H

Son NIIIIIJ'dI. 1Iah..1dI

and GocIavaIt
GBF and Mewar Faults

South India Mobile Belt

Himalayan Collison Zone

A.-avalli Fold
Belt

Mumbai

Bastar
Craton

Cuddapah
Basin

I aoOkms I
 CHAPTER 2
ARSENIC CONTAMINATION IN MINERALISED PARTS OF KANKER

DISTRICT OF CENTRAL-EAST INDIA: GEOLOGY AND HEALTH

EFFECTS

ABSTRACT

This chapter identifies newer areas of arsenic contamination in the District Kanker,

which adjoins the District Rajnandgaon where we had reported high contamination

earlier. A correlation with the mobile phase episodes of arsenic contamination has

been identified, which further hinges on the complex geology of the area. Arsenic

concentrations in water (both surface and ground water), aquatic organisms (snail

and water weeds), soil and vegetation of Kanker district and its adjoining area have

been reported here. The region has been found to contain an elevated level of

arsenic. All segments of environment are contaminated with arsenic of varying

degree. The levels of arsenic keep on changing depending on the season and

location. Analysis of groundwater sources from about 89 locations in the Kanker

district has shown high values of arsenic; iron and manganese (mean 144, 914 and

371 ~g/L respectively). The surface water of the region shows elevated levels of

arsenic, which is influenced by the geological mineralised zonation. Arsenic (III) is the

most prevalent species in the groundwater whereas the surface water of the rivers

shows a significant contamination of the As (V) species. The analysis shows a bio

concentration of the toxic metals viz. arsenic, nickel, copper and chromium. Higher

arsenic concentrations (ground water concentrations greater than 50 !-Igfl.) were

associated with sedimentary deposits derived from volcanic rocks. Similar appears to

be the reason of arsenic in Kanker district and the arsenic in groundwater appears to

65
 be caused by mineral leaching. Higher levels of arsenic and manganese in the Kanker

district have been found to cause impacts on the flora and fauna.

INTRODUCTION

Arsenic and fluoride are now recognized as the most serious inorganic contaminants

In drinking water on a worldwide basis. It is also clear that both the WHO gUidelines

value and the current national standard are quite frequently exceeded in drinking

water sources, and often unexpectedly. Arsenic contamination of the ground water is

harming the developing countries more vehemently, owing to the obvious reasons.

Arsenic is classified as a Group A and Category 1 human carcinogen by the U.S. EPA

(US EPA, 1997) and the International Association for Research on Cancer (lARC, 1987)

respectively. In 1997, the WHO acknowledged that arsenic in drinking water is a

"Major Public Health Issue" which should be dealt with on an "Emergency Basis" as it

has become an international problem. World's most affected region is Bengal Delta

Plain (BDP) comprising Bangladesh and West Bengal (WHO, 1999). Pandey et al.

(1999, 2000, and 2001) first reported arsenic contamination and human affliction at

places far away from BDP in erstwhile Madhya Pradesh state. We had further shown

that the arsenic contamination of the village Kourikasa district Rajnandgaon, now in

newly formed state of Chhattisgarh, was spreading and many new arsenic

contaminated hot~spots had been identified (Pandey et aI., 2002). We had reported

that the area between Dongatgaon to Mohla (about 500 sq. km.) is affected by the

presence of arsenic in varying concentration. These levels were highly fluctuating and

hence indicated the involvement of a complex geo~chemical system in its genesis.

This chapter reports newer area of arsenic contamination in the District Kanker,

which adjoins the District Rajnandgaon, and Jt identifies a clear correlation with the

mobile phase episodes of arsenic contamination, which further hinges on the

complex geology of the area. Arsenic concentrations in water (both surface & ground

66
 water). aquatic organisms (snail and water weeds). soil and vegetation of Kanker

district and its adjoining area have been reported here. The region has been found to

contain an elevated level of arsenic. All segments of environment are contaminated

with arsenic of varying degree. The levels of arsenic keep on changing depending on

the season and location. Genesis of arsenic is geological and the involvement of a

complex geochemistry is envisaged for high nuctuations.

MATERIAL AND METHODS

GEOGRAPHY OF THE STUDIED AREA

District Kanker is an important district of Bastar Commissionaire in the state of

Chhattisgarh. The Kanker District is situated in the southern region of the state. Four

districts namely Bastar. Dhamtan. Durg and Rajnandgaon surround it. Kanker is

situated within the longitudes 20.6-20.24 and latitudes 80.48-81.48. The total area

of the district is 5285.01 square kilometres. The district is situated on the National

Highway number 43 between the two well-developed cities of Chhattisgarh named

Raipur (Capital of Chhattisgarh) and Jagdalpur. The district is monsoon fed and the

average rainfall is 1492 mm mainly during the months of June to October.

Kanker district is divided in six tehsils named Kanker, Charama. Narharpur.

Bhanupratapur, Antagarh and Pakhanjoor and seven blocks named Kanker, Charama,

Bhanupratapur, Narharpur Antagarh, Ourgu-kondal and Koyalibeda. The number of

villages in the district is 1074. The literacy percentage in district is 74.7 and the total

population ofthe district is 651,333. The ratio of male female is 10:6. The density of

population is 100 per square kilometre.

Geographically the district is divided in five groups namely Vindhyan hill group,

Archean hill group, Oharwar hill group, Mahanadi plains and Kotri plains. Vindhyan

67
 hill group is situated in the Southeastern part of the district. Quartzite sand is a main

feature of this group. Archean hill group covers the 95% area of the district. Granite

and gneiss rocks are the major component and are spread over almost entire district.

Dharwar hill group comprises of weathered hills in Sambalpur and Bhanupratappur

blocks of the district.

The location of Chhattisgarh in India and district of Chhatisgarh state presented in

Fig. 2.1 and 2.2 respectively. The study area lies between 17· to 24·N, 78· to 88·E and

a simplified geology map (Sarkar 2001; GSI 2000) with main tectonic elements is

shown in Fig. 2.3. Tectonically the Bastar craton (B8) is separated from the Dharwar

(08) and Singhbhum cratons (58) by the Godavari (GG) and Mahanadi (MG) Gondwana

grabens respectively; with the Eastern Ghat Mobile belts (EGMB) lying to the

southeast. From detailed geological. petrological and structural studies the Central

Indian shear (CIS, Yedekar et aI., 1990) has been identified, which separates the

Bastar block from the northern (Bundelkhand) block. The western side of this shear is

buried under alluvium and traps while to the east it forks into two parts with the

northern part coming close to the Tan shear.

Mahanadi plain and Kotri plains are two plain areas in otherwise hilly district. Height

from the mean sea level is between 300~600 meters in this area. The Northeastern

part of Kanker falls under Mahanadi plain. The height of this plane is less than sao
meters. The main rivers draining this area are Mahanadi, Hatkul, Chinar, Doodh,

Sendoor, Nakti and Doori. The Kotri plains comprise mainly the Bhanupratappur area.

Kotri, Handi and Valier are the main rivers of this area. The height of this plain is less

than 400 meters.

68
 PAKISTAN

ARA8'ANau BAY OF BENGAL

..'..

FIG. 2.1: LOCATION OF CHHATTlSGARH IN INDIA.

69
 JHARKHAND

f MADHYA PRADESH

MAHARASHTRA DRIBBA

. '
O.nt.w.d. --.
•

ANDHRA
PRADESH

FIG. 2.2: DISTRiCT MAP OF CHHArnSGARH.

70
 l-l.t·J.:iullul
Il.·t·hlonit'
~dUp

~ Gondwana ~ Rl'H'ul

-- '"
ltDsnnlhtOJU.' ~ \111I,iullI

'"•
II\'
m
--- :::::: 8a\in
i

5.,.° E
DB-Dharwar block, BB-Bastar block, SB-Singhbhum block, CrTZ-Central Indian Tectonic
Zone, EGMB-Eastern Ghat Mobile Belt, GG-Godavari Graben, MG-Mahanadi Graben, 1-
Indravati Basin, C-Chhattisgarh Basin, I-Tapti Fault, 2-Gavilgarh Fault, 3-Tan Shear, 4-
Central Indian Shear, S-Bamni-Chilpa Fault, 6-Tatapani Fault, 7-Barabhum Shear, 8-
Singhbhum Shear, 9-Sukinda Thrust, IO-Sileru Shear, II-North Narmada Fault, 12-South
Narmada Fault, Hy-Hyderabad, Bn-Bhubhaneswar, Dn-Dhanbad, Jb-Jabalpur, Np-Nagpur,
Rp-Raipur.

FIG. 2.3: TECTONIC MAP OF STUDIED AREA.

71
 SAMPLING

Sampling of the contaminated area was carried out In year 2003 in monsoon Uune-

September), post monsoon (October-January), and premonsoon (February-May). The

sampling bottles were cleaned with chromic acid, detergent, tap water and finally

with double distilled water. Duplicate samples were collected for each sampling site.

Arsenic preservation was done with EDTA (Pandey et aI., 2004) and HN03 (till pH 2).

The aim of using two preservatives was to further ascertain the efficacy of

preservation. Soil, rocks, and vegetation sample were kept in clean, uncontaminated

polythene. Water samples were kept refrigerated at 4°C immediately after collection

and were kept so till analysis.

ANALYSIS PROCEDURE

All moist solid samples were dried at 40'C in uncontaminated petridishes till dryness.

Snails were washed with copious amount of tap water and then doubled distilled

water, dried at 40°C in hot air oven and left overnight. All solid samples were finally

crushed and weighted accurately by Digital weighing machine (Denver, USA).

Appropriate weight of sample was taken for digestion in clean uncontaminated

Teflon beakers with few glass beads. Standard digestion procedure was followed

(APHA, 1 992).HN03-HF-HclO. and HN03-H,SO.-HclO. of tertiary acid mixture was

followed for soil or similar matrices and vegetation respectively. Standard analytical

methods were used for all type of sample analysis i.e. measurement of pH and Eh by

single electrode pH and mV meter (Orion, USA), conductivity by conductivity meter,

chloride by silver nitrate method, Alkalinity by titrimetric method using N/30 HCI.

Magnesium, manganese, zinc, nickel, copper, cadmium, chromium by atomic

absorption spectrophotometer. Arsenic was analysed by atomic absorption

spectrophotometer with hydride generation and background correction facility

(Chemito 201), occasionally by SDDC method (Stratten et aI., 1962; NEERI, 1977).
72
 Sample generally did not require any preconcentration due to presence of

measurable concentration of arsenic.

Calcium and magnesium analysis in water sample

Calcium and magnesium were analysed titrimetrically by standard procedure. The

sample was buffered at pH 10 and titrated against 0.01 M EDTA solution, which was

prepared by dissolving 3.7224 gm. of disodium salt of ethylene diammine tetra

acetic acid to one litre of the double distilled water. The endpoint of the titration was

determined by visual colour change using indicator Eriochrome black-T for total

hardness and ammonium purpurate (Murexide) for Ca. The magnesium

concentration was determined by calculating the method of difference.

Sulphate analysis

Sulphate of the water sample were measured using a Nephelo-turbidity meter

equipped with a tungsten-filament lamp following the standard methods (APHA,

1992 Nephthalometric method). Stock sulphate solution was prepared by dissolving

1.479 gm of anhydrous sodium sulphate Na2S0., in 1 liter of deionized water (J 000

ppm).

DIGESTION OF THE SOIL AND SIMILAR MATRICES

The air dried soil and similar matrices were grounded with mixer mill. The 0.50rl gm

of the finely grounded sediment was transferred to a 250 ml Teflon beaker and

added 6 ml concentrated nitric acid and placed the beaker on hot plate. Heating was

continued until the reSidue was nearly dry; if sample was still evolving brown fumes

of Nox this step was repeated. After it content were allowed to cool for 5 miutes and

6 ml of HF, 2 ml of HCL04 was added to it, continued heating the beakers until the

evolution of dense white HCl04 fumes occurred and the solution reached incipient

dryness. The contents were cooled for 5 minutes and this step was repeated. Finely

25 ml concentrated HCI was added to it for dissolution and the solution was made up
73
 to SO ml with distilled water. Similar digestion process was followed for vegetation

except using of H,SO. instead of HF.

TABLE 2.1: BRIEF DETAIL OF THE ANAL YT7CAL AIETHODS ADOPTED IN

THE PRESENT WORK..

Sampl Preparation method Analytical Sample Percent Refere

e method detection recovery nce
matrix limit

Water Reduction to arsine in EPA Method I 0 ~g/ L 100 US

acid solution; reaction 206.4; SODC EPA,
with SDDC colorimetric 1983

spectrophotom

etry at 535 nm

Water/ Digestion with nitric/ HGAAS, EPA 2 ~g/ L 85- 95 US

soil/ sulphuric acid; reduction Methods 206.3 EPA,

solid to As +3 with tin and 7061 ; 1983,
waste chloride; reduction to APHA,1992 1986,
arsine with zinc in acid
APHA
solution
1992

DETAILS OF THE PRINCIPAL ANALYSIS METHOD

Method 7061 (US EPA, 1983; 1986) is an atomic absorption procedure for

determining the concentration of arsenic in wastes, mobility procedure extracts,

soils, and ground water. Method 7061 A is approved only for sample matrices that do

not contain high concentrations of chromium, copper, mercury, nickel, silver, cobalt,

and molybdenum. All samples must be subjected to an appropriate dissolution step

prior to analysis. Spiked samples and relevant standard reference materials are

74
 employed to determine the applicability of the method to a given waste. APHA, 1992

method is having one modification in the above I.e. sodium borohydride is used

instead of the zinc dust for the evolution of arsine gas.

Summary of method

Samples are prepared according to the nitric/sulphuric acid digestion procedure

described in this method. Next, the arsenic in the digestate is reduced to the

trivalent form with tin chloride or KI. The trivalent arsenic is then converted to a

volatile hydride using hydrogen produced from a zinc/hydrochloric acid reaction or

sodium borohydride. The volatile hydride is swept into an oxy-acetylene flame

located in the optical path of an atomic absorption spectrophotometer. The resulting

absorption of the lamp radiation is proportional to the arsenic concentration. The

typical detection limit for this method is 0.002 mg/L.

Interferences

High concentrations of chromium, cobalt, copper, mercury, molybdenum, nickel, and

silver can cause analytical interferences. Traces of nitric acid left following the

sample work-up can result in analytical interferences. Nitric acid must be distilled off

by heating the sample until fumes of nitrogen triOXide (NO,) are observed. Elemental

arsenic and many of its compounds are volatile; therefore, certain samples may be

subject to losses of arsenic during sample preparation.

Apparatus and materials

Atomic absorption spectrophotometer - The AAS used Chemito (AAS 201) is a single

channel, double-beam instrument having a grating monochromator, photo-

multiplier detector, adjustable slits, a wavelength range of 190 to 800 nm. The

burner used was special corrosion resistant metal as recommended by the particular

instrument manufacturer. The arsenic hollow cathode lamp used was manufactured

by Photron, Australia.
75
 Rea~nts

Analytical reagent grade chemicals (Merck. Germany/lndia) were used in all tests.

The reagent water used was deionized and double distilled. interference free

water. All references to water in the method refer to reagent water unless otherwise

specified. Acid viz. HNO,. H2S04. and HCI etc. were analysed to determine levels of

impurities. The acid was used only when the method blank was less than the

detection limit « MOL).

o Potassium iodide solution - 1 5/10 g KI was dissolved in 100 mL water.

• Stannous chloride solution/sodium borohydride solution - 40 9 SnC!, was

dissolved in 100 mL concentrated HCI/2.0 9 sodium borohydride in 0.05 N

sodium hydroxide solution.

• Silver diethyldithiocarbamate (SOOC reagent) (O.S%) - 0.5 gm of silver

diethyldithiocarbamate was dissolved in 100 ml pyridine with thorough

mixing.

Arsenic solutions

Arsenic stock solution (1,000 mg/L) - A certified aqueous standard was obtained

from Merck Germany and was verified by comparison with a second standard.

Subsequently 1.734 g of sodium arsenite (NaAS02) was dissolved in 1000 mL of

deionized water.

Intermediate arsenic solution_- J ml stock arsenic solution was pi petted into a J 00-

mL volumetric flask and make up to mark with deionized water. (l ml = J a jJg As).
Standard arsenic solution - J a ml intermediate arsenic solution was pipetted into a

J OO-mL volumetric flask and brought to volume with deionized water. (1 ml = 1.0 119

As).

76
 Exact 0.00, 0.1, 0.4, 0.6, 0.8, 1.00 ml standard solutions of As (III) was pi petted in

uncontaminated beaker and brught to volume of 1.00-ml with deionized water. This

yielded blank and standard solutions of 0.1, 0.4, 0.6, 0.8, 1.00 IJg /ml. (APHA,
1992).

A standard volume of sample was transferred to the reaction vessel and 20 ml of 20%

HCI andl mL K1 solution were added to it and the contents were allowed at least 10

minutes for the metal to be reduced to its lowest oxidation state. The metal hydride

was produced by adding 2 ml Sodium Borohydride solution, which produced a peak

almost immediately. The wavelength of 193.7-nm and background correction was

used for the analysis of arsenic.

TABLE 2.2: INSTRUMENTAL PARJUIETERS EMPLOYED IN HGMS METHOD.

Parameter Value

Wavelength (nm) 193.7/ 189.0 (Alterative)

Current (mA) 7 - 10

Flame Air-Acetylene (A-A)

Normal Working Range (mg/L) 0.1-1.0

Spectral band width (nm) 0.5

N2 flow rate (Litre/minute) 0.4-1.0

Procedure adopted in UV- Visible spectrophotometer

In a series of arsenic generator, 0.0, 1.0, 2.0, 10.0 ml of arsenic standard solution

was pipetted and diluted to 50 ml with deionized water. Added to it was 5-ml

concentrated HCI, 2-ml of 15% KI (freshly prepared), and 8 drops of 40% Snel2
77
subsequently in each arsenic generator with thorough mixing. Allowed 15 minutes

for complete reduction of As (V) to As (III). Taken 4.0 ml of SDDC regent in absorber

tube and connected to arsenic generator assembly. Added 3 gm of Zn metal powder

in arsenic generator assembly and allowed 30 minutes for the complete evolution of

arsine. Pored the solution from the absorber tube into I cm cell and measured the

absorbance of solution at 535 nm on UV-Visible spectrophotometer. Prepared the

calibration curve and same procedure was followed for sample with taken

appropriate volume of sample. A typical calibration curve are shown in Fig. 2.4 and

2.5.

..OA
u
li 0 3
-eo .
y~ 0.1009x- 0.0147
1l
..:0.2 R2~0.9907

0: +]---,---~-----c~--~--~----;
0.1 0.3 0.5 0.7 08 1
As (ppm)

[ -.-Pbsorbance -linear(Absorbance) i

FIG. 2.4: A 7YPICAL CALIBRATION GRAPH OBTAINED WITH HGAAS.

78
 $TlJ)£S 00 ENVtlCHoFNT~ Atn.w £SIN S<l.!£ MKAAJSm ZeN'S EmcTS C1' Mt!RH E)('!lar ATr.NAtI) MTlXYIIDH a: [)JRLWNT~ !w.ACT S

0.7

0.6

0.5

.,0.4
o
.eo" 03
y = 0 l06x - 0.0293
;'i'" 0.2
R'= 0.9947
0.1

0·--- -~---,----- - - - ; ------- -.,.------------r--- --- 1

0.02 0.04 0.08 o1 0.15 0.2

As (ppm)

L" Absorbance - - - Unear (Absorbance) I

FIG. 2.5: A TYPfCAL. CAUBRATJON GRAPH OBTAINED WJTH IN vrs.

REAGENTS

Merk grade chemicals (India/Germany) were used for preparing the solution.

Standard metal solutions were prepared as follows:

• Cadmium: 1.000 gm Cadmium metal was dissolved in 4 ml concentrated

HNO, then added 8 ml concentrated HNO, and diluted to 1000 ml with

deionized water.

1 ml= 1000119 Cd

• Chromium: Dissolved 3.735 9 of potassium chromate K2CrO•• in 1 liter of

deionized water.

I ml= 1000 Ilg Cr

79
 • Copper: 1.000 gm of copper metal was dissolved in minimum amount of

(1 + 1) HNO,. Diluted to 1000 ml with 1% (v/v) HNO,.

1 ml~ 1000 ~g Cu

• Iron: 1.000 gm of iron metal was dissolved in 50 ml of (l + 1) HNO, and

diluted to 1000 ml with deionized water.

1 ml~ 1000 Ilg Fe

• Manganese: 1.000 gm of manganese metal was dissolved in a minimum

volume of (1 + 1) HNO, diluted to 1000 ml with 1% (vjv) HC!.

1 ml~ 1000 ~g Mn

• Magnesium: 1.000 gm of magnesium ribbon was dissolved in a minimum

volume of (1 + 1) HC!. Diluted to 1000 ml with 1% (v/v) HCI.

1 ml~ 1000).Jg Mg

• Zinc: J .000 gm of zinc metal in a minimum volume of (1 + 1) HCI and diluted

to 1000 ml with J % (vtv) HC/.

1 ml~ IOOOl'g Zn

Typical calibration graph obtained with HGMS for studied metal are shown in Fig.

2.6-2.13.

80
SrlO£SOO E"MlOt'f,ArNTf>tA.to.w-II"SIN S<v MINf~ ~;mZOO[s EFl-fCTS()- MiNI IW EmalATOtNIJ Mnr:oATlONOf" QrTr~... NT,. IMP.ACTS

06

05

04
8
~
~

~ 0.3

.0
~
.Q
02
y=00814x.0OO33
R' -0.9894
0.1

0
0.5 0.8 125 15 2
Cd (ppm)

RG.2.fl: Cd CAUBRA nON CURVE BY MS.

08
0.7
0.6
0.5
~O.4
Ib 0.3 y =O.1068x -0.0129
0.2 R2 = 09966

0.1
o~-- __------__ --~-- __--__--__
2 3 5 6 7 8
Cu (ppm)

I-+-Cu (ppm) _Linear (Cu (ppm)) I

FIG. 2.7: Cu CALIBRATION CURVE BY MS.

81
STl.Dtrs(»4 EtMKNoIlH.... A.t!:t.w If SIN ScM: Mt£RN rID IrKS EFFfCTS(y" M!!lyt EmOOATOImJ Mrn(~TION Of OETRt.I£NT.... IMPACTs

01

0,

0'

t 04
I
( 03
v-o 1:1.9.1/- Q0087
0, R1 ·0987J

01

0
, 3 , 8
Cr (ppm)

.._._-
r~~~~~_~~ =::",:,~I~~(AbSOr~
~--·- .---~

FIG. 2.8: Cr CALlBRA1JON CURVE BY MS.

0.7

0.6

0.5

0.4
~
~0.3
y = 0.085x - 0.0171
0.2 R'=0.9852
0.1

0
2 3 5 6 7 8 10
Fe (ppm)

I _____ AbsOrbance - - Unear (Absorbance) I

FIG. 2.9: Fe CAL.lBRA1JON CURVE BY MS.

82
 07
06

05
04
203
"" 02 y = 0 0662' - 0.02
R' = 0.9817
01
0
3 5 6 7 8 10 12
Nil (ppm)

-- -- '. -_._---_._---_
, • ..-j!-- Absorbance
. _---_._- ---- -. '-j
--linear (Absorbance) I
: -.----- -_ .. ---- - ----- ---- --- _.I

FIG. 2.10: HI CAUBRATION CURVE BY AAS.

-_. --- ---. - _ . _ - - - - - - -

I 0.7

0.6

05

04

y = 0_0914x - 0.0171
R2 = 0.9814

2 3 3.5 4 4.5 5
Mn(ppm)

i
-48- Absorbance --linear (Absorbance) I

FIG. 2.11: lin CAUSRAlJONCURVCByAAS.

83
SHUI! S(~ EPM«''N.4! NTK At¥.J.W.lSIN S<J.4l MKIW r;,I) Z(J4f5 Err[cTs~ MiNlIW Em cnAIK~Nf) MIII(".... Tk~Ot P: T'W! NI". M'N,'TS

0.7

06

05

a.
"
"" 03 Y "00926x .0046
02
Rl =09738
01 "'.
0
0.1 02 03 0.35 A. 0.5
Mg(ppm)

I·:·.::· -A~~;b;~~e-==' Linea;(Abs~rt;~~~e) I

I . . . __ __" _ __ _ _ _

FIG. 2.12: "'9 CALlBRATlON CURVE BY AAS.

0.7

06

0.5

0.4
,;
:!i 0.3 ~
J
0.2 i y = 0.1 063x - 0.0287
!

01 i
o 1._~ _________
R2 =0.9898

0.2 0.3 0.4 0.6 0.8

Zn (ppm)

···i!Il-····Absorbance - - Unear (Absorbance) I

FIG. 2.13: Zn CAUBRAOOH CURVE BY AAS.

84
 STU)IfSON EtMlOf'fM NTI'/. At¥'J.JN IfSIN$<."),A{ M,NI ~ ~:mllMs E~f[CTS(! M!rfJW Exn.mArK)Nm)MlflGAr~Of OfTrfJAfNTAI. ""PICTS

QUALITY ASSURANCE AND QUALITY CONTROL PLAN

The accuracy of laboratory analytical data for the trace metals and major cations was

assessed by analyzing standard reference materials (SRM) and the recovery of known

concentration of analytes in spiked samples. For the SRMs, the percentage recovery

(REC) was calculated as:

RECSRM = MEASURED VAtlJES/CFRTlFJED OR MOST PROBABLE VALUES' 100

For the spiked samples, the REC was calculated as:

RECsPIK[ = MEASURED VALUES/EXPECTED VALUES * 100

For all analytes discussed in the table, the data quality objective with regard to

accuracy was to have REC values equal to 100± 30% for the concentration greater

than 10 times the detection limits, and 100± 60% for the concentration less than 10

times the detection limits. Precision (or invariability) is explained in this the study as

the degree of similarity among independent measurement of the same quantity. The

precision of laboratory analytical data was evaluated by randomly submitted split

samples and evaluated in terms of relative percentage difference (RPD), where

RPD= DIFFERENCE BETWEEN REPORTED VALUES/ AVERAGE REPORTED VALUES * 100.

For all analytes discussed in the table 2.3, data were considered sufficiently precise

when the RPD values were less than 25% for the concentration greater than 10 times

the detection limit, or less than 50% for the concentration less than 10 times the

detection limit.

85
 Accuracy

Three specific techniques were applied for the evaluation of levels of accuracy for the

major analytes: I. measurement of natural- matrix SRMs, 2. determination of spike

recovery information for selected elements, and 3. measurement of blanks, both in

the field and in the laboratory. These approaches provide information regarding the

proximity of reported analytical result to the best -known values of various analytes

in the measured samples. This information was used data interpretation to evaluate

bias or systematic error in the measured concentration of major elements In the

samples collected during the study.

Standard Reference Materials:

The SRMs used for the evaluation In this was natural-matrix certified SRMs produced

by the NIST -USA and about 15 percent of the total samples analysed consisted of

reference materials.

TABLE 2.3: HEAVY METALS IN STANDARD REFERENCE MATERIALS IN/TH

SAMPUNG BLANKS.

Element Method Detection Precision Accuracy

limit

As MS 0.002 Duplicate RPD < 30% at SRM REC or lab

concentration < 10 spike= 1 OO%± 30 or 60%

times the detection at concentration <10 ,

Ii mit. times the detection

1

,
limit.
i

86
 $nnll SUN [tMlOt~, NT.AI. At¥lN'Il.. SIN&"MI MINOW t~nZ(q 5 En rCfSrf" MtNIIW Em OIAlIONNI) Mnn-..TlIlN Of !Xl".... Nf.AI. .... 'N:T5

I'~'"

Cu
.-- ------
AAS
, -

0.002
_._- --~-------- .

Duplicate RPD < 30% at

. _- ~~--

SRM
-+--- --- .
REC
-
or
- ----
lab I

concentration < 10 spike~ 1OO%!. 30 or 60~, ,

times the detection at concentration <10

,
limit. times the detection:

limit.

Cd AAS 0.0007 Duplicate RPD < 30% at SRM REC or lab:

Ii concentration < 10 spike=100% ± 30 or

, times the detection 60% at concentration -

,
,
limit < 1 0 ti mes the detection
i
i i
I limit
I
,

l i Cr AAS 0.006 Duplicate RPD < 30% at SRM REC or lab'

concentration < 10 spike=100% ± 30 or :

times the detection 60% at concentration :

limit < 1 0 times the detection '

,

limit

I Fe AAS 0.005 Duplicate RPD < 30% at SRM REC or lab;

i
concentration < 10 spike= 100% ± 30 or i

times the detection 60% at concentration j

I
limit < 1 0 times the detection

1- limit

87
 ---------- -----_.- -- - ----- . - -- .- -----------._._-- - - - - - - - - - - - .-- ... - -I
Mn AAS 0.003 Duplicate RPD < 30% at SRM REC or Idb •
I
concentration < 10 spike -) 00% :': 30 or ,

times the detection 60% at concentration

"mit <" 10 times the detection

limit
I
Mg AAS 0.003 Duplicate RPD < 30% at SRM REC or lab

concentration < 10 spike= 100% ± 30 or

times the detection 60% at concentration

I limit < 10 times the detection
I
,I
limit
I
Ni AAS 0.006 I Duplicate RPD < 30% at SRM REC or lab

I concentration < 10 spike=100% ± 30 or

times the detection 60% at concentration

limit < 10 times the detection'

limit
I !

Zn AAS D.DDS Duplicate RPD < 30% at SRM REC or lab'

concentration < 10 spike=100% ± or ' 3D

i
times the detection 60% at concentration:,

limit < 1 0 times the detection

limit
i
RPD: Relative percentage difference_

88
 STUl" SONE~lOrUN'f!( &«INII.I SIN&'f.41 MltflWl'>tt)b)./ts ErrlCTs(Y- MlMlW EmmATIONNC)Mrrr!'T~(:I'OnH"'1 NrN I"'''PCIS

RPD: Relative percentage dIfference.

Elemental standards used were prepared by dilution of the stock certified single

element solution for AAS supplied by Merk, Germany. The dilution water used

deionised double distilled water. All other reagents used were analytical grade

chemicals obtained from Merk, India/Germany. Background checks were also made

and the intrinsic trace elements content thus deduced was appropriately integrated

in the result. The detection limits (Dl.) were calculated as three times the standard

deviation of the nine measurements of blanks for every wavelength.

General procedural protocol:

Apart from the above, the other QAiQC steps applied are as follows:

• Samples for inorganic analytes were first collected and filtered with 0.45 I'm

Millipore. A second set was collected unfiltered.

• Routine replicate surface water quality samples, including those for field

spikes, were collected in conjunction with the primary water quality samples.

Routine QC samples that use blank water were collected in the field after

ground water quality samples and after the decontamination of sample-

collection equi pments.

• Background checks were also made and the intrinsic trace element content

thus deduced was appropriately integrated in the result.

• Many of the samples collected from studied sites were heterogeneous in

nature. In such a case, it is important that these be properly processed and

SUb-sampled prior to analysis, to ensure representative results. To achieve

this, liquid samples containing visible amounts of sediment were filtered

before analysis.

------------------------------------------------------------89
 • Whenever the analysis was intended to obtained the total amounts of

contaminants presents in the samples the sediments were analysed separately

from the liquid.

TABLE 2.4: QuAUTY ASSURANCE AND QUAUTY CONTROL STEPS

ADOPTED IN THIS WORK..

r--------------,---------------------,----------------------
QA/QC Step Description I Adopted procedure
I
Laboratory reagent At least one determination of a Measurement of sample

blank blank to establish the blanks and laboratory blanks

contributIOn to the analytical I was carried out to control the

signal by reagents, glassware, instrument contamination and

etc. The blank should be the contamination arISing out
sUbtracted from the gross
of the sample preparation,
analytical signal for each analysis
respectively. Blank analysis
before calculation of sample
was carried out with every
analyte concentration.
determination and the signals

(00) were deducted from the

signal (00) of the analyte (As).

Replicate analysis Duplicate analysis of at least Carried out in every batch of

one sample from the batch. 10 samples and the variation

The variation between (nil or otherwise) were

replicate analysis should be recorded.

recorded for each batch to

provide an estimate of the

precision of the method.

90
! Quaii;~-- - control Analysis of at least one 'Elemental standards used

sample control sample, a standard were prepared by dilution

reference material, a of the stock certified

laboratory reference material single element solution for

or a control matrix fortified AAS supplied by Merck,

with analytes representative Germany.

of the analyte class. Recovery

check portions should be

'Measurements of
fortified at concentrations,
calibration check
which are easily quantified but
standards with known
within the range of
analyte concentration but
concentrations expected for
of different origin than the
real samples.
calibration standards.

maximum allowed

difference was 10%.

Standard reference material

(SRM) of urban dust from

National Institute of

Standards and Technology

(NISn SRM-1648 was used

for ensuring the quality

control and the maximum

allowed deviation was 20%.

----------------------------------------------------------- 91
 Surrogate analytes Surrogates should be added Laboratory check samples were

to all analyses for prepared from unexposed

determinations where it is containers with standard

appropriate. Surrogate spikes addition of elements (i. e. spiking

are known additions to each of the samples); maximum

deviation allowed was 10%.
sample and matrix spike or

reference sample analysis, of

compounds which are similar

to the analytes of interest

Internal standards Use of internal standards is Measurement of certified

highly recommended in calibration standards as

analysis of both inorganic and samples, maximum allowed

organics. Internal standards difference was 5%

are added, after all extraction,

clean up and concentration

steps, to each fi nal extract

solution.

Flame AAS (Chemito 201 equipped with background corrector) was used for analysis.

The major instrumental parameters are summarized in Table 2.5.

92
 $1101 Sf"" EPMltHM NT .... AtlJ.IAl.'-SIN $o.!T MIN(fWUnZOt·/fS Erncls(,* MINI fW E'<J\00 A.!ICfIAlfJ MIIK:ifllUNO [)cmMl.NTN. ~PIC1S

TABLE 2.5: AAS PARAMETERS FOR mE ANAL YS/S OF DIFFERENT IIErALS.

~-.- -~.-
--,------- -------
Element Absorbin Lamp Flame Flame Detection Workin

s g curren composition stoichiometry limit (ppm) g

t range
Line (nm)
----
As 193.7 7-10 Air- Hydride 0.002 0.1-

acetylene generation 1.0

Cd 228.8 3-7.5 Air- Oxidising 0.0007 0.5-

acetylene 2.0

Cr 357.9 5-10 Air- Reducing 0.005 2-8

acetylene
I
Cu 324.8 5-10 Air- Oxidising 0.002 2-8

acetylene

Fe 248.3 7-15 Air- Oxidising 0_006 2-10

acetylene

Mg 285.2 3-7.5 Air- Oxidising 0.003 0.1-

acetylene 0.5

Mn 279.5 5-15 Air- Oxidising 0.003 1-5

acetylene

Ni 232.0 7-15 Air- Oxidising 0.006 3-12

acetylene

Zn 214.0 4-10 Air- Oxidising 0_005 0.2-

acetylene 1.0

93
 RESULTS AND DISCUSSION

GROUND WATER AND SURFACE WATER CONTAMINATION

----------------------------

Water quality parameters for certain selected places of Durgukondal block in Kanker

dIStrict are depicted in Table 2_6_ Elemental analysIs with seasonal variation is shown

In Table 2.7. Speciation analysis was also carried out that is shown in Table 2.8.

Analysis of groundwater sources from certain locations in the Kanker district

(particularly Durgukondal block) has shown high values of arsenic, iron and

manganese (mean 144, 914 and 371 ilg/L respectively, Table 2.9) Sample variance

and standard deviations are high but that appears possible in view of Wide variations

In the levels of contaminants in groundwater and the complex geo-chemical

involvements in the process. In other water quality parameters the samples are

moderately hard and show a consistent presence of sulphate and chloride at

moderate to low values and the alkalinity of water are mostly bicarbonate and

carbonate in nature.

TABl.E2.6:WATERQIJALlTYPARAIIETERS(VALues'NIIGIl.)FORCERTAIN
LOCATIONS OF DfJRGUKONDAL BLOCK.

Locations pH Cond' T Ca Mg CI F S04 Alk'**

(mS) Hard*'

Dorde kadar 7.1 0.183 80 16 9.6 19.4 0.4 11.8 102

Jhikatola 7.2 0.31 295 78 24 13 O.S 10 68

Konde 6.7 0.342 310 80 26.4 13 0.2 12 170

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 94
 Kanapal 6.8 0.841 480 128 14.4 142.5 0.23 27 85

Hambapara 7.5 0.456 350 100 24 12.6 0.65 15 51

Harangarh 6.5 0.319 100 24 9.6 12.9 0.12 12 170

Rasoli 7.6 0.471 150 20 24 77.7 0.4 18.4 102

Nedgaon 6.5 0.412 130 40 72 45.4 0.3 12 85

Bargaon 7.2 0.31 295 78 24 13 0.5 10 68

Ankasa 6.7 0.342 310 80 26.4 13 0.8 12 170

Mohgaon 6.8 0.841 480 128 14.4 142.5 0.6 27 85

Hilchur 7.5 0.456 350 100 24 12.6 0.2 15 51

Pameli 6.5 0.412 130 40 72 45.4 0.1 12 85

Beludi 7.2 0.31 295 78 24 13 0.8 10 68

Hepurkasa 6.7 0.342 310 80 26.4 13 0.3 12 170

Gumdi 7.1 0.275 170 40 16.8 71 0.34 10 102

Jodekurse 7 0.26 270 60 28.8 13 0.6 6 51

Befudi 6.9 0.334 300 60 36 50 0.3 5 221

Bhurk 7.2 0.274 170 40 17 17 0.5 10 51

Koraki 7.5 0.32 310 80 26.4 13 0.2 15 85

Adgar 6.8 0.31 270 60 28.8 13 0.3 6 68

Bodeli 7.1 0.275 280 80 19.2 71 0.5 10 102

Kotepara 7.1 0.32 320 48 0.24 48 0.43 7 221

Chhindgaon 7.6 0.45 350 100 25 13 0.23 10 68

95
 SlInt SON EtMIO"'..1 NIAl A~¥JNoJ II ~INS<M MINI fLt4C10Z(Y-<fS EnICISOi- Mit"" fW E'\.n()lf"l~m)MfJI(j,-.mNof OrWMf NIAlIMPIICTS

Mindon 7.4 0.37 200 48 19.2 12 0.4 5 5I

Sedli 7 0.34 350 100 24 12 0.3 10 51

Hanpasari 7.6 0.471 150 20 24 77.7 0.2 18.4 102

Sukhai 6.5 0.412 130 40 72 45.4 0.6 12 85

Hahaladdi 7.2 0.31 295 78 24 13 0.2 10 68

Kusum 6.7 0.342 310 80 26.4 13 0.4 12 170

Durgukundal 7.1 0.275 170 40 16.8 71 0.3 10 102

Rengatola 6.5 0.319 100 24 9.6 12.9 0.6 12 170

Sheetalpur 7.6 0.471 150 20 24 77.7 0.3 18.4 102

Vetintola 6.5 0.412 130 40 72 45.4 0.2 12 85

Uikatola 7.2 0.31 295 78 24 13 0.4 10 68

Palhur 7.5 0.378 320 40 28.8 13 0.6 15 85

Narratitola 6.9 0.334 300 60 36 50 0.45 5 221

Dorde 7.2 0.274 170 40 17 17 0.23 10 51

Gumridih 7.5 0.456 350 100 24 12.6 0.21 15 51

Kodekurse 6.8 0.31 270 60 28.8 13 0.4 6 68

Mategaon 7.2 7.2 13 0.5 15 85

.435 230 80

Guruwandih 7.1 0.32 320 48 0.24 48 0.36 7 221

Cond': Conductivity (mS). Hard": Total Hardness. Alk"': Alkalinity

96
 STU.'JIt S(~ EN'v1IOtMNrPl W~ I('SIN $!M MINHMI: IStnZOOfS EI rrCI$t*" MiNt IW E)J\OOA'If»INI)Mru:~To.j()f OFmMfNTN U'1CTS

TABLE 2.7: ELEMENTAL ANAL YS/S (CONCENTRATION IN!1GIlJ OF

DURGUKONDAL BLOCK.wm SEASONAL VARIATION.

Pre-Monsoon Monsoon Post - Monsoon

",--
As As
Fe As (T) Mn Fe (T) Mn Fe (T) Mn

Oorde kadar 1250 250 250 1000 70 200 1500 140 300

Jhikatola 100 170 NO 60 124 NO 125 220 NO

l Konde 500 250 100 300 123 50 800 290 40

i Kanapal 300 165 40 NO 90 10 NO 200 50

! Hambapara 300 160 250 200 I 70 100 500 190 290

I
I Harangarh NO 160 NO NO 105 NO 190 NO

Rasoli 1300 100 NO 1000 123 NO 1600 230 NO

Nedgaon NO 240 NO NO 100 NO NO 280 NO

Bargaon 1500 20 50 1200 ND 20 1600 50 50

II Ankasa NO 80 50 NO 40 NO NO 100 NO
I
Mohgaon 450 140 60 200 80 20 900 180 70

, Hilchur 850 230 NO 500 100 NO 1000 300 60

Pameli 200 120 300 100 70 100 400 180 500

Beludi 100 190 NO 50 80 NO 300 100 NO

Hepurkasa 2500 70 NO 1200 30 NO 3000 90 NO

Gumdi 300 30 250 100 12 143 NO 400 50

Jodekurse NO 110 300 NO 60 150 ND 150 330

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 97
 Beludi NO 10 NO NO NO NO NO NO NO
_._--._--_. ---
Bhurk 300 10 300 200 NO 120 320 20 370
---- -------- --- --- -- ---- --- --~--

Koraki 600 400 600 500 500 400 650 780 640
--.--~-

Adgar 500
-- _.- 130 NO
100 NO 300 SO NO 640
--_._._------- - ------
Bodeli 200 200 NO 100 50 NO 260 280 NO
---- -
Kotepara 200 10 NO 130 NO NO 240 19 NO
---
Chhindgaon 2600 100 NO 1200 70 NO 3000 150 NO
,,
Mindon 1700 350 NO 1000 700 NO 1990 950 NO
I
Sedli 200 100 NO 110 80 NO 250 130 NO

Hanpasari 1800 100 NO 1000 78 NO 1870 150 NO

Sukhai 2100 300 500 1000 190 100 2300 340 560

hahaladdi 700 300 1300 400 170 1000 790 370 1500

Kusum 800 260 NO 350 188 NO 900 280 NO

Ourgukundal 600 400 400 400 150 200 700 350 450

Ren9atola 100 100 NO 70 70 NO 130 120 NO

I Sheetalpur 1400 100 NO 700 NO NO 1500 15 NO

Vetintola 200 100 NO 100 50 NO 240 130 NO

Uikatola 200 10 1500 100 NO 1000 240 13 1600

Narratitola 300 200 600 150 150 400 330 250 650

Oorde 300 120 NO 100 NO NO 345 175 NO

Gumridih 12 110 20 NO NO NO 15 NO 25

---------------------------------------------98
Kod ekurse 3200 350 ND 1700 ND ND 3500 ND ND

I- -- C--._

Mat egaon 700 250 ND 3000 ND ND 4700 ND 4800

~-

Gur uwandih ND 350

-
ND ND
- I 2- a -- ND 390 ND
ND
-~

"'As (n - Total arsenic. NO =: not detected

TABLE 2.8: ARSENIC SPEClAlJON ANALYSIS IN PRE MONSOON SEASON.

Pre-monsoon

(val ues in I'g I L)

As (T) As(lIl) As (V)

Dorde kadar 250 150 50

I
! !
Jhikatola 170 100 70

Konde 250 210 40

KanapaJ 165 100 65

I
Hambapara 160 120 40

harangarh 160 130 30

I
Rasoli 100 80 20

Nedgaon 240 200 40

Bargaon 20 20 r

Ankasa 80 50 30

Mohgaon 140 100 40

Hilchur 230 200 30

PameJi 120 100 20

BeJudi 190 110 80

99
 Hepurkasa 70 50 20
1--- ---- --- ---- - - -
Gumdi 30 30 NO
- - 1------ ---
Jodekurse 110 80 30

Beludi 10 NO NO

Bhurk 10 NO NO
I
Koraki 400 300 100
I
Adgar I
J
100 150 50
i
Bodel; i
i
200 10 NO

Kotepara 10 70 30
,
Chhindgaon , 100 650 250

Mindon 350 300 30

,,i
Sedl; II 100 80 20
I

Hanpasari 100 150 50

Sukhai 300 245 55

,
Hahaladdi 300 210 50

Kusum I 260 310 90

i
Durgukundal 400 87 13

Rengatola 100 80 20
I
I
Sheetalpur 100 75 25

Vetintola 100 10 NO

Uikatola 10 NO NO

-------------------------------------------------------------100
 S"t,n SUN ENVll(lNM NIN fy¥.J.W 1f51N StI.4I M1Nf rw. W~DZ{~ s EI rfCTst-. M,NlIW Em ()I1AlIllNNf)Mll~T~(" P-'HMI NIAI IMPACTS

Palhur NO NO NO
---- -- ----- ----- -

Narratitola 200 150 50

---- ------ -----
Dorde 120 80 40
- --
Gumridih 110 80 30
- ------ ----
Kodekurse 350 250 150

Mategaon 250 35 15
I
Guruwandih 350 250 100
!

Results of the standard deviation, kurtosis, and skewness are discussed here. The

standard deviation is a measure of how widely values are dispersed from the average

value (the mean). The statistical analyses have given values generally lower than the

means in most of the analyses. This means that the dispersion in arsenic

concentration does exist but the extent of dispersion is lower.

Kurtosis characterises the relative peakedness or flatness of a distribution compared

with the normal distribution. Positive kurtosis indicates a relatively peaked

distribution. Negative kurtosis indicates a relatively flat distribution. In this study the

kurtosis, values are generally negative but the values are small indicating a relatively

flat distribution.

Skewness characterises the degree of asymmetry of a distribution around its mean.

Positive skewness indicates a distribution with an asymmetric tail extending toward

values that are more positive. Negative skewness indicates a distribution with an

asymmetric tail extending toward values that are more negative. In this study, the

skewness values are again negative in nature, which signifies an increasing trend of

arsenic levels.

101
 TABLE 2.9: STAnIS OF GROUNDWATER PARAMETERS IN mE SAIIPtED
AREA OF DISTRICT KANKER IN 2003. (CONCENTRA noNS IN PAl,

UNLESS SHOWN OTHERWrSE).

- - -- - -- - - - - - ----r------ --- .-- -_.. ----
ICI
~.

pH !condo ~ard** Ca Mg 50, F ~Ik"· Fe ("gil) Mn ("gil) As ("gil)

Mean 6.7 0.6 203.3 48.~ IS.I 10.C 0.6 51.2 106.4 914.3 371.1 143.E

Standard Error 0.1 0.2 28.4 7.2 2.1 1.0 0.0 7.t 10.6 174.~ 93.S 27.(
----- '------ --- ---
Median 6.S 0.3 170.0 40.0 14.0 7.5 0.6 35.0 102.0 500.C 300.0 100.C

S. Deviation 0.5 0.9 120.3 30.8 12.2 6.C 0.2 37.6 46.1 1034.1 409.4 176.~

KurtoSIS 4.8 13.7 2.1 2.7 0.4 1.3 -0.6 0.6 0.9 3.3 3.2 S.!

Skewness -I.S 3.7 1.6 1. 1.0 1.2 0.4 1.1 1.1 I.E 1.8 Z.E

Range 2.2 3.8 420.0 112.( 43.2 25.C 0.7 130.1 170.0 4500.C 1500.0 900.C

MInimum 5.1 0.1 80.0 16.( 4.8 2.0 0.3 12.9 51.0 0.0 0.0 O.C

Maximum 7.3 3.9 500.0 128.C 4S.0 27.0 1.0 143.0 221.0 4500.0 1500.0 900.(

Cond*: ConductivIty (mS), Hard*"'- Total Hardness, Alk""**- Alkalinity

Most of the contaminated sites are located in the Kotri plains. Water samples from

variuos identified locations Situated in Durgukondal block were sampled throughout

the one hydrological year to see the variability of arsenic, Iron and manganese.

Results (Table 2.10) show that the levels of the three contaminants, probably of

geologic origin, are high in the post monsoon and summer season and low during

the monsoon season. This indicates the probability of dilution effects during the

monsoon season in view of heavy rainfall (-100 cm. In four months of monsoon) and

also the probable dissolution and mobilization effects corroborated by high post

monsoon periods (particularly in the month of Feb-March). Some of the bore well go

dry in the moth of summer, which indicates that they may not really be tapping any

deep aquifer hence; there exists a probability of local mobilization.

102
 $HJ)If 500 EtMlt""'" N'~ At¥.JNIJ.. SINSCtA_MINfH,. ~ilDZ('MS E~F[C150t MM R.Af Exn OOATKlNN-I)MIIICATK.'lNU 01 TRtKNTN M'N:lS

TABLE 2.10: ELEllENTAL ANAL YS/S IN THREE DIFFERENT SEASONS

SHOW A MARKED SEASONAL VARIA TtON IMTH IlAXlIIUII
CONCENTRA TtONS (IiGlII.. J OBSERVED DURJNG me POST-MONSOON
SEASON.
-..."-----..--.-.-.."---- .. ---- .. -----.~-------.--- ~- .. --.- ........--.- ....- .....-.- .. - --_ .....--_..------- .... -....---_.... _----
PR[ MONSOON MONSOON POs r MONSOON
.._-_.
Fe As Mn Fe As Mn Fe As Mn
- ------ _.---- . - ,--- - -- - - -_. ------ .
Mean 766.6 145.0 188.7 432.0 84.6 114.3 852.4 177.0 332.8

~tandard
150.0 26.8 55.2 88.9 19.3 40.1 161.8 29.2 135.4
Error

Median 300.0 100.0 10.0 200.0 70.0 0.0 375 145.0 28.5

~tandard
983.9 176.0 340.3 589.9 128.1 240.9 1073 193.6 834.7
Deviation

~ample 115124 69673

968103 30977 11 581 7 347951 16421 58024 37493
~ariance 0 7

Kurtosis 4.4 9.0 7.6 7.4 14.1 9.3 3.4 6.4 23.1

Skewness 2.0 2.6 2.7 2.4 3.5 3.0 1.8 2.2 4.5

4800.
Range 4500.0 900.0 1500.0 3000.0 700.0 1000.0 4700 950.0
0

Minimum 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0

4800.
Maximum 4500.0 900.0 1500.0 3000.0 700.0 1000.0 4700 950.0
0

Confidence

Level 302.8 54.2 111.9 179.3 39.0 81.5 326.2 58.9 274.4

(95.0%)

103
 SnJOlrs ().j ENVlRCNMrNT AL AIoMJ./fS IN Srl.4r: MiNrrw 1$f0 loors EtncTs (J' MINrRAL Em OIT Al~ AND MITK''''11(J.j a= D£TRI"KNTAl IWACTS

1000.
i

800 !

6001 Q Pre monsoon

i,
[J Monsoon
400 :
i I:1lI Post monsoon
2001I

0 1

Fe As Mn

FIG. 2.14: SEASONAL VARIATION IN SELECTED ELEMENTS LEVELS

(IlGIL) IN GROUNDWATER OF DURGUKONDAL BLOCK.

Correlation analysis provides useful information regarding the genesis of any

contaminant. This analysis was carried out in the drinking water of the area and the

result show a negative correlation of arsenic with pH, hardness and chloride. The

trend that arsenic is having positive correlation but lower degree of significance with

iron and manganese is noteworthy. Where it appears that the arsenic mobility is

closely related to the pH and the hardness of water i.e. the calcium and magnesium

ions act as a check on arsenic concentration. Similarly the iron and manganese

appear to be co-generated with arsenic however as their dissolved concentration is

affected by pH a lower mathematical value is obtained in correlation analysis. ArseniC

correlates negatively with major parameters, which depicts a differing chemical

behaviour (Table 2.11). A comprehensive picture of the contamination in

Durgukondal block is presented in Fig. 2.15

104
 STI()ff s(~EtMl'(.u Nlli A~l.W."slN&"'" MItf JW r!1)Zt'flfS EnrcTSa- MN 'lit EXn(!!A.IK~NI.)MIIKlA.n.W(. D:m... NT"" IIM'ACT S

TABLE 2.11: CORRELA TlON ANAL)'SIS OF GR()(A\/()WA TER.

ott (o"d- It.ud U Ca

". '0. r (' AI .. • .. r. "n A.

, 00
""
Cond -u 20 , 00

lI'Hd -010 07' , 00

c. -004 070 0.94 1.00

'Aq -0 19 070 067 0041 , 00

SO. 029 -0,29 -0.06 o OS -0 ",0 1.00

, -01{) () 31 0'6 O. J I 0.24 006 LOa

c, 017 064 0.71 0.71 031 0.29 -0.27 100

A'. -007 040 039 021 0.75 -0.36 027 004 1.00

r. -057 -0_10 -0.16 -0.1.2 -0.18 0.08 0'2 -009 000 1.00

'An -003 all 0.28 0.12 0.66 -0.40 0.17 0.0.2 0.72 -020 100

As -0.14 -028 -022 -0.17 -032 0.00 -0.14 -0.09 -0.26 004 024 1.00

Cond-: Conductivity. Hard-*": Total Hardness, Alk*U: Alkalinity

TABLE 2.12: WATER QUAUTY PARAMETERS OF HANOI & KOTRI RIVER OF

THE KANKER DISTRICT (C{)NCENTRATlONS IN PPM, UNLESS SHOWN
01JlERWfSE).

C, m
PH CONO
..HARD Mn«~
SAMPUNCi C. "9 SO. F Alk* Fe(("" As As(l As(

PO'NTS III giL) ("",ll II) V)

Ha.ndi river Pt. I 6.5 0.204 170 40 16. 10 0.3 13 5] lOa 90 lO 60

Ha.ndi river Pt. 2. 24 5 85 25

7.l 0.256 '60 40 0
" 225 0

Handi river Pt. 3 6.5 0.313 250 80 12 4 0.3 70 70 110 0 50 20 lO

Handj fiver Pt. 4 7.1 0.J34 110 l6 4.8 8 0.2 25 5] 325 0 lO 0 30

Katri nver Pt. J. 6.8 0.193 80 16 9.6 12 0.4 20 102 250 0 0

katri river Pt. 2. 7.1 0.312 270 60 28. 6 0 13 70 400 80 lO 50

Katri river Pt .3. 7.2 0.42 100 32 4.8 13 0.3 20 102 310 lOO 100 40 60

105
Kold riVi.'r Pt 4 6,9 0 ]09 120 12 96 15 0 10 8') 410 () 1}0 ]0 90

ConfluelKe Kolr! 6.7 O,ZI 110 40 16, S 06 0 lOa 100 ]00 90 110

8
"
Condit: Conductivity (mS), liard"'" Totaillardness, Alk·": Alkalinity

TABLE 2.13: SURFACE WA TER STATISTICAL ANAL VSIS OF THE KANKER

DISTRICT (CONCENTRATIONS IN PPM, UNLESS SHOWN OTHERWrSE).

pH Cond-Hard*- Ca Mg SO, F CI Alk'" Fe (.,g/l)Mn (.,g/l)As (l'9/l)

.-._---------_._----_ .. _-._--- ..._------------------._-_._.--_._-------------------------....... -......-.-..... -.•....................._....... __ ....... _...... -_ ..... ,_...... -...._-.......

Mean 6.9 0.3 157.542.013.8 9.1 0.230.5 77.0 294.4 89.3 74A
Standard Error 0.1 0.0 24.8 6.9 3.1 1.4 0.1 8.8 7.1 30.6 54.5 2L2
Median 7.0 0.3 140.038.010.8 9.0 0.320.0 77.5 300.0 0.0 80.0

Standard

Deviation 03 0.1 70.119.6 8.8 4.0 0.224.8 20.1 91.9 144.2 63]

Kurtosis 1.3 -0.1 -0.8 1.3-0.5-1.5 2.0-0.2 -13 1.0 -0.9 0.6

Skewness 0.5 0.2 0.8 1.0 0.8 0.1 OA 13 -0.1 -0.8 L2 0]

Minimum 6.5 0.1 80.016.0 4.8 4.0 0.013.0 51.0 110.0 0.0 0.0

Maximum 7.3 OA 270.080.028.815.0 OA70.0 102.0 410.0 300.0 200.0

Cond*: Conductivity (mS), Hard"""': Total Hardness, Alk***: AlkaJrn/[y

TABLE 2.14: CORRELATION ANALYSIS OFSURFACE WATER.

pH Condo Hard~· Ca Mg S04 F CI Alk*** Fe Mn As

PH 1.0

Cond 0.2 1.0

Hard -03 0.2 1.0

Ca -03 0.3 O.g 1.0

Mg 0.1 0.0 0.7 OA 1.0

SO. 0.0 0.2 -0.7 -0.7 -0.6 1.0

F -0.5 -0.2 -0.4 -0.2 -0.6 0.2 1.0

106
 CI -0.4 0.3 0.1 0.4 -0.4 O. J -0. J 1.0

Alk 0.3 0.5 -0.4 -0.4 -0.2 0.4 0.1 0.0 1.0

Fe 0.4 0.1 -0.2 -0.4 0.1 0.6 -0.5 ·0.2 0.0 1.0

Mn 0.4 0.7 -0.3 -0.2 -0.3 0.3 0.2 -0.3 0.5 0.3 1.0

As -0.2 0.6 O. J 0.1 -0. J O.S -0.2 0.3 -0. J 0.4 0.7 1.0

Cond*'; CondLJctlvlty. Hard"; Total Hardness. Alk· .... · Alkalinity

In view of the elevated concentrations in the groundwater; we analysed the river

water also. The result of these analyses with fixed point monitorng are presented in

Table 2.12 The surface water of the region (sampled during pre-monsoon) shows

elevated levels of arsenic, which is influenced by the geological mineralised zonation.

Accordingly, the surface water of mineralised zone comprising the area of

Ambagarh-Chowki shows a higher degree of contamination, which is followed by

rivers draining the Kotri plains. Arsenic (III) is the most prevalent species in the

groundwater whereas the surface water of the rivers shows a significant

contamination of the As (V) species. Dissolved As in surface water of Kotri planes

have shown the mean level of 74.4 Ilg/L and maxima of 200 Ilg/L (Table 2.13). In its

correlation study it shows a positive correlation (0.7) with Mn. This is again indicative

of geological genesis of the contaminants and signifying Similar source (Table 2.14).

We further sampled a large number of river snails in the rivers of the region. The

predominant species noted was Pluroceraidae. The analysis shows a bio

concentration of the toxic metals viz. arsenic, nickel, copper and chromium (Table

2.15 and 2.16). Bioaccumulation of toxic elements more particularly of arsenic and

nickel has been observed. The manganese and iron concentrations are not very high.

Snails sampled from this area have shown the mean arsenic value of 11 mg kg- 1

which is higher than the value of arsenic in naturally occurring snail i.e. 0.8 to 2.8

mg kg- 1 (Francesconi and Edmonds, 1997).

107
 Metals may occur in the aquatic environment as hydrated Ions or they may form a

number of soluble & insoluble complexes with different organic & inorganic ligands

(Vanlion, 1977). Heavy metals are incorporated in the body by aquatic organism and

their concentration gradually increases during the life span of an organism. The

concept of bioconcentration factor or accumulation factor (ratio of metal

concentration in organic body to that in ambient medium is an important tool for

calibration of biomonitoring in organism (Chan et al., 1990). It implies that

accumulated metal concentration is related to the bio available supply of metal in the

environment. The accumulation of heavy metals from water column by the bivalve

molluscs has been found to be relatively rapid and reflects ambient exposure level

closely (Boyan and Phillips, 1981). It has generally been found that the concentration

of heavy metal in bivalve molluscs change with those in the environment. Therefore,

the study on accumulation of these heavy metals by different molluscs facilitates the

assessment of water quantity as well as the selection of suitable bio- indicator

species. Factor influencing bioavailability of the concerned trace metals is also of

major significance (Bourgoin et aI., 1991 ;Absil et aI., 1990).

The bioconcentration factors of the snail (H. campanu/ata) exposed to As (III) (at

1,000 Ilg/l) and As (V) (at 100 Ilg/l) are 83 and 99, respectively. The snail (5.

emarginata) accumulated similar arsenic residues when exposed to the high

concentration of arsenic+3, arsenic+S, and OSMA, resulting in bioconcentration

factors ranging from 16 to 17. Residue concentrations were significantly less in

animals exposed to SOMA. Residue accumulation was also highest in S. emarginata

exposed to the low concentration of As (III), resulting in a bioconcentration factor of

92 (Irwin, 1997). Compared to the values reported, the bioconcentration factor

obtained in this work is -156. The high bioconcentration factor thus points to the

episodes of high arsenic concentration in the aquatic environment. It is also possible

that the arsenic level may be highly episodic and the intermittent sampling protocol

108
is not able to cover all such events. Another interesting feature is that the arsenic in

snail body does not correlate well with other elements (Table 2.17) and it shows a

negative (though not high) correlation with Iron and nickel. This is indicative of

differing elemental concentrations in surface water. Thus it can be inferred that

these elements do not co-generate and they follow a distinct pattern. A proof of the

fact stems from the fact that there exists a very low aquatic biodiversity in the Kotri

River, which is indicative of chronic to acute episodes of metal contamination of

overlaying water column. Sediment analysis was not found very useful from the

history of contamination point of view because the sediment of rivers was containing

a very small clay percentage and was dominated by sand and gravels.

TABLE 2.15: ELEIIEHTAL ANALYSIS IN PLUROCERAIOAE SPS. OF SNAIL OF

KANKER DISTRICT. (CoNcENrRAT1ONS IN PPM, UNlESS SHOWN

OTHERWISE).

As Ni Cu Cr Zn Fe(%)

11 15 15 20 10 0.4

15 12 15 15 12 0.8

12 18 12 18 15 0.6

8 15 11 19 8 0.8

16 14 8 25 10 0.5

13 12 16 14 12 0.35

10 15 10 15 14 0.7

8 14 11 16 10 0.5

109
STWIESOO ENVIlOI.ENT>\ ArQ.w!,s IN S<!'E MN1WJSru Z<KS Erm;rsa: Mmw. Em.OT"'~NO Mrr!3A~ (F [VRN(N!K M>N;rS

TABLE 2.18: STATISTICAL. ANALYSIS OF VARIOUS IIETALS OF SHAlL

LE1I£LS IN KANIfER DlSTTlfCT. (CONCENTRATIONS IN PAl).

As Ni Cu Cr Zn Fe (%)
-,--_._----
Mean 11,6 14,4 12,2 17,8 11.'1 0,6

Standard Error 1.1 0,7 1.0 1.3 0,8 0, I

Median 11.5 14.4 II.S 17,0 11.0 0,6

Standard Deviation 3,0 1.9 2.B 3,6 2,3 0,2

Sample Variance 8,8 3,7 7,8 13, I 504 0,0

Kurtosis -1.2 1.2 -1.2 1.3 -0,7 -1.5

Skewness 0.2 0,6 0,0 1.2 0.3 0,1

Range 8,0 6,0 B,O 11.0 7,0 0,5

Minimum 8,0 12.0 8,0 14,0 8,0 0.4

Maximum 16,0 I B,O 16,0 25,0 15,0 0,8

TABLE 2.17: CORRELATJON ANALYSIS OFSNAILLEVS.S OF TRACE

ELEMENTS.

As Ni Cu Cr Zn Fe
...---_._.... _._-,-----_._--
As 1.00

Ni -0.35 1.00

Cu 0.12 -0.41 1.00

Cr 0.30 0.30 -0.57 1.00

Zn 0,25 0.33 0,12 -0,43 1.00

Fe -0,14 0,13 -0,24 -0,15 0,04 1.00

110
 l)url!U I-:ondal Block
i..:ankrr Di<lrict

Arsenic
conrrnlralju" (ppb)
11-11. [.::J
tta.,.. :r:::J
2".1 ...-.Uf

fchegaort

Ventintola

• de

FIG. 2.15: LEVELS OF ARSENIC IN mE IIAXlIIUM ARSENIC AFFECTED

BLOCK OF DURGUKUNDAL IN KANKER DISTRICT.

ill
SOIL CONTAMINATION BY ARSENIC
- ------------
The soil analysis of the area presents another remarkable picture. Soil arsenic levels

are high and there is sizable presence of nickel. chromium. manganese and iron in

the soil. In few samples. cadmium was detected at sizable concentrations. The soil

analysis presents a picture of metal enrichment in the soil with a mean arsenic

concentration of 34± 13 ppm arsenic, 30±20 ppm concentration of nickel and 7.1-

ppm concentration of cadmium (Table 2.18 and 2.19). The correlation analysis in soil

shows significant positive correlation of arsenic with all major elements (Table 2.20).

This correlation is chemically plausible and point to genetic similarities between the

groups of metals.

TABLE 2.18: SOIL ELEMENTAL ANALYSIS OF CERTAIN PLACES OF KAHKER

DISTRICT. (CoNcENTRATIONS IN PPM, UNLESS SHOWN OTHERWISE).

As Ni Cu Cr Zn Cd Mn Mg Fe (%)
--_._._-----.._.-._------_._........_...---_."•.....• _----_ ..... _--...... ---_.._-_........._-_.....-_._-----_...--_....._--_............--_....--...-..
Guruwandih 34 21 10 0 50 0 350 1225 1.11

Dorde IRP 40 90 0 40 10 7.7 700 1300 2.94

Dorde kadar 49 10 8.5 0 20 0 120 980 0.8

Konde 8.8 20 19.8 55 40 0 456 1100 0.5

Hahaladdi 33 20 19.8 25 25 0 180 1163 1.3

Badegaon 40 20 34.8 35 60 0 560 1200 1.2

112
 STLOlfS~ EtMyMNT.At.At!!WJESIN 5cJ,!EMINfM1srn ZI.."N:S EfF[CTSCl' Mt!R.At Em.OOATKJNNOMrr1G'.TlON ~ OETRNENT.AlIMPN:'TS

TABLE 2.19: SOIL STAnSnCAL ANAL YSIS (CONCENTRATIONS IN 11010), FE

IN ("/0).

As Ni Cu Cr Zn Cd Mn Mg Fe

Mean 34.1 30.2 15.5 25.8 34.2 1.3 394.3 1161.3 1.3
Standard Error 5.6 12.1 4.9 9.1 7.8 1.3 90.9 45.2 0.3

Median 37.0 20.0 14.9 30.0 32.5 0.0 403.0 1181.5 1.2

Standard DeViation 13.7 20.6 12.1 22 2 19.1 3.1 222.6 110.8 0.9

Sample Vanance 186.6 876.2 145.8 4942 364.2 9.4 49568.712284.70.7

Kurtosis 3.1 5.6 0.4 -1.5 -1.5 6.0 -1.3 0.6 3.8

Skewness -1.5 2.3 0.5 -0.2 0.2 2.4 0.1 -0.7 1.8

Minimum 8.8 10.0 0.0 0.0 10.0 0.0 120.0 980.0 0.5

Maximum 49.0 90.0 34.8 55.0 60.0 7.5 700.0 1300.0 2.9

Confidence Level 14.3 31.1 12.7 23.3 20.0 3.2 233.6 116.3 0.9

TABLE 2.20: SOIL CORRELATION ANALYSIS SHOWS A HIGH CORRELATION

AMONG VARIOUS ELEMENTS.

As Ni Cu Cr Zn Mn Mg Fe

As 1.00

Ni 0.88 1.00

Cu 0.80 0.48 1.00

Cd 0.52 0.48 0.67 1.00

Zn 0.71 0.65 0.60 0.28 1.00

Mn 0.70 0.63 0.73 0.62 0.91 1.00

Mg 0.87 0.90 0.45 0.13 0.74 0.56 1.00

Fe 0.52 0.32 0.30 -0.350.21 -0.070.62 1.00

n view of the soil enrichment by arsenic, the vegetations commonly found the area

vas analysed to find out the arsenic levels. The studied vegetation land based and
,quatic of kanker was S.sphaerandra (Teek), B. monospermum (Palash), j. curcas
113
 (H ..u.a'tjol). I, Irh'I'('tl\,1 U'Ip .• I), .1 lI"h1.1 (Nf'com). \ (11"'1111 U .. mun>. r ,"""HI/llum

(HIj.t), () IlIrl.llltH) /,'/1 (I "'fut til. I /'''J''''''\,' (\u'(Jh .. (t.d. 1/ 'rIlle ,11",1.1 (llydllll.t), I

,1qll.I/I(.I (AIlI.I.tn) .",d .\ 'HUllb,', pt tllhc"\

R,'\IIIt .. 01 40 ,.Impl,·" .lfI.,I., .. ,·" (I.tblt'.' ll) ,how.t fllt'.'" I"'Vt'l uf .• P.t·OU 01 I} ·'1

ppm •• nd.1 m.U(lftlwn v.tlt ... c)1 1.• 1• ppm In onc' p.u\I(ul.u \1)tO(h· ... It ......lId 'Pl'ClCO\ 1\

h('IfHJ IflVt·")ti(J.1tNJ lor It, hype" .U(IIIllIIl.ltor ,(Jtu .. , SIOIII.uIV UIe' flvc·rwc·(·(t\ Itl Kotrl

'IVC" h •• e; ")flown tbt> P"'\{'''(I' of .H\{'m[ ~It SO ! 10 ppm. "Ihl\ ",.thll' .ttU'\l\ 10 .1

con\I\{('rlt pH'\rnn' of .H\l'lIl( 111 th(' ,tv .." w.lI(l( Jnd It\ po., .. thh- tHCM(( IHnul.HIOII.

1 liNe .u~ V"'y fI·w "'1""" of th,' wddl,(,' p"I\onln'l by ","'nlC (n,It·,. 1'lIlR), 1 h,-

"'~~nic conc~ntratl()11 111 tIlt' W.I!<·I w." ,·I~v.It,·d to 7.500 m'J/l ••lrId (.It("h in w.It,'r

the 'eservolr w<'le r~p",tl'd to (Ol1t.lln " Jnd 12 "HJ 1\~/k<J In ,hl.·t,11 mus, " ••Iftt-' ~

hour and 7 -week ~xposlJr"s (w~I'Jht basis not specIfied).

Arsenic is also relatively persistent in the aquatic environment, (Tanner and Clayton.

1990) reported elevated concentrations of arsenic in macrophytes (193 -1200 mg/kg

dryweight (dw» and surficial sediments (540-780 mg/kg dw) in Lake Rotoroa. New

Zealand, 24 years after an application of sodium arsenite herbicide; arsenic levels in

a nearby reference lake (Lake Rotokauri) were <20 mg/kg dw in macrophytes and

16.5-40 mg/kg dw in sediments, In tropical climate the slow moving river water

normally supports a rich aquatic flora and fauna but the same has not been observed

in the river Kotri and we have noted a very little aquatic biodiversity in the Kotri River

and whatever species are available appear to be tolerant to the arsenic and other

trace elements.

------------------------------------------------------------114
 TABLE 2.21: ARSENIC STAnsTICAL ANALYSIS IN VEGETAOON Born lAND
BASED ANO AQUATIC PUIHTS.

Parameter Value
Mean (mglkg)) 32.41

Standard Error 7.93

Median 34.00

Standard DeViatIOn 30.70

Sample Variance 942.76

KurtOSIS 5.68

Skewness 1.99

Range 122.50

Minimum 2.50

MaXImum 125.00

GEOLOGY OF THE STUDIED AREA AND ITS RELATIONSHIP WITH ARSENIC

CONTAMINATION

After establishing the arsenic contamination, it is important to establish the reasons for

its appearance in groundwater. Geologically the area is a part of the highly

heterogeneous central Indian shield, which comprises of three Archean cratons, two

Gondwana basins, Proterozoic mobile belts and basins interspersed with Phanerozoic

cover. The development ofthe regional geology is given in Table 2.22.

From detailed geological, petrological and structural studies the Central Indian Shear

(Yedekar et aI., 1990) has been identified, which separates the Bastar block from the

northern (Bundelkhand) block. The western side of this shear is buried under

alluvium and traps while to the east it forks into two parts with the northern part

coming close to the Tan shear.

Precambrian crustal evolution of the area is characterized by successive development

of supracrustal belts and orogens often associated with development of high-grade

115
 metamorphic belts. Regional and global correlation of such events is an onerous task

as younger tectono metamorphic ev~nts often over print (and rotate) earlier

structures and result in degradation of earlier mineral assemblages.

TABLE 2.22: REGIONAL GEOLOGICAL SET-UP OF me STUDIED REGION

WHICH INDICA 1£S mE INRUENCE OF OROGENIC EVENTS IN FORIIING THE

MINERAUSED ZONES.
---
. Chhattisgarh Supergroup Raipur Limestone; Chandarpur Sandstone

Intrusive Quartz Veins

Diorite, Gabbros, Pyroxenes

Khairagarh Organic Phase (.00 Ma)

Khairagarh Group Mangikhuta Formation (Basic Volcanics)

Karutola Formation (Coarse Clastics)

Sitagota Formation (Basic Volcanics and Intra-

trappeans)

Bortalao Formation (Coarse Elastics)

Unconformity

. Chilphi Group Chattuala Formation

(Shale/ I nterbeded / sandstone)

Jharia Formation (Conglomerates & Coarse

Elastics)

Unconformity

Dongargarh Granite 2270 ±90 to 2465 ±22 Ma)

Nandgaon Group Pitepani Formation (Basic Volcanics)

--------------------------------------------------------------116
,--_._------------- - --- ------ ---------------
Bijli Formation (Rhyolite/Tuff) (2180 - 2500 Il.a)

Unconformity

Amgaon Orogeny, Metamorphism and Granatization (,2500 I,a)

-----------~-------- -----------------
Aamgaon Group (Aamgaon Augen gneiss. banded and streaky gneisses and

Granitic Complex) megmatites with amphibolites and other super

crustal rocks.

The rocks of Bai/adila group comprise feldspathic quartzite; phyl/itic shales and iron

are (Crookshank, ) 963) whereas Kotri Group comprises volcanics of different

composition. In fact the rocks of Kotri Group converge northward into Dongar9arh

supergroup of rocks and considered to have been formed in one tectonic regime

(Bandyopadhyay et aI., ) 995).

The Nandgaon group unconformably overlays the Amgaon group comprises of older

RhyolitiC (Bijli Rhyolites) and younger andesitic (Pitepani andesite) volcanic suites.

The Dongargarh granites, which have intruded the rocks of Amgaon and Nandgaon

Groups, contain numerous ene/aves of rhyolites, basalt and metasediments.

However, the isochrone' s dating has established that origin of Bijli Rhyolite and

Dongargarh granite is comagmatic in nature (Sarkar 1980; Krishnamurthy, 1990).

The Khairagarh group unconformably overlying the rocks of Nandgaon Group is

represented by volcano sedimentary sequence. The Khairagarh volcanics are basic in

nature and overly unconformably on the rocks of Nandgaon group and Dongargarh

granite. All the three groups of Dongargarh Supergroup identified with three distinct

Orogenic cycles. The earliest orogenic activity is described as Amgaon Orogeny and

it is characterized by NNE-SSW to NNW-SSE trend. The subsequent Orogenic cycles

corresponding with younger groups namely. the Nandgaon cycle and the Khairagarh

-------------------------------------------------------~117
cycle almost follow the same trend and have caus~d low metamorphism of

associated rocks. (Sarkar, 1957-58,1994) The Kotri volcanic belt or Kotri lineament

is identified as southern extension of Dongargarh Supergroup. The N5 trending Kotri

linear belt is 250 km long and 50 km wide comprises of the acid and basic volcanics

along with conglomerate and arkose, intruded by granite.

We have identified a distinct presence of arsenopyrite in the surface outcrops of

rhyolite and deep borehole logs dug by a government agency in the Guruwandih

area. The level of arsenic in certain boreholes chips has been found to be as high as

15,000 ppm. Abundant arsenic was contained in the conglomerate layer, andesitic

and dacitic tuff layer, and altered basalt. Abundant arsenic appears to concentrate on

layer boundaries. These layer boundaries are the area where the aquifers exist. Most

abundant arsenic was contained in altered basalt layer. Certain samples of the area

were found to contain considerable amount of pyrite. So it is suggested pyrite is

involved in high amount of arsenic concentration in this area.

118
 TABLE 2.23: COMPARISON OF ARSENIC MEASURED VALUES OF

CONTAMINATED AREA IN ROCK SAMPLE.

- - - -- - -_. - -
, Rocks Arsenic
,I concentr,ltion Average Values of Arsenic
I'
(mg/kg) range usually measured (mg/kg) in

reported (NA5, 1977) studied area (This work)

I
Ultrabasic 0.3-16 3 0 2.0
1 .

IGabbros 0.06-113 I
i 2.0 2.5
i

Andesites 0.5-5.8
,,2.0 3.8

, Granites 0.2-13.8 1.5 2.9

!
I Silicic volcanic 0.2-12.2 3.0 8.2
I
i Shales and clays 0.3-490 14.5 12

Altered basalt - - 15,000

,i
(Deeply situated)
i
!

Conglomerate - , - 10,000

(Deeply situated) I,
,

Iron ores 1-2,900 i 400 100

(sedimentary) !

,
., Manganese ores (Uptol.5%) - 150
I ,
! (Sedimentary)
i
,

In the studied location the volcanic rocks have not shown very high levels (Table

2.23) yet the sedimentary deposits (though very small in geographical distribution)

have shown enrichment in arsenic levels. In their evaluation of the regional

---------------------------------------------------------------119
 distribution of arsenic in ground water in the western United States (Welch et aI.,

1988) evaluated the association between aquifer geology and arsenic concentrations

in ground water. Higher arsenic concentrations (ground water concentrations greater

than 50 Ilg(L) were associated with sedimentary deposits derived from volcanic

rocks. Similar appears to be the reason of arsenic in Kanker district and the arsenic

in groundwater appears to be caused by mineral leaching. Weathering of the volcanic

rocks may result in the concentration of arsenic onto ferric oxyhydroxide that are

deposited with sediments.

Despite models that explain and predict conditions controlling the uptake or release

of dissolved arsenic in ground waters remain incomplete, due partly to a lack of

knowledge of arsenic speciation in subsurface sediments. The shallow subsurface

under changing redox conditions the ratio of reactive iron to sulphur in the system

controls the distribution of solid phases capable of removing arsenic from solution

when conditions change from oxidized to reduced, the rate of which is influenced by

microbial processes. Because of the difference in solubility of iron versus arsenic

sulphides, precipitation of iron SUlphide may remove sulphide from solution but not

arsenic if precipitation rates are fast. The lack of incorporation of arsenic into iron

sulphides may result in the accumulation of dissolved As (III) if adsorption is weak or

inhibited. Aquifers particularly at risk for such geochemical conditions are those in

which oxidized and reduced waters mix, and where the amount of sulphate available

for microbial reduction is limited (O'Day et aI., 2004). The studied location,

particularly evince the changing redox conditions. The pH-Eh study of the aquifers of

region has shown that there are instances of changing redox conditions. This is the

reason that soluble As (III) and the Fe and Mn in variable oxidation states coexist in

the studied region and the amount of sulphate available in the system is low.

-----------------------------------------------------------120
 CONCLUSION

It is clear that a regional arsenic contamination is in taking place in the central-east

India. The arsenic is geological in origin and is related to the volcanic orogeny taken

place during Middle Proterozoic age. Presence of arsenopyrite in certain geological

formations has also been noted. This has also caused an elevated soil arsenic level.

Yet these levels are not as high as had been noted in some of the adjoining blocks of

Rajnandgaon district. The arsenopyrite-oxidation could to be a cause of arsenic

mobilisation in the Kanker district of Chhattisgarh state. Arsenic levels are high and

show a seasonal variation, which indicates the involvement of leaching/mineral

dissolution process. Higher levels of arsenic and manganese in the Kanker district

have been found to cause impacts on the flora and fauna. Surface water

contamination is resulting in the loss of aquatic species of both plants and animals.

Freshwater snails also provide a proof of the arsenic contamination of water. Arsenic

accumulation has also been witnessed in the surface plants and some of the plants

attest to the hyper-accumulation capacity for which further work in envisaged.

121
 REFERENCES

ihbSil. M.C.P., Hummel, H. Temmink, H.: 1990, BioJvailability of trace metals to macoma
i
balthica, Delta Industrial Hydrobiological Research Programme, Report, 35·-38.

APHA (American Public Health Association): 1992, Standard method for the examination of
I
I water and wastewater, Washington DC, US

Bandyopadhyay, B.K., Roy, A., Hwn, A.K.: 1995. Structure and tectonics of a part of the

Central Indian shield, Mem. GeoLi Soc. India 31. 433-467.

Bourgain, B.P., Risk, M.J. Aitken, A.E.: 1991. Factor controlling lead availability to deposit

feeding bivalve macoma balthica in sulphide nch oxic sediments, Est. Coastal Shelf

Sci. 32(6), 625-632.

Boyan, C.R., Phillips, D.J,H.: 1981, seasonal variation and inherent variability of trace

element in oysters and their implication for indirect studies, Marine Ecological

Programme Series 5(1), 29-40.

Chan, H.M., Rainbow, p.s., Phillips, D.J.H.: 1990, Barnacles and mussels as a monitor of

trace metal bioavailability in Hong-Kong waters. In: B. Morton (ed.) Marine flora and

fauna of Hong-kong and Southern China, Hong-Kong university Press, Hong-Kong,

1239-1268.

Crookshank H.: 1963, Geology of southern Bastar and Jeypore from Bailadila range to the

Eastern Ghats, Mem. Geo!. Surv. of India 87, 149.

Eisler, R.: 1988, Arsenic hazards to fish, wildlife, and invertebrates: a synoptic reView,

Biological Report, Laurel, MD, Department of the Interior, U.s., 85(1.12).

Francesconi, K.A., Edmonds, J.S.: 1997, Arsenic and marine organism, Advanced Inorganic

Chemistry 44, 147-189.

GSI (Geologic Survey of India): 2000, Seismo Tectonic Atlas of India and its Environs.
122
 IARC (International Association for Research on Cancer): 1987, IARC Monoqr~phs on the

Evaluation of Carcinogenic Risks of Chemicals to Humans, Suppl. 7, Overall

Evaluations of Carcinogenicity: Updating of IARC Monographs, IARC, lyon, 1(42).

Irwin: 1997, Environmental Contaminants Encyclopedia, Arsenic entry, July 1, 1997, Roy J-

Irwin (ed.), National Park service water resources divisions, Water Operations Branch

Fort Collins, Colorado.

Krishnamurthy, P.: 1990, Magmatic rocks of the Dongargarh Supergroup, Central India-their

petrological evolution and implication on metallogeny, Geol. Sur.of India Special Pub.

No.28,303-319.

Moore, J.W.: 1991, Inorganic Contaminants of surface water, Research and Monitoring

Priorities, Springer-Verlog, New York.

NAS (National Academy of Science): 1977, Arsenic medical and biological effects of

environmental pollutants, Washington, DC, US.

NEERI (National Environmental Engineering Research Institute): 1977, Technical Digest 54.

0' Day, Peggry A Dimitri Vlassopoulost, Root Robert and Rivera Nelson: 2004, The influence

of Sulphur and iron on dissolved arsenic concentration in the shallow subsurface

under changing redox conditions, PNAS 101 (38), 13703-13708.

Pandey, P.K., Khare, R.N., Sharma, S., Pandey, M.: 1999, Arsenocosis and deteriorating

ground water quality: unfolding crisis in central east Indian region. Curr, Sci. 77,

686-693.

Pandey, P.K., Nair, S., Bhui, A., Pandey, M.: 2004, Sediment contamination by arsenic in
parts of central-east India and analytical studies on its mobilization, CurL Sci. 86,
190-196.
Pandey, P.K., Yadav, 5., Nair, S. Bhui, A.: 2002, Arsenic contamination of the environment: A

new perspective from central-east India. Env. Inter. 28, 235-245.

-----------------------------------------------------:123
 Pandey, P.K., Yadav, S., Nair, S., Bhui, A., Pandey, M.: 2001, Holistic th~ory of Jrs~nic

contamination, In 3'd International India/Bangladesh symro~ia on "'<1 ucin 9 the

impact of toxic chemical in Bengal Basin, Kolkata, 10- 12 February, Indld

Pandey, P.K.:2000, Who should be credited for the discovery and first reporting of

arsenicosis in Kaudikasa in Madhya Pradesh? Curro Sci. 78, 1412.

Sarkar, A.N.: 2001, Explanatory brochure on the tectonic map of India, Geological Survey of

India.

Sarkar, S.N.: J 957-58, Stratigraphy and tectonics of the Dongargarh system: a new system

in the precambrian of Bhandara Durg-Balaghat area. Bombay and M.P. Indian

Institute of Technology Kharagpur, J. Sci. Eng. Res. I, 237-268, 2, 145 -160.

Sarkar, S.N.: 1980, Precambrian stratigraphy and geochronology of peninsular India: a

review, Indian J. Earth Sci. 7, 12-26.

Sarkar, S.N.: 1994, Chronostratigraphy and tectonics of the Dongargarh super group

precambrian rocks in Bhandara- Durg Region, Central India, Indian J. Earth Sci. 21,

19-31.
/

Stratten, G., Writehead, H.e.: 1962, J. Am. Water Works Asso. 54, 861.

Tanner, e.e., Clayton J.S.: 1990, Persistence of arsenic 24 years after sodium arsenite

herbicide application to lake Rotoroa. J. Mar. & Fresh Water Res., Hamilton, New

Zealand.

US EPA: 1983, Method 206.3 (atomic absorption-gaseous hydride). In: Methods for chemical

analysis of water and wastes. Cincinnati, OH: U.s. Environmental Protection Agency,

Environmental monitoring and support laboratory, EPA-600/4-79-020.

US EPA: 1986, National emission standard for inorganic arsenic emissions from arsenic trioxide

and metallic arsenic production facilities, U.s. Environmental Protection Agency, Code of

Federal Regulations. 40 CFR 61, Subpart P.

___________________________________________________124
US EPA: 1986, Quality Assurance /Quality Control (OA/QQ for 301(h) Monitoring Programs:

Guidance for Field and Laboratory Methods. EPA-430/9 -86 004. Waslllngton DC.

US EPA: 1997, ,RJS (Integrated Risk Information System) on line d,J(abase maintained in

toxicology data network (TOXNET) by the national library of mt'dlcine, Bethesda,

Maryland.

Vanllon, J.c.: 1977, Chemical analysis of inorganic constituents of water, CRC Press, Inc.,

New York.

Welch, A. H., Lico, M., Hughes, J.: 1988, Arsenic in ground water of the western United

States, Ground water 26(3), 333-347.

WHO (World Health Organisation): 1999, Arsenic in drinking water, Fact Sheet no. 210,

Geneva.

Yedekar, D.B., Jain, S.c., Nair, K.K.K. Dutta, K.K.: 1990, The Indian collIsion suture, Geo. Sur.

India Special Pub No 28, 1-43.

______________________--------------------------------------------125