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Peat Water Treatment Using Combination of Cationic Surfactant Modified Zeolite, Granular Activated Carbon, and Limestone
Tweet MyronLMeters.com attempts to provide its customers with the latest in water quality research and industry updates. Find more at https://www.myronlmeters.com/. Abstract This research was conducted essentially to treat fresh peat water using a series of adsorbents. Initially, the characterization of peat water was determined and five parameters, including pH, colour, COD, turbidity, and iron ion […]
MyronLMeters.com attempts to provide its customers with the latest in water quality research and industry updates. Find more at https://www.myronlmeters.com/.
This research was conducted essentially to treat fresh peat water using a series of adsorbents. Initially, the characterization of peat water was determined and five parameters, including pH, colour, COD, turbidity, and iron ion exhibited values that exceeded the water standard limit. There were two factors influencing the adsorption capacity such as pH, and adsorbent dosages that were observed in the batch study. The results obtained indicated that the majority of the adsorbents were very efficient in removing colour, COD, turbidity at pH range 2-4 and Fe at pH range 6-8. The optimum dosage of cationic surfactant modified zeolite (CSMZ) was found around 2 g while granular activated carbon (GAC) was exhibited at 2.5 g. In column study, serial sequence of CSMZ, GAC, and limestone showed that the optimal reduction on the 48 hours treatment were found pH = 7.78, colour = 12 TCU, turbidity = 0.23 NTU, COD = 0 mg/L, and Fe= 0.11 mg/L. Freundlich isotherm model was obtained for the best description on the adsorption mechanisms of all adsorbents.
Keywords: cationic surfactant modified zeolite, granular activated carbon, limestone, peat water
Water is essential and fundamental to all living forms and is spread over 70.9% of the earth’s surface. However, only 3% of the earth’s water is found as freshwater, of which 97% is in ice caps, glaciers and ground water (Bhatmagar & Minocha, 2006). In Malaysia, more than 90% of fresh water supply comes from rivers and streams. The demand for residential and industrial water supply has grown rapidly coupled with an increase in population and urban growth (WWF Malaysia, 2004). Water demand in affected populations such as rural areas also demands that attention is paid to providing more sustainable solutions rather than transporting bottled water (Loo et al., 2012). For this reason, it is essential to ensure availability of local sources of water supply and even develop new potential sources of water such as from peat swamp forest to overcome future water shortages.
River water surrounded by peat swamp forest is defined as peat water and is commonly available as freshwater since it has a low concentration of salinity. The previous study shows that peat swamp forest has high levels of acidity and organic material depending on its region and vegetation types (Huling et al., 2001). Under natural conditions, tropical peat lands serve as reservoirs of fresh water, moderate water levels, reduce storm-flow and maintain river flows, even in the dry season, and they buffer against saltwater intrusion (Wosten et al., 2008).
Due to the acidity and high concentration of organic material, selective treatment of peat water must be conducted prior to its use as water supply. Recently, many methods have been designed and have proven their effectiveness in treating raw water such as coagulation and flocculation (Franceschi et al., 2002; Liu et al., 2011; Syafalni et al., 2012a), absorption (Ćurković et al., 1997), filtration (Paune et al., 1998) and combining (Hidaka et al., 2003). Careful consideration of the most suitable method is important to ensure that the adsorption process is the most beneficial, economically feasible method as well as easy to operate for producing high quality of water in a particular location.
Many researchers have shown that activated carbon is an effective adsorbent for treating water with high concentrations of organic compounds (Eltekova et al., 2000; Syafalni et al., 2012b). Its usefulness derives mainly from its large micropore and mesopore volumes and the resulting high surface area (Fu & Wang, 2011). However, its high initial cost makes it less economically viable as an adsorbent. Low cost adsorbent such as zeolite nowadays has been explored for its ability in many fields especially in water treatment. Natural zeolite has negative surface charge which gives advantages in absorbing unwanted positive ions in water such heavy metal. These ions and water molecules can move within the large cavities allowing ionic exchange and reversible rehydration (Jamil et al., 2010). The effectiveness of zeolite has been improvised by modified zeolite with surfactant in order to achieve higher performance in removing organic matter (Li & Bowman, 2001). Among tested cationic surfactants, hexa-decyl-tri-methyl ammonium (HDTMA) ions adsorbed onto adsorbent surfaces are particularly useful for altering the surface charge from negative to positive (Chao & Chen, 2012). Surfactant modified zeolite has been shown to be an effective adsorbent for multiple types of contaminants (Zhaohu et al., 1999).
Zeolite is modified to improve its capability of exchanging the anion by cationic surfactants, called CSMZ. CSMZ adsorbs all major classes of water contaminants (anions, cations, organics and pathogens), thus making it reliable for a variety of water treatment applications (Bowman, 2003). Nowadays, interest in the adsorption of anions and neutral molecules by surfactant modified zeolite has increased (Zhang et al., 2002). Modification of zeolite by surfactant is commonly done by cationic or amphoteric surfactants. By introducing surfactant to the zeolite, an organic layer is developed on the external surfaces and the charge is reversed to positive (Li et al., 1998). However, the present study used zeolite that had been modified using Uniquat (QAC-50) as cationic surfactant (CSMZ) and their performance towards the removal of color, COD, turbidity and iron ion from peat water were investigated.
Four adsorbents were used in these experiments which are natural zeolite, zeolite modified by cationic surfactant, activated carbon and limestone. All adsorbents were prepared with equivalent sizes of 1.18 mm – 2.00 mm. Hydrochloric acid (HCl) and sodium hydroxide (NaOH) were used for polishing zeolite during the preparation phase and for pH adjustment of the sample. Furthermore, potassium dichromate (K2CrO7), silver sulphate (Ag2SO4), sulphuric acid (H2SO4) and mercury (II) sulphate (HgSO4) were used as digestion solution reagents and acid reagents for COD analysis. Lastly, Uniquat (QAC-50) was used as cationic surfactant to modify the zeolite.
2.1 Preparation of Surfactant Modified Zeolite
In these studies, 100 g of prewashed natural zeolite was contacted with 5.6 ml/l Uniquat (QAC-50) as cationic surfactant (CSMZ). The mixture was then stirred at room temperature for 4 hours at 300 rpm (Karadag et al., 2007). The zeolite then was filtered and washed with distilled water several times. After that, the absorbent was dried in an oven at a temperature of 105 °C for 15 hours.
2.2 est Procedures
2.2.1 Batch Studies
Serial batch studies were conducted at room temperature (28 ± 1 °C) to investigate the influence of pH and dosage for removing colour, COD, turbidity and iron ion from peat water. Shaking speed of 200 rpm for 20 minutes were fixed and operated respectively. A working volume of 150ml peat water sample was set up in 250 ml conical flasks. Preceding the batch studies, initial concentration for those parameters was determined. The optimum pH and dosage of absorbent were determined. Subsequently, the percentage of removal was finally determined, plotted, and compared.
2.2.2 Batch Column Studies
Column studies were carried out using a plastic column with dimensions: 5.4 cm diameter and 48 cm length. Three adsorbents were filled inside the column at a specific depth with the supporting layers of marbles, cotton wool, and perforated net. Total volume of 2000 ml peat water was pumped in the up flow mode from the vessel into the column by using a Masterflex peristaltic pump at a minimum flow rate of (30, 60, 90) ml/min. In this study, however, column studies were performed un-continuously (batch) due to limitations of time. All parameters related to the column design are summarized in the following Table 1.
Table 1. Column studies parameters
|Horizontal Surface Area, A||cm2||
|Column volume, V||cm3||1099.3|
|Flowrate, Q||ml/min||30, 60, 90|
|Surface Loading Rate, SLR= Q/A||cm/min||1.31, 2.62, 3.93|
The serial sequence arrangements of adsorbents were conducted as shown in Figure 1 below. Effluent samples were collected at various time intervals, whilst maintaining room temperature, and analysed.
Figure 1. Schematic diagrams of lab-scale column studies
3. Results and Discussion
3.1 eat Water Characterization
Surface water originating from the peat swamp forest was taken from Beriah peat swamp river along the Kerian River on several occasions as the main sample. The characterization of peat water was carried out at the sampling point (in-situ measurement) using a multi-parameter probe as well as in the environmental laboratory of civil engineering, USM. Fundamentally, the characterization procedures were based on the Standard Methods for the Examination of Water and Wastewater (APHA, 1992). Table 2 represents the peat water characteristics in average value and the comparison to the standard drinking water quality in Malaysia.
Table 2. The characteristics of peat water sample from Beriah Peat Swamp Forest
|4.67 – 4.98|
Thirteen parameters were successfully determined where the first six parameters, including pH, temperature, TDS, DO, conductivity, and salinity were measured at the sampling point, whilst the rest of the parameters, including colour, turbidity, COD, iron ion, Ammoniacal Nitrogen, NH3-N, Ammonia (NH3), and Ammonium (NH4+) were examined from the sample brought to the environmental laboratory on the same day.
Acidic pH of the peat water was predicted due to the composition of the surrounding peat soil itself which had been formed by decaying material possessing humic substances (Rieley, 1992). Besides that, humic substances also lead to the high organic content as humic substances are comprised of numerous oxygen containing functional group and fractions (humic acid, fulvic acids and humin) with different molecular weights which mean yielding high concentration of turbidity and COD as well as coloured water (Torresday et al., 1996). Moreover, composition of peat soil may also have an impact on the iron ion concentration of peat water (Botero et al., 2010).
From the thirteen parameters, five parameters were indicated exceeding the standard limit. These parameters were pH, colour, turbidity, COD, and iron ion that showed values of 4.67 – 4.98, 224.7 TCU, 20.8 NTU, 33.3 mg/l, and
1.24 mg/l respectively while the standard limit of these parameters are 6.5 – 9.0, 15 TCU, 5 NTU, 10 mg/l, and 0.3 mg/l accordingly.
3.2 Effect of Initial pH on the Efficiency of Colour, COD, Turbidity, and Iron Ion (Fe) Removal
Influence of initial pH on the adsorption capacity for removing colour, COD, turbidity, and iron ion were investigated.
Figure 2(a) to Figure 2(d) below, displayed the percentage removal of colour, COD, turbidity, and iron ion against pH of adsorbents respectively.
Figure 2(a) shows the maximum removal percentage of colour that was removed by natural zeolite, CSMZ, and granular activated carbon (GAC) which were 79%, 90%, 82% respectively. This adsorption is depended on the characteristic of adsorbents itself. For zeolite and CSMZ were related to the amount of cationic ions (Al3+) increased, resulting in high reaction activity and GAC was related to the adsorption capacity. It was observed that the adsorption capacity was highly dependent on the pH of the solution, and indicated that the colour removal efficiencies decreased with the increase of solution pH.
The pH of the system exerts profound influence on the adsorptive uptake of adsorbate molecules presumably due to its influence on the surface properties of the adsorbent and ionization or dissociation of the adsorbate molecule. Figure 2(b) represents the percentage removal of natural zeolite and CSMZ where they reach optimum efficiency in removing organic compound (COD) at pH 2 with efficiency of 53% and 60% respectively. Meanwhile, the highest percentage removal of COD for GAC was achieved at pH 4 with efficiency obtained about 61%. Identical trends in colour removal were exhibited in percentage removal of COD for natural zeolite, CSMZ and GAC. In fact, this result also reveals that GAC has the highest percentage removal among natural zeolite and CSMZ yet optimum in difference pH solution. Neutralization mechanism occurs in low pH makes color removal, COD removal and Turbidity removals at pH 2 are higher for most of absorbents in this process.
In Figure 2(c), percentage turbidity removal against pH for each adsorbent revealed that optimal reduction of turbidity was obtained in an acidic environment with efficiency removal of 96%, 98%, 95% for natural zeolite, CSMZ, and GAC respectively. When the pH of the solution was adjusted above pH 6 to pH 12, the tendencies of all adsorption performances were gradually decreased. Moreover, it also showed that the lowest efficiency for the three adsorbents were identified at pH 12 with percentage values removal 55%, 61%, and 59% for natural zeolite, CSMZ, and GAC respectively.
Figure 2(d) demonstrates the removal efficiencies of iron ion as a function of the influent pH. The maximum removal of iron ion was observed at pH 8 for both natural zeolite and CSMZ whereas GAC had its optimum removal at pH 6. Natural zeolite and CSMZ only yielded 73% and 62% removal efficiency while GAC had more significant removal with removal efficiency of 80% to the iron ion concentration. Further, it is evident from the graph that gradual increment of removal efficiency for natural zeolite, CSMZ, and GAC occurred when the initial pH of the solution was increased to higher values. Somehow, at pH values greater than 6 the removal efficiency of GAC reduced slightly while for natural zeolite and CSMZ the reduction occurred from pH values above 8.
3.3 Effect of Adsorbent Dosage on the Efficiency of Colour, COD, Turbidity, and Iron Ion (Fe) Removal
The effect of adsorbent dosage was studied for all adsorbents employed on colour, COD, turbidity, and iron ion removal by varying the dosage of adsorbent and keeping all other experimental conditions constant. The pH was set to acidic conditions which were most favourable in obtaining the highest removal efficiency. In this study, to find optimal adsorbent dosage of natural zeolite and CSMZ, the appropriate experiments were carried out at adsorbent dosages in the range of 0.5 g to 5.0 g while for GAC, the adsorbent dosage was varied from 0.01 g to 4.0
- The experimental results for all the adsorbents are represented by Figure 3(a) to Figure 4(d).
Figure 3. Percentage of color (a), COD (b), turbidity (c), and Fe (d) removal against pH for NZ, and CSMZ
Figure 3(a) displays the relationship between the amount of adsorbent mass (dosage) and adsorption efficiency for natural zeolite and CSMZ in terms of removing colour. The colour removal of peat water increased from about 25% to 52% with increasing adsorbent dosage of natural zeolite from 0.5 g to 3.5 g whereas for CSMZ, removal percentage increased from 41% to 53% with increasing adsorbent dosage from 0.5 g to 2.0 g. However, further increase in adsorbent dosage to 5.0 g only led to slight degradation of removal efficiency to 50% and 41% for natural zeolite and CSMZ respectively. This degradation with further increases in adsorbent dosage was due to the unsaturated adsorption active sites during the adsorption process since the adsorbates in the vessel were only shaken for 20 minutes (insufficient time). Besides, modification of zeolite by cationic surfactant had proven to have better colour removal as presented in the graph.
Percentage removal of COD against the adsorbent dosage is shown in Figure 3(b). It was observed that the highest percentage removal for both natural zeolite and CSMZ to remove COD were 51% and 59%, achieved at adsorbent dosage 3.5 g and 2.0 g respectively.
The variations in removal of turbidity of peat water at various system pH are shown in Figure 3(c). The removal rate of turbidity was highest at the adsorbent dosage of 0.5 g with 70% and 93% removal efficiency for respective natural zeolite and CSMZ. The removal rate showed a smooth downward trend with the increase in adsorbent dosage. Concurrently, the adsorption capacity gradually decreased with the increasing adsorbent dosage. The least efficient removal of turbidity was noted at dosage 5.0 g with percentage removal recorded for natural zeolite and CSMZ only 57% and 70% respectively.
Figure 3(d) demonstrates the percentage iron ion removal of natural zeolite and CSMZ with respect to their dosage. The result shows that there was a significant difference trend in iron ion adsorption efficiencies between natural zeolite and CSMZ. For natural zeolite, it was shown that the removal percentage of iron ion had increased until it reached 1.0g of dosage with 72% of removal efficiency. On the other hands, CSMZ was only able to remove about 63% of iron ion when its dosage was increased to 2.5 g. The lowest percentage removals were 47% and 57% recognized at the adsorbent dosage 5.0 g for respective natural zeolite and CSMZ.
Figure 4. Percentage of color (a), COD (b), turbidity (c), and Fe (d) removal against dosage for GAC
The result illustrated in Figure 4(a) shows the maximum removal percentage of colour for GAC at 2.5 g dosage was 62%. Moderate increment in colour removal was identified along with the addition dosage of 2.5 g whilst abatement of removal efficiency began subsequently at adsorbent dosage of 3.0 g to 4.0 g.
The results from Figure 4(b) indicated that increasing the GAC dosage would increase the efficiency in removing COD respectively. The optimum dosage was recorded at 3.0 g with 72% of removal efficiency. Meanwhile, increasing the dosage above 3.0 g exhibited a slight decrease in removal efficiency with 67% to 61% for COD removal. A better result in removing COD was also shown by GAC compared to the natural zeolite and CSMZ.
The percentage of turbidity removed by GAC in different dosages is described in Figure 4(c). The highest removal was indicated at adsorbent dosage 2.5 g with removal efficiency of 70% while the minimum removal was 52% recorded at the adsorbent dosage 0.01 g. However, starting from adsorbent dosage of 3.0 to 4.0 g, removal efficiency began to decrease to 68%, 67%, and 69% respectively.
The result of percentage removal of iron ion by GAC in peat water is presented in Figure 4(d). It was found that the rate of removal was rapid in the initial dosage between 0.01 g to 3.0 g at which the removal efficiency increased from 28% to 71% accordingly. Subsequently, a few significant changes in the rate of removal were observed. Possibly, at the beginning, the solute molecules were absorbed by the exterior surface of adsorbent particles, so the adsorption rate was rapid. However, after the optimum dose was reached, the adsorption of the exterior surface becomes saturated and thereby the molecules will need to diffuse through the pores of the adsorbent into the interior surface of the particle (Ahmad & Hameed, 2009).
3.4 Batch Column Experiment
On the first running, the column was packed with natural zeolite (1st layer), limestone (2nd layer), and GAC (3rd layer) as shown in Figure 5(a). Removal efficiency for colour, COD, turbidity, and iron ion was recognized to be increased when the contact time was increased. At the time interval 1 hour to 6 hours, however, the increment was not so significant. The removal efficiency at 1 hour treatment was 39%, 21%, 54%, 36% while at 6 hours treatment was 77%, 65%, 73%, 60% recorded for respective colour, COD, turbidity, and iron ion. Poor removal efficiency at 1 hour treatment indicated that the required time to remove all parameters were insufficient. It is evident that if the adsorption process is allowed to run for 24 hours on the column, the removal efficiency shows notable removal. Percentage removals of colour, COD, turbidity, and iron ion at 24 hours were 83%, 72%, 76%, 65% respectively. Furthermore, the highest removal for respective colour, COD, turbidity, and iron ion were obtained at 48 hours treatment with 87%, 81%, 86%, and 79% of removal efficiency.
Figure 5. Percentage removal of color, COD, turbidity, and Fe for 1st run(a), 2nd run(b), and 3rd run (c) at flowrate 30 ml/min
On the second running, the column was packed with CSMZ (1st layer), limestone (2nd layer), and GAC (3rd layer) as presented in Figure 5(b). The removal percentages of colour, COD, turbidity, and iron ion were noticed after 1 hour to be 52%, 49%, 71%, and 30% respectively. The time of contact between adsorbate and adsorbent is proven to play an important role during the uptake of pollutants from peat water samples by adsorption process. In addition, the development of charge on the adsorbent surface was governed by contact time and hence the efficiency and feasibility of an adsorbent for its use in water pollution control can also be predicted by the time taken to attain its equilibrium (Sharma, 2003). Removal efficiency of 90% for colour, 81% for COD, 91% for turbidity, and 57% for iron ion were obtained at 24 hours of contact time.
On the third running, the column was packed with a difference sequence of CSMZ (1st layer), GAC (2nd layer), and limestone (3rd layer) demonstrated in Figure 5(c). It can be seen that the adsorption of these four parameters were slightly rapid at time interval 1 hour to 6 hours treatment. Further gradual increment with the prolongation of contact time form 24 hours to 48 hours has also occurred. Observation at 1 hour treatment recorded the removal efficiency of 62%, 58%, 87%, and 48% for respective colour, COD, turbidity, and iron ion. Whereby, 6 hours treatment had yielded higher removal percentage removal of 75%, 77%, 93%, and 58% respectively for colour, COD, turbidity, and iron ion. Further removal of colour, COD, turbidity, and iron ion was recorded when the treatment was run for 24 hours which exhibited 92%, 91%, 98%, 77% of removal efficiency respectively. Prolonged time to 48 hours indeed showed better removal of colour, COD, turbidity, iron ion with percentage removal of 95%, 100%, 99%, and 89% respectively. It can be seen that the arrangement of CSMZ, GAC, and limestone has the highest removal efficiency for all parameters at the flow rate influent of 30 ml/min.
Figure 6. Percentage removal of color, COD, turbidity, and Fe against contact time for 2nd run(a) at flow rate 60 mL/min and at flowrate 90 mL/min (b)
The experimental adsorption behaviour was further seen for its adsorption capacity during 60 ml/min and 90 ml/min flow rate. In addition, the flow rate adjustment had also resulted in differences in surface loading rate in which the sample going through the surface area of adsorbent bed (horizontal surface area, A= 22.9 cm2) for 30 ml/min equals to 1.31 cm/min while the flow rate of 60ml/min equals to 2.62 cm/min, and the flow rate of 90 ml/min equals to 3.93 cm/min. The percentage removal for both flow rate adjustments of CSMZ, GAC, and limestone arrangement were exhibited in Figure 6 (a) and Figure 6 (b). Based on these Figures, lower removal efficiencies were indicated at 1 hour time interval of 6 hours of contact time. The percentage removals for both 60 ml/min and 90 ml/min flow rate at 1 hour were 57%, 56%, 80%, 38% and 49%, 58%, 61%, 35% for colour, COD, turbidity, and iron ion respectively. Subsequently, when the contact time was at 6 hours, the removal percentage were 70%, 79%, 88%, 56%, and 60%, 77%, 70%, 47%. However, the maximum removal efficiency at 48 hours for both flow rates was not much different from the 30ml/min flow rate.
3.5 Adsorption Isotherm
In the present investigation, the experimental data were tested with respect to both Freundlich and Langmuir isotherms. Based on the linearized Freundlich isotherm models for natural zeolite, CSMZ, GAC in terms of adsorptive capacity to remove colour, COD, turbidity, and iron ion, the majority of them exhibited fits for all adsorbate with regression value (R2) above 0.6, except for iron ion and turbidity for respective CSMZ, and GAC. On the other hand, the linearized Langmuir isotherm models for natural zeolite, CSMZ, GAC in terms of adsorptive capacity to remove colour, COD, turbidity, and iron ion, had exhibited fits for all adsorbate with regression value (R2) was at range of 0.242 to 0.912. The Langmuir isotherm model for all adsorption mechanisms were identified to have smaller R2 values compared to the Freundlich isotherm model. Thereby, it can be concluded that the Freundlich isotherm model was more applicable in determining the adsorption mechanisms for this study.
3.6 Peat Water Quality Post Column Treatment
Peat water treatment in column with serial sequence of natural zeolite, CSMZ, and limestone had exhibited the highest removal with percentage removal at 48 hours at 95%, 100%, 99%, and 89% for colour, COD, turbidity, and iron ion respectively. Final readings at 48 hours treatment on pH, TDS, DO, conductivity, salinity, colour, turbidity, COD, and iron ion were 7.78, 74 mg/l, 4.03 mg/l, 137 uS/cm, 0.05 ppt, 12 TCU, 0.23 NTU, 0 mg/l, and 0.11 mg/l respectively (see Table 3). These findings, on the other hand, have indicated that peat water treatment had successfully produced water which satisfied the standard drinking water quality.
Table 3. The characteristics of results of peat water treatment from Beriah Peat Swamp Forest
Note: 1. *)Malaysian standard for drinking water quality;2. NA = Not analyzed.
From the results presented in this paper, the following conclusions can be drawn:
1) The optimum removal of colour, COD, and turbidity for all adsorbents were observed to occur during acidic conditions at pH range 2 – 4 whereas for iron ion, the maximum removal was noted at pH range 6 – 8.
2) At pH 2, CSMZ yielded the highest removal for colour and turbidity with removal efficiency of 90% and 98% respectively. Meanwhile, GAC has the highest percentage removal of COD at pH 4 with removal efficiency obtained about 61% while at pH 6, GAC exhibited the best removal of iron ion with percentage removal around 80%.
3) CSMZ revealed stronger adsorptive capacity for colour, COD, and turbidity compared to natural zeolite.
4) The optimal removal was achieved for the serial sequence of CSMZ (1st layer), GAC (2nd layer), and Limestone (3rd layer) with the adsorbent media at 30 ml/min of flow rate.
5) Freundlich isotherm was more reliable to describe the adsorption mechanisms of colour, COD, turbidity, and iron ion for natural zeolite, CSMZ, and GAC.
The authors wish to acknowledge the financial support from the School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia and Universiti Sains Malaysia (Short Term Grant No. 304/PAWAM/60312015).
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Torresdey, J. L., Tang, L., & Salvador, J. M. (1996). Copper adsorption by esterified and unesterified fractions of sphagnum peat moss and its different humic substances. Journal of Hazardous Materials, 48, 191-206. http://dx.doi.org/10.1016/0304-3894(95)00156-5
World Wildlife Fund (WWF) Malaysia. (2004). The importance of rivers.
Wosten, J. H. M., Clymans, E., Page, S. E., Rieley, J. O., & Limin, S. H. (2008). Peat- Water interrelationships in a Tropical Peatland Ecosystem in Southeast Asia. Catena, 73, 212-224. http://dx.doi.org/10.1016/j.catena.2007.07.010
Zhang, P., Tao, X., Li, Z., & Bowman, R. S. (2002). Enhanced Perchloroethylene Reduction in Column Systems Using Surfactant Modified Zeolite/zero-valent Iron Pellets. Environmental Science and Technology, 36, 3597-3603. http://dx.doi.org/10.1021/es015816u
Modern Applied Science; Vol. 7, No. 2; 2013
ISSN 1913-1844 E-ISSN 1913-1852
Published by Canadian Center of Science and Education
S. Syafalni1, Ismail Abustan1, Aderiza Brahmana1, Siti Nor Farhana Zakaria1 & Rohana Abdullah1
1 School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia, Nibong Tebal, Penang, Malaysia. Correspondence: S. Syafalni, School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia,
Nibong Tebal 14300, Penang, Malaysia. E-mail: firstname.lastname@example.org
Received: December 3, 2012 Accepted: January 14, 2013 Online Published: January 22, 2013 doi:10.5539/mas.v7n2p39 URL: http://dx.doi.org/10.5539/mas.v7n2p39
Shared via Creative Commons Attribution 3.0 Unported license
Tweet Anyone responsible for operating and maintaining a swimming pool or spa has to test, monitor, and control complex, interdependent chemical factors that affect the quality of water. Additionally, aquatic facilities operators must be familiar with all laws, regulations, and guidelines governing what these parameters should be. […]
Anyone responsible for operating and maintaining a swimming pool or spa has to test, monitor, and control complex, interdependent chemical factors that affect the quality of water. Additionally, aquatic facilities operators must be familiar with all laws, regulations, and guidelines governing what these parameters should be.
Why? Because the worst breeding ground for any kind of microorganism is a warm (enough) stagnant pool of water. People plus stagnant water equals morbid illness. That’s why pools have to be circulated, filtered, and sanitized – with any number of chemicals or methods, but most frequently with chlorine compounds. However, adding chemicals that kill the bad microorganisms can also make the water uncomfortable, and in some cases unsafe, for swimmers. Additionally, if all the chemical factors of the water are not controlled, the very structures and equipment that hold the water and keep it clean are ruined.
So the pool professional must perform a delicate balancing act with all the factors that affect both the health and comfort of bathers and the equipment and structures that support this. Both water balance – or mineral saturation control – and sanitizer levels must constantly be maintained. This is achieved by measuring pertinent water quality factors and adding chemicals or water to keep the factors within acceptable parameters.
Water is constantly changing. Anything and everything directly and indirectly affects the relationship of its chemical parameters to each other: sunlight, wind, rain, oil, dirt, cosmetics, other bodily wastes, and any chemicals you add to it. Balanced water not only keeps swimmers comfortable, but also protects the pool shell, plumbing, and all other related equipment from damage by etching or build-up and stains.
The pool professional is already well acquainted with pH, Total Alkalinity (TA), and Calcium Hardness (CH); along with Total Dissolved Solids (TDS) and Temperature, these are the factors that influence water balance. Water that is in balance is neither aggressive nor oversaturated. Aggressive water lacks sufficient calcium to saturate the water, so it is hungry for more. It will eat anything it comes into contact with to fill its need, including the walls of your pool or spa or the equipment it touches. Over-saturated water cannot hold any more minerals, so dissolved minerals come out of solution and form scale on pool and equipment surfaces.
The pH of pool water is critical to the effectiveness of the sanitizer as well as the water balance. pH is determined by the concentration of Hydrogen ions in a specific volume of water. It is measured on a scale of 0-14, 0-7 being acidic and 7-14 being basic.
You must maintain the pH of the water at a level that assures the sanitizer works effectively and at the same time protects the pool shell and equipment from corrosion or scaling and the bathers from discomfort or irritation. If the pH is too high, the water is out of balance, and the sanitizer’s ability to work decreases. More and more sanitizer is then needed to maintain the proper level to kill off germs. Additionally, pH profoundly affects what and how much chemical must be added to control the balance. A pH of between 7.2 – 7.6 is desirable in most cases.*
As one of the most important pool water balance and sanitation factors, pH should be checked hourly in most commercial pools.* Even if you have an automatic chemical monitor/controller on your system, you need to double- check its readings with an independent pH test. With salt- water pools, pH level goes up fast, so you need to check it more often. Tests are available that require reagents and subjective evaluation of color depth and hue to judge their pH. But different users interpret these tests differently, and results can vary wildly. The PooLPRo and ULTRAPEN PT2 give instant lab-accurate, precise, easy-to-use, objective pH measurements, invaluable in correctly determining what and how much chemical to add to maintain water balance and effective sanitizer residuals.
Total Alkalinity (TA) is the sum of all the alkaline minerals in the water, primarily in bicarbonate form in swimming pools, but also as sodium, calcium, magnesium, and potassium carbonates and hydroxides, and affects pH directly through buffering. The greater the Total Alkalinity, the more stable the pH. In general, TA should be maintained at 80 – 120 parts per million (ppm) for concrete pools to keep the pH stable.* Maintaining a low TA not only causes pH bounce, but also corrosion and staining of pool walls and eye irritation. Maintaining a high TA causes overstabilization of the water, creating high acid demands, formation of bicarbonate scale, and may result in the formation of white carbonate particles (suspended solids), which clouds the water. Reducing TA requires huge amounts of effort. So the best solution to TA problems is prevention through close monitoring and controlling. The PoolPro PS9 Titration Kit features an in-cell conductometric titration for determining alkalinity.
Calcium Hardness (CH) is the other water balance parameter pool professionals are most familiar with. CH represents the calcium content of the water and is measured in parts per million. Low CH combined with a low pH and low TA significantly increases corrosivity of water. Under these conditions, the solubility of calcium carbonate also increases. Because calcium carbonate is a major component of both plaster and marcite, these types of pool finishes will deteriorate quickly. Low CH also leads to corrosion of metal components in the pool plant, particularly in heat exchangers. Calcium carbonate usually provides a protective film on the surface of copper heat exchangers and heat sinks, but does not adversely affect the heating process. Without this protective layer, heat exchangers and associated parts can be destroyed prematurely. At the other extreme, high CH can lead to the precipitation of calcium carbonate from solution, resulting in cloudy water, the staining of structures and scaling of equipment. The recommended range for most pools is 200 – 400 ppm.* Calcium hardness should be tested at least monthly. The PoolPro PS9 Titration Kit features an in-cell conductometric titration for determining hardness.
Total Dissolved Solids (TDS) is the sum of all solids dissolved in water. If all the water in a swimming pool was allowed to evaporate, TDS would be what was left on the bottom of the pool – like the white deposits left in a boiling pot after all the water has evaporated. Some of this dissolved material includes hardness, alkalinity, cyanuric acid, chlorides, bromides, and algaecides. TDS also includes bather wastes, such as perspiration, urine, and others. TDS is often confused with Total Suspended Solids (TSS). But TDS has no bearing on the turbidity, or cloudiness, of the water, as all the solids are truly in solution. It is TSS, or undissolved, suspended solids, present in or that precipitate out of the water that make the water cloudy.
High TDS levels do affect chlorine efficiency, algae growth, and aggressive water, but only minimally. TDS levels have the greatest bearing on bather comfort and water taste – a critical concern for commercial pool operators. At levels of over 5,000 ppm, people can taste it. At over 10,000 ppm bather towels are scratchy and mineral salts accumulate around the pool and equipment. Still some seawater pools comfortably operate with TDS levels of 32,000 ppm or more.
As methods of sanitization have changed, high TDS levels have become more and more of a problem. The best course of action is to monitor and control TDS by measuring levels and periodically draining and replacing some of your mature water with new, lower TDS tap water. This is a better option than waiting until you must drain and refill your pool, which is not allowed in some areas where water conservation is required by law. However, you can also decrease TDS with desalinization equipment as long as you compensate with Calcium Hardness. (Do not adjust water balance by moving pH beyond 7.8.)*
Regardless, you do need to measure and compensate for TDS to get the most precise saturation index and adjust your pH and Calcium Hardness levels accordingly. It is generally recommended that you adjust for TDS levels by subtracting one tenth of a saturation index unit (.1) for every 1,000 ppm TDS over 1,000 to keep your water properly balanced. When TDS levels exceed 5,000 ppm, it is recommended that you subtract half of a tenth, or one twentieth of unit (.05) per 1,000 ppm.* And as the TDS approaches that of seawater, the effect is negligible.
Hot tubs and spas have a more significant problem with TDS levels than pools. Because the bather load is relatively higher, more chemicals are added for superchlorination and sudsing along with a higher concentration of bather wastes. The increased electrical conductance that high TDS water promotes can also result in electrolysis or galvanic corrosion. Every hot water pool operator should consider a TDS analyzer as a standard piece of equipment.
A TDS analyzer is required to balance the water of any pool or spa in the most precise way. PoolPro, PoolMeter and ULTRAPEN PT1 instantly display accurate TDS levels giving you the information you need to take corrective action before TDS gets out of hand.
Temperature is the last and least significant factor in maintaining water balance. As temperature increases, the water balance tends to become more basic and scale- producing. Calcium carbonate becomes less soluble, causing it to precipitate out of solution. As temperature drops, water becomes more corrosive.
In addition to helping determine water balance, temperature also affects bather comfort, evaporation, chlorination, and algae growth (warmer temperatures encourage growth). Myron L’s PooLPRo also precisely measures temperature to one tenth of a degree at the same time any other parameter is measured.
In the pool and spa industry water balance is calculated using the Langelier Saturation Index (LSI) formula:
SI = (pH + TF + CF + AF ) – 12.1
PH = pH value
TF = 0.0117 x Temperature value – 0.4116 CF = 0.4341 x ln(Hardness value) – 0.3926 AF = 0.4341 x ln(Alkalinity value) – 0.0074
The following is a general industry guideline for interpreting LSI values:
• An index between -0.5 and +0.5 is acceptable pool water.
- An index of more than +0.5 is scale-forming.
- An index below -0.5 is corrosive.
pH, Total Alkalinity, and Calcium Hardness are the largest contributors to water balance. Pool water will often be balanced if these factors are kept within the recommended ranges.
The PoolPro PS9 Titration Kit features an LSI function that steps you through alkalinity & hardness titrations and pH & temperature measurements to quickly and accurately determine LSI. An LSI calculator allows you to manipulate pH, alkalinity, hardness and temperature values in the equation to determine water balance adjustments on the spot.
The most immediate concern of anyone monitoring and maintaining a pool is the effectiveness of the sanitizer – the germ-killer. There are many types of sanitizers, the most common being chlorine in swimming pools and bromine in hot tubs and spas. The effectiveness of the sanitizer is directly related to the pH and, to a lesser degree, the other factors influencing water balance.
To have true chemical control, you need to monitor both the sanitizer residual and the pH and use that information to chemically treat the water. To check chlorine residual, free chlorine measurements are made. For automatic chlorine dosing systems, ORP must also be monitored to ensure proper functioning.
Free Chlorine is the amount of chlorine available as hypochlorous acid (HOCl-) and hypochlorite ion (OCl-), the concentrations of which are directly dependent on pH and temperature. pH is maintained at the level of greatest concentration of HOCl- because hypochlorous acid is a much more powerful sanitizer than hypochlorite ion. Free chlorine testing is usually required before and after opening of commercial pools. Samples should be taken at various locations to ensure even distribution. Residual levels are generally kept between 1-2 mg/L or ppm.* PooLPRo V.4.03 and later features the ability to measure ppm free chlorine in pools and spas sanitized by chlorine only. With this feature PoolPro can measure a dynamic range of chlorine concentrations wider than that of a colorimetric test kit with a greater degree of accuracy.
ORP stands for Oxidation Reduction Potential (or REDOX ) of the water and is measured in millivolts (mV). The higher the ORP, the greater the killing power of all sanitizers, not just free chlorine, in the water. ORP is the only practical method available to monitor sanitizer effectiveness. Thus, every true system of automatic chemical control depends on ORP to work.
The required ORP for disinfection will vary slightly between disinfecting systems and is also dependent on the basic water supply potential, which must be assessed and taken into account when the control system is initialized. 650 mV to 700 – 750 mV is generally considered ideal.*
Electronic controllers can be inaccurate and inconsistent when confronted with certain unique water qualities, so it is critical to perform manual testing with separate instrumentation. For automatic control dosing, it is generally recommended that you manually test pH and ORP prior to opening and then once during the day to confirm automatic readings.*
Samples for confirming automatic control dosing should be taken from a sample tap strategically located on the return line as close as possible to the probes in accordance with the manufacturer’s instructions. If manual and automatic readings consistently move further apart or closer together, you should investigate the reason for the difference.*
ORP readings can only be obtained with an electronic instrument. PoolPro provides the fastest, most precise, easy-to-use method of obtaining ORP readings to check the effectiveness of the sanitizer in any pool or spa. This is the best way to determine how safe your water is at any given moment.
A relatively new development, saltwater pools use regular salt, sodium chloride, to form chlorine with an electrical current much in the same way liquid bleach is made. As chlorine – the sanitizer – is made from the salt in the water, it is critical to maintain the salt concentration at the appropriate levels to produce an adequate level of sanitizer. It is even more important to test water parameters frequently in these types of pools and spas, as saltwater does not have the ability to respond adequately to shock loadings (superchlorination treatments).
Most saltwater chlorinators require a 2,500 – 3,000 ppm salt concentration in the water (though some may require as high as 5,000-7,000 ppm).* This can barely be tasted, but provides enough salt for the system to produce the chlorine needed to sanitize the water.
(It is important to have a good stabilizer level – 30 – 50 ppm* – in the pool, or the sunlight will burn up the chlorine. Without it, the saltwater system may not be able to keep up with the demand regardless of salt concentration.)
Taste and salt shortages are of little concern to seawater systems that maintain an average of 32,000 ppm. In these high-salt environments, you need to beware of corrosion to system components that can distort salt level and other parameter readings.
Additionally, incorrect salt concentration readings can occur in any saltwater system. The monitoring/controlling components can and do fail or become scaled— sometimes giving a false low salt reading. Thus, you must test manually for salt concentration with separate instrumentation before adding salt.
You must also test salt concentration manually with separate instrumentation to re-calibrate your system. This is critical to system functioning and production of required chlorine. Both the PoolPro and PT1 conveniently test for salt concentration at the press of a button as a check against automatic controller systems that may have disabled equipment or need to be re-calibrated.
Though no one instrument or method can be used to determine ALL of the factors that affect the comfort and sanitation of pool and spa water, PoolPro is a comprehensive water testing instrument that is reliable durable, easy-to-use and easy-to-maintain and calibrate. As a pool professional, a PoolPro will not only simplify your life, it will save you time and money.
RECORD KEEPING – WHAT TO DO WITH ALL THOSE MEASUREMENTS …
Data handling should be done objectively, and data recorded in a common format in the most accurate way. Also, data should be stored in more than one permanent location and made available for future analysis. Most municipalities require commercial aquatic facilities to keep permanent records on site and available for inspection at any time.
PoolPro makes it easy to comply with record keeping requirements. The PoolPro is an objective means to test free chlorine, ORP, pH, TDS, temperature and the mineral/salt content of any pool or spa. You just rinse and fill the cell cup by submerging the waterproof unit and press the button of the parameter you wish to measure. You immediately get a standard, numerical digital readout – no interpretation required – eliminating all subjectivity. And model PS9TK features the added ability to perform in-cell conductometric titrations for Alkalinity, Hardness and LSI on the spot. Up to 100 date-time-stamped readings can be stored in memory and then later transferred directly to a computer wirelessly using the bluDock™ accessory package. Simply pair the bluDock with your computer, then open the U2CI software application to download data. The user never touches the data, reducing the potential for human error in transcription. The data can then be imported into any program necessary for record-keeping and analysis. The bluDock is a quick and easy way to keep records that comply with governing standards.*
*Consult your governing bodies for specific testing, chemical concentrations, and all other guidelines and requirements. The ranges and methods suggested here are meant as general examples.
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Tweet Myron L Meters thanks Dalscorp engineering consultants of Brunswick, Maine, proud owners of a new Ultrapen PT1 conductivity/TDS/salinity pen. ULTRAPEN PT1 Conductivity/TDS/Salinity Pen. This instrument is designed to be extremely accurate, fast and simple to use in diverse water quality applications. Advanced features include the ability to select from 3 different solution types that […]
Myron L Meters thanks Dalscorp engineering consultants of Brunswick, Maine, proud owners of a new Ultrapen PT1 conductivity/TDS/salinity pen.