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Tweet MyronLMeters.com brings you the latest in conductivity measurement research like the article below. Please click here for accurate, reliable, conductivity meters. Abstract Assessment of seed vigor has long been an important tool of seed quality control programs. The conductivity test is a promising method for assessment of seed vigor, but proper protocols for its […]
MyronLMeters.com brings you the latest in conductivity measurement research like the article below. Please click here for accurate, reliable, conductivity meters.
Assessment of seed vigor has long been an important tool of seed quality control programs. The conductivity test is a promising method for assessment of seed vigor, but proper protocols for its execution have yet to be established. The objective of this study was to assess the efficiency of electrical conductivity (EC) testing as a means of assessing the viability of freshly collected Kielmeyera Coriacea Mart. seeds. The test was performed on individual seeds rather than in a bulk configuration. Seeds were soaked for different periods (30 min, 90 min, 120 min., 180 min, and 240 min) at a constant temperature of 25°C. Conductivity was then measured with a benchtop EC meter.
Seeds are the primary factor of the seedling production process, despite their minor contribution to the end cost of each seedling. In order to estimate the success rate of seedling production, it is essential that seed characteristics such as vigor and germinability be known .
The importance of knowing the characteristics of Brazilian forest species to safer and more objective management of seedling production cannot be overstated. However, such studies are scarce, particularly in light of the vast number of species with this potential . Given the intensity of anthropogenic pressure and the importance of rehabilitating disrupted or degraded environments, in-depth research of forest species is warranted.
Routine methods used for determination of seed quality and viability include germination testing and the tetrazolium test. Methods such as measurement of soak solution pH, electrical conductivity, and potassium content of leachate, all based on the permeability of the cell membrane system, are increasingly being employed in the assessment of seed vigor, as they are reliable and fast and can thus speed the decision making process.
Electrical conductivity testing, as applied to forest seeds, has yet to be standardized. Studies conducted thus far have focused on assessment of seed soaking times, which may range from 4 to 48 hours. Even at 48 hours, the conductivity test is considered a rapid technique as compared to the germination test, which, despite its status as a widespread and firmly established method, can take anywhere from 30 to 360 days to yield results (depending on species), and is limited by factors such as dormant seeds.
The total concentration of electrolytes leached by seeds during soaking has long been assessed indirectly, mostly through the conductivity test, which takes advantage of the fact that inorganic ions make up a substantial portion of these electrolytes [3–5].
Rapid assessment of seed quality allows for preemptive decision-making during harvest, processing, sale and storage operations, thus optimizing use of financial resources throughout these processes.
K. coriacea Mart. is a species of the Clusiaceae (Guttiferae) family popularly known in Brazil as pau-santo (Portuguese for “holy wood”), due to its properties as a medicinal and melliferous plant and as a source of cork. In traditional Brazilian medicine, the leaves are used as an emollient and antitumor agent, and the resin as a tonic and in the treatment of toothache and various infections. The fruits are used in regional crafts and flower arrangements. Even if the dye is of the leaves and bark. The trunk provides cork .
K. coriaceae specimens grow to approximately 4 meters in height. The flowering period extends from January to April and the fruiting period from May to September, and seed collection can take place from September onwards. Leaves are alternate, simple, oval to elliptical, coriaceous, and clustered at the end of the branches, and feature highly visible, pink midribs. A white to off-white latex is secreted in small amounts upon removal of leaves. Flowers are white to pale pink in color, large, fragrant, with many yellow stamens and are borne in short clusters near the apex of the branches. Seedling production requires that seeds be sown shortly after collection.
In the fruit are found 60 to 80 seeds with anemochoric. The seed varies from round to oblong, winged at the ends, light brown color, has integument thin and fragile, with smooth texture, the sizes range from 4.3 to 5.6 cm long, 1.3 to 1.9 cm wide, and 0.2 to 0.5 centimeter thick. The individual weight of the seeds ranges from. 112 to.128 grams. Nursery radicle emission occurred at 7 days and the germination rate was 90%. Germination occurs within 7 to 10 days. The species is slow growing, both in the field and in a nursery setting .
The present study sought to assess the applicability of the conductivity test to freshly collected K. coriacea Mart. seeds by determining the optimal soak time for performance of the test and comparing results obtained with this method against those obtained by tetrazolium and germination testing of seeds from the same batch.
2. Materials and Methods
2.1. Seed Collection
Seeds were collected in the cerrado sensu stricto, in SCA (Clean Water Farm), area of study at the University of Brasília (UNB) in August 2010, matrixes marked with the aid of GPS, after the period of physiological maturation of the seeds. The collection of fruits was directly from the tree, with the help of trimmer, then the seeds were processed and stored in paper bags at room temperature in the laboratory.
2.2. Conductivity Test
The development of tests to evaluate the physiological quality of seeds, as well as the standardization of these is essential for the establishment of an efficient quality control . One of the main requirements for the seed vigor refers to obtain reliable results in a relatively short period of time, allowing the speed of decision making especially as regards the operations of collection, processing, and marketing . The literature indicates that rapid tests are most studied early events related to the deterioration of the sequence proposed by Delouche and Baskin  as the degradation of cell membranes and reduced activity, and biosynthetic respiratory . The measurement of electrical conductivity through the electrolyte amount released by soaking seeds in water has been applied by the individual method where each seed is a sample or more often, a sample of seed representative of a population (mass method). For this case, the results represent the average conductivity of a group of seeds, may a small amount of dead seeds affect the conductivity of a batch with many high-quality seed generating a read underestimated. To minimize this problem, we recommend choosing the seeds, excluding the damaged seeds.
The electrical conductivity is based on the principle that the deterioration process is the leaching of the cells of seeds soaked in water due to loss of integrity of cellular systems. Thus, low conductivity means a high-quality seed and high conductivity, that is, greater output seed leachate, suggests that less force .
The electrical conductivity is not yet widely used in Brazil, its use is restricted to activities related to research (Krzyzanowski et al., 1991). There are common jobs using this test to determine the physiological quality of tree seeds. However, it is a promising vigor test for possible standardization of the methodology, at least within a species. However, it is a promising vigor test for possible standardization of the methodology, at least within a species. However, there are factors which influence the conductivity values as the size, the initial water content, temperature and time of soaking, the number of seeds per sample, and genotype .
Five treatments were carried out to test the efficiency of the conductivity test as a means of evaluating the viability of freshly collected K. coriacea Mart. seeds.
Five runs of 20 seeds were tested for each treatment. Seeds were individually placed into containers holding 50 mL of distilled water and left to soak for 30, 90, 120, 180, and 240 minutes in a germination chamber set to a constant temperature of 25°C. The minimum time taken for the soaking of 30 minutes was adopted by the same authors and Amaral and peske , Fernandes et al. , and Matos  who concluded that the period of 30 minutes of soaking is more effective to estimate the germination of the seeds. After each period, the conductivity of the soak solution was immediately tested with a benchtop EC meter precise to +/−1% (Quimis). Readings were expressed as μS·cm−1/g−1 seed .
Data thus obtained were subjected to analysis of variance with partitioning into orthogonal polynomials for analysis of the effect of soaking times on electrical conductivity.
2.3. Tetrazolium Test
The tetrazolium test, also known as biochemical test for vitality, is a technique used to estimate the viability and seed germination. A fundamental condition for ensuring the efficiency of the test is the direct contact of the tetrazolium solution with the tissues of the seed to be tested. Due to the impermeability of the coats of most forest tree seeds, it is necessary to adopt a previous preparation of the seeds that were tested. This preparation is based on facilitating entry of the solution in the seed. Among the preparations that precede the test we have cutting the seed coat, seed coat removal, scarification by sandpaper scarification by soaking in hot water and water . In the previous preparation of the seeds, factors such as concentration of the solution or even the time of the staining solution can affect the efficiency of the test in the evaluation of seed quality. The time required for the development of appropriate color according to the Rules for Seed Analysis  varies depending on each species, can be between 30 and 240 minutes.
The tetrazolium test has been widely used in seeds of various species due to the speed and efficiency in the characterization of the viability and vigor, and the possibility of damage to the same distinction, assisting in the process of quality control from the steps of harvest storage (GRIS et al, 2007).
The tetrazolium test was also applied to freshly collected K. coriacea Mart. seeds, for a total of three runs and 20 seeds. Seeds were soaked in a 0.5% solution of 2,3,5-triphenyl-2H-tetrazolium for 24 hours in a germination chamber set to a constant temperature of 25°C. After each run, seeds were washed, bisected, and the half-containing the embryonic axis placed under a stereo viewer for examination of staining patterns .
2.4. Germination Test
The standard germination test is the official procedure to evaluate the ability of seeds to produce normal seedlings under favorable conditions in the field, but does not always reveal differences in quality and performance among seed lots, which can manifest in storage or in the field .
During the germination test optimum conditions are provided and controlled for seeds to encourage the resumption of metabolic activity which will result in the seedlings. The main objective of the germination test is the information about the quality of seeds, which is used in the identification of lots for storage and sowing .
Freshly collected K. coriacea Mart. seeds were placed in a germination chamber at a constant temperature of 25°C (Treatment 1) or an alternating temperature of 20–30°C (Treatment 2), on a standard cycle of 8 hours of light and 16 hours of dark. Each test consisted of five runs and was performed on 20 seeds.
Germination was defined as emergence of at least 2.0 mm of the primary root . Assessment was conducted daily, and emergence was observed between day 6 and day 7. At the end of the 14-day test period, the germination percentage was calculated on the basis of radicle emergence .
3.1. Conductivity Test
Different soaking times were not associated with any significant differences in conductivity results in K. coriacea Mart. seeds (Table 1).
Table 1: Conductivity ranges of freshly collected Kielmeyera coriacea Mart. seeds after soaking for different periods.
Seeds with a leachate conductivity range of 7–17.99 μS·cm·g were considered nonviable, confirming the hypothesis behind conductivity testing, which is the nonviable seeds that have higher soaking solution conductivity values (Table 2).
Table 2: Percentage of viable Kielmeyera coriacea Mart. seeds according to EC range.
Analysis of variance revealed a low coefficient of variation (20.26%), which suggests good experimental control (Table 3).
Table 3: Analysis of variance of various soaking times for electrical conductivity testing of Kielmeyera coriacea Mart. seeds.
After analysis of variance, the correlation between the soaking time and electrical conductivity variables was assessed. The cubic model yielded
which is indicative of a positive correlation between the study variables.
The following equation was obtained on the basis of the cubic model:
Analysis of a plot of the above function in the GeoGebra 2007 software package shows that variation in electrical conductivity as a function of soaking time is minor and approaches a constant, which is consistent with the study results, in which changes in soaking time had no influence on conductivity (Figure 1).
Figure 1: Leachate conductivity as a function of soaking time in Kielmeyera coriaceaMart. seeds.
Matos  reported that a 30-minute soak was enough for assessment of Anadenanthera falcata, Copaifera langsdorffii, and Enterolobium contortisiliquum seeds by the soaking solution pH method—that is, the amount of matter leached after this period sufficed for measurement.
Although the principle of conductivity is the same used for the test pH of exudate, the soaking time needed to analyze the differential seeds through the conductivity may be explained by the fact that this technique is quantitative, while pH in the art exudate analyzes are qualitative. In other words to the technique of pH values of the exudate it is important to detect the acidity of imbibition while on the electrical conductivity we draw a comparison between the analyzed values to separate viable from nonviable samples. To determine a value of electrical conductivity as a reference to determine viable seeds are to be considered the values obtained for fresh seeds and seeds stored.
The thickness of the K. coriacea Mart. seed coat may also have affected the soaking procedure; this species has very thin seed coats, which makes soaking a very fast process.
These results are consistent with those reported by Rodrigues , who subjected stored K. coriaceaMart. seeds to the conductivity test and found that 90 minutes is an appropriate soaking time for analysis.
Therefore, it can be inferred that for seed Kielmeyera coriacea Mart. the soaking time of 90 minutes can be applied to obtain satisfactory results.
3.2. Tetrazolium Test
Table 4 shows the results of tetrazolium testing of K. coriacea Mart. seeds in our sample. The mean viability rate was 96.6%. The testing procedure was based on Brazilian Ministry of Agriculture recommendations .
Table 4: Tetrazolium testing of Kielmeyera coriacea Mart. seeds.
The results of the tetrazolium test were quite similar to those obtained with the conductivity method, thus confirming the efficiency of the latter method as a means for assessing the viability of K. coriaceaMart. seeds.
3.3. Germination Test
The germination test results of freshly collected K. coriacea Mart. seeds are shown in Table 5. Regardless of temperature, both test batches exhibited good viability, and no seed dormancy was detected.
Table 5: Germination test results of Kielmeyera coriacea Mart. seeds.
Radicle emergence was observed between day 7 and day 9 of the test, according to the analysis criteria proposed by Labouriau .
These findings are consistent with those of Melo et al.,  who reported high and relatively rapid germination rates for K. coriacea seeds kept at 25°C on paper towels, with emergence of a perfect radicle on the 7th day of assessment.
The electrical conductivity can be used as an indicator of seed viability and presents two advantages: to provide rapid and reliable results and the technique is not destructive and can use the seeds after the conductivity test, so they can be used to produce seedlings.
The present study showed that different soaking times had no effect on the results of conductivity testing of freshly collected K. coriacea Mart. seeds, suggesting that the amount of leached matter was never below the threshold required for adequate testing.
Electrical conductivity testing proved to be a feasible option for viability testing of K. coriacea Mart. seeds, as the results obtained with conductivity testing were confirmed by germination testing and by the tetrazolium test.
- J. M. M. Matos, Evaluation of pH test on exudate check feasibility of forest seeds, dissertation, University of Brasília, Brasília, Brazil, 2009.
- F. Poggiani, S. Bruni, and E. S. Q. Barbos, “Effect of shading on seedling growth of three species forest,” in National conference on native plants, vol. 2, pp. 564–569, Institute of Forestry, 1992.
- M. B. Mcdonald Jr. and D. O. Wilson, “ASA-610 ability to detect changes in soybean seed quality,” Journal of Seed Technology, vol. 5, no. 1, pp. 56–66, 1980.
- S. Matthews and A. Powell, “A eletrical conductivity test,” in Handbook of Vigor Test Methods, D. A. Perry, Ed., pp. 37–42, International Seed Testing Associaty, Zurich, Switzerland, 1981.
- J. Son Mark, W. R. Singh, A. D. C. Novembre, and H. M. C. P. Chamma, “Comparative studies to evaluate dem’etodos physiological quality of soybean seeds, with emphasis the electrical conductivity test,” Brazilian Journal of Agricultural Research, vol. 25, no. 12, pp. 1805–1815, 1990.
- S. R. Singh, A. P. Silva, C. B. Munhoz, et al., Guide of Cerrado Plants Used in the Chapada Veadeiros, WWF-Brazil, Brasilia, Brazil, 2001.
- J. M. Felfili, C. W. Fagg, J. C. S. Silva, et al., Plants of the APA Gama Cabeça de Veado: Species, ecosystems and recovery, University of Brasilia, Brasília, Department of Engineering Forest, Brasília, Brazil, 2002.
- M. F. B. Muniz, et al., “Comparison of methods for evaluating the physiological and health quality of melon seeds,” Journal of Seeds, Pellets, vol. 26, no. 2, pp. 144–149, 2004.
- D. C. F. S. Dias and J. Marcos Filho, “Electrical conductivity to assess seed vigor of soybean (Glycine max (L.) Merrill),” Scientia Agricola, vol. 53, no. 1, Article ID article id, pp. 31–42, 1996.View at Publisher · View at Google Scholar
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- R. D. Vieira and F. C. Krzyzanowski, “Electrical conductivity test,” in Seed Vigor: Concepts and Tests, F. C. Krzyzanowski, R. D. Vieira, and J. B. França Neto, Eds., pp. 4.1–4.26, Abrates, London, UK, 1999.
- R. D. Vieira, “Electrical conductivity test,” in Seed Vigor Tests, R. D. Vieira and N. M. Carvalho, Eds., p. 103, FUNEP, Jaboticabal, Brazil, 1994.
- A. S. Amaral and S. T. Peske, “Exudate pH to estimate, in 30 minutes seed viability of soybeans,”Journal of seeds, vol. 6, no. 3, pp. 85–92, 1984.
- E. J. Fernandes, R. Sader, and N. M. Carvalho, “seed viability beans (Phaseolus vulgaris L.) estimated by the pH of the exudate,” in Congress Brazil’s Seeds, Gramado, Brazil, 1987.
- F. C. Krzyzanowski and R. D. Vieira, “Electrical conductivity test,” in Seed Vigor: Concepts and Tests, F. C. Krzyzanowski, R. D. Vieira, and J. B. France Neto, Eds., pp. 4.1–4.26, Abrates, London, UK, 1999.
- Ministry of Agriculture, Livestock and Supply, Rule for seed testing, SNPA/DNPV/CLAV, Brasilia, Brazil, 1992.
- Ministry of Agriculture, Livestock and Supply, Rule for seed testing, SNPA/DNPV/CLAV, Brasilia, Brazil, 2009.
- N. M. Carvalho and J. Nakagawa, Seeds: Science, Technology and Production, FUNEP, Jaboticabal, Brazil, 2000.
- Pina-Rodrigues, et al., “Quality test,” in Germination from Basic to Applied, A. Ferreira and G. F. Borghetti, Eds., pp. 283–297, 2004.
- A. G. Ferreira and F. Borghetti, from basic to Germination applied, Artmed, Porto Alegre, Brazil, 2004.
- L. G. Labouriau, seed germination, OAS, Washington, DC, USA, 1983.
- L. L. Rodrigues, Study of imbibition time for application the method of electrical conductivity in the verification of the feasibility forest seeds stored, monograph, University of Brasília, Brasília, Brazil, 2010.
- J. T. Melo, J. F. Ribeiro, and V. L. G. F. Lima, “Germination of Seeds of some tree species native to the Cerrado,” Journal of Seeds, vol. 1, no. 2, pp. 8–12, 1979.
Research article by: Kennya Mara Oliveira Ramos,1 Juliana M. M. Matos,1 Rosana C. C. Martins,1 and Ildeu S. Martins2
1Seed Technology Laboratory of Forestry, Department of Forestry, University of Brasilia, CP 04357, 70919970 Campus Asa Norte, DF, Brazil
2Department of Forestry, University of Brasilia, CP 04357, 70919970 Campus Asa Norte, DF, Brazil
Received 17 December 2011; Accepted 14 February 2012
Academic Editors: A. Berville, C. Gisbert, J. Hatfield, and Y. Ito
Copyright © 2012 Kennya Mara Oliveira Ramos 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.
admin 10 May, 2013
Tweet Water quality testing is vital to the design of an efficient, cost-effective RO system, and is one of the best ways to preserve system life and performance. Using an accurate Total Dissolved Solids (TDS) measurement to assess the system load prevents costly mistakes up front. The TDS measurement gives users the information they need […]
Water quality testing is vital to the design of an efficient, cost-effective RO system, and is one of the best ways to preserve system life and performance.
Using an accurate Total Dissolved Solids (TDS) measurement to assess the system load prevents costly mistakes up front. The TDS measurement gives users the information they need to determine whether or not pretreatment is required and the type of membrane/s to select. Ultrameter™ and ULTRAPEN PT1™ Series TDS instruments feature the unique ability to select from 3 industry standard solution models: 442 Natural Water™ NaCl; and KCl. Choosing the model that most closely matches the characteristics of source water yields measurements accurate enough to check and calibrate TDS monitor/controllers that can help alert to system failures, reducing downtime and increasing productivity. The same instruments provide a fast and accurate test for permeate TDS quality control. Measuring concentrate values and analyzing quality trends lets users accurately determine membrane usage according to the manufacturer’s specifications so they can budget consumption correctly. These daily measurements are invaluable in detecting problems with system performance where changes in the ionic concentration of post-filtration streams can indicate scaling or fouling. System maintenance is generally indicated if there is either a 10-15% drop in performance or permeate quality as measured by TDS.
Thin-film composite membranes degrade when exposed to chlorine. In systems where chlorine is used for microbiological control, the chlorine is usually removed by carbon adsorption or sodium bisulfite addition before membrane filtration. The presence of any chlorine in such systems will at best reduce the life of the membrane, thus, a target of 0 ppm free chlorine in the feedwater is desirable.
ORP gives the operator the total picture of all chemicals in solution that have oxidizing or reducing potential including chlorine, bromine, chloramines, chlorine dioxide, peracetic acid, iodine, ozone, etc. However, ORP can be used to monitor and control free chlorine in systems where chlorine is the only sanitizer used. ORP over +300 mV is generally considered undesirable for membranes. Check manufacturer’s specifications for tolerable ORP levels.
An inline ORP monitor/controller placed ahead of the RO unit to automatically monitor for trends and breakthroughs coupled with spot checks by a portable instrument will prevent equipment damage and failure. Myron L 720 Series II™ ORP monitor/controllers can be configured with bleed and feed switches as well as visible and audible alarms.
Ultrameter and ULTRAPEN portable handhelds are designed for fast field testing and are accurate enough to calibrate monitor/controllers. Our measurement methods are objective and have superior accuracy and convenience when compared to colorimetric methods where determination of equivalence points is subjective and can be skewed by colored or turbid solutions.
Monitoring pH of the source water will allow users to make adjustments that optimize the performance of antiscalants, corrosion inhibitors and anti-foulants. Using a 720 II Series Monitor/controller to maintain pH along with an Ultrameter Series or ULTRAPEN PT2™ handheld to spot check pH values will reduce consumption of costly chemicals and ensure their efficacy.
Most antiscalants used in chemical system maintenance specify a Langelier Saturation Index maximum value. Some chemical manufacturers and control systems develop their own proprietary methods for determining a saturation index based on solubility constants in a defined system. However, LSI is still used as the predominant scaling indicator because calcium carbonate is present in most water. Using a portable Ultrameter III 9PTKA™ provides a simple method for determining LSI to ensure the chemical matches the application.
The Ultrameter III 9PTKA computes LSI from independent titrations of alkalinity and hardness along with electrometric measurements of pH and temperature. Using the 9PTKA LSI calculator, alterations to the water chemistry can be determined to achieve the desired LSI. Usually, pH is the most practical adjustment. If above 7, acid additions are made to achieve the pH value in the target LSI. Injections are made well ahead of the RO unit to ensure proper mixing and avoid pH hotspots. A Myron L 720 Series II pH Monitor/controller will automatically detect and divert solution with pH outside the range of tolerance for the RO unit. ULTRAPEN PT2, TechPro II and Ultrameter Series instruments can be used to spot check and calibrate the monitor/controller as part of routine maintenance and to ensure uniform mixing.
Water hardness values indicate whether or not ion exchange beds are required in pretreatment. Checking hardness values directly after the softening process with the Ultrameter III 9PTKA ensures proper functioning and anticipates the regeneration schedule.
Alkalinity is not only important in its effect on the scaling tendency of solution, but on pH maintenance. Additions of lime are used to buffer pH during acid injection. Use a 9PTKA to measure alkalinity values for fast field analysis where other instrumentation is too cumbersome to be practical.
Though testing and monitoring pressure is a good way to evaluate system requirements and performance over time, measuring other water quality parameters can help pinpoint problems when troubleshooting. For example, if the pressure differential increases over the second stage, the most likely cause is scaling by insoluble salts. This means that any degradation in performance is likely due to the dissolved solids in the feed. Using a 9PTKA to evaluate LSI and calculate parameter adjustments is a simple way to troubleshoot a costly problem.
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Original story from International Filtration News V 32, no. 2
admin 7 May, 2013
TweetSoon Myron L Meters will be adding a Water Industry Resources page to MyronLMeters.com. The page will feature links to water industry events, water industry associations, and related technical resources. Please look over our draft page below and suggest anything we might be missing. Be sure to check back with us periodically for new features […]
Soon Myron L Meters will be adding a Water Industry Resources page to MyronLMeters.com. The page will feature links to water industry events, water industry associations, and related technical resources. Please look over our draft page below and suggest anything we might be missing. Be sure to check back with us periodically for new features and changes, including our upcoming Myron L Meters Users Forum.
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26.National Water Research Institute - Canada.
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The CWWA encourages the study, research and development in water supply and wastewater disposal, and the publication of the results of such work, so as to provide for appropriate and dynamic technological advances in the Caribbean.
Florida Water and Pollution Control Operators Association, Region 8
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Kentucky Water & Wastewater Operators Association (KWWOA)
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Maine Lagoon Systems
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Maine Wastewater Control Association (MWCA)
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Measurement, Control and Automation Association (MCAA)
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National Water Research Institute - Canada.
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Northeast Rural Water Association (NeRWA)
Started in 1982, a nonprofit association of water and wastewater systems in Massachusetts, New Hampshire, and Vermont. Among its many services, We offer training and onsite technical assistance to operators, managers, owners and boards.
South Carolina Rural Water Association (SCRWA)
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Water and Wastewater Equipment Manufacturers Association
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Water Education Foundation
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Water Organizations - [UWIN]
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Water Industry Training Specialists are a California Corporation in the business of training and certifying Backflow Technicians and Cross-Connection Control Inspectors.
Environmental-Expert.com hosts several courses from different companies in industrial wastewater, water treatment, and environmental engineering.
admin 1 May, 2013
TweetMyronLMeters.com has the most advanced lineup of pool analysis meters for the professional pool maintenance technician from the Ultrapen to the PoolPro PS9. Pool Draining Tips to Protect Water Quality With summer right around the corner, many swimming pool owners will be readying their swimming pools in anticipation of the season’s heat. As part of […]
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Pool Draining Tips to Protect Water Quality
With summer right around the corner, many swimming pool owners will be readying their swimming pools in anticipation of the season’s heat. As part of this process, some pool owners like to drain old swimming pool water which has been sitting all winter. Though not a necessary task, the following tips are provided for you to properly drain pool water in order to protect the water resources in your community.
Whenever possible, it is best to drain your pool onto your landscape. This recycles your pool water, conserves irrigation water, and avoids the environmental risks associated with draining your pool to the street. Before draining your pool water to the street or to your landscape, be sure to follow the guidelines outlined below.
While draining pool water to the street is a common practice, it can prove harmful to the environment if the pool owner does not properly plan and prepare prior to draining. When pool water is drained to the street, it can carry other pollutants such as oil, grease, sediment, bacteria and trash down the storm drain and into the nearest creek, river, or the ocean. Swimming pool water also often contains harmful additives and chemicals. If the water is not properly treated to remove these pollutants prior to draining, they can cause further damage to the health of our waterways and to the plants and animals that live there.
Also, prior to draining to the street, residents are asked to sweep the curb and gutter between the discharge point from their yard to the storm drain down hill from their home. This will remove any pollutants from the gutter that may be carried up by the drained pool water to the storm drain.
For chlorine pools, chlorine levels must be lowered to less than 1 part per million prior to draining. This can be done naturally, by simply allowing the pool water to sit in the sun for a minimum of three days. Alternatively, de-chlorination kits can be purchased at home supply stores at a very reasonable cost. These kits have the tools you need to reach the appropriate chlorine levels before draining your pool to the curb and gutter.
Some people have salt water pool systems which may be preferred due to the lower amount of chemicals required for their operation. However, these pools must not be drained to the storm drain system due to their high salt content relative to the fresh water systems they drain into. Total dissolved solids (TDS) must be below 500 parts per million in order to drain into the street.
“Green pools,” which are pools in which algae is growing, also must not be drained to the street. In these instances, algae must first be killed and removed. This is usually done by chlorinating the swimming pool until the algae is gone, then lowering chlorine to the allowable discharge level. Cartridge filters or diatomaceous earth (DE) filters should be rinsed onto a pervious surface such as landscaped areas or grass. While DE is actually beneficial in your garden, it can build up in storm drains and clog them. DE residues can be scooped up and simply thrown in the trash or put to use fending off worms in your garden.
For more information on how to reach acceptable chemical and TDS levels, call your pool maintenance specialist.
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admin 3 Apr, 2013
TweetThe thermal conductivity enhancement of nanofluids Abstract Increasing interests have been paid to nanofluids because of the intriguing heat transfer enhancement performances presented by this kind of promising heat transfer media. We produced a series of nanofluids and measured their thermal conductivities. In this article, we discussed the measurements and the enhancements of the thermal […]
The thermal conductivity enhancement of nanofluids
Increasing interests have been paid to nanofluids because of the intriguing heat transfer enhancement performances presented by this kind of promising heat transfer media. We produced a series of nanofluids and measured their thermal conductivities. In this article, we discussed the measurements and the enhancements of the thermal conductivity of a variety of nanofluids. The base fluids used included those that are most employed heat transfer fluids, such as deionized water (DW), ethylene glycol (EG), glycerol, silicone oil, and the binary mixture of DW and EG. Various nanoparticles (NPs) involving Al2O3 NPs with different sizes, SiC NPs with different shapes, MgO NPs, ZnO NPs, SiO2 NPs, Fe3O4 NPs, TiO2 NPs, diamond NPs, and carbon nanotubes with different pretreatments were used as additives. Our findings demonstrated that the thermal conductivity enhancements of nanofluids could be influenced by multi-faceted factors including the volume fraction of the dispersed NPs, the tested temperature, the thermal conductivity of the base fluid, the size of the dispersed NPs, the pretreatment process, and the additives of the fluids. The thermal transport mechanisms in nanofluids were further discussed, and the promising approaches for optimizing the thermal conductivity of nanofluids have been proposed.
More efficient heat transfer systems are increasingly preferred because of the accelerating miniaturization, on the one hand, and the ever-increasing heat flux, on the other. In many industrial processes, including power generation, chemical processes, heating or cooling processes, and microelectronics, heat transfer fluids such as water, mineral oil, and ethylene glycol always play vital roles. The poor heat transfer properties of these common fluids compared to most solids is a primary obstacle to the high compactness and effectiveness of heat exchangers. An innovative way of improving the thermal conductivities of working media is to suspend ultrafine metallic or nonmetallic solid powders in traditional fluids since the thermal conductivities of most solid materials are higher than those of liquids. A novel kind of heat transfer enhancement fluid, the so-called nanofluid, has been proposed to meet the demands .
“Nanofluid” is an eye-catching word in the heat transfer community nowadays. The thermal properties, including thermal conductivity, viscosity, specific heat, convective heat transfer coefficient, and critical heat flux have been studied extensively. Several elaborate and comprehensive review articles and books have addressed thermal transport properties of nanofluids [1,3-6]. Among all these properties, thermal conductivity is the first referred one, and it is believed to be the most important parameter responsible for the enhanced heat transfer. Investigations on the thermal conductivity of nanofluids have been drawing the greatest attention of the researchers. A variety of physical and chemical factors, including the volume fraction, the size, the shape, and the species of the nanoparticles (NPs), pH value and temperature of the fluids, the Brownian motion of the NPs, and the aggregation of the NPs, have been proposed to play their respective roles on the heat transfer characteristics of nanofluids [7-19]. Extensive efforts have been made to improve the thermal conductivity of nanofluids [7-19] and to elucidate the thermal transport mechanisms in nanofluids [20-23].
The authors have carried out a series of studies on the heat transfer enhancement performance of nanofluids. A variety of nanofluids have been produced by the one- or two-step method. The base fluids used include deionized water (DW), ethylene glycol (EG), glycerol, silicone oil, and the binary mixture of DW and EG (DW-EG). Al2O3 NPs with different sizes, SiC NPs with different shapes, MgO NPs, ZnO NPs, SiO2 NPs, Fe3O4 NPs, TiO2 NPs, diamond NPs (DNPs), and carbon nanotubes (CNTs) with different pretreatments have been used as additives. The thermal conductivities of these nanofluids have been measured by transient hot wire (THW) method or short hot wire (SHW) technique. In this article, the experimental results that elucidate the influencing factors for thermal conductivity enhancement of nanofluids are presented. The thermal transport mechanisms in nanofluids and promising approaches for optimizing the thermal conductivity of nanofluids are further presented.
Preparation of nanofluids
Two techniques have been applied to prepare nanofluids in our studies: two- and one-step techniques. Most of the studied nanofluids were prepared by the two-step technique. During the procedure of two-step technique, the dispersed NPs were prepared by chemical or physical methods first, and then the NPs were added into a specified base fluid, with or without pretreatment and surfactant based on the need. In the preparation of nanofluids containing metallic NPs, one-step technique was employed.
The process was quite simple in the preparation of nanofluids containing oxide NPs like Al2O3, ZnO, MgO, TiO2, and SiO2 NPs. The NPs were obtained commercially and were dispersed into a base fluid in a mixing container. The NPs were deagglomerated by intensive ultrasonication after being mixed with the base fluid, and then the suspensions were homogenized by magnetic force agitation.
Two-step method was used to prepare graphene nanofluids. The first step was to prepare graphene nanosheets. Functionalized graphene was gained through a modified Hummers method as described elsewhere . Graphene nanosheets were obtained by exfoliation of graphite in anhydrous ethanol. The product was a loose brown powder, and it had good hydrophilic nature. The graphene nanosheets could be dispersed well in polar solvents, like DW and EG, without the use of surfactant. For liquid paraffin (LP)-based nanofluid, oleylamine was used as the surfactant. The fixed quality of graphene nanosheets with different volume fractions was dispersed in the base fluids.
Severe aggregation always takes place in the as-prepared CNTs (pristine CNTs: PCNTs) because of the non-reactive surfaces, intrinsic Von der Waals forces, and very large specific surface areas, and aspect ratios . In CNT nanofluid preparations, surfactant addition is an effective way to enhance the dispersibility of CNTs [26-28]. However, surfactant molecules attaching on the surfaces of CNTs may enlarge the thermal resistance between the CNTs and the base fluid , which limits the enhancement of the effective thermal conductivity. The steps involved in the preparation of surfactant-free CNT nanofluids include (1) disentangling the nanotube entanglement and introducing hydrophilic functional groups on the surfaces of the nanotubes by chemical treatments; (2) cutting the treated CNTs (TCNTs) to optimal length by ball milling; and (3) dispersing the treated and cut CNTs into base fluids. CNTs including single-walled CNTs (SWNTs), double-walled CNTs (DWNTs), and multi-walled CNTs (MWNTs) were obtained commercially. Two chemical routes for treating CNTs were used for this study. One is oxidation with concentrated acid, and the other is mechanochemical reaction with potassium hydroxide (KOH). The detailed treatment processes have been described elsewhere [8,30].
Phase transfer method was used to prepare stable kerosene-based Fe3O4 magnetic nanofluid. The first step is to synthesize Fe3O4 NPs in water by coprecipitation. Oleic acid was added to modify the NPs. When kerosene is added to the mixture with slow stirring, the phase transfer process took place spontaneously. There was a distinct phase interface between the aqueous and kerosene. After the removal of the aqueous phase using a pipette, the kerosene-based Fe3O4 nanofluid was obtained .
Nanofluids containing copper NPs were prepared using direct chemical reduction method. Stable nanofluids were obtained with the addition of poly(vinylpyrrolidone) (PVP). The diameters of copper NPs prepared by chemical reduction procedure are in the range of 5-10 nm, and copper NPs disperse well with no clear aggregation .
Surface modification is always used to enhance the dispersibility of NPs in the preparation of nanofluids. For example, diamond NPs (DNPs) were purified and surface modified by acid mixtures of perchloric acid, nitric acid and hydrochloric acid according to the literature  before being dispersed into the base fluids. SiC NPs were heated in air to remove the excess free carbon and their surfaces modified to enhance their dispersibility.
Consideration on the thermal conductivity measurement
Inconsistent experimental results and controversial arguments arise unceasingly from different groups conducting research on nanofluids, indicating the complexity of the thermal transport in nanofluids. Through an investigation, a large degree of randomness and scatter have been observed in the experimental data published in the open literature. Given the inconsistency in the data, it is impossible to develop a convincing and comprehensive physical-based model that can predict all the trends. To clarify the suspicion on the scattered and wide-ranging experimental results of the thermal conductivity obtained by different groups, it is preferred to screen the measurement technique and procedure to guarantee the accuracy of the obtained results.
Several researchers observed the “time-dependent characteristic” of thermal conductivity [34-36], that is to say, thermal conductivity was the highest right after nanofluid preparation, and then it decreased considerably with elapsed time. We believe that the “time-dependent characteristic” does not represent the essence of thermal conduction capability of nanofluids. The following two factors may account for this phenomenon. The first one is the motion of the remained particle caused by the agitation during the nanofluid preparation. To make a nanofluid homogeneous and long-term stable, it is always subjected to intensive agitation including magnetic stirring and sonication to destroy the aggregation of the suspended NPs. In very short time after nanofluid preparation, the NPs still keep moving in the base fluid (different from Brownian motion). The motion of the remained particle would cause convection and enhance the energy transport in the nanofluids. Second, when a nanofluid is subjected to long-time sonication, its temperature would be increased. The temperature goes down gradually to the surrounding temperature (thermal conductivity measurement temperature). In very short time after the sonication stops, the process has been remaining. Although the temperature decrease is not severe, the thermal conductivity obtained is very sensitive to the temperature decrease when the transient hot-wire technique is used to measured the thermal conductivity. In our measurements, this phenomenon would be observed. When measuring the thermal conductivity at an unequilibrium state, it was found that the measured data might be very different for a nanofluid even at a specific temperature (see 25°C) if the process to reach this temperature is different. If the temperature is increasing, then the datum obtained of the thermal conductivity would be lower than the true value. While the temperature is decreasing, the datum obtained of the thermal conductivity would be higher than the true value. Therefore, keeping a nanofluid stable and initial equilibrium is very important to obtain accurate thermal conductivity data in measurements.
A transient short hot-wire method was used to measure the thermal conductivities of the base fluids (k0) and the nanofluids (k). The detailed measurement principle, procedure, and error analysis have been described in . In our measurements, a platinum wire with a diameter of 50 μm was used for the hot wire, and it served both as a heating unit and as an electrical resistance thermometer. The platinum wire was coated with an insulation layer of 7-μm thickness. Initially the platinum wire immersed in media was kept at equilibrium with the surroundings. When a regulation voltage was supplied to initiate the measurement, the electrical resistance of the wire changed proportionally with the rise in temperature. The thermal conductivity was calculated from the slope of the rise in the wire’s temperature against the logarithmic time interval. The uncertainty of this measurement is estimated to be within ± 1.0%. A temperature-controlled bath was used to maintain different temperatures of the nanofluids. Instead of monitoring the temperature of the bath, a thermocouple was positioned inside the sample to monitor the temperature on the spot. When the temperature of the sample reached a steady value, the authors waited for further 20 min to make sure that the initial state is at equilibrium. At every tested temperature, measurements were made three times and the average values were taken as the final results. A 20-min interval was needed between two successive measurements. After the above-mentioned careful check on the measurement condition and procedure, the authors could gain confidence on the experimental results.
Influencing factors of thermal conductivity enhancement
In the experiment of the study, it was found that the thermal conductivity enhancements of nanofluids might be influenced by multi-faceted factors including the volume fraction of the dispersed NPs, the tested temperature, the thermal conductivity of the base fluid, the size of the dispersed NPs, the pretreatment process, and the additives of the fluids. The effects of these factors are presented in this section.
The idea of nanofluid application originated from the fact that the thermal conductivity of a solid is much higher than that of a liquid. For example, the thermal conductivity of the most used conventional heat transfer fluid, water, is about 0.6 W/m · K at room temperature, while that of copper is higher than 400 W/m · K. Therefore, particle loading would be the chief factor that influences the thermal transport in nanofluids. As expected, the thermal conductivities of the nanofluids have been increased over that of the base fluid with the addition of a small amount of NPs. Figure 1 shows the enhanced thermal conductivity ratios of the nanofluids with NPs at different volume fractions [7,8,38-42]. (k - k0)/k0 and φ refer to the thermal conductivity enhancement ratio of nanofluids and the volume fraction of NPs, respectively, in this article. Figure1a presents oxide nanofluids, while Figure 1b presents nonoxide nanofluids. The results show that all the nanofluids have noticeable higher thermal conductivities than the base fluid without NPs. In general, the thermal conductivity enhancement increases monotonously with the volume fraction. For the graphene nanofluid with a volume fraction of 0.05, the thermal conductivity can be enhanced by more than 60.0%. There is an approximate linear relationship between the thermal conductivity enhancement ratios and the volume fraction of graphene nanosheets. The nanofluids containing graphene nanosheets show larger thermal conductivity enhancement than those containing oxide NPs. It demonstrates that graphene nanosheet is a good additive to enhance the thermal conductivity of base fluid. However, the enhancement ratios of nanofluids containing graphene nanosheets are less than those of CNTs with the same loading. Many factors have direct influence on the thermal conductivity of the nanofluid. One of the important factors is the crystal structure of the inclusion in the nanofluid. Graphene is a one-atom-thick planar sheet of sp2-bonded carbon atoms that are densely packed in a honeycomb crystal lattice. The perfect structure of graphene is damaged when graphite is chemically oxidized by treatment with strong oxidants. There is no doubt that the high thermal conductivity is diminished by defects, and the defects have direct influence on the heat transport along the 2-D structure.
Figure 1. Thermal conductivity enhancement ratios of the nanofluids as a function of nanoparticle loading. (a) Oxide nanofluids: MgO-EG ; Al2O3-EG ; ZnO-EG ; (b) Nonoxide nanofluids: CNT-EG ; DNP-EG ; Graphene-EG ; Cu-EG .
Some studies have demonstrated that the temperature has a great effect on the enhancement of the thermal conductivity for nanofluids. However, there is considerable disagreement in the literature with respect to the temperature dependence of their thermal conductivity. For example, Das et al. reported strong temperature-depended thermal conductivity for water-based Al2O3 and CuO nanofluids . The thermal conductivity enhancements of nanofluids containing Bi2Te3nanorods in FC72 and in oil had been experimentally found to decrease with increasing temperature . Micael et al. measured the thermal conductivities of EG-based Al2O3 nanofluids at temperatures ranging from 298 to 411 K. A maximum in the thermal conductivity was observed at all mass fractions of NPs .
Figure 2 shows our measured temperature-depended thermal conductivity enhancements of nanofluids [8,38-42]. For EG-based nanofluids containing MgO, ZnO, SiO2, and graphene NPs, the thermal conductivity enhancements almost remain constant when the tested temperature changes (see Figure 2a), which means that the thermal conductivity of the nanofluid tracks the thermal conductivities of the base liquid in the experimented temperature range of this study. The thermal conductivity enhancements of DW-EG-based nanofluids containing MgO, ZnO, SiO2, Al2O3, Fe2O3, TiO2, and graphene NPs also appear to have the same behavior. It was further found that kerosene-based Fe3O4 nanofluids presented temperature-independent thermal conductivity enhancements. Patel et al.  reported that the thermal conductivity enhancement ratios of Cu nanofluids are enhanced considerably when the temperature increases. The experimental results of this study shown in Figure 2b demonstrated similar tendency. At 10°C, the thermal conductivity enhancement of EG based Cu nanofluid with 0.5% nanoparticle loading is less than 15.0%. When the temperature is increased to 60°C, the enhancement reaches as large as 46.0%. Brownian motion of the NPs has been proposed as the dominant factor for this phenomenon. For the EG-based CNT nanofluids, cylindrical nanotubes with large aspect ratios were used as additions. The effect of Brownian motion will be negligible. Typical conduction-based models will give (k - k0)/k0, independent of the temperature. However, results shown in Figure 2b illustrate that (k - k0)/k0increases, though not drastically, with the temperature. CNT aggregation kinetics may contribute to the observed differences . It is worthy of bearing in mind that the temperatures of the base fluid and the nanofluid should be the same when compared with the thermal conductivities between them. Comparison of the thermal conductivities between the nanofluid at one temperature and the base at another one is meaningless.
Figure 2. Thermal conductivity enhancement varying with the tested temperatures. (a) Oxide nanofluids: MgO-EG ; ZnO-EG; Graphene-EG ; (b) Nonoxide nanofluids: Cu-EG ; CNT-EG; DNP-EG .
Figure 3 shows the relation between the enhanced thermal conductivity ratios of the nanofluids and the thermal conductivities of the base fluids [7,8,40,41]. It is clearly seen that no matter what kind of nanoparticle was used, the thermal conductivity enhancement decreases with an increase in the thermal conductivity of the base fluid. For pump oil (PO)-based Al2O3 nanofluid with 5.0% nanoparticle loading, the thermal conductivity can be enhanced by more than 38% compared to that of PO. When the base fluid is substituted with water, the thermal conductivity enhancement achieved is only about 22.0% . A greater dramatic improvement in thermal conductivity of CNT nanofluid is seen for a base fluid with lower thermal conductivity. At 1.0% nanoparticle loading, the thermal conductivity enhancements are 19.6, 12.7, and 7.0% for CNT nanofluids in decene, EG, and DW, respectively. No matter what kind of base fluid is used, the thermal conductivity enhancement of CNT nanofluids is much higher than that for Al2O3 nanoparticle suspensions  at the same volume fraction. The reason would lie in the substantial difference in thermal conductivity and morphology between alumina nanoparticle and carbon nanotube.
Figure 3. Thermal conductivity enhancement ratios as a function of the thermal conductivities of the base fluids: Al2O3 NFs ; CNT NFs ; Graphene NFs ; DNP NFs .
Figure 4 presents the thermal conductivity enhancement of the nanofluids as a function of the specific surface area (SSA) of the suspended particles . It is seen that the thermal conductivity enhancement increases first, and then decreases with an increase in the SSA, with the largest thermal conductivity at a particle SSA of 25 m2 · g-1. We ascribe the thermal conductivity change behavior to twofold factors. First, as particle size decreases, the SSA of the particle increases proportionally. Heat transfer between the particle and the fluid takes place at the particle-fluid interface. Therefore, a dramatic enhancement in thermal conductivity is expected because a reduction in particle size can result in large interfacial area. Second, the mean free path in polycrystalline Al2O3 is estimated to be around 35 nm, which is comparable to the size of the particle that was used. The intrinsic thermal conductivity of nanosized Al2O3 particle may be reduced compared to that of bulk Al2O3 due to the scattering of the primary carriers of energy (phonon) at the particle boundary. It is expected that the suspension’s thermal conductivity is reduced with an increase in the SSA. Therefore, for a suspension containing NPs at a particle size much different from the mean free path, the thermal conductivity increases when the particle size decreases because the first factor is dominant. However, when the size of the dispersed NPs is close to or smaller than the mean free path, the second factor will govern the mechanism of the thermal conductivity behavior of the suspension.
Figure 4. Enhanced thermal conductivity ratios as a function of the SSAs: Al2O3-EG ; Al2O3-PO .
Figure 5 depicts the thermal conductivity enhancements of nanofluids containing CNTs with different sizes . The base fluid is DW, and the volume fraction of the CNTs is 0.0054. It is observed from Figure 5 that the thermal conductivity enhancements show differences among these three kinds of nanofluids containing SWNTs, DWNTs, and MWNTs as the volume fraction of CNTs is the same. Two influencing factors may be addressed. The first one is the intrinsic heat transfer performance of the CNTs. It is reported that the thermal conductivity of CNTs decreases with an increase in the number of the nanotube layer. The tendency of the thermal conductivity enhancement of the obtained CNT nanofluids accords with that of the heat transfer performance of the three kinds of CNTs. The second one is the alignment of the liquid molecules on the surface of CNTs. There are greater number of water molecules close to the surfaces of CNTs with smaller diameter due to the larger SSA if the volume fractions of CNTs are the same. These water molecules can form an interfacial layer structure on the CNT surfaces, increasing the thermal conductivity of the nanofluid .
Figure 5. Thermal conductivity enhancements of nanofluids containing CNTs with different sizes: SWNT-DW ; DWNT-DW; MWNT-DW .
In the preparation of nanofluids, solid additives are always subjected to various pretreatment procedures. The initial incentive is to tailor the surfaces of the NPs to enhance their dispersibility, thereby to enhance the stability of the nanofluids. The morphologies would be significantly changed when CNTs were subjected to chemical or mechanical treatments. Theoretical research into the thermal conductivity of composites containing cylindrical inclusions has demonstrated that the morphologies, including the aspect ratio, have influence on the effective thermal conductivity of the composites. Therefore, it can be expected that the thermal conductivity of CNT contained nanofluids would be affected by the pretreatment process.
Figure 6 shows the dependence of the thermal conductivity enhancement on the ball milling time of CNTs suspended in the nanofluids . From theoretical prediction, the thermal conductivity of a composite increases with the aspect ratio of the included solid particles [49-51]. Intuition suggests that increasing the milling time should therefore decrease (k - k0)/k0 because of the reduced aspect ratio. Figure 6, however, shows clear peak and valley values in the thermal conductivity enhancement with respect to the milling time for all the studied CNT loadings. For nanofluid at a volume fraction of 0.01, the thermal conductivity enhancements present a peak value of 27.5% and a valley value of 10.4% when the milling times are 10 and 28 h, respectively. The maximal enhancement is intriguingly more than two and half times as the minimal one. Interestingly, when further increased the milling time from 28 to 38 h, (k - k0)/k0 increases from the valley value of 10.4 to 12.8%. Though the increment is not pronounced, it illustrates a difference in tendency from that in the milling time range from 10 to 28 h. Temperature-dependent thermal conductivity enhancement data further indicate that, at all the measured temperatures, nanofluid with CNTs milled for 10 h has the largest increment in thermal conductivity. Glory et al.  reported that the enhancement of the thermal conductivity noticeably increases when the nanotube aspect ratio increases. However, the thermal conductivity enhancement behavior of our CNT nanofluid is very different and cannot be explained only by the effect of the aspect ratio.
Figure 6. Dependence of the thermal conductivity enhancement on the ball milling time of CNTs suspended in the nanofluids .
The above results suggest other dominant factors that have the influence over the thermal conductivity of the CNT nanofluids. The authors proposed that the nonstraightness and the aggregation would play significantly roles. As is known, the walls of CNTs have similar structure of graphene sheet, and the thermal conductivity of CNTs shows greatly anisotropic behavior. Heat transports substantially quicker through axial direction than through radial direction . For a nonstraight CNT, the high thermal anisotropy of CNTs induces a unique property that individual CNTs are nearly perfect one-dimensional thermal passages with negligibly small heat flux losses during long distance heat conductions . For a nonstraight CNT with length L under a two-end temperature difference, the heat flux q goes through a curled passage. This CNT can be regarded as an equivalent straight thermal passage with a distance of Le. The same heat flux q is conducted between the two ends of this straight passage. Obviously, the equivalent length Le depends on the curvature of the actual nanotube in the nanofluid. A concept, straightness ratio η (η = Le/L), can be adopted to describe the straightness of a curled CNT. The lowest straightness ratio arises when a suspended nanotube forms ring closure .
When subjected to ball milling, CNTs were broken and cut short with appropriate average length. The straightness ratio was significantly increased and heat transports more effectively through the CNTs and across the interfaces between the CNT tips and the base fluid, resulting in the highest thermal conductivity enhancement in a nanofluid containing CNTs milled for 10 h. For nanofluids containing relatively straight nanotubes, the influence of the aspect ratio will surpass that of straightness ratio. Therefore, by further treatment on nanotubes with relatively high straightness ratio, the excessive deterioration of the aspect ratio would decrease the thermal conductivity of nanofluids, causing (k - k0)/k0 decrease from 10 to 28 h. Recent theoretical analysis has revealed that the aggregation of nanoparticle plays a significant role in deciding (k - k0)/k0 . Percolation effects in the aggregates, as highly conducting nanotubes touch each other in the aggregate, help in increasing the thermal conductivity. Our experiments demonstrate that aggregates are the dominant appearance of CNTs when the ball-milling time is increased to 38 h. The aggregation accounts for the increment of thermal conductivity enhancement when the ball-milling time is increased from 28 to 38 h. This result implies that the positive influence of the aggregation surpasses the negative influence of the aspect ratio deterioration.
For some nanofluids, the pH values of the suspensions have direct effects on the thermal conductivity enhancement. Figure 7 presents the thermal conductivity enhancement ratios at different pH values [7,40]. The results show that the enhanced thermal conductivity increases with an increase in the difference between the pH value of aqueous suspension and the isoelectric point of Al2O3 particle . When the NPs are dispersed into a base fluid, the overall behavior of the particle-fluid interaction depends on the properties of the particle surface. For Al2O3 particles, the isoelectric point (pHiep) is determined to be 9.2, i.e., the repulsive forces among Al2O3 particles is zero, and Al2O3 particles will coagulate together under this pH value. Therefore, when pH value is equal or close to 9.2, Al2O3 particle suspension is unstable according to DLVO theory . The hydration forces among particles increase with the increasing difference of the pH value of a suspension from the pHiep, which results in the enhanced mobility of NPs in the suspension. The microscopic motions of the particles cause micro-convection that enhances the heat transport process. Wensel’s study showed that the thermal conductivity of nanofluids containing oxide NPs and CNTs with very low percentage loading decreased when the pH value is shifted from 7 to 11.45 under the influence of a strong outside magnetic field .
Figure 7. Thermal conductivity enhancement ratios at different pH values: Al2O3-DW ; DNP-EG .
For DNP-EG nanofluids, it is observed from Figure 7 that the thermal conductivity enhancement increases with pH values in the range of 7.0-8.0. When pH value is above 8.0, there is no obvious relationship between pH value and the thermal conductivity enhancement. In our opinion, the influence of pH value on thermal conductivity is that pH value has a direct effect on the stability of nanofluids. When pH value is below 8.5, the suspension is not very stable, and DNPs are easy to form aggregations. The alkalinity of the solution is helpful to the dispersion and the stability of the nanofluids. In order to verify the above statement, the influence of settlement time on the thermal conductivity enhancement was further investigated. It is found that the thermal conductivity enhancement decreases with elapsed time for DNP-EG nanofluid when pH is 7.0. However, for the stable DNP-EG nanofluids with pH of 8.5, there is no obvious thermal conductivity decrease for 6 months .
Surfactant addition is an effective way to enhance the stability of nanofluids. Kim’s study revealed that the thermal conductivity decreased rapidly for the instable nanofluids without surfactants after preparation. However, no obvious changes in the thermal conductivity of the nanofluids with sodium dodecyl sulfate (SDS) as surfactant were observed even after 5-h settlement . Assael et al. investigated the thermal conductivities of the aqueous suspension of CNTs. When Sodium dodecyl sulfate (SDS) was employed as the dispersant, the maximum thermal conductivity enhancement obtained was 38.0% for a nanofluid with 0.6 vol% CNT loadings . When the surfactant is substituted with hexadecyltrimethyl ammonium bromide (CTAB), the maximum thermal conductivity enhancement obtained was 34.0% for same fraction of CNT loading . Liu et al. reported that the thermal conductivity of carbon nanotube-synthetic engine oil suspensions is higher compared with that of same suspensions without the addition of surfactant. The presence of surfactant as stabilizer has positive effect on the carbon nanotube-synthetic engine oil suspensions.
We used cationic gemini surfactants (12-3(4,6)-12,2Br-1) to stabilize water-based MWNT nanofluids. These surfactants were prepared following the process described in . Figure 8presents the thermal conductivity enhancement ratios of the CNT-contained nanofluids with different surfactant concentrations. The volume fraction of the dispersed CNTs is 0.1%. The critical micelle concentration of 12-3-12, 2Br-1 is reported as 9.6 ± 0.3 × 10-4 mol/l . Ten times critical micelle concentration of 12-3-12, 2Br-1 is 0.6 wt%. Solutions of 12-3-12, 2Br-1 with different concentrations (0.6, 1.8, and 3.6 wt% at room temperature) were selected to prepare CNT nanofluids. It is observed that at all the measured temperatures the thermal conductivity enhancement decreases with the surfactant addition. The surfactant added in the nanofluids acts as stabilizer which improves the stability of the CNT nanofluids. However, excess surfactant addition might hinder the improvement of the thermal conductivity enhancement of the nanofluids.
Figure 8. Thermal conductivity enhancement ratios with different surfactant concentrations.
The effect of the structures of cationic gemini surfactant molecules on the thermal conductivity enhancement is shown in Figure 9. The fractions of the dispersed CNTs and the cationic gemini surfactants is 0.1 vol% and 0.6 wt%, respectively. The spacer chain length of the cationic gemini surfactant increase from 3 methylenes to 6 methylenes. It is seen that the thermal conductivity enhancement ratio increases with the decrease of spacer chain length of cationic gemini surfactant. Zeta potential analysis indicates that the CNT nanofluids stabilized by gemini surfactant with short spacer chain length have better stabilities. Increase of spacer chain length of surfactant might give rise to sediments of CNTs in the nanofluids, resulting in the decrease of thermal conductivity enhancement of the nanofluids.
Figure 9. Effect of surfactant structures on the thermal conductivity enhancement ratio.
Nanofluids have great potential for heat transfer enhancement and are highly suited to application in practical heat transfer processes. This provides promising ways for engineers to develop highly compact and effective heat transfer equipments. More and more researchers have paid their attention to this exciting field. When addressing the thermal conductivity of nanofluids, it is foremost important to guarantee the accuracy in the measurement of the thermal conductivity of nanofluids. Two aspects should be considered. The first one is to prepare homogeneous and long-term stable nanofluids. The second one is to keep the initial equilibrium before measuring the thermal conductivity. In general, the thermal conductivity enhancement increases monotonously with the particle loading. The effect of temperature on the thermal conductivity enhancement ratio is somewhat different for different nanofluids. It is very important to note that the temperatures of the base fluid and the nanofluid should be the same while comparing the thermal conductivities between them. With an increase in the thermal conductivity of the base fluid, the thermal conductivity enhancement ratio decreases. Considering the effect of the size of the inclusion, there exists an optimal value for alumina nanofluids, while for the CNT nanofluid, the thermal conductivity increases with a decrease of the average diameter of the included CNTs. The thermal characteristics of nanofluids might be manipulated by means of controlling the morphology of the inclusions, which also provide a promising way to conduct investigation on the mechanism of heat transfer in nanofluids. The additives like acid, base, or surfactant play considerable roles on the thermal conductivity enhancement of nanofluids.
CNTs: carbon nanotubes; DNPs: diamond NPs; DW: deionized water; DWNTs: double-walled CNTs; EG: ethylene glycol; KOH: potassium hydroxide; LP: liquid paraffin; MWNTs: multi-walled CNTs; NPs: nanoparticles; PVP: poly(vinylpyrrolidone); SDS: sodium dodecyl sulfate; SHW: short hot wire; SSA: specific surface area; SWNTs: single-walled CNTs; THW: transient hot wire; TCNTs: treated CNTs.
The authors declare that they have no competing interests.
HQ supervised and participated all the studies. He wrote this paper. WY carried out the studies on the nanofluids containing copper nanoparticles, graphene, diamond nanoparticles, and several kinds of oxide nanoparticles. YL carried out the studies on the nanofluids containing other oxide nanoparticles. LF carried out the studies on the nanofluids containing carbon nanotubes.
This study was supported by the National Science Foundation of China (50876058), Program for New Century Excellent Talents in University (NCET-10-883), and the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning.
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Huaqing Xie*, Wei Yu, Yang Li and Lifei Chen
School of Urban Development and Environmental Engineering, Shanghai Second Polytechnic University, Shanghai 201209, China
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Nanoscale Research Letters 2011, 6:124 doi:10.1186/1556-276X-6-124
The electronic version of this article is the complete one and can be found online at:http://www.nanoscalereslett.com/content/6/1/124
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TweetAbstract Access to safe drinking water is important as a health and development issue at national, regional, and local levels. About one billion people do not have healthy drinking water. More than six million people (about two million children) die because of diarrhea which is caused by polluted water. Developing countries pay a high cost […]
Access to safe drinking water is important as a health and development issue at national, regional, and local levels. About one billion people do not have healthy drinking water. More than six million people (about two million children) die because of diarrhea which is caused by polluted water. Developing countries pay a high cost to import chemicals including polyaluminium chloride and alum. This is the reason why these countries need low-cost methods requiring low maintenance and skill. The use of synthetic coagulants is not regarded as suitable due to health and economic considerations. The present study was aimed to investigate the effects of alum as coagulant in conjunction with bean, sago, and chitin as coagulants on the removal of color, turbidity, hardness, and Escherichia coli from water. A conventional jar test apparatus was employed for the tests. The study was taken up in three stages, initially with synthetic waters, followed by testing of the efficiency of coagulants individually on surface waters and, lastly, testing of blended coagulants. The experiment was conducted at three different pH conditions of 6, 7, and 8. The dosages chosen were 0.5, 1, 1.5, and 2 mg/l. The results showed that turbidity decrease provided also a primary E. coli reduction. Hardness removal efficiency was observed to be 93% at pH 7 with 1-mg/l concentration by alum, whereas chitin was stable at all the pH ranges showing the highest removal at 1 and 1.5mg/l with pH 7. In conclusion, using natural coagulants results in considerable savings in chemicals and sludge handling cost may be achieved.
Alum; Chitin; Sago; Bean; Coagulation; Turbidity
The explosive growth of the world’s human population and subsequent water and energy demands have led to an expansion of standing surface water . Nowadays, the concern about contamination of aquatic environments has increased, especially when water is used for human consumption. About one billion people do not have healthy drinking water. More than six million people (about two million children) die because of diarrhea which is caused by polluted water[2,3].
In most of the cases, surface water turbidity is caused by the clay particles, and the color is due to the decayed natural organic matter. Generally, the particles that determine the turbidity are not separated by settling or through traditional filtration. Colloidal suspension stability in surface water is also due to the electric charge of particle surface. Thus, there is great importance in either the development of more sophisticated treatments or the improvement of the current ones .
The production of potable water from most raw water sources usually entails the use of a coagulation flocculation stage to remove turbidity in the form of suspended and colloidal material. This process plays a major role in surface water treatment by reducing turbidity, bacteria, algae, color, organic compounds, and clay particles. The presence of suspended particles would clog filters or impair disinfection process, thereby dramatically minimizing the risk of waterborne diseases [5,6].
Many coagulants are widely used in conventional water treatment processes, based on their chemical characteristics. These coagulants are classified into inorganic, synthetic organic polymers, and natural coagulants . Alum has been the most widely used coagulant because of its proven performance, cost effectiveness, relatively easy handling, and availability. Recently, much attention has been drawn on the extensive use of alum. Aluminum is regarded as an important poisoning factor in dialysis encephalopathy. Aluminum is one of the factors which might contribute to Alzheimer’s disease [7-9]. Alum reaction with water alkalinity reduces water pH and its efficiency in cold water [10,11]. However, some synthetic organic polymers such as acrylamide have neurotoxicity and strong carcinogenic effect [8,12].
In addition, the use of alum salts is inappropriate in some developing countries because of the high costs of imported chemicals and low availability of chemical coagulants . This is the reason why these countries need low-cost methods requiring low maintenance and skill.
For these reasons, and also due to other advantages of natural coagulants/flocculants over chemicals, some countries such as Japan, China, India, and the United States have adopted the use of natural polymers in the treatment of surface water for the production of drinking water . A number of studies have pointed out that the introduction of natural coagulants as a substitute for metal salts may ease the problems associated with chemical coagulants.
Natural macromolecular coagulants are promising and have attracted the attention of many researchers because of their abundant source, low price, multi-purposeness, and biodegradation[11,14,15]. Okra, rice, and chitosan are natural compounds which have been used in turbidity removal [16-18]. The extract of the seeds has been mentioned for drastically reducing the amount of sludge and bacteria in sewage .
In view of the above discussion, the present work has been taken up to evaluate the efficiency of various natural coagulants on the physico-chemical contaminant removal of water. To date, most of the research has been concentrated on the coagulant efficiencies in synthetic water, but in this study, we move ahead making an attempt to test the efficiency of the natural coagulants on surface water. The efficiencies of the coagulants as stated by  might alter depending on many factors: nature of organic matter, structure, dimension, functional groups, chemical species, and others.
Natural coagulants and their preparation
Sago is a product prepared from the milk of tapioca root. Its botanical name is ‘Manihot esculentaCrantz syn. M. utilissima’. Hyacinth bean with botanical name Dolichos lablab is chosen as another coagulant. Both the coagulants were used in the form of powders (starches). Starch consists mainly of a homopolymer of α-D-glucopyranosyl units that comes in two molecular forms, linear and branched. The former is referred to as amylose and the latter as amylopectin . These have the general structure as per  (Figure 1) .
Figure 1. General structure of amylose and amylopectin.
The third coagulant was chitin ([C8H13O5N]n), which is a non-toxic, biodegradable polymer of high molecular weight. Like cellulose, chitin is a fiber, and in addition, it presents exceptional chemical and biological qualities that can be used in many industrial and medical applications. The two plant originated coagulants were taken in the form of powder or starch. Chitin was commercially procured.
The first stage included testing the efficiency of the four coagulants on the synthetic waters. Synthetic waters with turbidity of 70 and 100 nephelometric turbidity units (NTU) were prepared with fuller’s earth in the laboratory and were used in this part of the study. The experiment was carried out using a jar test apparatus. The experiments were conducted in duplicates to eliminate any kind of error. Efficiency was evaluated by determination of reduction in turbidity of both the synthetic samples.
In the second stage of the experiment, the individual coagulants were evaluated for their efficiency on the surface waters. The water samples for this stage and the preceding stage were collected from the surface reservoir, Mudasarlova, located at a distance of 5 km from the Environmental Monitoring Laboratory, GITAM University, where the experiments were carried out. This is the reservoir which serves as a source of domestic water for the nearby residents.
Care was taken while collecting the samples so that a representative sample is obtained. All samples were collected in sterile plastic containers. The samples were transported to the laboratory, and all the experiments were conducted within a duration of 24 h. The physical parameters like temperature and color were noted at the point of sample collection. The water samples were analyzed for the following parameters pre- and post-treatment with the coagulants (Table 1).
Table 1. Physico-chemical parameters tested (stage II)
The coagulants were tested at various concentrations like 0.5, 1, 1.5, and 2 mg/l at three pH ranges of 6, 7, and 8.
The results obtained from the second stage of the study have encouraged us to further extend the study in terms of blended coagulants. The blending of coagulants was taken up from the fact that alum was the most widely used coagulant, and hence, it was taken as one part. The remaining combinations were 2, 3, 4, and 5 parts of the natural coagulants, i.e., 1:2, 1:3, 1:4, and 1:5.
Testing of the following parameters was adopted for evaluating the efficiency of the blended coagulants (pre- and post-coagulation) (Table 2). All the analysis has been performed as per the standard methods given by APHA, 2005 .
Table 2. Physico-chemical parameters tested (stage III)
E. coli presence
The E. coli bacterial presence and absence were determined in the pre- and post-coagulated water using H2S strip bottle. The water sample was filled into the bottle and allowed to stand for 24 h at room temperature. After 24 h, the water sample was observed for color change; black color change indicates the presence of E. coli.
Coagulant actions onto colloidal particles take place through charge neutralization of negatively charged particles. If charge neutralization is the predominant mechanism, a stochiometric relation can be established between the particles’ concentration and coagulant optimal dose.
In the initial stage of the experiment, the coagulants were tested against synthetic turbid samples with 70 and 100 NTU. According to Figure 2a,b, the optimum dosage of alum was observed to be 1mg/l for both the turbid samples, and the optimum pH is observed to be 7.
Figure 2. Turbidity removal efficiency of alum with initial turbidities of (a) 100 and (b) 70 NTU.
It is understood from Figure 3a,b that the optimum dosage for chitin as coagulant is 1.5 mg/l (turbidity to 40 NTU) for 100 NTU, whereas not much difference was observed between pH 7 and 8 for both the turbid samples. The optimum pH is observed to be 7 for both 70 and 100 NTU samples.
Figure 3. Turbidity removal efficiency of chitin with initial turbidities of (a) 100 and (b) 70 NTU.
Figure 4a,b exemplifies the trends of sago on the turbidity removal of the synthetic solutions. It is observed that sago was effective at both 1 and 1.5 mg/l (turbidity reduced to 50 and 45 NTU, respectively) for 100 NTU solution, and the efficiency was stable at pH 7 and 8.
Figure 4. Turbidity removal efficiency of sago with initial turbidities of (a) 100 and (b) 70 NTU.
Figure 5a,b illustrates the effect of bean on the synthetic turbid samples and turbidity removal. It is observed that bean was effective at 1mg/l (turbidity reduced to 55 NTU) for 100 NTU solution, and the efficiency was stable at pH 7 and 8.
Figure 5. Turbidity removal efficiency of bean with initial turbidities of (a) 100 and (b) 70 NTU.
Implications from the stage 1 experiment articulate that the coagulants are quite stable at the pH ranges tested; hence, in the proceeding experiments, all the three pH ranges were considered. In the second stage of experiment, the environmental samples from the surface water source were collected and tested for the removal of turbidity and other chemical parameters. The dosages were the same as the previous stage. The results are graphically represented as shown in Figures 6, 7,8, 9.
Figure 6. Turbidity removal efficiency of individual coagulants.
Figure 7. Total hardness removal efficiency of individual coagulants.
Figure 8. Calcium hardness removal efficiency of individual coagulants.
Figure 9. Chloride removal efficiency of coagulants.
The turbidity removal efficiencies of the individual coagulants are depicted in Figure 6 wherein there was a broad variation among the pH ranges. The maximum reduction was observed with 1 mg/l (87%) of bean at pH 6 followed by 1 mg/l (82%) sago at the same pH. At pH 7, the maximum efficiency was shown by bean with 1.5 mg/l dosage (85.37%) followed by bean and sago with 1 (82.49%) and 1.5 mg/l (82.49%), respectively. Removal efficiencies of 41.46% and 36.59% were reported by 1 mg/l of bean and sago, respectively, at pH 8. The minimum reductions are not reported as there was a negative competence of the coagulants at different doses and pH variations. It can be observed from the graph that there was an increase in the turbidity of the water at these dosages like with 2 g of chitin the turbidity removal was −19.51. In the entire study, the best results were obtained with total hardness removal wherein no negative competence was reported as shown in Figure 7. The utmost removal was observed with 0.5-mg/l (97.67%) sago at pH 7. At pH 6, it was (90.70%) with 1.5 mg/l of bean. At pH 8, the reduction was (93.02%) with 0.5 mg/l of alum. Apart from these, the general observation was that all the coagulants were effective in an average removal of 65% total hardness at all pH variations and doses. The tracking for the least efficiency has showed chitin at pH 6 with 2-mg/l dose (34.88%).
The calcium hardness removal efficiencies are directly proportional with the total hardness removal; the highest removal was recorded by chitin (93.33%) at pH 7 with 1.5-mg/l dose as shown in Figure 8. Removal of 90% is at pH 8 and 7 with 0.5-mg/l alum and 1-mg/l chitin, respectively. Minimum effectiveness was observed by chitin (6.67%) at pH 6 with 2-mg/l dose. On an average, the removal competence was more than 60% with all coagulants at doses at all the pH conditions.
Figure 8 illustrates the chloride removal efficiency of the coagulants tested. The average competence was observed to be 40%. The maximum competence was noted at pH 7 by chitin (83.64%) at 1.5 mg/l followed by sago (81.82%) at 1 mg/l. Indeed at pH 7, the removal was observed to be superior as a whole. Similarly, pH has shown inferior effectiveness in the amputation of chloride. The remarkable point that was noted is that at pH 8, where the removal was superior, the increase in doses of sago and bean (1.5 and 2 mg/l) has shown a depressing outcome.
With the results obtained from the second stage experimentation, the study was carried forward for the evaluation of blended coagulants. From the literature, it was understood that blended coagulants show improved competence than that of the individual ones.
The regular test of turbidity was substituted with conductivity to establish a relation and test the difference with these parameters. The conductivity diminution was observed to be preeminent at the ratio of 1:2 of all the blended coagulants 26.12%, 26.00%, and 21.35% with alum/bean, alum/chitin, and alum/sago, respectively. The highest reduction was observed with alum/sago at pH 8 with 1:2 ratio (32.28%) (Figure 10).
Figure 10. Conductivity removal efficiency of blended coagulants.
The total hardness reduction trend of the blended coagulants was recorded as follows: at pH 7, all combinations of alum/bean have resulted in negative competence. Amputation of 100% was observed with alum/chitin and alum/sago at 1:2 and 1:4 and 1:5 doses, respectively (Figure 11). The overall competence of the alum/chitin and alum/sago were registered to be more than 80%. The calcium hardness efficiencies of the blended coagulants were similar to that of the total hardness. The highest removal efficiency was shown by alum/chitin with 1:5 ratio at pH 7 (Figure 12).
Figure 11. Total hardness removal efficiency of blended coagulants.
Figure 12. Calcium hardness removal efficiency of blended coagulants.
As said earlier, the turbidity was replaced by color determination taking into account the fact that turbidity is directly related to the color. pH 7 has been remarkably effective in the highest removal of color from the water. The blended coagulant alum/sago was found to be very effective with 98% to 100% reduction in color at all the ratios of dosage (Figure 13). The blended coagulants alum/chitin and alum/sago were relatively successful at an average rate of 80% decline in the color at almost all ratios of dosage at pH 7 and 8.
Figure 13. Color removal efficiency of blended coagulants.
Alum/sago blend has a noteworthy effect on the removal of chloride from the water samples in which no negative result was noted. The highest reduction was observed with alum/chitin with dose of 1:5 (85.71%) at pH 7. Indeed, pH 7 can be optimized as perfect pH for this blend as all the ratios of dosages were quite efficient in the removal of chloride (Figure 14).
Figure 14. Chloride removal efficiency of blended coagulants.
Although many studies have used synthetic water in the experiments, this work chose to use raw water collected directly from the surface source. Therefore, it is important to consider that the natural compounds may cause variations in their composition, which interfere in the treatment process. All those factors are taken into account when evaluating the obtained results.
The characteristics of the superficial water used in this study are observed as that the water used has apparent color, turbidity, solids, and amount of compounds with a relatively high absorption in UV (254 nm). It is noticeable that the water has high turbidity and color.
The effectiveness of alum, commonly used as a coagulant, is severely affected by low or high pH. In optimum conditions, the white flocs were large and rigid and settled well in less than 10 min. This finding is in agreement with other studies at optimum pH [24,25]. The optimum pH was 7 and was similar to the obtained results by Divakaran . At high turbidity, a significant improvement in residual water turbidity was observed. The supernatant was clear after about 20-min settling. Flocs were larger and settling time was lower. The results showed that above optimum dosage, the suspensions showed a tendency to restabilize.
The effectiveness of the chitin in the present study in the removal of various contaminants with varied pH individually and also in blended form can be traced to the explanation from the literature that chitin has been studied as biosorbent to a lesser extent than chitosan; however, the natural greater resistance of the former compared to the last, due to its greater crystallinity, could mean a great advantage. Besides, the possibility to control the degree of acetylation of chitin permits to enhance its adsorption potential by increasing its primary amine group density. Recent studies regarding the production of chitin-based biocomposites and its application as fluoride biosorbents have demonstrated the potential of these materials to be used in continuous adsorption processes. Moreover, these biocomposites could remove many different contaminants, including cations, organic compounds, and anions .
Chitosan has high affinity with the residual oil and excellent properties such as biodegradability, hydrophilicity, biocompability, adsorption property, flocculating ability, polyelectrolisity, antibacterial property, and its capacity of regeneration in many applications . It has been used as non-toxic floccules in the treatment of organically polluted wastewater .
The effects of coagulation process on hardness are observed for varying levels of hardness, which resulted in significant decrease of hardness removal. The study correlates with the results obtained by , wherein they had a maximum hardness removal of 84.3% by chitosan in low turbid water with initial hardness of about 204 mg/l as CaCO3.
Several experiments were carried out to determine the comparative performance of chitosan on E. coli in different turbidities. E. coli negative is present in the chitin-treated waters in all of the turbidities. The conclusive evidence was found for the negative influence of chitosan on E. coli. The regrowth of E. coli was not observed in the experiments after 24 h, which was similar to the observations by .
As far as sago is considered, the starch was effective both individually and as blended coagulant. Unlike polyaluminium chloride, the efficiency of the natural coagulants is not affected by pH. The pH increased their efficiency, which is one of the advantages of natural coagulants. The principle behind the efficiency of the sago from the literature can be stated as follows: Sago starch is a natural polymer that is categorized as polyelectrolyte and can act as coagulant aid. Coagulant aid can be classified according to the ionization traits, which are the anions, cations, and amphoteric (with dual charges). Bratskaya et al.  mentioned that among the three groups, cation polymer is normally used to remove adsorbed negatively charged particles by attracting the adsorbed particles through electrostatic force. They discovered that anion polymer and those non-ionized cannot be used to coagulate negatively charged particles.
The chemical oxygen demand (COD) reduction is influenced by the concentration of sago used; the lower the concentration the better the removal of the COD. Using less than 1.50 g L-1, better COD reduction is observed. At this low concentration, settling time did not influence the COD reduction. Similarly, concentration of sago used at lower than 1.50 g L-1 reduced the turbidity in less than 15 min of settling time. Sago concentration higher than 1.50 g L-1 increased the turbidity; however, settling time has an influence on the turbidity reduction at higher sago concentrations. This pattern is congruent with the COD removal .
The sago starch-graft-polyacrylamide (SS-g-PAm) coagulants were found to achieve water turbidity removal up to 96.6%. The results of this study suggest that SS-g-PAm copolymer is a potential coagulant for reducing turbidity during water treatment .
At its optimum concentration, D. lablab seed powder does not affect the pH of the water. Total and calcium hardness remained almost constant and were within acceptable levels according to World Health Organization standards for drinking water. Moreover, coagulation of medium to high turbidity water with D. lablab seed powder with the finest grain size reduced turbidity further. The best performance of the finest seed powder could be due to its large total surface area, whereby most of the water-soluble proteins are at the solid–liquid interface during the extraction process as stated by Gassenschmidtet al. . This might have increased the concentration of active coagulation polymer in the extract, which improved the coagulation process. The coagulant extract from seeds has shown antimicrobial activity in the comparative culture test, which was also observed in the study of Tandonet al. .
D. lablab demonstrated the best performance with turbid water, in which a turbidity removal efficiency of 87% was observed. The restabilization of destabilized colloidal particles, which was associated with higher residual turbidities, occurred at dosages above the optimum. It is commonly observed that particles are destabilized by small amounts of hydrolyzing metal salts and that optimum destabilization corresponds with neutralization of the particles’ charge. Larger amounts of coagulants cause charge reversal so that the particles become positively charged and, thus, restabilization occurs, which results in elevated turbidity levels . It has also been observed that the reduction in turbidity is associated with significant improvements in bacteriological quality. The effect of natural coagulants on turbidity removal and the antimicrobial properties against microorganisms may render them applicable for simultaneous coagulation and disinfection of water for rural and peri-urban people in developing countries .
It is observed that blended coagulants gave utmost efficiency as compared to the traditional alum coagulants. Here in this blending process, we reduce the alum dose up to 80%; thus, we reduce the drawbacks of the alum. Also, we can reduce the cost of the treatment using the natural coagulants instead of the traditional coagulant.
E. coli is the best coliform indicator of fecal contamination from human and animal wastes. E. colipresence is more representative of fecal pollution because it is present in higher numbers in fecal material and generally not elsewhere in the environment . Results showed the absence of E. coli increases with increasing time. A greater percentage of E. coli was eliminated in higher turbidities. The aggregation and, thus, removal of E. coli was directly proportional to the concentration of particles in the suspension. Chitosan and other natural coagulants showed antibacterial effects of 2 to 4 log reductions.
Antimicrobial effects of water-insoluble chitin and coagulants were attributed to both its flocculation and bactericidal activities. A bridging mechanism has been reported for bacterial coagulation by chitosan . Especially with reference to chitosan, molecules can stack on the microbial cell surface, thereby forming an impervious layer around the cell that blocks the channels, which are crucial for living cells . On the other hand, cell reduction in microorganisms, such as E. coli, occurred without noticeable cell aggregation by chitosan.
This indicates that flocculation was not the only mechanism by which microbial reduction occurred. It was found that when samples were stored during 24 h, regrowth of E. coli was not observed for all turbidities. It should be noted that the test water contained no nutrient to support regrowth of E. coli, and chitosan is not a nutrient source for it. Another experiment was designed to check the effect of alum alone. Regrowth of E. coli was not observed for unaided alum after 24 h. The number of E. coli after resuspension of sediment reached to the initial numbers after 24 h and showed that it cannot be inactivated by alum. Such findings have been previously reported by Bina.
Access to clean and safe drinking water is difficult in rural areas of India. Water is generally available during the rainy season, but it is muddy and full of sediments. Because of a lack of purifying agents, communities drink water that is no doubt contaminated by sediment and human feces. Thus, the use of natural coagulants that are locally available in combination with solar radiation, which is abundant and inexhaustible, provides a solution to the need for clean and safe drinking water in the rural communities of India. Use of this technology can reduce poverty, decrease excess morbidity and mortality from waterborne diseases, and improve overall quality of life in rural areas.
The application of coagulation treatment using natural coagulants on surface water was examined in this study. The surface water was characterized by a high concentration of suspended particles with a high turbidity. At a varied range of pH, the suspended particles easily dissolved and settled along with the coagulants added. Research has been undertaken to evaluate the performance of natural starches of sago flour, bean powder, and chitin to act as coagulants individually and in blended form. In all three cases, the main variable was the dosage of the coagulant. The study shows that natural characteristics of starch and other coagulants can be an efficient coagulant for surface water but would need further study in modifying it to be efficient to the maximum. Thus, it can be concluded that the blended coagulants are the best which give maximum removal efficiency in minimum time.
It is chitin and chitosan which can readily be derivatized by utilizing the reactivity of the primary amino group and the primary and secondary hydroxyl groups to find applications in diversified areas. In this work, an attempt has been made to increase the understanding of the importance and effects of chitin at various doses and pH conditions, upon the chemical and biological properties of water. In view of this, this study will attract the attention of academicians and environmentalists.
This is an Open Access article distributed under the terms of the Creative Commons Attribution License ( http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
International Journal of Energy and Environmental Engineering 2012, 3:29 doi:10.1186/2251-6832-3-29
Department of Environmental Studies, GITAM Institute of Science, GITAM University, Visakhapatnam, Andhra Pradesh 530045, India
The electronic version of this article is the complete one and can be found online at:http://www.journal-ijeee.com/content/3/1/29
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© 2012 Vara; licensee BioMed Central Ltd.
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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.
2.1. 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/
admin 31 Jan, 2013
Tweet Anyone responsible for operating and maintaining a swimming pool or spa has to test, monitor, and control complex, interdependent chemical factors that affect the quality of water. Additionally, aquatic facilities operators must be familiar with all laws, regulations, and guidelines governing what these parameters should be. […]
Anyone responsible for operating and maintaining a swimming pool or spa has to test, monitor, and control complex, interdependent chemical factors that affect the quality of water. Additionally, aquatic facilities operators must be familiar with all laws, regulations, and guidelines governing what these parameters should be.
Why? Because the worst breeding ground for any kind of microorganism is a warm (enough) stagnant pool of water. People plus stagnant water equals morbid illness. That’s why pools have to be circulated, filtered, and sanitized – with any number of chemicals or methods, but most frequently with chlorine compounds. However, adding chemicals that kill the bad microorganisms can also make the water uncomfortable, and in some cases unsafe, for swimmers. Additionally, if all the chemical factors of the water are not controlled, the very structures and equipment that hold the water and keep it clean are ruined.
So the pool professional must perform a delicate balancing act with all the factors that affect both the health and comfort of bathers and the equipment and structures that support this. Both water balance – or mineral saturation control – and sanitizer levels must constantly be maintained. This is achieved by measuring pertinent water quality factors and adding chemicals or water to keep the factors within acceptable parameters.
Water is constantly changing. Anything and everything directly and indirectly affects the relationship of its chemical parameters to each other: sunlight, wind, rain, oil, dirt, cosmetics, other bodily wastes, and any chemicals you add to it. Balanced water not only keeps swimmers comfortable, but also protects the pool shell, plumbing, and all other related equipment from damage by etching or build-up and stains.
The pool professional is already well acquainted with pH, Total Alkalinity (TA), and Calcium Hardness (CH); along with Total Dissolved Solids (TDS) and Temperature, these are the factors that influence water balance. Water that is in balance is neither aggressive nor oversaturated. Aggressive water lacks sufficient calcium to saturate the water, so it is hungry for more. It will eat anything it comes into contact with to fill its need, including the walls of your pool or spa or the equipment it touches. Over-saturated water cannot hold any more minerals, so dissolved minerals come out of solution and form scale on pool and equipment surfaces.
The pH of pool water is critical to the effectiveness of the sanitizer as well as the water balance. pH is determined by the concentration of Hydrogen ions in a specific volume of water. It is measured on a scale of 0-14, 0-7 being acidic and 7-14 being basic.
You must maintain the pH of the water at a level that assures the sanitizer works effectively and at the same time protects the pool shell and equipment from corrosion or scaling and the bathers from discomfort or irritation. If the pH is too high, the water is out of balance, and the sanitizer’s ability to work decreases. More and more sanitizer is then needed to maintain the proper level to kill off germs. Additionally, pH profoundly affects what and how much chemical must be added to control the balance. A pH of between 7.2 – 7.6 is desirable in most cases.*
As one of the most important pool water balance and sanitation factors, pH should be checked hourly in most commercial pools.* Even if you have an automatic chemical monitor/controller on your system, you need to double- check its readings with an independent pH test. With salt- water pools, pH level goes up fast, so you need to check it more often. Tests are available that require reagents and subjective evaluation of color depth and hue to judge their pH. But different users interpret these tests differently, and results can vary wildly. The PooLPRo and ULTRAPEN PT2 give instant lab-accurate, precise, easy-to-use, objective pH measurements, invaluable in correctly determining what and how much chemical to add to maintain water balance and effective sanitizer residuals.
Total Alkalinity (TA) is the sum of all the alkaline minerals in the water, primarily in bicarbonate form in swimming pools, but also as sodium, calcium, magnesium, and potassium carbonates and hydroxides, and affects pH directly through buffering. The greater the Total Alkalinity, the more stable the pH. In general, TA should be maintained at 80 – 120 parts per million (ppm) for concrete pools to keep the pH stable.* Maintaining a low TA not only causes pH bounce, but also corrosion and staining of pool walls and eye irritation. Maintaining a high TA causes overstabilization of the water, creating high acid demands, formation of bicarbonate scale, and may result in the formation of white carbonate particles (suspended solids), which clouds the water. Reducing TA requires huge amounts of effort. So the best solution to TA problems is prevention through close monitoring and controlling. The PoolPro PS9 Titration Kit features an in-cell conductometric titration for determining alkalinity.
Calcium Hardness (CH) is the other water balance parameter pool professionals are most familiar with. CH represents the calcium content of the water and is measured in parts per million. Low CH combined with a low pH and low TA significantly increases corrosivity of water. Under these conditions, the solubility of calcium carbonate also increases. Because calcium carbonate is a major component of both plaster and marcite, these types of pool finishes will deteriorate quickly. Low CH also leads to corrosion of metal components in the pool plant, particularly in heat exchangers. Calcium carbonate usually provides a protective film on the surface of copper heat exchangers and heat sinks, but does not adversely affect the heating process. Without this protective layer, heat exchangers and associated parts can be destroyed prematurely. At the other extreme, high CH can lead to the precipitation of calcium carbonate from solution, resulting in cloudy water, the staining of structures and scaling of equipment. The recommended range for most pools is 200 – 400 ppm.* Calcium hardness should be tested at least monthly. The PoolPro PS9 Titration Kit features an in-cell conductometric titration for determining hardness.
Total Dissolved Solids (TDS) is the sum of all solids dissolved in water. If all the water in a swimming pool was allowed to evaporate, TDS would be what was left on the bottom of the pool – like the white deposits left in a boiling pot after all the water has evaporated. Some of this dissolved material includes hardness, alkalinity, cyanuric acid, chlorides, bromides, and algaecides. TDS also includes bather wastes, such as perspiration, urine, and others. TDS is often confused with Total Suspended Solids (TSS). But TDS has no bearing on the turbidity, or cloudiness, of the water, as all the solids are truly in solution. It is TSS, or undissolved, suspended solids, present in or that precipitate out of the water that make the water cloudy.
High TDS levels do affect chlorine efficiency, algae growth, and aggressive water, but only minimally. TDS levels have the greatest bearing on bather comfort and water taste – a critical concern for commercial pool operators. At levels of over 5,000 ppm, people can taste it. At over 10,000 ppm bather towels are scratchy and mineral salts accumulate around the pool and equipment. Still some seawater pools comfortably operate with TDS levels of 32,000 ppm or more.
As methods of sanitization have changed, high TDS levels have become more and more of a problem. The best course of action is to monitor and control TDS by measuring levels and periodically draining and replacing some of your mature water with new, lower TDS tap water. This is a better option than waiting until you must drain and refill your pool, which is not allowed in some areas where water conservation is required by law. However, you can also decrease TDS with desalinization equipment as long as you compensate with Calcium Hardness. (Do not adjust water balance by moving pH beyond 7.8.)*
Regardless, you do need to measure and compensate for TDS to get the most precise saturation index and adjust your pH and Calcium Hardness levels accordingly. It is generally recommended that you adjust for TDS levels by subtracting one tenth of a saturation index unit (.1) for every 1,000 ppm TDS over 1,000 to keep your water properly balanced. When TDS levels exceed 5,000 ppm, it is recommended that you subtract half of a tenth, or one twentieth of unit (.05) per 1,000 ppm.* And as the TDS approaches that of seawater, the effect is negligible.
Hot tubs and spas have a more significant problem with TDS levels than pools. Because the bather load is relatively higher, more chemicals are added for superchlorination and sudsing along with a higher concentration of bather wastes. The increased electrical conductance that high TDS water promotes can also result in electrolysis or galvanic corrosion. Every hot water pool operator should consider a TDS analyzer as a standard piece of equipment.
A TDS analyzer is required to balance the water of any pool or spa in the most precise way. PoolPro, PoolMeter and ULTRAPEN PT1 instantly display accurate TDS levels giving you the information you need to take corrective action before TDS gets out of hand.
Temperature is the last and least significant factor in maintaining water balance. As temperature increases, the water balance tends to become more basic and scale- producing. Calcium carbonate becomes less soluble, causing it to precipitate out of solution. As temperature drops, water becomes more corrosive.
In addition to helping determine water balance, temperature also affects bather comfort, evaporation, chlorination, and algae growth (warmer temperatures encourage growth). Myron L’s PooLPRo also precisely measures temperature to one tenth of a degree at the same time any other parameter is measured.
In the pool and spa industry water balance is calculated using the Langelier Saturation Index (LSI) formula:
SI = (pH + TF + CF + AF ) – 12.1
PH = pH value
TF = 0.0117 x Temperature value – 0.4116 CF = 0.4341 x ln(Hardness value) – 0.3926 AF = 0.4341 x ln(Alkalinity value) – 0.0074
The following is a general industry guideline for interpreting LSI values:
• An index between -0.5 and +0.5 is acceptable pool water.
- An index of more than +0.5 is scale-forming.
- An index below -0.5 is corrosive.
pH, Total Alkalinity, and Calcium Hardness are the largest contributors to water balance. Pool water will often be balanced if these factors are kept within the recommended ranges.
The PoolPro PS9 Titration Kit features an LSI function that steps you through alkalinity & hardness titrations and pH & temperature measurements to quickly and accurately determine LSI. An LSI calculator allows you to manipulate pH, alkalinity, hardness and temperature values in the equation to determine water balance adjustments on the spot.
The most immediate concern of anyone monitoring and maintaining a pool is the effectiveness of the sanitizer – the germ-killer. There are many types of sanitizers, the most common being chlorine in swimming pools and bromine in hot tubs and spas. The effectiveness of the sanitizer is directly related to the pH and, to a lesser degree, the other factors influencing water balance.
To have true chemical control, you need to monitor both the sanitizer residual and the pH and use that information to chemically treat the water. To check chlorine residual, free chlorine measurements are made. For automatic chlorine dosing systems, ORP must also be monitored to ensure proper functioning.
Free Chlorine is the amount of chlorine available as hypochlorous acid (HOCl-) and hypochlorite ion (OCl-), the concentrations of which are directly dependent on pH and temperature. pH is maintained at the level of greatest concentration of HOCl- because hypochlorous acid is a much more powerful sanitizer than hypochlorite ion. Free chlorine testing is usually required before and after opening of commercial pools. Samples should be taken at various locations to ensure even distribution. Residual levels are generally kept between 1-2 mg/L or ppm.* PooLPRo V.4.03 and later features the ability to measure ppm free chlorine in pools and spas sanitized by chlorine only. With this feature PoolPro can measure a dynamic range of chlorine concentrations wider than that of a colorimetric test kit with a greater degree of accuracy.
ORP stands for Oxidation Reduction Potential (or REDOX ) of the water and is measured in millivolts (mV). The higher the ORP, the greater the killing power of all sanitizers, not just free chlorine, in the water. ORP is the only practical method available to monitor sanitizer effectiveness. Thus, every true system of automatic chemical control depends on ORP to work.
The required ORP for disinfection will vary slightly between disinfecting systems and is also dependent on the basic water supply potential, which must be assessed and taken into account when the control system is initialized. 650 mV to 700 – 750 mV is generally considered ideal.*
Electronic controllers can be inaccurate and inconsistent when confronted with certain unique water qualities, so it is critical to perform manual testing with separate instrumentation. For automatic control dosing, it is generally recommended that you manually test pH and ORP prior to opening and then once during the day to confirm automatic readings.*
Samples for confirming automatic control dosing should be taken from a sample tap strategically located on the return line as close as possible to the probes in accordance with the manufacturer’s instructions. If manual and automatic readings consistently move further apart or closer together, you should investigate the reason for the difference.*
ORP readings can only be obtained with an electronic instrument. PoolPro provides the fastest, most precise, easy-to-use method of obtaining ORP readings to check the effectiveness of the sanitizer in any pool or spa. This is the best way to determine how safe your water is at any given moment.
A relatively new development, saltwater pools use regular salt, sodium chloride, to form chlorine with an electrical current much in the same way liquid bleach is made. As chlorine – the sanitizer – is made from the salt in the water, it is critical to maintain the salt concentration at the appropriate levels to produce an adequate level of sanitizer. It is even more important to test water parameters frequently in these types of pools and spas, as saltwater does not have the ability to respond adequately to shock loadings (superchlorination treatments).
Most saltwater chlorinators require a 2,500 – 3,000 ppm salt concentration in the water (though some may require as high as 5,000-7,000 ppm).* This can barely be tasted, but provides enough salt for the system to produce the chlorine needed to sanitize the water.
(It is important to have a good stabilizer level – 30 – 50 ppm* – in the pool, or the sunlight will burn up the chlorine. Without it, the saltwater system may not be able to keep up with the demand regardless of salt concentration.)
Taste and salt shortages are of little concern to seawater systems that maintain an average of 32,000 ppm. In these high-salt environments, you need to beware of corrosion to system components that can distort salt level and other parameter readings.
Additionally, incorrect salt concentration readings can occur in any saltwater system. The monitoring/controlling components can and do fail or become scaled— sometimes giving a false low salt reading. Thus, you must test manually for salt concentration with separate instrumentation before adding salt.
You must also test salt concentration manually with separate instrumentation to re-calibrate your system. This is critical to system functioning and production of required chlorine. Both the PoolPro and PT1 conveniently test for salt concentration at the press of a button as a check against automatic controller systems that may have disabled equipment or need to be re-calibrated.
Though no one instrument or method can be used to determine ALL of the factors that affect the comfort and sanitation of pool and spa water, PoolPro is a comprehensive water testing instrument that is reliable durable, easy-to-use and easy-to-maintain and calibrate. As a pool professional, a PoolPro will not only simplify your life, it will save you time and money.
RECORD KEEPING – WHAT TO DO WITH ALL THOSE MEASUREMENTS …
Data handling should be done objectively, and data recorded in a common format in the most accurate way. Also, data should be stored in more than one permanent location and made available for future analysis. Most municipalities require commercial aquatic facilities to keep permanent records on site and available for inspection at any time.
PoolPro makes it easy to comply with record keeping requirements. The PoolPro is an objective means to test free chlorine, ORP, pH, TDS, temperature and the mineral/salt content of any pool or spa. You just rinse and fill the cell cup by submerging the waterproof unit and press the button of the parameter you wish to measure. You immediately get a standard, numerical digital readout – no interpretation required – eliminating all subjectivity. And model PS9TK features the added ability to perform in-cell conductometric titrations for Alkalinity, Hardness and LSI on the spot. Up to 100 date-time-stamped readings can be stored in memory and then later transferred directly to a computer wirelessly using the bluDock™ accessory package. Simply pair the bluDock with your computer, then open the U2CI software application to download data. The user never touches the data, reducing the potential for human error in transcription. The data can then be imported into any program necessary for record-keeping and analysis. The bluDock is a quick and easy way to keep records that comply with governing standards.*
*Consult your governing bodies for specific testing, chemical concentrations, and all other guidelines and requirements. The ranges and methods suggested here are meant as general examples.
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