum relativeabundance ( 98% in pond 1 and 94% in pond 2). The study revealed lower diversity of aquaticinsects in pond 2 than that in pond 1.

Key words: Chatla floodplain, Pond, Human interference, Water quality, Aquatic insects.

extinction 6. Since, fluctuations in aquatic insectcommunity can give quick information of theirsurrounding water quality and are commonly usedas tools for marking an integrated assessment ofwater quality, investigation on water quality of twofishery ponds of Chatla wetland with specialreference to aquatic insects was carried out.


The topography of the Chatla floodplainis fenland type with small hillocks strewn amonglarge stretches of lowland. Pond 1 is a fish pondand is relatively undisturbed. Pond 2 is a fisherycum community pond. Water and insect sampleswere collected in replicates from both the sitesduring 2009-2010. Physico-chemical parameterssuch as Air temperature (AT), Water temperature(WT), Transparency, pH, Electrical Conductivity(EC), Dissolved oxygen (DO), Free CO2 , Totalalkalinity (TA), Nitrate (NO3

-) and Phosphate (PO4 3-

), Nitrite (NO2- ), and Ammonium (NH4

+) content ofwater were analyzed by standard methods 7,10. Theaquatic insects were collected by kick methodwhereby the vegetation was disturbed and the

244 PURKAYASTHA & GUPTA, Curr. World Environ., Vol. 7(2), 243-250 (2012)

circular net (mesh size 60µm) was dragged aroundthe vegetation for one minute11-12. They wereimmediately sorted, preserved in 70% ethyl alcoholand were later identified using Dewinter advancedstereo zoom microscope with the help of standardkeys13-19. A number of identified insects wereconfirmed in the entomological laboratory ofZoological Survey of India. Statistical analyses weredone by MS EXCEL 2007; SPSS 15.0 for Windows,Shannon Wiener Index of Diversity (H/ ), EvennessIndex (J/) and Berger–Parker Index of Dominance(d) were calculated by Biodiversity professionalversion 2 for windows.


Different physico-chemical parameters(AT, WT, Transparency, pH, EC, DO, Free CO2,TA,PO4

3-, NO3

-, NO2

-, NH4

+) in pond 1 and 2 during Postmonsoon 2009 to Monsoon 2010 and their meanconcentrations are shown in Table 1. Table 2 showedthe distribution of aquatic insects in pond 1 and 2.The significant correlations that exist amongenvironmental variables, diversity and density ofinsect are shown in Table 3. Fig.2 showed therelative abundance of aquatic insect ordersrecorded from pond 1 and pond 2 during the studyperiod. Relative abundance of aquatic insectfamilies and aquatic insect species in pond 1 and 2

are shown in the Fig.3 and Fig.4 respectively.Pattern of variation in the levels of Shannon –Weiner Diversity index (H’) and Evenness index(J’) and Berger-Parker index of Dominance (d) areshown in the Fig.5.The study revealed that in pond1 and 2 both air and water temperature did notshow much variation. In pond 1 DO, EC, NH4 andNO3

- concentration were slightly higher than that of

pond 2 while other parameters such asTransparency, Free CO2, TA, pH, and PO4

3-

concentration were recorded to be higher in pond2. The solubility and availability of nutrients isaffected by oxygen content of water and thereforethe productivity of aquatic ecosystems 18. The rangeof DO recorded in the present study is similar to theDO concentration reported in a previous study inthe same area21. In pond 1 correlation coefficientanalyses revealed a significant negativerelationship of WT with pH and DO. Classicalnegative relationship of WT with DO was alsorecorded in a previous study on Chatla floodplain22 which is attributed to the fact that in lowertemperature oxygen carrying capacity of waterincreases23. Negative relationship of DO withRainfall might be an indication that surface runofftransported sewage, fertilizer etc. into the pondwhich have lowered DO value by bacterialrespiration 22. EC was found to be higher in pond 1(4.59ms/ppt ± 2.93) compared to pond 2 ( 3.24ms/

Table 1: Physico-chemical properties of water of Pond 1 and Pond 2

Study SitesPond 1 Pond 2

Parameters Range Mean±Std dev. Range Mean±Std dev.

AT(0C) 22.6-29.83 25.93±0.75 22.6-29.3 25.09 ± 0.88WT(0C) 23.37-31.5 26.13±1.40 23-30.5 26.83 ± 0.75Rainfall(cm) 0-1484.7 551.98±590.2 0-1484.7 551.98±590.2pH 5.24-6.88 6.27 ± 0.31 6.38 – 7.8 7.15 ± 0.52EC (ms/ppt) 0.10-3.57 4.59 ± 2.93 0.09-7.82 3.24 ± 0.20Transparency (cm) 0-33.67 14.79 ± 1.60 13.08-24.83 17.19 ± 2.77DO ( mg l-1 ) 5.91-10.43 8.84 ± 0.86 6.77-9.18 7.83 ± 0.72Free CO2( mg l-1 ) 2.31-11.65 8.28 ± 0.57 8.42-35.60 16.15 ± 1.60TA( mg l-1 ) 11-30.53 19.93 ± 2.26 10.43-52.37 26.89 ± 3.49PO4

3- ( mg l-1 ) 0.32-1.88 0.86 ± 0.27 0.40-2.16 1.25± 0.72NO3

- ( mg l-1 ) 0.14-1.01 0.53 ± 0.23 0.13-0.66 0.46 ± 0.19

NO2-( mg l-1 ) 0.007-0.02 0.01 ± 0.01 0.01-0.08 0.03± 0.03

NH4 + 0.08-0.48 0.30 ± 0.13 0.07-0.33 0.17 ± 0.09

245PURKAYASTHA & GUPTA, Curr. World Environ., Vol. 7(2), 243-250 (2012)

Table 2: Distribution of aquatic insect species inPonds 1 and 2 of Chatla floodplain during study period

Order Family Sp. Name Pond 1 Pond 2

Hemiptera Gerridae Gerris lepcha Distant + +Limnogonus nitidus Mayr + +Neogerris parvula Stål + -

Mesoveliidae Mesovelia vittigera Horvath + +Notonectidae Enithares fusca Brooks + +

Anisops barbata Brooks + +Odonata Coenagrionidae Enallagma sp. + +Diptera Culicidae Culex sp. - +

Table 3: Significant Correlations among environmental variables,diversity and density of aquatic insects for pond 1 and pond 2

Parameters Pond 1 Pond 2

WT Vs pH -.956(*) -WT Vs DO -.989(*) -pH Vs DO .989(*) -pH Vs Rainfall -.987(*) -EC Vs DO - .995(**)EC Vs Free CO2 - .954(*)EC Vs TA .970(*) .973(*)EC Vs NO3

- .983(*) -DO Vs Rainfall -.961(*) -DO Vs TA - .977(*)Free CO2 Vs Insect Density - .993(**)TA Vs NO3

- .997(**) -NO3

- Vs Rainfall - -.993(**)NO2

- Vs NH4+ - .967(*)

NO2- Vs Rainfall - .960(*)

PO43- Vs NO2

- .955(*) -PO4

3- Vs Insect density -.984(*) -NO2

- Vs Insect density -.963(*) -Transparency Vs Diversity of insects - .977(*)

* Correlation is significant at the 0.05 level (2-tailed). ** Correlation is significant at

the 0.01 level (2-tailed).

ppt ± 0.20) where it showed significant positivecorrelation with TA and NO3

-. The range of NO3-.

between 0.1 - 3.0 mgl-1 is considered favorable forfish productivity25. In both the ponds, NO3

-.

concentration was found within the said rangeindicating their suitability for fish production. In pond2 EC showed significant positive correlation with

TA, Free CO2, and DO. Higher free CO2

accompanied by higher TA and higher pH in pond2 could be due to external application of lime. It isknown that addition of lime increases fish productionin soft (low total hardness) waters by stabilizing thepH of bottom mud and increasing the availability ofPhosphorus and Carbon dioxide for


Fig. 1: Location of the two Ponds , 1 and 2 in the floodplain of Chatla Wetland

Fig. 2: Relative abundance of insect orders in Pond 1 and Pond 2

Fig. 3: Relative abundance of aquatic insect families in Pond 1 and Pond 2


photosynthesis. The overall effect of liming is toincrease phytoplankton production which resultsin increased fish production26. Another reason mightbe that in heavily stocked fish ponds, Carbondioxide (CO2) concentration can become high as aresult of respiration. High CO2 concentrations arealmost always accompanied by low DOconcentrations (high respiration). Acidity of rainwater has impact on the pH of natural water bodies.As rain falls to the earth, each droplet becomessaturated with CO2 and pH is lowered27. This

explained the negative relationship of Rainfall withpH in pond 1. However in pond 2 no suchrelationship could be found due to application oflime. In pond 1 DO has shown significant positivecorrelation with pH , such type of positive correlationin between DO and pH have been recorded fromthe study of Asa lake llorin , Nigeria28 where DOdistribution followed a similar annual cycle withthe pH. In pond 2 DO has shown a positivesignificant correlation with TA. These alkalinityrelationships are extremely important in water

Fig. 5: Pattern of variation in the levels of Shannon diversity index, Evenness indexand Berger-Parker dominance of different insect species in both the Ponds

Fig. 4: Relative abundance of aquatic insect species in Pond 1 and Pond 2


chemistry, since the most prominent waterproblems are deposits and corrosion, andthese are closely related to the instability ofeach specific water caused by the tendencyof CaCO3 to dissolve in or precipitate from it 29.Range of PO4

3- ( 0.86 ± 0.27 in pond 1 and1.25 ± 0.72 in pond 2) recorded in the presentstudy is supported by the previous study in amarsh of the same floodplain30. Relatively highconcentration of PO4

3- in pond 2 might be dueto its use as community pond where PO4

3- iscontributed by household activities such aswashing, bathing etc. In pond 1 PO4

3- hasshown significant positive correlation with NO3-. Actually large concentration of PO4

3- and NO3- reported together from a water body indicatethat water is eutrophic in nature31 but as thewater of this pond showed low concentrationof bo th , i t ind ica tes the water i s no teutrophicated. Rainfal l showed signif icantnegative relationship with NO3

- and positivecorrelation with NO2

- in pond 2. A previousstudy conducted in the same study area alsoreported relatively high concentration of NO3

-

during dry months 32. A positive correlationbetween NO2

- and NH4+ is supported by the fact

that the most possible way of Nitrate entry inan aquatic system is through oxidation ofAmmonia form of Nitrogen to NO2

- and to NO3- consequently 31.

Aquatic insect community of pond 1 wasrepresented by two orders- Hemiptera, Odonata;four fami l ies- Gerr idae, Notonect idae,Mesoveli idae (Hemiptera), Coenagrionidae(Odonata) and seven species. Pond 2 wasrepresented by three orders Hemiptera,Odonata, Diptera; five families- Notonectidae,Gerr idae, Mesovel i idae (Hemiptera),Coenagrionidae (Odonata); Culicidae (Diptera)and seven species (Table 2). In both the pondsorder Hemiptera was the most prominent order,having 98% relative abundance in pond 1 and94% in pond 2. The most abundant family inPond 1 is Notonectidae (64%), followed byGerr idae (32%), Mesovel i idae (2%), andCoenagrionidae (2%). In Pond 2 the relative

abundance of Gerridae was highest (76%)fol lowed by Notonect idae (16%),Coenagrionidae (5%), Mesoveliidae (2%) andCulicidae (1%) (Fig.2 and 3). The aquatic insectspecies found common in both the ponds wereGerris lepcha Distant, Limnogonus nitidus Mayr,Enithares fusca Brooks, Mesovelia vittigeraHorvath, Enallagma sp. and Anisops barbataBrooks. In addition to these species Neogerrisparvula Stål was recorded in pond 1 and Culexsp. in pond 2 (Fig.4). Values of Shannon –WeinerDiversity index (H’) and Evenness index (J’)were found higher in pond 1 than that of Pond 2while Berger-Parker index of Dominance (d)value was found higher in pond 2 (Fig. 5).However the H’ values were found to be lessthan 1 in both the ponds indicating pollutednature of water35. In pond 1 insect density hasshown negative correlations with PO4

3- and NO2-

. This might be due to the reason that increasedpollution level with high concentration of PO4

3-

and NO2-.might have disturbed the colonization

as many species of aquatic insects are verysusceptible to pollution or alteration of theirhabitat 33. In pond 2 density of aquatic insectsshowed positive correlation with Free CO2 whichmight be due to increased respiration by morenumber of insects. Rainfall 34 has shown nosignificant relationship with diversity or densityof aquatic insects in both the ponds. The diversityof aquatic insects showed positive correlationwith Transparency. Such kind of posi t ivecorrelation was reported from lake Victoria37.From the study, it can be said that differentphysico chemical parameters of water qualityare inter related and these factors influencediversity, density and distribution of aquaticinsects in a particular water body.

ACKNOWLEDGEMENTS

The authors are thankful to UniversityGrants Commission, New Delhi, India for financialsupport. Authors are also thankful to the Head,Department of Ecology and Environmental Science,Assam University, Silchar, Assam for providinglaboratory facilities.


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2. Thorne, R.S.T.J. and Williams, W.P. , Theresponse of benthic macroinvertebrates topollution in developing countries: amultimetric system of bioassessment,Freshwater Biol.,37: 671-686 (1997).

3. Kazanci, N. and Dugel , M., Ordination andclassification of macro invertebrates andenvironmental data of stream in Turkey,Water Sci. Tech., 47: 7-8 (2000).

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5. Phukon, P. and Laskar , A.A., WetlandMapping and Change Detection in Part ofBarak Valley Using Remote Sensing andGIS, Map India, (2006).

6. Primack, R.B. and Rodrigues , E., Biologiada Conservação, Londrina ( Edited by Viva),p-328 (2001) .

7. Michael, P., Ecological Methods for Field andLaboratory Investigations, Tata Mc. Graw-Hillpublishing Company Ltd., New Delhi , p-434(1984).

8. APHA, Standard methods for theExamination of Water and Wastewater, 19th

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12. Subramanian, K.A. and Sivaramakrishnan ,K.G., Aquatic insects for biomonitoring freshwater ecosystems: A methodology manual,Trust for Ecology and Environment (ATREE),

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Bangalore, India, p-31(2007).13. Kumar, A., Description of the last instar larvae

of Odonata from Dehra Dun Valley (India)with notes on biology. I. Suborder Zygoptera,Oriental Insects, 7: 83-118 (1973a).

14. Kumar, A., Description of the last instar larvaeof Odonata from Dehra Dun Valley (India)with notes on biology. II. Suborder Anisoptera,Oriental Insects, 7: 291-331(1973b).

15. Thirumalai, G., Aquatic and semi aquatichemiptera (Insecta) of Javadi Hills,Tamilnadu, Zool. Surv. of India, 18: 63 (1989).

16. Thirumalai, G., Aquatic and semi aquatichemiptera (Insecta) of Tamilnadu-1,Dharampuri and Pudukkatai districts,Zool.Surv.India, Occasion 165: 45 (1994).

17. Bal, A. and Basu , R.C., Insecta: Hemiptera:Mesovellidae, Hydrometridae, Veliidae andGerridae, In: State fauna series 5, Fauna ofWest Bengal, India, p-511-534(1994 a).

18. Westfall , M.J. Jr. and Tennessen , K.J.,Odonata, In: An introduction to the aquaticinsects of North America, (Edited by Merritt ,R. W. and Cummins, K. W. ) , Dubuque ,Kendall Hunt Publishing, IA3,p-164-169(1996) .

19. ZSI, State fauna series 10. Fauna of Manipur,(Part -2) Insects, Zoological Survey of India,Kolkata, India (2004).

20. Wetzel, R.G., Detrial dissolved andparticulate organic carbon functions inaquatic ecosystems, Bulletin of MarineScience, 33: 503-509 (1984).

21. Bhuiyan, J.R. and Gupta, S.A., ComparativeHydrobiological Study of a Few Ponds ofBarak Valley, Assam, and Their Role asSustainable Water Resources, J.Environmental Biol., 28(4): 799-802 (2007).

22. Laskar, H.S. and Gupta, S., Phytoplanktondiversity and dynamics of Chatla floodplainlake, Barak Valley, Assam, North East India– A seasonal study, J Environmental Biol.30(6): 1007-1012 (2009).

23. Wetzel, R.G., Limnology, 2nd edn.,Philadelphia :Saunders Coll. Publication, p-860 (1983).

24. Singhal, R.N., S, and Davies, R.W. ,The


physicochemical environment and theplankton of managed ponds in Haryana,India, Proc Ind Acd Ani Sci., 95: 353-364(1986).

25. Verma, S.K. , Fresh water toxic blue-greenalgal blooms - A response to extra nutrientenrichment, In: Ecology of polluted waters(Edited by Kumar, A.). Voll. II, A.P.H.Publishing Corporation, New Delhi, 1161-1175 (2002).

26. Lewis, G.W., Pond Fertilization and Liming.Cooperative Extension Service, Universityof Georgia College of Agricultural &Environmental Sciences, Athens (1998).

27. William, A.W. and Durborow. , M.R.,Interactions of pH, Carbon Dioxide, Alkalinityand Hardness in Fish Ponds, SRACPublication No. 464 (1992).

28. Araoye, P.A., The seasonal variation of pHand dissolved oxygen (DO2) concentrationin Asa lake Ilorin, Nigeria, Int. J. of PhysicalSciences, 4(5): 271-274 (2009).

29. www.onlinewatertreatment.com (Technifax).30. Laskar, H.S. and Gupta, S., Ecology of a

marsh in Chatla floodplain, BarakValley,North-East India, EcologyEnvironment & Conserv., 16(3): 333-339

(2010).31. Ahmad, U., Parveen, S. Khan , A.A. , Kabir ,

H.A. , Mola , H.R.A. and Ganai, A.H.,Zooplankton population in relation tophysico-chemical factors of a sewage fedpond of Aligarh (UP), India, Biology and Med.3(1): 336-341 (2011).

32. Duttagupta, S., Gupta S. and Gupta, A.,Gupta Euglenoid blooms in the floodplainwetlands of Barak Valley, Assam, NorthEastern India, J Environmental Biol., 25: 369-373 (2004).

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34. Staub, R., Appling, J.W. , Hofsteiler , A.M.and Hass, I.J., The effect of industrial wastesof Memphis and Shelby county on primaryplankton producers, Bioscience, 20: 905-912(1970).

35. Voshell, J.R. Jr. ,A Guide to CommonFreshwater Invertebrates of North America,McDonald & Woodward PublishingCompany, Granville, Ohio, p-.442 (2002).

36. Cachar College Meteorological Observatorydata , Cachar College, Silchar , Assam(Rainfall data) (2009-10).

INTRODUCTION

Water- the elixir of the life system andwithout it life cannot exist. The diverse uses of waterfor drinking, cooking, washing, bathing a lot of otherpurposes. The presence of safe and reliabledrinking water is an essential prerequisite for astable community. So quality of water is to bedetermined for a locality of various purposes. Watercovers about 71 percent of the earth’s surface andit is abundant natural resource on the earth. Itincludes various resources such as rivers, seas,lakes, oceans, glaciers, groundwater, surface water,streams etc. Without water, life of any kind is notpossible.

Drinking water quality is a matter ofconcern as it is related to human health and manyhazardous problems may arise due to variouspollutants in it. Drinking water sources have beenpoisoned by directly or indirectly by sewage,pesticides, fertilizers, excess salt, agricultural runoff and drainage water from households and alsofrom industrial run off or due to natural geologicalfactors. It is difficult to get pure potable water forpublic health and water scarcity has led to takeunsafe, unconventional water sources. The water


The Occurrence of TDS and Conductivity of Domestic Waterin Lumding Town of Nowgong District of Assam, N.E. India

M.K. PAUL1 and SUJATA SEN2

1Department of Chemistry, Lumding College, Lumding - 782 447, India.2Department of Geology, Lumding College, Lumding - 782 447, India.


ABSTRACT

Total dissolved solid (TDS) and Conductivity are important parameters to determine thequality of water. The seasonal variations in TDS are mainly due to the ionic composition of water. Inthe present study the seasonal variations in TDS and Conductivity of Lumding Town were studiedfrom May, 2001 to April, 2004. It was found that the TDS of Dug well, Ring well and Ponds weremaximum high, but the TDS of River water and Supply water were appreciable.

Key words: TDS, Conductivity, Domestic Water

balance is also causing change due to humanactivities like industrialization, deforestation andpopulation explosion.

Water is a “ Cradle of life” on which allorganism play. As water balances human body in apositive way, it has a negative role in transmittingvariety diseases and other pathogenic germs. Manyphysico-chemical parameters in water is not in aproper way, they have harmful factor. In developingand underdeveloped countries to get pure potablewater is a difficult term and contamination ofdrinking water by domestic and industrial water aswell as human and animal excreta is a commonfeature. If the amount of certain chemicals crossesthe permissible limit causes harmful to publichealth. Many studies have carried out on the qualityof drinking water in various parts of the country butfor Lumding Town no attempt has been taken sofar.

Study areaThe district of Nowgong is situated on the

South bank of Brahmaputra occupies a centralgeographical position in the state of Assam. Thedistrict lies between 25045" and 26045" Northlatitudes and 91050" and 93020" East longitudes.

252 PAUL & SEN, Curr. World Environ., Vol. 7(2), 251-258 (2012)

Lumding Town is 90 Kilometer far South Eastdirection of the Nowgong from the district. TheLumding town is surrounded by Mikir hills (NowN.C. hills/Dima Hasao District) on its three sides(east, west and south) and in the west it is coveredby deep forest, which is named as Lanka Forest.The area of Greater Lumding is 411.8 Sq.km as per1971 census (Assam District Gazetters, 1978).Lumding Town is a valley like place surrounded byhills and the place is important as it connects theBarak Valley, Upper Assam and Lower Assam byvarious trains. Its projected population is 2 lakhs.The railway people are dependent on its ownsupply water, which is irregular, insufficient andlimited to only railway areas. The other peopledepend on dug wells, ring wells, ponds, rivers etc.The place is highly dry area, i.e., during March toMay. Weather is pleasant due to high humidity.During the month July – August the temperaturebecomes very high 350C to 390C. The southwestmonsoon continues during June to September andduring this period 85 - 90% rainfall occurs.

There is no major industrial establishmentin this town. There are a few factories like soaps,biscuits, potteries, plywood, and brick industries.The brick industries contribute to the soil and theland becomes unfertile and polluted. The big railwayindustry distributes effluent like burning diesel etc.to the soil and water. There are a few big drain ofthe railway and its attached area to release pollutedwaters from the town but there is no proper outletfor them. In civil areas many new drain constructionare going on by municipality and PWD. Thecommercial wastes of the market and householdwastes are dumped hither and thither inside thetown. Sometimes these wastes are burnt withoutincinerators. Sometimes proper sanitary systemsare not observed. They produce odor pollution andcontamination and sewerage goes to the drinkingwater.

Increase of vehicles with leaded petrolcontaminates to the nearby drinking water adjacentto the roads. Sometimes pitching makes water andsoil pollution and the people are affected bycarcinogen. Village people are dependent on rabiand kharif crops and for them they use variousfertilizers and pesticides and ultimately affect theirland use pattern and these washed away by surface

run off. Overall the modern society uses variousnon-biodegradable polymeric products theyaccumulates in water bodies and also penetratesto the soil – thus pollutes the ground and surfacewater.

During the summer and rainy seasonsvarious people of the locality are affected by waterborne diseases like typhoid, dysentery, diarrhea,jaundice etc. and many lives have gone due to thesediseases. Aquatic biotas are also affected byconsuming polluted water. Common people are notconcerned with the chemistry of water becausepolluted waters occur 80% of diseases. So it isimportant to determine the chemical quality of waterfor human welfare.

Aims and objectivesWater and its quality is deteriorated day

by day by modern civilization, population explosion,household byproducts and sewage materials. Thegeochemical position of an area are alsodetermines the presence of various chemicalspresent in drinking and other types of water in alocality. Due to direct relationship of water withhuman health and so very limited supply offreshwater for domestic purposes, the problems ofthem were considered.

The following objectives was aim of this study:-1. To determine the quality of water from various

drinking water sources with respect to thetotal dissolved solid (TDS) and Conductivity.

2. To determine the conclusion regarding thedrinking water quality in Lumding Town ofNowgong District of Assam, India.


To study the water quality parameters fromdifferent sources of Lumding Town of NowgongDistrict, the samples were collected season wisedepending on climatic and geographical conditionsof the town.

The samples were collected in differentseasons throughout the whole year from to May,2001 to April, 2004. Water samples were collectedin pre- cleaned polythene containers of 2 litrescapacity from Dug well (DW), Ring well (RW), Pond

253PAUL & SEN, Curr. World Environ., Vol. 7(2), 251-258 (2012)

(P), River water (R), Public Health Engineering(PHE) and Railway supply water (RSW).

Total Dissolved Solids(TDS)TDS is determined as according to the

APHA procedure. TDS is determined as the residueleft after evaporation of the filtered sample

( )TDS, mg/l = 1000

A B

V

− ×

WhereA = Mass of dried residue and beaker in g, (afterevaporation),B = Initial weight of the beaker in g,V = Vol. of water taken.

The process is as above of the total solidsdetermined, but here the water samples are filteredby Whatman 40 and having 50 ml. sample and thenevaporated to dryness and then the beaker dried

Table 1: The name of the sampling stations,serial no. and nature of the sources are given below

S. No. Sampling stations Nature of source

1. Nadirpar DW2. Halflong Road DW3. Subash Palley DW4. Patupather DW5. Khanger basti DW6. Santipara RW7. Subash Palley RW8. Ananda Palley RW9. Lanka Road RW10. Upper Babupatty RW11. Nadirpar (East Lumding) RW12. Bazar Area (Main Bazar) RW13. Jarangdisha RW14. New Coloney RW15. Samajbari Area RW16. Buddhamandir RW17. Murabasti RW18. Kamakhya Colony RW19. Loco Coloney P20. Nadirpar (Sitlabari Area) P21. Ananda Palley P22. Halflong Road P23. Santipara P24. Jarangdisha P25. Jhulanpool R26. Lanka Road R27. Near DRM Office R28 Balunala R29. Railway Coloney RSW30. ASEB Area PHE

Abb : DW – Dugwell, P = Pond, RSW – Railway supply water, RW –

Ring Well, R – River, PHE – Public Health Engineering supply water.


Fig. 1: Relative variation of Conductivity with respect to TDS for Dugwells, RSW and PHE water samples

Fig. 3: Relative variation of Conductivity with respect to TDS for Pond and River water samples

Fig. 2: Relative variation of Conductivity with respect to TDS for Ringwell water samples


Fig. 4: Relative variation of TDS, Conductance and Chloride(All Season Mean) for dugwells, RSW and PHE water samples

Fig. 5: Relative variation of TDS, Conductance and Chloride (All Season Mean) for ringwell water samples

Fig. 6: Relative variation of TDS, Conductance and Chloride(All Season Mean) for Pond and River water samples


in an oven at 103 – 1050C and weighed. Initialweight of the beaker was also taken.

TDS affects water quality in different ways.Excessive TDS in water imparts a bad taste in waterdue to mineralization of various salts. A dissolvesolid over 2000 mg/l produces a laxative effect(Kumaraswamy, 1991, Dembere 1998) This is dueto Magnesium sulphate along with some sodiumsulphate. Sodium parts affect the cardiac part andwomen with toxemia associated with pregnancy(Train, 1979). The maximum permissible limit of TDSin drinking water is 1000 mg/l (WHO). For irrigationit is 500 mg/l and above this limit crops havedetrimental effect (Dieborg 1991).

Total dissolved solids can be determinedby two methods. In the first method the EC valuesare multiplied with factor, which is usually, variesfrom 0.55 mg/l to 0.75 mg/l depending upon thenature of ions present. Because electricalconductance and total dissolved solids areindependent it is generally agreed that, if the TDSare less than 3000 mg/l, the factor 0.64 (Kumar andking, 2004) can be used to multiply the EC valuesto obtain the TDS values. In other method, the TDSvalues can be determined by evaporation techniquein which the total solid material will be collectedand determined gravimetrically.

ConductivityConductance of water is measured by a

digital Conductivitymeter (systronic Model, 304,India) and first calibrated with standard 0.01 M KClsolution (of conductivity 1287 ms/cm at 298 K).

The conductivity is not a direct pollutionparameter. It helps to give idea about themineralization of water. The mineralization of groundwater is due to perfect entrapment as well asrecharge of solubilisation of minerals from soils.Higher mineralization may impart bad taste aspotable water (Jain, 1998). Freshly distilled waterhas a conductivity value of 0.5 to 2 ms/cm whichchanges to ~ 4 ms/cm on standing due to absorptionof atmospheric CO

2. Drinking water has aconductivity in the range of 1500 mmho/cm (WHO,1993).


Total Dissolved Solids (TDS)The TDS contents of water samples are

given in the ranges below –15 mg/l to 530 mg/l (Dug well water),10 mg/l to 300.6 mg/l (Ring well water),5.8 mg/l to 350 mg/l (Pond water),45 mg/l to 253 mg/l (River water),80.1 mg/l to 251 mg/l (Railway supply water) and65 mg/l to 188 mg/l (PHE supply water).

In this investigation, the highest TDScontent (530 mg/l) was recorded in the dugwell ofNadirpar (DW1) in the premonsoon season andthe lowest value 5.8 mg/l was recorded in the pondwater of Loco colony (P1) during monsoon season.

Maximum TDS was observed in the dugwells and ring wells during the pre monsoon wasdue to the addition of lime and bleaching powderin the wells as well as in the monsoon season forthe treatment of water. The maximum permissiblelimit of TDS in drinking water is 500 mg/l by USEPA(1996) and 1000 mg/l (WHO, 1993). In drinkingwater, the dissolved solids may be due to inorganicsalts, organic matter and dissolved gas. Aconcentration of dissolved solids over 2000 mg/lproduces laxative effect (Dhembare et al, 1998).

The TDS contents of dug well water inCuddaph town (Andhra Pradesh) were found to beextended over a range of 800-13,464 mg/l, with anaverage value of 2528 mg/l, which was very muchhigher than the permissible limit (Kumarswamy,1991). A high TDS (8704 mg/l) was observed in theeast coast of South India (Guru Prasad and SatyaNarayan, 2004). Normally ground water has ahigher TDS load compared to surface water (VeeraBhadram et al., 2004). Murugesan et al., (2004)showed high TDS (1000 to 1800 mg/l) in the groundwater quality of seashore, due to seawater enterinto the aquifers of the Chennai city of Tamilnadu.High values of TDS are due to salt-watercontamination and industrial pollution (Kumar etal., 2005). The TDS content at deeper levels (> 40m depth) is comparatively low in all the samplesand lies well within desirable limit of 500 mg/l. It


may conclude that there is more mineralization ofground water at depth upto 40 meters (Jain, 2004).

ConductanceThe values of conductance of water

samples are given in Table 4.3 (a, b and c). Themeasurement were found in the ranges of99 mmhocm-1 to 1483 mmhocm-1 (Dugwell water),97 mmhocm-1 to 1378 mmhocm-1 (Ringwell water),89 mmhocm-1 to 1410 mmhocm-1 (Pond water),99 mmhocm-1 to 1040 mmhocm-1 (River water),130 mmhocm-1 to 300 mmhocm-1 (Railway supplywater),179 mmhocm-1 to 400 mmhocm-1 (PHE supplywater).

Figs 1 to 6 represent ranges and seasonalaverages of the conductance of various sources.The highest value of conductance was observedfor the water samples of ring well of Patupather(DW4) in monsoon season. Again, the lowest valuewas observed in the pond water (P5).

The conductivity qualitatively measuresthe extent of mineralization. The mineralization may

be caused of entrapment, ground water rechargeand solubisation of minerals from soils. Highermineralization may impact a bad taste to the potablewater (Jain 1998). Drinking water can have aconductivity range of 1500 mmho/cm (WHO). Theconductance values changed from season toseason but no clear trend was observed.

Viswanath and Anantha Murthy (2004)showed that high electrical conductivity (1580mmho/cm) due to septic leakage from households.Prasad et al (2004) showed high conductivity(13390 mmho/cm) in different sources of groundwater Machilipatnam town of Andhra Pradesh,Electrical conductivity of the ground water samplesin both Mandya and Maddur towns (Andra Pradesh)ranged from 1524 to 2409 ms/cm which indicatesthe presence of high dissolved solids in groundwater samples. (Shivashankara and Sharmila,2004). A maximum conductivity value of 2210 ms/cm and 1914 ms/cm was observed at Shasradhara(Dehradun, Uttranchal) was observed during preand postmonsoon season (Jain, 2004)respectively.

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16. WHO, Guidelines for drinking water quality(2nd edn.), WHO, Geneva (1993).

INTRODUCTION

The increasing anthropogenic activities inand around the aquatic ecosystems and theircatchments areas in recent years, have contributedto large scale mineral enrichment and incidence ofmany pathogenic micro-organisms in different waterbodies. Besides, many major water bodies are beingdegraded due to continuous heavy discharge ofuntreated waste and surface run-off, causingdeleterious effects in flora and fauna and otheraquatic organisms (Sah et al., 2000). The distributionpattern and periodicity of different organisms inwater solely depends upon the imprint of preceedingenvironmental factors (Badge and Verma, 1982). Assuch the significance of those factors as potentecological parameters can be appreciated byconsidering the structure, physico-chemicalcharacteristics, flora and fauna, primary andsecondary productivities of the water bodies.

Out of the many bacteria found in water,some are indicator of pollution and a small numberof them are pathogenic. The coliform groups ofbacteria are of great importance and include anumber of organisms (Mc Kinney, 1962), causing


Distribution Pattern of Enteropathogens in GreaterImphal Area of Imphal River, Manipur

TH. ALEXANDER SINGH1, L. BIJEN MEITEI2 and N. SANAMACHA MEETEI3

1Research Scholar, CMJ University, Laitumkhrah Shillong, Meghalaya - 793 003, India.2Junior Research Officer, Directorate of Environment, Porompat, Imphal East - 795 005, Manipur.

3Directorate of Environment, Imphal East - 795 010, Manipur, India.


ABSTRACT

An investigation on enteropathogens in the water of Imphal river at five different sites withingreater Imphal area of Manipur was carried out as a part of water quality documentation at monthlyintervals for one year. Densities of enteropathogens were found to be high during rainy seasonand low during summer and winter seasons. The degrees of survival for the different bacteria wereinfluenced by various environmental factors as well as anthropogenic activities.

Key words: Enteropathogens, anthropogenic, allochthonous, indicator organism, pollution.

different water borne diseases. Coliform bacterialcontamination in urban and rural surface water hasbeen a major public health concern for decades(Burton et al, 1987). The sources for thecontamination of different water bodies (Weibel etal, 1964, Crane et al., 1983, Tunnicliff and Brinkler,1984) and relationship between land use andcoliform level (Faust, 1982) had already beenestablished.

Water qualities especially those of rivershave been deteriorating due to disposal of garbage,religious offerings, sewage, recreational andconstructional activities in the catchments areas.While many pollution problems affecting waterquality are the direct result of human activity, someare less easily isolated (Cooper and Night, 1989).Contaminated water provides shelter to a variety ofdiverse micro-organisms (Khulbe et al., 1989),which many cause various water borne diseases.

Therefore, the present investigation hasbeen carried out with the objectives to assess thedegree of persistence and distribution patterns ofenteropathogenic groups of bacteria in greaterImphal area of Imphal river.

260 SINGH et al., Curr. World Environ., Vol. 7(2), 259-265 (2012)


Samples for the enumeration of bacteriawere collected at monthly intervals from five (5)experimental sites within greater Imphal area ofImphal City, Manipur (1-Koirengei, 2-Lamlong, 3-Sanjenthong,4-Ningom Thongjao, and 5-Lilong)during July, 2011 to June, 2012. Water samplesfrom different sites were collected by means ofshallow water sampler in a wide-mouthed bottlewhich is pre-sterilized. Samples were chilled andreturned to the laboratory on the same day foranalysis. Total coliform and fecal coliform werequantitatively estimated by using standardmembrane filter technique with appropriate dilutions(APHA, 1989). Triplicate analysis was done for eachparameter. Further qualitative characterization andverification, selective medium for subsequentbiochemical test were carried out (Buchanan andGibbons, 1984; APHA, 1989). For the calculation ofANOVAR (Analysis of variance) in differentseasons, the methods of parker (1973) and Trivedi,Goel and Trisal (1987) were used in computing theanalysis.

RESULT AND DISCUSSIONS

Coliform bacterial density at the dilutionlevel of 101 in the course of the river was found tobe gradually increased from January onwardsexhibiting peak value of 820.00 CFU 100-1 ml duringrainy season of October and lowest value of 240.00CFU 100-1 ml during winter season of January(Table-1). Similar observations was reflected in thefindings of Sharma and Bharadwaj (2000) andSharma and Rajput (1996) that coliform bacterialdensity was found to be correlated with rainfall dueto fecal runoff from the disturbed as well asundisturbed catchment areas. Similar observationswere also reported by Geldreich (1976), Das andPande (1986), Baxter-potter and Gilliand (1988),Cooper and Knight (1989) and Rajender and Khulbe(1998).

This trend of fluctuating density of totalcoliform population depend upon many factors suchas physical chemical and environmental factors,including rainfall temperature, oxygen profile etc(Akpata, et al., 1993). The rainfall pattern influencesthe environmental condition of the water body

Tab

le 1

: M

on

thly

var

iati

on

s in

the

mic

rob

ial p

op

ula

tio

ns

of I

mp

hal

riv

er (J

uly

, 201

1 to

Ju

ne,

201

2)(T

ota

l Co

lifo

rm C

ou

nt x

10 1

00-1 m

l)

Sit

esJu

l. ‘1

1A

ug

. ‘11

Sep

. ‘11

Oct

. ‘11

Nov

‘11

Dec

. ‘11

Jan

‘12

Feb

. ‘12

Mar

. ‘12

Ap

r. ‘1

2M

ay. ‘

12Ju

n ‘1

2

134

2.67

400.

0041

0.00

450.

0034

7.33

290.

0023

8.67

298.

6731

0.00

350.

0042

0.00

480.

002

389.

3348

2.67

524.

6751

2.67

379.

3327

3.33

257.

3334

7.33

380.

0046

2.67

510.

0053

6.67

348

2.00

520.

0061

0.00

820.

0042

0.00

376.

6734

6.67

437.

3345

6.67

530.

0062

6.67

682.

674

756.

6756

1.33

458.

6767

1.33

426.

6738

4.00

297.

3338

1.33

359.

3351

7.33

733.

3373

0.00

568

0.00

458.

0047

0.00

607.

3336

0.00

296.

6724

0.00

312.

0031

8.67

420.

0066

0.00

658.

67

261SINGH et al., Curr. World Environ., Vol. 7(2), 259-265 (2012)

during which many biodegradable materials arewashed and carried down, thus explainingincreasing in high bacterial population (Hill andWebb, 1958).The survival of bacteria in water isdirectly correlated with the presence of someorganic materials and there is fluctuation in thepopulation with the increasing and decreasing loadsof biodegradable waste input in the water system(Flint, 1989). On the other hand, Knox (1986)suggested those bacteria and algae as food sourcesfor primary consumer such as zooplankton, benthicinvertebrates and some fishes resulting in thedecrease of bacterial density. Therefore, the resultsof the present findings were also closely relatedwith the observations of Nwachukwu et al. (1989),Jama et al. (1986) and McSwain and Swank (1997).

The high count in fecal coliform populationin the river might be resulted from fecal material ofboth human beings and animals. The same wasreported by Sharma and Rajput (1996), Fatma etal. (1997), Shidhu and Khulbe (1998) and Khalil(2000) that they are mainly resulted from thecontinuous contamination of human and animalexcreta. But, according to Faust et al. (1975), survivalof fecal coliform was affected by many factors likeinteraction with metal, algal toxins, temperature,dissolved nutrients, ions, organic matters,protozoa, etc. Ranges of fecal coliform populationof 106.67 to 420.00 CFU 100-1 ml (Table-2) at thedilution level of 101 was also found in closeassociation with Sharma and Rajput (1996) andSharma and Bhardwaj (2000). In the present finding,high population of fecal coliform during rainyseasons and low population during winter season(Table-2) were in consistent with the observation ofGeldreich (1991), Joshi and Rajput (1992) andIslam et al. (1993). According to Thomas and Levin(1978) and Watnabe et al. (1981), fecal streptococciare mainly originated from the animal excretabecause they are the normal habitat in thegastrointestinal tracts of warm blooded animals.

It is difficult to monitor the actualcontamination sources in mixed cover watershedssince total coliform enumeration is general in natureand several streptococci are ubiquitous in soil andaquatic environment (Kebbey et al., 1978; Faust,1982). The best data application for separatinghumans sources of contamination from other warm

Tab

le 2

: Mo

nth

ly v

aria

tio

ns

in th

e m

icro

bia

l po

pu

lati

on

s o

f Im

ph

al r

iver

(Ju

ly, 2

011

to J

un

e, 2

012)

(Fae

cal C

olif

orm

Co

un

t ×

10 1

00-1 m

l)

Sit

esJu

l. ‘1

1A

ug

. ‘11

Sep

. ‘11

Oct

. ‘11

Nov

‘11

Dec

. ‘11

Jan

‘12

Feb

. ‘12

Mar

. ‘12

Ap

r. ‘1

2M

ay. ‘

12Ju

n ‘1

2

121

0.00

273.

3320

6.67

226.

6712

0.00

106.

6723

7.33

126.

6712

0.00

156.

6722

0.00

246.

672

289.

3331

6.67

310.

0024

7.33

143.

3311

9.33

259.

3315

9.33

130.

0016

9.33

287.

3331

0.00

332

6.67

328.

6742

0.00

376.

6714

9.33

126.

6734

6.67

186.

6716

8.67

280.

0034

0.00

360.

004

330.

0027

0.00

347.

3334

9.33

246.

6718

9.33

297.

3313

3.33

139.

3321

6.67

370.

0034

9.33

540

1.33

263.

3323

6.67

310.

0021

9.33

160.

0024

0.00

126.

6712

6.67

169.

3331

4.67

326.

67


blooded sources of contamination may be fecalcoliform (FC): fecal streptococci (FS) ratio over time(Cooper and Knight, 1989). According to Geldreich(1976), Baxter-potter and Gilliland (1988), the ratioless than 1.0 indicated warm blooded animalpollution while ratio of 4.0 or more suggesteddomestic waste pollution. During the study period66 percent of all the samples had a ratio greaterthan 4.0 while 50 percent had a ratio greater and1.0 (Table-4). These ratio indicated that domesticwaste pollution is common than the warm bloodedanimal pollution.

According to Cooper and Knight (1989)coliform count could not be linked statistically withphysical parameters because variability of indicatorbacteria masked relationships as shown by largesite-to-site fluctuations in bacterial count. He alsostated that coliform counts did not vary withincremental changes in stage (± 0.1m) or withinstream suspended sediment concentrations,which were excellent indicators of rainfall and run-off. In the present study, it was observed that duringsummer there were insignificant variations ofcoliform count, which might be due to low rainfallactivity. This is in agreement with the findings ofRobbins et al., (1972) that all coliform indicatorgroups were significantly higher in rainy seasonthan the preceding summer or following winter.Robbins et al., (1972) also indicated that coliformconcentrations were overshadowed by large-scalehydrologic events but most water quality parametersdid not produce statistically significant equation forpredicting bacterial pollution.

In the rainy season coliform bacterialpopulation were found to be significantly fluctuating.This might be due to input of allochthonous materialby influx of rainwater and soil, which impartsignificant variation of bacterial population. In thepresent study, analysis of variance of the criticalvalue of ‘F’ at 5% level during rainy season revealedsignificant effect on the density of total coliform(P<0.05) and fecal coliform (P<0.05), while fecalstreptococci revealed insignificant effect (P<0.05).However, significant differences were observed insummer and winter at the level of p<0.05 to P<0.01for all the bacteria except faecal coliform whichshown insignificant differences during winter(P>0.05). Their significance differences indicated

Tab

le 3

: Mo

nth

ly v

aria

tio

ns

in th

e m

icro

bia

l po

pu

lati

on

s o

f Im

ph

al r

iver

(Ju

ly, 2

011

to J

un

e, 2

012)

(Fae

cal S

trep

toco

cci C

ou

nt

× 10

100

-1 m

l)

Sit

esJu

l. ‘1

1A

ug

. ‘11

Sep

. ‘11

Oct

. ‘11

Nov

‘11

Dec

. ‘11

Jan

‘12

Feb

. ‘12

Mar

. ‘12

Ap

r. ‘1

2M

ay. ‘

12Ju

n ‘1

2

147

.33

63.3

357

.33

59.3

342

.00

37.3

327

.33

31.3

327

.33

31.3

352

.00

47.3

32

56.6

772

.00

62.0

062

.00

45.3

340

.00

32.0

037

.33

30.0

035

.00

61.3

363

.33

379

.33

86.6

789

.33

76.0

062

.00

42.6

740

.00

46.0

036

.67

56.6

782

.00

87.3

34

86.6

770

.00

66.0

764

.00

66.6

750

.00

47.3

342

.67

29.3

348

.00

87.3

382

.00

511

0.00

56.0

062

.00

60.0

057

.33

47.3

345

.33

39.3

322

.00

42.0

062

.00

73.3

3


continuous contamination of domestic and animalwastes along with run-off during rainy season. Thisis also in agreement with the finding of Sharmaand Bharadwaj (2000). They also stated thatcorrelation between total coliform and rainfall wasfound to be positively significant and it appears thathuman inhabitation and other activities based onland usage around the water body were responsiblefor the input of indicator organisms. Cooper andKnight (1989) also showed marked significantseasonal and monthly differences (P<0.05) of fecalcoliform and fecal streptococci at two differentlocations of Agarian hill land streams due to rainfallpattern over the area. Hill and Webb (1958) alsoreported that the variability of bacterial count atdifferent sites was found correlated with the sourcesof pollution. They found that bacteria formed animportant link between primary producers andconsumers, so it would appear that pollution affectsthe aquatic food chain. Flint (1989) reported that

survival of E. coli in filtered water was due to thepresence of some organic materials. It is therefore,possible that specific bacterium survives withspecific form of organic matter and this impart inthe variability of species composition. So, the resultsin the present study were closely associated withthe above observations.

Thus, from the above results it is clear thatthe bacterial population had varied densities indifferent seasons which was influenced by thedifferent environmental factors and theirpersistence at different densities in the river waterthroughout the study period offer an excellentopportunity to characterize the microbial quality ofthe water system and it is suggested that the riverwater is not suitable even for domestic purposesand need to be treated before use from hygienicpoint of view.

Table 4: Fecal Coliform : Fecal Streptococci ratioof Imphal River from July, 2011 to June, 2012

Months Sites

1 2 3 4 5

July ‘11 4.43 5.11 4.12 3.81 3.65Aug. ‘11 4.31 4.40 3.79 3.86 4.70Sep. ‘11 3.60 5.00 4.70 5.25 3.81Oct. ‘11 3.82 3.99 4.96 5.46 5.16Nov. ‘11 2.86 3.16 2.41 3.70 3.83Dec. ‘11 2.86 4.98 2.97 3.79 3.38Jan. ‘12 8.67 8.10 8.67 6.28 5.29Feb. ‘12 4.04 4.27 4.06 3.12 3.22Mar. ‘12 4.44 4.33 4.60 4.75 5.75Apr. ‘12 5.00 4.84 4.94 4.51 4.03May ‘12 4.23 4.68 4.15 4.24 3.84Jun. ‘12 5.21 4.89 4.12 4.26 4.45

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5. Buchanan, R.E. and Gibbon, N.E., Bergey’sMannual of Determinative Bacteriology (9thEdn.), The Williams and Wikkins Co.Baltimore, M.D (1984).

6. Burton, G.W., Gunnison, Jr. D. and Lanza, G.D.Survival of pathogenic bacteria in variousfreshwater sediments. Appl. Environ.Microbiol. 53: 633-638 (1987).

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11. Faust, M.A., Aotakey, A.E. and Hargadon, M.T.Effect of physical parameters on the in situsurvival of Escherichia coli MS-6 in estuarineenvironment. Appl. Microbiol., 30: 800-806(1975).

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13. Flint, K.P., The long-term survival ofEscherichia coli in river water. J. Appl.Bacteriology 63: 261-270 (1989).

14. Geldreich, E.E., Fecal coliform and fecalstreptococci density relationships in wastedischarges and receiving waters. CRC. Crit.Rev. Environ. Control 6: 349 (1976).

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16. Hill, M.B. and Webb, J.E., The ecology ofLagos lagoon II. The topography andphysical feature of Lagos harbour and Lagonlagoon. Philosophical Transaction of the

Royal Society of London 214(B): 319-333(1958).

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19. Joshi, A and Rajput, S. Distribution of somehuman pathogenic bacteria in twofreshwater lakes at Jabalpur. Ind. J. Env.Protection 12 (5): 321-323 (1992).

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INTRODUCTION

Urban areas and inhabitants of cities tendto increase. Nowadays, about half of the world totalpopulation live in urban settlements. This largenumber of dwellers produce variety of activities andmodify urban air quality and pattern. Urban windflow is driven by a deep, stratified urban boundarylayer with significant wind fluctuations. Solar heatingeffects include shadows from buildings and trees,aerodynamic drag, heat exchange affected by thesurface property variations and turbulent heattransport.

Causes of wind field modifications in urban areasIn urban areas, main air flows from

prevailing winds are strongly modified, dependingon constructions’ morphology and urbanmicroclimate effects.3 Wind field modifications havebecome particularly significant because of theincreasing number of high-rise buildings, industrialand vehicular activities etc. Significant differencescan be found in wind speed frequency distributions


Wind Field Modifications in Habitable Urban Areas

SEEMI AHMED and ALKA BHARAT

Department of Architecture and Planning, M.A.Natonal Institute of Technology, Bhopal, India.


ABSTRACT

This paper discusses different criteria for the assessment of wind field environments inurban areas and how they relate to field observations. The importance of the inclusion of windenvironment studies in the planning process is also discussed. The increasing influence of the builtenvironment on wind speed and direction makes any forecast for heights below 50 meter veryhazardous1. This increase in the areas with more built form where the roughness is extremely high.It is not always possible to make a quantitative forecast of wind speed and direction in urbanenvironment. Examples are provided to illustrate how development controls can be designed toensure that pedestrian amenity is not compromised by new development while at the same timenot become a burden to innovative design approaches or good design practice due to windmodification. The paper concludes with a number of case studies that provide examples of howinnovative techniques for mitigation of adverse wind environments can achieve the desired levelof pedestrian amenity without having to compromise with the architectural design intent.

Key words: Wind engineering, pedestrian environment comfort, Urban Heat Island (UHI) effect

at vertical levels in urban areas due to followingelements and phenomenon.´ Buildings, Vegetation ( Physical and thermal

Obstacles/ Roughness)´ Air conditioners (thermal)´ Natural Topography (moisture properties of

the surface, undulations etc)´ Street canal effects due to Vehicular

movements. (thermal)´ Tall buildings - Turbulence, Roughness´ Local Climatic conditions/ Seasonal

Variations´ Shelter from nearby buildings,´ Urban Heat Island Effect (UHI)

Wind field modifications due to UHI effectUrban surfaces act as a giant reservoir of

heat energy. Concrete can hold roughly 2,000 timesas much heat as an equivalent volume of air.

The large daytime surface temperaturewithin the UHI is easily seen via thermal remotesensing. At night time an inversion layer is formed

268 AHMED & BHARAT, Curr. World Environ., Vol. 7(2), 267-273 (2012)

This traps urban air near the surface, and keepingsurface air warm from the still-warm urban surfaces,forming the nighttime warmer air temperatureswithin the UHI. Lose of heat at night is blocked bythe buildings in an urban area.

Difficulties and peculiarities of an urban windregimeUrban Roughness

Prediction of the wind speed in the builtenvironment is difficult. One of the reasons is“surface roughness”. The many obstacles anddifferent heights of buildings give the builtenvironment a high roughness coefficient2,compared to open, rural locations. The roughnesscoefficient is generally used to extrapolate wind

speed at different heights from measurement at onlyone or two heights and locations. A high roughnesscoefficient means slower acceleration of speed asheight increases and therefore lower energy yields.

Table 1a gives the roughness coefficient(or length) generally used for a type of surface. It isworth noting the difference between openagricultural area (even with some houses and

Table 1(b): Urban BuildingRoughness – Flow Regime

Low Density –isolated flowBuildings and trees are small and widely

spaced, eg. Modern single family housing with largelots and wide roads, light industrial area or shoppingmall with large paved or open space.Medium Density- wake interference flow

Two to four storey buildings and maturetrees elements of various heights occupy more than30% surface area and create semi enclosedspaces (street canyons and courtyards), closelyspaced and large and semi detached hoses, blockof apartments in open surroundings. Mixed houseswith shops, light industry, churches, and schoolsHigh Density- Skimming flow

Buildings and trees closely packed and ofsimilar height, narrow street canyons eg. Old towncentres dense row and semidetached housing,dense factory sites.High rise- chaotic or mixed flow

Scattered or clustered tall towers ofdifferent heights jutting up from dense urbansurroundings, eg. Modern city core, tall apartment,major institutions

Fig. 1: The wind speeds at Ground andhigher levels (Grimmond et al., 2007)

Table 1(a): Roughness coefficientsfor different surfaces 2

Roughness Landscape Typelength m

0.0002 Water surface0.0024 Complete open terrain with a

smooth surface eg. Concretewalkways, airports, mowed grassetc.

0.03 Open agricultural area withoutfences and hedgesrows and veryscattered buildings, only smoothlyrounded hills

0.055 Agricultural land with some housesand 8 mtrs tall shelteringhedgerows with a distance ofapproximately 1250mtrs.



0.4 Villages small towns with many ortall hedgerows, forests or veryuneven and rough terrain

0.8 Large cities with tall buildings1.6 Very large cities with tall buildings

and skyscrapers

269AHMED & BHARAT, Curr. World Environ., Vol. 7(2), 267-273 (2012)

hedgerows) at 0.055 to 0.1 roughness, comparedto 0.8 for larger cities with tall buildings – which aretypical of the locations now being considered forsmall wind installations.

Due to the high roughness in the builtenvironment, the wind speed close to the groundbecomes a local parameter (dependent on localconditions near the ground). It is then not possibleto measure a local parameter (wind speed) on thebasis of some average characteristics of theroughness of the broader area of the builtenvironment.

TurbulenceThe roughness of the earth’s surface,

which causes drag on the wind, converts some ofthe wind’s energy into mechanical turbulence. Sincethe turbulence is generated at the surface, thesurface wind speed is much less than the windspeeds at higher levels fig.1. Turbulence includesvertical as well as horizontal air movement andhence the effect of the surface frictional drag ispropagated upwards. The mechanical turbulenceand the effect of frictional drag gradually decreasewith height and at the “gradient” level (around 1000to 2000 feet) the frictional effect is negligible. Thepressure gradient at this level is balanced by theCoriolis force (and possibly the centrifugal force),and the wind blows almost parallel to the isobars

Wind Assessment and Planning ControlsThe development of appropriate planning

guidelines is an important step in avoiding adverse

wind environments in urban areas. Currently thereare a diverse range of wind assessment criterialike placing and spacing of buildings on site. Mostof these are effective in general agreement witheach other and with field observations. Other criteriatend to be either unnecessarily stringent or slightlylenient. In the case of former, this is also undesirableas it will present unnecessary restrictions to theform and appearance of a building. The use of windtunnel testing remains the most reliable techniqueto model the wind environment effects aroundbuildings in urban and suburban environments..The use of Computation Fluid Dynamics (CFD) orwind tunnel visualisation techniques such as thescouring technique may be useful only as form ofinitial qualitative assessment and should not besolely relied upon.

Planning Controls Care should be takenin the formulation of planning controls such that therequirements are not overly restrict innovativedesign. Features such as aerodynamic tower forms,adequate podiums, provision of awnings, strategicplanting should be encouraged but not mandatory.At the same time, controls should be provided withregards to adequate modelling of the wind effects.

The most critical areas around an exposedbuilding are usually the areas near the corners atthe base of the building (side-stream effects), at thebase of a wide face of the exposed building(downwash effect, which is applicable for buildingsmore than 12 levels in height) and though arcadesor openings at the base of the building that are

Fig. 2(a): Wind movements inand around an exposed building

Fig. 2(b): Flow patterns around tall, slab-likebuilding. areas of increased wind

speeds at pedestrian level


open to opposite aspects of the base of the tallbuilding (gap effect). The extent of each will dependon the level of exposure, the strength anddirectionality of the wind climate and the shieldingor funneling effects from the surrounding buildings.Other aspects that need to be investigated are thewind conditions like turbulent wind, funneling effectof wind in any planned outdoor areas within oradjacent to the proposed development.

Urban Wind Environment CriteriaIf a low building is located in the wind

shadow of a tall building fig. 3b., the increase inheight of a obstructing block will increase the airflow through the low building in a direction oppositeto that of the wind. The lower wing of a large vortexwould pass through the building.

It is has been established experimentallythat wind comfort is more closely related to the gustwind speeds rather than the mean wind speeds.1

This is particularly so in the case of extreme windswhich can lead to people losing balance in the wind.Rofail (2005) proposed a set of criteria that convertsthe mean comfort criteria into a set of criteria formaximum gusts, or peak wind speeds. However,this set of criteria is based on an assumption of15% turbulence intensity, which in the vast majorityof cases is very conservative. An alternative set ofpeak wind speed criteria has been proposed byRofail (2007). The average airflow, the dynamicfluctuations, and the building scale turbulence areall closely coupled to the complicated geometry ofthe building. An equally valid approach would beto compare the mean wind speed criteria such asthose by Davenport5 against a Gust-EquivalentMean (the maximum of either the mean or the gustwind speed divided by a gust factor). In addition tocomfort criteria there is a safety limit that isapplicable to all accessible outdoor areasregardless of type or frequency of use. The safetylimit suggested by Melbourne (1978) of 23m/s forannual maximum1 gust has been adopted by mostconsultants and forms part of most sets of criteria.Requirements for Reliable Wind Tunnel Tests Thekey factors that ensure a reliable set of wind speedmeasurements in the wind tunnel are:´ The scale model of the building and

surrounds,´ The modelling of the behaviour of the

approach wind and´ The sampling parameters and type of

instruments that are used to measure thewind speeds.

Main Factors for wind modellingThese three factors are Comparison of

Various Mean and Gust Wind Environment Criteria,assuming 15% turbulence and a Gust Factor of 1.5.Wind tunnel model scales should not be less than1:500m in scale.1) The model must include the effect of the

surrounds, including the local landtopography. The study building(s) as well asthe buildings in the immediate vicinity needto be modelled to a greater accuracy. Theproximity model should extend to a radius ofat least 400m. Care should be taken inmodelling of porous elements such as trees,louvres or porous screens to ensure the sameaerodynamic properties such as Reynold’sNumber similarity. To achieve this, it may benecessary to distortion of the model’sgeometry. The modelling of features such asbalustrades in balconies may over-constrictthe flow through these areas in the modelscale and require special treatment. Similarlythe modelling of gaps through a buildingmay need to be distorted to achieve similarityin the flow regime between model-scale andfull-scale.4

2) The key parameter in modelling thebehaviour of the approach wind is to ensurethat the flow correctly matches with the full-scale in terms of the variation of the meanwind speed as well as the turbulenceintensity with height to within 10 percent. Theother parameter is the modelling of theintegral length scale of turbulence to withina factor of 3 (AWES, 2002). The referencewind speeds need to be based on ananalysis of the wind climate data obtainedfrom an observation station located within areasonable distance from the study site. It isrecommended that the climate data used ofwind speeds for a period of at least 10years7.The wind climate data should be properlycorrected for the effect of upstream terrain,shielding effects and the effect of the localland topography.7


3) Measurements should be made of the peakand mean wind speeds. Filtering of thevelocity signal needs to be applied for themaximum gust to represent a 3-second peak.Measurements should be taken from at least8 wind directions, although 16 winddirections is currently the standard practiceand is recommended. There are two types ofinstruments that can be used, hot-wireanemometry and pressure-based sensorssuch as the Irwin probe7. Note that sometypes of pressure based sensors are verysensitive to wind direction and should beavoided. Pressure based sensors should beproperly calibrated to ensure that theyprovide a reliable wind speed estimate forthe range of wind speeds within which theyoperate in the wind tunnel. The results shouldbe expressed as either gust wind speeds orboth gust and gust-equivalent mean windspeeds. The gust-equivalent mean is definedas the maximum between the mean and agust-equivalent mean wind speed.

The latter is the gust wind speed divided byan appropriate gust factor. Initial tests should be carriedout without the effect of vegetation to enable the windengineering consultant to properly identify theprevailing wind flow mechanisms. It is also importantto ensure that any recommendation suggested in thereport shall be adequately modelled and tested inthe wind tunnel. This is important since a solution thatwould work for one project may not necessarily besufficiently effective for another project even if the windflow mechanism is similar.

Case StudiesTo ensure a viable Design, the formulation

of strategies needs to be carried out in closecollaboration with the architect or designerresponsible for the project. Below are some examplesof wind effects from projects undertaken by Wind-techConsultants and details of solutions that wererecommended after confirmation of their effectivenessthrough wind tunnel testing. Note that in some cases,more than one solution may be presented.

Case Study 1The tower illustrated in Figure 3 is for a

45-storey tower project in Melbourne.

Fig. 3: Is for a 45-storey tower project in Melbourne

Fig. 4: Redevelopment of propertyat Civil Lines, located in Delhi

The tower is located at a corner of a cityblock and the wide face fronts a narrow street aswell as the prevailing wind direction for Melbourne(north). Furthermore, the site is relatively exposedin that direction. The result is that the tower canpotentially generate a significant downwash andside-stream effect around the corner of that cityblock. Figure 6 shows a side profile of the towerwith the wind incident from the north direction. Twooptions were presented. One required the tower tobe set back from the lane. The second treatmentrequired a small podium with a high wall to capturethe down-washed winds and direct them to apermeable car parking level.

Case Study 2The development shown in Figure 4 is

located in Delhi. This development is exposed toall 3 prevailing wind directions for Delhi.6

The north-easterly winds and westerlywinds were of particular concern for thisdevelopment as the two towers are aligned in thenorth-south direction. This particular site happensto be situated near the top of a ridgeline in the landform that runs north-south. This results in potentiallystrong funneling effects between the two tower


system. Eco-friendly absorption technology adoptedfor air-conditioning. Careful planning of airdistribution system. Air-conditioning standards setby acceptance level of office staff and not byinternational norms. Energy-efficient lighting systemand daylight integration with controls. Optimizationof structure and reduction of embodied energy byuse of less energy-intensive materials6

Case Study 4Another example is a development in

Waterloo, Sydney fig. 6. The results indicate thatthis development will be subject to un-favourablewind conditions due to the effect of the westerlywinds

It was established that this is due to acombination of direct ground level winds as well asa side-stream effect that was accentuated by theeffect of the proposed high colonnade at the north-west corner of the proposed building. This effect isfurther complicated by the fact that an outdoor caféis proposed under the high colonnade at that cornerof the building. The optimum solution involved theuse of strategic tree planting along the westernaspect of the development as well as a free-standing canopy under the north-western corner ofthe colonnade area to act a deflector. With thistreatment the wind conditions were improved fromexceeding the safety limit to being acceptable forseating and therefore acceptable for use as anoutdoor café area.

Fig. 5: Transport Corporation of India Ltd, Gurgaon

buildings that are well in excess of the safety limit.A number of treatment options were investigatedincluding large canopies along the entire length ofthe two tower buildings and over the gap. This ispossibly due to the significant contribution from theupwash of the ground level winds over the northernedge of the podium. This effect seems to have beenaccentuated in case by the fact that the site issituated at the apex of a saddle formation in thelandform, being exposed to the north-east windsalong the wide aspect. The only treatment thatworked effectively was the least expensive.

Case study 3Transpor t Corporation of India Ltd,

Gurgaon- Inward-looking compact form, withcontrolled exposure.

Two types of windows designed: peepwindows for possible cross-ventilation and view,the other being for day-lighting. The courts towardswhich the building has more transparency havestructural framework to provide support for shadingscreens. Landscaping acts as a climate modifier.The window reveals of the peep window cut outsummer sun and let in winter sun. AdjustableVenetian blinds in double window sandwich to cutof insulation and allow daylight. Polyurethane boardinsulation on wall and roof. Fountain court with watercolumns as environment moderator. Buildingsystems designed so as to draw upon externalenvironment to supplement the air-conditioning

Fig. 6: Photographs of the model of the Waterloo,Sydney development in Windtech Consultants’wind tunnel showing details of the optimumtreatment for the effect of the westerly winds onthe wind conditions at the north-western corner 1


Fig. 7: The Abu Dhabi development with theareas affected by the gap effect indicated

A wind tunnel model study was carriedout and indicated that a significant speed up effectoccurs within these gaps due to the gap effect. Foreach gap, the effect was successfully amelioratedby means of a baffle screen located at each end ofthe gap.

One of these screens served as a wall fora covered gazebo. Other areas that requiredtreatment included one of the street corners andthe base of one of the towers. The wind effects therewere successfully ameliorated by means of strategicplanting. Fig. 7. The Abu Dhabi development withthe areas affected by the gap effect indicated.

CONCLUSION

This paper demonstrates how it is possibleto plan for habitable wind environments, while stillaccommodating the architectural intent. Theaverage airflow, the dynamic fluctuations, and thebuilding scale turbulence are all closely related tothe complicated geometry of the building. Featuressuch as aerodynamic building forms, adequatepodiums, provision of awnings, strategic plantingshould be encouraged in the design.

With the proper modeling and simulationtechniques and appropriate wind field study. it ispossible to achieve a favourable outcome for boththe owners and end users. Local authorities canalso have a role in stipulating development controlswithout over-specifying the building form, whichruns the risk of stifling innovation.

Case Study 5A wind environment study was conducted

for the project in Abu Dhabi described in Fig. 7. Thisdevelopment includes 3 linked residential towerbuildings with two 9-level high undercroft areaslocated below the linkages.

REFERENCES

1. Ahmed Siraj Wind Energy Theory andPractice, PHI Publication first edition (2010).

2. BorisJay P.Dust in the Wind: Challenges forUrban Aerodynamics,, Laboratory forComputational Physics and Fluid Dynamics(2002).

3. Campbell Neil et. al "Wind Energy For TheBuilt Environment" Paper published in Procs.European Wind Energy Conference &Exhibition, Copenhagen, (2001).

4. Davenport, A.G. An approach to human

comfort criteria for environmental conditions,Colloquium on Building Climatology, (1972).

5. Rafail, Tony "Developing habitable BuiltEnvironment" CUTBH 8th World Congress(2008).

6. Representative designs of energy-efficientbuildings in India Published by Tata EnergyResearch Institute (2001).

7. Urban Wind Assessment in UK, Anintroduction to wind resource assessmentin the urban environment, (2007).

INTRODUCTION

Cancer represents the largest cause of themortality, which claims over 6 million lives eachyear, in present world (Abdullaev 2012). Insensitivityof cancer types to most of the oncological therapiessuch as chemotherapy, radiotherapy andimmunotherapy (Ghaneh et al. 2007, Sarkar et al.2007) has forced to strengthen new therapeuticstrategies to combat this deadly form of disease. Apromising strategy to cure cancer ischemoprevention through natural agents. Naturalagents, extracted from diverse sources like that ofplants, had been extensively used for curing manyailments including cancer. Natural products andrelated drugs are used to treat 87% of allcategorized human diseases infectious and non-infectious (Chin et al. 2006). Molecularepidemiological studies have provided evidencethat an individual’s susceptibility to cancer likediseases is modulated by both genetic andenvironmental factors via. their interaction and theiraffect on enzymes involved in the metabolism of


Extracts of Kashmiri Saffron in Service toHuman Race and Present Ground Realities

MOHAMMAD IMRAN KOZGAR*and NEELOFAR JABEEN

*Mutation Breeding Laboratory, Department of Botany, Aligarh Muslim University,Aligarh - 202 002, India.

Department of Education, Government of Jammu and Kashmir, Srinagar, India.


ABSTRACT

The Kashmir valley is well known for producing high quality of saffron (Crocus sativus L.)and represents one of the major saffron-producing areas of the world. Saffron has been traditionallyused in preparation of indigenous medicines and also as a dye. The extracts of the parts of saffronplant is being used in cosmetics and in many drugs to cure different ailments. In present documentthe potential role of the saffron and its parts cultivated in Kashmir valley and the diseases likecancer to be cured from them are being discussed. Concerns on the low production rate due tourbanization and shrinking of the cultivated land and probable adoptions to be implemented toavoid the loss of economy are being discussed.

Kew words: Kashmir, Saffron, Cancer, Treatment, Crocin, Mechanism, Apoptosis.

carcinogens (Gattoo et al. 2011). Chemopreventionmay act to cure cancer as per the possiblemechanism illustrated in Fig. 1. One of theconstituents which have shown the results ofinducing apoptosis is Crocin (Fig. 2) extracted fromthe Kashmir Saffron, Crocus sativus L. (Bakshi etal. 2010)

Outline of Kashmirri SaffronKashmir, one of the biotic provinces of the

Himalayas, supports a rich and unique floristicdiversity, including at least 450 known medicinalplants species (Jabeen and Kozgar 2011)including saffron. Saffron is cultivated commerciallyto limited extent in India and mostly confined to thispart (Kashmir), however, it is also found to becultivated in Azerbaijan, France, Greece, Iran, Italy,Spain, China, Israel, Morocco, Turkey, Egypt, andMexico with high commercial cost outputs (Negbi1999). In Kashmir saffron cultivation is mostly seenin the table-land of Pampore, at the outskirts ofSrinagar city, which is well known for quality saffronand represents one of the major saffron-producing

276 KOZGAR & JABEEN, Curr. World Environ., Vol. 7(2), 275-280 (2012)

areas of the world, and infact some authors reflectthat the saffron originated from Kashmir from wherePhoenicians introduced it to the Greek and Romanworld (Alberini 1990; Winterhalter and Straibinger2000) and to Britain world in XIV century (Caiolaand Canini 2010).

Constituents and usages of Kashmiri SaffronSaffron belongs to the iris family

(Iridaceae) and constitutes different chemicalagents like crocin, crocetin anthocyanin, caroteneand lycopene (Abdullaev and Espinosa-Aguirre,2004), especially in its stigma parts of the flower

Fig. 2: Chemical structure of Crocin

Fig. 1: Possible mechanisms for chemoprevention by the extracts of medicinal plants

(Modified from Steinmeta and Potter 1996; Kelloff et al. 2000; Lampe 2003)

277KOZGAR & JABEEN, Curr. World Environ., Vol. 7(2), 275-280 (2012)

(Giaccio et al., 2004). These constituents are knownto have various usages in relation to health relatedproblems. They have pharmacological effects ondifferent illness, including anti-tumor effects byinhibition of cell growth (Abdullaev 1993, Dhar etal. 2009). Bakhsi et al. (2010) has demonstratedthat the crcocin extracted from the saffron cultivatedin Pampore belt of Kashmir vale has potential rolein inducing cell cycle arrest and henceforth couldplay a key role in cancer treatments (Fig. 3). Inaddition, the extract of this saffron has also revealedto inhibit cell proliferation (Fig. 4) and modulatesignal transduction. All these factors viz. inducingapoptosis, inhibit proliferation of cell and/or

modulating signal transduction are currently usedin cancer treatment and Guzman (2003) reportedthat the combination of multi-chemopreventiveagents or agents with multiple targets is consideredto be more effective than a single agent.

Cultivation problems and strategies for exploringsaffron sustainably

Over than three decades from now theland under cultivation of saffron in Pampore(Kashmir) region is shrinking rapidly due toencroachment of local people. Increase inurbanization and presence of anthropogenicpressures are other problems. In addition, the

Fig. 3: Induction of Apoptosis and Cell Cycle Arrest

Morphology of apoptotic cells control (a) vs treated with crocin (b) Hoechst stainx400

(Adopted from Bakshi et al 2011; Permission granted for using from Journal Editorial Offcie and also from Main author)

(A)

(B)


Fig. 4: Agarose gel electrophoreses demonstrating DNA fragmentation

BxPC-3 cells (HPCL) treated with 10 µg/mL crocin (extracted from saffron) for 0,6, 12, 24, 36 h, inducedDNA fragmentation in time dependant manner from 12 hours. Actinomucin D for 36 h was a positivecontrol (PC) at a concentration of 10 µg/mL (Adopted from Bakshi et al .2011; Permission granted for

using from Journal Editorial Office and also from Main author)

genetic diversity is not upto so much extent in thisparticular plant as it reproduces vegetativelythrough corms. Due to absence of ample geneticdiversity saffron plants are constantly under siegeby a multitude of disease-causing organismsincluding bacteria, fungi, viruses and nematodes(Ahrazem et al. 2010). In addition, limitedavailability of daughter corms is also one of themajor handicaps for the expansion of acreageunder saffron (Sharma and Piqueras 2010).

In order to get full benefit from the extractsof the saffron plant of Kashmir cultivated one,various techniques and sustainable approachedhas to be introduced. Techniques like inducedmutagenesis and tissue culture has to beimplemented and reserving the land for itscultivation has to be promoted. Cultivation in indoorpots and promotion of its cultivation in kitchengardens has to be enhanced. Hussiani et al. (2010)has advocated the need for using quality plantingmaterials and a sprinkler irrigation system as oneof the major means to enhance the production.

CONCLUSION

In order to obtain high economy from thesaffron parts grown in Kashmir new areas shouldbe covered under cultivation. Analysis of differentconstituents and their probable applications in thehealthcare using cutting edge techniques, in asustainable way, be promoted from all corners.Looking for procedures and their amplifications

should be increased, which directly or indirectlyenhance the genetic diversity among the cultivarsof saffron. Encroachment in the field of saffroncultivated belt, either for domestic life or forcommercial purposes, should totally banned.Biophysiological studies for various types ofstresses especially cold stress be analyzed todevelop the variety resistant to cold, which is mostlyfollowing the later stages of saffron growth period.

279KOZGAR & JABEEN, Curr. World Environ., Vol. 7(2), 275-280 (2012)

1. Abdullaev FI, Biological effects of saffron.Biofactors 4: 83-86 (1993).

2. Abdullaev FI, Cancer chemopreventive andtumoricidal properties of saffron (Crocussativus L.). Experimental Biology andMedicine 227: 20-25 (2002)

3. Abdullaev FI, Espinosa-Aguirre JJ,Biomedical properties of saffron and itspotential use in cancer therapy andchemoprevention trials. Cancer Detectionand Prevention Journal 28: 426-32 (2004).

4. Abdullaev FI, Rivera LR, Roitenburd BV,Espinosa AJ, Pattern of childhood cancermortality in Mexico. Archives of MedicalResearch 31(5): 526-531 (2000).

5. Alberini M, Saffron: sapore e colore. Lozafferano. Proceedings of the InternationalConference on Saffron (Crocus sativus L.).L’Aquilla, Italy, pp 39-46 (1990).

6. Bakshi H, Sam S, Rozati R, Sultan P, Islam T,Rathore B, Lone Z, Sharma M, TriphatiJ,Saxena RC, DNA Fragmentation and CellCycle Arrest: A Hallmark of ApoptosisInduced by Crocin from Kashmiri Saffron ina Human Pancreatic Cancer Cell line. AsianPacific Journal of Cancer Prevention 11:675-679 (2010).

7. Caiola MG, Canini A, Looking for saffron’s(Crocus sativus L.) parents. In: Husaini AM(Ed) Saffron. Functional Plant Science andBiotechnology 4(Special Issue 2), 1-14(2010).

8. Chin YW, Balunas MJ, Chai HB, et al., Drugdiscovery from natural sources. The AAPSJournal 8: 239-53 (2006).

9. Dhar A, Mehta S, Dhar G, Dhar K, BanerjeeS, Veldhuizen PV, Campbell DR, Bnerjee SK,Crocetin inhibits pancreatic cancer cellproliferation and tumor progression in axenograft mouse model. Molecular CancerTherapeutics 8(2): 315-323 (2009).

10. Gatoo MA, Siddiqui M, Farhan AK, KozgarMI, Owais M. Oral cancer and genepolymorphism: International Status withspecial reference to India. Asian Journal ofBiochemistry 6(2): 113-121 (2011).

11. Ghanesh P, Costello E, Neoptolemos JP,

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Biology and management of pancreaticcancer. Gut 56: 1134-1152 (2007).

12. Giaccio M., Crocetin from saffron: an activecomponent of an ancient spice. CriticalReviews in Food Science and Nutrition 44:155-72 (2004).

13. Guzman M, Cannabinoids: Potentialanticancer agents. Nature Reviews Cancer3: 745-755 (2003).

14. Jabeen N, Kozgar MI, The Genus Aconitumin Kashmir Himalaya. LAP LambertAcademic Publishing GmbH & CoSaarbrücken Germany (2011).

15. Kelloff GJ, Crowell JA, Steele VE, LubetRA, Malone WA, Boone CW, KopelovichL, Hawk ET, Lieberman R, Lawrence JA, AliI, Viner JL, Sigman CC, Progress in cancerchemo-preventionm: Development of diet-derived chemopreventive agaents. Journalof Nutrition 130(Suppl): 467S-471S (2000).

16. Lampe JW, Spicing up a vegetarian diet:Chemopreventive effects of phytochemicals.American Journal of Clinical Nutrition78(Suppl): 579S-583S (2003).

17. Negbi M, Saffron cultivation: past, presentand future prospects. In: Negbi M, Ed. SaffronCrocus sativus L. Amsterdam: HarwoodAcademic Publishers, pp 1-19 (1999).

18. Sarkar FH, Banerjee S, Li YW., Pancreaticcancer: Pathogenesis, prevention andtreatment. Toxicology and AppliedPharmacology 224: 326-36 (2007).

19. Steinmetz KA, Potter JD, Vegetables, fruit,and cancer prevention: A review. Journal ofAmerican Dietetic Associatin 96: 1027-1039(1996).

20. Winterhalter P, Straubinger M, Saffron-renewed interest in an ancient spice. FoodReviews International 16: 39-59 (2000).

21. Sharma KD, Piqueras A, Saffron (Crocussativus L.) Tissue Culture: Micropropagationand secondary metabolite production. In:Husaini AM (Ed) Saffron. Functional PlantScience and Biotechnology 4(Special Issue2): 15-24 (2010).

22. Ahrazem O, Rubio-Moraga A, Castillo-LópezR, Mozos AT, Gómez-Gómez L, Crocus


sativus Pathogens and Defence Responses.In: Husaini AM (Ed) Saffron. Functional PlantScience and Biotechnology 4(Special Issue2): 81-90 (2010).

23. Husaini AM, Hassan B, Ghani MY, Teixeirada Silva JA, Kirmani NA, Saffron (Crocus

sativus Kashmirianus) cultivation in Kashmir:Practices and problems. . In: Husaini AM (Ed)Saffron. Functional Plant Science andBiotechnology 4(Special Issue 2): 108-115(2010).

INTRODUCTION

Groundwater resources are dynamic innature. These are affected by factors such as, theexpansion of irrigation activities, industrializationand urbanization. Hence, monitoring andconserving this important resource is essential. Thequality of water is defined in terms of its physical,chemical and biological parameters. Ascertainingthe quality of groundwater is crucial before its use.Water may be used for various purposes such asdrinking, agricultural, recreational and industrialactivities3, 4. Groundwater assessment has beenbased on laboratory investigation, but the adventof Satellite Technology and GeographicalInformation System (GIS) has made it very easy tointegrate various databases5.


Spatial Distribution of Ground water Quality in SomeSelected parts of Pune city, Maharashtra, India using GIS

SUVARNA TIKLE1, MOHAMMAD JAWID SABOORI2 and RUSHIKESH SANKPAL2

1EME, Division, Mitcon Consultancy and Engineering Services ltd., Pune - 411 005, India.2Department of Environmental Science, University of Pune, Pune - 411 007, India.


ABSTRACT

Pune is one of the major developing cities in India; its area is rapidly increasing as neighboringvillages like Aundh, Baner, Pashan and Sutarvadi are merged into the Pune Municipal Corporation(PMC). Majority of the people are using the groundwater as a prime source for their domesticneeds, besides the PMC is supplying them with an allocation of treated water. Assessing thequality of groundwater is an important issue in the modern times. Spatial variations in ground waterquality in some selected parts of Pune Municipal Corporation, Maharashtra, India, have beenstudied using geographic information system (GIS) technique. 29 bore well water samples werecollected representing the newly merged. The water samples were analyzed for physico-chemicalparameters as prescribed by APHA, using standard techniques and compared with WHO (2006,2008) drinking water quality standards (1, 2). The ground water quality information maps of theentire study area were prepared by GIS Inverse Distance Weighting (IDW) technique for all theabove parameters. The results obtained in this study with the spatial database established in GISwill be helpful for monitoring and managing ground water quality and its pollution in the study areaof Pune city.

Key words: Ground water, Spatial distribution, Physico-chemical parameters,Drinking water quality, GIS, inverse distance weighting technique.


The study area includes Aundh, Baner,Pashan and Sutarvadi. The Base map of study areawas drawn from Survey of India topographic mapno. Toposheets 41F/14. The bore well locationswere identified. The samples were collected from29 boreholes from selected locations. As part of thestudy, groundwater samples were collected from29 bore wells. The samples collected duringDecember 2011 were analyzed for various physico-chemical parameters. Physico-chemical analysiswas carried out as per the standard proceduresprescribed by American Public Health Association(APHA), to determine Electrical Conductivity (EC),Total Dissolved Solids (TDS), Total Hardness (TH), pH, HCO3-, Mg2+, Ca2+, K+, Na+, Cl-, SO4

2-, NO3- and

F- 6-7. The results were compared with standard

282 TIKLE et al., Curr. World Environ., Vol. 7(2), 281-286 (2012)

values recommended by World HealthOrganization WHO (2006 and 2008) guidelines fordrinking water quality.

GIS technology proved to be very usefulfor enhancing the accuracy. We obtained thelocation of the well by using the GPS and Arc GISsoftware. The IDW was applied to find out the spatialdistribution of groundwater quality. In interpolationwith the spatial analyst method of IDW, a weight isattributed to the point to be measured. The amountof this weight is dependent on the distance of thepoint to another unknown point6. These weights arecontrolled on the bases of power of ten. Withincrease of power of ten, the effect of the points thatare farther diminishes. Lesser power distributes theweights more uniformly between neighboringpoints. In this method the distance between thepoints count, so the points of equal distance haveequal weights7. The advantage of IDW is that it isintuitive and efficient. This interpolation works bestwith evenly distributed points. Similar to the SPLINEfunctions, IDW is sensitive to outliers. Furthermore,unevenly distributed data clusters result inintroduced errors8.


Understanding the groundwater quality isimportant as it is the main factor determining itssuitability for drinking use9. The groundwater qualitymaps were prepared for each selected parameter.

Electrical Conductivity (EC)The importance of EC is its measure of

salinity; which greatly affects the taste. Thus EC hasa significant impact on determining the potability ofwater9. The EC of water at 25°C is due to the presenceof various dissolved salts. The EC varies with watersample and ranges between 469.2µS/cm and1173µS/cm with an average of 800µS/cm. Knowingthat the maximum limit of EC for drinking water isprescribed as 1,500µS/cm at 25°C, all the valuesare within the permissible limit. Figure 1 shows thespatial distribution of EC in the study area.

pHIn general, pH is the measure of acidity or

alkalinity of water. It is one of the most importantoperational water quality parameters with the

optimum pH required often being in the range of7.0-8.5 (10). The maximum permissible limit for pHfor drinking water as given by the WHO is 9.2. ThepH values in the groundwater samples collectedvaried from 7.05 to 7.76 with an average value of7.27. This shows that groundwater of the study areais mainly neutral to slightly alkaline in nature. Spatialdistributions of pH concentrations are shown inFigure 2. The values of pH show that all of thesamples displayed a pH value within the maximumpermissible limit.

Total Dissolved Solids (TDS)TDS in water are represented by the

weight of residue left when a water sample hasbeen evaporated to dryness WHO (2006). TDS arecompounds of inorganic salts (principally Ca, Mg,K, Na, HCO

3-, Chlorides and SO4

2-) and of smallamounts of organic matter that are dissolved in water.The TDS amount ranges between 50mg/l to 650mg/l with an average of 367 mg/l. In this study, 3 samples(BW7, BW12 and BW18) showed the concentrationof TDS exceeds the permissible limits. Figure 3shows the spatial distribution of TDS in the studyarea.

Carbonates and Bi-CarbonatesWith respect to HCO3-96.5 % of the

sampling stations are exceeding the permissiblelimit set by the WHO (2006) Guidelines for drinkingwater limit of 240mg/l. The values of HCO3- rangebetween minimum 196 mg/l to maximum 855 mg/lwith an average of 423 mg/l. Figure 4 shows thespatial distribution of HCO3-.

Calcium(Ca) And Magnesium (Mg)Ca and Mg are from natural sources like

granitic terrain which contain large concentrationof these elements. The result shows that Mg isexceeding the permissible limit of 30mg/l in morethan 82% of the sampling stations, while Ca is withinthe permissible limits of 75 mg/l except one station(BW 15) where it is exceeding the permissible limit.Ca and Mg are ions of total hardness and hencethey are interrelated. The values of Mg varies from12 mg/l to maximum 125 mg/l with an average of50 mg/l while the minimum value of Ca is 6 mg/land maximum 80 mg/l with an average of 34 mg/l.Spatial distribution of Mg and Ca in the study areaare represented in figures 5 and 6.

283TIKLE et al., Curr. World Environ., Vol. 7(2), 281-286 (2012)

Fig. 3: Spatial variation ofdistribution of TDS in study area

Fig. 2: Spatial variation of pH in study areaFig. 1: Spatial variation of EC in study area

Fig. 4: Spatial variation of distributionof HCO3- in study area

Fig. 5: Spatial variation ofdistribution of Mg in study area

Fig. 6: Spatial variation of distributionof Ca in study area


Fig. 7: Spatial variation ofdistribution of Chloride in the study area

Fig. 8: Spatial variation of distributionof TH in the study area

Fig. 9: Spatial variation ofdistribution of sodium in study area

Fig. 10: Spatial variation of distributionof potassium in study area

Fig. 12: Spatial variation of distributionof Sulfate in study area

Fig. 11: Spatial variation ofdistribution of Nitrate in the study area

285TIKLE et al., Curr. World Environ., Vol. 7(2), 281-286 (2012)

Fig. 13: Spatial Fluoride distribution in the study area

Chloride (Cl)Chloride occurs naturally in all types of

water. Chloride in natural water may results fromagricultural activities, industries and chloride richrocks. The results obtained shows that all thesampling stations are well within the permissiblelimit of 250 mg/l guided by WHO (2008) guidelinesfor drinking water quality. The values vary from 21mg/l minimum to 87 mg/l maximum with an averageof 43 mg/l. Spatial distribution of Chlorideconcentration in the study area is shown in figure7.

Total Hardness (TH)The TH is an important parameter of water

quality whether it is to be used for domestic,industrial or agricultural purposes. It is due to thepresence of excess of Ca, Mg and Fe salts. Thecarbonate and bicarbonate concentrations areuseful to determine the temporary hardness andalkalinity. Since the analysis of carbonate in thisstudy has given negative results for most of thesamples, the alkalinity is mainly due tobicarbonates. Figure 8 indicates the TH obtainedshows that 25% of the samples are exceeding thepermissible limit of 200 mg/l set by WHO (2008).The values vary from minimum 116 mg/l tomaximum 590 mg/l with an average of 292 mg/l.

Sodium (Na) and Potassium (K)Na and K are the most important minerals

occurring naturally. The major source of both thecations may be weathering of rocks (11) besidesthe sewage and industrial effluents. Their values ofstudy area show that both Na and K are well withinthe permissible limits. The values varies fromminimum 45mg/l to maximum 77 mg/l with anaverage of 62 mg/l and 0.188 mg/l minimum to 10.73mg/l maximum with an average of 0.88 mg/lrespectively. Figure 9 and 10 shows the spatialvariation of Na and K in the study area respectively.

Nitrate (NO3-)

The high nitrogen content is an indicatorof organic pollution. It may results from the addednitrogenous fertilizers, decay of dead plants andanimals, animal urine, or feces. They are all oxidizedto nitrate by natural process and hence nitrogen ispresent in the form of nitrate. The increase in one orall the above factors is responsible for the increaseof nitrate content (12). The ground watercontamination is due to the leaching of nitratepresent on the surface with percolating water. Figure11 shows the spatial distribution of Nitrate in thestudy area. The values of nitrate in the study areavary from minimum 1.858 mg/l to 111 mg/l maximumwith an average of 31 mg/l. The results show that21% of the sampling stations are exceeding thepermissible limit of 50 mg/l guided by WHO (2008).

Sulphate (SO42-)

Sulphate is found in small quantities in


ground water. Sulphate may come into groundwater by industrial or anthropogenic additions inthe form of Sulphate fertilizers. The results showthat the values from the study area are all within thepermissible limit of 250 mg/l guided by WHO (2008)for drinking water purpose. The values of sulfateranges from 73 mg/l minimum to 77 mg/l maximumwith an average of 74 mg/l (Figure 12).

Fluoride (F)Fluoride occurs as fluorspar (fluorite), rock

phosphate, triphite, phosphorite crystals etc. innature. The factors which control the fluorideconcentration includes the climate of the area andthe presence of accessory minerals in the rockmineral assemblage through which the groundwater is circulating (13). In the present study theconcentration of fluoride is within the permissiblelimits of WHO (2008). They range from 1.094 mg/lminimum to maximum 1.128 mg/l with average of1.1029 mg/l. from the results obtained it can benoticed that the values of fluoride are exceedingthe desirable limit of 1 mg/l. with the increase

anthropogenic activities the concentration offluoride may have an increasing trend, as Bhosleet al., 2001 (14) has noted that the discharge ofdomestic wastes from the surrounding industriesincreases fluoride values. Fluoride distribution inthe study area is shown in figure 13.

CONCLUSION

Spatial variations in ground water qualityin the study area were studied successfully by usinggeographic information system (GIS). The resultsobtained in this case study and the spatial databaseestablished in GIS shows the same approach canbe used for determining, monitoring and managingground water quality and its pollution for wide areas.The database formed can be very useful for futureresearch and reference.

ACKNOWLEDGEMENTS

Authors sincerely acknowledge supportprovided by GSDA Pune.

REFERENCES

1. WHO, Guidelines of drinking water qualityRecommendation: the 3rd edition. Geneva:World Health Organisation. 2 (2006).

2. APHA.Standard methods for examination ofwater and waste water, 19th Edition.Washington, DC:American Public HealthAssociation (1995).

3. Khan, F., Husain T., and Lumb A.,Environmental Monitoring and Assessment,88: 221-242 (2003).

4. Sargaonkar, A. and V. Deshpande,Environmental Monitoring and Assessment,89: 43-67 (2003).

5. MounaKetata-Rokbani, MoncefGueddariand RachidaBouhlila, Iranica Journal ofEnergy & Environment 2(2): 133-144 (2011).

6. M. Hussain, T.V.D.P. Rao, H.A. Khan and M.Satyanarayan, Orient J. Chem., 27(4): 1679-1684 (2011).

7. A. Malviya, S.K. Diwakar, Sunada, O.N.Choubey, Orient J. Chem., 26(1): 319-323(2010).

7. Balakrishnan P., Abdul Saleem andMallikarjun, N. D., Afr ican Journal ofEnvironmental Science and Technology,5(12): pp. 1069-1084 (2011).

8. Burrough PA, McDonnell RA, Principles ofGeographical Information Systems Oxford:Oxford University Press, p. 333. (1998).

9. Sivasankar, K., Gomathi, R. Water QualityExposure Health,1: 123-134 (2009).

10. Pradeep Jain, K., Poll. Res. 17(1): 91-94(1998).

11. Dahyia, S., Datta, D., Kushwaha, H. S.,Environmental Geology, 8: 158-165 (2005).

12. Singh, T. B., IndhuBala and D. Singh, Poll.Res. 18(1): 111-114 (1999).

13. Rahman:,‘Groundwater quality of Oman’,Groundwater Quality, London, pp. 122-128(2002).

14. Handa BK, Ground Water 13: 275-28 (1975)15. Bhosle, A. B., Narkhede, R. K., BalajiRao and

Patil, P. M., Eco. Env.&Conserv.7(3): 341–344(2001).

INTRODUCTION

Decreasing water level and shortage ofwater is being a major problem world wide. Foragriculture purpose this problem gives rise to theuse of alternative sources of water. Most of thesewater sources are affected by the dumping of wastefrom various types of industries like mining, textiles,chemical etc. Due to reason this waste water maycontains many organic toxic substances that couldhave hazardous impact on human health. Inaddition, technological development hascontributed to increase other industrial dumpingthat contaminates surface waters.

The irregular disposal of industrial wasteshas created pollution problems since this waste isdisseminated in the environment or is accumulatedin sediments, aquatic organisms, and water.

There are many studies on the possibleeffects of chemical substances on humans throughlaboratory.


Use of Industrial Waste Water for Agricultural Purpose:Pb and Cd in Vegetables in Bikaner City, India

RAJENDRA SINGH1, R.S.VERMA2 and YOGITA YADAV3

1Department of Chemistry, IGBN PG college Jhunjhunu India.2Department of Chemistry, Government Dungar College Bikaner, India.

3Department of Chemistry, Banasthaly Vidhyapeeth, Tonk, India.


ABSTRACT

Shortage of irrigation water resources is leading to the use of domestic and industrialwaste water in agriculture especially. In urban areas. Being contaminated by metals and varioustoxic chemicals these waste waters leads to the exposure of heavy metals and hazardouschemicals and the subsequent human health hazards through agriculture products and livestocks. Increasing cases of cancer and kidney problems is also related with this aspect. Inpresent study human health risk assessment taken in concern with the respect of some heavymetals of toxicological interest.

Key words: Waste water, Contaminated, Health hazards, Health assessment, Heavy metals.

Experiments in animals and informationare available on the incidence of cancer byprolonged exposure to toxic substances.Experiments in plants and insects, as the Drosophila(fruit fly), demonstrate that toxic substances ofchemical origin induce genetic mutations andchromosome aberrations. These experimentsdemonstrate that exists a risk, but it is not simple toextrapolate these results to human beings.

The population is exposed to toxicchemical compounds through the use of wastewaterin agriculture. Theoretically, wastewater of industrialorigin should not be used for this purpose but indeveloping countries formal and clandestineindustries dispose of their effluents to the municipalsewerage with or without authorization and withoutany treatment. This exposes the population, torelatively small quantities for chemical compoundsand may produce chronic intoxications with seriousconsequences.

Another health hazard pose byinadequate disposal of wastewater is the use of


sediments for soil improvement because theycontain toxic elements that may accumulate (PAHO,1989).

The environmental impact of chemicalresidues in wastewater used for irrigation and theprediction of their effects on human health are avery complex matter. In addition, it should beconsidered that the standards of developedcountries do not apply to areas with differentcharacteristics. The factors that influence the natureand intensity of the impact on health are: the climate,nutritional status, genetic predisposition, type ofwork and exposure level.

The indiscriminate use of pesticides alsoinfluences the deterioration of water quality. Thisresource can be contaminated by runoffs from crops,atmospheric precipitations and, to a lesser extent,by domestic sewage. Polychlorinated biphenyls(PCB), present in lager quantity in pesticides andother organochlorine compounds, are degraded veryslowly in the environment and are bioaccumulative,thus, they represent a potential danger. Air and waterare vehicles through which PCB are dispersed inthe environment, although food also constitute animportant vehicle. As a consequence, PCB residuesare found in living organisms form many regions.The highest concentrations are usually present neatindustrial areas .

Industrialization and urban developmentwithout adequate planning increase human healthhazards by exposure to chemical substancesthrough air, water sediments, and food. The natureof this risk and its potential danger has beenrecognized a few years ago and its effects still havenot been evaluated (PAHO, 1990).

The identification and confirmation of sucheffects are difficult because epidemiological studieslast long, the population migrates, and exposuretime is unknown. In addition, chronic diseases canhave various causes and, in many cases, they arenot classified correctly.

Usually, in developing countries there isnot statistical information on the trends and causesof diseases produced by ingestion of chemicalsubstances through agricultural and livestock

products. However, several studies havedeconstructed adsorption of heavy metals by plants,such as wheat and rich that can affect the consumers(WHO, 1992). An epidemiological evidence wasthe case of Toyama, Japan, where the populationwas affected by the ingestion of cadmium containedin rice; the origin of this element was a nearby minethat contaminated the irrigation water.

The nature of human health hazards byexposure to toxic chemical compounds variesconsiderably. In general, they increase birth defects,abortions and certain forms of cancer, and decreasethe average weight of children at birth.

Case study: wastewater use in agriculture inBikaner, India

The study “health risk evaluation due towastewater use in agriculture” was conducted infour agricultural areas (Bikaner East, Karni Industrialarea, central market, Reliance fresh retail outlet).

General objective of the studyTo evaluated the chemical-toxicological

level of contamination of the agricultural productsirrigated with raw and treated wastewater.

Specific objectives´ To determine the concentration of toxic heavy

metals and synthetic organic compounds(pesticides and polychlorinated biphenyls)in rivers, raw wastewater and treatedwastewater used for irrigation.

´ To determine to concentration of toxic heavymetals, pesticides, and polychlorinatedbiphenyls in agricultural and livestockproducts (vegetables and milk) form areasirrigated with water of rivers, raw wastewaterand treated wastewater.

´ To compare the potential risk associated withtoxic chemical compounds present in watersof rivers, raw wastewater and treatedwastewater used to irrigate agricultural andlivestock products.

´ To train professionals in the measurementof metallic organic toxic substances and,thus, to increase the local analytical capacity.

´ However the present paper is mainlyconcerned with some heavy metals oftoxicological interest.


MethodologyThe study was conducted in Bikaner, India

to evaluate the presence and concentration of toxicchemical compounds in waters used for irrigationand in agricultural and livestock products fromareas of reuses, a control area, and markets. Inaddition, soils and sludge were analyzed. The areasselected for the study were: Bikaner East, (controlarea), karni industrial area (use of industrial anddomestic waste water) central market (use ofground water and canal water) reliance fresh retailoutlet. Analyses of metals, pesticides, and PCBwere carried out in all water samples.

The following analytical procedures were appliedWater

The analytical methodologies proposedby the Health and Welfare, Ottawa, Canada,National Water Research (Burlington) and by theStandard Methods (15a. edition, 1985) were used.

Agricultural productsThe recommendations of the Health

Protection Branch Laboratory, Food Laboratory,Toronto, Canada, and the analytical methodologiesof CEPIS developed with the support of JICA wereapplied.

Soil and sludgeThe methodologies proposed by USPEA

and by the standard Methods (15a. edition, 1985)were adopted.

For analytical quality control,measurements were subject to an analytical qualitycontrol program developed by CEPIS laboratoryand the methodology used by internationalauthorities.

Recovery tests were performed withselected samples to which known quantities ofanalite were added, in addition, control tests ofdistilled water and solvents for pesticides and PCBwere done.

RESULTS

With respect to the results, in industrialwastewater high levels of heavy metals were found:arsenics (7 to 220µg/1), (5 to 43µg/1), lead (10 1

253µg/1), copper (50 to 250µg/1), iron (1.800 to6.400µg/1), and zinc (60 to 2.460µg/1), (see Figure1). Chlorinated pesticides in different samplingpoints were very low (<700ng/1). With regard toPCB, the highest value was detected in Bikanereast (270µg/1). In general, removal of heavy metals,pesticides, and PCB is produced in stabilizationponds.

The agricultural and livestock productsselected for the study were: Reddish Potato, Brinjal,Carrot, Cabbage, and milk from the areas of studyand nearby markets. The highest value of lead wasdetected in brinjal samples from markets (0,037µg/) (see Table 1). Cadmium does not constitute andproblem in the areas studies. With regard to metalconcentration and hygiene agriculture productsavailable at Reliance fresh outlet were found to bebest.

Fig. 1: Metals of toxicologicalinterest in irrigation water


Table 1: Lead and cadmium in agricultural products

Area Sampling place Species Concentration

Pb (µg/g) Cd(µg/g)

Bikaner east Agricultural Reddish <0.004 <0.013Area Potato 0.004 <0.003

Brinjal 0.014 <0.003Carrot <0.002 <0.003

Market Reddish Potato <0.004 <0.033Brinjal Carrot 0.004 <0.003Cabbage 0.003 <0.033

<0.002 <0.003<0.003 <0.003

ReddishPotato

Karni industrial Brinjal Carrot 0.004 <0,003area Tomato 0.003 <0,003

Agricultural Area 0.037 <0,003<0,002 <0,003

Reddish Potato <0,002 <0,003Centeral Markets Market Brinjal CarrotTomatoof Bikaner <0,003 <0,003

Reddish Potato <0,002 <0,003Brinjal Carrot <0,003 <0,003Tomato <0,002 <0,003

Reliance <0,002 <0,003Fresh Retail Retail Chain <0,002 <0,003outlet shop <0,002 <0,003

<0,002 <0,003<0,002 <0,003<0,002 <0,003

CONCLUSIONS

The use of industrial wastewater inagriculture and livestock represent and potentialrisk for health, due to the toxic nature of chemicalcompounds and to the concentrations to which theproducts are exposed. Irrigation water with lowlevels of lead (around 30 µg/1) has a minimuminfluence in the toxicological quality of vegetableswhose edible part grows beneath the soil.

Vegetables growing at the soil surface levelmay be contaminated by atmospheric emissionscontaining lead.

For irrigation water, the permissible limitvalues of toxic chemical compounds should not beregarded as absolute values, but should be adaptedto the local conditions considering contributionsfrom other sources. Wastewater treatment by meansof stabilization ponds as well as commonlyavailable treatment plants removes toxic elementswhen low concentrations are found in rawwastewater.´ The establishment of permissible maximum

limits of toxic substances should be studiedfor irrigation water considering conditions ofsoil, types of plant, and bioaccumulation.

´ Metal Toxicity seems to be a significant factorfor the increasing cases of cancer and kidney


diseases.´ A continuous study with this respect and

keen public awareness is required.´ A responsible planning implementation

and strict regulation of environmental lawsis required.

´ State government seems to do only table

and data work as posing itself aware withthe respect of human health andenvironmental perspective on national undinternational desk.

´ Delayed effects of this governmental andpublic unawareness may result as serioushuman health hazard.

REFERENCES

1. Anderson PR, Christensen TH., Distributioncoefficients of Cd, Co, Ni and Zn in soils. JSoil Sci 39:15-22 (1988).

2. Baes CF III, Sharp RD, Sjoreen AL, Shor RW.A Review and Analysis of Parameters forAssessing Transport of EnvironmentallyReleased Radionuclides throughAgriculture. DE85-000287. Springfield,VA:US Departmen of Commerce, NationalTechnical Information Service (1984).

3. Calabrese EJ, Stanek EJ, Pekow P, BarnesRM., Soil ingestion estimates for childrenresiding on a superfund site. Ecotox EnvironSafe 36: 258-268 (1997).

4. Chronopoulos J, Haidouti C, Chronopoulou-Sereli A, Massas I., Variations in plant andsoil lead and cadmium content in urbanparks in Athens, Greece. Sci Total Environ196: 91-98 (1997).

5. Dalenberg JW, Van Driel W., Contribution ofatmospheric deposition to heavy-metalsconcentrations in field crops. Neth J Agrci38: 396-379 (1990).

6. DEFRA (Department of Environment, Foodand Rural Affairs). Total Diet Study—Aluminium, Arsenic, Cadmium, Chromium,Copper, Lead, Mercury, Nickel, Selenium, Tinand Zinc. London:The Stationery Office(1999).

7. DEFRA (Department of Environment, Foodand Rural Affairs) and Environment Agency.Contaminated Land Exposure AssessmentModel (CLEA): Technical Basis andAlgorithms. Bristol, UK:Department for theEnvironment, Food and Rural Affairs and TheEnvironment Agency.. 2002b. Contaminantsin Soil: Collation of Toxicological Data andIntake Values for Humans. CLR9. Bristol

(2002a).8. Hawley JK., Assessment of health risk from

exposure to contaminated soil. Risk Anal 5:289-302 (1985).

9. Hérbert CD., Subchronic toxicity of cupricsulphate administered in drinking water andfeed to rats and mice. Fundam Appl Toxicol21: 461-475 (1993).

10. Hough RL. 2002. Applying Models of TraceMetal Transfer to Hough RL, Young SD, CroutNMJ., Modelling of Cd, Cu, Ni, Pb and Znuptake, by winter wheat and forage maize,froma sewage disposal farm. Soil UseManage 19: 19-27 (2003).

11. Keefer RF, Singh RN, Horvath DJ., Chemicalcomposition of vegetables grown on anagricultural soil amended with sewagesludges. J Environ Qual 15: 146-152 (1986).

12. Konz J, Lisi K, Friebele E., Exposure FactorsHandbook. EPA/600/8-89/043. Washington,DC:U.S (1989).

13. Northwood Geoscience Ltd., Vertical Mapperfor MapInfoVersion 1.5. Nepean, Ontario,Canada:Northwood Geoscience Ltd (1996).

14. Reilly C., Metal Contamination of Food. 2nded.speciation of Pb2+ and Cu2+. EnvironToxicol Chem 17: 1481-1489 (1991).

15. Shao J., Linear model selection by cross-validation. J Am Stat Assoc 88: 486-494(1993).

16. Stanek EJ, Calabrese EJ, Zorn M., Soilingestion estimates for Monte Carlo riskassessment in children. Hum Ecol RiskAssess 7: 357-368 (2001).

17. Sterrett SB, Chaney RL, Gifford CH, MeilkeHW., Influence of fertilizer and sewage sludgecompost on yield of heavy metalaccumulation by lettuce grown in urban soils.


Environ Geochem Health 18: 135-142(1996).

18. B.D. Gharde, Orient J. Chem., 26(1): 175-180(2010).

19. Trowbridge PR, Burmaster DE., A parametricdistribution for the fraction of outdoor soil inindoor dust. J Soil Contam 6: 161-168 (1997).

20. Teuschler LK, Dourson ML, Stiteler WM,McClure P, Tully H., Health risk above thereference dose for multiple chemicals. RegulToxicol Pharm 30: S19-S26 (1999).

21. Arokiyaraj, R. Vijayakumar and P. Martin,Orient J. Chem., 27(4): 1711-1716 (2011).

22. Van Lune P., Cadmium and lead in soils andcrops from allotment gardens in theNetherlands. Neth J Agric Sci 35: 207-210(1987).

23. Waalkes MP, Rehm S., Cadmium andprostate cancer. J Toxicol Environ Health 43:251-269 (1994).

24. Wang XJ, Smethhurst PJ, Herbert AM.,Relationships between three measures oforganic matter or carbon in soils of eucalyptplantations in Tasmania. Aust J Soil Res 34:545-553 (1996).

INTRODUCTION

Contamination of aquatic ecosystems byheavy metals has been observed in sediment,water and aquatic flora and fauna (Forstner andWhittmann, 1983). Different aquatic organisms oftenrespond to external contamination in different ways,where the quantity and form of the element in water,sediment or food will determine the degree ofaccumulation (Langston & Spence, 1995). Heavymetals entering the aquatic ecosystem originatefrom different sources such as decay of plants andvegetation, atmospheric particulate, discharge ofdomestic and municipal wastes etc. (Abo et al.,2005, Fatma A.S.M., 2008).

Like soils in the terrestrial system, sedimentis the primary sinks for heavy metals in the aquaticenvironment. Heavy metals once absorbed on thesediments sre not freely available for aquaticorganisms. Under changing environmentalconditions (temp., pH, redox potential, salinity) ofthe overlying water these toxic metals are releasedback to the aqueous phase (Soares et al., 1999).Hence, the assessment of sediment is significantto study the risk of aquatic ecosystem. Similarly


Bioaccumulation of Heavy Metals in DifferentComponents of two Lakes Ecosystem

AMIYA TIRKEY*, P. SHRIVASTAVA2 and A. SAXENA1

1M.P. Pollution Control Board, Bhopal - 462 016, India.2Department of Life Sciences and Limnology, Barkatullah University, Bhopal, India.


ABSTRACT

Bioaccumulation of heavy metals (Cu, Cd, Ni, Fe and Pb) was examined by atomicabsorption spectrophotometer in sediment, water and fish samples of two different lakes; freshwaterand sewage fed water namely Upper and Shahpura Lake respectively of Bhopal, (M.P.) India.All these trace metals were greater in polluted lake as compared to freshwater lake, except Pb.The experimental results clearly indicated heavy metal accumulation in different trophic level ofboth lakes.

Key words: Bioaccumulation, heavy metals, Upper Lake, Shahpura Lake, trophic level.

fishes assimilate these heavy metals throughingestion of water, food materials and constant ionexchange process of dissolved metals acrosslipophilic membranes like gills or adsorption onsurface membrane like skin. The region ofaccumulation of heavy metals within fish varies withroute of uptake, heavy metal species and speciesof fish concerned. Their potential use as biomonitorsis therefore significant in the assessment ofbioaccumulation and biomagnifications ofcontaminants within the ecosystem.


Study AreaTwo major artificial water resources were

selected for the study. Both lakes are of commercialimportance due to their beautiful location, but alsoface severe environmental stress.

Shahpura Lake (23° 18' N, 77° 27' E) and488 m above mean sea level. The lake covers anarea of 2.6 km2, has a mean depth of 3.0 m and acatchment’s area of 8.3 km2. Approximately 110 tons/ day solid waste is generated within the catchmentand 9.6 millions litres per day of sewage enters the

294 TIRKEY et al., Curr. World Environ., Vol. 7(2), 293-297 (2012)

lake from residential areas in the catchment(Shrivastava et al., 2003). It is located in the southeast of the city and receives heavy loads of domesticand municipal sewage. The lake water is used inpisciculture, idol immersion, cattle bathing, washingand minor irrigation.

Upper Lake (23°12' E - 23°16’N, 77° 18' -77° 23' E) has an area of 31 km², and drains acatchment or watershed of 361 km². The watershedof the Upper Lake is mostly rural, with someurbanized areas around its eastern end. Thetopography of the lake indicates that the basin isnatural, as northern and southern sides of the lakeare hilly while the western end has flat contoursand forms the agricultural land (Dixit S. et al., 2005).It is a major source of drinkable water for theresidents of the city, serving around 40% of theresidents with nearly 30 million gallons per day.The lake water is used for fishing, boating, idolimmersion and irrigation.

Field SamplingThe sampling of water and sediment from

Shahpura and Upper Lake were based on theprinciples and procedures outlined in standardmethods for the examination of heavy metals inwater (APHA, 1995). Sampling was done eachmonth of summer season (March-May, 2010). Fishsamples were collected from the local fishermenand brought to laboratory for dissection and further

heavy metal determination.

Heavy metal determinationSurface water was collected by dipping

one litre capacity white jerricane. The water samplewas acidified with 2ml HNO3 at the sampling site.The heavy metals in water samples were analysedby AAS. Sediment samples were dried at roomtemperature and ground with pestle and mortar.They were further sieved through 0.2mm mesh sizefilter and stored in clean polybags till analysis. Withthe help of stainless steel scalpel liver, gills andmuscle tissues of fishes were removed. The aciddigestion of sediment and fish tissues was doneaccording to the standard methods. Theconcentrations of the heavy metals were estimatedwith Atomic Absorption Spectrophotometer (GBCAvanta PM, Australia). All reagents used were ofAnalaR grade and all glass wares andpolypropylene were properly cleaned with acidcleansing reagents and rinsed thoroughly withdistilled deionised water.


The concentrations of heavy metalsestimated in sediment, water and fish samplescollected from both lakes are given in Table 1.

The concentrations of heavy metals variedin all different components.

Table 1: Heavy metal concentrations in different components ofUpper Lake and Shahpura Lake (Mean ±SD) (n=4)

Cu Cd Ni Fe Pb

Water (mg/l)Upper Lake 0.00±0.00 0.00±0.00 0.032±0.015 0.785±0.209 0.109±0.007Shahpura Lake 0.001±0.001 0.00±0.00 0.025±0.01 0.567±0.128 0.00±0.00WHO (2004) 1.0 0.05 0.05 1.0 0.05Sediment (mg/kg) Upper Lake 32.75±19.88 0.00±0.00 29.0±19.51 14025±6709 364.25±307.28Shahpura Lake 233.45±238.54 0.05±0.10 47.0±14.94 56650±43888 50.20±38.05Fish muscle (mg/kg) Upper Lake 0.7±0.2 0.726±0.045 0.33±0.57 22.11±4.01 1.76±0.25Shahpura Lake 0.61±0.17 0.41±0.19 2.0±1.0 82.66±4.50 0.00±0.00WHO (2004) 3.0 2.0 0.6 10.0 2.0

n: number of samples

295TIRKEY et al., Curr. World Environ., Vol. 7(2), 293-297 (2012)

CopperIt is essential for human life, but in high

doses it may cause anaemia, liver and kidneydamage, stomach and intestinal irritation etc. Theaverage concentration of Cu observed were, inwater (0.00 ± 0.00 mg/l, 0.001 ± 0.001 mg/l) andfishes (0.7±0.2 mg/kg, 0.61±0.17 mg/kg) in Upperand Shahpura Lake respectively, which were withinthe limits of WHO (2004). In sediment samples UpperLake accumulated 32.75±19.88mg/kg whereasShahpura Lake accumulated 233.45±238.54mg/kg of Cu (Fig. 1). Traces of Cu in drinking water maybe due to the lining of copper pipes, as well as fromadditives used to control algal growth.

CadmiumCadmium derives its toxicological

properties from its chemical similarity to Zn anessential micronutrient for plants, animals andhumans. Cd is biopersistent and once absorbed byan organism, remains resident for many years (over

decades for humans) although it is eventuallyexcreted. High exposure leads to obstructive lungdisease and can even cause lung cancer. Cdproduce bone defects in humans and animals. Cdwas below detectable limit (0.00mg/l) in water ofboth lakes (Fig. 2). Fish muscles showed0.726±0.045mg/kg and 0.61±0.17mg/kg ofbioaccumulation respectively in Upper andShahpura Lake.

NickelSmall amount of Ni is needed by human

body to produce red blood cells, however, inexcessive amounts, it can become mildly toxic.Short term over exposure to Ni is not known to causeany health problems, but long term exposure cancause decreased body weight, heart and liverdamage and skin irritation. Average concentrationof Ni was 29.0±19.51 mg/kg and 47.0±14.94 mg/kg in sediment, 0.032±0.015 mg/l and 47.0±14.94mg/l in water and 0.33±0.57 mg/kg and 2.0±1.0

Fig. 1: Variation of Cu betweenUpper and Shahpura Lake

Fig. 2: Variation of Cd betweenUpper and Shahpura Lake

Fig. 3: Variation of Ni betweenUpper and Shahpura Lake

Fig. 4: Variation of Fe betweenUpper and Shahpura Lake

296 TIRKEY et al., Curr. World Environ., Vol. 7(2), 293-297 (2012)

mg/kg in muscles of fishes of Upper and ShahpuraLake respectively (Fig. 3). Fishes of polluted waterbody showed bioaccumulation of Ni and may beconsidered unsafe for human consumption.

IronFe is essential for plant and animal

metabolism. Fe overload in man is not common butmay occur due to genetic defect. Such overloadresults in oxidative degradation of lipids, destructionof intercellular and extracellular proteins and DNAdamage. Extreme values of Fe was detected in fishmuscles i.e. 22.11±4.01 mg/kg and 82.66±4.50 mg/kg in Upper and Shahpura Lake which is muchhigher than WHO (2004) limits. The reason may bebecause of absorption of Fe residues through theintestinal walls of fishes (Bu-Olayan A.H., 2008).Likewise sediment samples showed theconcentration of 14025±6709 mg/kg and56650±43888 mg/kg in Upper and Shahpura Lakerespectively (Fig. 4). Water showed permissiblelimits for safe consumption of humans and aquaticlife in freshwater and polluted lakes.

LeadLead in the environment arises from both

natural and anthropogenic sources. Exposure canoccur through drinking water, food, air, soil and dustfrom old paint containing Pb. High levels of exposuremay result in biochemical effects in humans which

in turn cause problems in the synthesis ofhaemoglobin, effects on the kidneys,gastrointestinal tract, joints and reproductivesystem, and acute or chronic damage to the nervoussystem. The average concentration of Pb insediment is 364.25 mg/kg and 50.20 mg/kg in Upperand Shahpura Lake respectively (Fig. 5). This valueis very high when compared to the average Pblevels in Indian river sediment of about 14mg/kg(Dekov et al., 1999). The Pb concentration in waterof Upper Lake, 0.109 mg/l is above the permissiblelimits for drinking water by WHO (2004). Thisindicates a high anthropogenic activity surroundingthe lake which includes idol immersion, motor boatsfor recreation, traffic pollution. Fishes of Upper Lakeshowed higher bioaccumulation of 1.76±0.25mg/kg as compared to Shahpura Lake.

The results of this study showed that thewater, sediment and fish of both lakes werecontaminated by the heavy metals Cu, Cd, Ni, Feand Pb. Sediments from both lakes showed highconcentration of toxic metals. The results furthershowed that water could be used for irrigationalpurposes but unsafe for drinking as traces of Pbfound in Upper Lake. These results agree with thatobtained by Saxena A. et al., (1998) and ShahpuraLake is fit for pisciculture and minor irrigation. Fishesof Upper Lake are safe for human intake. It isproposed that continuous monitoring and intensivemanagement in the area should be carried out toascertain long term effects of anthropogenic impactand to assess the effectiveness of minimising thehuman activity to maintain our lake ecosystem.

ACKNOWLEDGEMENTS

The author would like to thank the staff ofCentral Laboratory, M.P. Pollution Control Board,Bhopal for providing support during sampling andlaboratory facilities to fulfil my experiments. Specialthanks to Dr. Sadhya Mokhle for her assistance inheavy metal analysis in AAS.

Fig. 5: Variation of Pb betweenUpper and Shahpura lake

REFRENCES

1. Forstner, U. and G. T. Whittmann: Metalpollution in aquatic environment, Springer-Verlag, Berlin, Heidelberg, New York, Tokyo,

pp 486 (1983).2. W.J. Langston and S.K. Spence: Metal

speciation and bioavailability in aquatic

297TIRKEY et al., Curr. World Environ., Vol. 7(2), 293-297 (2012)

systems. A Tessier & D.R. Turner, Editors,IUPAC Series on Analytical and PhysicalChemistry of Environmental Systems, 3:Chapter 9 (1995).

3. Abo El Ella, S.M., M.M. Hosny and M.F. Bakry:Utilizing fish and aquatic weeds infestationas bioindicators for water pollution in LakeNubia, Sudan. Egypt. J. Aq. Biol Fish. 9: 63-84 (2005).

4. Fatma A.S. Mohamed: Bioaccumulation ofselected metals and histopathologicalalterations in tissues of Oreochromisniloticus and Lates niloticus from lakeNasser, Egypt. Glob. Veter. 2(4): 205-218(2008).

5. Soares, H.M.V.M., R.A.R. Boaventura,A.A.S.C. Machado and J.C.G. Esteves daSilva: Sediments as monitors of heavy metalcontamination in Ave river basin (Portugal):multivarioate analysis of data. Env. Poll. 105:311-323 (1999).

6. Shrivastava P., Saxena A. and Swarup A:Heavy metal pollution in a sewage fed lakeof Bhopal, (M.P.) India. Lakes and Res, 8: 1-4 (2003).

7. Dixit S., Gupta S.K. and Tiwari Suchi: Anutrient overloading of a freshwater lake inBhopal, India. Earth Day, Issue 21 (2005).

8. APHA: Standard methods for theexamination of water and wastewater 19th

Ed. American Public Health Association

(1995).9. P. Sannasi and S. Salmijah, Orient J. Chem.,

27(2): 461-467 (2011).10. Dekov, V.M., Subramanian, V., Van Grieken,

R.: Chemical composition of riverinesuspended matter and sediments from theIndian sub-continent. In: Ittekkot, V.,Subramanian, V. And Annadurai S. (Eds),Biogeochemistry of Rivers in Tropical Southand Southeast Asia. Heft 82, SCOPESonderband Mitteilug aus dem Geologisch-Palaontolgischen Institut der Universitat,Hamburg, pp. 99-109 (1999).

11. WHO: Guidelines for Drinking Water Quality,3rd Ed. World Health Organisation, Geneva(2004).

12. B.M. Bheshdadia, D.S. Kundariya and P.K.Patel, Orient J. Chem., 27(2): 685-689(2011).

13. Bu-Olayan A.H., Thomas B.V. :Trace metalstoxicity and bioaccumulation in mudskipperPeriophthalmus waltoni Koumans1941(Gobiidae: Perciformes). T. Jour. ofFisheries and Aquatic Sciences, 8 :215-218(2008).

14. Dixit S., Gupta S.K. and Tiwari Suchi: Anutrient overloading of a freshwater lake inBhopal, India. Earth Day, Issue 21(2005).

15. Saxena A. and Shrivastava P. And SwarupA.: Heavy metal pollution in a tropicalwetland. Lakes and Res (1998).

INTRODUCTION

Warud is a Taluka place located on theborder of Maharashtra and M.P. States. It is situatedat the base of satpuda Ranges and covered by densewoods with many medicinal plants and water bodies.It is famous for oranges and commonly known as“California of Vidarbha”. The major crops of the districtis ‘Oranges’. The famous historical and holy placesalbardi is only 30Km, away from Warud. The mainwater supply is from Uppar Wardha Dam andShekhdari dam water to this Warud Region.

Water is most common and importantresource on the earth (Suther et al., 2001). However,the availability of water varies from place and timeto time. As a result, there is a persistent scarcity ofwater is many parts of the world. Exponential growthin population creates an ever increasing demandof water for irrigation, industry and domestic use(Shankar et al., 2004, Wright 2007).

Due to the population growth of this areaand in the villages, the scarcity of water arisesespecially during summer season Warud Regionis famous for orange crops. Farmers of this areausing 50% land for orange irrigation purpose. Fromlast 100 years ago they are using water for arigationpurposes. Due to this water level of this regionbecome deeper and deeper. Upper Wardha Damwater is insufficient to provide it for agriculture as


Equilibrium Sorption Studies for Fluoride content in Drinking Waterof Bore wells of Warud Region on Ferronia Elefuntum Fruit Shell

U.E. CHAUDHARI

Department of Chemistry, Mahatma Flue Mahavidyalaya, Warud – 444 906, India.

(Received: October 12, 2012; Accepted: December 05, 2012)

ABSTRACT

Major water supply for agriculture and domestic purpose in Warud Region is from UpperWardha and Shekhadari Dam Water. Even then, resident of most of the areas are mainly dependent onbore well water for domestic and Agriculture purpose especially in summer season. Hence largenumbers of bore wells are existed. Fluoride content of selected bore-well water in an around of Warudwas analyzed in the month of May, 2011. The study reveals that the fluoride concentration is within thepermissible limits in few places as prescribed by BIS and WHO. But in some places it is more thanprescribed by BIS and WHO. Hence it is essential to remove these excess fluorides by adsorption.

Key words: Bore well water Fluoride concentration, Fluorosis Adsorption

well as drinking purposes to this area. As a result, alarge number of bore well existed in this area tomeet the water demands. Now a days, these Borewell is 500 to 800 feets deep. it is found that waterfrom these bore well contain fluoride. The poorquality or drinking water is more due to thecontamination than due to natural inferiority of thesources. Fluorides are present in both surface waterand ground water. Most of the fluoride found inground water result from weathering and circulationof water in rocks and soils. The chemical quality ofground water varies even at short distances. Thisvariation may be attributed to the variations in thehydro chemical process (Maniraju, 2006). Fluoridein small dosages has remarkable influence on thedental system inhibiting denta curies, whileconsumption of high dosage fluoride water causesfluorosis (Shukla et al., 2004). In India about 62million people including 6 million children, sufferfrom fluorosis due to high content of Fluoride inwater (Susheela, 1990). The present analysis is anattempt to evaluate the fluoride content of bore wellwater in Warud Region.

Adsorbent PreparationThe Ferronia Elefuntum Fruit Shell was first

died at a temperature of 160°C for 6 hours. Aftergrinding it was sieved to obtain average particlesize of 200 mesh. It was then washed several timeswith distilled water to remove dust and otherimpurities. Finally it was dried again in an ovan at

300 CHAUDHARI et al., Curr. World Environ., Vol. 7(2), 299-300 (2012)

50°C for hours. The adsorbent was then stored indesiccator for final studies.


In the present study, fifteen bore well watersamples of selected areas in and around Warudanalyzed. The samples were collected in cleanpolythene bottles of 2 ltr. capacity. The bottles were firstrinsed with distilled water and then two to three timesby the sample water before collecting for analysis.

Initial Fluoride concentration in watersamples were determined using the parametersprescribed in standard methods for the Examinationof water and wastewater APHA (1995).

In reagent bottle two hundred ml. of this

water is mix with 100 mg of Granular tree bark andshake for 3 hour. After shaking filteral it withwhatmann filtered paper and content is analisedand final flourides concentration is given in table 1.


Fluoride has little significance in industrialwater, where as ingestion of excess fluoride indrinking water can cause fluorosis (Shukla et al.,2004), which affects the teeth and bones. Belowthe permissible, limits, it is an effective preventiveof dental curies, but above the permissible limitsmay causes disfigurement of teeth and severeskeletal flurosis. Such water should bedefluorinated to reduce fluoride concentration bythe process of adsorption on Ferronia ElefuntumFruit shell to the acceptable levels for drinkingpurpose. The observed results were compared withthe standard values of BIS and WHO (i.e. 0.6 – 1.5ppm.)

CONCLUSION

The present analysis concludes that, thefluoride concentration (Table 1) of few samples arewell within the permissible limits as prescribed byBIS and WHO and the results reveals that the somebore wells water of Warud are fit for drinking withoutany pretreatment for fluoride contents. But fewsample cantain excess concentration thanprescribed by BIS and WHO. These excessconcentration were removed by adsorption offluoride on FEFS. These cheap and efficientabsorbents can carry to cater the need of populationin the rural areas and the population in the industrialarea where safe drinking water is not available. Butother physico-chemical parameters of these bore-wells water have to be analyzed for its suitability.

Table 1: Fluoride ion concentration in bore wellwater samples before and after adsorption in ppm

Samples Initial Final concentrationconcentration of fluoride

S1 0.8 0.60S2 0.9 0.65S3 1.0 0.75S4 0.95 0.67S5 0.75 0.65S6 0.89 0.82S7 1.6 1.2S8 0.85 0.65S9 0.92 0.67S10 0.56 0.50S11 0.60 0.52S12 1.32 0.95S13 0.92 0.62S14 0.97 0.67S15 0.76 0.55

REFERENCES

1. APHA: AWWA and WEF, Standard methodsof examination of water and waste waster(19th edition) American Public HealthAssociation, Washington, D.D. (1995).

2. BIS : Specification for drinking water IS :10500 : Bureau of Indian Standards, NewDelhi (1991).

3. Maniraju, Y.M., Vijrappa, H.C. andNellakantrama, J.M. Fluoride concentrationof water in Vrishabharathi river Basin,Bangalore District, Karnataka, Indian J.Environ. and Ecoplan, 12: 665-668 (2006).

4. Shukla, J.B. and Kaur, H., EnvironmentalChemistry, Meerut, India. Susheela, A.K.1999. Fluorosis management programme inIndia. Curr. Sci., 77: 1250-1256 (1994).

5. Susheela, A.K. Fluorosis managementprogramme in India. Curr. Sci., 77: 1250-1256 (1999).

6. WHO, Guidelines for drinking water quality1 (1984).

7. W.H.O. Guide lines for drinking water quality,3rd Edition, would Health OrganisationGeneva (2004).

INTRODUCTION

Bhopal the capital of Madhya Pradeshterritory the largest state of India. Bhopal is situatedon 23°16’N Latitude and 77°25' Longitude and islocated on Hard pink sand stone of Vindhya regionFluoride concentration in India, creates healthproblems and fluorosis. The disease previouslycalled as “Mottled teeth” reported in Madras City(1933). Most of the population of 18 states out of 35states in India are well affected with dental, skeletaland non-skeletal fluorosis, which southern India isbadly affected by “Fluorosis”. Fluoride in drinkingwater is 1.0-1.5 mg/l recommended by WHO(2004).

Fluoride concentration has analyzed byusing ion selective electrode and ORION 407Ameter followed by standards as prescribed by APHA(1992) . The water samples was preserved byadding total ionic strength adjustment Buffer(TISAB) in 1:1 radi and analysis for fluoride levelsis calculate by standard curve platted on a semiloggraph conc.(Log axis) vs mV. Teofia and Teofia index(TTI 1991) has commonly used to score dentalfluorosis in several endemic areas of this country


A Study on Seasonal Variation in the Physico-chemicalAssessment of MPN and Fluoride Analysis of Drinking

Water of Gandhinagar Area of Bhopal

H.C. KATARIA1 and SANTOSH AMBHORE2

1Department of Chemistry, Government Geetanjali Girls College, Bhopal - 462 038, India.2Department of Chemistry, Government Motilal Vigyan Mahavidalaya, Bhopal - 462 003, India.


ABSTRACT

Determination of fluoride concentration of sampling stations from different sites in andaround villages near Gandhinagar of Bhopal was carried out by using selective fluoride ion-electode. Determination of coliform bacteria/MPN of drinking water samples collected fromvarious places by using H2S paper strip method and checked form black coloration in paper strip.

Key words: Determination, Fluoride ion concentration, Drinking water,Fluorosis, Coliforms, MPN (myeloproliferative neoplasm)

The present investigation describe the qualitativeand quantitative assessment of different watersamples collected different sampling stations ofstudy are collected from various sampling placesin 2011-2012. by using H2S paper strip method andchecked for black coloration in paper strip. A totalof 5 types of bacterial colonies were identified bybiochemical, cultural and microscopic examinationtechnique. Escherichia coli, enterobacter weredominant followed by Klebsiella pneumonae,Salmonella typhi, and Proteus vulgeris.concentration of bacterial colonies was maximumin October followed by November, December andminimum in May.

The goal of household water treatmentprograms, like the CDC safe water system, is toreduce diarrheal disease in users by improving themicrobiological quality of stored household water.Thus, testing for microbiological contaminants isuseful to determine it:´ Household drinking water is contaminated

before program initiation; and´ An intervention improves the microbiological

quality of stored household water.

302 KATARIA & AMBHORE, Curr. World Environ., Vol. 7(2), 301-303 (2012)

Microbiological indicators are bacteria shown tobe associated with disease-causing organisms, butdo not cause disease themselves. The threecommon micorbiological indicators are : (1) totalcoliform bacteria; (2) fecal (thermotolerant) coliformbacteria; and (3) Escherichia coli. A fourth indicator,production of hydrogen sulfide, has recently beenused as well.

Total Coliform BacteriaDisease-causing organisms can be

present in water in small numbers and pose ahuman health risk. Because of this, indicators ofdisease-causing organisms present in higherconcentrations were initially developed to assessdrinking water safety. Because there are numerouscoliform bacteria in the intestinal tracts of humans,and each person discharges between 100-400billion per day, this group was initially chosen asthe indicator organism for drinking water safety.

Fecal (Thermotolerant) Coliform BacteriaTo provide a more accurate indicator of

human health risk, the fecal coliform group wasdeveloped. This group is also defined by thelaboratory method, and includes those Gram-negative rod bacteria that, at 44 ± 0.2 degreesCelsius, either: 1) ferment lactose with gasproduction (for MPN and P/A testing), or 2) producea distinctive colony on a suitable mediu (for MFtesting). This subgroup includes the genusEscherichia, and some species of Klebsiella,Enterobacter, and Citrobacter. The terms fecalcoliform bacteria and thermotolerant coliform

bacteria are used interchangeably.

E. coli. Escherichia coli (E. coli)is a bacteria that colonizes the

gastrointestinal tract of humans and other mammalsshortly after birth and is considered part of ournormal intestinal flora. Some types of E. coli, suchas E. coli O157:H7 possess virulence factors andcan cause diarrheal disease in humans, but mosttypes of E. coli are harmless. A single gram of freshfeces may contain as many as 1,000,000,000 E.coli. The mammalian gut is the normal habitat for E.coli, and, unlike other coliform bacteria, they arenot normally found in uncontaminated waters. Thismakes E. coli an ideal indicator for human healthrisk. WHO states, “The presence of E. coli in wateralways indicates potentially dangerouscontamination requiring immediate attention” (4).Due to its high prevalence and disease-causingproperties, E. coli is a solid microbiologicalindicator. However, in some less contaminatedenvironments, there is not enough E. coli presentto calculate treatment process efficiency. Whensampling for both human health risk and treatmentefficiency a combined total coliform/fecal coliformbacteria test and E. coli test may need to becompleted.

The World Health Organisation (WHO)and united states environmental protection Agency(USEPA) both use microbiological indicators asthe guideline value or standard for safe drinkingwater. The WHO guideline value is that E. coli andthermotolerant (Fecal) Coliform bacteria “Must not

Table 1: Physico-chemical assessment of drinking water of Gandhi NagarArea of Bhopal City 2011-12

Mean Seasonal Value (Pre and Post monsoon )

Parameters Unit SS1 SS2 SS3 SS4 SS5 SS6 SS7 SS8

Fluoride ppm 0.16 0.27 0.18 0.40** 0.30 0.28 0.20 0.10*MPN No./100ml 64 98** 90 65 36 70 44 32*

SS1 = Pardi Mohalla SS5 = Badbai

SS2 = Jhirniya SS6 = Sector no. 5

SS3 = Jodhpur Dhaba SS7= Dawarika Dham

SS4 = Pipalner SS8= Nai Basti

**= maximum value * = minimum value

303KATARIA & AMBHORE, Curr. World Environ., Vol. 7(2), 301-303 (2012)

be detectable in any 100 ml sample” of waterintended for drinking (1) The guidelines also notethat “immediate investigative action must be takenif E. coli are detected”, and that “medium-termtargets for the progressive improvement of watersupplies should be set” in developing countrieshaving difficulties meeting the standards.

Hydrogen Sulfide productionA relatively new microbiologic indicator

test is measuring hydrogen sulfide production. Somebacteria excrete hydrogen sulfide in their metabolicprocesses. Because hydrogen sulfide is easy andinexpensive to measure, this has been suggestedas a new indicator. However, hydrogen sulfide can

be produced via other mechanisms than bacterialmetabolism, and so hydrogen sulfide productionis, in effect, measuring an indicator (Hydrogensulfide presence of bacterial) of an indicator(bacteria of human health risk).

The finding are similar with Kataria (1996)(2000) most of value found within the permissiblelimit as recommended by WHO 1978. The value offaceal/coliform recommended 10/100 ml index byWHO. Some values are found beyond the limits.Hence water samples analysed in the present studyhas found a suitable for drinking after properrequired treatment.

1. Kataria, H.C., Gupta S.S. and Jain, O.P. PollRes. 14(4): 455-562 (1996)

2. Kataria, H.C. Preliminary study of drinkingwater of Pipariya township, Poll, Res, 19(4):645-649 (2000)

3. Rangwala, K.S. and Rangwala P.S., watersupply and sanitary, engineering characterpub. House Anand (vely), India, 12th ed. 4344(1927).

4. BIS : Specification for drinking water IS :10500: Bureau of Indian Standards, NewDelhi (1991).

5. Kataria, H.C., Analytical study of traceelements in groundwater of Bhopal city. Ind.J. Environment Prot. IJEP, 24(12): 894-896(2004)

6. Kataria, H.C., et al., Physiochemical analysis

of water of Kubza river of Hoshangabad,Orient J. Chem., 11(2): 157-159 (1995).


8. K.C. Gupta and Jagmohan Oberai, Orient J.Chem., 26(1): 215-221 (2010).

9. APHA : Standard methods for theexamination of water and waste water,Americal Public Health association(Greenberg, AE, Clexeri, L.S. and Eaton A.D.,18th ed. Washington DC.) (1992)

10. Kataria, H.C., et al., Flurosis with specialreference to fluroide contents in drinkingwater of Bhopal city (M.P.) Research Link,143(4): 12: 13 (2004)

11. Teotia, SPS and Teotia, Endemic Fluoride,Bomes and teeth update, J. Environ. Toxicol1: 1-16 (1991).

REFERENCES

INTRODUCTION

Hazardous waste effluents coming outfrom the Process industries creating lot ofenvironmental problems. Waste effluent from metalplating, refining, battery and power source arefound to have varying degree of contaminants withhigh toxicity1. There are various methods andtechniques available for treatment of toxic waste tomaintain the toxic material below the prescribeddisposable limit. However, these techniques sufferthe load of physical and chemical pollutants. Forthe fastness of main treatment process and toincrease the efficiency of full fledged treatmentprocess a kind of prior treatment can be given towaste in form of flocculation and coagulation.

By pretreatment the size of impuritiesincreases to such extent that they can be easilyfiltered out from the effluents. Generally in thepretreatment of electroplating waste many inorganiccoagulants or flocculants are used but they havesome disadvantages with them i.e. they mayincrease the unwanted ionic load. To avoid such


Studies in the Applicability of Organic Polymerfor Pretreatment of Industrial Waste

DHANANJAY DWIVEDI1, KIRTI YADAV2 and VIJAY R. CHOUREY3*

1P.M.B. Gujarati Sc. College, Indore, India.2Government Autonomous Holkar Science College, Indore - 452 001, India

3* 2603-E Sudama Nagar, Indore - 452 009, India.


ABSTRACT

The applicability of organic polymer in form of polyeletrolytes as a pretreatment material fordeionizer have been studied in the laboratory prepared electroplating waste solutions. Load ofmetal and non metal ions, present together or alone in the waste can be reduced by flocculation ofwaste with organic polymer. Change in the concentration of TDS and dissolved oxygen have beenstudied. The paper also describes the effect of pH on the flocculation process.

Key words: Organic polymer, polyelectrolyte, flocculation.

type of unrequired ionic loading the organicpolymers can be used as flocculation agents2-4.

Organic polymers or polyelectrolyte’s arewater soluble. They may be synthetic or natural inorigin like cellulose derivatives, starch product etc.They are nontoxic and their small dosing is requiredfor the flocculation5-6.


SS-120 is an anionic polymer with highmolecular weight and in form of white granulatedpowder is used as flocculation agent. It was suppliedby Thermax India Pvt. Ltd. Other chemicals as NiCl2,CuSO4, EDTA, ZnCl2, CuCl2 etc. were used of ARgrade. All the solutions were prepared in doublydistilled water.

Experimental ProcedureThe stock solution of organic polymer SS-

120 was prepared as 1 mL of this stock solution togive 1mg/L of polyelectrolyte concentration whenadded to the 1 liter of test solution. For required

306 DWIVEDI et al., Curr. World Environ., Vol. 7(2), 305-308 (2012)

dosing different mL of stock solution have beenused. The mixture of required amount of polymer indistilled water was kept on the magnetic stirrer toget homogenous solution which should be viscousin nature. Ion containing test solutions wereprepared by dissolving their required amount indistilled water.

Treatment procedureRequired dosing of organic polymer from

stock solution was added to definite amount ofprepared waste solution. For complete and constantmixing it is continuously stirred for 25 minutes then

kept for 10 minutes to get settled. The flocs formedby flocculation get separated by routine methods.The filtrate was tested for ions, TDS, DO and pHestimation. Ni+2, Cu+2 and Cl- were tested bycomplexometrically, iodometrically andargentometrically respectively6-7.


Experiments were performed and theirfindings and related discussions have beensummarized below:

Table 1: Removal of Ni+2, Cu2+, Cl - individually and Ni+2 + Cu2+ while present together

S. Species/ Parameter Initial After Reduction/changeNo. Conc. treatment in value %

mg/L Conc.mg/L

1. Ni+2 ion 168 140 16.502. Cl- (pH 7) ion 250 200 20.003. Cu+2 ions 200 146 27.004. Cu+2 Ni+2 present together Ni+2 260 240 7.60

Cu+2 160 138 13.755. DO 5.5 6.4 16.506. pH Acidic Medium Cu+2 200 200 No Change

Ni+2 168 168 No change7. pH alkaline medium Cu+2 200 20 91.00

Ni+2 168 34 74.76

Experiment was also carried out to seethe change in flocculation efficiency with changingpH. For this effluent with Cu+2 & Ni+2 ions weretreated with organic polymer in two different pHrangesa) between 2 to 3 pH (acidic range)b) at 7.3 pH (slightly alkaline range)

From the result it has been observed thatin the acidic pH range there is no change in theinitial concentration after treatment while in alkalinepH range change in concentration is observed. Ni+2

reduced from 168 mg/L to 34 mg/L & Cu2+ from 200mg/L to 20 mg/L with reduction percentage of 80%& 90% respectively.

The observation exhibit that increase inthe solubility of metal ions in acidic medium reduces

the flock formation with polyelectrolyte, while inalkaline medium metal ions precipitated ashydroxide. Hydroxides are colloidal in nature andquickly form flocks with organic polymer and getsettled. Hence high change in the value is obtainedin alkaline range.

Concentration of dissolved oxygen wasalso tested in the untreated and treated (withbiopolymer) electroplating waste effluent.

The results of this filtrate were recorded.There is an increase of DO by 16.5% in thebiopolymer mixed effluent.

The studies has also been carried out forthe determination of TDS (Total Dissolve Solids) atsolution pH level in untreated Cu+2 and Ni+2 mixed

307DWIVEDI et al., Curr. World Environ., Vol. 7(2), 305-308 (2012)

effluents and in the effluent treated with biopolymer.The value of TDS reduced from 5260 mg/L to 1315mg/L with 75% reduction. These studies also showthat addition of aluminum sulphate in the treatedeffluent increases the TDS.

It has also been observed that if pH isadjusted to slightly alkaline side then TDSdecreased from 5260 mg /L to 684 mg /L. The resultsare given in the table 2

Table 2: Determination of TDS

Without Adjusting pH

Condition Total DissolvedSolids (TDS)In mg/L

Initial TDS in Untreated mixed 5260After treatment with polyelectrolytes 1315After addition of aluminium sulphate in treated effluents 2130

After adjusting pH to slightly alkaline sideTDS in Ni++ and Cu++ mixed effluents after pH adjustment 684

Table 4: Tendency of biopolymer to form the flock with ions

S. No. Ions Magnitude of flock

1. Non-metal Ions Na2SO4 > H3PO4 > NaCl (no flock formed)2. Metal Ions ZnCl2> NiCl26H2O >CuCl2.2H2O3. Metal ion with 0.2 gm. Alum CuCl2.2H2O and ZnCl2 >NiCl2

Observation reveals that SS-120biopolymer reduces the TDS, while addition ofAl2(SO4)3, increases the TDS7. TDS decreases afteradjusting pH to slightly alkaline side because ofthe metal hydroxide gets precipitated.

Work has also been performed on theeffect of polyelectrolyte, Al2(SO4)3 and of pH on thesludge volume. Results are given in the table -3.

Table 3: Sludge volume at different conditions

S. Conditions Total Sludge % of sludgeNo. volume of Volume formed

the effluent in mL in mL

1 When the biopolymer is present 105 7 6.602. When both biopolymer and Al2(SO4)3 are present. 89 28 31.463. At pH 7.5 in presence of biopolymer 105 8 7.604. At pH 7.5 when both biopolymer and Al2(SO4)3 are present. 200 18 9.00

It shows that presence of biopolymer andalum affect the sludge volume in greater extent.

Work has also been carried out to knowthe tendency of the biopolymer to form the flock

with ions. For these solutions containing differentmetal and non metal ions were used. The results ofvisual observations are given in the table - 4

308 DWIVEDI et al., Curr. World Environ., Vol. 7(2), 305-308 (2012)

These results confirmed that biopolymerSS-120 is more active than other metal ions as theflock of zinc formed has greater magnitude. In caseof non-metal ions biopolymer exhibit more affinitytowards the sulphate ion than chloride ions.

After the pretreatment of effluent, now itwas treated by one of the selected full flaggedtreatment process. Here it was applied on ionexchange technique. In first step it was allowed topass through the cationic exchanger for removal ofCu2+ and Ni2+ and then through the anionicexchanger to remove Cl- ions. With This experimentcomplete removal of anions and cations has beenobserved. The experiment was also monitored forany adverse effect of biopolymer on resin, but nosuch adverse effect was noticed.

It is assumed that the capacity ofbiopolymer to trap the colloidal pollutants is due to

their long chain structure. The colloidal particlesentangle or trapped with them and form compactand big size flocks.

The work performed, confirm that pre-treatment of industrial waste by use of biopolymernot only reduces various pollutants to remarkableextent but faster the main treatment process by quiteand good margin.

The method is very much useful tominimize the load of impurities in the industrialeffluents having high concentration of metal ionsand anions by using biopolymer.

ACKNOWLEDGEMENTS

Authors are thankful to authority of PMBGujarati Science College, Indore for providingresearch facilities.

REFERENCES

1. S.S. Rogers and P. Venema, Biopolymer,82(3): 241 (2006).

2. K. Nakanura and Rawarnura, Bul.Chem.Soc., Japan, 44: 330 (1971).

3. K.E. Langford and J.E. Parkar, Analysis ofelectroplating and related solutions RobertDraper Ltd. Teddngton, (1971).

4. N.V. Parathasardhy, Environ. Health, 11, 358,(1969).

5. Nusoibah Naahidhan Rukman, Siti Zaleha

SA'AD and Rozana Mohd Danan, Orient J.Chem., 28(2): 741-748 (2012).

6. M. Sadeghi and M. Yarahmadi, Orient J.Chem., 27(1): 13-21 (2011).

7. C.E. Van Hall and V.A. Stranger, Anal.Chem.,35: 315 (1963).

8. E.W. Meeker and E.C. Wagner, 2nd Eng.Chem. Anal. Ed. , 5: 396 (1993).

9. M. Ali and N. Deo, Indian J. Environ. Protect.,12(3): 202 (1992).

INTRODUCTION

The history of human civilization revealsthat water supply and civilization are almostsynonymous. several cities and civilizations havedisappeared due to water shortage originating fromclimatic and other changes. The absence of waterhas resulted in the absence of life on the moon.Water, The nectar of life is one of the most importantnatural resource for all living organisms, whetherunicellular or multicellular ,since it is required fortheir various metabolic activities. In fact life on theearth is possible only because of the presence ofabundant water. An understanding of waterchemistry is the basis of knowledge of the multidimensional aspects of aquatic environmentalchemistry, which involve the source composition,reaction and transport of water. More than 71% ofthe earth’s surface is covered by water,97% of wateris in oceans and not generally useful withouttreatment. The remaining 3% is fresh water and isfound in rivers, lakes, and underground aquifersand locked up as ice. In fact, 79% of fresh water isin the form of ice mainly in two polar ice sheets andin the high mountain glaciers.


Pre and Post-monsoon Physico-chemical Assessment ofDrinking Water Quality of Gandhinagar Area of Bhopal




ABSTRACT

Physico-chemical assessment of drinking water quality of Gandhi Nagar area of Bhopalhas evaluated in various stations for one year 2011-2012 in pre and post monsoon season. In thispresent study temperature, pH, BOD, COD, EC, free CO2, T-H, Ca-H, Mg-H, total alkalinity hasanalyzed. The present study has its significance for public hygiene in public interest.

Key words: Parameters, physico-chemical assessment, pre and post monsoon,Hygiene, treatment, drinking water.

Rivers, lakes, man made reservoirs andunderground water are our water wealth. Somecenturies ago, water from these sources was cleanand potable, but due to heavy industrialization,excessive use of fertilizers and pesticides,unscientifically disposal of sewage now a day’swater pollution is the main problem for all livingorganisms.

Water quality is commonly defined by itsphysical, chemical, biological and aesthetic(appearance and smell) characteristics. A healthyenvironment is one in which the water qualitysupports a rich and varied community of organismsand protects public health.”

The quality of drinking water is maintainedby individual water bodies of all the metropolitancities. Sydney Water and Hunter Water are the twolarge organisations that aim to provide high qualitydrinking water for all in these regions. Drinkingwater is treated to meet the Australian DrinkingWater Guidelines(ADWG). ADWG is concernedwith the safety and aesthetic quality of drinkingwater for human consumption. Drinking water does


not need to be absolutely pure to be safe, as wateris such a good solvent, pure water containingnothing else is almost impossible to attain. What isrequired is that drinking water should be safe todrink for people in most stages of normal life,including children over six months of age and thevery old. It should contain no harmful concentrationsof chemicals or pathogenic microorganisms, andideally it should be aesthetically pleasing in regardto appearance, taste and odour.

Water quality has also become a big issue.The amount of clean water that is available hasdecreased within the past decade. Although sometypes of water pollution occur through naturalprocesses, most of the pollution is caused by humanactivities. The water we use is taken from rivers,lakes and underground, and these are the sameplaces the water returns to after we have finishedusing it – or actually, not finished using it but finishedcontaminating it. Water pollutants categorizes intofour basic categories: pathogens and other organicmaterials, chemicals including organic andinorganic toxic substances, thermal heat, and

suspended materials. Organic materials such aspesticides, fertilizers, plastics, detergents, gasoline,oil, factory waste water, and fossil fuels are amongthe most severe pollutants.

Many researchers have studied in detailthe physic-chemical characteristics of groundwater,rivers, lakes, water reservoirs and other waterresources. The findings of some such work arerelevant to the present study.

Present district of Bhopal was carved outof Sehore district in 1972. Bhopal is the picturesquecapital of Madhya Pradesh and known as “city oflakes”. Water is one of the very precious substanceson the earth. it is very essential for the existenceand survival of life. As population grows and theirneed for water increases, the pressure on ourground resources also increases . in many areas ofthe world ground water is now being over extracted,in some places massively so, the results is fallingwater levels and declining well yield ,landsubsidence and ecological damage such as thedrying out of wetlands.


Parameters Mean Seasonal Value (Pre and Post monsoon )

Unit SS1 SS2 SS3 SS4 SS5 SS6 SS7 SS8

Temperature °C 19 18* 21 20 19 24** 22 23pH - 5.00 4.5* 6.24 6.50 5.80 6.40 7.4** 7.20Electrical conductivity µmhos 220 212* 310 418** 232 278 232 384

/cmFree CO2 ppm 6.42 6.20* 8.42 9.12 7.42 11.80** 10.94 11.20Total Alkalinity ppm 216 240** 232 182 152 220 142 110*Total Hardness ppm 212 224 420** 312 216 284 210* 238Calcium Hardness ppm 117 130 290** 208 110* 190 114 178Magnesium Hardness ppm 95 94 130** 104 106 94 96 60*Dissolved Oxygen ppm 2.12 2.40** 1.82 2.10 1.10* 2.32 1.72 2.26B.O.D. ppm 4.92** 1.52 2.18 1.60 3.28 2.16 1.42* 4.60C.O.D. ppm 13.20 12.12* 17.20 52.2** 16.80 14.10 17.40 12.80

SS1 = Sant Aasharam Bapu Asharam SS5 = Sector no. 11

SS2 = Tagore ward SS6 = Parewakhedi

SS3 = Gondipura SS7= Dobra

SS4 = Rajiv Gandhi technology university SS8= Chandpur



Water samples of bore-wells are collectedin 2 litre clean polythene jerry-cane after flushingthe bore wells to analysis. The procedure hasadopted as prescribed by APHA (1985),NEERI(1986), presterilized bottles are used tocollect DO and BOD samples. In present studytemperature varied from 18-24 °C. pH ranges as4.50-7.40 indicates the intensity of acidity.Free CO2

ranges from 6.20-11.80 ppm, Electrical conductivity212-418, total alkalinity 110-240 ppm, DO, BODand COD ranges as 1.10-2.40,1.42-4.92, and12.12-52.20 .Total Hardness, Ca-H, Mg-H rangesas 210-420,110-290, and 60-130 ppm respectivelyas summarized in table-1. eight sampling stationsare as follows:

1. Sant Aasharam Bapu aashram2. Tagore ward3. Gondipura4. Rajiv Gandhi Technology University5. Sector No-116. Parewakhedi7. Dobra8. Chandpur

The above findings are similar with thoseof Handa (1994), Kataria (1995); 2000, 2004. Mostof the parameters are found well with in therecommended limits of BIS and some parametersare found beyond the limits. Hence water samplesanalyzed in present study has found suitable fordrinking purpose after proper required treatment.

REFERENCES

1. Standard method for the examination ofwater and waste water APHA, 13th Ed. NewYork (1985).

2. NEERI: manual on water and waste wateranalysis, national environmentalengineering research institute Nagpur 340(1986).

3. BIS: specification for drinking water IS: 10500:Bureau of Indian standards, New Delhi(1991).

4. WHO: guideline for drinking water qualityvolume 1 (1984).

5. B.M. Bheshdadia, D.S. Kundariya and P.K.Patel, Orient J. Chem., 27(2): 685-689(2011).

6 Kataria, H. C., Analytical study of traceelements in ground water of Bhopal City Ind.J. Environment Prot. IJEP, 24(12): 894-896(2004).

7. Kataria, H.C. Preliminary study of drinkingwater of Pipariya township, Poll, Res, 19(4):645-649 (2000).

8. WHO, Environmental health criteria, 5,Genewa (1978).

9. APHA : Standards methods for theexamination of water and waste water,American Public Health Association(Greenberg, AE, Clexri, L.S. and Eaton A.D.,18 th ed. Washington DC. ) (1992)

10. Iqbal S.A.,Khan S.S.,Chaghtai S.A. and IrfanHusain; Assesment of pollution levels of riverBetwa, J.Sci.Res., 6(3): 165-170 (1984).

11. C.N. Sawyer, et.al, chemistry forEnvironmental Engineering and Science,Fifth edition by Tata McGraw-Hill 659-665(2003).

12. B.D. Gharde, Orient. J. Chem., 26(1): 175-180 (2010).

INTRODUCTION

The recent studies have indicated that thewater bodies becoming increasingly Contaminateddue to the domestic and industrial wastes. Theeffluent discharge from sugar Mill consists of anumber of chemical pollutants that can bring aboutchanges in temperature, Humidity and oxygensupplies amounting to a partial or completealteration in the physical, chemical andphysiological sphere of the biota. Such changesdisrupt the ecological cycle of Living organisms.Further, the letting of effluents sugar mill run intothe natural water is responsible for bad quality waterwhich affects aquatic life severely. It is, therefore,very essential to study the physico-chemicalparameters and heavy metal contents of theeffluents to ensure their proper treatment prior totheir disposal into open land or natural waterResources.

The present paper deals with theestimation of physicochemical parameters of sugarmill effluents collected from Neoly Sugar Mill, districtKhargone M.P (India). This study was conductedduring the December to January month 2012, whensugar mill remained in its full crushing capacity.


Analysis and Physico-Chemical Parameters ofSarvar Devla Sugar Mill Studies of Effluents

JANESHWAR YADAV1* and R.K. PATHAK2

1Jawaharlal Institute of Technology, Borawan, Khargone - 451 228, India.2New G.D. College, Moti Tabela, Indore, India.


ABSTRACT

The physico-chemical characteristics contents in the effluents discharged from Neolysugar mill have been explored. The physico-chemical parameters such as colour, odour, temperature,pH, electrical conductivity, COD, BOD, alkalinity, total hardness,Ca+2, Mg+2, chloride, of the effluentcollected from the various sites between the exit point at the mill and discharge point In, have beendetermined.

Key words: Sugar mill effluents, Physico-chemical parameters.


Samples of sugar mill effluents werecollected from the different points on the drain viz.point-1 (the exit in the premises) point-2 (1/2 km.from point-1) and point-3 (1/2 km. from point-2) inthe month of February 2012. The physico-chemicalanalysis of sugar mill effluents was carried out asper the standard methods for analysis of water,waste water and industrial effluents. All the testingwere done at our institute laboratory. Wherealkalinity. Hardness, chloride content determinedby standard titration methods.


Physico-chemical parametersThe results related to the physico-

chemical parameters of the sugar mill effluentscollected at different time intervals from the varioussites have been listed in the given table 1.

ColourThe colour of the effluent was found

variable at different points. The effluents are yellowin colour and intensity decrease from Point-1 toPoint-3.

314 YADAV & PATHAK, Curr. World Environ., Vol. 7(2), 313-315 (2012)

OdourThe odour of effluents of the mill was found

sweet to alcoholic from Point-1 to Point-3.

TemperatureThe temperature is the highest at Point-3

and decreases appreciably up to Point -1.

pHThe pH value of the effluent sample varies

from 5.32 to 5.89. pH values are increased withincrease in the distance travelled by the effluent.The ISI permits a range of pH from 5.5 to 9 for theeffluents that could be released into any naturalwater source (ISI 1974).

TH (Total hardness)The term ‘Total hardness’ indicates the

concentration of Ca2+ and Mg2+ ions only. It isexpressed in terms of calcium carbonate. Totalhardness varied from 760 to 800 mg/L.

Calcium (Ca2+)Calcium values range from 160.32 to

200.4 mg/L.

Magnesium (Mg2+)Magnesium values range from 599.68 to

625.5 mg/L, which are higher than the ISI limits.

AlkalinityAlkalinity found at varying distance during

winter season is of the order 83 to 90 mg/L. It isevident that the alkalinity at all the sampling siteswas much greater than the recommended value,50 mg/L.

Table 1: Physico-chemical analysis of Neolysugar mill effluents at different time intervals

Parameter Point 01 Point 02 Point 03

Colour yellow Light yellow Light yellowOdour Light sweet Light sweet Light alcoholicpH 5.32 5.45 5.89Temperature 32 34 35Total hardness 760 785 800Ca hardness 160.32 165.2 200.4Mg hardness 599.68 602.32 625.5Alkalinity 83 85 90Chloride content 78.1 63.9 71.0

(All concentration are reported in ppm (mg/L) except pH, temperature in (°C)

Chloride (Cl–)The concentration values of chloride in the

effluent samples ranged over 63.9 to 78.1 mg/L.

It is explicit from the data that the pH of theeffluents increases. The values for alkalinity andthe concentration of the magnesium as well as ionsare higher than the recommended value for theindustrials effluents.

The present study exhibits that the

treatment of the effluent is being done regularlybefore its disposal into the natural water sourse.However, the maintenance of the treatment plantas well as the periodic training of the workforce arerequired.

ACKNOWLEDGEMENTS

The Authors are thankful to the Principal,Jawaharlal Instituite of Technology Borawan forproviding thenecessary facilities.

315 YADAV & PATHAK, Curr. World Environ., Vol. 7(2), 313-315 (2012)

REFERENCES

1. C. Manas, Ind. Chem Man, 14(3): 13-14(1979).

2. R. Deshbandu, et al. Ecology andDevelopment, Vth (Eds), Indian Env. Soc.,New Delhi, 178-190 (1979).

3. S. R. Verma and G. R. Shukla, the Env. Health,11: 145-162 (1969).

4. B. K. Behra and B. N. Mishra, Ind. Res., 37:390-398 (1985).

5. S. Khurshid et al., Indian J. Environ, Health,40(1): 45 (1998).

6. N. Manivaskam, Physico-chemicalExamination of Water Sewage and IndustrialEffluents, IIIrd (Eds), Pragati PrakashanMeerut (1996).

7. ISI, Tolerance Limits for Industrial Effluentsdischarged into Inland Surface Water IS,

2490, New Delhi (1974).8. BIS, Specifications for Drinking Water, IS,

10500, Bureau of Indian Standards, NewDelhi (1991).

9. P. R. Pratt, Quality Criteria for Trace Elementsin Irrigation Waters, University of CaliforniaExperiment Station, Riverside, California(1972).

10. Vibha Agrawal, S.A. Iqbal and DineshAgrawal, Orient J. Chem., 26(4): 1345-1351(2010).

11. B.M. Bheshdadia, D.S., Kundariya and R.K.Patel, Orient J. Chem., 27(2): 685-689(2011).

12. M. Hussain, T.V.D. Prasad Rao, H.A. Khanand M. Satyanarayan, Orient J. Chem., 27(4):1679-1684 (2011).

INTRODUCTION

Bhopal the capital of Madhya Pradeshterritory the largest state of India. Bhopal is situatedon 23°16’N Latitude and 77°25' Longitude and islocated on Hard pink sand stone of Vindhya regionFluoride concentration in India, creates healthproblems and fluorosis. The disease previouslycalled as “Mottled teeth” reported in Madras City(1933). Most of the population of 18 states out of 35states in India are well affected with dental, skeletaland non-skeletal fluorosis, which southern India isbadly affected by “Fluorosis”. Fluoride in drinkingwater is 1.0-1.5 mg/l recommended by WHO(2004).

Fluoride concentration has analyzed byusing ion selective electrode and ORION 407Ameter followed by standards as prescribed by APHA(1992) . The water samples was preserved byadding total ionic strength adjustment Buffer(TISAB) in 1:1 radi and analysis for fluoride levelsis calculate by standard curve platted on a semiloggraph conc.(Log axis) vs mV. Teofia and Teofia index(TTI 1991) has commonly used to score dentalfluorosis in several endemic areas of this country

Current World Environment Vol. 7(2), 317-319(2012)

A Study on Seasonal Variation in the Physico-chemicalAssessment of MPN and Fluoride Analysis of Drinking

Water of Gandhinagar Area of Bhopal




ABSTRACT

Determination of fluoride concentration of sampling stations from different sites in andaround villages near Gandhinagar of Bhopal was carried out by using selective fluoride ion-electode. Determination of coliform bacteria/MPN of drinking water samples collected fromvarious places by using H2S paper strip method and checked form black coloration in paper strip.

Key words: Determination, Fluoride ion concentration, Drinking water,Fluorosis, Coliforms, MPN (myeloproliferative neoplasm)

The present investigation describe the qualitativeand quantitative assessment of different watersamples collected different sampling stations ofstudy are collected from various sampling placesin 2011-2012. by using H2S paper strip method andchecked for black coloration in paper strip. A totalof 5 types of bacterial colonies were identified bybiochemical, cultural and microscopic examinationtechnique. Escherichia coli, enterobacter weredominant followed by Klebsiella pneumonae,Salmonella typhi, and Proteus vulgeris.concentration of bacterial colonies was maximumin October followed by November, December andminimum in May.

The goal of household water treatmentprograms, like the CDC safe water system, is toreduce diarrheal disease in users by improving themicrobiological quality of stored household water.Thus, testing for microbiological contaminants isuseful to determine it:´ Household drinking water is contaminated

before program initiation; and´ An intervention improves the microbiological

quality of stored household water.


Microbiological indicators are bacteria shown tobe associated with disease-causing organisms, butdo not cause disease themselves. The threecommon micorbiological indicators are : (1) totalcoliform bacteria; (2) fecal (thermotolerant) coliformbacteria; and (3) Escherichia coli. A fourth indicator,production of hydrogen sulfide, has recently beenused as well.

Total Coliform BacteriaDisease-causing organisms can be

present in water in small numbers and pose ahuman health risk. Because of this, indicators ofdisease-causing organisms present in higherconcentrations were initially developed to assessdrinking water safety. Because there are numerouscoliform bacteria in the intestinal tracts of humans,and each person discharges between 100-400billion per day, this group was initially chosen asthe indicator organism for drinking water safety.

Fecal (Thermotolerant) Coliform BacteriaTo provide a more accurate indicator of

human health risk, the fecal coliform group wasdeveloped. This group is also defined by thelaboratory method, and includes those Gram-negative rod bacteria that, at 44 ± 0.2 degreesCelsius, either: 1) ferment lactose with gasproduction (for MPN and P/A testing), or 2) producea distinctive colony on a suitable mediu (for MFtesting). This subgroup includes the genusEscherichia, and some species of Klebsiella,Enterobacter, and Citrobacter. The terms fecalcoliform bacteria and thermotolerant coliform

bacteria are used interchangeably.

E. coli. Escherichia coli (E. coli)is a bacteria that colonizes the

gastrointestinal tract of humans and other mammalsshortly after birth and is considered part of ournormal intestinal flora. Some types of E. coli, suchas E. coli O157:H7 possess virulence factors andcan cause diarrheal disease in humans, but mosttypes of E. coli are harmless. A single gram of freshfeces may contain as many as 1,000,000,000 E.coli. The mammalian gut is the normal habitat for E.coli, and, unlike other coliform bacteria, they arenot normally found in uncontaminated waters. Thismakes E. coli an ideal indicator for human healthrisk. WHO states, “The presence of E. coli in wateralways indicates potentially dangerouscontamination requiring immediate attention” (4).Due to its high prevalence and disease-causingproperties, E. coli is a solid microbiologicalindicator. However, in some less contaminatedenvironments, there is not enough E. coli presentto calculate treatment process efficiency. Whensampling for both human health risk and treatmentefficiency a combined total coliform/fecal coliformbacteria test and E. coli test may need to becompleted.

The World Health Organisation (WHO)and united states environmental protection Agency(USEPA) both use microbiological indicators asthe guideline value or standard for safe drinkingwater. The WHO guideline value is that E. coli andthermotolerant (Fecal) Coliform bacteria “Must not


Mean Seasonal Value (Pre and Post monsoon )

Parameters Unit SS1 SS2 SS3 SS4 SS5 SS6 SS7 SS8

Fluoride ppm 0.16 0.27 0.18 0.40** 0.30 0.28 0.20 0.10*MPN No./100ml 64 98** 90 65 36 70 44 32*

SS1 = Pardi Mohalla SS5 = Badbai

SS2 = Jhirniya SS6 = Sector no. 5

SS3 = Jodhpur Dhaba SS7= Dawarika Dham

SS4 = Pipalner SS8= Nai Basti



be detectable in any 100 ml sample” of waterintended for drinking (1) The guidelines also notethat “immediate investigative action must be takenif E. coli are detected”, and that “medium-termtargets for the progressive improvement of watersupplies should be set” in developing countrieshaving difficulties meeting the standards.

Hydrogen Sulfide productionA relatively new microbiologic indicator

test is measuring hydrogen sulfide production. Somebacteria excrete hydrogen sulfide in their metabolicprocesses. Because hydrogen sulfide is easy andinexpensive to measure, this has been suggestedas a new indicator. However, hydrogen sulfide can

be produced via other mechanisms than bacterialmetabolism, and so hydrogen sulfide productionis, in effect, measuring an indicator (Hydrogensulfide presence of bacterial) of an indicator(bacteria of human health risk).

The finding are similar with Kataria (1996)(2000) most of value found within the permissiblelimit as recommended by WHO 1978. The value offaceal/coliform recommended 10/100 ml index byWHO. Some values are found beyond the limits.Hence water samples analysed in the present studyhas found a suitable for drinking after properrequired treatment.

1. Kataria, H.C., Gupta S.S. and Jain, O.P. PollRes. 14(4): 455-562 (1996)

2. Kataria, H.C. Preliminary study of drinkingwater of Pipariya township, Poll, Res, 19(4):645-649 (2000)

3. Rangwala, K.S. and Rangwala P.S., watersupply and sanitary, engineering characterpub. House Anand (vely), India, 12th ed. 4344(1927).

4. BIS : Specification for drinking water IS :10500: Bureau of Indian Standards, NewDelhi (1991).

5. Kataria, H.C., Analytical study of traceelements in groundwater of Bhopal city. Ind.J. Environment Prot. IJEP, 24(12): 894-896(2004)

6. Kataria, H.C., et al., Physiochemical analysis

of water of Kubza river of Hoshangabad,Orient J. Chem., 11(2): 157-159 (1995).


8. K.C. Gupta and Jagmohan Oberai, Orient J.Chem., 26(1): 215-221 (2010).

9. APHA : Standard methods for theexamination of water and waste water,Americal Public Health association(Greenberg, AE, Clexeri, L.S. and Eaton A.D.,18th ed. Washington DC.) (1992)

10. Kataria, H.C., et al., Flurosis with specialreference to fluroide contents in drinkingwater of Bhopal city (M.P.) Research Link,143(4): 12: 13 (2004)

11. Teotia, SPS and Teotia, Endemic Fluoride,Bomes and teeth update, J. Environ. Toxicol1: 1-16 (1991).

REFERENCES

cwe journal volume 7 number 2

Documents

perceivedthe odor

odor quality7

human perception of

plant process annoying

health status8

working places

working activity

daily exposure