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
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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: email@example.com
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
Study of Physico-Chemical Characteristics of Wastewater in an Urban Agglomeration in Romania – MyronLMeters.com
TweetStudy of Physico-Chemical Characteristics of Wastewater in an Urban Agglomeration in Romania Abstract This study investigates the level of wastewater pollution by analyzing its chemical characteristics at five wastewater collectors. Samples are collected before they discharge into the Danube during a monitoring campaign of two weeks. Organic and inorganic compounds, heavy metals, and biogenic compounds [...]
Study of Physico-Chemical Characteristics of Wastewater in an Urban Agglomeration in Romania
This study investigates the level of wastewater pollution by analyzing its chemical characteristics at five wastewater collectors. Samples are collected before they discharge into the Danube during a monitoring campaign of two weeks. Organic and inorganic compounds, heavy metals, and biogenic compounds have been analyzed using potentiometric and spectrophotometric methods. Experimental results show that the quality of wastewater varies from site to site and it greatly depends on the origin of the wastewater. Correlation analysis was used in order to identify possible relationships between concentrations of various analyzed parameters, which could be used in selecting the appropriate method for wastewater treatment to be implemented at wastewater plants.
Sources of wastewater in the selected area are microindustries (like laundries, hotels, hospitals, etc.), macroindustries (industrial wastewater) and household activities (domestic wastewater). Wastewater is collected through sewage systems (underground sewage pipes) to one or more centralized Sewage Treatment Plants (STPs), where, ideally, the sewage water is treated. However, in cities and towns with old sewage systems treatment stations sometimes simply do not exist or, if they exist, they might not be properly equipped for an efficient treatment. Even when all establishments are connected to the sewage system, the designed capacities are often exceeded, resulting in a less efficient sewage system and occasional leaks.
Studies of water quality in various effluents revealed that anthropogenic activities have an important negative impact on water quality in the downstream sections of the major rivers. This is a result of cumulative effects from upstream development but also from inadequate wastewater treatment facilities. Water quality decay, characterized by important modifications of chemical oxygen demand (COD), total suspended solids (TSSs), total nitrogen (TN), total phosphorous (TP), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), lead (Pb), and so forth  are the result of wastewater discharge in rivers. Water-related environmental quality has been shown to be far from adequate due to unknown characteristics of wastewater . Thus an important element in preventing and controlling river pollution by an effective management of STP is the existence of reliable and accurate information about the concentrations of pollutants in wastewater. Studies of wastewater in Danube basins can be found, for instance, in central and eastern European countries, but we are not aware of extensive studies of wastewater quality at regional/national level in Romania.
This paper analyses the chemical composition of wastewater at several collectors/stations in an important Romanian city, Galati, before being discharged into natural receptors, which in this case are the Danube and Siret Rivers. No sewage treatment existed when the monitoring campaign took place, except the mechanical separation. The study presented here is part of a larger project aiming at establishing the best treatment technology of wastewater at each station. Presently this project is in the implementation stage at all stations. Possible relationships between concentrations of various chemical residues in wastewater and with pollution sources are also investigated. The study is based on daily measurements of chemical parameters at five city collectors in Galati, Romania, during a two-week campaign in February 2010.
2. Experimental Analysis
2.1. Location of Sampling Sites
Galati-Braila area is the second urban agglomeration in Romania after Bucharest, which is located in Romania at the confluence of three major rivers: Danube, Siret, and Prut. The wastewater average flow is about 100000 m3/day . The drainage system covers an area of 2300 ha, serving approximately 99% of the population (approximately 300000 habitants). The basic drainage system is very old, dating back to the end of the 19th century, and was extended along with the expansion of the city due to demographic and industrial evolution. There are several collectors that collect wastewater and rainwater from various areas with very different characteristics, according to the existing water-pipe drainage system. There is no treatment at any station, except for simple mechanical separation. However, industrial wastewater is pretreated before being discharged in the city system. The five wastewater collectors are denoted in the following as S 1 , S 2 , … , S 5. Four of them discharge in the Danube River and the fifth discharges in the Siret River (which is an affluent of Danube River). Figure 1 shows the distribution of the monitoring sites and highlights the type of collecting area (domestic, industrial, or mixed). For the sake of brevity, these stations will be named in the present paper as “domestic,” “mixed,” and “industrial” stations, according to the type of collected wastewater. The mixture between domestic and industrial water at the two mixed collectors is the result of changes in city planning and various transformations of small/medium enterprises.
Figure 1: Monitoring sampling sites of wastewater from Galati city.
Technical details about each collector/station can be found in Table 1. The first station, S1, collects 10% of the total quantity of wastewater. A high percentage of the water collected at this station comes from domestic sources from the south part of the city (more than 96%). Station S2 collects 64% of the total daily flow of wastewater, out of which 30% comes from domestic sources and the rest (70%) is industrial. Most of the industrial sources in this area are food-production units (milk, braid, wine) while the domestic sources include 20 schools, 4 hospitals, and important social objectives. Station S3 is located in the old part of the city and collects 5% of the total wastewater and has domestic sources. At the fourth station, S4, 11% of the quantity of wastewater is collected from domestic (70%) and industrial (30%) sources. The last collector, S5, collects wastewater from the industrial area of the city, where the most important objectives are a shipyard, metallurgical, and mechanical plants and transport stations.
Table 1: Characteristics of collectors S 1 , … , S 5.
2.2. Physico-Chemical Parameters and Methods of Analysis
The physico-chemical parameters which were measured are the following:(i)pH;(ii)chemical oxygen demand (COD) and dissolved oxygen (DO);(iii)nutrients such as nitrate (N-NO3) and phosphate (P-PO4) (these were included due to their impact on the eutrophication phenomenon);(iv)metals such as aluminum (Al+3), soluble iron (Fe+2), and cadmium (Cd+2).
The pH and DO were determined in situ using a portable multiparameter analyzer. Other chemical parameters such as COD, metals and nutrients were determined according to the standard analytical methods for the examination of water and wastewater .
The COD values reflect the organic and inorganic compounds oxidized by dichromate with the following exceptions: some heterocyclic compounds (e.g., pyridine), quaternary nitrogen compounds, and readily volatile hydrocarbons. The concentration of metals (Al+3, Cd+2, Fe+2) was determined as a result of their toxicity.
The value of pH was analyzed according to the Romanian Standard using a portable multiparameter analyzer, Consort C932.
COD parameter was measured using COD Vials (COD 25–1500 mg/L, Merck, Germany). The digestion process of 3 mL aliquots was carried out in the COD Vials for 2 h at 148°C. The absorbance level of the digested samples was then measured with a spectrophotometer at λ = 605 nm (Spectroquant NOVA 60, Merck, Germany), the method being analogous to EPA methods , US Standard Methods, and Romanian Standard Methods.
The DO parameter was analyzed according to Romanian Standard using a portable multiparameter analyzer, Consort C932.
Aluminum ions (Al+3) were determined using Al Vials (Aluminum Test 0.020–1.20 mg/L, Merck, Germany) in a way analogous to US Standard Methods. The absorbance levels of the samples were then measured with a spectrophotometer (Spectroquant NOVA 60; Merck, Germany) at λ = 550 nm. The method was based on reaction between aluminum ions and Chromazurol S, in weakly acidic-acetate buffered solution, to form a blue-violet compound that is determined spectrophotometrically. The pH of the sample must be within range 3–10. Where necessary, the pH will be adjusted with sodium hydroxide solution or sulphuric acid.
Iron concentration (Fe+2) was determined using Iron Vials (Iron Test 0.005–5.00 mg/L, Merck, Germany) and their absorbance levels were then measured using a spectrophotometer (Spectroquant NOVA 60; Merck, Germany) at λ = 565 nm. The method was based on reducing all iron ions (Fe+3) to iron ions (Fe+2). In a thioglycolate-buffered medium, these react with a triazine derivative to form a red-violet complex which is spectrophotometrically determined. The pH must be within range 3–11. Where necessary the pH was adjusted with sodium hydroxide solution or sulphuric acid.
Cadmium ions (Cd+2) were determined using Cadmium Vials (Cadmium Test 0.005–5.00 mg/L, Merck, Germany), their absorbance levels being measured with a spectrophotometer (Spectroquant NOVA 60; Merck, Germany) at λ = 525 nm. The method was based on the reaction of cadmium ions with a cadion derivative (cadion-trivial name for 1-(4-nitrophenyl)-3-(4-phenylazophenyl)triazene), in alkaline solution, to form a red complex that is determined spectrophotometrically. The pH must be within the range 3–11, and, if not, the pH will be adjusted with sodium hydroxide solution or sulphuric acid.
Nitrogen content was determined using Nitrate Vials (Nitrate Cell test in seawater 0.10–3.00 mg/L NO3-N or 0.4–13.3 mg/L N O3 −, Merck, Germany). The method being based on the reaction of nitrate ions with resorcinol, in the presence of chloride, in a strongly sulphuric acid solution, to form a red-violet indophenols dye that is determined spectrophotometrically. The absorbance levels of the samples were then measured with a spectrophotometer (Spectroquant NOVA 60; Merck, Germany) at λ = 500 nm.
Phosphorous content was determined using Phosphate Vials (Phosphate Cell Test 0.5–25.0 mg/L PO4-P or 1.5–76.7 mg/L P O4 − 3, Merck, Germany) with a method that was analogous to the US Standard Methods . The method was based on the reaction of orthophosphate anions, in a sulphuric solution, with ammonium vanadate and ammonium heptamolybdate to form orange-yellow molybdo-vanado-phosphoric acid that is determined spectrophotometrically (“VM” method). The absorbance levels of the samples were then measured with a spectrophotometer (Spectroquant NOVA 60; Merck, Germany) at λ = 410 nm.
All results were compared with standardized levels for wastewater quality found in accordance with European Commission Directive  and Romanian law .
3. Results and Discussion
3.1. The Acidity (pH)
The results for pH for all the investigated five collectors are shown in Figure 2.
Figure 2: Daily variation of pH at all sites.
Generally, the wastewater collected at the monitored sites is slightly alkaline. The pH varies between 6.8 and 8.3—average value 7.82—thus the pH values are within the accepted range for Danube River according to the Romanian law, which is between 6.5 and 9.0. The pH variation is relatively similar at collectors S1–S4 (domestic and/or mixed domestic-industrial contribution). Lower pH values are observed at S5, which is dominated by industrial wastewater, originating from major enterprises and heavy industry. However, these values are not too low, since usually pH values for industrial wastewater are smaller than 6.5.
A significant decrease in the pH value was observed during the 8th day of the analyzed period at each station. Interestingly, a heavy snowfall took place at that particular time, thus the decrease could be attributed to the mixing between wastewater and a high quantity of low pH water, resulted from the melting of snow . One could speculate that the snowfall, which has an acidic character, might have affected the pH of the wastewater through “run off” phenomena.
No other snowfall took place during the monitoring campaign, thus no definite conclusion can be drawn for a possible relationship between pH and snowfalls.
3.2. Results for Chemical Oxygen Demand (COD)
Detection of COD values in each sampling site of wastewater is presented in Figure 3.
Figure 3: Daily variation of COD at all sites.
All COD values are higher than the maximum accepted values (125 mg O2/L) of the Romanian Law . Both organic and inorganic compounds have an effect on urban wastewater’s oxidability since COD represents not only oxidation of organic compounds, but also the oxidation of reductive inorganic compounds. That means some inorganic compounds interfere with COD determination through the consumption of C r2O7 − 2. Two different behaviors can be observed, which are associated with the type of the collected wastewater as follows.(i)The first group consists of stations S2, S4 and S5 where the wastewater has an important industrial component. At these stations, COD values are approximately between 150 and 300 mg O2/L, smaller, for instance, than COD values found by in the raw wastewater produced by an industrial coffee plant where COD values were between 4000 and 4600 mg O2/L. Also, the temporal variation of COD values at all three stations is similar with no significant deviations from the average value, which is about 250 mg O2/L. Interestingly, the lowest COD level can be seen, on the average, at S5, which has the highest percentage of industrial wastewater. The second group comprises the “domestic” stations S1 and S3. The COD levels are higher, with values of 500 mg O2/L or more. Also, the variability is clearly higher than at the industrial-type stations. No clear association between the variations at the two sites can be seen. A peak in COD was measured in the 14th day of the study at site S1 (1160 mg O2/L). Since S1 is a domestic type station, it is unlikely that some major discharge led to such a high variation of COD. Unfortunately, no other information exists that might indicate a possible cause for this increase.
3.3. Results for Dissolved Oxygen (DO)
The amount of DO, which represents the concentration of chemical or biological compounds that can be oxidized and that might have pollution potential, can affect a sum of processes that include re-aeration, transport, photosynthesis, respiration, nitrification, and decay of organic matter. Low DO concentrations can lead to impaired fish development and maturation, increased fish mortality, and underwater habitat degradation . No standards are given by Romanian or European Law for DO in wastewater. The DO values for the analyzed wastewater at all five sites are shown in Figure 4.
Figure 4: Daily variation of DO at all sites.
Concentration of DO varies at all sampling sites and has values between 0.96 (at S2) and 11.33 (at S4) mg O2/L with a mean value of 6.39 mg O2/L. These are clearly higher than DO values measured, for instance, in surface natural waters in China, where the Taihu watershed had the lowest DO level (2.70 mg/L), while in other rivers DO varied from 3.14 to 3.36 mg O2/L . On the other hand, such high values of DO (9.0 mg O2/L) could be found, for instance, in the Santa Cruz River , who argued that discharging industry and domestic wastewater induced serious organic pollution in rivers, since the decrease of DO was mainly caused by the decomposition of organic compounds. Extremely low DO content (DO < 2 mg O2/L) usually indicates the degradation of an aquatic system .
The DO levels vary similarly for all selected sampling sites. The DO levels cover a wide range, with a minimum value of 1.0 mg O2/L at S1 and S3 and a maximum value of 11.33 mg O2/L at S4. There is a drop in DO at all stations, observed is in the 8th day of the monitoring interval, which coincides with the day when a similar decrease in pH took place. The lowest values of DO are observed for S1, one of the two “domestic” stations. It is interesting to note that DO at S5 is low although the wastewater here comes only from industry sources.
The variation of Al+3, Fe+2, and Cd+2 concentrations in wastewater are shown in Figures 5, 6, and 7. Al+3 concentrations (Figure 5) were mostly within the 0.05–0.20 mg/L range at all the sampling sites. However, during the beginning and the end of the monitoring campaign, Al+3 concentration at station S2 is high (reaching even 0.65 mg/L), nonetheless below the limit imposed by the Romanian law, which is 5 mg/L . The fact that in the beginning of the time interval, the concentration of Al+3 is high at two neighboring stations (S1 and S2) suggests that some localized discharge affecting both runaway and waste water, might have happened in the southern part of the city, which led to the increase of Al+3concentration in the collected wastewater. This is supported by the fact that the concentration gradually decreases at S2.
Figure 5: Daily variation of Al at all sites.
Figure 6: Daily variation of Fe at all sites.
Figure 7: Daily variation of Cd at all sites.
The variation of Fe+2 concentrations is shown in Figure 6. Fe+2 concentration is within the 0.07–0.4 mg/L interval, below 5.0 mg/L, which is the maximum accepted value of the Romanian law . Two higher values were observed at S2 and S4 (both with industrial component) during the third and fourth days of the monitoring campaign.
Besides Al+3 and Fe+2, concentrations of Cd+2 were determined and the variations at the five stations are shown in Figure 7. Cd+2 is a rare pollutant, originating from heavy industry. Leakages in the sewage systems can also lead to Cd+2. Except for two days, Cd+2 varies between 0.005 and 0.04 mg/L. The two high values of 0.11 mg/L were observed in the first and fourth days at S5, which collects industrial wastewater. However, Cd+2 concentrations do not exceed the maximum accepted values of the Romanian law  for the monitoring interval which is 0.2 mg/L.
Water systems are very vulnerable to nitrate pollution sources like septic systems, animal waste, commercial fertilizers, and decaying organic matter . Important quantities of nutrients, which are impossible to be removed naturally, can be found in rivers and this leads to the eutrophication of natural water (like Danube River). As a result, an increase in the lifetime of pathogenic microorganisms is expected. Measurement of nutrient (different forms of nitrogen (N) or phosphorous (P)) variations in domestic wastewater is strongly needed in order to maintain the water quality of receptors . Nitrogen by nitrate (Figure 8) and phosphorous by phosphate (Figure 9) are considered as representative for nutrients.
Figure 8: Daily variation of N-NO3 at all sites.
Figure 9: Daily variation of P-PO4 at all sites.
Figure 8 shows that N-NO3 concentrations vary, on the average, between 0 and 5.0 mg/L.
At all four stations with a domestic component, S1, S2, S3 and S4, the concentration of N-NO3 is low (between 0 and 1.5 mg/L) and the daily variation is relatively similar at all sites. Noticeable drops of the N-NO3 concentration are observed at all stations in the 8th day of the monitoring interval, coinciding with pH (Figure 2) and DO strong variations (Figure 4). This supports the conclusion that the heavy snowfall recorded at that period had an important impact on wastewater quality most likely due to the runoff joining the sewage system.
The behavior of N-NO3 clearly differs at station S5, which collects only industrial wastewater. Significantly higher values of N-NO3, ranging from 2.0 to 5.0 mg/L, were detected. However, the mean concentration of N-NO3 remained below the maximum concentration given by the Romanian law . Obviously, if treatment stations have to be set up, the priority for this particular nutrient component should concentrate on stations where industrial wastewater is collected.
Another nutrient that was analyzed for our study was orthophosphate expressed by phosphorous. The P-PO4 concentration varies, on the average, between 1.0 and 6.0 mg/L (Figure 9). For this component, concentrations are higher at domestic stations, S1 and S3, than at the other three stations. P-PO4 is expected to increase in domestic wastewater because of food, more precisely meat, processing, washing, and so forth. The lowest values were observed at S5, which has a negligible domestic component. Peaks in the P-PO4 concentration are observed at S1. Interestingly enough, P-PO4 temporal variations correlated pretty well at stations S2, S4, and S5 (which collect industrial wastewater). Unlike most of the other analyzed compounds, for which the concentrations were within the accepted ranges, the maximum level of P-PO4 is exceeded at all five collectors. Both Romanian law and the European law stipulate 2.0 mg/L total phosphorous for 10000–100000 habitants, and for more than 100000 habitants (as in Galati City’s case) 1.0 mg/L total phosphorus. Interestingly, domestic stations seem to require more attention with respect to the quality of water then industrial stations.
Our results regarding the variation and levels of the analyzed parameters are grouped below as the following.(1)The values of pH are within the accepted range for Danube, and their daily variations are relatively similar for both domestic and mixed wastewater. Significantly smaller pH values were measured in the wastewater with a high industrial load. A clear minimum was observed at all sites in the 8th day of the monitoring period, when a heavy snowfall took place. One could speculate that the snowfall, which has an acidic character, might have affected the pH of the wastewater through “run off” phenomena. However, a clear connection cannot be established relying on one event only.(2)The COD level clearly depends on the type of wastewater. Higher values were observed for domestic wastewater, while “pure” industrial wastewater has the lowest COD. This might be explained by the fact that industrial wastewater benefits from some treatment before being discharged into the city sewage system. However, COD does exceed the maximum accepted values according to the Romanian law  at all sites thus additional treatment is required at all stations.(3)Concentrations of all analysed metals, Al+3, Cd+2 and Fe+2, are within the limit of the Romanian law. No association with the type of wastewater could be inferred. Isolated peaks could not be linked with any specific polluting factors, except for Cd+2, for which accidental concentration increases are observed for pure industrial wastewater.(4)The level of P-PO4, one of the two nutrients that were analyzed, was high at all stations; however, the highest concentrations are associated with domestic loads.(5)Opposingly, the N-NO3 level is the highest, by far, in wastewater with a high industrial contribution.
3.6. Possible Relationships between Various Parameters
The experimental results have shown that some parameters might be related and that their behavior greatly depends on the type of collected wastewater. Differences between the behavior of physico-chemical parameters at the domestic sites (S1 and S3), on one hand, and at the other sites, on the other, was observed. Pearson correlation coefficients have been calculated between all parameters at all the selected five sites and corresponding significances. Although most of correlations were not significant, some interesting connections between various parameters at sites with similar characteristics were revealed. Table 2 shows correlation coefficients between various parameters for all five stations. Significant correlations at different types of stations are denoted as follows: italicized fonts for domestic stations, boldface italicized fonts for the industrial station and boldface fonts for mixed stations.
Table 2: Correlation coefficients calculated for station S1 to S5. Significant correlations at each type of stations are identified as follows: boldface italicized fonts for industrial station (S5), italicized fonts for domestic stations (S1 and S3) and boldface fonts for mixed stations (S2 and S4).
An important relationship seems to exist between pH and N-NO3 at all stations except for the industrial wastewater collecting site, S5 (i.e., at all stations collecting wastewater resulting from domestic activities). Similarly, pH correlates well with DO at all stations except the industrial one.
COD correlates with two metals, Cd+2 and soluble Fe+2, which is expected , but only at S1 and S3, where the daily variations of the concentration for these two metals (Cd+2 and soluble Fe+2) were similar.
No conclusion can be drawn for the industrial wastewater collector that was analyzed, where both positive and negative correlations were observed. The lack of correlation between the two metals and COD at the industrial wastewater collectors suggests that other processes, that alter the chemical equilibrium between the two chemical compounds, must be taken into account. For example some metals are complexed by organic compounds that are present in the water and the pH values can influence these phenomena.
DO correlates with pH and N-NO3 at all four sampling stations with domestic component (S1–S4) but the relationship vanish at S5 (industrial). There is also a negative correlation between DO and Fe+2 and Cd+2 only for domestic wastewater, which is expected because of the natural oxidation of metals. The correlation vanishes at the other three stations which collect wastewater from industrial areas.
Heavy metals, Fe+2 and Cd+2 correlate only at domestic stations and no relationships can be defined to link the concentration of Al+3 with other components.
The P-PO4 variation is linked to the variation of soluble Fe+2 at the two stations that collect domestic wastewater. Interestingly, these two elements exist together in reductive domestic systems because these are dominated by proteins, lipids, degradation products. This relationship disappears at the other stations, where the industrial load is significant. The other metals, Al+3, seems to be linked with P-PO4at stations S5 and S2, which collect wastewater with the highest industrial load. No link is observed for the rest of stations and for Cd+2 which can be explained by a higher probability of iron (II) orthophosphate to form in wastewater compared to Al+3 or Cd+2 orthophosphates.
Positive correlations can also be seen between P-PO4 and COD for all sampling sites except S1, where the relationship is still positive but less significant. The other nutrient, N-NO3, is anticorrelated with COD but only at S3 and is well correlated with pH and DO at all four stations with domestic component. The only exception is station S5, which collects mostly industrial wastewater.
Concluding, positive correlations were observed between the following parameters.(1)pH and N-NO3 everywhere except “purely” industrial water.(2)COD and soluble Fe+2 at domestic stations.(3)DO and pH, on the one hand, and DO and N-NO3 at domestic stations.(4)P-PO4 and soluble Fe+2 at domestic stations.(5)P-PO4 and COD everywhere, which, taking into account the high level of P-PO4 at domestic stations, might suggest that one important contributor to water quality degradation are household discharges.(6)Al+3 and P-PO4.
In the present paper we have analyzed the daily variation of several physico-chemical parameters of the wastewater (pH, COD, DO, Al+3, Fe+2, Cd+2, N-NO3, and P-PO4) at five collectors that have been characterized as domestic, industrial and mixed, according to the type of collecting area. Different results have been obtained for domestic and industrial wastewater. Most of the chemical parameters are within accepted ranges. Nevertheless, their values as well as their behavior depend significantly on the type of collected wastewater.
The overall conclusion is that wastewater with a high domestic load has the highest negative impact on water quality in a river. On the other hand, industrial wastewater brings an important nutrient load, with potentially negative effect on the basins where it is discharged. Our results suggested that meteorological factors (snow) might modify some characteristics of wastewater, but a clear connection cannot be established relying on one event only.
Significantly smaller pH values were measured in the wastewater with a high industrial load. The COD level clearly depends on the type of wastewater. Higher values were observed for wastewater with domestic sources, while “pure” industrial wastewater has the lowest COD. This might be explained by the fact that industrial wastewater benefits from some treatment before being discharged into the city sewage system. COD does exceed the maximum accepted values according to the Romanian law at all sites thus additional treatment is required at all stations. Accidental increases of Cd+2 concentrations are observed for pure industrial wastewater. The highest concentrations of P-PO4 are associated with domestic loads. Opposing, the N-NO3 level is clearly the highest in wastewater with a high industrial contribution.
Correlation analysis has been used in order to identify possible relationships between various parameters for wastewater of similar origin.
Positive correlations between various physico-chemical parameters exist for the domestic wastewater (DO, pH and N-NO3, on the one hand, and P-PO4, COD and soluble Fe+2, on the other hand). Except for two cases, these relationships break when the industrial load is high. Some of the existing correlations are expected as discussed above, thus any removal treatment should be differentiated according to the type of collector, before discharging it into the natural receptors in order to be costly efficient. Correlations between DO and COD and nutrient load suggest that the most important threat for natural basins in the studied area, are domestic sources for the wastewater.
The different percentages of industrial and domestic collected wastewater vary at each station, which has a clear impact on concentrations of the selected chemical components. Our results show that domestic wastewater has a higher negative impact on water quality than wastewater with a high industrial load, which, surprisingly, seems to be cleaner. This might be related to the fact that most industries are forced, by law, to apply a pretreatment before discharging wastewater into the city sewage system. Industrial wastewater affects the nutrient content of natural water basins. Although the time period was relatively short, our study identified specific requirements of chemical treatment at each station. An efficient treatment plan should take into account the type of wastewater to be processed at each station. Results presented here are linked with another research topic assessing the level of water quality in the lower basin of the Danube before and after implementing the complete biochemical treatment plants.
The work of Catalin Trif was supported by Project SOP HRD-EFICIENT 61445/2009.
Copyright © 2012 Paula Popa et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited – original found here: http://www.hindawi.com/journals/tswj/2012/549028/
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.
Save 10% when you order online here at MyronLMeters.com.
TweetEnvironmental Applications Keeping the water in our lakes, rivers, and streams clean requires monitoring of water quality at many points as it gradually makes its way from its source to our oceans. Over the years ever-increasing environmental concerns and regulations have heightened the need for increased diligence and tighter restrictions on wastewater quality. Control of [...]
Keeping the water in our lakes, rivers, and streams clean requires monitoring of water quality at many points as it gradually makes its way from its source to our oceans. Over the years ever-increasing environmental concerns and regulations have heightened the need for increased diligence and tighter restrictions on wastewater quality. Control of water pollution was once concerned mainly with treating wastewater before it was discharged from a manufacturing facility into the nation’s waterways. Today, in many cases, there are restrictions on wastewater that is discharged to city sewer systems or to other publicly owned treatment facilities. Many jurisdictions even restrict or regulate the runoff of storm water — affecting not only industrial and commercial land, but also residential properties as well.
In its simplest form, water pollution management requires impoundment of storm water runoff for a specified period of time before being discharged. Normally, a few simple tests such as pH and suspended solids must be checked to verify compliance before release. If water is used in any way prior to discharge, then the monitoring requirements can expand significantly. For example, if the water is used for once-through cooling, testing may include temperature, pH, total dissolved solids (TDS), chemical oxygen demand (COD), and biochemical oxygen demand (BOD), to name a few.
Once water is used in a process, some form of treatment is often required before it can be discharged to a public waterway. If wastewater is discharged to a city sewer or publicly owned facility, and treatment is required, the quality is often measured and the cost is based not only on the quantity discharged, but also the amount of treatment required. As a minimum requirement suspended solids must be removed. Filtering or using clarifiers often accomplishes such removal. Monitoring consists of measuring total suspended solids (TSS) or turbidity.
If inorganic materials have been introduced into the water, their concentration must be reduced to an acceptable level. Inorganics, such as heavy metals, typically are removed by raising the pH to form insoluble metal oxides or metal hydroxides. The precipitated contaminants are filtered or settled out. Afterward, the pH must be adjusted back into a “normal” range, which often requires continuous monitoring of pH.
Organic materials by far require the most extensive treatment. Many different methods have been devised to convert soluble organic compounds into insoluble inorganic matter. Most of these involve some form of biological oxidation treatment. Bacteria are used to metabolize the organic materials into carbon dioxide and solids, which can be easily removed. To insure that these processes work smoothly and efficiently requires regular monitoring of the health of the biological organisms. The level of food (organic material), nutrients (nitrogen and phosphorous), dissolved oxygen, and pH are some of the parameters that must be controlled. After bio-oxidation the wastewater is filtered or clarified. Often the final effluent is treated with an oxidizing compound such as chlorine to kill any remaining bacterial agents, but any excess oxidant normally must be removed prior to discharge. Oxidation Reduction Potential (ORP)/Redox is ideal for monitoring the level of oxidants before and after removal. The final effluent stream must be monitored to make sure it meets all regulatory requirements.
The monitoring of wastewater pollution does not end there. Scientists are continuously testing water in streams, ground water, lakes, lagoons, and other bodies of water to determine if and what effects any remaining contamination is having on the receiving waters and its associated aquatic life. Measurements may include pH, conductivity, TDS, temperature, dissolved oxygen, TSS and organic levels (COD and BOD).
Environmental testing is not limited to monitoring of wastewater systems. Control of air emissions often includes gas-cleaning systems that involve the use of water. Wet scrubbers and wet electrostatic precipitators are included in this group. A flue gas desulfurization (FGD) system is one type of wet scrubber that uses slurry of lime, limestone, or other caustic material to react with sulfur compounds in the flue gas. The key to reliable operation of these units is proper monitoring of solids levels and pH. After use, the water in these systems must be treated or added to other wastewater from the plant, where it is treated by one of the methods previously discussed.
With proper monitoring, systems that maintain cleaner air and water can be operated efficiently and effectively. Such operation will go a long way toward maintaining a cleaner environment for future generations.
Myron L Meters offers a full line of handheld instruments and in-line monitor/controllers that can be used to measure or monitor many of the parameters previously mentioned. The following table lists some of the model numbers for measuring, monitoring, or controlling pH, conductivity, TDS and ORP. For additional information, please refer to our data sheets or Ask An Expert at MyronLMeters.com.
Note: When using a monitor/controller to measure pH in streams that contain heavy metals, sulfides, or other materials that react with silver, Myron L Meters recommends using a double junction pH sensor with a potassium nitrate (KNO3) reference gel to avoid fouling the silver electrode. See our 720II Sensor Selection Guide for pH and ORP Monitor/controllers for more information.
Ultrameter II 6P
Multi-Parameter: Conductivity, TDS, Resistivity, pH, ORP, Temperature, Free Chlorine (FCE)
+/-1% Accuracy of Reading
Memory Storage: Save up to 100 samples w/ Date & Time stamp
Wireless Download Module Optional
TweetWhat is pH and why do I need to measure it? pH measures the amount of acidity or alkalinity in a food or solution using a numerical scale between 1 and 14. A pH value of 1 is most acidic, a pH value of 7 is neutral, and values above 7 are referred to as [...]
What is pH and why do I need to measure it?
pH measures the amount of acidity or alkalinity in a food or solution using a numerical scale between 1 and 14. A pH value of 1 is most acidic, a pH value of 7 is neutral, and values above 7 are referred to as basic or alkaline. Acidified foods have a pH value less than or equal to 4.6. The proper pH of a canned food product can be critical to ensuring the safety of the product. It is very important that pH testing be done correctly and accurately.
How is pH measured?
If you process acidified foods, you will be required to monitor the pH of the product that you produce. Depending on the pH of the product, you may be able to use paper pH strips (often referred to as litmus paper), or required to use a pH meter. Paper strips that measure pH rely on a color change in the paper to indicate product pH. Paper strips can be used to measure pH if the product pH is less than 4.0. Paper strips are an inexpensive way to test pH, but can be inaccurate or difficult to read. A pH meter measures the amount of hydrogen-ion (acid) in solution using a glass electrode immersed in the solution. A pH meter must be used when product pH is greater than, or equal to, 4.0. If you are canning acidified foods, accurately monitoring and recording the product pH is key to knowing that you are selling a safe product.
What is equilibrium pH?
Equilibrium pH is the pH of a food product after the added acid has reached throughout the food; the pH of the acid brine and the food that have equilibrated. When you monitor pH as part of process monitoring, it is the equilibrium pH that you are measuring. For a proper pH reading, you should test the pH of the product roughly 24 hours after processing, once the jars have cooled to room temperature and stabilized. Do not take the pH of a product just before or right after canning because it will not be an accurate measure of the equilibrium pH.
What should I look for if I need to purchase a pH meter?
If you are required to check your product pH with a meter, there are several things to consider.
Accuracy. Accuracy is listed as a range of +0.XX pH units. This means that the meter may read so many pH units above or below the actual pH of the product. Purchase a pH meter with an accuracy of +0.02 units or better. For instance, a pH meter with an accuracy of
+0.01 is a good choice. A pH meter with an accuracy of +0.10 is not a good choice, it is not accurate enough for all products.
All pH meters must be calibrated (checked against a known standard) to assure accuracy. Standards are colored liquids of known pH. Buy a meter that uses at least a 2-point calibration; for acidified foods you will calibrate your meter with pH 4.0 and 7.0 buffers.
Electrode. The electrode is the part of the instrument that is immersed in solution. When considering which pH meter to purchase, consider the cost of replacement electrodes. Some electrodes have special non-clog tips and these may be useful is you will be measuring the pH of foods that are not easily blended.
Temperature. pH readings are affected by temperature. In order to get an accurate reading, the pH meter must be calibrated at the same temperature as the samples being tested. More expensive meters will compensate for variations in sample temperature (too warm or too cold). Myron L meters have automatic temperature compensation. If you can afford a meter with this feature, it’s nice to have.
What should I buy?
The cost of a pH meter ranges from under $100 to well over $500. As a starting point, there are several styles that small food and beverage processors currently use.
Testing the Equilibrium pH of an Acidified Food Product
1. Open one jar and take a representative sample of your food product once it has cooled, usually 12 to 24 hours after processing. You should sample each batch. Heating will drive the acid into your food product; sampling after processing (and cooling) will give you an accurate reading of the equilibrium pH.
2. Strain the solids, draining out the liquid (brine) from the jar. Place the strained solids into a blender.
3. Blend the product, adding distilled water if necessary, to produce a slurry. Added distilled water will not change the pH of the product and will allow for effective blending. You can purchase distilled water at many grocery stores or drug stores.
4. Use a calibrated pH meter to measure pH.
The pH meter must be calibrated using at least 2-point calibration with pH 4.0 and 7.0 buffers. Myron L Meters recommends a three point calibration.
The pH meter must be calibrated each day that you use it. A pH meter must be used to monitor the pH of foods with an equilibrium pH greater than 4.0.
5. Record the results in your batch log.
*Myron L meters are used by Tyson, Sara Lee, Gordon Food Service, Better Baked Foods, Schreiber Foods, Homestead Slow Foods, and others in the food
These are our two most popular handheld pH meters:
ULTRAPEN PT2 pH and Temperature Pen
Accuracy of +/- 0.01 pH
Reliable Repeatable Results
Automatic Temperature Compensation
Durable, Fully Potted Circuitry
Comes with 2oz bottle of pH Storage Solution
Ultrameter II – 6PII
Multi-Parameter: Conductivity, TDS, Resistivity, pH, ORP, Temperature, Free Chlorine (FCE)
+/-1% Accuracy of Reading
Memory Storage: Save up to 100 samples w/ Date & Time stamp
Wireless Download Module Optional
TweetWhat is pH? pH measures the activity of the (solvated) hydrogen ion. Pure water has a pH very close to 7 at 25°C. Solutions with a pH less than 7 are acidic and solutions with a pH greater than 7 are basic or alkaline. The pH scale is traceable to a set of standard solutions [...]
What is pH?
pH measures the activity of the (solvated) hydrogen ion. Pure water has a pH very close to 7 at 25°C. Solutions with a pH less than 7 are acidic and solutions with a pH greater than 7 are basic or alkaline. The pH scale is traceable to a set of standard solutions whose pH is established by international agreement. Measuring pH for aqueous solutions can be done with a glass electrode and a pH meter, or using indicators.
Measuring pH is important in water treatment, medicine, biology, chemistry, agriculture, forestry, food science, environmental science, oceanography, civil engineering, chemical engineering, and many other applications.
p[H] was first introduced by Danish chemist Søren Peder Lauritz Sørensen at the Carlsberg Laboratory in 1909 and revised to the modern pH in 1924 to accommodate definitions and measurements in terms of electrochemical cells. According to the Carlsberg Foundation pH stands for “power of hydrogen”.
pH is defined as the decimal logarithm of the reciprocal of the hydrogen ion activity, aH+, in a solution.
A pH meter is an electronic device used for measuring the pH (acidity or alkalinity) of a liquid (though special probes are sometimes used to measure the pH of semi-solid substances). A typical pH meter consists of a special measuring probe (a glass electrode) connected to an electronic meter that measures and displays the pH reading.
The pH probe measures pH as the activity of the hydrogen cations surrounding a thin-walled glass bulb at its tip. The probe produces a small voltage (about 0.06 volt per pH unit) that is measured and displayed as pH units by the meter. For more information about pH probe care or replacement, please consult your Myron L meter operations manual.
Calibration and use
*Please consult your Myron L meter operations manual before calibrating.
For very precise work the pH meter should be calibrated before each measurement. For normal use calibration should be performed at the beginning of each day. The reason for this is that the glass electrode does not give a reproducible e.m.f. over longer periods of time. Calibration should be performed with at least two standard buffer solutions that span the range of pH values to be measured. For general purposes buffers at pH 4 and pH 10 are acceptable. The pH meter has one control (calibrate) to set the meter reading equal to the value of the first standard buffer and a second control (slope) which is used to adjust the meter reading to the value of the second buffer. A third control allows the temperature to be set. Standard buffer solutions, which can be obtained from MyronLMeters.com here:
usually state how the buffer value changes with temperature. For more precise measurements, a three buffer solution calibration is preferred. As pH 7 is essentially, a “zero point” calibration (akin to zeroing a scale), calibrating at pH 7 first, calibrating at the pH closest to the point of interest ( e.g. either 4 or 10) second and checking the third point will provide a more linear accuracy to what is essentially a non-linear problem. Some meters will allow a three point calibration and that is the preferred scheme for the most accurate work, and is recommended by Myron L Meters. Higher quality meters will have a provision to account for temperature coefficient correction, and high-end pH probes have temperature probes built in. The calibration process correlates the voltage produced by the probe (approximately 0.06 volts per pH unit) with the pH scale. After each single measurement, the probe is rinsed with distilled water or deionized water to remove any traces of the solution being measured, blotted with a scientific wipe to absorb any remaining water which could dilute the sample and thus alter the reading, and then quickly immersed in another solution.
Storage conditions of the glass probes
When not in use, the glass probe tip must be kept wet at all times to avoid the pH sensing membrane dehydration and the subsequent dysfunction of the electrode. You can get your sensor storage solution here:
A glass electrode alone (i.e., without combined reference electrode) is typically stored immersed in an acidic solution of around pH 3.0. In an emergency, acidified tap water can be used, but distilled or deionised water must never be used for longer-term probe storage as the relatively ionless water “sucks” ions out of the probe membrane through diffusion, which degrades it.
Combined electrodes (glass membrane + reference electrode) are better stored immersed in the bridge electrolyte (often KCl 3 M) to avoid the diffusion of the electrolyte (KCl) out of the liquid junction.
Cleaning and troubleshooting of the glass probes
Occasionally (about once a month), the probe may be cleaned using pH-electrode cleaning solution; generally a 0.1 M solution of hydrochloric acid (HCl) is used, having a pH of one.
In case of strong degradation of the glass membrane performance due to membrane poisoning, diluted hydrofluoric acid (HF < 2 %) can be used to quickly etch (< 1 minute) a thin damaged film of glass. Alternatively a dilute solution of ammonium fluoride (NH4F) can be used. To avoid unexpected problems, the best practice is however to always refer to the electrode manufacturer recommendations or to a classical textbook of analytical chemistry.
Types of pH meters
A pH meter for every industry
pH meters range from simple and inexpensive pen-like devices to complex and expensive laboratory instruments with computer interfaces and several inputs for indicator and temperature measurements to be entered to adjust for the slight variation in pH caused by temperature. Specialty meters and probes are available for use in special applications, harsh environments, etc. Myron L Meters offers a simple pen-style pH meter, analog handheld meters, digital handheld multiparameter meters, and inline monitor/controllers.
ULTRAPEN PT2 pH and Temperature Pen
Accuracy of +/- 0.01 pH
Reliable Repeatable Results
Automatic Temperature Compensation
Durable, Fully Potted Circuitry
Comes with 2oz bottle of pH Storage Solution
Agri-Meter – Ag-6: 0-5 millimhos; 2-12 pH
Instant and accurate TDS tests
Electronic Internal Standard for easy field calibration
Fast Auto Temperature Compensation
Rugged design for years of trouble-free testing
Simple to use
Multi-Parameter: Conductivity, TDS, Resistivity, pH, ORP, Temperature, Free Chlorine (FCE)
+/-1% Accuracy of Reading
Memory Storage: Save up to 100 samples w/ Date & Time stamp
Wireless Download Module Optional
The advanced “isolated” circuitry of the 720 Series II pH/ORP Monitor/ controllers guarantees accurate and reliable measurements — completely eliminating ground-loop and noise issues.
The unique sensor preamp allows for longer distances between the sensor and the Monitor/controller without the loss of accuracy or reliability.
All Myron L Monitor/controllers feature a highly refined and precise Temperature Compensation circuit. This feature perfectly matches the NERNST equation correcting the displayed reading to 25′C. The TC may be disabled to conform to USP requirements.
TweetBoilers and cooling towers share two major water related problems: deposits and corrosion. As a boiler or water evaporating from a cooling tower generates steam, dissolved minerals are left behind, increasing the concentration of these minerals. Additional minerals are introduced via the water added to makeup the water lost to steam/evaporation. Eventually, the minerals reach [...]
Boilers and cooling towers share two major water related problems: deposits and corrosion. As a boiler or water evaporating from a cooling tower generates steam, dissolved minerals are left behind, increasing the concentration of these minerals. Additional minerals are introduced via the water added to makeup the water lost to steam/evaporation. Eventually, the minerals reach a level (or cycle) of concentration that will cause either loss of efficiency due to scale or damage from corrosion. This level can be determined by the Ryznar or Langlier indices and correlated to a conductivity or TDS range. Most people recognize problems associated with corrosion. Effects from scale deposits, however, are equally important. For example, as little as 1/8″ of scale can reduce the efficiency of a boiler by 18% or a cooling tower heat exchanger by 40%!
A variety of water treatment methods are employed in an effort to control these problems. Even with water treatment, it is still necessary to regularly blow down or bleed off part of the concentrated water and make up with lower salinity water to reduce the overall mineral concentration.
To conserve water and treatment chemicals, it is desirable to allow the dissolved minerals to reach a maximum cycle of concentration while still avoiding problems. Because feed water/make-up waters vary in the types and amounts of minerals present, the allowable cycles of concentration will vary. As a result, regular testing of boiler and cooling waters is essential to optimize water treatment programs and blow down schedules. Tests commonly performed include conductivity or TDS, pH and ORP. Myron L meters provide you with a simple, fast, and accurate means of testing these parameters.
Many cooling towers and boilers have inline controllers used to release water from the tower or boiler and feed chemical(s) into the system. The controllers must be calibrated regularly to ensure fouling or drift of the sensor has not occurred. Our portable instruments in conjunction with NIST traceable standard solutions provide rapid verification of the accuracy of inline controllers. This method reduces manpower and the likelihood of disturbing or damaging sensors.
Conductivity is the measurement of a solution’s ability to transmit an electrical current. It is usually expressed in microsiemens/cm (micromhos/cm). Pure water is actually a poor electrical conductor (18,200,000 ohms/cm of resistance). It is the amount of ionized substances (or salts) dissolved in water, which determines the conductivity. Because the vast majority of the dissolved minerals in water are these conductive inorganic impurities, conductivity measurement is an excellent indicator of mineral concentration.
Myron L meters were developed for just this purpose. Models are available which display conductivity and/or ppm of TDS. For detailed information regarding the relationship between conductivity and TDS, please see the our Application Bulletin: Standard Solutions and Buffers.
pH, the measurement of acid or base, is one of the most important factors affecting scale formation or corrosion in a boiler or cooling system. The types of impurities comprising the mineral concentration behave differently at various pHs. Low pH waters have a tendency to cause corrosion, while high pH waters may cause scale formation.
Boiler water requirements can range from very pure to more than 6500 microsiemens, depending on size, pressure, application, and feed water. Once the maximum cycles of concentration has been established, a conductivity instrument can conveniently help you to determine if the blow down schedule is adequate. Samples should be cooled to at least 160°F/71°C to ensure accurate temperature compensated readings.
Boiler condensate samples are often tested to determine if there is any carryover of boiler water solids or contaminants entering from outside the system. Condensate is relatively pure water, and values of 2-100 microsiemens are common. Because of these low values, a multiple-range instrument is recommended to increase the resolution and accuracy of the reading. Monitoring the pH of condensate is also important since condensate is very corrosive at low pHs. Treatment additives are often added to elevate the pH to minimize corrosion in condensate lines.
Cooling tower water
Cooling tower water has become more challenging since the reduced use of acid and the elimination of chromate. Monitoring conductivity and pH has become imperative to maintain a proper treatment program. Although many systems have controls on these parameters, the possibility of a system upset is always present. Even slight upsets can cause rapid scaling of heat exchangers.
Biological growth is another extremely important facet to proper cooling water management. Microbes can cause corrosion, fouling, and disease. Oxidizing biocides (chlorine, chlorine dioxide, ozone and bromine) have been employed to keep bacteria under control. Monitoring of the ORP (Oxidation Reduction Potential)/redox is very useful in its ability to correlate millivolt readings to sanitization strength of the water. The ULTRAMETER II™ 6P includes this parameter for quick on-site determinations.
Tweet OSMOSIS Osmosis is the phenomenon of lower dissolved solids in water passing through a semi-permeable membrane into higher dissolved solids water until a near equilibrium is reached. Reverse Osmosis (RO) is a membrane process of purification which removes most of the total dissolved solids (TDS) in water by reversing the natural process of osmosis. [...]
Osmosis is the phenomenon of lower dissolved solids in water passing through a semi-permeable membrane into higher dissolved solids water until a near equilibrium is reached. Reverse Osmosis (RO) is a membrane process of purification which removes most of the total dissolved solids (TDS) in water by reversing the natural process of osmosis. Pressure is applied to a TDS-concentrated solution against a semi-permeable membrane, causing pure water to diffuse through the membrane. RO has become an important process for a wide variety of applications including: medical, laboratory, desalination, industrial wastewater, Deionized (Dl) pretreatment, and drinking water.
TESTING RO WATER QUALITY
Electrical conductivity is the most convenient method for testing RO water quality and membrane performance. Pure water is actually a poor electrical conductor. The amount of ionized substances (salts, acids, or bases) dissolved in water determines its conductivity. Normally, the vast majority of the dissolved minerals in tap, surface or ground water are conductive impurities. Myron L Company has conducted extensive research relating conductivity to TDS, resulting in instrumentation and calibration solutions which have become the standard of the RO industry.
When calibrating your conductivity instrument for testing fresh water, the “442 Natural Water Standard™” solutions are the best choice. These solutions are available in various concentrations.
442 solutions contain the following salts diluted in pure water: 40% sodium bicarbonate, 40% sodium sulfate and 20% sodium chloride. These are the most common salt compounds in surface and ground water. A sodium chloride solution provides better results in brackish or sea water because the predominant salt in these waters is sodium chloride.
ORP (Oxidation Reduction Potential/REDOX) and pH are important parameters in measuring the success and useful life of an RO membrane. The ORP may be used to determine the activity of an oxidizer. RO membranes are susceptible to attack by oxidizers such as chlorine, bromine, ozone and hydrogen peroxide. The activity of the oxidizer is more informative than the chemical residual because it determines the ability and speed of oxidation. A high ORP reading would indicate a need for pretreatment. A low ORP may indicate biological activity which may cause fouling of the membranes.
ORP can also be used to determine an overfeed of sodium bisulfite, which is used to reduce chlorine. If the ORP reading is under 200 mV, you have a reducing condition. This overfeed costs extra money and can lead to environmental discharge problems. It is best to check the reject water, where the concentration is highest. This will show even minute quantities of oxidizers or reducers.
pH is very useful in predicting membrane life and the scaling potential of feedwater. The higher the pH and calcium, the more likely it is that scale will form on the membranes. However, with silicon based compounds, a low pH will increase the tendency for scaling. Membranes also have a pH range where operation is optimal. It is often useful to check the pH of the reject water to help determine scaling potential.
Myron L Meters carries single and multiple range handheld instruments. Model RO-1 and RO-1NC are reliable, single range instruments used to demonstrate the RO process to a prospective buyer. The color coding of the model RO-1 dial dramatizes the difference between high TDS (red- above EPA recommended limits for drinking water), medium TDS (orange – within EPA recommended standards for drinking water), and low TDS RO water (blue-high purity water). Installers prefer the three range 532 models or TechPro II™ TP1 or TPH1 because they are ideal for accurately testing both feed and product water.
Larger RO systems such as those found in bottled water plants, hospitals, industrial process, or seawater desalination require continuous monitoring to verify water quality and membrane condition. For continuous measurement of water quality, Myron L Meters carries the 720 and 750 Series II Monitor/ controllers. Monitor only, and monitor/controller models are available. Monitor/controller models contain an adjustable set point and a heavy-duty 10 amp relay which can be used to activate alarms, valves, autodialers, etc. A variety of options and outputs are available to cost-effectively tailor the monitor to the particular RO application.
The Ultrameter™ 9PTK, 6PII and 4PII are preferred by water treatment professionals for calibrating and checking Commercial/industrial RO systems. They appreciate the waterproof case, ability to store and record 100 memory data records, and three preprogrammed solution curves. Ultrameters are compact, but their multiple parameters give them the versatility of several instruments.
Myron L Meters also carries pen style meterss for dip or scoop sampling. The ULTRAPEN PT1 delivers stable, lab-accurate readings of Conductivity, TDS, Salinity and Temperature. The PT2 pH and Temperature pen is also available for spot checks and pretreatment screening. Both pens are waterproof, durable, and easy to use with one-button functioning.
Visit us here to save 10% on any of our Myron L meters: http://www.myronlmeters.com/Digital-Multiparameter-Meters-s/48.htm
Tweet Nestled in the foothills of the Green Mountains of Vermont with a trout stream behind the nursery, Mill Brook Bonsai is devoted to the art of Bonsai. Founded in 1997 after many years as a hobby, the nursery has grown to include native trees, tropical trees and imported trees as well as tools, pots [...]
Nestled in the foothills of the Green Mountains of Vermont with a trout stream behind the nursery, Mill Brook Bonsai is devoted to the art of Bonsai. Founded in 1997 after many years as a hobby, the nursery has grown to include native trees, tropical trees and imported trees as well as tools, pots and accessories.
Come and visit, feed the attack-trained Koi in our small pond and enjoy the quiet and serenity that is associated with this ancient Chinese and Japanese art form.
Mill Brook Bonsai was founded in 1997 after Sandy & Trudy Anderson had spent a number of years as amateur bonsaiists. The first greenhouse went up in ‘97, the second one, for tropical trees a few years later and then, as the collection grew, a third greenhouse was added. Much of our initial knowledge came from such folk as Gil Klein, a bonsaiist who moved to VT from the NY area. Later, Eric Schalk of Waterbury, VT added his knowledge to our early store of information and then, over the past years, David Easterbrook, Curator of the Bonsai Exhibit at the Montreal Botanical Gardens has graced us with his talents.
Over the years we have been fortunate enough to have guest speakers here such as Suthin Sukolsovisit, Harry Thomlinson, Chase Rosade, Mary Miller, Mike Sullivan, Colin Lewis and a host of others that have added to our own knowledge as well as the members of Green Mountain Bonsai Society who have hosted many of these events.
We have a large number of trees ranging in price from $45 to $2,000. There is a tree for every budget and for every environment. Here is a photograph of recently arrived Chinese Elms in the foreground; Taiwan Figs appear to the front left of the picture.
Myron L Meters is proud to do business with Mill Brook Bonsai.
Please visit us on the web at:
TweetIn order to test the swimming pool water quality, you need to know what you’re testing. Some of the basic parameters that are measured for pools include pH, Chlorine, Total Alkalinity, Calcium Hardness, and Total Dissolved Solids. A balanced swimming pool really only needs to have the pH and chlorine levels checked and corrected on [...]
In order to test the swimming pool water quality, you need to know what you’re testing. Some of the basic parameters that are measured for pools include pH, Chlorine, Total Alkalinity, Calcium Hardness, and Total Dissolved Solids.
Many swimming pool and spa professionals use portable instruments to test the water quality during treatment. If you are a homeowner with a pool, you may want to consider using an instrument as opposed to the simple test kits with liquid droplets or tablets. If you need an instrument, check out the selection here: MyronLMeters.com. The instruments are much more accurate and can provide immediate, reliable results. If you are using the test kits, there are a few things to note. Expired tablets/ test liquids (reagents) should be thrown out as they very often give inaccurate readings, resulting in improper treatment, wasting expensive chemicals and possibly damaging the pool and filtration equipment. Always keep the test kit in a cool dry place out of the sun and out of the reach of children.
When testing the pool water, rinse the cell cups of your instrument or test kit thoroughly before filling them with water from at least 20-30 cm below the surface of the swimming pool. When you’re finished testing the water be sure not to pour the samples back into the pool.
As a general rule of thumb, tests for pH and chlorine should be done weekly. If there are no obvious problems in your swimming pool (algae growth, cloudy water, lime scale buildup, etc) then you can test for Total Alkalinity, Calcium Hardness, and Total Dissolved Solids approximately every month.
Swimming pool chemistry can seem intimidating, so consulting a swimming pool professional is not a bad idea. Some will visit your pool and perform the test or you can take a sample directly to your local pool supply store and they may be able to test it for you.
If the water in your area is free from any metals and your swimming pool shows none of the symptoms of iron or copper presence, the test for these metals is unnecessary. If, however, you notice staining on the walls and floor of the swimming pool, you should have the levels of these metals checked and treated if necessary.
For a more in-depth study of pool water testing, visit the link below:
The Association of Pool and Spa Professionals (APSP) is a great resource for individuals and companies that want to learn more about water treatment for pools and spas.