DESALINATION

ELSEVIER Desalination 147 (2002) 251-255

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Use of ATR/FTIR spectrometry to study fouling of microfiltration membranes by natural waters

Kerry J. Howe a*, Kenneth P. Ishida b' Mark M. Clark a
"University of Illinois, Department of Civil Engineering, 205 N. Mathews Ave., Urbana, Illinois 61801-2352, USA Tel. +1 (217) 3339663; Fax +1 (217) 3336968; emails: khowe@uiuc.edu, m-clark3@uiuc.edu ~'Orange Coun~ Water District, PO. Box 8300; Fountain Valley, CA 92728-8300, USA Tel. +1 (714) 3783200; Fax +1 (714) 3783373; email: kishida@ocwd.com

Received 1 February 2002; accepted 26 March 2002

Abstract Attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectrometry provided insight into the chemical nature of deposits on polypropylene microfiltration membranes after filtration of two North American surface waters. The spectra of the foulants were easy to distinguish from the spectra of the membrane material. The results did not show strong evidence for the presence of carboxylic acid, carboxylate, phenolic, or hydroxyl functional groups in the foulants, although these functional groups are common in natural waters. ATR/FTIR also indicated the presence of inorganic foulants; the ratio of inorganic to organic foulants varied between the two water sources. The spectra of the foulants were significantly more distinct than spectra of other natural waters, suggesting that relatively few components present in Medina River and Beaver Lake surface waters may adsorb to this membrane material. ATR/FTIR appears to be a valuable tool for studying membrane fouling by natural waters.
Keywords: ATR/FTIR spectrometry; DOM; Dissolved organic matter; Microfiltration; Fouling

1. I n t r o d u c t i o n Microfiitration membranes are severely fouled by natural water; 9 0 - 9 5 % of the permeability of a virgin m e m b r a n e can be lost rapidly. Natural waters are a complex mix of particulate and soluble *Corresponding author.

components of both inorganic and organic origin that vary f r o m one source to the next. M a n y studies have examined fouling of membranes by various components of natural waters; however, the specific relationship between the components of natural waters and m e m b r a n e fouling has been elusive. The objectives of this manuscript are to

Presented at the International Congress on Membranes and Membrane Processes (ICOM), Toulouse, France, July 7-12, 2002.

0011-9164/02/$- See front matter 2002 Elsevier Science B.V. All rights reserved
P11:S0011-9164(02)00545-3

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describe a study in which ATR/FTIR spectrometry was used to investigate the components in natural waters that caused fouling.

2. Background
Dissolved organic matter (DOM) is an important contributor to membrane fouling [1]. DOM is a heterogeneous mixture of thousands of chemicals produced by biological activity on land and in water. DOM includes aquatic humic substances (humic acids and fulvic acids) as well as other organic compounds. To better understand the effect of DOM on natural and engineered processes, researchers have attempted to characterize DOM by hydrophobicity, molecular weight distribution, and functional chemistry. The functional chemistry is particularly important because it controls the reactions between DOM and other constituents. The major functional groups in aquatic humic substances are carboxylic acid, hydroxyl, phenolic, and carbonyl groups [2]. Over 90% of DOM contains carboxylic acid groups, which are ionized at neutral pH. As a result, almost all DOM is negatively charged under natural conditions, which affects DOM's solubility and ability to foul membranes. FTIR spectrometry is used to determine the functional chemistry of unknown materials. Samples exposed to infrared light absorb energy corresponding to the vibrational energy of atomic bonds. Functional groups absorb energy at specific wavelengths, which can be shifted in intensity or position by substituent effects from adjacent atoms. The resulting absorption spectrum is a unique fingerprint of a compound. Although some functional groups produce sharp absorption bands, the h e t e r o g e n e i t y of natural waters produces broad overlapping bands that make the identification of specific functional groups more difficult. Nevertheless, several characteristic absorption bands are often seen in aquatic humic substance spectra, including bands around 3000 to 3400 cm -j (hydroxyl), 2900 cm -l (aliphatic carbon), 1725 cm -l (carboxylic acids), 1600 to

1660 cm -l (carboxylate, carbonyl, or amide I), 1550 cm -~ (amide II), and 1400 cm -l (carboxylate). Strong absorption bands at 1000 to 1050 cm -t can be due to at least two different functional groups, and some researchers have interpreted absorption here to be due to silicates [2,3] while others have attributed it to polysaccharides [4].

3. Experimental methods
Surface waters from the Medina River, Texas, and Beaver Lake, Arkansas, were filtered through 0.2-~m polypropylene microfiltration membranes, and the fouled membranes were examined by ATR/FTIR spectrometry. The water was prefiltered through a 0.2 to 0.6-pm glass-fiber filter to remove suspended material. Filtration was done with 62-mm diameter membranes in an unstirred dead-end cell (Amicon Model 8200, Millipore Corp., Bedford, MA) at a pressure of 0.69 bar. Polypropylene has only C-C and C-H functional groups and the FTIR absorption spectrum contains sharp, well-defined absorption bands. Therefore, the polypropylene spectrum is easy to subtract from the composite spectrum, making the spectrum of the foulants easier to interpret. Additional experimental details are provided elsewhere [5]. ATR/FTIR analyses were p e r f o r m e d on samples of about 45 by 10 mm. The membranes were dried by placing them in a glove box purged with dry air. A membrane sample was pressed against each side of a zinc selenide internal reflection element (50x 10x2 mm, 45). The pressure plates of the Harrick Scientific Corporation (Ossining, NY) accessory were adjusted to 10 ozin with a torque wrench. A series of 256 scans were collected and added at 4-cm -l resolution with a Magna 550 Fourier transform infrared spectrometer (Thermo Nicolet Instrument Corporation, Madison, WI) equipped with a mercury-cadmiumtelluride detector. The sample spectra were ratioed against a bare zinc selenide background spectrum and converted to absorbance with GRAMS/32 software, version 6.00 (Thermo Galactic, Salem, NH). Spectra were corrected to take into account

K.J. Howe et al. / Desalination 147 (2002) 251-255

253

the wavelength dependence of ATR and baseline corrected. Difference spectra were obtained by digital subtraction with the GRAMS/32 software.
4. Results

0.14 0.12 0.10 0.08 0.06

C: I~t3A

Fig. 1 shows the FTIR spectrum of components in Medina River water that fouled a polypropylene m e m b r a n e (the p o l y p r o p y l e n e m e m b r a n e spectrum has been digitally subtracted; the negative peaks near 2900 cm -~ are due to overs u b t r a c t i o n of C - H stretching bands). The strongest absorption band is observed at 1034 cm~. Absorption in this region is due to C-O or Si-O bonds and is commonly associated with alcohols, ethers, polysaccharides, and silicates. Cho et al. [4] attributed FTIR absorption in this region to polysaccharides or polysaccharide-like membrane foulants, whereas Thurman [2] attributed this absorption to silicate impurities in humic samples. Examination of other regions of the spectrum can clarify whether the foulants are polysaccharides or silicates. Polysaccharides contain a significant number of hydroxyl groups, which exhibit a broad rounded absorption band above 3000 cm-L The absorption in that region of Fig. 1 does not have the rounded trait typical of hydroxyls, which suggests that the Medina River foulants are not polysaccharides. Two small peaks observed at 3696 and 3620 cm -j in Fig. 1 correspond to absorption by aluminum silicate (kaolin clay, AI203.SiO2H20), and very few organic materials absorb in this region. Aluminum silicate is common in clay and might be suspected to be present in natural waters. Thus, one component of the fouling material appears to be aluminum silicate. Carboxylates typically absorb around 1600 and 1400 cm -~, and amides typically absorb around 1650 and 1550 cm -~. The triplet of peaks at 1655, 1513, and 1447 cm -~ do not fit either of these patterns, but may be due to a combination of amides and c a r b o n y l groups with other substituents. The peak at 875 cm -~ is probably due to aromatic carbon. The presence of absorption

,n-

t
4000

0'~

-0.02

-0041
~OlO6 2 ;

!
, ,
3000

2boo
Waven umber (cm -1)

1 oo

Fig. 1. ATR/FrlR spectra of foulant on polypropylene membrane from Medina River water.

in these regions suggests a significant amount of organic fouling on the membrane surface. One method for verifying the presence of carboxylates in an ATR/FTIR analysis is to vary the pH of the sample. At neutral pH values, absorption bands due to carboxylate are present near 1600 and 1400 cm-L At pH values below the pKa of the carboxylic acids, the carboxylates protonate, decreasing the intensity of the absorption bands near 1600 and 1400 cm -1 and increasing the intensity of bands near 1725 cm -~ (C=O) and 3000 to 3400 cm -I (hydroxyl). To investigate this, Beaver Lake water was adjusted to a series of pH values and filtered through polypropylene membranes. The spectra of the foulants in this series are shown in Fig. 2. The spectra at each of the five pH values are similar, indicating that the material that adsorbed to the membrane did not change significantly as the pH changed, and that carboxylates are not a significant component of the foulant on these membranes. The most dominant feature of the Beaver Lake spectra is a strong absorption band at 1035 cm -~. This band, along with the triplet at 3699, 3653, and 3622 cm -l, is indicative of aluminum silicate. Three weak bands are observed near 1741, 1653,

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K.J. Howe et al. / Desalination 147 (2002) 251-255

1.4

Table 1 Elementalcompositionof polypropylenemembranesfouled with MedinaRiver and Beaver Lake water

O3O304 Ob tt3 ~ 1 (.o f-O (.o 030303
03 i~- t.O O t.O Q

1.2

Element

1.0 - L ~
g

"' ~--.--~PH 7.5

Medina River BeaverLake (Percent mass of (Percent mass of element) element) 68 19 6 4 2 1 26 39 5 18 12 1

0.8

<

0.6

0.4 0.2

pH 5 ,. ~ . . ~

_A
2000 1000

Carbon Oxygen Nitrogen Silica Aluminum Calcium

pH 4

o -----~--------~
4000 3000

Wa,~number (cm -1 )

Fig. 2. ATR/FTIR spectra of foulant on polypropylene membrane from Beaver Lake water.

and 1543 cm -l. These bands may correspond to carbonyl, amide I, and amide II bands of an amide structure, which would be indicative of organic matter (possibly proteins). The intensity of the absorption at each pH value, when compared to the absorption due to the base material (not shown), suggests that the amount of foulant was nearly the same on each membrane. The flux was recorded as a function of time during preparation of each fouled membrane, and the flux decline was virtually identical during filtration of each sample after pH adjustment [5]. The flux decline results are consistent with the observation that changing the pH did not change the nature of the foulant, and a lack of pH dependence of the foulant suggests that carboxylates are not a significant component of the foulant. The material in Beaver Lake water that adsorbed to the polypropylene membrane is primarily aluminum silicate with lesser amounts of organic matter.

Summarizing Figs. 1 and 2, it appears that the foulant from both waters contains aluminum silicates, and that the Medina River membrane has a significant quantity of organic foulants but that the Beaver Lake membranes have considerably less organic foulants. X-ray photoelectron spectrometry (XPS) was used to evaluate the elemental composition of a fouled membrane from each water to corroborate the ATR/FFIR results. The elemental composition of these two membranes is shown in Table 1. The membrane fouled with Beaver Lake water c o n t a i n s a significant amount of silica and aluminum, 30% of the total mass at the surface of the sample. Since the membrane is entirely carbon, the presence of some nitrogen and excess oxygen indicates the presence of organic matter on the surface. Thus, the foulant on the membrane consists of both aluminum silicate and organic matter. The membrane fouled with Medina River water contains less aluminum and silica. This suggests that some aluminum silicate is present on the Medina River membrane, but organic matter is the primary foulant. The XPS results are consistent with the ATR/FTIR results for these two waters. The FFIR spectra of the fouled membranes can be contrasted with spectra of natural water samples from other researchers. FTIR spectra of Suwannee River water [2,3] and Platte River water [3] are broad and lacking in sharp spectral

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bands. This suggests that the bulk DOM in these rivers consists of many compounds with overlapping absorption bands that tend to mask any sharp features. In contrast, the spectra in Figs. 1 and 2 contains distinct and sharply defined peaks and large regions with no absorption, suggesting that fewer compounds may have adsorbed on the membranes than are present in bulk DOM. The spectra of Suwannee and Platte River water show significant absorption around 1700 cm -~, which is indicative of carboxylic acids, and a broad, rounded band of absorption between 3000 and 3400 cm -~, which is characteristic of hydroxyl. Recall that little or no evidence is seen for hydroxyls or carboxylic acids in the foulants from the Medina River and Beaver Lake waters. Since hydroxyl and carboxylic functional groups are prevalent in DOM, the lack of these functional groups also suggests that fewer compounds adsorb to the polypropylene membrane than are present in bulk DOM. Dissolved organic carbon (DOC) concentrations were measured before and after the filtration experiments [5]. The DOC results showed that significant fouling could occur even when 85 to 95% of the DOC passed through the membrane. The DOC results corroborate the conclusions drawn from the ATR/FTIR spectra: a significant portion of bulk DOM does not appear to adsorb to polypropylene membranes, and fouling may be due to a small subset of bulk DOM.

phenolic, or hydroxyl functional groups, although these are common components in DOM. These results suggest that a substantial portion of DOM did not adsorb to the m e m b r a n e s in these experiments, a conclusion that was corroborated by DOC measurements. Carboxylate and hydroxyl groups impart significant solubility to molecules, so it is reasonable to expect that DOM molecules rich in these functional groups would not partition onto the membrane surface. The chemical compositions of the foulants in the two sources were different from each other. Both inorganic and organic compounds appeared to be present, although the proportion of inorganic and organic foulants varied b e t w e e n the sources. This conclusion was corroborated by elemental analysis of the membrane surfaces. The inorganic foulants appeared to contain aluminum silicates and the organic foulants may have contained carbonyl or amide functional groups. The functional chemistry of the deposited material did not appear to change significantly when the pH of the feed water was varied between values of 4.0 and 9.0.

Acknowledgments
This research was funded by the American Water Works Association Research Foundation.
References
[1 ] AWWA Membrane Technology Research Committee, Committee report: membrane processes, J. AWWA, 90(6) (1998) 91-105. [2] E.M. Thurman, Organic Geochemistry of Natural Waters, Martinus Nijhoff/Dr W. Junk Publishers, Boston, MA, 1985. [3] J-P. Croue, G.V. Korshin and M.M. Benjamin, Characterization of Natural Organic Matter in Drinking Water, AWWARF and AWWA, Denver, CO, 2000. [4] J. Cho, G. Amy, J. Pellegrino and Y. Yoon, Characterization of clean and natural organic matter (NOM) fouled NF and UF membranes, and foulants characterization, Desalination, 118 (1998) 101-108. [5] K.J. Howe, Effect of Coagulation Pretreatment on Membrane Filtration Performance. Ph.D. Thesis, University of Illinois. 2001.

5. Conclusions
Two natural surface waters were filtered through 0.2%tm polypropylene membranes and examined by ATR/FTIR spectrometry. The vibrational bands associated with the foulants could be clearly distinguished from those of the membrane material. The foulants on these membranes produced relatively sharp absorption bands; in contrast to the broad bands natural waters typically produce. There was no strong evidence for the presence of carboxylic acid, carboxylate,