Use of surfactant modified ultrafiltration for perchlorate (Cl(O)(4-)) removal.

Determinations of perchlorate anion (ClO(4)(-)) transport and rejection were performed using a surfactant modified ultrafiltration (UF) membrane. Perchlorate anion (at a concentration of 100 microg/L of ClO(4)(-), spiked with KClO(4)) was introduced to the membrane as a pure component, in binary mixtures with other salts, cationic and anionic surfactants, and at various ionic strength conditions (conductivity). Also, a natural source water was spiked with perchlorate in the presence of cationic and anionic surfactants and used to determine the effects of a complex mixture (including natural organic matter (NOM)) on the observed rejection. All filtration measurements were performed at approximately the same permeate flow rate in order to minimize artifacts from mass transfer at the membrane interface. The objective of this study was to modify a negatively charged UF membrane in terms of the fundamental mechanisms, steric/size exclusion and electrostatic exclusion and to enhance perchlorate rejection, with synthetic water and a blend of Colorado River water and State Project water (CRW/SPW). Previous work suggested that perchlorate was dominantly rejected by electrostatic exclusion for charged nanofiltration (NF) and UF membranes (Rejection of perchlorate by reverse osmosis, nanofiltration and ultrafiltration (UF) membranes: mechanism and modeling. Ph.D. dissertation, University of Colorado, Boulder, USA, 2001). In that research, perchlorate rejection capability was quickly lost in the presence of a sufficient amount of other ions. However, this study showed that ClO(4)(-) was excluded from a (negatively) charged UF membrane with pores large with respect to the size of the ion. Although perchlorate rejection capability due to apparent electrostatic force was reduced in the presence of a cationic surfactant, a desired amount of the ClO(4)(-) was excluded by steric exclusion. The steric exclusion was due to decreasing membrane pore size caused by the adsorption of the cationic surfactant.

Varations of molecular weight estimation by HP-size exclusion chromatography with UVA versus online DOC detection.

High performance size exclusion chromatography (HPSEC) with ultraviolet absorbance (UVA) detection has been widely utilized to estimate the molecular weight (MW) and MW distribution of natural organic matter (NOM). However, the estimation of MW with UVA detection is inherently inaccurate because UVA at 254 nm only detects limited components (mostly pi bonded molecules) of NOM, and the molar absorptivity of these different NOM constituents is not equal. In comparison, a SEC chromatogram obtained with a DOC detector showed significant differences compared to a corresponding UVA chromatogram, resulting in different MW values as well as different estimates of polydispersivity. The MWs of Suwannee River humic acid (SRHA), Suwannee River fulvic acid (SRFA), and various mixtures thereof were estimated with HPSEC coupled with UVA and DOC detectors. The results show that UVA is not an adequate detector for quantitative analysis of MW estimation but rather can be used only for limited qualitative analysis. The NOM in several natural waters (Irvine Ranch, California groundwater, and Barr Lake, Colorado surface water) were also characterized to demonstrate the different MWs obtained with the two detectors. The results of the SEC-DOC chromatograms revealed NOM constituent peaks that went undetected by UVA. Utilizing online DOC detection, a better representation of NOM MWs was suggested, with NOM displaying higher weight-averaged MW (Mw) and lower number-averaged MW (Mn) as well as higher polydispersivity. A method for estimation of the MWs of NOM fractional components and polydispersivities is presented.

Optimization of method for detecting and characterizing NOM by HPLC-size exclusion chromatography with UV and on-line DOC detection.

High-performance liquid chromatography (HPLC)-size exclusion chromatography (SEC) with ultraviolet absorbance (UVA) and on-line dissolved organic carbon (DOC) detectors has been adapted and optimized under various conditions. An enhanced HPSEC-UVA system employing a modified commercially available DOC detector provides a better understanding of the qualitative and quantitative natural organic matter (NOM) properties in water samples by detecting aromatic and nonaromatic fractions of NOM as a function of molecular weight (MW). The most critical merit of this system is that the DOC detector is readily available and widely used. With only a few modifications, a commercially available TOC analyzer served as a DOC detector, integrated with the HPSEC to measure DOC along with UVA, and provided a specific UVA (SUVA) chromatograph that is useful information for drinking water plant design and operation. Without preconcentration, samples can be analyzed with a small amount of sample, with a DOC detection limit as low as 0.1 mg/L (as DOC).