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Advances in Environmental Biology
Advances in Environmental Biology, 8(11) Special 2014, Pages: 1387-1394 AENSI Journals Advances in Environmental Biology ISSN-1995-0756 EISSN-1998-1066 Journal home page: http://www.aensiweb.com/AEB/ The Introduction of Chemical Contaminants Present in the Effluent Pulp and Paper Industry and Reviews the Methods Determine the Extent of the Degree of Pollution of Organic Compounds Jafar Azimvand and Aazam Monfared Payam Noor University of Tehran ARTICLE INFO Article history: Received 15 April 2014 Received in revised form 22 May 2014 Accepted 25 May 2014 Available online 15 June 2014 Keywords: Paper industries, industrial effluents, lignin, chlorinated compounds, resin acids, BOD, COD, TOD ABSTRACT In addition to lignin and its compounds, Wood extractives such as tannins, fatty acids, aromatic acids, terpenes and plant gums With the creation of the suspended organic matter, coloring and inorganic solids, in paper pulp production processes also play a major role in establishing biochemical contamination. These pollutants are mainly polar, hydrophobic, negatively ionic charged, high molecular weight and are containing functional groups, hydroxyl, carboxyl attached to the aromatic rings, alkenes bonds, organic- metal complexes, radicals free and quinonic buildings. The major pollutants in the water supplies of the paper industry originate of two important chlorinated compounds based on bleached processes unsaturated resin acids in pulp . Different measures designed to detect and measure the amount of organic pollutants in aqueous,that the most important parameters is DO ،BOD ، COD ، TOD and TOC . Values obtained for the COD was between 5000 to 6000 that is representing highly concentrated wastewater and contaminated. The COD (total organic compounds in sewage) Most of the BOD is an indicator of biodegradation organic matter . So the ratio COD / BOD can be used as a criterion be considered for the biological degradation of the aquatic environment . Whatever this ratio is closer to 1,destruction of biological compounds was more and Fewer toxic effects may lead to . COD test for most organic compounds have shown good agreement with the values of the TOD, However, the BOD value indicate lower values almost always . The reason for this is the lack of complete oxidation aqueous biological . Also comparison BOD data with TOC does not appropriate based on the equations and BOD5/TOC rate is always between 1/2 and 2 are variable. © 2014 AENSI Publisher All rights reserved. To Cite This Article: Jafar Azimvand and Aazam Monfared., The Introduction of Chemical Contaminants Present in the Effluent Pulp and Paper Industry and Reviews the Methods Determine the Extent of the Degree of Pollution of Organic Compounds. Adv. Environ. Biol., 8(11), 1387-1394, 2014 INTRODUCTION Paper industry despite the growing need to produce, However, are one of the largest industries in the production of contaminated wastes. The wastewater due to various compounds extracted from trees such as lignin, resin and other polymer pollutants, In addition, very intense color, also strongly affects on aquatic life and has a heavy environmental consequences [24]. The colored wastewater discharged to the environment be prevented photosynthetic activity of plants, so reducing the influence of sunlight to the water and reduction of the amount of oxygen dissolution, apart from the direct effects of acute and chronic toxicity on aquatic. These issues determines the necessity of the discharge of effluents before discharge into rivers or the environment. The pollution load reduction and color removal from wastewater, Has been one of the greatest research topics during a few decades ago and many efforts have been done in this field,to the addition to the practical effect of local standards, is Economic justification of the appropriate. production wastes Color in the paper industry is one the most important pollutants. Generating of colors in the wood and paper effluents have a large variety. The most important of them is lignin that has the organic-polymer structure . Lignin derivatives which are formed due to the destruction and degradation are also important factors in the production Color. Other components of wood extractives such as resin, wood extracts, synthetic pigments, tannins (gallic acid), organic acids aromatic terpenes and degradation products from Chlorine and lignin reaction of and …are other resources of colorimetric in the wastewater. These compounds due to the negatively charged are ions. Because of Corresponding Author: Jafar Azimvand, Payam Noor University of Tehran. 1388 Jafar Azimvand and Aazam Monfared, 2014 Advances in Environmental Biology, 8(11) Special 2014, Pages: 1387-1394 macromolecules, are high molecular weight. Compounds are hydrophobic and polar structure. The severity of pollution and the importance of preserving natural ecosystems, apparent necessary to study in more serious about the of the wastewater treatment of paper manufacturing [22,11]. 1 - Measure and determine the degree of severity of organic pollution in wastewater: To assess and determine the degree of severity of organic wastewater contaminants, used of the specific tests,that Some of them are discussed in the following explanation. 1-1 - dissolved oxygen (Do): The amount of dissolved oxygen in the water and wastewater depends on the activity of biochemical, chemical and physical water environment. Test (Do) is a major and determinant in the evaluation water and wastewater treatment and control of waters pollution biological process. The amount of dissolved oxygen in the water and wastewater depends on the chemical and biochemical activities and physical on the water [18]. 1-2 - biochemical oxygen demand (BOD): The amount of dissolved oxygen consume during the biochemical oxidation of organic matter by bacteria and aerobic microorganisms is called the BOD. Because this value is a function of time and temperature are measured at 20 C ̊ . In biological processes, organic matter or reach nutrients consumed by the bacteria Or on the Oxidation of And break bonds with the enzyme secreted by substances such as phosphates, Are converted to other substances such as CO2, H2O and NH3 or is the mere formation of new cell mass [21,8]. 1-3 - chemical oxygen demand (COD): COD is the total amount of oxygen for the oxidation of organic matter in the solution, whit convert to the water and CO2. This is the criterion for diagnosis amount Sewage contaminated and wastewater organic impurities. Also by having BOD and COD values the possible options, the maneuver for refining operations the further. For example, what the BOD and COD values are closer to me, It is more possible capability wastewater treatment by biological methods. This feature can be estimated based on the ratio of COD/DOD and if this ratio was larger of 5, It seems appropriate treatment by biodegradation. COD values are always higher than BOD, Because this the parameters are indicated total the material that both biological and chemical that have the ability to oxidize. COD less than 400ppm reagent diluted sewage and COD higher than 1500ppm reagent waste is highly concentrated [4,16,5,3]. 1-4 - total organic carbon (TOC): Carbon total in the sample solution is called TC and carbon total attached to the organic material in the sample solution is called TOC. overall organic carbon in water and wastewater (TC), is Contains a number of organic compounds in different oxidation states. Some of these compounds can be oxidized during chemical and biological treatment. Therefore, BOD and COD parameters are used to determine this the quantity . But TOC unlike BOD and COD, is independent of the oxidation state of the organic matter and is not measured the amounts of other elements such as oxygen and nitrogen that the bound in organic matter, [2]. 1.5 - total Oxygen Demand (TOD): 2 - Building pigment and Chromogenic compounds found in wastewater: 2-1 - The origin of color in waste paper industry: Color is the most important pollutants in paper waste to remove it is always are important in terms of waste control and environmental conditions . Among the polymeric complex compounds available in wood, such as lignin and its derivatives, the most Pollutants and productive colors in the paper waste. In addition to lignin and its derivatives, Wood extractives such as resin, tannins, fatty acids, aromatic acids, terpenes, plant gums and also play an important role in the development of the contaminants. These are compounds polar and hydrophobic and having the negative charge, the ionic, high molecular weight, hydroxyl and carboxyl groups that whit cations are held and by physical methods are separable easily . Along those chemical materials are used during the production process with additives and pigments, are major causes of pollution and effluent color paper. Another part of dyes wastewater, extractives are that the effect of heat treatment of wood before burning isolated of the wood and the causing Colored effluents. The main Color in the paper industry wastewater, occurs of the chips production process of pulp and black liquor bleaching process and another portion of the carbohydrate analysis of available of wood building. Major causes of color in paper industry waste is formed by the quinone, free radicals, organic-metal complexes, alkenyl groups (-CH = CH-) and carbonyl groups (C = O) attached to the aromatic ring. Among the above, the double bond groups attached to the aromatic ring and the quinone groups, been announced the main causes of color in the effluent. Also results of nuclear magnetic resonance (NMR) in the waste water produced in the Kraft process, Showed that the chemical groups caused the Color, are benzilic compounds, aromatics, acid anhydride, cyclic aromatics, ketones, phenols, carboxylic acids and alkynes [17,12]. 1389 Jafar Azimvand and Aazam Monfared, 2014 Advances in Environmental Biology, 8(11) Special 2014, Pages: 1387-1394 2-2 - lignin and its derivatives: Lignin is a major contributor in establishing effluent color, Lignosulfonatha is the Compounds derived from lignin degradation and are very complex. Because a variety of factors including color, dual band, benzene ring and the carbonyl group are present in lignin, identifying and separating them is a very difficult of the paper Waste. Hydroxyl groups, phenyl, benzyl hydroxyl, carbonyl group have the important role of the chemical activity of lignin. Lignin in normal mode insoluble in water and many solvents. Lignin has a high affinity for reaction and this feature is controlled by the Group of phenolic and aliphatic hydroxyl. The presence of carbon in the diphenyl carbon rings, have been introduced the main factor of stability of lignin and its derivatives . Due to lignin react with strong oxidizing agents, Lignin components are divided into two groups of the acidic solution (such as aromatic compounds by low molecular weight) Insoluble acid groups (including aliphatic components with high molecular weight). The second part consists of a mass production of color is due to lignin. In both groups,carry of negative with a high density in aqueous solution, So they exist in solution as colloidal. Shown that over 63% of TOC in the paper industry effluent is Consequently, the presence of acid insoluble lignin (15,30,12]. MATERIALS AND METHODS Organic pollutants may cause odor, color, flavor unpleasant to water. Because of the great variety of organic materials and requires to the long tests, The usual procedure is that organic impurities are reported with some testing on these indexes. 1. Chloride measurements: This is the method involves titration with bromine chloride or silver nitrate standard at approximately neutral pH and exposed to chromate ions as reagent. At the end appears brick-red precipitate of silver chromate. This method is used for relatively transparent waters. To do this experiment, if the sample is highly color, 3cc of aluminum hydroxide was added and shake, then smooth it. If there is a sulfide ions in the sample, with the addition of the hydrogen peroxide solution to the value of 1ml remove the Disturbance . Then we set the PH of the sample Between 7-10 by the hydroxide sodium solution and hydrochloric acid 1N. adding 1ml of Potassium chromateas the indicator, and titration with a solution of 0.0141 N silver nitrate. The final point is seen whit a brick red precipitate. Do the same operation with distilled water. Use silver nitrate to distilled water is between 0.2 and to 0.3/ml [12]. 2. Measure dissolved oxygen (DO) to the method iodometry (Method Winkler): In this method, the dissolved oxygen in the water with the manganese salt Produces manganese oxide and the effect Hydrochloric acid to produce oxygen, That is the result of oxygen causes of the release of iodine of the(KI), and (2I-) released by 0.01N sodium hyposulphite Be measured in the presence of starch adhesive. The oxidation of Mn+ 2 to Mn+ 4 in an alkaline environment by oxygen, and then Mn+4 iodide ion (I-) in acidic environment (H2SO4) is oxidized to Free iodine (I2). And amount of free iodine can be measured by titration with sodium thiosulfate [18]. For this experiment in the BOD bottles Pour to the extent 250ml water samples. adding of 2ml manganese sulfate and 2ml alkaline iodide reagent (KI, NaOH), If there is oxygen is formed Brown sediment Mno2. Mn 2 2OH MnOH 2 1 MnOH 2 O2 MnO2 H 2O 2 Then we adding amount 2ml of concentrated acid (H2SO4), to be solved the sediment . MnO2 2 I 4 H Mn 2 I 2 2 H 2O Finally, the amount of 200ml of the solution was titrated with thiosulfate until the appearance of yellow color. I 2 2 NaS 2O3 Na2 S 4 O6 2 NaI Iodine against Starch adhesive is blue that to reduction I2 to I- is colorless. In order to eliminate nitrite interference is used of the Sodium azide that the conversion of nitrite to N2 gas. Finally, we note the volume of thiosulfate used and to obtain of the following equation in terms mg/l of the amount of dissolved oxygen [20,31,6,27,12,19,28,9]. A N 8000 DO mg l Vsam 1390 Jafar Azimvand and Aazam Monfared, 2014 Advances in Environmental Biology, 8(11) Special 2014, Pages: 1387-1394 A = volume consumed of thiosulphate N = thiosulfate normality Vsam = volume of sample (200 ml) 3. Measuring biological oxygen demand (BOD): Is one of the indicators the Water pollution in the organic material. This index shows the contaminants that aerobic bacteria are able to decompose it. This test is not present in the Toxic Substances and are present all the essential nutrients required for bacterial growth, such as nitrogen and phosphorus. should be present Group of organisms called seed. To perform this test, two bottles are filled from a contaminated water. The DO level is measured, then is another bottle into the water flow to the 5 days. After 5 days, measured the DO the second dish and DO difference dish the first two determine the BOD 5. The test must be performed at a temperature 20°C [20,31,6,27,12,19,28,9]. Then the dilution water Not been seeding: D D2 BOD mg 1 l P Then the dilution water been seeding: D D2 B1 B2 1 P BOD mg 1 l P D1 = DO of diluted sample after 15 minutes no seeds volume +water volume) / volume of waste P with = (wastewater D2 = DO of diluted sample after 5 days of incubation with no seeds B1 = DO of diluted sample containing seeds after 15 minutes B2 = DO of diluted sample after 5 days in an incubator containing seed P = dilution factor (percentage of samples diluted) 4. Measuring chemical oxygen demand (COD): Another test that can be done in addition to BOD on the Sewage samples to assess the amount of organic material (organic load), is C.O.D test. This test is used to determine the oxygen required for the oxidation of organic material in the sample, which is talented oxidation by a strong oxidizing agent such as permanganate or dichromate. Cn H aOb N c dCr2O7 2 8 d c H nCO2 a 8 d 3c H 2O cNH 4 2dCr 3 2 d 2n a b c 3 6 3 2 So COD test results are usually greater than BOD. COD test can be done much faster than BOD and only takes 3 to 4 hours but BOD takes at least 5 days. To determine the amount of residual potassium dichromate in the COD test, Use of a substance that contains bivalent iron, having high regenerative power and are the titration by residual potassium dichromate. This article is called ferrous ammonium sulfate (FAS). Here for the removal of nitrite ions, chlorine and bivalent iron is used respectively of the soulfumic acid, mercuric sulfate and phenanthroline [2]. We need to COD test to the a control sample and a sample of sewage. In the control sample is used of the Distilled water. First, 20cc distilled water Pour into the distiller flask and then adding 0.4gr of mercury sulfate. Then adding 10cc of potassium dichromate 0.25N . adding amount 30cc of concentrated sulfuric acid the top of the condenser and distilled in the temperature 150°C and for 2 hours. 2 to 3 drops adding of ferroin to be blue. Finally, Will titrated with ammonium ferrous sulphate, Beginning the solution color convert of the blue to Green. Then the much titers continue to be a soluble the red-brown. Color changes from green to red-brown is shown in the below [20,31,6,27,12,19,28,9]. 2 6 Fe3 Cr2O7 14H 6 Fe3 2Cr 3 7 H 2O This test need to a control always. Ferroin reagent in the following reaction will change from blue to red. Ph 3 Fe 3 e Ph 3 Fe 2 Then put it in the following formula: 8000 A B N COD mg l Vsam 1391 Jafar Azimvand and Aazam Monfared, 2014 Advances in Environmental Biology, 8(11) Special 2014, Pages: 1387-1394 A: ferrous ammonium sulfate used to control B: ferrous ammonium sulfate, for example N: ferrous ammonium sulfate normality 5. Total organic carbon (TOC): If the effluent sample is heated . Carbon and organic matter available in the samples burned, and is converted to the carbon dioxide, So carbon dioxide produced by heating the sample, is a good measure of the concentration of organic matter in samples,that the TOC test is based on it. In the TOC test method is used to heat, oxygen, ultraviolet radiation, chemistery Oxidizing, and TOC measures with an infrared analyzer or other devices . In fact some of the organic compounds such as lignin, tannin, humic substances, and various aromatic compounds are found naturally in water and wastewater, that strongly absorb UV light [2]. RESULTS AND DISCUSSION The amount of oxygen absorbed by the flow of contaminated water can be measurement and estimated with the methods of BOD5, COD, TOC, and TOD. The most common test is, biological oxygen demand(BOD5)in the 5-day.But apply the BOD test data is not easy. And knowledge of the properties of the tested water It is essential [10,32]. Since the BOD5 test takes 5 days, For faster access the Many attempts have been made to achieve faster test methods and techniques. As compared to BOD and TOC data show (diagram 1), Between BOD and each of these tests, there is no substantial correlation. Diagram 1: Comparison of TOC and BOD5 samples mixed in seven factories bleached kraft pulp. In the case of some of the wastewater has been observed Strong correlation (diagram 2), But rapid detection one or two the BOD waste flow, does not provide sure basis for pollution control and decisions [10]. Diagram 2: Total soluble Solids in comparison to the BOD5 filtrate Solution. Toxic pollution: Intense toxicity not considered In the case of pulp and paper industry of effluents usually. But the number of toxic components in this type of waste are : A. chlorine Phenols: The most important cause of toxic contaminants in the paper industry, Discharge of effluent from bleached with is based processes chlorine compounds. Many chlorinated organic compounds, are produced chlorinated lignin remaining in the pulp [25]. For the detection and measurement of halogenated organic compounds, is used of the Chromatographic separation techniques and mass spectrometry. But for everyday testing in industrial units, Use these methods are 1392 Jafar Azimvand and Aazam Monfared, 2014 Advances in Environmental Biology, 8(11) Special 2014, Pages: 1387-1394 not practical and most used to the general measure methods. The first method for measuring the total amount of halogenated organic compounds is TOX and the method second AOX. TOX represents the amount of organic halogen samples are smooth, while AOX is measured the sample not smooth [25]. Dioxins are of particular groups of the chlorinated organic compounds that are associated with pulp and paper production. Dioxins are worrying because of its toxicity extremely high. In terms of molecular, dioxins are divided into two categories Poly-chloro di-benzyl-dioxins (PCDD5) and poly-chloro di-benzyl- furan (PCDF5) [25]. B. Resin and unsaturated acids: Is known that resin acids in pulp, especially acids from of the softwoods, are high toxicity to aquatic organisms. The amount this of the material in the wood of different species vary greatly (Table 1) [25]. Table 1: Levels of resin acids in wood of different. Typical Normal lobeloly monterey southern Pine Pine pines pines Resin 3.3-17 3.9-12.3 6.9-15.2 6.5-3.3 acids )gr/ton( White cypress 1.2-2 sysco cypress 7.2 douglas yew 2-4 alpine yew 0.3 western hemlock 8.0 red cedar 21 Toxicity of each of these materials is also variable (table 2). Table 2: Introduced Toxicity of resin acids. resin dehydroabietic palustric acids acid acid 96h L 1.1 0.5 C50 (mg/l) abietic acid 0.7 Isopimaric acid 0.4 Pimaric acid 0.8 neoabieti c acid 0.6 sandara copymaric acid 0.4 levopimaric acid 0.7 The main limitation is that the traditional toxicological tests,only fatal and severe toxic effects just detectable and is not considered cumulative poisoning of long-term [25,32]. A comparison of the theoretical oxygen demand, chemical and biological, Some of the chemicals material are listed in Table 3. Table 3: Comparison between TOD, COD and BOD multiple chemical contaminants in food. Chemical composition TOD COD Glucose C6H12O6 1.2 1.1 Acetic acid CH3COOH 1.06 1.05 Phenol C6H5OH 2.38 2.24 Formic acid HCOOH 0.34 0.34 BOD 0.6 0.5 1.8 0.2 COD/BOD 1.83 2.1 1.24 1.7 The experiment determination of COD for most organic compounds are consistent with the values of the TOD. But the amount of BOD almost always shows the less values. The reason for this is the lack of complete oxidation of aqueous environment (Biological). The ratio of COD/BOD can be used as a criterion for biological degradation of the water environmen, Whatever this is closer to 1 ratio, is more destruction of biological compounds. In the discharge of industrial food, we're dealing usually, with a mixture of food with the unknown combination. As a result could not be determined by TOD, Hence the amount of COD to be determined by laboratory methods. Determination of COD or BOD that represents the amount of dissolved oxygen, appropriate criteria to determine the effects of effluent on the receiving water resources. A simulation of the pollution effect of food on the water is drawn in the diagram 3 . Diagram 3: Models discharge an effluent containing nutrients (sewage) on a river. 1393 Jafar Azimvand and Aazam Monfared, 2014 Advances in Environmental Biology, 8(11) Special 2014, Pages: 1387-1394 Conclusions: In the process of the production of paper and cardboard industries, to consume large volumes of water. In this industry the natural plants are used as raw materials. In this process, a chemical material added to natural plants, and the resulting mixture is cooked at a certain temperature. Finally, the from mixture is extracted only cellulosic materials and the remaining impurities are excreted the form of wastewater. Pulp and paper industry is among the most polluting industrial waterways. 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