Study on Seasonal Variations and Spatial Distribution of Major Ions with focus on Paper Industry Effluents-A Case Study of Sirpur Paper Mills (SPM) Telangana

The present paper examines the seasonal variations in groundwater quality (Pre-monsoon & PostMonsoon) with an emphasis on paper industry effluents from the Sirpur-Kaghaznagar area. Spatial distribution of samples from 24 sites collected during pre and post-monsoon using surfer software gives an insight of important parameters such as pH, EC, TDS, BOD, COD, DO, Ca+, Mg2+, Na+, F, Cl-, NO3, SO4 2and TH to be significantly elevated beyond the acceptable and permissible levels prescribed by BIS limits. Also, the Physico-chemical analysis of paper mill effluent collected from 12 different sites revealed that parameters such as pH, EC, TDS, BOD, COD, Alkalinity, SO4 2-, Cu, and Fe were beyond the BIS permissible limits for effluent discharge and designated a profound negative impact on groundwater quality and lead us to conclude that the overall quality is deteriorated due to the influx of paper industry effluents Current World Environment www.cwejournal.org ISSN: 0973-4929, Vol. 15, No. (3) 2020, Pg. 406-429 CONTACT Harish Kumar Agre agre.harsh@gmail.com School of Interdisciplinary Sciences, Symbiosis Skills & Professional University, Pune-412101, India. © 2020 The Author(s). Published by Enviro Research Publishers. This is an Open Access article licensed under a Creative Commons license: Attribution 4.0 International (CC-BY). Doi: http://dx.doi.org/10.12944/CWE.15.3.05 Article History Received: 2 May 2020 Accepted: 11 December 2020


Introduction
Water is a prime resource, its effective use and management are considered very important for the future demands of the increasing population. The quality and quantity of water is of much value specifically in the rural areas. The quality of water is characterized by various physico-chemical parameters influenced by many natural and anthropogenic factors like weathering, sources of water, type of pollution, seasonal fluctuations, etc. causing a diverse change. A tremendous change and growth in the industrial sector that benefit mankind on one side and another side of the advancement, there is an ever increased concern on the burden of pollution load on each sphere of the environment. The altered environments may pose a great threat to the living organization in the world. Pulp and paper industry is considered as one of the major polluting industry which consumes large quantities of water for processing the pulp and paper. Nearly it consumes about 250-300 m 3 of water per ton of paper produced and the estimated production capacity soon will be huge. Both water and soil systems are at higher risk of contamination due to direct discharge of toxic effluents making the water and soil unsuitable for drinking and irrigation purposes. Also, people living in nearby surrounding areas are more prone to long term health hazards. So far there is no serious attempt and significant contributions were made by any investigator in this area to investigate the impact of paper mill effluent, uses a wide range of resources and contributes to maximum pollution load in the surrounding area. Considering the long term adverse effects of pulp and paper industry, the research work was begun to know the exact status of water quality due to the influence of paper mill effluents surrounding area of kaghaznagar, Telangana.

Study Area
Sirpur-Kaghaznagar located in the eastern Telangana being part of Adilabad district is a small town. It lies between 19.33330 N-79.48330 E (Fig-1) with an average elevation of the area is 174 meters (574 feet). The total study area is 59.6 sq. km. The district is bounded by Yeotmal and Chandrapur districts of Maharashtra, on the East by Chandrapur, on the South by Karimnagar and Nizamabad districts and the West by Nanded districts of Maharashtra. As per the 2011 census, the population of the Sirpur-Kaghaznagar area is 57,583. The study area receives water from Peddavagu River which is a tributary of Godavari. The types of soils in the study area are red loamy soils derived from country rocks and black cotton soils mainly derived from basaltic rocks. The climate in the region is usually hot and reach to a peak of 46 0 C during the summers. Usually the rainfall in kaghaznagar area ranges around 1094 mm, during that year it recorded a rainfall of 861.4 mm, geologically the area represents the Sullavai formation comprising grits, conglomerates, and sandstones of the Gondwana age. The sandstone, limestone, and shale of Penganga and sullavai formations belong to sedimentary origin but are mostly hard and compact due to which they perform like crystalline rocks and aquifers are formed due to weathering and fracturing. Water in the study area is usually found in shallow sub surface aquifers and deeper aquifers in the saturated zone. Water level difference observed during pre-monsoon was 0.22-31.25 m below the ground and post-monsoon recorded 0.3-17.15 m.

Materials and Methods
Groundwater samples were collected individually from water locations including boreholes and dug wells in acid cleaned high-density 1-liter linear polythene sampling bottles with strict adherence to the sampling protocols between 7 A.M to 9.A.M as described by American Public Health Association (APHA 2012). 24 water sampling stations were randomly fixed, covering an extended area of 59 km 2 in the Sirpur-Kaghaznagar. Sampling was done twice in a month for a year i.e. during March 2011 (pre-monsoon) and February 2012 (post-monsoon). Samples collected underwent for analysis in the lab adhering to the guidelines prescribed. For effluent sampling 2.5 litre sized polythene bottles cleansed with hydrochloric acid were used, again washed with distilled water and then collected the effluent. Proper care was taken to seal the sample bottles with paraffin wax and were shifted to the laboratory with extreme care. The collected effluent samples were stored at -4 0 C to stop the chemical reactions and the samples were characterized for its chemical properties by adopting standard protocols.

Result and Discussion (Effluent Characterization) Temperature & pH
Temperature plays an important role in chemical reactions and increase the evaporation rate of wastewater making it unsuitable for beneficial uses such as irrigation (Metcalf and Eddy 2003). The temperature recorded ranged between 30 to 32 0 C with a mean value of 31±1 depicted in (Table 1) for the year 2011-2012. pH: The Acidity and alkalinity of effluent depend upon various chemicals used in paper manufacturing. The pH of the raw effluent ranged from 8.1 to 8.9 with a mean value of 8.5 ± 0.4 for the year 2011-2012. Addition of caustic soda to obtain colour and bleaching agents in the pulping process is the reason for enhanced alkalinity (Table 1) (Table.1). High value of TDS could be due to solubilisation of maximum chlorolignin compounds present in the effluent which would create problems and ailments in humans. The results confirmed with those studied by (Giri et al., 2014) which were found to be beyond the BIS limits.

BOD & COD
BOD and COD values of Paper mill effluent ranged between 150 to 188 mg/L and 1090 to1155 mg/L with a mean value of 169.0 ±19 and 1122.50 ± 32.50 (Table 1). It would be complex to exactly indicate the chemical composition of Paper mill effluent, however BOD and COD is high and contains lignin and its derivatives including chlorinated compounds, acetic acid, formic acid, sulphur compounds (Jukka et al., 1994). Paper industry uses significant amounts of organic material, specific chemical compounds implies excess pollution levels. Paper mill effluent with substantial BOD and low levels of oxygen content alter metabolism of most animals. (Sawyer CC and Mc Carty 1978) whereas high COD levels indicate the toxic state of wastewater along with the presence of biologically resistant organic substances. The results are in agreement with those of (Anju Bhatnagar 2015), wherein the values of BOD & COD were above permissible limits.

Suspended Solids & Alkalinity
The number of suspended solids ranged from 180 to 225 mg/L with a mean value of 202.5 ± 22.5 for the year 2011-2012 in (Table 1). Alkalinity: The values of Alkalinity ranged between 252.0 to 485.0 mg/L with a mean value of 368.5 ± 116.5 for the year 2011-2012 (Table 1). Microbial activity degrades the organic matter and forms carbonate and bicarbonate in the water. Alkalinity does not show any harmful effect but the bicarbonates present in the wastewater can release fluoride from CaF 2 present in the soils with precipitation of CaCO 3 due to the high rate of evapotranspiration caused by semi-arid climate (Keshav Deshmukh, 2013).

Chlorides & Sulphates
Chloride content in the effluent varied from 302 to 325 mg/L with arithmetic mean 313.5 ± 11.5 for the year 2011-2012 as shown in (Table 1). In the study area significant primary source of chloride is the paper mill itself where an excess amount of chloride is used in the pulping process. However, chloride values were within the prescribed limits given by BIS for irrigation. Sulphate concentration in the effluent ranged between 1050 to 1075 mg/L with an average value of 1062.5 ± 12.5 for the year 2011-2012 in (Table 1) (Table 1). The results indicated that the values of Cd, Cu and Fe were found higher than the prescribed limits of BIS standards for irrigation water which reflect the toxic nature of paper mill effluents. The Findings confirmed to those of (Kumar et al., 2015 andTariq et al., 2006).

P hy s i c o -ch e m i c a l C h a r a c t e r i z a t i o n o f Groundwater pH
The normal range of pH is 6.5 to 8.5 as per the WHO and IS standards. In the present study carried out on Sirpur-Kaghaznagar town of Adilabad district, Telangana has shown moderate fluctuation in pH from 8.76 to 8.9 with a mean value of 8.83 ± 0.07 (Table 2) for the year 2011-2012. pH values were observed to be less in post monsoon compared to values recorded in Pre monsoon season. Average pH observed during both the seasons was 8.84 ± 0.06 and 8.83 ± 0.07 (Table 3). pH variation in the study area for both the seasons is shown in (Fig.2) which is mostly alkaline, the raised pH above 8.7 could be due to interface with subsurface water     (Table 2). Seasonal fluctuation in the values of conductivity in both the seasons varied from 2270 ± 10 and 2259 ± 9.0 µmhos/ cm and depicted in (Table.3). The Spatio-temporal variation in EC concentration is shown in (Fig.3)

Total Dissolved Solids (TDS)
Elevated values observed in the groundwater may be due to the presence of dissolved solids like bicarbonates, carbonates, sulphates, chlorides, nitrates, calcium, magnesium, sodium, potassium and some heavy metals. Usually, major ions in the water are present due to weathering or disintegration of rocks, surface runoff, atmospheric deposition, and anthropogenic activities. TDS content in high rainfall areas may be as less as 20 mg/L and it may go beyond 100000 mg/L in some desert brines (Hem 1985). As per Indian Standards 500 mg/L is the required range of desirability and the highest limit is 2000 mg/L. TDS has been reported in the range between 1972 ± 2005 mg/L with a mean value of 1988.50 ± 16.50 for the year 2011-2012 as represented in (Table 2). Analysis for the two seasons indicated high values of TDS in pre-monsoon and lowered values in postmonsoonal season. The mean TDS values for premonsoon and post-monsoon period are reported as 1993 ± 12.0 and 1986 ± 14.0 mg/L respectively for the period 2011-2012 from ( Table 3). TDS values in groundwater for both periods shown in (fig 4) indicating higher values of TDS in pre-monsoon season at Vijay Basthi and Ram Mandir area which reflects the influence of the paper industry and the improper treatment of industry effluents in the study area. Research carried out by (Bamakanta, et al., 2013) on water quality around JK paper mills also found similar type of observations. Also investigated results are concerning that of observations made by (Patil and Patil, 2011;Srinivas et al., 2000).

Fig. 4: Contour maps showing variations in TDS during Pre Monsoon season & Post Monsoon seasons Biological Oxygen Demand (BOD)
It is the most commonly used parameter which represents a quantitative index of degradable organic waste and measures the strength of the sewage. BOD ranged from 4 to 8.32 mg/L with an average of 6.16 ± 2.16 mg/L as depicted in (Table 2) (Table 2). Seasonal variation in COD value for the year 2011-2012 observed is 116.75 ± 6.75 and 114.5 ± 7.50 mg/L for pre-monsoon and post-monsoon periods (Table 3.) (Fig.6) show the variations in COD values. The maximum prescribed limit for COD is 4 mg/L by USPHS for drinking water. The present investigated results are attributed to observations made by (Abdo et al., 2010;Giri et al., 2014).  Table 2). The data on seasonal variations (Pre-monsoon and post-monsoon) were also reported as 5.11 ± 1.60; and 4.95 ± 1.65 mg/L (Table 3) however standard limit for DO by WHO is 5.0 mg/L. The variation in DO concentration is shown in (Fig.7). 50% of the samples in pre-monsoon and 54% in post-monsoon seasons had less DO than the standard limits.

Carbonates & Bicarbonates
The values pertaining to the parameters are clearly shown in (Table 2) and (Table 3) and depicted in (Fig.8) and (Fig.9).  (Table 3) for the study period of 2011-2012 and were found to be quite higher than the BIS acceptable limits. However, they were within the BIS permissible limits. High concentration of chloride was found at Vijay Basthi and Ram Mandir area as shown in (Fig.10) which is very near to the paper industry.

Fluoride
In general fluoride content in water is through geological pathway. Dissolution of minerals like fluorite and fluorapatite is considered the chief mechanism behind the contamination of fluoride in groundwater. Fluoride concentrations in the Sirpur-Kaghaznagar area ranged from 0.14 to 4 mg/L with a mean of 2.06 ± 1.94 mg/L for the year 2011-2012 (Table 2). Seasonal variations for Fluoride ranged as 0.14 ± 4.0 and 0.14 ± 3.90 mg/L for pre-monsoon and post-monsoon seasons (Table 3) (Handa, 1975).

Sulphates
High concentrations of sulphates can lead to dehydration and gastrointestinal problems, Ellen horn, and Barceloux, (1988) if it exceeds a concentration of more than 400 mg/l it imparts a bitter taste to cause laxative effects (Raghunath 1987). The use of sulphur-rich fertilizers can be considered as a potential source in groundwater. In the present investigation carried out in the Sirpur-Kaghaznagar area, the Sulphate content fluctuated between 386.0 to 420.0 mg/L with a mean value of 403.0 ± 17.0 for the year 2011-2012 (Table 2). Sulphate content in the study area during the two periods was also observed and its values were 412.5 ±7.5 and 393 ± 7.0 mg/L for pre-monsoon and post-monsoon respectively as shown in (Table 3).The raised sulphate values far from standard limit specifically in pre-monsoon indicated amalgamation of wastewater from industry and sewage from domestic areas. The highest concentration was observed at Vijay Basthi and Ram Mandir area as depicted in (Fig.12). The results were similar to those of (Patterson et al., 2008).  (Table.2). The seasonal variations were also studied during the study period and the values recorded are 69.50±11.50 and 66.0±14.0 mg/L for pre-monsoon and post monsoonal seasons as depicted in (Table 3). Significantly high levels of nitrate beyond the prescribed standards by BIS (< 45 mg/L) were observed in both the seasons as shown in (Fig.13) indicate the use of nitrogenbased chemicals in agriculture and mixing of paper mill effluents along with groundwater in the vicinity.  (Table 3). The highest value of 238.0 mg/L was observed at the Sarsilk colony in pre-monsoon as shown in (Fig.14) which is very close to the paper industry. The high values are due to the open dumping of municipal solid waste and the industrial effluents released. The range of calcium values in all the seasons was beyond the permissible limit mentioned by BIS.  (Table.2). Seasonal variation was also recorded as 146.5±6.5 and 141.5± 9.5 mg/L for pre-monsoon and post-monsoonal seasons respectively (Table 3). Magnesium concentrations in the study area in both the seasons exceeded the BIS permissible limits are depicted in (fig.15). This shows the clear influence of industry on groundwater quality. Study carried out by (Sharma et al., 2013) supports the findings.

Sodium, Potassium and Total Hardness
Discharge of soluble salts during the weathering of plagioclase feldspars are the prime source of sodium in water. Sodium concentrations in soils can be increased by the repetitive use of irrigated water thereby changing the soil permeability and texture and therefore making it unsuitable for irrigation (Trivedi and Goel, 1984). The recommended value for sodium in drinking water by WHO is 200 mg/L (WHO, 2004). In the present investigated area the sodium content observed for the year 2011-2012 ranged between 460.0 to 486.0 mg/L with an average value of 473.0 ± 13.0 mg/L from (Table 2) and the seasonal variations found ranged as 478.0±8.0 and 471.0±11.0 mg/L for pre-monsoon and postmonsoon periods which were quite higher than the permissible limit suggested by WHO ( Table 3)

Potassium
Geochemical weathering of mineral compounds like orthoclase, microcline, biotite, leucite and nepheline in the bedrocks is considered the basic source for the occurrence of potassium in groundwater. Potassium concentrations during the study period of 2011-2012 ranged between 47 to 66.29 mg/L with a mean value 56.64 ± 9.64 mg/L (Table 2). Similarly, the seasonal variations recorded ranged as 58.14 ± 8.14 and 55.5 ± 8.5 mg/L for pre-monsoon and post-monsoon seasons as depicted in ( fig.17) & (Table 3).

Cluster Analysis
An easy way to understand the extent of the relationship between two different variables is through the application of cluster analysis, wherein it gives an understanding of maximum and minimum relationship. This tool was used to interpret the similarity between parameters of two different datasets and interpolate the sequence of clusters they form. Cluster analysis was applied to two different datasets of groundwater quality from the Sirpur-Kaghaznagar area (Pre-monsoon and Postmonsoon) to understand the cohesive wellness among similar parameters by means of the resulted dendrogram. Cluster analysis connote the correlation between various water quality parameters and based on the study, the 17 parameters of two seasons were grouped into statistically significant clusters as shown in (Fig.19 & Fig.20).

Conclusion
The overall results obtained from the study carried out on the spatial distribution of major ions during pre and post-monsoon seasons and the chemical characterization of paper mill effluent in the Sirpur-Kaghaznagar area is of immense help in yielding the information on the genuine condition of water quality and the pollution outcome prevailing in that area. Since its inception in the year 1942, the industry is responsible for discharging various toxic chemical contaminants into the nearby surroundings; the long term release of industrial effluents with indefinite treatment methods along with domestic sewage and use of pesticides and fertilizers in agriculture has led to pollution load altering the quality of the same in the research area. Furthermore, the effluent parameters such as pH, EC, TDS, BOD, COD, Alkalinity, SO 4

2-
, Cu, and Fe were exceeding the BIS limits. The spatial distribution of major ions with few other parameters through contour maps clearly depicts that the pollution load is high in the vicinity of the paper industry in the pre-monsoon season. Therefore from the above study, it is very much evident that the paper industry effluents are acting as one of the factors influencing the water quality besides domestic and agricultural activity in the Sirpur-Kaghaznagar area.