1.0 INTRODUCTION:

In order to manufacture white paper in pulp paper industry, only high quality fiber containing wood are preferred, with an extra chemical process involving extensive prehydrolysis of wood chips at elevated temperature and pressure followed by alkaline digestion. This process ensures the removal of waste materials and remaining fibers with high cellulose content. The color of the pulp paper mill wastewater is due to lignin and its derivatives. A significant number of organic compounds present in pulp-paper mill wastewater have been classified as mutagenic and clastogenic thereby turning these wastewaters into ‘a Pandora’s box of waste chemicals’ (Pokhrel and Viraraghavan, 2004). Some of these compounds are naturally occurring (mainly lignin and its derivatives), and others are formed during the process of paper making (chlorinated lignins, resin acids and chlorinated phenols, dioxins, furans) (Chandra and Singh, 2012).

In most cases, this wastewater (row or treated) is discharged into the rivers, stream or other water bodies; resulting in negative social and environmental impacts (Chandra et al., 2011). Thus it is obligatory to treat the wastewater before disposal. Despite the fact that, several physical and chemical methods are available for the treatment of wastewater, but they are less desirable than biological process because of cost-ineffectiveness and residual effect.

Microorganisms are nature’s innovative recyclers, converting toxic organic compounds to innocuous species. The biological methods tried so far, most of the literature is confined to a few genera of white rot fungi. But, bacteria seem to be more effective than fungi for the bioremediation of environmental pollutants due to their immense environmental adaptability and biochemical versatility (Raj et al., 2007). However, the bacterial treatment studies have confined themselves to the evaluation of microorganism, basic mechanism behind the treatment, detection and optimization of ligninolytic enzyme (Singh et al., 2007). Although, decolorization of pulp paper wastewater is well reported by pure culture (Morii et al., 1995), the results of such studies are not necessarily relevant to the field because microorganisms in nature grow mostly in mixed condition. In our previous study, various authors used bacterial consortium as an indigenous decolorizer for the treatment of wastewater release from pulp paper industry (Chandra et al., 2011).

2.0 Paper Process description

It has been studied in the year 1994 by Rintala and Puhakka that the paper is made up of interlinked cellulose fibers. Raw material used during paper production are numerous plant bio-resources like wheat, jute, sarkanda, grass, baggase, eucalyptus, bamboo and remaining of agricultural waste such as rice straw. In paper (20-30%) and cellulose (40-45%). The nature of cellulose is fibrous, and tightly attached to hemicellulose by lignin interlinkages. In paper production the fibers of cellulose is first detached by liberating it from lignin bindings and hemicelluloses and afterward rolled into paper. A large amount of contaminated waste water is generated during paper making process that involves a string of operations which employ huge amount of fresh water (Swamy, 2012)

Stages of paper production involves debarking, pulping, rolling and dying (Rintala et al., 1994; Pokhrel Viraraghavan, 2004).The majority of these processes used an outsized quantity of water and eventually produce effluents. Among the assembly processes, the processes that are the foremost sources of pollution are mentioned below.

2.1 Debarking

Wood preparation also known as debarking method, is the initiative in paper production and involves removal of muddy material and barks from surface of wood. In debarking method the water is employed to thaw the frozen logs, take away the bark and wash the logs once debarking (Rintala and Puhakka, 1994; Singh, 2004). Biological and chemical oxygen demand values of debarking effluent are low. It is observed that the effluent of debarking process contains low resin, simple carbohydrates, monomeric phenols and tannins (Field et al., 1993).

2.2 Pulp Making Process

Pulping is a method to detach fibers of cellulose from remainder of wood. Mechanical or chemical or alternative strategies are used for pulping (Rintala and Puhakka, 1994). The aim of any chemical pulping processes is to take out enough lignin to separate cellulosic fibers one from another, generating a pulp appropriate for the manufacture of paper and other related products (Chakar et al., 2004).

Sulfate pulping: - In a standard kraft cook, wood chips are reacted with white liquor (a mixture of NaOH and Na₂S) in a large pressure vessel known as a digester. The chips and white liquor are heated to 170°C which is cooking temperature for about 2hr (Smook, 1992).Throughout this treatment lignin is fragmented into smaller alkali/water soluble fragments because of reaction of lignin with hydroxide and hydrosulfide anions (Gellerstedt and Lindfors, 1984).

Sulfite pulping: - This methodology uses similar tools as kraft method however here the raw material is cooked in reactive metal base liquor (usually ammonium, magnesium, sodium or calcium) using hydrogen sulfite or sulfuric acid. The wood lignin is solubilized by cooking liquor as lignosulfuric acids in acidic and neutral conditions and turn out spent sulfite liquor (Rintala and Puhakka, 1994).

Among the manufacturing plant, pulp making generate a high-strength effluent particularly by chemical pulping. About 55% weight of wood is dissolve in pulping liquor during kraft pulping that contain degradation products of polysaccharides lignin and wood extractives (Rydholm, 1965). Concerning 5% of total volume of mill’s wastewater are produced by evaporator condensates and digester and are rich in phenols, ketones, terpenes and reduced sulfur compounds. The effluent from kraft pulping method mainly contains acetic acids, methanol, furfural, carbohydrates and lignosulphonates as major constituents (Rintala and Puhakka, 1994).

2.3 Bleaching Processes

From pulping stage the pulp fibers are tined brown as a result of they contain non-degraded lignin at low concentration. After pulping, bleaching is utilized on the brown pulp so as to fulfill the required color dictated by product standards. In bleaching method, the pulp fibers are treated with appropriate chemicals to boost its brightness, the bleaching is multistage process namely: chlorination stage(C), extraction stage (E), hypochlorite stage (H), Chlorine dioxide stage(D), peroxide bleaching stage(P), oxygen stage (O) and ozone stage(Z). Many bleaching agents such as, hydrogen peroxide, ozone, chlorine, oxygen, chlorine dioxide etc. are used. It’s during this step that, lignin, resin acids; phenols etc. get chlorinated and transformed into extremely toxic xenobiotics (Field et al., 1993; Ali and Sreekrishnan, 2001).

The pulp is brightens and whitens by removing the maximum amount of lignin as possible to create prime quality pulp. Chlorinated organic compounds like furans, chlorophenols and dioxins are present in effluents releasing from bleaching process and are highly polluted. These compounds are carcinogenic and toxic in nature (Rintala and Puhakka, 1994; Nagarathnamma et al., 1999).

3.0 Bacterial degradation of kraft lignin

Bacteria are extensively studied for ligninolytic potential due to their enormous biochemical versatility and environmental adaptability. Several bacterial species capable of detoxifying various industrial contaminants have been isolated from the natural environment. Microbrevis luteum have removed lignin from anaerobically treated effluents in two step bioreactor (singh and Thakur, 2006). Three potential aerobic bacterial strains Bacillus sp., Aneurinibacillus and Paenibacillus were reported to effectively degrade karft lignin (Chandra et al., 2007). Aneurinibacillus aneurinilyticus was isolated from sludge of pulp and paper mill. It was reported that A. aneurinilyticus could not degrade kraft lignin in the absence of glucose. The degradation on addition of glucose in culture medium is clear evidence of co-metabolism of Kraft lignin. Chandra et al. (2008) demonstrated that Paenibacillus and Bacillus sp. have most potential for degradation of the highest concentration of KL. Pseudomonas putida and Rhodococcus sp. RHA1has been reported as soil bacteria to degrade lignocellulose, producing a number of monocyclic phenolic products (Ahmad et al., 2010). decolorization of black liquor by bacterial consortium consisting Citrobacter sp., Klebsiella pneumoniae and Serratia marcescens was studied by Chandra et al. (2011). Bholay et al. (2012) isolated lignin degrading bacteria from different sources i.e. lake water containing decomposing plant material, rhizosphere soil with cow dung, compost feedstock, scrapes of decaying bark. Total eleven isolates were obtained. Among the eleven two bacterial strain Pseudomonas aeroginosa and Serratia marcescens showed highest results. Comamonas sp. B-9 was isolated from steeping fluid of the erosive bamboo slips for degradation of kraft lignin (Chen et al., 2012). The Pandoraea sp. B-6 was reported by Shi et al. in 2013 and this bacterium was able to degrade KL without any co-substrate under high alkaline Conditions. An alkali lignin degrading bacterium was isolated from forest soil sample throughout Japan from Rokkaido to Okinawa and identified as Bacillus sp. (Chang and Kikuchi, 2014).

Table.1 Bacterial decolorization and degradation of pulp and paper mill wastewater.

Bacterial strain

Percent color reduction and Kraft lignin (KL) degradation

References

Klebsiella pneumoniae

Pseudomonas aerungenosa

Acinetobacter calcoaceticus

25% color, 24 % KL

48% color, 50% KL

39% color, 48% KL

(Thakur , 2004)

Aneurinibacillus aneurinilyticus

Bacillus sp.

Paenibacillus

56% color, 33% KL

65% color, 37% KL

43% color, 30% KL

(Chandra et al., 2007)

Pseudochrobactrum glaciale,

Providencice ettgeri

Pantoea sp.

96.02% color,

84.13% KL

(Chandra and Singh, 2012)

Comamonas sp.

32% KL

(Chen et al., 2012)

Citrobacter sp. Citrobacter freundii

49% , 54% color

(Chandra and Bharagava , 2013)

Beta-proteobacterium Cupriavidus basilensis

31.3% KL

(Shi et al., 2013)

4.0 Chemical nature and characteristics of effluent

The characteristics of the wastewater released from various processes of pulp and paper mill depend upon the type of the raw materials, type of process, internal recirculation of effluent for recovery process technology applied and the amount of water used in particular process. The color and BOD as high as 65,000 CU and 16,000 mg/L respectively were reported (Singh et ai., 1996). However, most paper mill wastewaters are characterized by extreme color, suspended solids, high concentration of nutrients, bad smell, Chemical oxygen demand, Biological oxygen demand, Total suspended Solids and toxicity (Pokhrel and Viraraghavan, 2004). Organic compounds including natural products, such as resin and fatty acids (wood extractives), additives used during paper-making, such as surfactants], biocides, and phenolic compounds and by-products generated during bleaching, such as furans and dioxins (Lacorte et al., 2003). The characteristics of wastewater produced at various pulp and paper processes are shown in Table 2.

Table.2 Effluent characteristics at various pulp and paper mill process (Pokhrel and Viraraghavan, 2004)

Process	pH	TS (mgl^-1)	TSS (mgl^-1)	BOD (mgl^-1)	COD (mgl^-1)	Color (Pt-Co)
Large mills (India)	11.0	5250	1233	983	2530	Black
Small mills (India)	12.3	15,120	4890	2628	6145	DB
Digester house	11.6	51,589	23,319	13,088	38,588	16.6
Combined effluent	7.6	3318	2023	103	675	1.0
TMP whitewater	4.7	-	91	1090	2440	-
TMP whitewater	4.7	-	105	1125	2475	-
Kraft mill	8.2	8260	3620	-	4112	4667.5
Pulping	10	1810	256	360	-	-
Kraft mill (unbleached)	8.2	1200	150	175	-	250
Bleached pulp mill	7.5	-	1133	1566	2572	433
Bleaching	2.5	2285	216	140	-	-
Pulp and paper	7.8	4200	1400	1050	4870	DB
News air and land paper	8.3	450	400	16	78	-
Paper making	7.8	1844	760	561	953	Black
Paper mill	8.7	2415	935	425	845	DB
Paper machine	4.5	-	503	170	723	243
Paper machine	8.3	-	1032	240	-	-
TS: Total solids, TSS: Total suspended solids, BOD: Biological oxygen demad, COD:Chemical oxygen demand, DB: Dark brown.

5.0 Environmental Consequences

Mandal and Bandana (1996) reported on the slight health impacts like vomiting, nausea, eye irritation and diarrhea on worker and children’s caused by effluents. The pollutants released from mill have an effect on all aspects of environment such as soil, water and air. Loss of environmental aesthetic beauty, color problem, scum formation, thermal impact, and slime growth is caused by waste water released from mill (Pokhrel and Viraraghavan 2004).Increase in amount of toxic substances by effluent in water causing death of fish and zooplankton, and extremely has an effect on the terrestrial ecosystem. (Kovacs et al., 2002; Fentress et al., 2006; Merilainen et al., 2008).

5.1 Aquatic systems

Color isn’t only aesthetically intolerable however conjointly inhibits the usual process of photosynthesis in streams because of sunlight absorbance (Kringstad et al., 1984). The dark brown color of pulp and paper effluent is principally attributable to their partially degraded and high contents of oxidized lignin..Because of these, aquatic ecosystem chains, as the growth of primary as well as secondary and tertiary consumer is adversely affected (Joyce et al, 1984; Sahoo et al., 2005). Delayed sexual maturity, changes in fish reproduction, smaller gonads, and depression in secondary sexual characteristics is demonstrated (Munkittrick et al., 1997). Aquatic life is affected by pulp and paper effluents that are discharged into estuarine, marine ecosystem and fresh water. At different times various authors reported that the effluents have toxic effects on various fish species. Many authors studied the occurrence of toxic compounds in fish and toxic effects on them like mixed function oxygenase activity, respiratory stress, mutagenicity and toxicity, genotoxic effect or liver damage (Owens et al., 1994; Vass et ai., 1996; Baruah et al., 1997; Johnsen et al., 1998 Lindstrom et al., 1998; Leppanen et al., 1999; Erisction et al., 2000; Schnell et al., 2000). In terms of lignin, the combined pollution load of is concerning fourfold higher than that of larger paper mills. The high chemical diversity of these pollutants causes a variety of mutagenic, carcinogenic, clastogenic and endocrinic effects on fishes were reported due to the presence of large diversity of contaminants bodies (Ali and Sreekrishnan, 2001). The environmental effect of paper and pulp mills is of particular concern since these units release 150-200 m3 effluent/ton paper with a high pollution loading of 85-370 kg biochemical oxygen demand (BOD)/ton paper, 90-240 kg suspended solids /ton paper, and 500-1100 kg chemical oxygen demand (COD)/ton paper (Mathur et al., 2004). Apart from the pollution, there is a increasing water paucity and deterioration in water quality in many parts of India. Thus, in the context of reduced freshwater availability, declining water quality and environment pollution from inadequately treated effluent, there is an urgent need for efficient water management in pulp and paper mills. About 500 different chlorinated organic compounds have been identified in paper mill effluents (Savant et al., 2006). The maximum permissible limit as per Central Pollution Control Board and Ministry of Environment and Forest for pulp and paper mills wastewater discharge shown in Table 3.

Table.3 Permissible limit as per Central Pollution Control Board and Ministry of Environment and Forest for pulp and paper mills wastewater discharge (Garg, 2012)

Parameters	Permissible limit
Color (PtCo units)	-
pH	5.5-9.0
Temperature	Should not exceed 5°C above receiving water temperature
Biological oxygen demand	30(inland surface water, 100(land irrigation)
Chemical oxygen demand	250
Total dissolved solids	1,500
Total suspended solids	100(inland surface water), 200(land irrigation), 600 (public sewers)
Total solids	-
Chloride	600 (inland surface water),250 (land irrigation)
Alkalinity	-
Hardness	-

5.2 Agriculture (crop and soil)

Howe and Michael in 1988 resulted that the serious change in soil chemistry is caused by treated pulp and paper mill effluent. It was also showed serious concerns associated to the surface plankton population change in wetland ecosystem caused by effluent (Baruah, 1997).The toxic effects on paddy field is studied by Datta et al, 1999. Paper mill effluent causes slow down germination of crops, leaf blade damage and reduced crop yield (Somshekar et al, 1984; Sundari and Kanakarni, 2001).

6.0 CONCLUSION:

It is concluded from this review that Pulp and paper industrial effluent contains high diversity of xenobiotic and recalcitrant compounds. The main contributor of toxicity and color of wastewater is Kraft lignin. Although color removal is a demanding process to the waste water treatment of pulp and paper mill, the outcome of this findings and literature suggest a great potential for bacteria to be used to decolorize wastewaters. The microorganisms are adaptive in nature and can degrade contaminants. However, potential of the strain desires to be established for its application in wastewater treatment. Bacterial bioremediation was found to cover wide range of pollutant degradation and is known to be a improved choice because of its nature of degradation.

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Received on 13.05.2015 Modified on 28.05.2015

Res. J. Pharmacognosy & Phytochem. 7(3): July-Sept. 2015; Page 175-181

DOI: 10.5958/0975-4385.2015.00022.9