Electrocatalytic water treatment of per- and polyfluoroalkyl substances reduces adsorbable organofluorine and bioaccumulation potential.

Per- and polyfluoroalkyl substances (PFAS) are pervasive in industrial processes, eliciting public concern upon their release into municipal sewers or the environment. Removing PFAS from the environment has become an urgent need. However, because potential endpoints span from energy-intensive complete mineralization to partial PFAS transformation, understanding and developing metrics for evaluating PFAS treatment can be a challenge. The goal of this study was to evaluate and compare the effectiveness of electrocatalytic degradation of PFAS with boron-doped diamond (BDD) electrodes using four techniques: LC-MS/MS target analysis, fluoride ion (F-), adsorbable organofluorine (AOF), and bioaccumulation potential using lipid-bilayer partition (LBP) tests. After 3 hours of electrocatalysis, >99% perfluorooctanoic acid (PFOA) degradation was achieved and corresponded with 84% conversion to F-, which was substantial - though intentionally not complete - defluorination. For the same 3 hour treatment time, AOF and LBP coefficient were reduced by 95% and 83%, respectively. LBP's detection limit was 2 orders of magnitude higher than that of AOF, so the positive correlation observed between LBP and AOF (r = 0.86) suggests AOF's practical utility as a design metric for assessing bioaccumulation potential of various organofluorine transformation by-products.

Advanced oxidation processes may transform unknown PFAS in groundwater into known products.

Per- and polyfluoroalkyl substances (PFAS) are a group of fluorinated organic contaminants classified as persistent in the aquatic environment. Early studies using targeted analysis approaches to evaluate the degradation of PFAS by advanced oxidation processes (AOP) in real water matrices may have been misinterpreted due to the presence of undetected or unknown PFAS in these matrices. The aims of the present study were to (1) screen selected commercially available AOPs (UV, UV + H2O2, O3/H2O2) and UV photocatalysis in a pilot system using commercially used and novel photocatalysts (TiO2, boron nitride [BN]) for removing PFAS contaminants and (2) evaluate their role on the conversion of non-detected/unknown to known PFAS compounds in real groundwater used as drinking water supplies. Results indicated that, while AOPs have the potential to achieve removal of the EPA method 533 target PFAS compounds (PFDA [100%], PFNA [100%], PFOA [85-94%], PFOS [25-100%], PFHxS [3-100%], PFPeS [100%], PFBS [100%]), AOPs transformed non-detected/unknown longer-chain PFAS compounds to detectable shorter-chain ones under very high-dose AOP operating conditions, leading to an increase in ∑PFAS concentration ranging from 95% to 340%. As emerging PFAS treatment processes transition from lab-scale investigations of target PFAS to pilot testing of real water matrices, studies will need to consider impact of the presence of non-target long-chain PFAS to transform into targeted PFAS compounds. A promising approach to address the potential risks and unforeseen consequences could involve an increased reliance on adsorbable organic fluorine (AOF) analysis before and after advanced oxidation process (AOP) treatment.

Mechanistic Study of Arsenate Adsorption onto Different Amorphous Grades of Titanium (Hydr)Oxides Impregnated into a Point-of-Use Activated Carbon Block.

Millions of households still rely on drinking water from private wells or municipal systems with arsenic levels approaching or exceeding regulatory limits. Arsenic is a potent carcinogen, and there is no safe level of it in drinking water. Point-of-use (POU) treatment systems are a promising option to mitigate arsenic exposure. However, the most commonly used POU technology, an activated carbon block filter, is ineffective at removing arsenic. Our study aimed to explore the potential of impregnating carbon blocks with amorphous titanium (hydr)oxide (THO) to improve arsenic removal without introducing titanium (Ti) into the treated water. Four synthesis methods achieved 8-16 wt.% Ti loading within the carbon block with 58-97% amorphous THO content. The THO-modified carbon block could adsorb both oxidation states of arsenic (arsenate and arsenite) in batch or column tests. Modified carbon block with higher Ti and amorphous content always led to better arsenate removal, achieving arsenic loadings up to 31 mg As/mg Ti after 70,000 bed volumes in continuous flow tests. Impregnating carbon block with amorphous THO consistently outperformed impregnation using crystalline TiO2. The best-performing system (TTIP-EtOH carbon block) was an amorphous THO derived using titanium isopropoxide, ethanol, and acetic acid via sol-gel technique, aged at 80° for 18 hours and dried overnight at 60°. Comparable pore size distribution and surface area of the impregnated carbon blocks suggested that chemical properties play a more crucial role than physical and textural properties in removing arsenate via amorphous Ti-impregnated carbon block. Freundlich isotherms indicated energetically favorable adsorption for amorphous chemically synthesized adsorbents. The mass transport coefficients for the amorphous TTIP-EtOH carbon block were fitted using a pore surface diffusion model, resulting in Dsurface = 3.1×10-12 cm2/s and Dpore = 3.2×10-6 cm2/s. Impregnating the carbon block with THO enabled effective arsenic removal from water without adversely affecting the pressure drop across the unit or the carbon block's ability to remove polar organic chemical pollutants efficiently.

Opportunities for in situ electro-regeneration of organic contaminant-laden carbonaceous adsorbents.

Adsorptive separation technologies have proven to be effective on organic contaminant removal in aqueous water. However, the breakthrough of contaminants is inevitable and can be at relatively low bed volumes, which makes the regeneration of spent adsorbents an urgent need. Electrochemically induced regeneration processes are given special attention and may provide ease of operation through in situ regeneration avoiding (i) removal and transport adsorbents, and (ii) avoiding use of hazardous chemicals (i.e., organic solvents, acids, or bases). Therefore, this review article critically evaluates the fundamental aspects of in situ electro-regeneration for spent carbons, and later discusses specific examples related to the treatment of emerging contaminants (such as per- and polyfluoroalkyl substances or PFAS). The fundamental concepts of electrochemically driven processes are comprehensively defined and addressed in terms of (i) adsorbent characteristics, (ii) contaminant properties, (iii) adsorption/regeneration driving operational parameters and conditions, and (iv) the competitive effects of water matrices. Additionally, future research needs and challenges to enhance understanding of in situ electro-regeneration applications for organic contaminants (specifically PFAS)-laden adsorbents are identified and outlined as a future key perspective.

Do Surface Charges on Polymeric Filters and Airborne Particles Control the Removal of Nanoscale Aerosols by Polymeric Facial Masks?

The emergence of facial masks as a critical health intervention to prevent the spread of airborne disease and protect from occupational nanomaterial exposure highlights the need for fundamental insights into the interaction of nanoparticles (<200 nm) with modern polymeric mask filter materials. While most research focuses on the filtration efficiency of airborne particles by facial masks based on pore sizes, pressure drop, or humidity, only a few studies focus on the importance of aerosol surface charge versus filter surface charge and their role in the net particle filtration efficiency of mask filters. In this study, experiments were conducted to assess mask filter filtration efficiency using positively and negatively charged polystyrene particles (150 nm) as challenge aerosols at varying humidity levels. Commercial masks with surface potential (Ψf) in the range of -10 V to -800 V were measured by an electrostatic voltmeter and used for testing. Results show that the mask filtration efficiency is highly dependent on the mask surface potential as well as the charge on the challenge aerosol, ranging from 60% to 98%. Eliminating the surface charge results in a maximum 43% decrease in filtration efficiency, emphasizing the importance of electrostatic charge interactions during the particle capture process. Moreover, increased humidity can decrease the surface charge on filters, thereby decreasing the mask filtration efficiency. The knowledge gained from this study provides insight into the critical role of electrostatic attraction in nanoparticle capture mechanisms and benefits future occupational and environmental health studies.

Implication of cell culture methods and biases on UV inactivation of viruses.

Inactivation of human respiratory viruses in air and on surfaces is important to control their spread. Exposure to germicidal ultraviolet (UV-C) light damages viral nucleic acid rendering them non-infectious. Most of the recent viral inactivation studies have not considered potential artifacts caused by interactions between UV-C light and culture media used to suspend and deposit virus on surfaces. We show that the reactive oxygen and nitrogen species (ROS and RNS) form when commonly used virus culture media is exposed to 265 nm irradiation from light emitting diodes (LEDs) at UV-C doses (4 or 40 mJ/cm2) commonly considered to achieve multiple log-inactivation of virus. Surface viral inactivation values were enhanced from 0.49 to 2.92 log10 of viruses in DMEM, EMEM or EMEM-F as compared to absence of culture media (only suspended in Tris-buffer). The mechanisms responsible for the enhanced surface inactivate is hypothesized to involve photo-activation of vitamins and dyes present in the culture media, deposited with the virus on surfaces to be disinfected, which produce ROS and RNS. Given the rapidly growing research and commercial markets for UV-C disinfecting devices, there is a need to establish surface disinfecting protocols that avoid viral inactivation enhancement artifacts associated with selection and use of common cell culture media in the presence of UV-C light. This study addresses this weak link in the literature and highlights that inadequate selection of virus suspension media may cause a bias (i.e., over-estimation) for the UV-C dosages required for virus inactivation on surfaces.

Pretreatment strategies for ion exchange to control brominated disinfection byproducts in potable reuse.

The application of ion exchange (IX) resins to remove disinfection byproduct (DBP) precursors in wastewater effluents is challenging due to relatively high concentrations of competing anions. This study examined various pretreatment strategies to target competing ions to improve IX removal of DBP precursors, bromide and dissolved organic matter (DOM), measured as trihalomethane and haloacetic acid formation potentials (THMFP and HAAFP). IX batch experiments were performed with four commercial anion exchange (AIX) resins selective for bromide (BrP), DOM (A860), sulfate (MTA) and PFOA/PFOS (PFA), and one cation exchange (CIX) resin selective for iodide (CT). For single AIX treatments the bromide removal ranking was the following: PFA (58%) > MTA (51%) > BrP (43%) > A860 (16%), which corresponded with decreasing brominated THMFP removals and increasing bromine incorporation factors. For dual AIX combinations (PFA and BrP, MTA and BrP), either simultaneous or sequential treatments had the highest bromide (PFA + BrP [69%], MTA + BrP [67%], (PFA→BrP [77%], MTA→BrP [74%]) and Br-THMFP (THMFP [∼80%]) and Br-HAAFP (HAAFP [∼77%]) removals, and therefore the lowest fractions of brominated DBPs (Br-DBPs). Despite ozone (O3), biological active carbon (BAC), and granular activated carbon (GAC) pretreatments reducing the overall DOM concentration (33%), these pretreatment steps did not improve the bromide removals of the resins, although it did increase the Br-THMFP and Br-HAAFP removals by 2-38% and 13-20%, respectively. Nanofiltration (NF) pretreatment significantly removed sulfate (97%) resulting in an increased bromide removal of 19% by the AIX resins, which led to increased removal of Br-THMFP and Br-HAAFP by 93% and 96%, respectively. Among all the IX resins the CT resin had the highest bromide removal (83%) and lowest fraction of Br-DBPs. The results reveal pretreatment with existing technologies including AIX, O3/BAC/GAC, or NF can potentially enhance the removal of brominated DBP precursors by IX resins during potable reuse applications.

Preferential Halogenation of Algal Organic Matter by Iodine over Chlorine and Bromine: Formation of Disinfection Byproducts and Correlation with Toxicity of Disinfected Waters.

The increasing occurrence of harmful algal blooms (HABs) in surface waters may increase the input of algal organic matter (AOM) in drinking water. The formation of halogenated disinfection byproducts (DBPs) during combined chlorination and chloramination of AOM and natural organic matter (NOM) in the presence of bromide and iodide and haloform formation during halogenation of model compounds were studied. Results indicated that haloform/halogen consumption ratios of halogens reacting with amino acids (representing proteins present in AOM) follow the order iodine > bromine > chlorine, with ratios for iodine generally 1-2 orders of magnitude greater than those for chlorine (0.19-2.83 vs 0.01-0.16%). This indicates that iodine is a better halogenating agent than chlorine and bromine. In contrast, chlorine or bromine shows higher ratios for phenols (representing the phenolic structure of humic substances present in NOM). Consistent with these observations, chloramination of AOM extracted from Microcystis aeruginosa in the presence of iodide produced 3 times greater iodinated trihalomethanes than those from Suwannee River NOM isolate. Cytotoxicity and genotoxicity of disinfected algal-impacted waters evaluated by Chinese hamster ovary cell bioassays both follow the order chloramination > prechlorination-chloramination > chlorination. This trend is in contrast to additive toxicity calculations based on the concentrations of measured DBPs since some toxic iodinated DBPs were not identified and quantified, suggesting the necessity of experimentally analyzing the toxicity of disinfected waters. During seasonal HAB events, disinfection practices warrant optimization for iodide-enriched waters to reduce the toxicity of finished waters.

Predictive modeling of haloacetonitriles under uniform formation conditions.

The objective of this study was to develop models to predict the formation of HANs under uniform formation conditions (UFC) in chlorinated, choraminated, and perchlorinated/chloraminated waters of different origins. Model equations were developed using multiple linear regression analysis to predict the formation of dichloroacetonitrile (DCAN), HAN4 (trichloroacetonitrile [TCAN], DCAN, bromochloroacetonitrile [BCAN], and dibromoacetonitrile [DBAN]) and HAN6 (HAN4 plus monochloroacetonitrile, monobromoacetonitrile). The independent variables covered a wide range of values, and included ultraviolet absorbance,(UV254) dissolved organic carbon (DOC), dissolved organic nitrogen (DON), specific UV absorbance at 254 (SUVA254), bromide (Br-), pH, oxidant dose, contact time, and temperature. The regression coefficients (r2) of HAN4 and HAN6 models for natural organic matter (NOM), algal organic matter (AOM), and effluent organic matter (EfOM)  impacted waters were within the range of 60-88%, while the r2 values of HAN4 and DCAN models for both groundwater and distribution systems were lower, in the range of 41-66%. The r2 values for the DCAN model were mostly higher in the individual types as compared to the cumulative analysis of all source water data together. This was attributed to differences in HAN precursor characteristics. For chlorination, among all variables, pH was found to be the most significant descriptor in the model equations describing the formation of DCAN, HAN4, and HAN6, and it was negatively correlated with HAN formation in the distribution system, groundwater, AOM, and NOM samples, while it showed an inverse relationship with HAN6 formation in EfOM impacted waters. During chloramination, pH was the most influential model descriptor for DCAN formation in the NOM. Prechlorination dose was the most predominant parameter for prechlorination/chloramination, and it was positively correlated with HAN4 formation in AOM impacted waters.

Toxicity of chlorinated algal-impacted waters: Formation of disinfection byproducts vs. reduction of cyanotoxins.

Seasonal algal blooms in surface waters can impact water quality through an input of algal organic matter (AOM) to the pool of dissolved organic matter as well as the release of cyanotoxins. The formation and speciation of disinfection byproducts (DBPs) during chlorination of algal-impacted waters, collected from growth of Microcystis aeruginosa were studied. Second-order rate constants for the reactions of microcystins (MCs) with chlorine and bromine were determined. Finally, the toxicity of chlorinated algal-impacted waters was evaluated by Chinese hamster ovary (CHO) cytotoxicity and genotoxicity assays. Under practical water treatment conditions, algal-impacted waters produced less regulated trihalomethanes (THMs) and haloacetic acids (HAAs), haloacetonitriles (HANs), and total organic halogen (TOX) than natural organic matter (NOM). For example, the weight ratios of DBP formation from AOM to NOM (median levels) were approximately 1:5, 1:3, 1:2 and 1:3 for THMs, HAAs, HANs, and TOX, respectively. Increasing initial bromide level significantly enhanced THM and HAN concentrations, and therefore unknown TOX decreased. The second-order rate constant for the reactions of MC-LR (the most common MC species) with chlorine was 60 M-1 s-1 at pH 7.5 and 21 °C, and the rate constants for MC congeners follow the order: MC-WR > MC-LW > MC-YR > MC-LY > MC-LR ≈ MC-RR. The reaction rate constant of bromine with MC-LR is two orders of magnitude higher than that of chlorine. Unchlorinated algal-impacted waters were toxic owning to the presence of MCs, and chlorination enhanced their cytotoxicity and genotoxicity due to the formation of toxic halogenated DBPs. However, the toxicity of treated waters depended on the evolution of cyanotoxins and formation of DBPs (particularly unknown or emerging DBPs).

Removal of bromide from natural waters: Bromide-selective vs. conventional ion exchange resins.

The presence of bromide (Br-) in water results in the formation of brominated disinfection byproducts (DBPs) after chlorination, which are much more cytotoxic and genotoxic than their chlorinated analogs. Given that conventional water treatment processes (e.g., coagulation, flocculation, and sedimentation) fail to remove Br- effectively, in this study, we systematically tested and compared the performance of different anion exchange resins, particularly two novel Br-selective resins, for the removal of Br-. The resins performance was evaluated under both typical and challenging background water conditions by varying the concentrations of anions and organic matter. The overall Br- removal results followed the trend of Purolite-Br ≥ MIEX-Br > IRA910 ≥ IRA900 > MIEX-Gold > MIEX-DOC. Further evaluation of Purolite-Br resin showed Br- removal efficiencies of 93.5 ±â€¯4.5% for the initial Br- concentration of 0.25 mg/L in the presence of competing anions (i.e., Cl-, NO3-, NO2-, SO42-, PO43-, and a mixture of all five), alkalinity and organic matter. In addition, experiments under challenging background water conditions confirmed the selectivity of the resins (i.e. Purolite-Br and MIEX-Br) in removing Br-, with SO42- and Cl- exhibiting the greatest influence upon the resin performance followed by NOM concentration, regardless of the NOM characteristic. After Br- removal, both the subsequent formation of brominated DBPs (trihalomethanes, haloacetic acids, and haloacetonitriles), and the total organic halogens (TOX), decreased by ∼90% under the uniform formation conditions. Overall, Br-selective resins represent a promising alternative for the efficient control of Br-DBPs in water treatment plants.

Chloramination of iodide-containing waters: Formation of iodinated disinfection byproducts and toxicity correlation with total organic halides of treated waters.

The formation of iodinated disinfection byproducts (I-DBPs) in drinking waters is of a concern due to their higher cyto- and genotoxicity than their chlorinated and brominated analogues. This study investigated the formation of I-DBPs under chloramination conditions using preformed chloramine and associated cyto- and geno-toxicities obtained with Chinese Hamster Ovary (CHO) cell assay. Cyto- and geno-toxicity of the samples were also calculated using DBP toxicity index values and correlated with total organic halide (TOX) formation. In low iodide (I-) (0.32 µM, 40 µg L-1) water, increasing dissolved organic carbon (DOC) concentration of selected waters from 0.1 to 0.25 mg L-1 increased the formation of iodinated trihalomethanes (I-THMs), while further increases from 0.25 to 4 mg L-1 produced an opposite trend. In high iodide water (3.2 µM, 400 µg L-1), increasing DOC from 0.5 to 4 mg L-1 gradually increased the I-THM formation, while a decrease was observed at 5.4 mg L-1 DOC. Iodoform was the most influenced species from the changes in DOC concentration. While increasing the initial iodide concentration from 0 to 5 µM increased the formation of iodoform, it did not make any considerable impact on the formation of other I-THMs. The measured cytotoxicity of samples was significantly correlated with increasing DOC concentration. Unknown TOCl and TOI showed a high correlation with measured cytotoxicity, while calculated total organic chlorine (TOCl) and total organic iodine (TOI) did not correlate. The comparison of measured and calculated cytotoxicity values showed that the calculated values do not always represent the overall cytotoxicity, since the formation of unknown DBPs are not taken into consideration during the toxicity calculations.

Formation of iodinated trihalomethanes and noniodinated disinfection byproducts during chloramination of algal organic matter extracted from Microcystis aeruginosa.

The increasing occurrence of harmful algal blooms in surface waters may increase the input of algal organic matter (AOM) to the dissolved organic matter pool. The formation of iodinated trihalomethanes (I-THMs) and noniodinated disinfection byproducts (DBPs) in synthetic waters containing AOM extracted from Microcystis aeruginosa was investigated in chloramination (preformed and in-situ formed chloramine, NH2Cl and Cl2-NH2Cl, respectively) and chlorination (Cl2) processes. AOM is much more favorable for iodine incorporation than natural organic matter (NOM). For example, the formation of I-THM from AOM is much higher than NOM isolate extracted from treated water (e.g., 3.5 times higher in the NH2Cl process), and thus higher iodine utilization and substitution factors from AOM were observed. Short contact time (2 min) chlorination in Cl2-NH2Cl process leading to the formation of halogenated intermediates favored I-THM formation, compared with NH2Cl process. However, further increasing chlorine contact time from 5 min to 24 h facilitated the conversion from iodide to iodate and thus I-THM formation decreased. Meanwhile, the formation of noniodinated THM4, haloacetonitriles (HANs), and haloacetaldehydes (HALs) increased. Factors including concentrations of AOM and bromide, pH, and chlorine/nitrogen ratios influenced the formation of I-THMs and noniodinated DBPs. To evaluate the benefit of mitigating I-THM formation over the risk of noniodinated DBP formation, measured DBPs were weighed against their mammalian cell toxicity indexes. Increasing the chlorine exposure increased the calculated cytotoxicity based on concentrations of measured I-THMs and noniodinated DBPs since unregulated HANs and HALs were the controlling agents.

Adsorption kinetics and aggregation for three classes of carbonaceous adsorbents in the presence of natural organic matter.

In this study, adsorption kinetics of phenanthrene (PNT) and trichloroethylene (TCE) by a graphene nanosheet (GNS), a graphene oxide nanosheet (GO), a single-walled carbon nanotube (SWCNT), a multi-walled carbon nanotube (MWCNT), and two coal based activated carbons (ACs) (F400 and HD3000) were examined in distilled and deionized water (DDW) and under natural organic matter (NOM) preloading conditions. The results showed the times needed for the adsorption of PNT and TCE to reach apparent equilibrium (i.e., ≤3% change per day) followed the order of GO ≥ MWCNT > GNS > SWCNT ∼ HD3000∼F400 and SWCNT > GNS ∼ HD3000 > F400 ∼ MWCNT > GO, respectively. The pseudo second order model successfully represented kinetics data for three classes of carbonaceous adsorbents. The Weber-Morris intraparticle diffusion model indicated three steps adsorption process for PNT and two step adsorption for TCE. In addition, the times needed to reach apparent equilibrium for the adsorption of PNT and TCE in the presence of hydrophobic (HPO) and hydrophilic (HPI) NOM solutions increased for all adsorbents (except for GO). In general, both NOM showed similar impacts on the adsorption rates of PNT and TCE. Aggregation of both GNS and CNTs rapidly occurred during initial couple hours of contact time during preloading, and spiking both PNT and TCE further increased their aggregation.

The interplay between natural organic matter and bromide on bromine substitution.

This study examined the interplay between bromide and DOM characteristics, described with SUVA254, in terms of formation and speciation of selected DBPs [trihalomethanes (THMs), haloacetic acids (HAAs), and haloacetonitriles (HANs)] during chlorination under various water treatment conditions. Cytotoxicity evaluations were also conducted based on the types and amounts of DBPs formed and their corresponding cytotoxicity index values. The results showed that the formation of THMs and HAAs increased as the specific UV absorbance at 254 nm (SUVA254) of the waters increased; however, there was no clear trend for HANs. THM and HAN formation increased with increasing bromide levels, while there was no bromide effect on the HAA formation. Lower HAA5 (monochloroaceticacid, monobromoaceticacid, dichloroaceticacid, trichloroaceticacid, dibromoaceticacid) to HAA9 (monochloroaceticacid, monobromoaceticacid, dichloroaceticacid, trichloroaceticacid, dibromoaceticacid, bromochloroaceticacid, bromodichloroaceticacid, dibromochloroaceticacid, tribromoaceticacid) ratios, independent of SUVA254, were observed with increasing bromide levels. Bromine substitution factor (BSF) values were in the order of BSFDHAN > BSFTHAA > BSFTHM ≈ BSFDHAA. BSF values for all class of DBPs decreased with increasing SUVA254. TOX formation increased with increasing SUVA254 without an impact of bromide concentration. UTOX/TOX ratios were higher in treated low SUVA254 waters than raw waters having higher SUVA254 values, and they decreased with increasing initial bromide concentration in all sources. Increasing bromide concentration from 0.5 µM to 10 µM elevated the calculated cytotoxicity index values of waters. Despite their much lower (approximately ~10 times) formation as compared to THMs and HAAs, HANs controlled the calculated cytotoxicity of studied waters.

Formation of regulated and unregulated disinfection byproducts during chlorination of algal organic matter extracted from freshwater and marine algae.

Seasonal algal blooms in freshwater and marine water can increase the input of algal organic matter (AOM) to the pool of dissolved organic matter. The impact of bromide (Br-) and iodide (I-) on the formation of regulated and unregulated disinfection byproducts (DBPs) was studied from chlorination of AOM solutions extracted from three species of cultured isolates of freshwater and marine algae (Microcystis aeruginosa (MA), Synechococcus (SYN), and Alexandrium tamarense (AT)). Comparable concentrations of DBPs were formed from three types of AOM. In the absence of Br-, trihalomethanes (THMs), haloacetic acids (HAAs), and haloacetaldehydes (HALs) were the main groups of DBP formed, and haloacetonitriles (HANs) were formed at lower concentrations. In contrast, the formation of iodinated THMs was <8 nM (1.7 µg/L) since most of initial I- was oxidized to iodate. Increasing initial Br- concentrations increased the formation of THMs and HANs, while concentrations of total organic halogen and HAA remained stable. On the contrary, total HAL concentrations decreased due to the instability of bromated HALs. Decreasing the specific UV absorbance (SUVA) value of AOM favours bromine substitution since bromine more preferentially reacts with low reactivity organic matter than chlorine. Increasing the pH enhanced the formation of THMs but decreased the formation of HANs. Concentrations of HANs and HALs decreased at high pH (e.g., 9.0), high initial chlorine concentration and long reaction time due to the decomposition. Based on the cytotoxicity calculations, unregulated HANs and HALs were the main contributors for the total toxicity of DBPs measured, even though based on the weight regulated THMs and HAAs predominated.

The control of N-nitrosodimethylamine, Halonitromethane, and Trihalomethane precursors by Nanofiltration.

Nanofiltration (NF) is a promising technology for removing precursors of disinfection byproducts (DBPs) from source waters prior to oxidant addition in water treatment. The aims of this study were to investigate (i) the removal efficiencies of N-nitrosodimethylamine (NDMA), halonitromethane (HNM), and trihalomethane (THM) precursors by NF membranes from different source water types (i.e. surface water, wastewater impacted surface water, and municipal and industrial wastewater treatment effluents), (ii) the impact of membrane type, and (iii) the effects of background water components (i.e., pH, ionic strength, and Ca2+) on the removal of selected DBP precursors from different source waters. The results showed the overall precursor removal efficiencies were 57-83%, 48-87%, and 72-97% for NDMA, HNM, and THM precursors, respectively. The removal of NDMA precursors decreased with the increases in average molecular weight cut off and negative surface charge of NF membranes tested, while the removal of THM precursors was slightly affected. pH changes increased the removal of NDMA precursors, but pH did not affect the removal of THM and HNM precursors in municipal WWTP effluent. On the other hand, pH changes had little or no effect on DBP removal from industrial WWTP effluent. In addition, regardless of the membrane type or background water type/characteristics, ionic strength did not show any impact on DBP precursor removals. Lastly, an increase in Ca2+ concentration enhanced the removal of NDMA precursors while a slight decrease and no effect was observed for THM and HNM precursors, respectively, in municipal WWTP effluent.

Temporal variations of disinfection byproduct precursors in wildfire detritus.

The Rim Fire ignited on August 17, 2013 and became the third largest wildfire in California history. The fire consumed 104,131 ha of forested watersheds that were the drinking water source for 2.6 million residents in the San Francisco Bay area. To understand temporal variations in dissolved organic matter (DOM) after the wildfire and its potential impacts on disinfection byproduct (DBP) formation in source water supply, we collected the 0-5 cm ash/soil layer with surface deposits of white ash (high burn severity) and black ash (moderate burn severity) within the Rim Fire perimeter in Oct 2013 (pre-rainfall) for five sequential extractions, and in Dec 2013 (∼87 mm cumulative precipitation) and Aug 2014 (∼617 mm cumulative precipitation) for a single water extraction. Water-extractable DOM was characterized by absorption and fluorescence spectroscopy and DBP formation tests. Both increasing cumulative precipitation in the field or number of extractions in the lab resulted in a significant decrease in specific conductivity, dissolved organic carbon, and DBP formation potential, but an increase in DOM aromaticity (reflected by specific UV absorbance). However, the lab sequential leaching failed to capture the increase of the NOx(-)-N/NH4(+)-N ratio and the decrease in pH and dissolved organic carbon/nitrogen ratio of ash/soil extracts from Oct 2013 to Aug 2014. Increasing cumulative precipitation, inferring an increase in leaching after fire, led to an increase in DOM reactivity to form trihalomethanes, haloacetic acids, and chloral hydrate, but not for haloketones, haloacetonitrile, or N-nitrosodimethylamine, which were more related to the original burn severity. This study highlights that fire-affected DBP precursors for different DBP species have distinct temporal variation possibly due to their various sensitivity to biogeochemical alterations.

Wildfire altering terrestrial precursors of disinfection byproducts in forest detritus.

Wildfire occurrence and intensity are increasing worldwide causing severe disturbances to forest watersheds used for potable water supply. The effects of wildfire on drinking water quality are not well understood, especially in terms of terrestrial dissolved organic matter (DOM) and DOM-associated formation of disinfection byproducts (DBP). As the forest floor layer is a major source of terrestrial DOM, we investigated characteristics and DBP formation of water extractable organic matter (WEOM) from the 0-5 cm depth of nonburned detritus (control) and burned detritus with black ash (moderate severity) and white ash (high severity) associated with the 2013 Rim Fire in California. Spectroscopic results suggested that the aromaticity of WEOM followed white ash > control > black ash and fluorescence region II (excitation 220-250 nm; emission 330-380 nm) of the emission-excitation-matrix was identified as a potential burn severity indicator. Compared to the control, WEOM from white and black ashes had lower reactivity in forming trihalomethanes (55%-of-control) and haloacetic acids (67%-of-control), but higher reactivity in forming the more carcinogenic haloacetonitrile after chlorination (244%-of-control) and N-nitrosodimethylamine after chloramination (229%-of-control). There was no change in reactivity for chloral hydrate formation, while WEOM from black ash showed a higher reactivity for haloketone formation (150%-of-control). Because wildfire consumed a large portion of organic matter from the detritus layer, there was lower water extractable organic carbon (27%-of-control) and organic nitrogen (19%-of-control) yields in ashes. Consequently, the wildfire caused an overall reduction in water extractable terrestrial DBP precursor yield from detritus materials.

Petroleum hydrocarbon contamination of the Southern Black Sea Shelf, Turkey.

INTRODUCTION: In this study, total petroleum hydrocarbon (TPH) contents and some aliphatic and aromatic hydrocarbon concentrations were analysed in coastal sediments of hot points collected from along the Southern Black Sea Shelf. MATERIALS AND METHODS: Surface sediment (0-2 cm) samples were collected from the locations using a Van Veen type grab sampler in September 2008 during a cruise on the Pollution Monitoring R/V ARAR. All sampling procedures were carried out according to internationally recognized guide-lines (UNEP 1991). Samples were analysed using a UV-fluorescence spec-trophotometry (UNEP/IOC/IAEA 1992) and gas chromatog- raphy (GC) via a Hewlett-Packard HP6890N series with a selective detector (GC-MSD) after hexane/ dichloromethane extraction. RESULTS AND DISCUSSION: The ratio C(17)/C(18) varied between 2.2 and 2.9 for the surface sediments of TRK 34Y (Samsun), TRK46 (Giresun), and TRK55 (Rize), respectively. These results showed higher marine organic matter accumulation. However, pyrolytic PAHs were found predominant in these areas. In contrast, petrogenic contributions were found at Stations TRK1 (Igneada), TRK13 (Zonguldak), TRK53 (Trabzon) and TRK61 (Hopa). TPH contents of surface sediments varied between 0.29 and 363 µg g(-1) (dry wt) throughout the shelf. The lowest values were measured at Stations TRK1 (Igneada) and TRK 19 (Bartin), whereas the highest values were found at Stations TRK13 (Zonguldak) and TRK 53 (Trabzon).