Adsorption of Selected Pharmaceutical Compounds onto Activated Carbon in Dilute Aqueous Solutions Exemplified by Acetaminophen, Diclofenac, and Sulfamethoxazole.

The adsorption of three pharmaceuticals, namely, acetaminophen, diclofenac, and sulfamethoxazole onto granular activated carbon (GAC), was investigated. To study competitive adsorption, both dynamic and steady-state adsorption experiments were conducted by careful selection of pharmaceuticals with various affinities and molecular size. The effective diffusion coefficient of the adsorbate was increased with decease in particle size of GAC. The adsorption affinity represented as Langmuir was consistent with the ranking of the octanol-water partition coefficient, K(ow). The adsorption behavior in binary or tertiary systems could be described by competition adsorption. In the binary system adsorption replacement occurred, under which the adsorbate with the smaller K(ow) was replaced by the one with larger K(ow). Results also indicated that portion of the micropores could be occupied only by the small target compound, but not the larger adsorbates. In multiple-component systems the competition adsorption might significantly be affected by the macropores and less by the meso- or micropores.

Ex Situ CO2 capture by carbonation of steelmaking slag coupled with metalworking wastewater in a rotating packed bed.

Both basic oxygen furnace (BOF) slag and cold-rolling wastewater (CRW) exhibiting highly alkaline characteristics require stabilization and neutralization prior to utilization and/or final disposal. Using CO2 from flue gases as the stabilizing and neutralizing agents could also diminish CO2 emissions. In this investigation, ex situ hot stove gas containing 30 vol% CO2 in the steelmaking process was captured by accelerated carbonation of BOF slag coupled with CRW in a rotating packed bed (RPB). The developed RPB process exhibits superior results, with significant CO2 removal efficiency (η) of 96-99% in flue gas achieved within a short reaction time of 1 min at 25 °C and 1 atm. Calcite (CaCO3) was identified as the main product according to XRD and SEM-XEDS observations. In addition, the elimination of lime and Ca(OH)2 in the BOF slag during carbonation is beneficial to its further use as construction material. Consequently, the developed RPB process could capture the CO2 from the flue gas, neutralize the CRW, and demonstrate the utilization potential for BOF slag. It was also concluded that carbonation of BOF slag coupled with CRW in an RPB is a viable method for CO2 capture due to its higher mass transfer rate and CO2 removal efficiency in a short reaction time.

Systematic approach to determination of maximum achievable capture capacity via leaching and carbonation processes for alkaline steelmaking wastes in a rotating packed bed.

Accelerated carbonation of basic oxygen furnace slag (BOFS) coupled with cold-rolling wastewater (CRW) was performed in a rotating packed bed (RPB) as a promising process for both CO2 fixation and wastewater treatment. The maximum achievable capture capacity (MACC) via leaching and carbonation processes for BOFS in an RPB was systematically determined throughout this study. The leaching behavior of various metal ions from the BOFS into the CRW was investigated by a kinetic model. In addition, quantitative X-ray diffraction (QXRD) using the Rietveld method was carried out to determine the process chemistry of carbonation of BOFS with CRW in an RPB. According to the QXRD results, the major mineral phases reacting with CO2 in BOFS were Ca(OH)2, Ca2(HSiO4)(OH), CaSiO3, and Ca2Fe1.04Al0.986O5. Meanwhile, the carbonation product was identified as calcite according to the observations of SEM, XEDS, and mappings. Furthermore, the MACC of the lab-scale RPB process was determined by balancing the carbonation conversion and energy consumption. In that case, the overall energy consumption, including grinding, pumping, stirring, and rotating processes, was estimated to be 707 kWh/t-CO2. It was thus concluded that CO2 capture by accelerated carbonation of BOFS could be effectively and efficiently performed by coutilizing with CRW in an RPB.

Health risk assessment of exposure to selected volatile organic compounds emitted from an integrated iron and steel plant.

Workplace air samples from sintering, cokemaking, and hot and cold forming processes in the integrated iron and steel industry were analyzed to determine their volatile organic compound (VOC) concentration. Sixteen VOC species including three paraffins (cyclohexane, n-hexane, methylcyclohexane), five chlorinated VOC species (trichloroethylene, 1,1,1-trichloroethane, tetrachloroethylene, chlorobenzene, 1,4-dichlorobenzene), and eight aromatics (benzene, ethylbenzene, styrene, toluene, m,p-xylene, o-xylene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene) were selected to measure their noncancer risk for workers. Concentrations of toluene, xylene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, dichlorobenzene, and trichloroethylene were high in all four processes. Carbon tetrachloride and tetrachloroethylene concentrations were high in the hot and cold forming processes. The noncancer risk followed the increasing order: cokemaking > sintering > hot forming > cold forming. 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene contributed 44% to 65% and 13% to 20% of noncancer risk, respectively, for the four processes. Benzene accounted for a high portion of the noncancer risk in cokemaking. The hazard index (HI: 17-108) of the average VOC concentrations suggests that health risks can be reduced by improving workplace air quality and protecting workers.

Modeling the formation and assessing the risk of disinfection by-products in water distribution systems.

The effect of water quality parameters and operation conditions of water treatment on the formation of trihalomethanes (THM) and haloacetic acids (HAA) in pilot-scale reactor and water distribution system were investigated. Results indicated that dissolved organic carbon and THM formation increased while the concentration of free chlorine decreased along the length of pipeline from the water treatment plant; but HAA formation showed no relationship with the pipeline length. THM concentration was predicted with hydraulic analytic software, namely WaterCAD. The predicted THM data were within +/-10% of measurements; HAA had a relatively high error of +/-16% due to complex bio-decomposition reactions occurred in the distribution system. Both the hazardous quotient and cancer risk of THM in the water distribution system of an advanced water treatment plant were much lower than those of a conventional water treatment plant; there was no significant difference in hazard quotient and cancer risk of HAA in the above two water distribution systems.

The effects of synoptical weather pattern and complex terrain on the formation of aerosol events in the Greater Taipei area.

The aerosol in the Taipei basin is difficult to transport outward under specific weather patterns owing to complex terrain blocking. In this study, seven weather patterns are identified from synoptic weather maps for aerosol events, which occurred from March 2002 to February 2005. Among the identified weather patterns, High Pressure Peripheral Circulation (HPPC), Warm area Ahead of a cold Front (WAF), TYPhoon (TYP), Pacific High Pressure system stretching westerly (PHP), Weak High Pressure system (WHP), and Weak Southern Wind (WSW) are related to terrain blocking. The remaining pattern is High Pressure system Pushing (HPP). The classification of the pollution origin of the air masses shows that 15% of event days were contributed by long-range transport (LRT), 20% by local pollution (LP), and 65% by LRT/LP mix. Terrain blocking causes aerosol accumulation from high atmospheric stability and weak winds occurring under HPPC, TYP, and PHP weather patterns when the Taipei basin is situated on the lee side of the Snow Mountains Chain (SMC). Terrain blocking also occurs when the Taipei basin is situated on the upwind of SMC and Mt. Da-Twen under WAF and WSW patterns. To study the variation of aerosol properties under the mixed influence of terrain and pollution origin, we conducted a field observation simultaneously at the urban, suburban, and background sites in the Greater Taipei area from April 14 to 23, 2004. Terrain blocking plays an important role in aerosol accumulation in the stagnant environment when the Taipei basin is on the lee side of SMC. On the other hand, the PM(2.5) sulfate level is stable with a fraction of 30% in PM(2.5) during the observation period at the urban (25%-33%) and background (25%-41%) sites. It indicates that background PM(2.5) sulfate is high on the West Pacific in winter.

The chemical and biological characteristics of coke-oven wastewater by ozonation.

A bench-scale bubble column reactor was used to investigate the biological and chemical characteristics of coke-oven wastewater after ozonation treatment through the examination of selected parameters. Color and thiocyanate could be removed almost entirely; however, organic matter and cyanide could not, due to the inadequate oxidation ability of ozone to remove ozonated byproducts under given experimental conditions. The removal of cyanide and total organic carbon were pH-dependent and were found to be efficient under neutral to alkaline conditions. The removal rate for thiocyanate was about five times that of cyanide. The ozone consumption ratio approached to about 1 at the early stage of ozonation (time <20 min), indicating that easily degraded matter was present, and mostly ozone was used to oxidize the pollutants. As ozonation progressed, the consumption ratio decreased to 0.2, and TOC removal (eta(TOC)) increased to 30%, indicating that easily degraded pollutants were degraded almost entirely. The effect of ozonation on the subsequent biological treatment unit (i.e., activated sludge process) was determined by observing the ratio of 5-day biological oxygen demand to chemical oxygen demand (BOD(5)/COD) and the specific oxygen utilization rate (SOUR). The results indicated that the contribution of ozonation to inhibition reduction was very significant but limited to the enhancement of biodegradation. The operation for ozonation of coke-oven wastewater was feasible under neutral condition and short ozone contact time in order to achieve better performance and cost savings.

Modeling the behaviors of adsorption and biodegradation in biological activated carbon filters.

This investigation developed a non-steady-state numerical model to differentiate the adsorption and biodegradation quantities of a biological activated carbon (BAC) column. The mechanisms considered in this model are adsorption, biodegradation, convection and diffusion. Simulations were performed to evaluate the effects of the major parameters, the packing media size and the superficial velocity, on the adsorption and biodegradation performances for the removal of dissolved organic carbon based on dimensionless analysis. The model predictions are in agreement with the experimental data by adjusting the liquid-film mass transfer coefficient (k(bf)), which has high correlation with the Stanton number. The Freundlich isotherm constant (N(F)), together with the maximum specific substrate utilization rate (k(f)) and the diffusion coefficient (D(f)), is the most sensitive variable affecting the performance of the BAC. Decreasing the particle size results in more substrate diffusing across the biofilm, and increases the ratio of adsorption rather than biodegradation.

Removal of small trihalomethane precursors from aqueous solution by nanofiltration.

The removal of small trihalomethane precursors (THMPs) from aqueous solution by two commercial nanofiltration membranes (NF70 and NF270) was investigated. Resorcinol, phloroglucinol, and 3-hydroxybenzoic acid were selected as model compounds of small THMPs, while tannic acid was chosen as a medium molecular disinfection by-product (DBP) precursor for comparison. The performance of nanofiltration membranes were evaluated by introducing polyethylene glycol (PEG) solutions and uncharged saccharides to estimate molecular weight cut-off (MWCO) and membrane pore radii, respectively. The streaming potential was measured to estimate the membrane surface charge at different pH values, which reveals that the NF270 membrane is more pH-sensitive than the NF70 membrane. The rejections of the above selected THMPs were assessed under various pH values, and the removal efficiencies of THMPs for both membranes at high pH values are reasonably well. Charge exclusion is the prevailing mechanism for the selected small model compounds retended by the negatively charged nanofiltration membranes, while size exclusion and adsorption are controlled mechanisms but not sufficient for the rejection of unionized small organic molecules. In general, the NF270 membrane exhibits the superior permeation rate value, which takes an advantage over the NF70 membrane from the aspect of energy conservation.

The decolorization and mineralization of acid orange 6 azo dye in aqueous solution by advanced oxidation processes: a comparative study.

The comparison of different advanced oxidation processes (AOPs), i.e. ultraviolet (UV)/TiO(2), O(3), O(3)/UV, O(3)/UV/TiO(2), Fenton and electrocoagulation (EC), is of interest to determine the best removal performance for the destruction of the target compound in an Acid Orange 6 (AO6) solution, exploring the most efficient experimental conditions as well; on the other hand, the results may provide baseline information of the combination of different AOPs in treating industrial wastewater. The following conclusions can be drawn: (1) in the effects of individual and combined ozonation and photocatalytic UV irradiation, both O(3)/UV and O(3)/UV/TiO(2) processes exhibit remarkable TOC removal capability that can achieve a 65% removal efficiency at pH 7 and O(3) dose=45mg/L; (2) the optimum pH and ratio of [H(2)O(2)]/[Fe(2+)] found for the Fenton process, are pH 4 and [H(2)O(2)]/[Fe(2+)]=6.58. The optimum [H(2)O(2)] and [Fe(2+)] under the same HF value are 58.82 and 8.93mM, respectively; (3) the optimum applied voltage found in the EC experiment is 80V, and the initial pH will affect the AO6 and TOC removal rates in that acidic conditions may be favorable for a higher removal rate; (4) the AO6 decolorization rate ranking was obtained in the order of O(3)

Relationship between chlorine consumption and chlorination by-products formation for model compounds.

The objective of this research is to investigate the relationship between chlorine decay and the formations of disinfection by-products (DBP), including trichloromethane (TCM) and chloroacetic acid (CAA) in the presence of four model compounds, i.e., resorcinol, phloroglucinol, p-hydroxybenzoic acid, and m-hydroxybenzoic acid. The chlorine degradation in model compounds with OH and/or COOH functional groups were rapid after chlorination. The TCM yields of carboxylic group substituted compounds (3-hydroxybenzoic acid [3-HBA], 4-hydroxybenzoic acid [4-HBA]) were found to be lower than that of the m-dihydroxy substituted compounds. Phloroglucinol, with one more OH substitution group than resorcinol, tends to form significant amounts of CAA after chlorination. However, it was observed that with the COOH substitution of 3-HBA and 4-HBA tend to exhibit more CAA formation potential than resorcinol. The developed parallel second and first-order reaction model for chlorine demand has been successfully utilized for TCM, CAA and DBP formation modeling. A high correlation between CAA and TCM was observed for the model compounds.

Reduction of disinfection by-products precursors by nanofiltration process.

This research is dedicated to determine the rejection ratios of disinfection by-products (DBPs) precursors including resorcinol, phloroglucinol, 3-hydroxybenzoic acid, and tannic acid solution in the presence of calcium by nanofiltration with NF70 membrane. The rejections of these model compounds also were studied at various compositions of a feed solution by changing pH and concentrations of model compounds. It was found that the model compound rejection and membrane permeability increase with pH due to the conformational transformation of ionizable molecules and electric interaction between the model compounds and NF70 membrane. The interactions of model compounds with calcium have no significant effect on model compounds retentions. Because of the complexation of calcium with model compounds, calcium rejection rises with the presence of model compounds and with an increase of pH.

Validating carbonation parameters of alkaline solid wastes via integrated thermal analyses: Principles and applications.

Accelerated carbonation of alkaline solid wastes is an attractive method for CO2 capture and utilization. However, the evaluation criteria of CaCO3 content in solid wastes and the way to interpret thermal analysis profiles were found to be quite different among the literature. In this investigation, an integrated thermal analyses for determining carbonation parameters in basic oxygen furnace slag (BOFS) were proposed based on thermogravimetric (TG), derivative thermogravimetric (DTG), and differential scanning calorimetry (DSC) analyses. A modified method of TG-DTG interpretation was proposed by considering the consecutive weight loss of sample with 200-900°C because the decomposition of various hydrated compounds caused variances in estimates by using conventional methods of TG interpretation. Different quantities of reference CaCO3 standards, carbonated BOFS samples and synthetic CaCO3/BOFS mixtures were prepared for evaluating the data quality of the modified TG-DTG interpretation, in terms of precision and accuracy. The quantitative results of the modified TG-DTG method were also validated by DSC analysis. In addition, to confirm the TG-DTG results, the evolved gas analysis was performed by mass spectrometer and Fourier transform infrared spectroscopy for detection of the gaseous compounds released during heating. Furthermore, the decomposition kinetics and thermodynamics of CaCO3 in BOFS was evaluated using Arrhenius equation and Kissinger equation. The proposed integrated thermal analyses for determining CaCO3 content in alkaline wastes was precise and accurate, thereby enabling to effectively assess the CO2 capture capacity of alkaline wastes for mineral carbonation.

Multiple model approach to evaluation of accelerated carbonation for steelmaking slag in a slurry reactor.

Basic oxygen furnace slag (BOFS) exhibits highly alkaline properties due to its high calcium content, which is beneficial to carbonation reaction. In this study, accelerated carbonation of BOFS was evaluated under different reaction times, temperatures, and liquid-to-solid (L/S) ratios in a slurry reactor. CO2 mass balance within the slurry reactor was carried out to validate the technical feasibility of fixing gaseous CO2 into solid precipitates. After that, a multiple model approach, i.e., theoretical kinetics and empirical surface model, for carbonation reaction was presented to determine the maximal carbonation conversion of BOFS in a slurry reactor. On one hand, the reaction kinetics of BOFS carbonation was evaluated by the shrinking core model (SCM). Calcite (CaCO3) was identified as a reaction product through the scanning electronic microscopy and X-ray diffraction analyses, which provided the rationale of applying the SCM in this study. The rate-limiting step of carbonation was found to be ash-diffusion controlled, and the effective diffusivity for carbonation of BOFS in a slurry reactor were determined accordingly. On the other hand, the carbonation conversion of BOFS was predicted by the response surface methodology (RSM) via a nonlinear mathematical programming. According to the experimental data, the highest carbonation conversion of BOFS achieved was 57% under an L/S ratio of 20 mL g(-1), a CO2 flow rate of 0.1 L min(-1), and a pressure of 101.3 kPa at 50 °C for 120 min. Furthermore, the applications and limitations of SCM and RSM were examined and exemplified by the carbonation of steelmaking slags.

Effects of polyelectrolytes on reduction of model compounds via coagulation.

The objective of this research work was to evaluate the performance of enhanced coagulation by alum and polymer. Synthetic source waters containing high molecular weight humic acids, medium molecular weight tannic acids and low molecular weight p-hydroxybenzoic acid were formulated by adjusting the concentration of turbidity and pH; and jar tests were used to study the effect of various types and dosages of polymer on reducing the above model compounds. At a specific pH condition, the applied alum dosage would efficiently decrease the turbidity to 2 NTU follows the order: humic>tannic>p-hydroxybenzoic acid. Adjustment of pH influenced the performance of alum obviously but not of p-DADMAC. High p-DADMAC dosage overwhelming the effects of alum is less affected by pH adjustment. The results of this investigation reveal that enhanced coagulation with p-DADMAC was founded to be very effective for removing high-molecular-weight THM precursors, i.e., humic acid and tannic acid, and markedly reduced the alum dosages required for turbidity removal. The other two polymers, i.e., cationic PAM and non-ionic PAM, which had higher molecular weight but lower charge density than p-DADMAC, were not capable of removing organic precursors. It was thus concluded that enhanced coagulation with polymer, p-DADMAC, could be considered as a promising technique for removal of NOMs with hydrophobic and higher-molar-mass (>1K) in water treatment plants.

Seasonal source-receptor relationships in a petrochemical industrial district over northern Taiwan.

This study investigated the relationships between meteorological data, pollution sources, and receptors over northern Taiwan. During the intensive sampling period in summer 1992, the weather was controlled predominantly by a Pacific subtropical high and by Typhoon Mark. During the other intensive sampling period in winter 1993, while a cold frontal system approached Taiwan, the northeasterly winds prevailed most of the time. The local circulation such as land-sea breeze only developed under weak synoptic environment. Particle concentrations and element composition in winter were higher than in summer. This can be attributed to the high convection of air mass, which leads to the vertical dispersion of pollutants in summer. In addition to the subtropical high pressure, typhoons are frequently accompanied with high-wind speeds and unstable weather conditions that also dilute and eliminate the pollutants. In winter, the prevailing northeasterlies might carry pollutants from Midland China. Furthermore, the anticyclone system develops a stagnant condition that easily leads to pollutant accumulation. In this case, the wind direction affected the source contribution of the receptor and the PM10 displays a higher correlation with coarse and fine particulate than meteorological parameters in summer. In addition, the mixing height shows a high correlation with PM10 in winter.

Accelerated carbonation using municipal solid waste incinerator bottom ash and cold-rolling wastewater: Performance evaluation and reaction kinetics.

Accelerated carbonation of alkaline wastes including municipal solid waste incinerator bottom ash (MSWI-BA) and the cold-rolling wastewater (CRW) was investigated for carbon dioxide (CO2) fixation under different operating conditions, i.e., reaction time, CO2 concentration, liquid-to-solid ratio, particle size, and CO2 flow rate. The MSWI-BA before and after carbonation process were analyzed by the thermogravimetry and differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy equipped with energy dispersive X-ray spectroscopy. The MSWI-BA exhibits a high carbonation conversion of 90.7%, corresponding to a CO2 fixation capacity of 102g perkg of ash. Meanwhile, the carbonation kinetics was evaluated by the shrinking core model. In addition, the effect of different operating parameters on carbonation conversion of MSWI-BA was statistically evaluated by response surface methodology (RSM) using experimental data to predict the maximum carbonation conversion. Furthermore, the amount of CO2 reduction and energy consumption for operating the proposed process in refuse incinerator were estimated. Capsule abstract: CO2 fixation process by alkaline wastes including bottom ash and cold-rolling wastewater was developed, which should be a viable method due to high conversion.

NOM characteristics and treatabilities of ozonation processes.

The objectives of this study were intended to evaluate the effects of the characteristics of natural organic matter on the treatabilities of ozonation, coagulation, filtration, and granular activated carbon processes. The ultra-violet absorbance (UV254) was used as a surrogate parameter to assess each process in reducing the disinfection by-product formation potential (DBPFP). The results indicate that the DBPFP varies with the sources of water samples and treatment processes, but is closely related to the measurement of UV254/DOC. Coagulation/sedimentation can eliminate large molecular weight organic fractions. Both pre- and post-ozonation processes can reduce some of DBP precursors than the conventional treatment process, and are more reliable for reducing the overall DBPFP.

Effects of bromide on the formation of THMs and HAAs.

The role of bromide in the formation and speciation of disinfection by-products (DBPs) during chlorination was investigated. The molar ratio of applied chlorine to bromide is an important factor in the formation and speciation of trihalomethanes (THMs) and halogenacetic acids (HAAs). A good relationship exists between the molar fractions of THMs and the bromide incorporation factor. The halogen substitution ability of HOBr and HOCl during the formation of THMs and HAAs can be determined based on probability theory. The formation of HAAs, and their respective concentrations, can also be estimated through use of the developed model.

Development of surrogate organic contaminant parameters for source water quality standards in Taiwan, ROC.

The objective of this research was to develop a rationale for selecting representative water quality parameters for organic contaminants and microorganisms and determining their respective contaminant level (or regulated value) for the source water quality standards in Taiwan. It was observed that chemical oxygen demand (COD) and total organic carbon (TOC) have strong correlation with UV254 in spite of the raw water which suggests, TOC and COD should be regarded as the surrogate parameters for water quality concerns. It was also proposed to implement 4.0 mg/L of TOC as a source water criteria at the present time and to adopt a more stringent value (2.0 mg/L of TOC) in the next phase (at 2002). The total coliform regulated from 10,000 to 20,000 most probable number (MPN)/100 ml level appears to be the most economic and logical way to control trihalomethanes (THM) formation and disinfection efficiency at the water treatment plant in Taiwan.