Assessing the role of feed water constituents in irreversible membrane fouling of pilot-scale ultrafiltration drinking water treatment systems.

Fluorescence excitation-emission matrix (EEM) approach together with principal component analysis (PCA) was used for assessing hydraulically irreversible fouling of three pilot-scale ultrafiltration (UF) systems containing full-scale and bench-scale hollow fiber membrane modules in drinking water treatment. These systems were operated for at least three months with extensive cycles of permeation, combination of back-pulsing and scouring and chemical cleaning. The principal component (PC) scores generated from the PCA of the fluorescence EEMs were found to be related to humic substances (HS), protein-like and colloidal/particulate matter content. PC scores of HS- and protein-like matter of the UF feed water, when considered separately, showed reasonably good correlations with the rate of hydraulically irreversible fouling for long-term UF operations. In contrast, comparatively weaker correlations for PC scores of colloidal/particulate matter and the rate of hydraulically irreversible fouling were obtained for all UF systems. Since, individual correlations could not fully explain the evolution of the rate of irreversible fouling, multi-linear regression models were developed to relate the combined effect of HS-like, protein-like and colloidal/particulate matter PC scores to the rate of hydraulically irreversible fouling for each specific UF system. These multi-linear regression models revealed significant individual and combined contribution of HS- and protein-like matter to the rate of hydraulically irreversible fouling, with protein-like matter generally showing the greatest contribution. The contribution of colloidal/particulate matter to the rate of hydraulically irreversible fouling was not as significant. The addition of polyaluminum chloride, as coagulant, to UF feed appeared to have a positive impact in reducing hydraulically irreversible fouling by these constituents. The proposed approach has applications in quantifying the individual and synergistic contribution of major natural water constituents to the rate of hydraulically irreversible membrane fouling and shows potential for controlling UF irreversible fouling in the production of drinking water.

Identification of humic acid-like and fulvic acid-like natural organic matter in river water using fluorescence spectroscopy.

Identifying the extent of humic acid (HA)-like and fulvic acid (FA)-like natural organic matter (NOM) present in natural water is important to assess disinfection by-product formation and fouling potential during drinking water treatment applications. However, the unique fluorescence properties related to HA-like NOM is masked by the fluorescence signals of the more abundant FA-like NOM. For this reason, it is not possible to accurately characterize HA-like and FA-like NOM components in a single water sample using direct fluorescence EEM analysis. A relatively simple approach is described here that demonstrates the feasibility of using a fluorescence excitation-emission matrix (EEM) approach for identifying HA-like and FA-like NOM fractions in water when used in combination with a series of pH adjustments and filtration steps. It is demonstrated that the fluorescence EEMS of HA-like and FA-like NOM fractions from the river water sample possessed different spectral properties. Fractionation of HA-like and FA-like NOM prior to fluorescence analysis is therefore proposed as a more reasonable approach.

Acquiring reproducible fluorescence spectra of dissolved organic matter at very low concentrations.

A method that would allow for fast and reliable measurements of dissolved organic matter (DOM), both at low and high concentration levels would be a valuable tool for online monitoring of DOM. This could have applications in a variety of areas including membrane treatment systems for drinking water applications which is of interest to our group. In this study, the feasibility of using fluorescence spectroscopy for monitoring DOM at very low concentration levels was demonstrated with an emphasis on optimizing the instrument parameters necessary to obtain reproducible fluorescence signals. Signals were acquired using a cuvette or a fibre optic probe assembly, the latter which may have applications for on-line or in-line monitoring. The instrument parameters such as photomultiplier tube (PMT) voltage, scanning rate and slit width were studied in detail to find the optimum parameter settings required. The results showed that larger excitation and emission slit widths were preferred, over larger PMT voltage or lower scanning rates, to obtain reproducible and rapid measurements when measuring very low concentration levels of DOM. However, this approach should be implemented with caution to avoid any reduction of the signal resolution.

BOD5 estimation for pulp and paper mill effluent using UV absorbance.

A novel method based on UV absorbance, is presented for estimating the BOD5 in pulp and paper mill effluent. This method could eventually be incorporated into an on-line sensor for BOD5 that is suitable for process control applications. Two streams, the reactor entrance and the final effluent, from two different mills were studied. One mill employed the Kraft pulping process, while the second mill was a thermo-mechanical one. The absorbance over the range 200-350 nm showed significant differences between the two mills. Because the two mills use very distinct processes, separate correlations were used to relate the absorbance to the BOD5 for both the mills. Results indicate that prediction of reactor entrance BOD5 was reasonable, whereas prediction of final effluent BOD5 was inaccurate, for both mills. Also studied was the effect of aeration on BOD5 results obtained at low BOD5 values for the Kraft mill.

Effect of temperature on the inhibition kinetics of phenol biodegradation by Pseudomonas putida Q5.

The temperature-dependent performance of mixed-culture wastewater treatment processes may be strongly influenced by their content of psychrotrophic bacteria. In this work, the effect of temperature on cell growth and phenol biodegradation kinetics of the psychrotrophic bacterium Pseudomonas putida Q5 were determined using both batch and continuous cultures in the range of 10-25 degrees C. The Haldane equation was found to be the most suitable substrate-inhibition model for the specific growth rate. The Haldane parameters mu(max) and K(I) were best modeled by a square-root dependency on temperature. However, the Arrhenius model provided a better prediction of the temperature dependence of K(S). The variation of the yield constant with temperature also was studied experimentally. Comparisons with results of previous workers are presented.

Double inhibition model for degradation of phenol by Pseudomonas putida Q5.

A semiempirical model, based on the presence of an inhibitory intermediate metabolite excreted to the broth, was developed to better predict the dynamic responses to shock loadings of Pseudomonas putida Q5 degrading phenol. Compared to the Haldane equation, the new model exhibited better prediction capabilities for a broad range of inlet concentration and dilution rate step changes. The experiments were performed at 10 degrees and 25 degrees C and ranged from stable responses to washouts. The time delays observed experimentally were successfully predicted with the dual-inhibition model and a very good agreement with the observed phenol profile also was found in a pulse experiment. A possible intermediate metabolite was detected by HPLC analyses based on the high correlation shown with the predicted inhibitory intermediate metabolite in the model.

Analysis of the inverse problem of freezing and thawing of a binary solution during cryosurgical processes.

An integral solution for a one-dimensional inverse Stefan problem is presented. Both the freezing and subsequent thawing processes are considered. The medium depicting biological tissues, is a nonideal binary solution wherein phase change occurs over a range of temperatures rather than at a single one. A constant cooling, or warming, rate is imposed at the lower temperature boundary of the freezing/thawing front. This condition is believed to be essential for maximizing cell destruction rate. The integral solution yields a temperature forcing function which is applied at the surface of the cryoprobe. An average thermal conductivity, on both sides of the freezing front, is used to improve the solution. A two-dimensional, axisymmetric finite element code is used to calculate cooling/warming rates at positions in the medium away from the axis of symmetry of the cryoprobe. It was shown that these cooling/warming rates were always lower than the prescribed rate assumed in the one-dimensional solution. Thus, similar, or even higher, cell destruction rates may be expected in the medium consistent with existing in vitro data. Certain problems associated with the control of the warming rate during the melting stage are discussed.

Controlled freezing of nonideal solutions with application to cryosurgical processes.

Success of a cryosurgical procedure, i.e., maximal cell destruction, requires that the cooling rate be controlled during the freezing process. Standard cryosurgical devices are not usually designed to perform the required controlled process. In this study, a new cryosurgical device was developed which facilitates the achievement of a specified cooling rate during freezing by accurately controlling the probe temperature variation with time. The new device has been experimentally tested by applying it to an aqueous solution of mashed potatoes. The temperature field in the freezing medium, whose thermal properties are similar to those of biological tissue, was measured. The cryoprobe temperature was controlled according to a desired time varying profile which was assumed to maximize necrosis. The tracking accuracy and the stability of the closed loop control system were investigated. It was found that for most of the time the tracking accuracy was excellent and the error between the measured probe temperature and the desired set point is within +/- 0.4 degrees C. However, noticeable deviations from the set point occurred due to the supercooling phenomenon or due to the instability of the liquid nitrogen boiling regime in the cryoprobe. The experimental results were compared to those obtained by a finite elements program and very good agreement was obtained. The deviation between the two data sets seems to be mainly due to errors in positioning of the thermocouple junctions in the medium.

Control of the cryosurgical process in nonideal materials.

A study of a controlled cryosurgical process is presented. This study is based on the energy equations describing the probe response and the phase change occurring in the medium. First-order nonlinear differential equations (state equations) are obtained by applying the integral-solution method. In order to obtain maximal cell destruction, it is desired to control a specific cooling rate at the solid-liquid interface. This cooling rate defines the desired trajectories of the state variables through the state equations. In order to satisfy the cooling rate condition on the freezing front, a closed-loop is designed to control the probe temperature program. A simple analysis of the system stability employed linearization at several points along the desired trajectories. Ranges of stability were obtained for a system containing a proportional-integral controller. It was demonstrated that these stability ranges depend mainly on the selected sampling time of the discrete control loop and that the phase-change process does not significantly affect the stability results. A complete study of the nonlinear equations was performed by a computer simulation program which enables the selection of the final values of the controller parameters, in order to minimize the error and to ensure stability. In addition, the simulation program gives information about the effects of the A/D and D/A converters accuracy on the performance of the control loop. An A/D converter accuracy of 12 bits was found necessary in order to reduce the oscillations in probe temperature to acceptable values. The simulation also yields a complete calculated temperature field in the tissue during the controlled process. From these simulated results it can be seen that oscillations of +/- 0.5 degrees C in the desired probe temperature do not significantly affect the desired cooling rate at the freezing front. An initial overshoot of 1.5 degrees C in the desired probe temperature was obtained both experimentally and theoretically from the simulation. When this initial overshoot occurs at the beginning of the freezing process, it causes an error in freezing front velocity and consequently in ice-front position. From the numerical simulation, it can be deduced that the cooling rate obtained at the front deviates from the desired value by approximately 1%. The probe-temperature error increases at two instants: a) during the super-cooling effect and the subsequent sudden crystallization, and b) when the probe temperature is below -80 degrees C and unstable boiling of the cooling medium causes oscillations.

Investigation of temperature fields around embedded cryoprobes.

The temperature fields around cryoprobes were investigated analytically and experimentally. Two cryoprobes were employed: a spherically shaped general purpose probe utilizing liquid nitrogen and a cylindrical "glaucoma" probe utilizing the Joule-Thomson effect in gaseous CO2. Both probes were operated by commercial cryostats. The analytical solutions included a one-dimensional integral solution for the general purpose cryoprobe, and finite element solutions for both cryoprobes. Both solutions were based on the enthalpy method. Analytical and experimental results compared reasonably well. Deviations of these results are believed to be due, mainly, to the incomplete specification of the boundary conditions on the surface of the cryoprobe.