Efficacy of selected pretreatment processes in the mitigation of low-pressure membrane fouling and its correlation to their removal of microbial DOM.

Membrane fouling by dissolved organic matter (DOM), especially microbially-derived DOM, is a major challenge for ultrafiltration (UF) membranes in water purification. Fouling may be mitigated by pretreating feed waters; however, there are no comprehensive studies that compare the fouling reduction efficacies across different pretreatment processes. Further, there is a limited understanding of the relationship between fouling reduction efficacy and microbially-derived DOM removal from source waters. Accordingly, the objectives of this study were to: (i) evaluate and compare the efficacies of five pretreatment processes in reducing UF membrane fouling by DOM; and (ii) investigate whether a relationship exists between membrane fouling reduction and microbially-derived DOM removal by pretreatment processes. We investigated seven water sources and a polyvinylidene fluoride hollow-fiber UF membrane using bench-scale fouling tests. Dissolved organic carbon content, ultraviolet absorbance and fluorescence excitation-emission matrix spectroscopy were used to assess DOM concentration and composition. Alum and ferric chloride coagulation were the most effective pretreatment processes in reducing membrane fouling, anion exchange was moderately effective, and PAC adsorption and chlorine pre-oxidation were the least effective. Consistent with previous studies, microbially-derived DOM was the major contributor to UF membrane fouling regardless of water source or pretreatment type. Fouling reduction was strongly correlated with the reduction of microbially-derived DOM in foulant layers but not from source waters. This result indicates that a fraction of the total microbially-derived DOM in feed waters was responsible for UF fouling. Overall, pretreatment processes that remove microbially-derived DOM are well-suited for UF membrane fouling reduction.

Minimization of short-term low-pressure membrane fouling using a magnetic ion exchange (MIEX(®)) resin.

Two challenges to low-pressure membrane (LPM) filtration are limited rejection of dissolved organic matter (DOM) and membrane fouling by DOM. The magnetic ion exchange resin MIEX(®) (Ixom Watercare Inc.) has been demonstrated to remove substantial amounts of DOM from many source waters, suggesting that MIEX can both reduce DOM content in membrane feed waters and minimize LPM fouling. We tested the effect of MIEX pretreatment on the reduction of short-term LPM fouling potential using feed waters varying in DOM concentration and composition. Four natural and two synthetic waters were studied and a polyvinylidene fluoride (PVDF) hollow-fiber ultrafiltration membrane was used in membrane fouling tests. To evaluate whether MIEX removes the fractions of DOM that cause LPM fouling, the DOM in raw, MIEX-treated, and membrane feed and backwash waters was characterized in terms of DOM concentration and composition. Results showed that: (i) the efficacy of MIEX to reduce LPM fouling varies broadly with source water; (ii) MIEX preferentially removes terrestrial DOM over microbial DOM; (iii) microbial DOM is a more important contributor to LPM fouling than terrestrial DOM, relative to their respective concentrations in source waters; and (iv) the fluorescence intensity of microbial DOM in source waters can be used as a quantitative indicator of the ability of MIEX to reduce their membrane fouling potential. Thus, when ion exchange resin processes are used for DOM removal towards membrane fouling reduction, it is advisable to use a resin that has been designed to effectively remove microbial DOM.

Evaluating Evidence for Association of Human Bladder Cancer with Drinking-Water Chlorination Disinfection By-Products.

Exposure to chlorination disinfection by-products (CxDBPs) is prevalent in populations using chlorination-based methods to disinfect public water supplies. Multifaceted research has been directed for decades to identify, characterize, and understand the toxicology of these compounds, control and minimize their formation, and conduct epidemiologic studies related to exposure. Urinary bladder cancer has been the health risk most consistently associated with CxDBPs in epidemiologic studies. An international workshop was held to (1) discuss the qualitative strengths and limitations that inform the association between bladder cancer and CxDBPs in the context of possible causation, (2) identify knowledge gaps for this topic in relation to chlorine/chloramine-based disinfection practice(s) in the United States, and (3) assess the evidence for informing risk management. Epidemiological evidence linking exposures to CxDBPs in drinking water to human bladder cancer risk provides insight into causality. However, because of imprecise, inaccurate, or incomplete estimation of CxDBPs levels in epidemiologic studies, translation from hazard identification directly to risk management and regulatory policy for CxDBPs can be challenging. Quantitative risk estimates derived from toxicological risk assessment for CxDBPs currently cannot be reconciled with those from epidemiologic studies, notwithstanding the complexities involved, making regulatory interpretation difficult. Evidence presented here has both strengths and limitations that require additional studies to resolve and improve the understanding of exposure response relationships. Replication of epidemiologic findings in independent populations with further elaboration of exposure assessment is needed to strengthen the knowledge base needed to better inform effective regulatory approaches.

Anion exchange resins as a source of nitrosamines and nitrosamine precursors.

Anion exchange resins are important tools for the removal of harmful anionic contaminants from drinking water, but their use has been linked to the presence of carcinogenic nitrosamines in treated drinking water. In bench-scale batch and column experiments, anion exchange resins from a large, representative group were investigated as sources of the nitrosamines N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), N-nitrosodi-n-propylamine (NDPA), and N-nitrosodi-n-butylamine (NDBA) and their precursors. Several resins were found to release high levels (up to >2000 ng/L, orders of magnitude above drinking water regulatory levels) of nitrosamines upon initial rinsing with lab-grade water, with levels subsiding within 50-100 bed volumes of rinsing. Resins released similarly high levels of nitrosamine precursors, with spikes in precursor release triggered by regeneration of resins with sodium chloride or by interruptions in flow resulting in prolonged contact times. Free chlorine or preformed monochloramine in feedwater led to the production of nitrosamines. Resins released different nitrosamines and precursors depending on their functional groups, with some resins releasing as many as three different nitrosamines and their precursors. These findings have significant implications for the pretreatment and appropriate use of anion exchange resins by drinking water utilities and for the production of anion exchange resins by manufacturers.

Effect of magnetic ion exchange and ozonation on disinfection by-product formation.

The purpose of this research was to investigate the performance of treatment with magnetic ion exchange (MIEX) resin followed by ozonation in achieving disinfection goals while controlling bromate and chlorinated disinfection by-product (DBP) formation. Three water samples were collected from raw water supplies impacted by the San Francisco Bay Delta to represent the varying levels of bromide and total organic carbon (TOC) that occur throughout the year. A fourth water was prepared by spiking bromide into a portion of one of the samples. Samples of each water were pre-treated with alum or virgin MIEX resin, and the raw and treated waters were subsequently ozonated under semi-batch conditions to assess the impact of treatment on ozone demand, ozone exposure for disinfection ("CT"), and bromate formation. Finally, aliquots of raw, coagulated, resin-treated, and ozonated waters were chlorinated in order to measure trihalomethane formation potential (THMFP). In the waters studied, MIEX resin removed 41-68% of raw water TOC, compared to 12-44% for alum. MIEX resin also reduced the bromide concentration by 20-50%. The removal of TOC by alum and MIEX resin significantly reduced the ozone demand of all waters studied, resulting in higher dissolved ozone concentrations and CT values for a given amount of ozone transferred into solution. For a given level of disinfection (CT), the amount of bromate produced by ozonation of MIEX-treated waters was similar to or slightly less than that of raw water and significantly less than that of alum-treated water. MIEX resin removed 39-85% of THMFP compared to 16-56% removal by alum. Ozonation reduced THMFP by 35-45% in all cases. This work indicates that in bromide-rich waters in which ozone disinfection is used, MIEX resin is a more appropriate treatment than alum for the removal of organic carbon, as it achieves superior TOC and THM precursor removal and decreases the production of bromate from ozone.

Comparison of trihalomethanes in tap water and blood: a case study in the United States.

BACKGROUND: Epidemiological studies have used various measures to characterize trihalomethane (THM) exposures, but the relationship of these indicators to exposure biomarkers remains unclear. OBJECTIVES: We examined temporal and spatial variability in baseline blood THM concentrations and assessed the relationship between these concentrations and several exposure indicators (tap water concentration, water-use activities, multiroute exposure metrics). METHODS: We measured water-use activity and THM concentrations in blood and residential tap water from 150 postpartum women from three U.S. locations. RESULTS: Blood ΣTHM [sum of chloroform (TCM), bromodichloromethane (BDCM), dibromo-chloromethane (DBCM), and bromoform (TBM)] concentrations varied by site and season. As expected based on variable tap water concentrations and toxicokinetic properties, the proportion of brominated species (BDCM, DBCM, and TBM) in blood varied by site (site 1, 24%; site 2, 29%; site 3, 57%) but varied less markedly than in tap water (site 1, 35%; site 2, 75%; site 3, 68%). The blood-water ΣTHM Spearman rank correlation coefficient was 0.36, with correlations higher for individual brominated species (BDCM, 0.62; DBCM, 0.53; TBM, 0.54) than for TCM (0.37). Noningestion water activities contributed more to the total exposure metric than did ingestion, but tap water THM concentrations were more predictive of blood THM levels than were metrics that incorporated water use. CONCLUSIONS: Spatial and temporal variability in THM concentrations was greater in water than in blood. We found consistent blood-water correlations across season and site for BDCM and DBCM, and multivariate regression results suggest that water THM concentrations may be an adequate surro-gate for baseline blood levels.

The effect of water disinfection by-products on pregnancy outcomes in two southeastern US communities.

OBJECTIVE: To determine if exposure to disinfection by-products (DBPs) during gestation increases the risk of adverse birth outcomes, specifically term small for gestational age (SGA) birth, preterm birth (PTB), and very PTB (<32 weeks' gestation). METHODS: We used weekly measurements total trihalomethanes (TTHMs), five haloacetic acids (HAA5), and total organic halides (TOX) collected from two distribution systems to evaluate the associations between DBP concentrations and term SGA, PTB, and very PTB using logistic regression. RESULTS: We found no associations between DBPs and term-SGA. In the site with higher concentrations of bromine-containing DBPs, we found an association between TOX and PTB; this association was larger, though less precise, for very PTB. CONCLUSIONS: Our results do not support an association between TTHMs or HAA5 and the birth outcomes investigated, but an association was found between increased TOX and PTB.

Occurrence and removal of pharmaceuticals and personal care products (PPCPs) in an advanced wastewater reclamation plant.

The occurrence of nineteen pharmaceutically active compounds and personal care products was followed monthly for 12 months after various stages of treatment in an advanced wastewater reclamation plant in Gwinnett County, GA, U.S.A. Twenty-four hour composite samples were collected after primary clarification, activated sludge biological treatment, membrane filtration, granular media filtration, granular activated carbon (GAC) adsorption, and ozonation in the wastewater reclamation plant. Compounds were identified and quantified using high performance liquid chromatography/tandem mass spectrometry (LC-MS/MS) and gas chromatography/mass spectrometry (GC-MS) after solid-phase extraction. Standard addition methods were employed to compensate for matrix effects. Sixteen of the targeted compounds were detected in the primary effluent; sulfadimethoxine, doxycycline, and iopromide were not found. Caffeine and acetaminophen were found at the highest concentrations (∼10(5) ng/L), followed by ibuprofen (∼10(4) ng/L), sulfamethoxazole and DEET (∼10(3) ng/L). Most of the other compounds were found at concentrations on the order of hundreds of ng/L. After activated sludge treatment and membrane filtration, the concentrations of caffeine, acetaminophen, ibuprofen, DEET, tetracycline, and 17α-ethynylestradiol (EE2) had decreased by more than 90%. Erythromycin and carbamazepine, which were resistant to biological treatment, were eliminated by 74 and 88%, on average, by GAC. Primidone, DEET, and caffeine were not amenable to adsorption by GAC. Ozonation oxidized most of the remaining compounds by >60%, except for primidone and DEET. Of the initial 16 compounds identified in the primary effluent, only sulfamethoxazole, primidone, caffeine and DEET were frequently detected in the final effluent, but at concentrations on the order of 10-100 ng/L. Removal of the different agents by the various treatment processes was related to the physical-chemical properties of the compounds.

Removal of bromide and natural organic matter by anion exchange.

Bromide removal by anion exchange was explored for various water qualities, process configurations, and resin characteristics. Simulated natural waters containing different amounts of natural organic matter (NOM), bicarbonate, chloride, and bromide were treated with a polyacrylate-based magnetic ion exchange (MIEX) resin on a batch basis to evaluate the effectiveness of the resin for removal of bromide. While bromide removal was achieved to some degree, alkalinity (bicarbonate), dissolved organic carbon (DOC), and chloride were shown to inhibit bromide removal in waters with bromide concentrations of 100 and 300 microg/L. Water was also treated using a two-stage batch MIEX process. Two-stage treatment resulted in only a slight improvement in bromide removal compared to single-stage treatment, presumably due to competition with the high concentration of chloride which is present along with bromide in natural waters. In view of the relatively poor bromide removal results for the MIEX resin, a limited set of experiments was performed using polystyrene resins. DOC and bromide removal were compared by treating model waters with MIEX and two polystyrene resins, Ionac A-641 and Amberlite IRA910. The two polystyrene resins were seen to be more effective for bromide removal, while the MIEX resin was more effective at removing DOC.

Removal of dissolved organic matter by anion exchange: effect of dissolved organic matter properties.

Ten isolates of aquatic dissolved organic matter (DOM) were evaluated to determine the effect that chemical properties of the DOM, such as charge density, aromaticity, and molecular weight, have on DOM removal by anion exchange. The DOM isolateswere characterized as terrestrial, microbial, or intermediate humic substances or transphilic acids. All anion exchange experiments were conducted using a magnetic ion exchange (MIEX) resin. The charge density of the DOM isolates, determined by direct potentiometric titration, was fundamental to quantifying the stoichiometry of the anion exchange mechanism. The results clearly show that all DOM isolates were removed by anion exchange; however, differences among the DOM isolates did influence their removal by MIEX resin. In particular, MIEX resin had the greatest affinity for DOM with high charge density and the least affinity for DOM with low charge density and low aromaticity. This work illustrates that the chemical characteristics of DOM and solution conditions must be considered when evaluating anion exchange treatment for the removal of DOM.

Impact of simulated solar irradiation on disinfection byproduct precursors.

The Sacramento-San Joaquin Delta is the major drinking water source for 23 million California residents. Consequently, many studies have examined disinfection byproduct (DBP) formation in relation to Delta dissolved organic carbon (DOC) concentration. However, DOC characteristics within the Delta are not the same as those entering downstream water treatment facilities. As water is transferred to Southern California through the California Aqueduct, a 714.5 km-open channel, it is exposed to sunlight, potentially altering DBP precursors. We collected water from three sites within the Delta and one nearthe California Aqueduct, representing different DOC sources, and irradiated them in a solar simulator at a dose equivalent to that received during four days conveyance in the aqueduct. Photolytic changes in DOC were assessed by measuring CO2 and organic acid production, fluorescence, and ultraviolet absorbance over time. Trihalomethane (THM) and haloacetic acid (HAA) formation potentials, as well as the distribution of hydrophobic, transphilic, and hydrophilic acid fractions were determined at exposures equivalent to one and four days. Solar irradiation significantly decreased ultraviolet absorbance and fluorescence intensity, produced organic acids, and increased the hydrophilic fraction of waters. These changes in DOC caused a shift in bromine incorporation among the THM and HAA species. Our results are the first to demonstrate the importance of sunlight in altering DOC with respect to DBP formation.

Development and interpretation of disinfection byproduct formation models using the Information Collection Rule database.

Multiple linear regression models were used to examine relationships between water quality, treatment, and disinfection byproduct (DBP) formation in Information Collection Rule field data. Finished water models were specified using a cross-validation approach based on data for 225 free chlorine treatment plants. Turbidity, bromide, temperature, alkalinity, total organic carbon, ultraviolet absorbance at 254 nm, pH, chlorine residual, chlorine consumed, and chlorine contact time were employed as independent variables. Important trends within the trihalomethane, dihaloacetic acid, and trihaloacetic acid classes were observed. Bromide was a significant predictor for all DBP species and its influence changed in sign and magnitude with the extent of bromine substitution. A similar pattern followed by alkalinity suggested it plays an important role as an indicator of natural organic matter hydrophobicity and reactivity. Chlorine consumed and organic precursor variables were significant predictors in almost all DBP species models, exhibiting trends opposite to those for alkalinity and bromide. Temperature was the most significant variable in chloroform and chloral hydrate models and its significance declined with increasing bromine substitution within the trihalomethane class. pH had a strong positive influence on chloroform formation, a negative influence on trihaloacetic acid formation, and no influence on dihaloacetic acid formation.

Drinking water disinfection by-product exposure and fetal growth.

BACKGROUND: Previous studies suggest that elevated exposure to drinking water disinfection by-products (DBPs)--in particular, total trihalomethanes (TTHMs)--may lead to fetal growth restriction. We examined the effects of exposure to TTHMs, haloacetic acids, and total organic halide on the probability of delivering a small-for-gestational-age (SGA) infant and on birth weight at term. METHODS: Women early in pregnancy (< or =12 weeks' gestation) or planning a pregnancy were enrolled in a prospective pregnancy study conducted in 3 US communities from 2000 through 2004. Weekly (or biweekly) water samples were collected at each site as well as individual-level participant data. Associations between DBP exposures (TTHMs, haloacetic acids, total organic halide) and fetal growth were assessed using log-binomial regression for SGA (n = 1958) and linear regression for term birth weight (n = 1854). We conducted a Bayesian analysis to examine associations between individual DBP species and fetal growth. RESULTS: Haloacetic acids and total organic halide were not associated with SGA or term birth weight. The probability of delivering an SGA infant was elevated when comparing women with an average third-trimester residential TTHM concentration > or =80 microg/L to women with exposure <80 microg/L (risk ratio = 2.0 [95% confidence interval = 1.1-3.6]), but not when examining other exposure contrasts. Bayesian analyses did not support a consistent association between any DBP species and fetal growth, although these analyses were based on small sample sizes. CONCLUSIONS: Our results do not suggest an adverse effect of haloacetic acid or total organic halide exposure on fetal growth. An association of TTHM with SGA was seen only for average residential concentrations above the current regulatory standard.

Drinking water disinfection by-product exposure and duration of gestation.

BACKGROUND: Recent studies suggest elevated exposure to drinking water disinfection by-products (DBPs) may be associated with decreased risk of preterm birth. We examined this association for exposure to total trihalomethanes (TTHMs), 5 haloacetic acids (HAA5), and total organic halides. METHODS: Analysis included 2039 women in a prospective pregnancy study conducted from 2000 through 2004 in 3 study sites. Water samples were collected and analyzed for DBP concentrations. Participant data were collected through interviews, an early ultrasound, and birth records. We assessed the associations between DBPs and preterm birth (<37-weeks' gestation) using log-binomial regression. Discrete-time hazard analysis was used to model the conditional odds of delivery each week in relation to DBP exposure. RESULTS: Average second trimester DBP levels were associated with lower risk of preterm birth. Adjusted risk ratios for TTHM levels of 33.1-55.0, 55.1-66.3, 66.4-74.8, and 74.9-108.8 microg/L versus 2.2-4.6 microg/L were 0.8 (95% confidence intervals = 0.5-1.3), 0.9 (0.6-1.4), 0.7 (0.4-1.1), and 0.5 (0.3-0.9), respectively. Risk ratios for HAA5 levels of 17.9-22.0, 22.1-31.5, 31.6-40.4, and 40.5-52.8 microg/L versus 0-0.9 microg/L were 1.1 (0.8-1.7), 0.8 (0.5-1.2), 0.5 (0.3-0.8), and 0.7 (0.4-1.1), respectively. The conditional odds of delivery each week were decreased for the highest TTHM and HAA5 exposure groups versus the low exposure group for gestational weeks 33-40. CONCLUSIONS: The probability of preterm birth was not increased with high DBP exposure.

Drinking water disinfection by-products and time to pregnancy.

BACKGROUND: Laboratory evidence suggests tap water disinfection by-products (DBPs) could have an effect very early in pregnancy, typically before clinical detectability. Undetected early losses would be expected to increase the reported number of cycles to clinical pregnancy. METHODS: We investigated the association between specific DBPs (trihalomethanes, haloacetic acids, brominated-trihalomethanes, brominated-haloacetic acids, total organic halides, and bromodichloromethane) and time to pregnancy among women who enrolled in a study of drinking water and reproductive outcomes. We quantified exposure to DBPs through concentrations in tap water, quantity ingested through drinking, quantity inhaled or absorbed while showering or bathing, and total integrated exposure. The effect of DBPs on time to pregnancy was estimated using a discrete time hazard model. RESULTS: Overall, we found no evidence of an increased time to pregnancy among women who were exposed to higher levels of DBPs. A modestly decreased time to pregnancy (ie, increased fecundability) was seen among those exposed to the highest level of ingested DBPs, but not for tap water concentration, the amount absorbed while showering or bathing, or the integrated exposure. CONCLUSIONS: Our findings extend those of a recently published study suggesting a lack of association between DBPs and pregnancy loss.

Stoichiometry of removal of natural organic matter by ion exchange.

Five anion exchange resins, including a magnetic ion exchange (MIEX) resin, were evaluated for removal of Suwannee River Fulvic Acid (SRFA) in the presence of bicarbonate and chloride. The charge density of SRFA, obtained by potentiometric titration, was used to perform charge balances for ion exchange reactions involving SRFA, bicarbonate, and chloride under different solution conditions. The results clearly show the equivalence of SRFA uptake and chloride release by ion exchange. Although the structure of the anion exchange resins did not affect the stoichiometry of the reaction, the polyacrylic resins did exhibit greater removal of SRFA than the polystyrene resins. The hindered removal of SRFA by the polystyrene resins was hypothesized to be a result of size exclusion. The MIEX resin, which has a polyacrylic structure, performed similarly to the other polyacrylic resins. For the MIEX resin, the separation factor for SRFA over chloride was approximately 8 times greater than for bicarbonate over chloride. This work provides an improved understanding of the interactions between natural organic matter (NOM), inorganic anions, and anion exchange resins, and should result in more effective applications of ion exchange for the removal of NOM in the treatment of drinking water.

Modeling the removal of dissolved organic carbon by ion exchange in a completely mixed flow reactor.

A mathematical model was developed to describe removal of dissolved organic carbon (DOC) by a macroporous, strong-base anion exchange resin in a completely mixed flow reactor with resin recycle and partial resin regeneration. The two-scale model consisted of a microscale model describing the uptake of DOC by the resin coupled with a macroscale model describing the continuous-flow process. Equilibrium and kinetic parameters were estimated from batch laboratory experiments. The model was validated using continuous-flow data from two pilot plant studies. Model predictions were found to be in good agreement with the observed pilot plant data.

The healthy men study: an evaluation of exposure to disinfection by-products in tap water and sperm quality.

BACKGROUND: Chlorination of drinking water generates disinfection by-products (DBPs), which have been shown to disrupt spermatogenesis in rodents at high doses, suggesting that DBPs could pose a reproductive risk to men. In this study we assessed DBP exposure and testicular toxicity, as evidenced by altered semen quality. METHODS: We conducted a cohort study to evaluate semen quality in men with well-characterized exposures to DBPs. Participants were 228 presumed fertile men with different DBP profiles. They completed a telephone interview about demographics, health history, water consumption, and other exposures and provided a semen sample. Semen outcomes included sperm concentration and morphology, as well as DNA integrity and chromatin maturity. Exposures to DBPs were evaluated by incorporating data on water consumption and bathing and showering with concentrations measured in tap water. We used multivariable linear regression to assess the relationship between exposure to DBPs and adverse sperm outcomes. RESULTS: The mean (median) sperm concentration and sperm count were 114.2 (90.5) million/mL and 362 (265) million, respectively. The mean (median) of the four trihalomethane species (THM4) exposure was 45.7 (65.3) microg/L, and the mean (median) of the nine haloacetic acid species (HAA9) exposure was 30.7 (44.2) microg/L. These sperm parameters were not associated with exposure to these classes of DBPs. For other sperm outcomes, we found no consistent pattern of increased abnormal semen quality with elevated exposure to trihalomethanes (THMs) or haloacetic acids (HAAs). The use of alternate methods for assessing exposure to DBPs and site-specific analyses did not change these results. CONCLUSIONS: The results of this study do not support an association between exposure to levels of DBPs near or below regulatory limits and adverse sperm outcomes in humans.

Redox reactions in the Fe-As-O2 system.

We have examined two redox reactions involving arsenic and iron at near-neutral pH: the reduction of As(V) by Fe(II) under anoxic conditions, and the co-oxidation of As(III) during Fe(II) oxygenation. We also considered the impact of goethite, pH buffers, and radical scavengers on these reactions. In a series of anoxic experiments, Fe(II) was found to reduce As(V) in the presence of goethite, but not in homogeneous solution. The reaction rate increased with increasing pH and Fe(II) concentration, but in all cases was relatively slow. In aerobic experiments, the kinetics of Fe(II) oxygenation at neutral pH, and the corresponding oxidation of As(III) were found to depend heavily on pH buffer type and concentration. The classic formulation of Fe(II) oxidation by oxygen, involving four single-electron transfers, was reviewed and found to be inadequate for explaining observed oxidation of Fe(II) and As(III). Widely cited rate constants for Fe(II) oxygenation originate from experiments conducted in carbonate buffer, and do not match observations made in phosphate, MES, or HEPES systems. In phosphate buffer, Fe(II) oxidation is rapid and dependent on phosphate concentration. In MES and HEPES buffers, Fe(II) oxidation is much slower due to the lack of labile ferrous iron species. Oxygenation of Fe(II) appears to proceed through different mechanisms in phosphate and MES or HEPES systems. In both cases, reactive intermediary species are produced which can oxidize As(III). These oxidants are not the hydroxyl radical, but may be Fe(IV) species.

UV degradation kinetics and modeling of pharmaceutical compounds in laboratory grade and surface water via direct and indirect photolysis at 254 nm.

Direct and indirect photolysis of pharmaceutically active compounds (PhACs) was investigated in laboratory-grade water (LGW) and a local surface water using a low-pressure ultraviolet batch reactor. The PhACs selected in this study belong to different therapeutic classes and are known to occur in environmental samples. Fundamental photolysis and advanced oxidation process parameters obtained in LGW (such as the decadic molar absorption coefficient, quantum yield, and degradation rate constants) are reported and discussed. These parameters, together with the incident photon irradiance, solution depth, and solution absorbance were used to develop UV and UV/ H202 photolysis models that were compared with experimental results obtained in the surface water. The model predicted the experimental UV photolysis removals well but underestimated the UV/H2O2 photolysis results. These models were used to discuss the effects of optical path length and H2O2 concentration on the UV-based rate constant predictions.