INVESTIGATION OF MAGNETIC CLAYS EFFECTIVENESS IN REMOVING POLYCYCLIC AROMATIC HYDROCARBONS FROM WATER SOLUTION IN COMPARISON TO A CHARCOAL STANDARD By Phillip

Thane ABSTRACT The process of creating and testing magnetic clay as a filter of polycyclic aromatic hydrocarbons using an imitator, procion red, and comparing the filtering agents effectiveness against charcoal using a spectrophotometer was investigated. The result being that charcoal is a significantly more effective filtering agent than clay. INTRODUCTION The long term goal of this experiment is to find a cheaper way to filter harmful polycyclic aromatic hydrocarbons from water on a large-scale suitable to city water treatment facilities. The usage of magnetic clay as a filter was tested against charcoal using a PHA simulant and then watching for color change. Further testing was done through the use of a spectrophotometer which tests transmittance by wavelength through the filtered solutions. 1 MATERIALS AND METHODS To begin a hot water bath was prepared using 250 mL of deionized water in a 600 mL beaker and a thermometer. Then a 250 mL Erlenmeyer flask was placed into the bath with the use of a ring stand and 40 mL of deionized water was placed within it. When a temperature of 70 degrees Celsius was reached for the water within the Erlenmeyer flask .78 grams of FeCl 3 and .39 grams of FeSO4*7H2O to the flask and the solution was stirred using a stir rod. After the compounds appeared to dissolve .30 grams of Bentonite was added to the flask and the solution was again stirred until the clay dissolved. At this point the flask was removed from the hot water bath and 20 mL of 2.5 M NaOH was immediately added to the solution. After waiting for the flask to cool down enough to be manipulated the solution was transferred to two centrifuge tubes and centrifuged for ten minutes. Following this the supernatant was discarded and the precipitate was suspended in solution again in order for the solution to be centrifuged a second time. Last of all the precipitate was scooped out into a communal storage of magnetic clay for drying.1

Using the .1 mM procion red as the PHA imitator a series of dilutions were performed for a 50%, 25% and 12.5% solution using a 10 mL volumetric flask and deionized water. The concentration, transmittance, and absorbance of these stock solutions was found using a spectrophotometer and were used to create a plot of concentration vs. absorbance in order to later find the concentration of the filtered solutions. Furthermore the lambda max was found using the 50% dilution and the spectrophotometer by testing on a wavelength range of 495 to 570 nanometers. A mortar and pestle were used to grind up .3 grams of charcoal and .3 grams of clay which were then placed into 50 mL beakers. Following this 15 mL of the .1 mM procion red solution was slowly poured into the beakers. The solution was stirred occasionally over a period of 10 minutes to allow the substrate to soak up the dye. To remove the charcoal from the solution filter paper was placed into a funnel and the solution was slowly poured through into a cuvette until the appropriate amount was achieved. The remove the clay the same method as used to remove the charcoal was used but was not as effective. As a result the clay solution was filtered again using a cotton ball inside the funnel in place of the filter paper to get a satisfactory level of clay removal. To test compare the effectiveness of the filter the cuvettes were placed into the spectrophotometer and the transmittance was found at the lambda max for the procion red. The transmittance was also tested for both solutions at 400 nanometers to determine the

amount of absorption from contaminants within the solutions. RESULTS AND DISCUSSION In the first week the standard solutions of the procion red and the corresponding absorbances was found and the lambda max for the 50% solution was determined to be 517 nanometers. This data was used to create the procion red standard solution table and graph of the concentration versus the absorbance for procion red. The usage of procion red as a PHA substitute is questionable. Despite the usage of procion red in place of a PHA, the molecular structures of the two molecules do not seem to argue for their similarity. The structure of procion red is much more complex with many more atoms involved in the bond than the simple penta-hexagonal shape of a real polycyclic aromatic hydrocarbon. The clay filters out procion red through the process of intercalation, meaning it catches the molecules between very fine

layers of the clay. So the result of the extra size of the procion red molecule would cause the clay to appear to be a more effective filter than the experimental data would represent.

Procion Red Standard Solution Data

Standard Sol. 100% 50% 25% 12.50% Concentration .1 mM .05 mM .025 mM .0125 mM % Transmittance 5.4 18.2 47 66.2 Absorbance 1.27 0.74 0.33 0.18

Concentration Based Absorbance for Procion Red Stock Solutions

1.40 1.20 1.00 Absorbance y = 13.116x 0.80 0.60 0.40 0.20 0.00 0 0.02 0.04 0.06 0.08 0.1 0.12 Concentration of Procion Red (mM)

The clay and charcoal are fundamentally different on many levels. For one, they clay is much cheaper and readily available nearly anywhere there is enough unpaved area to dig a hole. On the other hand, charcoal must be mined which is an expensive and time consuming process. Secondly the removal of each from the water after filtration is very different. Charcoal must be filtered through some sort of medium that will catch the charcoal but allow the water through. While with the magnetic clay as the word suggests may be filtered through the use of its inherent magnetism. Last of all the charcoal is mostly carbon, while the clay is a mixture of

FeSO4*7H2O, FeCl3, NaOH, and bentonite.1 This could be a disadvantage due to possible reactions
with other contaminants in the water other than PHAs with the clay.

During the experiment the transmittance of the charcoal filtered solution was 61.4% meaning the absorbance was 0.212, by using the graph this value corresponds to a 0.0162 mM concentration of procion red dye. The transmittance of the clay filtered solution was 16.4% meaning a 0.785 absorbance and 0.0599 mM concentration of procion red. From these results it is evident the charcoal is a much more effective filter of polycyclic aromatic hydrocarbons. So overall, even if the extra size of the procion red caused a divergence from the true effectiveness of clay as a filter, it did not change the results to the effect that the more effective filtering agent was not evident. CONCLUSION The spectrophotometer was used to find a calibration curve for procion red which was used successfully to find the filtering capability of charcoal and magnetic clay. And, the magnetic clay was found to be an inferior filtering agent of polycyclic aromatic hydrocarbons to charcoal, even with benefits to bulk process efficiency the magnetic clay was simply not an adequate filter of the polycyclic aromatic hydrocarbon simulant.

REFERENCES 1. Texas A&M University, CHEM 111/112 Laboratory Manual, 1st ed. 2008-2009. 2. Park, Y, GA AAyoko, and RL LFrost. "Application of organoclays for the adsorption of recalcitrant organic molecules from aqueous media." Journal of colloid and interface science 354.1 (2011):292-305. 3. "Producers are key in trials to cut water pollution." Farmers Weekly 153.13 (2010): 14. Academic Search Complete. EBSCO. Web. 21 Apr. 2011.