Environ Monit Assess (2015) 187: 98

DOI 10.1007/s10661-015-4330-z

Impact of pulp and paper mill effluents and solid wastes on soil
mineralogical and physicochemical properties
Gopi Adhikari & Krishna G. Bhattacharyya

Received: 23 April 2014 / Accepted: 26 January 2015 / Published online: 7 February 2015
# Springer International Publishing Switzerland 2015

Abstract The present study was carried out to evaluate clay transformation. The significance of the mixed
the impact of the effluents and the solid wastes mineralogy in relation to the disposal of effluents
generated by a giant pulp and paper mill in the and dumping of solid wastes is discussed in details.
northeastern part of India on soil mineralogy of the
area. The impacts were monitored by analysis of soil Keywords Soil aggregate analysis . Mineralogical
samples from seven sites located in the potential composition . Influence of pollutants on soil properties .
impact zone and a control site where any kind of Soil organic carbon . Texture analysis
effluent discharge or solid waste dumping was absent.
The soil belonged to medium texture type (sandy clay
loam, sandy loam, loamy sand, and silt loam), and the
Introduction
soil aggregate analysis indicated higher levels of
organic carbon, pH, electrical conductivity, effective
Soil mineralogy is an important tool to provide infor-
cation exchange capacity, and mean weight diameter
mation regarding fertility status, stage of weathering,
at sites receiving effluents and solid wastes from the
etc. and is helpful in inferring the soil status (Miller
pulp and paper mill. Depletion in soil silica level
and Donahue 1992). Soil clays are considered to be
and in feldspar and quartz contents and rise in iron
the most important components, as any contaminant
and calcium contents at the sites receiving effluents
making its way into soil has to interact with the clays
from the pulp and paper mill indicated significant
(Prost and Yaron 2001). The transformation of soil
influence on soil mineralogy. The soil contained a mix-
mineralogical composition depends on the clay, silt,
ture of minerals consisting of tectosilicates (with silicate
and sand fractions, which exist in a dynamic equilibrium
frameworks as in quartz or feldspar), phylosilicates
in the soil. Clays are highly polar and are considered as
(layered clays like kaolinite, smectite, chlorite, illite,
the reactive component in soil. Soil clay is also well
etc.), and carbonates. Absence of pure clay minerals
known for providing a large reactive surface area per
indicated a state of heterogeneous intermediate soil
unit weight. The polar nature of soil clay accounts for its
cation exchange capacity. Amongst the most prominent
G. Adhikari
cation exchangers, the naturally available alkali and
Department of Chemistry, Jagiroad College, Jagiroad 782410,
India alkaline earth metal ions are the pioneers in the overall
e-mail: kgbhattacharyya@gmail.com weathering processes resulting in transformation of soil
clay mineralogy.
K. G. Bhattacharyya (*)
Pulp and paper industry is a water-intensive industry,
Department of Chemistry, Gauhati University,
Guwahati 781014, India and it generates large volumes of effluents. It is ranked
e-mail: kgbhattacharyya@gmail.com at the third position in terms of fresh water consumption
98 Page 2 of 13
after the primary metal and chemical industries (Asghar
et al. 2008). A large amount of solid wastes is also
simultaneously generated, and these include the
causticizing wastes (in the form of lime sludge), ash
from boilers, sludge from wastewater treatment process-
es, and unused raw materials (such as bamboo dust)
(Amini et al. 2012). On an average, a typical paper mill
produces 45 kg of waste sludge per ton of paper pro-
duced (Edalatmanesh et al. 2010) and effluent genera-
tion ranges from 1.5 to 60 m3 (Thompson et al. 2001;
Szolosi 2003), based on technology and nature of raw
materials. Indiscriminate and unplanned waste disposal
has been an unwelcome common practice with the pulp
and paper mills, particularly in the developing and the
underdeveloped countries, which is a matter of concern
(Whitehead and Geary 2000). The waste products are
always evaluated as ecological burden contributed by
paper industries. The paper wastes make their way to the
three major components of the environment viz. soil, air,
and water. Based on the waste disposal methods, the
effluents and the solid wastes have different contribu-
tions to the overall ecological health and each carries
distinct ecological burden. It is frequently reported that
the conventional methods of effluent treatment like the
use of biological oxidation using activated sludge and
aerated lagoon are often inadequate to get rid of the
composite organic and inorganic mixture of pollutants
(Raj et al. 2014).
In many cases, the bio-solids discarded from the
activated sludge treatment system are spread over agri-
cultural fields to improve soil fertility and other physi-
cochemical properties (Park et al. 2011). The added
organic matter contains low-molecular-weight organic
acids, capable of chelating Al3+ and Si4+ ions present in
the clay minerals in the soil framework (Chatterjee et al.
2013). As a result of this type of chelation, the clay
minerals in the soil become deficient in Al3+ and Si4+
ions that occupy the centers of the tetrahedral and octa-
hedral basic structural units. This deficiency is adjusted
by a forced rearrangement of the constituents leading to
soil clay transformation. Moreover, it is known that the
pulp and paper mill wastes, enriched with organic mat-
ter, are alkaline in nature, and the OH groups, contrib-
uting to alkalinity, can link the clay octahedra through
the O-end in intertype and intratype of combinations.
During the rearrangement processes, the inclusion and
exclusion of metallic moieties that are the abundant
constituents of the chemical wastes have greater chances
to be inserted, resulting in the clay transformation.
Environ Monit Assess (2015) 187: 98
Moreover, components like organic carbon from the
effluent and solid wastes in association with the soil
mineral particles contribute to the lowering in the parti-
cle as well as bulk density. They contribute to higher
porosity resulting into alteration of soil processes like
aeration, water holding capacity, etc. Higher soil aera-
tion increases the oxidation processes in soil, and higher
water retention leads to an anaerobic situation. These are
considered as the factors responsible for changes in the
natural oxidation processes in soil. The altered oxidation
activity, abundance of ionic species contributed by the
effluents, and predominant alkaline environments are
sure to alter the soil natural environment along with its
clay, the most active soil component in its content and
nature.
The present work tries to find out the changes in soil
mineralogical composition including the clay minerals
upon exposure to the paper mill effluents and the solid
wastes over a long period of time.
Materials and methods
Soil sampling sites
The site selection for soil sampling was based on the
proportionate area of location of the pulp and paper mill
(Nagaon Paper Mill of Hindustan Paper Corporation
Limited, situated at Jagiroad, India; installed capacity
100,000 t per annum of high-quality printing paper).
The soil samples were collected from eight locations
(CS, S1–S7) (Table 1) that include the control site (CS)
(at a distance of 1 km from the effluent treatment plant
of the mill where any kind of effluent discharge or solid
waste dumping is absent), two sites, S1 and S2, from
solid waste dumping locations, and five sites, S3–S7,
from effluent discharge locations. These are also shown
in Fig. 1. The sampling sites belong to tropical rainforest
climate region, subjected to a humid subtropical climate.
The average rainfall in the area is 1530 mm, with
average temperature 25.5–32.9 °C (summer) and 19.8–
24.8 °C (winter), with annual average of 19.8–30.4 °C.
Soil sampling and preparation
At each site, three soil samples were collected from a
1-m2 area up to 20-cm depth (average conventional
tillage depth) using a 5-cm corer and the soil samples
were homogenized to form a composite sample that
Environ Monit Assess (2015) 187: 98 Page 3 of 13 98

Table 1 Location, land use pattern, and a brief description of the sampling sites

Site Soil type Location Description of the site

CS Control site 26° 07′ 25.1″ N Rural site away from the mill, not receiving effluent discharge or
92° 11′ 28.5″ E solid waste dumping
S1 Solid waste dumping 26° 07′ 43.0″ N Dumping of lime waste from caustic chlorine plant near the
92° 14′ 05.6″ E residential colony
S2 Solid waste dumping 26° 07′ 38.5″ N Dumping of coal fly ash from the mill near the residential colony
92° 14′ 30.7″ E
S3 Waste sludge disposal 26° 07′ 50.8″ N Dumping of the sludge from the effluent treatment plant (ETP)
92° 12′ 41.9″ E
S4 Treated effluent discharge 26° 08′ 07.1″ N Treated effluent from the ETP discharged through an underground
92° 12′ 31.4″ E channel to a natural wetland, the Elenga Beel
S5 Treated effluent route 26° 07′ 52.6″ N Agriculture land at a distance of 50 m from S3
92° 12′ 40.8″ E
S6 Treated effluent route 26° 07′ 53.5″ N Agriculture land at a distance of 100 m from S3
92° 12′ 40.9″ E
S7 Treated effluent route 26° 07′ 57.4″ N Agriculture land at a distance of 500 m from S3
92° 12′ 35.5″ E

was likely to be representative of the specific soil type at
a particular location. The samples were air-dried and
passed through a 2-mm sieve, after which they were
preserved for laboratory analysis. The samples were
collected in three seasons viz. hot dry summer (April
to June), Wet hot summer (July to September), and cold
dry winter (November to February) to take into account
the impact of change in climate.
Analysis of soil samples
Analysis of soil physicochemical parameters was done
by following standard methods, i.e., soil composition
with respect to sand, clay, and silt percentage by the
hydrometer method; soil texture by ISSS triangle
method (Reeuwijk 2002); soil organic carbon (SOC) by
modified Walkley-Black method (Sarkar and Halder
2010); and electrical conductivity (EC) (1:5 soil/water
suspension, Elico CM 180) (Sarkar and Halder 2010),
pH (1:5 soil/water suspension, Elico LI 120) (Jackson
1958), and effective cation exchange capacity (ECEC) by
ammonium acetate method (Hasse 1994). Soil aggregate
analysis was done following the wet-sieving technique of
Yoder 1936 (Baruah and Barthakur 1997). Soil stability
was expressed in terms of percentage as well as mean
weight diameter (MWD), which is defined as the sum of
the product of the mean diameter, Xi, and the total sample
weight, Wi, of each size fraction (MWD=∑ Xi Wi)
(Baruah and Barthakur 1997). Each analysis was done
in triplicate, and the means of the three values are
reported here. Portions of the soil samples were pul-
verized and subjected to XRF analysis to obtain soil
mineralogical composition.
The soil samples were soaked in water and treated
with 30 % H2O2 to remove organic matter, and the soil
clay was separated by dispersion and gravity separation.
The clay fraction (<2 μm) was freeze-dried overnight to
remove any excess moisture within the sample.
Approximately 1.5 mg of the sample and 80 mg of
spectroscopic grade KBr were weighed out and ground
in an agate mortar until thoroughly homogenized. The
mixture was pressed into a disc and analyzed for IR
spectra (IR Affinity-1 Fourier transform infrared spec-
troscopy (FTIR) spectrophotometer, Shimadzu; range
4000 to 400 cm−1; 4-cm−1 resolution). Powder X-ray
diffraction (XRD) patterns were obtained with a Phillips
Analytical X-ray spectrometer (PW 1710) using Cu K-
alpha radiation at 40 kV, 30 mA, and Ni filter with
continuous scan. The diffractograms were analyzed
and compared with the existing database.
Results and discussion
Observed physicochemical properties of soil
The soil samples were found to belong to medium
texture type (sandy clay loam, sandy loam, loamy sand,
98 Page 4 of 13
Fig. 1 Locations of the sampling sites
and silt loam). The physicochemical properties appear
in the following sequences:
1. 1. Clay content (Fig. 2): S3 > CS > S4 > S5 > S7 >
S1 > S6 > S2
Environ Monit Assess (2015) 187: 98
2. pH (Fig. 3): S5 > S6 > S1 > S7 > S4 > S2 > S3 > CS
3. Conductivity (Fig. 3): S3 > S7 > S5 > S4 >
S6 > S1 > S2 > CS
4. ECEC (Fig. 3): S5 > S6 = S7 > S4 > S3 > S1 >
S2 > CS
 Environ Monit Assess (2015) 187: 98 Page 5 of 13 98

S7 10 SOC %

S6
MWD
8

SOC and MWD

S5
6
Sampling sites

S4
4
S3
2
S2

S1
CS
0 10 20
30
Siilt (%)
Fig. 2 Relative composition of clay, silt, and sand at the sampling
sites
5. Organic carbon (Fig. 4): S3 > S2 > S4 > S5 > S6 >
CS > S1
6. Aggregate stability in MWD (Fig. 4): S1 > S5 >
S3 > S6 > S4 > S2 = S7 > CS
Though the soil of the CS possesses higher clay
content (except S3), its organic carbon content is slightly
higher than S1 (waste lime dumped area). Effective
cation exchange capacity (ECEC), pH, and conductivity
of the soil had the minimum values in the CS. Similarly,
when aggregate stabilities of the soils are compared on
the basis of mean weight diameter (MWD), all the soils
receiving pollutants have greater MWD, i.e., higher
aggregate stability than the CS soil. This may be due
to the presence of higher concentration of calcium car-
bonate in the effluents from causticizing plant along
with higher organic matter. Calcium carbonate contrib-
utes to aggregate stability through its cementing effect,
and similar enhancement is possible with high organic
matter that increases overall negative charge. These
45
pH
40
Conductivity dS/m
pH, conductivity, CEC
0
CS S1 S2 S3 S4 S5 S6 S7
Sampling sitees
0
40 50 600 70 80 Fig. 4 Interrelationships between soil organic carbon (%) and soil
Composition
C n (%) aggregation (MWD)
Sand (%) Clay (%))
observations suggest that there may be organic, alkaline,
and soluble salt inputs to the sampling points along with
the effluents and wastes from pulp and paper mill.
Soil mineralogy
The average chemical composition of the soil samples
(Table 2) shows the presence of abundant amount of
CaO (except at the site, S2, where coal ash is regularly
dumped) and drastically reduced SiO2 in the soil of
the sampling sites affected by the pulp and paper
mill effluents and solid wastes. The CS had higher
SiO2 content than the other sites receiving either
solid wastes or treated effluent discharge from the
paper mill. However, the soil from the CS had less
Fe2O3 and CaO compared to the other sites. Higher
CaO in the sites having impacts from the paper mill
operations suggests presence of carbonates of Ca that
broke down into CaO during heating to determine LOI
through loss of CO2. The soil in the sites receiving
pollutant loads from the mill had much higher values of
loss on ignition (LOI) indicating the presence of higher
amounts of organic matter and possibly carbonates.
It has been shown from Si-isotopic signature studies
that Si is the key factor of clay mineralogy, often in-
duced by the climate gradient (Opfergelt et al. 2012).

35
CE
EC cmol/ kg The observed reduction in SiO2 and, hence, Si in the
30 present work is apparently due to the enrichment of the
25
soil by organic wastes discarded by the paper mill, and
20
15
this is likely to have important consequences for the clay
10 mineralogy of the soil.
5
0
CS S1 S2 S3 S4 S5 S6 S7
Soil clay mineralogy
Sampling site

Fig. 3 Variation of pH, electrical conductivity, and cation ex- When the separated clay fraction of the soil samples was
change capacity (CEC) for the different sampling sites subjected to FTIR and XRD measurements, the samples
98 Page 6 of 13 Environ Monit Assess (2015) 187: 98

Table 2 Soil chemical composition (in weight %) and loss on ignition (LOI) from XRFS measurements

Oxides CS S1 S2 S3 S4 S5 S6 S7

SiO2 70.83 40.48 50.37 60.21 30.8 29.8 30.13 31.85

Al2O 10.8 9.96 11.72 10.39 11.38 10.46 10.74 11.29
Fe2O 0.03 0.25 3.74 0.08 1.94 0.09 0.26 0.93
MnO 0.008 0.017 0.017 0.005 0.069 0.005 0.002 0.027
MgO 0.09 0.08 0.05 0.16 0.7 0.1 0.77 0.95
CaO 0.15 6.05 0.87 1.95 18.88 22.3 20.73 21.74
Na2O 2.12 2.17 2.16 1.99 2.19 2.08 2.08 2.16
K2O 0.63 0.28 0.74 0.33 0.65 0.38 0.43 0.71
Ti O2 0.22 0.82 0.77 0.19 0.55 0.11 0.16 0.28
P2O 0.07 0.04 0.05 0.05 0.07 0.03 0.18 0.04
LOI% 14.8 38.13 28.55 22.76 31.41 33.55 33.96 29.47
Total 99.75 98.28 99.04 98.12 98.64 98.91 99.44 99.45

were found to contain a mixture of minerals instead
of pure clay minerals indicating heterogeneous inter-
mediate metastable stages of soil clay transformations.
These minerals could be classified on the basis of
their classes as tectosilicates (with silicate frameworks
as in quartz or feldspar), phylosilicates (layered clays
like kaolinite, smectite, chlorite, illite, etc.), and
carbonates.
The FTIR spectra of the separated clay fractions are
shown in Fig. 5a, b. The principal FTIR frequencies and
their assignments (Madejová and Komadel 2001;
Schroeder 2002; Pironon et al. 2003; Vaculikova and
Plevova 2005; Nayak and Singh 2007; Ravisankar et al.
2010; Davarcioglu 2011) are given in Table 3. These are
discussed below.
Feldspar Two types of feldspars, viz. albite and ortho-
clase, could be found in the soil, based on assignment of
the FTIR bands, ~779 cm−1 (Si–O sym stretching) in
albite and 648 cm −1 (Si–O sym stretching) and
~536 cm−1 (Si–O asym bending) in orthoclase. Other
prominent FTIR bands such as ~470 cm−1 (O–Si–O
bending) and ~435 cm−1 (Si–O sym stretching) also
point to the presence of orthoclase. On the other hand,
the bands, ~424 cm−1 and ~408 cm−1 (O–Si–O bending)
in the clay fractions of the soil samples indicate the
presence of albite. Since feldspar exists as a mixture of
orthoclase and albite in all the sampling locations, it is
not likely to be in highly crystalline form.
Phylosilicates

Kaolinite The presence of the clay mineral, kaolinite,

Tectosilicates
Quartz The abundance of this tectosilicate in the clay
fraction of the sampling locations is indicated by the
presence of all or some of ~1086-, ~798-, and 779-cm−1
bands (Si–O symmetrical stretching), ~694- and
538-cm−1 bands (Si–O symmetrical and asymmetrical
bending), and ~468-cm−1 band (Si–O–Si deformation)
in the clay fractions of soil samples from all the loca-
tions. The characteristic ~800- and ~700-cm−1 bands
indicating crystallinity of quartz are also found in the
soil of most of the sampling locations excepting at S1
and S4 showing poor crystalline state of quartz at these
two locations.
in the soil samples is indicated by the appearance of
the characteristic FTIR bands: 3691 cm−1 assigned to
in-phase symmetric OH stretching; ~3669- and
~3653-cm−1 bands due to anti-phase OH stretching;
~3620 cm−1 from inner hydroxyl groups lying between
the tetrahedral and octahedral sheets; ~3457 cm−1
assigned to OH stretching of adsorbed water molecules;
~1635 cm−1 due to OH deformation frequency; ~1102-,
755-, and 697-cm−1 bands assigned to Si–O perpendic-
ular stretching; ~1033, 1011, and 791 cm−1 due to in
plane Si–O stretching; ~938 and ~915 cm−1 arising from
OH deformation in inner surface hydroxyl groups;
~541 cm−1 from Al–O–Si deformation; ~472 cm−1
from Si–O–Si deformation; and ~432 cm−1 due to
Environ Monit Assess (2015) 187: 98 Page 7 of 13 98

a
60 45

55
40
50

35
45

Transmission
Transmission

40 30

35
25
30

25 20

20
15
4000 3400 2800 2200 1600 1000 400
4000 3400 2800 2200 1600 1000 400
Wavenumber cm -1
Wavenumber cm -1

65 45

40
60

35
55
Transmission
Transmission

30

50
25

45
20

40 15
4000 3400 2800 2200 1600 1000 400 4000 3400 2800 2200 1600 1000 400

Wavenumber cm -1 Wavenumber cm -1

Fig. 5 a FTIR spectra of the clay fraction of (i) control site (CS), (ii) site S1, (iii) site S2, and (iv) site S3 (clockwise from top left). b FTIR
spectra of the clay fraction of (i) site 4, (ii) site S5, (iii) site S6, and (iv) site S7 (clockwise from top left)

Si–O deformation. However, kaolinite in the soil
samples is poorly crystalline form as the peaks
around 3696, 3688, 3669, 3652, and 3621 cm−1 are
not well resolved (Shoval et al. 1999).
Illite Occurrence of illite in the soil samples is shown by
the appearance of the FTIR bands ~3620 cm−1 (inner
hydroxyl groups lying between the tetrahedral and oc-
tahedral sheets); ~3450 cm−1 (OH stretching in water
molecule); ~1635,~688, and 622 cm−1 (OH deformation
in water); 1090 cm−1 (Si–O normal to plane stretching);
915 cm−1 (OH deformation in inner surface hydroxyl
groups); ~832 cm −1 (Al–Mg–OH deformation);
~756 cm −1 (Al–O–Si inner surface vibration);
~525 cm−1 (Al–O–Si deformation); and ~472 cm−1
(Si–O–Si deformation) in the clay fraction.
Chlorite The characteristic bands for chlorite were
seen in the clay fraction of the soil from the location,
S2 (adjacent to fly ash dumping area) only. FTIR
98 Page 8 of 13 Environ Monit Assess (2015) 187: 98

b
46 70

65
41

60
36
Transmission

Transmission
55
31
50

26
45

21
40

16 35
4000 3400 2800 2200 1600 1000 400 4000 3400 2800 2200 1600 1000 400
Wavenumber cm -1 Wavenumber cm -1

70 63

65
58
Transmitance

60
Transmission

53

55

48
50

45 43
4000 3400 2800 2200 1600 1000 400 4000 3400 2800 2200 1600 1000 400
Wavenumber cm -1 Wavenumber cm -1

Fig. 5 (continued)

frequencies characteristic of chlorite were ~3620 cm−1

Table 3 Assignment of FTIR bands to soil clay minerals
(due to inner hydroxyl groups lying between the tetra-
Minerals Characteristic FTIR band (cm−1) hedral and octahedral sheets), ~3565 and ~3434 cm−1
(OH stretching), ~988 cm −1 (Si–O stretching),
Kaolinite 3694, 3669, 3653, 3620, 3457, 1635, 1102, 1033, 1011,
~543 cm−1 (Al–O–Si deformation), and ~441 cm−1
938, 915, 791, 755, 697, 541, 472, 432
(Si–O–Mg deformation).
Illite 3622, 3450, 1633, 1090, 1031, 916, 832, 790, 756,
688, 622, 525, 468
Chlorite 3622, 3565, 3434, 988, 819, 766, 667, 543, 441 Smectite The presence of the clay mineral, smectite,
Smectite 3620, 1088, 1008, 916, 798, 525, 467 was observed only at the location, S3 from its FTIR
Calcite 2922, 2874, 2513, 1797, 1426, 876, 713, 693 bands, i.e., ~3620 cm−1 (inner hydroxyl groups lying
Quartz 1086, 798, 779, 694, 538, 467
between the tetrahedral and octahedral sheets),
Feldspar 585, 540, 435, 405
~1090 cm−1 (Si–O normal to plane stretching), ~1010
and 791 cm−1 (in plane Si–O stretching), ~915 cm−1
Environ Monit Assess (2015) 187: 98 Page 9 of 13 98

a
30 90

80
25
70

Intensity counts/sec
Intensity counts/sec

20 60

50
15
40

10 30

20
5
10

0 0
3 6 9 12 15 18 21 24 27 30 3 6 9 12 15 18 21 24 27 30
2θ
2θ

25 10

20 8
Intensity counts/sec
Intensity counts/sec

15 6

10 4

5 2

0 0
3 6 9 12 15 18 21 24 27 30 3 6 9 12 15 18 21 24 27 30
2θ 2θ

Fig. 6 a XRD spectra of the clay fraction of (i) control site (CS), (ii) site S1, (iii) site S2, and (iv) site S3 (clockwise from top left). b XRD
spectra of the clay fraction of (i) site 4, (ii) site S5, (iii) site S6, and (iv) site S7 (clockwise from top left)

(OH deformation in inner surface hydroxyl groups), Carbonates

~525 cm−1 (Al–O–Si deformation), and ~470 cm−1
(Si–O–Si deformation). This location also showed Calcite Presence of CO3 ion is the distinguishing fea-
the presence of illite-smectite mixed layer indicated ture of carbonates from other phylosilicates. All the
by the FTIR bands, 1034, 748, 536, and 471 cm−1. sampling locations except the CS are found to contain
Usually, when the absorption minima shift to higher calcite. The bands ~2922, 2874, 2513, 1426, and
than 2200 cm−1, it is considered as an indication of 693 cm−1 (due to CO3 vibrations), which are known to
lower Al content in the mineral (Duke 1994). The be characteristic FTIR bands for calcite, were observed
location, S3, showed an IR absorption band at in all the soil samples. Other bands supporting the
2137 cm−1 indicating presence of Al-enriched clay presence of calcite in the soil were ~1797 cm−1 (combi-
mineral in the soil. nation band of calcite), ~876 cm−1 (out of plane
98 Page 10 of 13 Environ Monit Assess (2015) 187: 98

b
35 70

30 60

25 50
Intensity counts/sec

Intensity counts/sec
20 40

15 30

10 20

5 10

0 0
3 6 9 12 15 18 21 24 27 30 3 6 9 12 15 18 21 24 27 30
2θ 2θ

35 35

30 30

25 25
Intensity counts/sec

Intensity counts/sec

20 20

15 15

10 10

5 5

0 0
3 6 9 12 15 18 21 24 27 30 3 6 9 12 15 18 21 24 27 30
2θ 2θ

Fig. 6 (continued)

bending), and ~713 cm−1 (in plane bending). According Powder XRD data
to Clark et al. (1990), overtones of fundamental
bands in IR occur in the range of 2500–2550 and The powder diffractograms of the separated clay frac-
2300–2350 cm−1 and other weaker bands at 2120– tions are shown in Fig. 6a, b. The d-spacings are assigned
2160, 1970–2000, and 1850–1870 cm−1 indicating on the basis of literature reports (Vaculikova and Plevova
the presence of carbonate minerals in mixtures. 2005; Nayak and Singh 2007; Harris and White 2008;
Presence of these bands in the observed FTIR Ravisankar et al. 2010; Davarcioglu 2011; Diko and
spectra of the clay fraction in the soils of all the Ekosse 2012). It is reported that d (mean)–d (measured)
locations excepting the CS definitely indicates entry of ranges from ±0.05 to 0.01 for calcite and from ±0.2 to
some carbonate mineral to the sites receiving the paper 0.01 for illite and kaolinite, while the deviations for
mill effluent or solid waste. smectites are very large (Olphen and Fripiat 1979).
Environ Monit Assess (2015) 187: 98 Page 11 of 13 98

Table 4 Mineral assignments on the basis of the powder XRD data any particular clay minerals. The presence of kaolinite,
2 θ (°) d-spacing (Å ) Mineral identified illite, chlorite, calcite, feldspar, and quartz, shown by the
FTIR measurements, might have been masked by over-
12.6±0.2 7±0.13 Kaolinite lapping of the bands of a large number of minerals. This
20.8±0.6 4.3±0.1 Kaolinite may also be due to attachment of the soil clay with unburnt
25.2±0.3 3.54±0.04 Kaolinite coal carbon (arising from dumping of coal fly ash) leading
09.14 9.67 Illite to loss of crystallinity.
18.5±0.6 4.75±0.15 Illite In the site, S3, the soil clay shows the presence of
26.9±0.2 3.31±0.01 Illite smectite (confirmed by d-spacings of 6.09 and 3.09 Å)
14.5 6.1 Smectite and illite (3.32 Å) and also randomly oriented illite-
28.9 3.1 Smectite smectite mixed layer (9.17 Å). The XRD of the clay
23.25±0.1 3.82±0.02 Calcite fraction of the site, S4, shows the presence of calcite
29.54±0.05 3.02 Calcite (3.01 Å) and illite (3.32 Å). The site, S5, had calcite
20.90, 26.87±0.22 4.25 and 3.32±0.03 Quartz (3.82 and 3.01 Å) and illite (3.32 Å), but the poor
27.74 3.22 Feldspar crystallinity of the clay fraction might have been respon-
sible for not showing the characteristic d-spacings for
kaolinite, quartz, and feldspar as detected by FTIR.
These variations are supposed to be due to the differences The clay fraction from the site, S6, shows the pres-
in pretreatment of the soil clay or state of hydration of the ence of calcite (3.02 Å), illite (3.32 Å), and polygorskite
clay being studied. The clay mineralogical assignments or quartz (4.25 Å). The XRD data for the site, S7, show
in this work are given in Table 4. the presence of calcite (3.84 and 3.02 Å) and illite
The data for the clay fraction of the CS show the (3.32 Å). No other clay mineral could be detected.
presence of kaolinite (7.06 and 4.35 Å) and illite On the basis of results of FTIR and powder XRD
(3.31 Å). Due to the possible overlapping of quartz peak studies, the mineralogical composition of the clay frac-
(4.26 Å) with that of kaolinite (4.35 Å) and feldspar tions in the soil of all the locations is presented in
(3.19 and 3.31 Å) with illite (3.31 Å), both quartz and Table 5. The results indicate that the pulp and paper mill
feldspar could not be confirmed in the clay fractions of effluents and the solid wastes introduce considerable ex-
the soil samples, but their presence was clearly indicated tent of organic matter and alkalinity to the exposed soil.
in the FTIR measurements. Decomposition of organic matter is a microorganism-
The clay fraction of the soil at S1 shows calcite (3.81 initiated process and releases CO2 to the atmosphere along
and 3.01 Å) in it while the presence of kaolinite, quartz, with the formation of organic acids. The increased soil pH
and feldspar could not be confirmed, possibly due to takes out the H+ from the acids as well as the silicate clays.
poor crystallinity of the components (Brindley et al. As a result, the surface negative charge increases. This
1986). The diffraction pattern of the clay from the site, increase is supposed to be adjusted with the configura-
S2, does not show characteristic d-spacings to assign to tional rearrangements. It is observed that smectite is found

Table 5 Availability position of different soil clay minerals

Site Kaolinite Illite Chlorite Smectite Calcite Quartz Feldspar

CS + + − − − + +
S1 + − − − + + +
S2 + + + − + + +
S3 + + − + + + +
S4 + + − − + + +
S5 + + − − + + +
S6 + + − − + + +
S7 + + − − + + +

(+) indicates presence, (−) indicates absence of a particular mineral in the clay part
98 Page 12 of 13
at S3, chlorite at S2, and calcite at all the sampling sites.
Under the influence of abundant water and the ionic
species, it is likely that the interlayer potassium ions in
illite mineral are either replaced by Na+, Ca2+, or H2O
converting the mineral to smectite. Alternatively, during
rearrangement of the octahedral layer in illite, potassium
ions might have been replaced leading to the formation of
chlorite. Carbonate minerals belong to the basic anhy-
drous group having a single cation in a hexagonal close
packed structure. The basic anionic CO3‾ group has
carbon in sp2-hybridized state resulting in a planar trian-
gular coordination. Since carbonate is known as a gangue
mineral, it is most likely to have originated from the
sediments in the pulp and paper mill effluent.
Conclusions
The results indicated that the sites receiving treated
effluent and solid wastes from the paper mill are either
water-logged or remain wet almost throughout the year,
and it has resulted in the soil having less ordered clay
minerals. XRD and FTIR measurements showed mixed
mineral composition of the soil. In the mixed layers, the
normal crystal structure of the minerals gets modified
due to replacement of existing ions in the crystal lattice.
The presence of carbonate minerals was observed in all
the sampling sites receiving paper mill effluents and
solid wastes. Since, in these sites, calcite is detected, it
might be in the form of calcite mud analogous to
siliciclastic sedimentary rocks with extremely fine cal-
cite crystals. The chlorite minerals in the soil are likely
to have been contributed by the fly ash discarded by the
paper mill. The presence of smectite clay in the sediment
contained in the effluent from the paper industry sug-
gests an anaerobic mechanism of interconversion of
either calcite or illite to smectite.
Acknowledgments This work was carried out under the Faculty
Improvement Programme of University Grants Commission, New
Delhi, India, to one of the authors (GA).
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