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J. Earth Syst. Sci. (2018) 127:119 c© Indian Academy of Scienceshttps://doi.org/10.1007/s12040-018-1020-6
Fluvial geochemistry of Subarnarekha River basin, India
Abhay Kumar Singh*, Soma Giri and Aaditya Chaturvedi
Natural Resource and Environmental Management Division, CSIR – Central Institute of Miningand Fuel Research, Barwa Road, Dhanbad 826 015, India.*Corresponding author. e-mail: [email protected]
MS received 25 July 2017; revised 30 January 2018; accepted 12 March 2018; published online 26 October 2018
The fluvial geochemistry of the Subarnarekha River and its major tributaries has been studied ona seasonal basis in order to assess the geochemical processes that explain the water compositionand estimate solute fluxes. The analytical results show the mildly acidic to alkaline nature of theSubarnarekha River water and the dominance of Ca2+ and Na+ in cationic and HCO−
3 and Cl− inanionic composition. Minimum ionic concentration during the monsoon and maximum concentrationin the pre-monsoon seasons reflect concentrating effects due to decrease in the river discharge andincrease in the base flow contribution during the pre-monsoon and dilution effects of atmosphericprecipitation in the monsoon season. The solute acquisition processes are mainly controlled by weatheringof rocks, with minor contribution from marine and anthropogenic sources. Higher contribution ofalkaline earth (Ca2++ Mg2+) to the total cations (TZ+) and high (Na++K+)/Cl−, (Na++K+)/TZ+,HCO−
3 /(SO2−4 +Cl−) and low (Ca2++Mg2+)/(Na++K+) equivalent ratios suggest that the Subarnarekha
River water is under the combined influence of carbonate and silicate weathering. The river water isundersaturated with respect to dolomite and calcite during the post-monsoon and monsoon seasonsand oversaturated in the pre-monsoon season. The pH–log H4SiO4 stability diagram demonstrates thatthe water chemistry is in equilibrium with the kaolinite. The Subarnarekha River annually delivered1.477 × 106 ton of dissolved loads to the Bay of Bengal, with an estimated chemical denudation rateof 77 ton km−2 yr−1. Sodium adsorption ratio, residual sodium carbonate and per cent sodium valuesplaced the studied river water in the ‘excellent to good quality’ category and it can be safely used forirrigation.
Keywords. Subarnarekha River basin; weathering; solute acquisition; dissolved flux; saturation index;water quality.
1. Introduction
Water is the most essential natural resource forsustaining all forms of life, food production, eco-nomic development and general well-being. Wateris also one of the most manageable naturalresources as it can be diverted, transported, storedand recycled. India accounts for 2.4% of the global
land and 4% of the world water resources, but it hasto support 16% of the world’s human and 20% oflivestock populations (Kumar et al. 2005). Riversare the major source of fresh water for agricul-tural and industrial usage. River processes forma major link in the geochemical cycle and thehydro-chemical study of river basins reveals thenature of weathering at a basin scale and helps
1
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119 Page 2 of 22 J. Earth Syst. Sci. (2018) 127:119
in understanding the exogenic cycling of elementsin the continent–river–ocean system. Nearly 90%of the natural weathered as well as man-madematerials that are transported in both dissolvedand particulate phases are delivered to the oceansby rivers (Meybeck 1987, 2003). The quantifica-tion of the major-ion composition of river waterhas broad implications in assessing the hydrogeo-logical characteristics; weathering processes, waterquality type and rainfall chemistry (Drever 1988;Gaillardet et al. 1999; Brennan and Lowenstein2002). In addition, information on river waterchemistry is essential to assess the water qual-ity for domestic, agricultural and industrial usesand useful in environmental impact assessment andpollution control. India is gifted with a river sys-tem comprising more than 20 major rivers withseveral smaller river basins and its tributaries.Many of these rivers are perennial and some ofthem are seasonal (Rao 1975). The rivers of Indiadrain a total area of about 3.1×106 km2 andannually discharge 1650 km3 of water, accountingfor 4.5% of the global river discharge (Krish-naswami and Singh 2005). The hydrological cyclein most of the Indian river basins is being mod-ified quantitatively and qualitatively as a resultof developmental activities such as constructionof dams and reservoirs; land use change; indis-criminate disposal of anthropogenic, industrial andmining wastes; unplanned application of agro-chemicals and discharges of improperly treatedsewage/industrial effluents (Chakrapani and Sub-ramanian 1990; Ramanathan et al. 1994; Singh andHasnain 1999; Subramanian 2000).
Previous studies have revealed the major-ionchemistry of some of the world’s large- andmedium-sized river systems including the Amazon(Gibbs 1972; Stallard and Edmond 1983, 1987;Gaillardet et al. 1997), Orinoco (Nemeth et al.1982), Mackenzie (Reeder et al. 1972), Missis-sippi (Presley et al. 1980), Mekong (Carbonneland Meybeck 1975), Changjiang and Huanghe(Hu et al. 1982; Zhang et al. 1990, 1995; Chenet al. 2002), Ganges–Brahmaputra (Abbas andSubramanian 1984; Sarin et al. 1989; Galy andFrance-Lanord 1999), Godavari (Biksham and Sub-ramanian 1988; Jha et al. 2009), Krishna (Rameshand Subramanian 1988; Das et al. 2005), Cau-very (Ramanathan et al. 1994; Pattanaik et al.2013), Mahanadi (Chakrapani and Subramanian1990); Damodar (Singh and Hasnain 1999) andMahi (Sharma et al. 2012). These extensive stud-ies not only reported the signatures of river systems
responding to natural processes, such asatmospheric precipitation and chemical weather-ing, but also detected the significant signaturesresponding to human activities. The chemical com-position of river water is determined by sev-eral factors such as relief and altitude of thecatchment, tectono-climatic setup, rainfall quan-tity and quality, bedrock geology, soil and vegeta-tion cover, biological and anthropogenic activitiesin the drainage basin (Berner and Berner 1987;Stallard and Edmond 1987; Rajamani et al. 2009).In comparison to large rivers, the smaller riversinvariably flow in less diverse geological terrains,having limited tectono-climatic variations and theeffect of human interventions could be better con-strained in a smaller river basin. The presentstudy deals with the fluvial geochemistry of theSubarnarekha River basin – a moderate size rain-fed river of eastern India flowing through India’simportant mining and industrial belt. This studyaims to characterise the major-ion chemistry andevaluates weathering and solute acquisition pro-cesses and anthropogenic influences on the surfacewater quality of the Subarnarekha River. Thisstudy also envisages the seasonal and downstreamcompositional changes, dissolved fluxes and suit-ability of surface water resources for irrigationuses.
2. Subarnarekha River basin
The Subarnarekha is a moderate sized river basin,extending over 19,296 km2 and covering 0.6% ofthe geographical area of India. The total annualyield of water flowing within the basins is inthe order of 7940 million m2 (CBPCWP 1986).It is a rain-fed river that rises from a seriesof contact springs located near the Nagri village(23◦18′N, 85◦11′E) at an elevation of 740m onthe Ranchi Plateau in Chhota Nagpur highland(figure 1). The Subarnarekha empties its enor-mous volume of water and sediment load intothe Bay of Bengal after its 395 km long jour-ney from its source at Nagri village to its mouthnear Kirtania port (21◦33′18′′N, 87◦23′31′′E). Outof its total length of 395 km, 269 km are in Jhark-hand, 64 km in West Bengal and 62 km in Odissastates. The Subarnarekha is a very important riverto satisfy the irrigation, industrial and munici-pal water demands of these three states. Raru,Kanchi, Karkari, Kharkai and Dulung are themajor tributaries of the Subarnarekha River.
J. Earth Syst. Sci. (2018) 127:119 Page 3 of 22 119
Figure 1. Location map of Subarnarekha River basin showing sampling locations, major mines, minerals and industrialzones.
The major part of the Subarnarekha basin lieson the Indian Shield, where the ancient Precam-brian igneous and metamorphic rocks are exposed.In the lower reaches of the basin, the youngergeological formation such as Tertiary Gravels,Pleistocene Alluvium and Recent Alluvium areexposed. Pelitic schist, calc-magnesium metased-iments, ortho-amphibolites, tonalite-trondhjemite,banded iron formation, mafic lavas, phyllites,shales, metapellites, quartzites, soda-granites,granitic-gneiss, dolerite dyke swarms and gravelsare the major litho units associated with the geo-logical formations of the basin. The Subarnarekhabasin is rich in mineral resources mainly compris-ing ores of metals such as copper, iron, uranium,chromium, gold, and vanadium and non-metalssuch as kyanite, asbestos, barytes, apatite, chinaclay, talc, limestone, dolomite and building stones(figure 1). The basin is studded with a largenumber of mineral-based industries and mines
both working and abandoned with the attendantproblems of environmental hazard. Heavy Engi-neering Corporation (HEC), Usha Martin Indus-tries, Steel Authority of India (SAIL), HindalcoIndustries Ltd., Tata Steel and Iron Company,Hindustan Copper Ltd. (HCL) and Uranium Cor-poration of India (UCIL) are the major industrialunits in the basin.
The Subarnarekha basin is dominated by humidtropical climate with hot summers and mild win-ters. The mean monthly temperature varies from40.5◦C in May to 9.0◦C in December. The meanannual rainfall in the basin is ∼1400 mm. Therainfall distribution is not uniform and 85–95%of the annual precipitation and about 82% ofthe total annual flow actually occurs over onlyfour wet months (June–September), while in theremaining part of the year, the Subarnarekha Riverand its tributaries run almost dry. Agriculturalland accounts for 62% of the total basin area
119 Page 4 of 22 J. Earth Syst. Sci. (2018) 127:119
Table
1.Chem
icalcompositionofsurface
waterofSubarn
arekhaRiver
anditsmajortributaries.
Sit
eco
de
Sit
enam
e/tr
ibuta
rypH
EC
(µS
cm−1)
TD
S(m
gl−
1)
F−
(µM
)C
l−(µ
M)
HC
O− 3
(µM
)SO
2−
4(µ
M)
NO
− 3(µ
M)
Silic
a(µ
M)
Subarn
are
khamain
channel
1a
Nagri
6.2
6116
87
12
274
533
22
154
187
b6.3
3138
99
16
305
590
25
189
232
c6.2
090
71
997
464
11
124
210
2a
Nam
kum
7.2
0570
427
18
1260
3623
149
186
392
b7.5
71000
645
27
3179
5229
256
4198
c7.0
8408
305
23
1175
1934
154
420
292
3a
Tati
silw
ai
6.7
2499
404
13
1817
2547
142
529
362
b7.3
81220
847
23
5802
5016
196
963
387
c6.9
5431
309
22
1533
1770
155
404
298
4a
Hundru
7.9
1183
157
19
229
1443
68
17
280
b8.0
0265
212
22
865
1557
95
9312
c7.8
5167
136
17
327
1213
61
9210
5a
Muri
7.7
2216
176
16
284
1600
96
28
284
b7.9
3762
599
65
1424
5000
629
38
323
c8.1
5190
129
22
555
902
97
36
135
6a
Chandil
8.2
5165
135
18
133
1229
56
10
320
b7.6
9177
154
31
177
1439
52
12
280
c8.0
9119
95
23
97
820
52
17
228
7a
Bara
bin
da
7.9
8162
140
21
131
1311
55
34
293
b8.1
9190
162
28
170
1500
48
30
315
c7.6
2125
100
22
92
852
57
27
230
8a
Kander
ber
a7.9
7154
134
55
141
1229
62
10
252
b8.5
4185
154
28
167
1500
44
2243
c8.0
8143
118
21
101
1066
70
22
228
9a
Jam
shed
pur
(Sonari
)7.7
2290
254
17
281
2459
131
28
343
b7.3
1221
187
22
272
1744
86
11
288
c7.7
9190
162
19
168
1475
91
28
256
10
aJam
shed
pur
(Mango)
7.6
2249
206
18
258
1956
93
23
355
b7.5
3216
190
20
279
1744
67
37
315
c7.8
2209
156
20
211
1311
113
59
256
11
aG
alu
dih
7.8
0395
340
37
581
2295
729
17
332
b7.5
1259
208
46
486
1672
151
37
278
c7.9
4163
138
24
150
1229
79
46
213
12
aM
oosa
baniU
/S
8.1
7293
246
26
316
2131
273
25
258
b8.7
3305
244
48
587
1744
347
1302
c7.8
4261
193
23
236
1311
423
52
218
J. Earth Syst. Sci. (2018) 127:119 Page 5 of 22 11913
aM
oosa
baniD
/S
8.1
4313
262
21
312
2377
265
26
248
b7.5
1297
227
48
574
1639
279
1315
c7.7
8186
150
23
223
1279
90
81
224
14
aShyam
sunder
pur
8.3
9249
210
39
301
1885
184
25
257
b7.7
9293
249
45
535
2016
240
34
280
c7.7
2174
143
23
164
1246
92
50
229
15
aB
ahara
gora
8.0
2238
209
19
275
1836
182
17
293
b7.6
5285
223
52
558
1621
247
19
315
c8.1
1165
137
22
188
1180
85
46
229
16
aG
opib
allav
pur
7.9
2227
201
33
253
1803
152
14
303
b8.3
8279
236
49
552
1852
229
18
290
c8.0
0168
137
22
131
1229
82
24
233
17
aM
ahapal
7.6
0304
275
17
259
2852
92
4280
b8.0
2283
227
44
531
1805
206
14
287
c7.7
8176
139
24
161
1262
64
22
235
18
aSonaka
niy
a7.9
1219
189
18
218
1718
121
7340
b8.9
3249
198
45
480
1500
190
7303
c8.0
3158
131
25
128
1213
70
16
221
19
aR
ajg
hat
7.8
3229
197
16
236
1803
126
23
321
b8.6
6246
221
44
406
1885
184
34
307
c8.2
0156
139
23
127
1279
74
16
249
Tributa
ries
20
aK
anch
i7.7
4165
140
15
122
1311
40
11
327
b7.8
9207
177
23
248
1623
57
14
305
c7.7
7148
118
20
346
869
58
18
270
21
aK
hark
ari
7.8
3198
174
14
384
1475
82
18
307
b8.0
2294
256
15
550
2361
70
20
342
c7.6
5186
163
16
344
1410
55
35
263
22
aK
hark
hai
7.8
7319
280
23
307
2705
146
46
338
b8.6
5566
453
28
1408
3449
376
197
375
c7.7
3231
197
18
234
1770
128
36
263
23
aG
arr
a7.6
0504
410
43
700
2623
943
23
326
b7.7
0803
585
57
2202
1621
2172
37
372
c7.8
7291
229
24
283
1836
336
19
254
24
aSankh
7.8
0253
219
34
118
2192
86
2377
b8.7
7315
247
48
518
1787
325
18
318
c7.9
7175
141
19
85
1295
73
13
305
119 Page 6 of 22 J. Earth Syst. Sci. (2018) 127:119
Table
1.(C
ontinued.)
Sit
eco
de
Sit
enam
e/tr
ibuta
ryC
a2+(µ
M)
Mg2+(µ
M)
Na+(µ
M)
K+(µ
M)
SA
R(m
eq)
%N
aR
SC
(meq
)T
Z−
(meq
)T
Z+(m
eq)
NIC
B(%
)
Subarn
are
khamain
channel
1a
Nagri
188
102
406
54
0.7
644.3
−0.0
51.0
21.0
41.1
b203
118
441
58
0.7
843.7
−0.0
51.1
51.1
4−
0.4
c178
91
244
53
0.4
735.6
−0.0
70.7
20.7
95.0
2a
Nam
kum
1347
342
1687
278
1.3
036.8
0.2
45.3
85.3
4−
0.4
b1746
541
3230
492
2.1
444.9
0.6
58.9
58.2
9−
3.8
c1025
293
1208
268
1.0
535.9
−0.7
03.8
64.1
13.2
3a
Tati
silw
ai
1537
330
1601
239
1.1
733.0
−1.1
95.1
95.5
73.6
b3229
576
3209
419
1.6
532.3
−2.5
912.2
011.2
4−
4.1
c1111
284
1233
209
1.0
434.1
−1.0
24.0
44.2
32.3
4a
Hundru
440
214
449
66
0.5
628.2
0.1
31.8
41.8
2−
0.6
b672
232
910
114
0.9
636.1
−0.2
52.6
42.8
33.4
c384
170
371
69
0.5
028.4
0.1
01.6
91.5
5−
4.3
5a
Muri
475
204
578
76
0.7
032.5
0.2
42.1
22.0
1−
2.6
b420
301
5713
127
6.7
380.2
3.5
57.7
87.2
8−
3.3
c297
171
615
107
0.9
043.6
−0.0
41.7
11.6
6−
1.5
6a
Chandil
381
172
365
45
0.4
927.0
0.1
21.5
01.5
20.5
b482
200
472
42
0.5
727.4
0.0
71.7
61.8
83.2
c272
129
273
31
0.4
327.5
0.0
21.0
61.1
12.1
7a
Bara
bin
da
378
174
391
46
0.5
328.4
0.2
01.6
11.5
4−
2.1
b520
213
448
46
0.5
225.2
0.0
31.8
21.9
63.6
c319
137
259
37
0.3
824.5
−0.0
61.1
11.2
14.5
8a
Kander
ber
a395
189
393
45
0.5
127.3
0.0
61.5
61.6
11.5
b509
205
418
44
0.4
924.4
0.0
71.7
81.8
92.8
c384
185
262
31
0.3
520.5
−0.0
81.3
51.4
32.9
9a
Jam
shed
pur
(Sonari
)758
403
725
58
0.6
725.2
0.1
33.0
53.1
10.9
b591
247
548
61
0.6
026.7
0.0
62.2
22.2
81.4
c472
300
495
48
0.5
626.0
−0.0
71.8
72.0
95.4
10
aJam
shed
pur
(Mango)
557
268
623
62
0.6
929.3
0.3
02.4
42.3
4−
2.2
b599
246
595
55
0.6
527.8
0.0
52.2
12.3
42.7
c462
282
467
61
0.5
426.2
−0.1
81.8
32.0
14.8
11
aG
alu
dih
1050
626
1176
79
0.9
127.2
−1.0
74.3
94.6
12.4
b652
248
782
117
0.8
233.3
−0.1
32.5
42.7
02.9
c501
182
327
58
0.4
022.0
−0.1
41.6
11.7
54.3
12
aM
oosa
baniU
/S
816
406
679
76
0.6
123.6
−0.3
23.0
43.2
02.5
b769
300
947
127
0.9
233.4
−0.4
03.0
73.2
12.2
c661
301
470
80
0.4
822.2
−0.6
22.4
72.4
70.1
J. Earth Syst. Sci. (2018) 127:119 Page 7 of 22 11913
aM
oosa
baniD
/S
885
423
635
90
0.5
621.7
−0.2
53.2
73.3
41.1
b750
289
805
123
0.7
930.9
−0.4
42.8
23.0
13.2
c546
192
359
47
0.4
221.6
−0.2
01.7
91.8
82.7
14
aShyam
sunder
pur
631
255
631
77
0.6
728.5
0.1
12.6
22.4
8−
2.7
b777
310
879
137
0.8
431.8
−0.1
63.1
13.1
91.3
c519
177
342
52
0.4
122.0
−0.1
51.6
71.7
93.4
15
aB
ahara
gora
616
391
585
71
0.5
824.6
−0.1
82.5
12.6
73.0
b654
293
886
145
0.9
135.3
−0.2
82.7
42.9
23.1
c489
202
324
22
0.3
920.0
−0.2
11.6
11.7
33.7
16
aG
opib
allav
pur
594
376
551
59
0.5
623.9
−0.1
42.4
12.5
52.9
b714
295
923
139
0.9
234.5
−0.1
72.9
33.0
82.5
c504
182
323
29
0.3
920.4
−0.1
51.5
71.7
24.6
17
aM
ahapal
836
552
735
49
0.6
222.0
0.0
73.3
23.5
63.5
b670
308
896
127
0.9
134.4
−0.1
62.8
12.9
83.0
c490
212
331
44
0.3
921.1
−0.1
41.6
01.7
85.3
18
aSonaka
niy
a559
342
481
51
0.5
122.8
−0.0
92.2
02.3
32.9
b593
277
752
107
0.8
133.1
−0.2
52.4
12.6
03.8
c439
190
330
40
0.4
222.7
−0.0
51.5
21.6
33.4
19
aR
ajg
hat
536
362
537
65
0.5
725.1
0.0
02.3
32.4
01.4
b614
284
779
90
0.8
232.6
0.0
92.7
42.6
6−
1.4
c484
201
327
42
0.4
021.2
−0.0
91.5
91.7
44.4
Tributa
ries
20
aK
anch
i377
191
478
10
0.6
330.0
0.1
71.5
41.6
22.7
b482
210
750
51
0.9
036.7
0.2
42.0
22.1
93.9
c337
166
452
44
0.6
433.0
−0.1
41.3
71.5
04.7
21
aK
hark
ari
454
370
584
54
0.6
427.9
−0.1
82.0
52.2
95.3
b761
428
851
77
0.7
828.1
−0.0
23.0
93.3
13.4
c504
314
513
46
0.5
725.5
−0.2
31.9
12.2
06.8
22
aK
hark
hai
908
529
644
59
0.5
419.6
−0.1
83.3
73.5
82.9
b1394
540
1889
219
1.3
635.3
−0.4
35.8
35.9
81.2
c748
282
484
42
0.4
820.3
−0.2
92.3
12.5
95.5
23
aG
arr
a1567
711
1279
79
0.8
523.0
−1.9
45.2
85.9
15.7
b2306
478
2665
220
1.6
034.1
−3.9
58.2
68.4
51.2
c816
374
624
46
0.5
722.0
−0.5
52.8
33.0
53.6
24
aSankh
696
490
369
36
0.3
414.6
−0.1
92.5
22.7
84.9
b816
359
942
99
0.8
730.7
−0.5
73.0
23.3
95.8
c470
258
271
29
0.3
217.1
−0.1
71.5
61.7
66.0
Unit
s:C
once
ntr
ati
ons
are
inµM
l−1,ex
cept
pH
,E
C(µ
Scm
−1),
TD
S(m
gl−
1)
TZ+
(meq
l−1),
TZ−
(meq
l−1)
and
NIC
B(%
).
EC
,el
ectr
icalco
nduct
ivity;T
DS,to
taldis
solv
edso
lids;
TZ+,to
talca
tions;
TZ−
,to
talanio
ns;
NIC
B,norm
alise
din
org
anic
charg
ebala
nce
;a,post
-monso
on
(Sep
tem
ber
2011);
b,pre
-monso
on
(May
2012);
c,m
onso
on
(July
2012).
119 Page 8 of 22 J. Earth Syst. Sci. (2018) 127:119
and nearly 31% of the area is devoted to forests.A number of dams/reservoirs (Getasuld, Hatia,Chandil, Galudih) have been constructed on theSubarnarekha and its tributaries mainly for thepurpose of electricity generation, flood control andirrigation.
3. Methodology
Seventy-two water samples were collected from 24sites along the Subarnarekha River and its majortributaries during the post-monsoon (September2011), pre-monsoon (May 2012) and monsoon(July 2012) seasons (figure 1). The sampling sea-sons were selected according to the hydrologicalregime in the basin. The samples were mostlycollected from the middle of the river, eitherfrom the bridge or with the help of a boat toavoid local heterogeneity and possible human influ-ence near the river banks. Water samples werecollected in the pre-washed narrow mouth 1-lhigh-density polyethylene bottles. Electrical con-ductivity (EC) and pH values were measured inthe field using a portable conductivity and pHmeter after recalibration with the standard buffersolutions. The water samples were filtered through0.45µm Millipore membrane filter to separate thesuspended particulates. The concentration of bicar-bonate (HCO−
3 ) and dissolved silica (SiO2) weredetermined by acid titration and molybdosilicatemethods, respectively (APHA 1998). The concen-tration of major F−, Cl−, SO2−
4 and NO−3 were
analysed by Dionex ion chromatograph (DX-120)using anions AS12A/AG12 columns. The majorcations (Ca2+, Mg2+, Na+, K+) were determinedby atomic absorption spectrophotometer (Varian680 FS) in flame mode. Three replicates were runfor each sample and the instrument was recali-brated after every 15 samples analysis. An overallprecision, expressed as per cent relative standarddeviation, was obtained below 5% for the entiresamples. Total cations (TZ+) and anions (TZ−)are coupled by the relation TZ+ = 0.947 × TZ− ±0.237 with a correlation coefficient of 0.989 andthe normalised inorganic charge balance (NICB)is within ±10% (table 1). USGS hydrogeochemicalsoftware (PHREEQC) is used for the estimationof saturation index values of carbonate mineralphases (Parkhurst and Appelo 1999). Aquachemand Grapher software of Waterloo Hydrologic havebeen used for Piper diagram and other graphicalpresentation.
Water quality parameters such as sodiumadsorption ratio (SAR), per cent sodium (%Na)and residual sodium carbonate (RSC) were com-puted to assess the suitability of the SubarnarekhaRiver basin water for irrigation by the followingequations:
SAR = Na+/√(
Ca2+ + Mg2+)/2, (1)
%Na = Na + K/ (Ca + Mg + Na + K) × 100, (2)
RSC =(CO2−
3 + HCO−3
) − (Ca2+ + Mg2+
). (3)
(All ionic concentrations used for the calculationare expressed in meq l−1.)
4. Results and discussion
4.1 Fluvial geochemistry
The analytical results of surface water samplesof the Subarnarekha River and its major tribu-taries during the post-monsoon, pre-monsoon andmonsoon seasons are given in table 1. Table 2shows the range and average concentration of themeasured parameters and ionic ratios in the Sub-arnarekha River water during the post-monsoon,pre-monsoon and monsoon seasons.
The pH of the Subarnarekha River water var-ied from 6.20 (mildly acidic) to 8.93 (alkaline),with most samples falling within a range of 7.0–8.0. The pH was slightly higher during the leanflow pre-monsoon (avg. 7.95) period as comparedto the high flow regimes of monsoon (7.74) andpost-monsoon (7.75). The water was slightly acidicin nature at the Nagri site, which might be dueto comparatively more organic loading near theorigin site of the Subarnarekha River. EC var-ied from 116 to 570µS cm−1 in post-monsoon,138 to 1220 µS cm−1 in pre-monsoon and 90 to431µS cm−1 during the monsoon season. On anaverage, the lowest EC is observed during themonsoon (196µS cm−1) and the highest in the pre-monsoon (377µS cm−1), while the post-monsoonseason is characterised by an intermediate value(271µS cm−1). Total dissolved solids (TDS) inthe Subarnarekha basin water ranged from 71 to847 mg l−1 with an average concentration valueof 225 mg l−1. The low TDS value is observednear the river origin site at Nagri village andit increases randomly at the downstream sites.Like EC, TDS concentration was relatively higher
J. Earth Syst. Sci. (2018) 127:119 Page 9 of 22 119
Table
2.Range
andaverage
concentrationofmeasuredparametersandmajor-ionratiosin
Subarn
arekhaRiver
basinwaterforpost-m
onsoon,pre-m
onsoonandmonsoon
seasons.
Aver
age
(n=
72)
Post
-monso
on
(n=
24)
Pre
-monso
on
(n=
24)
Monso
on
(n=
24)
Para
met
ers
Range
Aver
age
±Std
.dev
.R
ange
Aver
age
±Std
.dev
.R
ange
Aver
age
±Std
.dev
.R
ange
Aver
age
±Std
.dev
.
pH
6.2
0–8.9
37.8
1±
0.5
16.2
6–8.3
97.7
5±
0.4
66.3
3–8.9
37.9
5±
0.6
6.2
0–8.2
27.7
4±
0.4
4
EC
(µS
cm−1)
90–1220
282
±195
116–570
271
±117
138–1220
377
±282
90–431
196
±81
TD
S(m
gl−
1)
71–847
225
±136
87–427
228
±91
99–847
292
±190
71–309
156
±57
F−
(µM
)9–65
27
±13
12–55
23
±11
15–65
36
±14
9–25
21
±3
Cl−
(µM
)85–5802
536
±822
118–1817
383
±389
167–5802
928
±1254
85–1533
298
±347
HC
O− 3
(µM
)464–5229
1792
±904
533–3623
1956
±667
590–5229
2162
±1222
464–1934
1259
±343
SO
2−
4(µ
M)
11–2172
187
±285
22–943
179
±214
25–2172
274
±428
11–423
107
±91
NO
− 3(µ
M)
0.8
1–963
65
±143
2.4
0–529
53
±110
0.8
1–963
73
±196
8.5
–420
67
±109
SiO
2(µ
M)
135–392
283
±52
187–392
307
±47
198–387
303
±43
135–305
239
±35
Ca2+
(µM
)178–3229
699
±476
188–1567
708
±363
203–3229
872
±673
178–1111
517
±221
Mg2+
(µM
)91–711
294
±130
102–711
351
±154
118–576
312
±118
91–374
220
±70
Na+
(µM
)200–5713
808
±831
365–1687
691
±368
418–5713
1280
±1246
200–1233
453
±261
K+
(µM
)10–492
92
±84
10–278
76
±59
42–492
135
±110
22–268
64
±57
TZ−
(meq
)0.7
2–12.2
02.7
9±
1.9
41.0
2–5.3
82.7
7±
1.2
21.1
5–12.2
03.7
5±
2.7
70.7
2–4.0
41.8
6±
0.7
7
TZ+
(meq
)0.7
9–11.2
42.8
8±
1.8
51.0
4–5.9
12.8
8±
1.3
31.1
4–11.2
43.7
8±
2.5
30.7
8–4.2
31.9
9±
0.8
2
NIC
B(%
)−4
.3-6
.83
2.2
0±
2.5
8−2
.71−5
.69
1.6
0±
2.4
1−4
.09–5.7
71.7
3±
2.5
7−4
.30–6.8
33.2
7±
2.5
7
Ionic
ratios
Na+
+K
+/C
l−0.6
3–4.1
02.2
6±
0.7
21.0
1–4.0
2.4
6±
0.6
60.6
3–4.1
02.0
2±
0.7
50.9
4–3.5
52.3
1±
0.7
1
*C
a2+/N
a+
0.0
7–1.8
81.0
3±
0.3
30.4
6–1.8
81.0
4±
0.2
70.0
7–1.2
20.8
2±
0.2
40.4
8–1.7
31.2
3±
0.3
3
*M
g2+/N
a+
0.0
5–1.3
30.4
7±
0.2
00.2
0–1.3
30.5
5±
0.2
30.0
5–0.5
60.3
3±
0.1
10.2
3–0.9
50.5
4±
0.1
6
*H
CO
− 3/N
a+
0.6
1–5.9
42.7
8±
0.9
61.3
1–5.9
43.0
8±
0.9
40.6
1–4.5
92.1
3±
0.7
31.4
4–4.7
83.1
2±
0.8
7
(Ca2+
+M
g2+)/
HC
O− 3
0.2
9–3.4
31.1
2±
0.3
90.8
4–1.7
41.0
6±
0.2
20.2
9–3.4
31.1
5±
0.5
30.9
1–1.5
71.1
5±
0.8
0
(Ca2+
+M
g2+)/
TZ+
0.2
0–0.8
50.7
1±
0.0
90.5
6–0.8
50.7
3±
0.0
60.2
0–0.7
60.6
5±
0.1
10.5
6–0.8
30.7
5±
0.0
6
(Ca2+
+M
g2+)/
Na+
+K
+0.2
5–5.8
52.6
9±
0.9
11.2
6–5.8
52.8
9±
0.9
00.2
5–3.0
92.0
5±
0.6
01.3
0–4.8
63.1
3±
0.8
6
(Na+
+K
+)/
TZ+
0.1
5–0.8
00.2
9±
0.0
90.1
5–0.4
40.2
7±
0.0
60.2
4–0.8
00.3
5±
0.1
10.1
7–0.4
40.2
5±
0.0
6
*H
CO
− 3/SiO
22.2
1–26.4
66.2
9±
3.1
72.8
5–10.1
96.3
2±
1.8
92.5
5–26.4
67.2
7±
4.9
02.2
1–7.2
25.2
6±
1.1
8
Ca2+/SO
2−
40.6
7–16.9
05.9
4±
3.1
31.4
4–10.8
55.8
0±
2.5
10.6
7–16.5
05.8
8±
4.0
11.5
6–16.9
06.1
4±
2.8
0
Ionic
rati
oin
equiv
ale
nt
unit
,ex
cept
*m
ola
rra
tio.
119 Page 10 of 22 J. Earth Syst. Sci. (2018) 127:119
in the pre-monsoon (292 mg l−1) as comparedto the post-monsoon (228 mg l−1) and monsoon(156 mg l−1) seasons. Seasonal variation of EC andTDS values indicates an increase in ionic concen-trations during the pre-monsoon season, probablydue to excessive evaporation and/or contributionfrom the groundwater in the summer months anddilution effects of atmospheric precipitation in themonsoon season. The elevated temperature in thehot summer months increases water evaporationand causes a reduction in river flow, resultingin an enhancement in solute concentration. Spa-tial variations in ionic concentration show a sharpincrease at the Namkum–Tatisilwai–Muri indus-trial zone (sites 2, 3 and 5) and for the Garratributary (T-4). Namkum, Tatisilwai and Muriare under the influence of industrial activities.Huge quantities of industrial and urban effluentsare discharged into the Kharkai and the mainSubarnarekha River at these locations. TributaryGarra receives highly polluted water and effluentswith high sulphate contents and has high con-centration of total suspended and dissolved solidsmainly in the Jaduguda–Ghatsila mining complexareas.
HCO−3 , Ca2+, Na+ and dissolved silica account
for >75% of the total dissolved loads and domi-nate the major-ion chemistry of the SubarnarekhaRiver water. The HCO−
3 was the most domi-nant anion in the surface water of the Sub-arnarekha River followed by Cl−, SO2−
4 , NO−3
and F−. The major anions constitute 65% ofthe TDS. The plot of the analytical data onanion diagram relating HCO−
3 , Cl− and SO2−4
shows the clustering of plotted points near theHCO−
3 apex with a secondary trend towards Cl−
and SO−24 (figure 2a). Bicarbonate concentration
ranged from 464 to 5229µM with an averagevalue of 1792µM and it contributed 69% (20–87%) to the total anionic (TZ−) charge balancein equivalent unit. Bicarbonate in river water ismainly contributed from the dissolution of atmo-spheric CO2 and weathering of carbonates and/orsilicate minerals by the carbonic acid. The CO2
in the subsurface environment is mainly origi-nated from the decomposition of organic matter,which in turn combines with rainwater to formbicarbonates.
Chloride (Cl−) concentration in the analysedwater samples of the Subarnarekha River rangedfrom 85 to 5802µM (avg. 536µM) and it accountsfor 16% of the total anionic charge (TZ−). Excepthalite, most of the rock types contain very low
Figure 2. (a) Ternary anion diagram relating HCO3, SO4
and Cl and (b) ternary cation diagram relating Ca, Mg and(Na + K).
concentration of chloride and it is believed that themajor portion of Cl− in water is primarily derivedfrom either the atmospheric source or the sea water(Berner and Berner 1987). Leaching of salt andsaline residues in the soil, municipal, industrial,animal wastes and usage of fertiliser also plays avital role as the source of chloride (Appelo andPostma 1996; Singh et al. 2008). Large spatialvariations and increased chloride concentrations atsites W-2, W-3 and W-23 may be attributed toanthropogenic sources. The concentration of SO2−
4
and NO−3 in the surface water of the Subarnarekha
River basin was found in the range of 11–2172and 0.81–963 µM and it accounted for 12% and2.3% of the total anionic charge (TZ−) balance,respectively. Relatively the higher concentration ofnitrate at Namkum (W-2) and Tatisilwai (W-3)sites indicates the anthropogenic contribution from
J. Earth Syst. Sci. (2018) 127:119 Page 11 of 22 119
1
10
100
1000
10000
Con
cent
ratio
n in
µM
, exc
ept E
C (µ
S/cm
) and
pH
pH EC TDS F- Cl- HCO3- SO4
2- NO3- SiO2 Ca2+ Mg2+ Na+ K+
Post-monsoonPre-monsoonMonsoon
Measured Parameters
Figure 3. Average concentration of measured parameters in Subarnarekha basin water.
the leaching of fertiliser from agricultural fields.The concentration of F− varied from 9 to 65µM(avg. 27µM) and on an average it contributed 1.2%to the total anions (TZ−).
Ca2+, Mg2+, Na+ and K+ together constitute25% of the TDS. Calcium was the most dom-inant cation in the water of the SubarnarekhaRiver, contributing 49% of the total cations (TZ+)followed by Na+ (26%), Mg2+ (22%) and K+ (3%).The calcium concentration ranged from 178 to3229µM, while the concentration of Na+ var-ied from 200 to 5713µM. The concentration ofMg2+ and K+ ranged from 91 to 711 and 10 to492µM, respectively, with an average value of 294and 92µM. Ca2+ and Mg2+ together account forabout 71% of the total cationic charge balance inthe equivalent unit. The cation concentration inthe Subarnarekha basin water generally followedthe decreasing order of Ca2+ >Na+>Mg2+ >K+
with some minor exceptional samples, where Na+
concentration was found to be higher than theCa2+ or Mg2+ exceeding the Na+ concentration.The plot of the analytical data on cation dia-gram relating Ca2+, Mg2+ and (Na+ + K+) showsthat the plotted points of the water samplesfall either in the ‘calcium’ or in ‘no dominant’zone (figure 2b). Dissolved silica (SiO2) concen-tration in the Subarnarekha River water variedfrom 187 to 392µM during the post-monsoon,198 to 387 µM in the pre-monsoon and 135 to305µM in the monsoon (table 2). On average,
the dissolved silica accounted for 9% (2–19%)of the TDS and it exceeds the chloride andsulphate concentrations at many sites. The aver-age concentration of dissolved silica (283µM) inthe studied river water is higher than the aver-age global (200µM) and Indian (117µM) rivers(Ramanathan et al. 1994). The higher concentra-tion of dissolved silica in the Subarnarekha Riverreflects the important contribution from the weath-ering of silicate rocks. The average HCO3/SiO2
molar ratio for the Subarnarekha and its tribu-taries vary between 2 and 26 (avg. 6.3); however,in a majority of samples it ranges between 5 and10, indicating the combined influence of carbonateand silicate weathering (Hounslow 1995). The highHCO3/SiO2 ratio (>10) in some water samplescan result from the supply of alkalinity from car-bonates, salt affected soils and/or anthropogenicsources. No specific trend has been observed in thedownstream variation of dissolved ionic concentra-tions. In general, the temporal variation of averageconcentration of major ions on the river basin scalefollows a decreasing order of pre-monsoon>post-monsoon>monsoon (figure 3).
The trilinear Piper plot (Piper 1944) for theSubarnarekha River water reveals the dominanceof alkaline earth (Ca2+ + Mg2+) metals overalkalis (Na+ + K+) and weak acid (HCO−
3 ) overstrong acids (SO2−
4 + Cl−). The plotted points ofmajority of samples fall in the field 5, signify-ing the carbonate hardness (secondary salinity)
119 Page 12 of 22 J. Earth Syst. Sci. (2018) 127:119
1
2 3
45
6
7
8
9
9
Fields Characteristics/Nature of water
1 Alkaline earths (Ca+Mg) exceeds alkalies (Na+K)2 Alkalies exceeds alkaline earths3 Weak acids (CO3+HCO3) exceeds strong acids (SO4+Cl)4 Strong acids exceed weak acid5 Carbonate hardness (secondary alkalinity) exceeds 50%6 Non-carbonate hardness (secondary salinity) exceeds 50%7 Non carbonate alkali (primary salinity) exceeds 50%8 Carbonate alkali (primary alkalinity) exceeds 50%9 None of the cation or anion pairs exceed 50%
Post-monsoonPre-monsoonMonsoon
Figure 4. Piper trilinear diagram showing the hydrogeochemical character of river water and hydrochemical facies (afterPiper 1953).
that exceeds 50% (figure 4). Only five watersamples fall in the field 9, indicating water of anintermediate (mixed) chemical character having noone cation–anion pair exceeding 50%. Ca−HCO3
and Ca−Mg−HCO3−Cl are identified as the domi-nant hydrogeochemical facies in the surface waterof the Subarnarekha River basin.
The average chemical composition of theSubarnarekha River basin water along with someother Indian Rivers and the world and Indianaverages is summarised in table 3. The TDS con-tent of the Subarnarekha basin water is higherthan that of the Indus, Brahmaputra, Godavari,Damodar and the Indian and world average rivers,but it is lower as compared to the Krishna, Cau-very, Narmada, Tapti, Mahi and Gomti rivers andcomparable to Mahanadi, Son and Ganges aver-ages. Like other Indian rivers, the Subarnarekhahas high alkalinity, indicating the extent of mixingwith HCO3-rich groundwater and atmosphericallyregulated PCO2–water reactions, which mayfurther enhance the carbonate alkalinity. Potas-sium concentrations do not show much variation in
the Subarnarekha water as in the other river basins,suggesting conservative behaviour of this element.Berner and Berner (1987) reported that only 15%of the river transport of potassium is in the dis-solved form. The low concentration of dissolvedK in water may be attributed to the resistanceof potassium bearing minerals (orthoclase, micro-cline) against weathering. Potassium is commonlyfixed in specific clay minerals, after being releasedduring the primary weathering reactions and there-fore does not behave in the same way as the otherweathering derived ions (Stott and Burt 1997). Thehigher contributions of dissolved silica, Na+ andSO2−
4 to the TDS in comparison to the other riverbasins may be attributed to silicate weatheringand inputs from the sulphide weathering andanthropogenic sources in the drainage basin.
4.2 Weathering and solute acquisition processes
Chemical load in the river basin is consideredto be a reflection of its watershed and flood-plains and processes occurring in the tributaries
J. Earth Syst. Sci. (2018) 127:119 Page 13 of 22 119Table
3.Average
compositionofSubarn
arekhabasinwaterin
comparisonto
other
majorIndianRiver
basins.
Riv
ers
Dra
inage
are
aD
isch
arg
eM
CM
HC
O3
Cl
SO
4H
4SiO
4C
aM
gN
aK
TD
SR
efer
ence
s
Subarn
are
kha
19,2
96
7940
109
19
18
17
28
719
3.6
225
Pre
sent
study
Dam
odar
25,8
20
12,2
10
94
11
21
22
15
916
4.0
191
Sin
gh
and
Hasn
ain
(1999)
Kri
shna
258,9
48
62,8
00
178
38
49
24
29
830
2.4
360
Ram
esh
and
Subra
mania
n(1
988)
Cauver
y87,9
00
20,9
50
135
20
13
23
21
943
4.0
272
Ram
anath
anet
al.
(1994)
Godav
ari
312,8
12
118,0
00
105
17
810
22
512
3.0
181
Bik
sham
and
Subra
mania
n(1
988)
Mahanadi
141,5
89
66,6
40
122
23
317
24
13
14
8.3
224
Chakra
paniand
Subra
mania
n(1
990)
Indus
321,2
89
79,5
00
64
915
527
11
2.1
122
Subra
mania
n(1
983)
Narm
ada
98,7
95
54,6
00
225
20
59
14
20
27
2.0
322
Subra
mania
n(1
983)
Tapti
65,1
45
17,9
82
150
65
116
19
22
48
3.0
322
Subra
mania
n(1
983)
Mahi
34,8
41
11,8
00
246
38
19
21
31
17
55
2.7
436
Sharm
aet
al.
(2012)
Gom
ti30,4
37
7390
262
915
14
29
18
27
4.8
380
Gupta
and
Subra
mania
n(1
994)
Son
71,2
50
22,4
20
125
18
10
18
29
814
3227
Mahara
naet
al.
(2015)
Ganges
861,4
04
468,7
00
128
10
11
18
25
811
3.0
214
Subra
mania
n(1
983)
Bra
hm
aputr
a258,0
08
627,0
00
38
15
10
729
7.4
12
2.5
148
Subra
mania
n(1
983)
India
nav
g.
3,2
87,7
82
1,8
58,1
00
74
15
13
730
712
3.0
159
Subra
mania
n(1
983)
Worl
dav
g.
––
62
49
12
16
44.4
1.5
115
Sari
net
al.
(1989)
Unit
s:m
gl−
1.T
DS:to
taldis
solv
edso
lids;
MC
M:m
illion
m3.
(Richey et al. 1990). Berner and Berner (1996)identified three possible sources of dissolved saltinto the inland waters as (i) sea salt carried in theatmosphere and deposited on the land; (ii) weath-ering reaction taking place in the drainage basinand (iii) anthropogenic input. The proportions ofcontribution from these sources vary in space andtime, resulting in seasonal and downstream varia-tions in the chemical composition within the riverbasin. The atmospheric contribution to the dis-solved salt in the inland water has been discussedby various authors (Stallard and Edmond 1983;Sarin et al. 1989; Berner and Berner 1996). Theinput of chloride concentration through precipita-tion is generally used as a parameter for evaluatingthe atmospheric contribution. This is because ofthe fact that Cl− is regarded as a conservativeelement as it reacts very little with other ions,does not form complexes and also does not par-ticipate in the biogeochemical cycling, except insmall basins where biota plays a dominant role(Viers et al. 2001). The atmospheric contributionto the dissolved salts in the aquatic water canbe assessed by comparing the chemical compo-sition with the local rainwater chemistry or bytaking the ratios of elements to Cl− (Sarin et al.1989; Pandey et al. 1994; Singh et al. 2005). Theaverage Na+/Cl−(2.03) and K+/Cl−(0.23) ratiosin the surface water of the Subarnarekha Riverwere found to be higher as compared to marineaerosols (Na+/Cl− = 0.85 and K+/Cl− = 0.0176).This indicates a limited contribution from theatmospheric precipitation and suggests that highproportions of dissolved ions in this water arederived from the weathering of rock-formingminerals and anthropogenic sources. The plot ofgeochemical data on Gibbs’s diagram (Gibbs 1970)that represents the ratio of (Na+ + K+)/(Na++K+ + Ca2+) and Cl−/(Cl− + HCO−
3 ) as a functionof TDS also indicates the dominance of weatheringof rocks as a major controlling factor to determinethe surface water chemistry of the Subarnarekhabasin (figure 5).
Weathering of different parent rocks (e.g.,carbonates, silicates and evaporites) yields differentcombinations of dissolved cations and anions in thewater (Drever 1988; Berner and Berner 1996). Forinstance, calcium and magnesium in the river waterare mainly derived from the weathering of carbon-ate and silicate minerals and evaporite dissolution.Silicate weathering along with evaporite dissolu-tion and atmospheric precipitation are the majorsources of sodium and potassium in the river water.
119 Page 14 of 22 J. Earth Syst. Sci. (2018) 127:119
Weathering Dominance
Evaporation Dominance
Precipitation Dominance
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Na+K/(Na+K+Ca)
1
10
100
1000
10000
100000
Tota
l Dis
solv
ed S
olid
s (m
g L-
1 )
Weathering Dominance
Evaporation Dominance
Precipitation Dominance
0.6 0.80.0 0.2 0.4 1.0 1.2
Cl/(Cl+HCO3)
1
10
100
1000
10000
100000
Tota
l Dis
solv
ed S
olid
s (m
g L-
1 )
(a) (b)
Post-monsoonPre-monsoonMonsoon
Post-monsoonPre-monsoonMonsoon
Figure 5. Gibbs’s diagram representing the ratio of (a) Na+K/(Na+K+Ca) and (b) Cl/(Cl + HCO3) as a function of TDS(after Gibbs 1970).
Dissolved silica is exclusively derived from theweathering of silicates. The plot of (Ca2+ + Mg2+)vs. (HCO−
3 + SO2−4 ) will be close to 1:1 line if the
dissolution of calcite, dolomite and gypsum is thedominant reaction in a system. Figure 6(a) showsthat plotted points of the majority of the Sub-arnarekha water samples fall below the theoretical1:1 trend line in the variation diagram relat-ing (Ca2++Mg2+) to (HCO−
3 +SO2−4 ). The excess
of (HCO−3 +SO2−
4 ) over (Ca2++Mg2+) suggestscontribution from the non-carbonate source anddemanding that the required portion of(HCO−
3 +SO2−4 ) to be balanced by the alkalis
(Na++K+). (Ca2++Mg2+)/HCO−3 ratio demar-
cates the maximum portion of bicarbonate that canbe derived from the carbonate weathering (Stallardand Edmond 1983). The variation diagram between(Ca2++Mg2+) and HCO−
3 for the Subarnarekhabasin water shows that in the majority of samples(Ca2++Mg2+) the contents are in excess of alkalin-ity and the magnitude of excess being larger for thetributaries (figure 6b). The excess of (Ca2++Mg2+)over bicarbonate in these waters indicates someextra source of Ca2+ and Mg2+ and excess partof the positive charges is balanced by other anionssuch as SO2−
4 and/or Cl−. The data plot along theequiline on (Ca2++Mg2+) vs. TZ+ at lower concen-tration range suggests a significant contribution ofCa2+ and Mg2+ to the total cations. Deviations ofplotted points from 1:1 equiline at higher concen-tration especially during the pre-monsoon indicate
the increasing contribution of alkalis (Na++K+)to the total cations with increasing ionic concen-trations (figure 6c).
The concentrations of (Na++K+) in theanalysed water samples are significantly in excessover chloride and high (Na++K+)/Cl− ratio i.e.,2.26 suggests non-atmospheric source of alkaliswhich might be derived from silicates weathering(figure 6d). (Na++K+)/TZ+ and (Ca2++Mg2+)/(Na++K+) ratios can be used as an index to assessthe contribution of cations through silicate weath-ering (Stallard and Edmond 1983; Sarin et al.1989). The plot of (Na++K+) vs. TZ+ showsthe deviation of plotted points from the 1:1 equi-line and the (Na++K+)/TZ+ ratio varies between0.15 and 0.80 (figure 6e). The (Ca2++Mg2+)/(Na++K+) molar abundance ratio in the silicatesof upper crust is generally 1.0 (Taylor and McLen-nan 1985). The average (Ca2++Mg2+)/(Na++K+)ratio in the Subarnarekha River water is 2.7,comparable to the world (2.2) and Indian (2.5)river water averages (figure 6f). The observedlow (Ca2++Mg2+)/(Na++K+) ratio, i.e., 2.7 andhigher (Na++K+)/TZ+, i.e., 0.29 ratio in theanalysed waters suggest that the chemical com-position of the Subarnarekha River is under thecombined influence of carbonate and silicateweathering (Sarin et al. 1989; Singh et al. 2005).
Small rivers draining only carbonates arecharacterised by higher calcium and magnesiumconcentrations and have high Ca2+/Na+, i.e., 50;
J. Earth Syst. Sci. (2018) 127:119 Page 15 of 22 119
100 1000 10000
TZ+ (µeq/l)
100
1000
10000
Na
+ K
(µeq
/l)
1000 10000
HCO3 + SO4 (µeq/l)
1000
10000
Ca
+ M
g (µ
eq/l)
Post-monsoonPre-monsoonMonsoon
100 1000 10000
Cl (µeq/l)
100
1000
10000
Na
+ K
(µeq
/l)
100 1000 10000Na + K (µeq/l)
100
1000
10000
Ca
+ M
g (µ
eq/l)
(e)
(c)
(b)
(d)
(f)
1000 10000
HCO3 (µeq/l)
1000
10000
Ca
+ M
g (µ
eq/l)
(a)
1000 10000
TZ+ (µeq/l)
1000
10000
Ca
+ M
g (µ
eq/l)
Figure 6. Scatter plot between (a) Ca+Mg vs. HCO3+SO4, (b) Ca+Mg vs. HCO3, (c) Ca+Mg vs. total cations, (d) Na+Kvs. Cl, (e) Na+K vs. total cations and (f) Ca+Mg vs. Na + K.
Mg2+/Na+, i.e., 10; and HCO−3 /Na+, i.e., 120
ratios (Gaillardet et al. 1999). The dissolved loadsof water draining silicate terrains is expected tohave a low Ca2+/Na+ molar ratio because of highersolubility of Na+ relative to Ca2+. The molarratios of Ca2+/Na+ = 0.35 ± 0.15, Mg2+/Na+ =0.24 ± 0.12, HCO−
3 /Na+ = 2 ± 1 are assignedfor the silicate end member. The observed molarratios of Ca2+/Na+ (1.04), Mg2+/Na+ (0.48) and
HCO−3 /Na+ (2.78) in the Subarnarekha River
waters are much lower than those of the watersdraining carbonate lithology and higher than thatdrain silicate rocks, indicating that the solutechemistry of the Subarnarekha River is essen-tially controlled by two-component mixing fromthe dissolution of silicates and carbonates. Theplots of HCO−
3 /Na+ vs. Ca2+/Na+ and Ca2+/Na+
vs. Mg2+/Na+ relating carbonate and silicate end
119 Page 16 of 22 J. Earth Syst. Sci. (2018) 127:119
Silicates
Evaporites
Carbonates
100
Ca2+/Na+ (mM/mM)
0.01
0.1
1
10
Mg2+
/Na+ (
mM
/mM
)
Pre-monsoonMonsoonPost-monsoon
Silicates
Evaporites
Carbonates
0.01 0.1 1 10
0.01 0.1 1 10 100
Ca2+/Na+ (mM/mM)
0.1
1
10
100
HC
O3- /N
a+ (m
M/m
M)
(a)
(b)
Figure 7. Mixing diagrams using sodium normalised ratioof (a) Mg2+/Na+ vs. Ca2+/Na+ and (b) HCO−
3 /Na+ vs.Ca2+/Na+ relating carbonate and silicate end members(after Gaillardet et al. 1999).
members show the dominance of silicateweathering over the carbonate dissolution in soluteacquisition processes in the Subarnarekha Riverbasin (figure 7).
4.3 Saturation index and water mineralequilibrium
The saturation index (SI) of the studied waterwith respect to calcite (SIc) and dolomite (SId)was estimated using the USGS hydrogeochemical
software PHREEQC (Parkhurst and Appelo 1999)in order to investigate the level to which thenatural water has equilibrated with the carbon-ate mineral phases. PHREEQC is a widely usedmodelling code that employs various approachesand thermodynamic databases for solving solution–solid–gas equilibria (Lecomte et al. 2005; Binetet al. 2009; Tiwari and Singh 2014). The satura-tion index of a particular mineral phase can bedefined as SI = log10(IAP/Ksp), where IAP is theion activity product of the solution and Ksp is thesolubility product at a given temperature (Garrelsand Mackenzie 1967). A positive saturation indexspecifies that the water is being supersaturatedwith respect to a particular mineral phase andtherefore incapable of dissolving more of themineral and the mineral phase in equilibrium pre-cipitate under suitable physico-chemical condition.Undersaturation condition is denoted by a nega-tive index and suggests the dissolution of mineralphase, while neutral SI denotes the equilibriumstate with the mineral phase. The plot of sat-uration index of calcite (SIc) vs. dolomite (SId)demonstrates that most of the post-monsoon andmonsoon water samples are undersaturated withrespect to dolomite and calcite, while water issupersaturated with respect to both during the pre-monsoon (figure 8). The supersaturation conditionin pre-monsoon may be attributed to evaporationeffects during the lean water level period of sum-mer season which causes the preferential extractionof Ca by precipitation (Hardie and Eugster 1970).The undersaturation condition represents waterthat has come from an environment where rockmatrices contain insufficient calcite and dolomite orwhere Ca and Mg exist in other forms. Undersatu-rated waters are capable to dissolve calcite and/ordolomite when it comes in contact with sourcerocks.
The clay mineral assemblages, which wouldbe consistent with the natural water chemistry,can be established through thermodynamic data(Garrels and Christ 1965). The thermodynamicstability relationships of the Subarnarekha Riverwater are plotted in the silicate systems: (a)Na2O−Al2−SiO2−H2O, (b) K2O−Al2−SiO2−H2O, (c) CaO−Al2−SiO2−H2O and (d) MgO−Al2−SiO2−H2O at 25◦C to predict the possibleclay mineral assemblages which would be in equi-librium with the river water chemistry (figure 9).The pH–log H4SiO4 stability diagram demon-strates that the majority of data points fall inthe range of kaolinite stability field except some
J. Earth Syst. Sci. (2018) 127:119 Page 17 of 22 119
DolomiteDolomite
SaturationUndersaturation
Und
er s
atur
atio
nS
atur
atio
nC
alci
teC
alci
te
Dol
omite
sat
urat
ion
inde
x (S
I d)
Calcite saturation index (SIc)
-3 -2 -1 0 1 2 3
-6
-5
-4
-3
-2
-1
0
1
2
3
4
5
6Post-monsoonPre-monsoonMonsoon
Figure 8. Relationship between saturation indices of calcite (SIc) and dolomite (SId).
pre-monsoon samples which fall in the chlorite andCa-feldspar zones in MgO−Al2−SiO2−H2O andin CaO−Al2−SiO2−H2O system. The enrichmentof Mg and Ca in the water during pre-monsoonmay explain it (Das and Dhiman 2003). Water–mineral equilibria imply that the SubarnarekhaRiver water chemistry is in equilibrium with thekaolinite. Stability in the kaolinite field suggeststhat the CO2-enriched water reacts with silicateminerals contained in the host rock, particularly inplagioclase feldspar and converted into allophone–hallosite–kaolinite. The reactive water leached outCa, Mg, Na and HCO3 from the host silicates andresults in a more silica-rich clay minerals by thereaction:
(Na,K,Ca,Mg) silicates + H2O + CO2
= H4SiO4 + HCO3 + Na + K
+ Ca + Mg + Al2Si2O5 (OH)4 Clay mineral.
4.4 Dissolved fluxes and chemical denudation rate
The Subarnarekha River shows enormous spatialand temporal variations in the water discharge.Figure 10 shows the variation in water discharge
for the monsoon and non-monsoon seasons atfive locations. About 69–98% of the annual waterdischarge from the river occurs during the mon-soon (June–September) and 2–31% in the leanflow period of non-monsoon (October–May). Theannual dissolved fluxes and chemical denudationrates of the Subarnarekha River at various loca-tions and its major tributaries were calculated byusing the average TDS, catchment area and annualwater discharge (table 4). The Subarnarekha Riverannually transported 0.179 × 106 ton of dissolvedchemical loads to the Muri site and the esti-mated chemical denudation rate of the catchmentat this site was 135 ton km−2 yr−1. The dissolvedload and water discharge increase unsystemati-cally at downstream sites and the annual solutefluxes at Ghatsila and Rajghat sites were esti-mated to be in the range of 1.585 × 106−1.477 ×106 ton, respectively. Kharkai, the largest Sub-arnarekha tributary, annually delivered 1.023×106
ton of dissolved loads to the Subarnarekha Riverat Adityapur. The annual solute fluxes of the othertributaries such as Sankh (0.016 × 106 ton), Garra(0.082 × 106 ton), Kanchi (0.109 × 103 ton) andKarkari (0.188 × 103 ton) were low as comparedto the Kharkai (1.023 × 106 ton). The chemical
119 Page 18 of 22 J. Earth Syst. Sci. (2018) 127:119
Gib
bsite
Kaolinite
Na-Montimorilinite
K-Mica
Gib
bsite
Kaolinite
Amor
phou
s Si
lica
Qua
rtz s
atur
atio
n
Am
orph
ous
silic
a
-5 -4 -3Log H4SiO4
1
3
5
7
9
Log
(Na+ )
/(H+ )
Post-monsoonPre-monsoonMonsoon
-5 -4 -3Log H4SiO4
3
5
7
9
Log
(K+ /H
+ )
Qua
rtz s
atur
atio
n
Ca-Feldspar
Kaolinite
Gib
bsite
Gib
bsite
Kaolinite
Chlorite
Am
orph
ous
Sili
ca
-5 -4 -3Log H4SiO4
6
8
10
12
14
16
Log
(Ca++
)/(H
+ )
-5 -4 -3Log H4SiO4
6
8
10
12
14
16
Log
(Mg++
)/(H
+ )
(a)
(b)
(c)
(d)
Amor
phou
s Si
lica
Albite
K- Feldspar
Figure 9. Mineral stability diagrams for the silicate system: (a) Na2O−Al2−SiO2−H2O; (b) K2O−Al2−SiO2−H2O;(c) CaO−Al2−SiO2−H2O; (d) MgO−Al2−SiO2−H2O (after Garrels and Christ 1965).
denudation rates of the Kharkai, Garra, Karkariand Kanchi catchments were estimated to be inthe range of 176, 169, 119 and 105 ton km−2 yr−1,respectively.
4.5 Water quality assessment for irrigation uses
EC and Na are the most important parametersfor determining the suitability of water for irri-gation uses. High salt concentrations in theirrigation water affect the soil structure, per-meability and aeration, which indirectly affectthe plant growth. Irrigation water can be clas-sified into low (EC =< 250µS cm−1), medium(250−750µS cm−1),high (750−2250µS cm−1)and
0
1000
2000
3000
4000
5000
6000
7000
Muri Jamshedpur Ghatsila Baharagora Adityapur
Wat
er d
isch
arge
(m
illio
n m
3 )
Site Name
MonsoonNon-monsoonAnnual
Figure 10. Seasonal variations in water discharge of the Sub-arnarekha and Kharkai rivers at different sites.
J. Earth Syst. Sci. (2018) 127:119 Page 19 of 22 119
Table 4. Average annual solute fluxes and chemical denudation rate of the Subarnarekha and its tributaries.
River/tributarySite/tributaries
name
Area
(km2)
Discharge
(million m3)
TDS
(mg l−1)
Solute flux
(×106)(ton yr−1)
Chemical
denudation rate
(ton km−2 yr−1)
Subarnarekha Muri 1330 596 301 0.179 135
Adityapur 6309 2831 310 0.878 139
Jamshedpur 12,649 6593 201 1.325 105
Ghatsila 14,176 6950 228 1.585 112
Baharagora − 4974 190 0.945 −Rajghat 19,296 7940 186 1.477 77
Tributaries Kanchi 1036 750 145 0.109 105
Karkari 1575 950 198 0.188 119
Kharkai 5825 3300 310 1.023 176
Garra 483 200 408 0.082 169
Sankh 196 80 202 0.016 82
very high (2250−5000µS cm−1) salinity classesbased on the total concentration of soluble saltsin water (USSL 1954). The excess sodium in waterproduces undesirable effects on soil properties andreduces its permeability. High salt concentrationin water results in the formation of saline soil,whereas a high sodium concentration leads to thedevelopment of alkaline soil. The alkali hazardin the use of water for irrigation is expressedin terms of sodium absorption ratio (SAR) anddetermined by the absolute and relative concen-tration of cations. On the basis of SAR value,water can be classified as low (SAR<6), medium(6–12), high (12–18) and very high (>18) alkaliwater.
The calculated value of SAR in the surface waterof the Subarnarekha River basin ranges from 0.32to 6.73 (avg. 0.79). The plotted data of the major-ity of water samples on the US salinity diagramfall in the category of C1S1 and C2S1, i.e., low-to-medium salinity and low alkali water (figure 11).Such water can be used for irrigation in most of thesoil and crops with little danger of development ofexchangeable sodium and salinity. Four water sam-ples of the pre-monsoon season fall in the zonesof C3S1 and C3S2 indicating high salinity andlow-to-medium alkali hazard. High saline watersare not suitable to irrigate the agricultural fieldswith restricted drainage and it requires specialmanagement for salinity control. For utilisation ofsuch water, soil must be permeable, drainage mustbe adequate and irrigation water must be appliedin excess to provide considerable leaching.
%Na in water is a parameter computed toevaluate the suitability of water for irrigation use.%Na denotes the relative proportions of alkali
Sod
ium
Ads
orpt
ion
Rat
io (S
AR
)
100 250 750 2250
S1
S2
S3
S4
Low
Med
ium
Hig
hV
. Hig
hS
OD
IUM
(ALK
ALI
) HA
ZAR
D
SALINITY HAZARD
C1 C2 C3 C4Low Medium High V.High
Electrical Conductivity (µS/cm)
Post-monsoonPre-monsoon
0
4
8
12
16
20
24
28
32
0
10
20
30Monsoon
Figure 11. US salinity diagram for classification of irrigationwaters (USSL 1954).
to the total cations. The role of sodium in theclassification of irrigation water was emphasisedbecause of the fact that sodium reacts with soiland affects its physical condition and soil structureincluding the formation of crusts and reduction insoil aeration, infiltration rate and soil permeabil-ity. Maximum %Na of 60% is recommended forirrigation water. %Na in the analysed river waterranges between 15 and 44% in the post-monsoon,24 and 80% in the pre-monsoon and 17 and 44%in the monsoon seasons. The plot of analyticaldata on Wilcox (1955) diagram relating EC and%Na placed the Subarnarekha River water under
119 Page 20 of 22 J. Earth Syst. Sci. (2018) 127:119
Exc
elle
ntto
good
Goo
dto
perm
issi
ble
Dou
btfu
lto
unsu
itabl
e
Permissible to doubtful
Unsuitable
Uns
uita
ble
Post-monsoonPre-monsoon
0 500 1000 1500 2000 2500 3000 3500Electrical Conductivity (EC) µS/cm
0
20
40
60
80
100
Per
cent
Sod
ium
0 5 10 15 20 25 30 35Total Concentration (meq/l)
Monsoon
Doubtful to unsuitable
Figure 12. Plot of %Na vs. EC (after Wilcox 1955).
excellent to good and good to permissiblecategories for irrigation uses (figure 12).
The relative abundance of alkaline earths (Ca2+
+Mg2+) with respect to bicarbonate and carbonatealso influences the suitability of water for irriga-tion uses. The excess of carbonates (CO2−
3 +HCO−3 )
over alkaline earths (Ca2++Mg2+) in irrigationwater may cause the complete precipitation ofCa and Mg as carbonates (Karanth 1989). Thewater with high RSC has high pH and land irri-gated with such water becomes infertile owing tothe deposition of sodium carbonate (Eaton 1950).Irrigation waters having RSC values >5 meq l−1
have been considered harmful to the growth ofplants, while waters with RSC values above2.5 meq l−1 are unsuitable for irrigation. A RSCvalue between 1.25 and 2.5 meq l−1 is consideredas the marginal quality and value <1.25 meq l−1
as the safe limit for irrigation. The calculated RSCvalues in most of the analysed water samples are<2.5 meq l−1, suggesting marginal to safe qualityof the Subarnarekha River water for irrigation use(table 1).
5. Conclusion
The hydro-geochemical study of the SubarnarekhaRiver basin has been carried out to evaluate the
major-ion chemistry, solute acquisition processes,dissolved fluxes and suitability of river water forirrigation uses. The analytical result shows that theSubarnarekha water is alkaline in nature like othermajor Indian rivers. Ca2+ and Na+ were the domi-nant cations, while HCO−
3 and Cl− dominate in theanion chemistry of the Subarnarekha River water.Seasonality in the ionic concentration is related tothe rainfall dilution and river flow regime. Increasein TDS and ionic concentrations during the pre-monsoon season may be attributed to enhance-ment in groundwater contribution during the lowflow regime of summer months. The SubarnarekhaRiver water chemistry is largely controlled byweathering of rocks with minor contribution fromthe atmospheric and anthropogenic sources. Thehigh concentration of HCO−
3 and (Ca2++Mg2+)and observed Ca2+/Na+, Mg2+/Na+, HCO−
3 /Na+
and HCO−3 /SiO2 ratios suggest that the major-
ion chemistry of the Subarnarekha River isessentially controlled by two-component mixingfrom the dissolution of silicates and carbonates.The high concentration of dissolved silica,low ratio of (Ca2++Mg2+)/(Na++K+) and high(Na++K+)/TZ+ ratio suggest significant contribu-tion of dissolved ions from the silicate weathering.The water chemistry is largely undersaturated withrespect to calcite and dolomite; however, most ofthe pre-monsoon water samples are supersaturatedwith respect to both. The supersaturation condi-tion in pre-monsoon may be attributed to evapo-ration effects during the lean water level periodwhich causes preferential extraction of Ca by pre-cipitation. The chemical behaviour of the riverwater in the silicate systems demonstrates kaoli-nite as the possible mineral that is in equilibriumwith the water. The Subarnarekha River annuallydelivered 1.477 × 106 ton of dissolved loads to theBay of Bengal and the estimated chemical denuda-tion rate of the catchment is 77 ton km−2 yr−1.The annual solute fluxes of the tributaries variedfrom a minimum of 0.016×106 ton (Sankh) to amaximum of 1.023×106 ton (Kharkai). The calcu-lated parameters of SAR, %Na and RSC show thatthe Subarnarekha River water is of the ‘excellentto good’ category for irrigation and can be usedto irrigate all soils for tolerant, semi-tolerant andsensitive crops.
Acknowledgements
Dr. Soma Giri is grateful to the Department ofScience and Technology, Government of India for
J. Earth Syst. Sci. (2018) 127:119 Page 21 of 22 119
funding under Fast Track Young Scientist Scheme(Grant No. SR/FTP/ES-185/2010(G)). Authorsare thankful to Dr. P K Singh, Director, CSIR-CIMFR for providing the laboratory and otherinfrastructural facilities and lab colleagues for theirhelp during the study.
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Corresponding editor: Partha Pratim Chakraborty