Feasibility studies: UV/chlorine advanced oxidation treatment for the removal of emerging contaminants

UV/chlorine (UV/HOCl and UV/ClO₂) Advanced Oxidation Processes (AOPs) were assessed with varying process layout and compared to the state of the art UV/H₂O₂ AOP. The process comparison focused on the economical and energy saving potential of the UV/chlorine AOP. Therefore the experiments were performed at technical scale (250 L/h continuous flow reactor) and at process energies, oxidant and model contaminant concentrations expected in full scale reference plants. As model compounds the emerging contaminants (ECs): desethylatrazine, sulfamethoxazole, carbamazepine, diclofenac, benzotriazole, tolyltriazole, iopamidole and 17α-ethinylestradiol (EE2) were degraded at initial compound concentrations of 1 μg/L in tap water and matrixes with increased organic load (46 mg/L DOC).UV/chlorine AOP organic by-product forming potential was assessed for trihalomethanes (THMs) and N-Nitrosodimethylamine (NDMA). A process design was evaluated which can considerably reduce process costs, energy consumption and by-product generation from UV/HOCl AOPs.     

Evaluation of enhanced coagulation pretreatment to improve ozone oxidation efficiency in wastewater

Enhanced coagulation (EC) using ferric chloride was evaluated as a pretreatment process to improve the efficiency of ozone (O₃) for the oxidation of trace organic contaminants in wastewater. At the applied dosages (10-30 mg/L as Fe), EC pretreatment removed between 10 and 47% of the dissolved organic carbon (DOC) from the three wastewaters studied. Size exclusion chromatography (SEC) showed that EC preferentially removed higher apparent molecular weight (AMW) compounds. Subsequent O₃ testing was performed using an O₃:DOC ratio of 1. Results showed that O₃ exposures were similar even though the required doses were reduced by 10-47% by the EC pretreatment process. Hydroxyl radical (HO) exposure, measured by parachlorobenzoic acid (pCBA), showed 10% reduction when using a FeCl₃ dose of 30 mg/L, likely due to the lower O₃ dose and decreased production of HO during the initial phase of O₃ decomposition (t < 30 s). The oxidation of 13 trace organic contaminants (including atenolol, carbamazepine, DEET, diclofenac, dilantin, gemfibrozil, ibuprofen, meprobamate, naproxen, primidone, sulfamethoxazole, triclosan, and trimethoprim) was evaluated after EC and O₃ treatment. EC was ineffective at removing any of the contaminants, while O₃ oxidation reduced the concentration of compounds according to their reaction rate constants with O₃ and HO.     

Natural versus wastewater derived dissolved organic carbon: implications for the environmental fate of organic micropollutants

The interaction of organic micropollutants with dissolved organic carbon (DOC) can influence their transport, degradation and bioavailability. While this has been well established for natural organic carbon, very little is known regarding the influence of DOC on the fate of micropollutants during wastewater treatment and water recycling. Dissolved organic carbon-water partition coefficients (K_DOC) for wastewater derived and reference DOC were measured for a range of micropollutants using a depletion method with polydimethylsiloxane disks. For micropollutants with an octanol-water partition coefficient (log K_OW) greater than 4 there was a significant difference in K_DOC between reference and wastewater derived DOC, with partitioning to wastewater derived DOC over 1000 times lower for the most hydrophobic micropollutants. The interaction of nonylphenol with wastewater derived DOC from different stages of a wastewater and advanced water treatment train was studied, but little difference in K_DOC was observed. Organic carbon characterisation revealed that reference and wastewater derived DOC had very different properties due to their different origins. Consequently, the reduced sorption capacity of wastewater derived DOC may be related to their microbial origin which led to reduced aromaticity and lower molecular weight. This study suggests that for hydrophobic micropollutants (log K_OW > 4) a higher concentration of freely dissolved and thus bioavailable micropollutants is expected in the presence of wastewater derived DOC than predicted using K_DOC values quantified using reference DOC. The implication is that naturally derived DOC may not be an appropriate surrogate for wastewater derived DOC as a matrix for assessing the fate of micropollutants in engineered systems.     

Tracking natural organic matter (NOM) in a drinking water treatment plant using fluorescence excitation-emission matrices and PARAFAC

Natural organic matter (NOM) in water samples from a drinking water treatment train was characterized using fluorescence excitation emission matrices (F-EEMs) and parallel factor analysis (PARAFAC). A seven component PARAFAC model was developed and validated using 147 F-EEMs of water samples from two full-scale water treatment plants. It was found that the fluorescent components have spectral features similar to those previously extracted from F-EEMs of dissolved organic matter (DOM) from diverse aquatic environments. Five of these components are humic-like with a terrestrial, anthropogenic or marine origin, while two are protein-like with fluorescence spectra similar to those of tryptophan-like and tyrosine-like fluorophores. A correlation analysis was carried out for samples of one treatment plant between the maximum fluorescence intensities (F_max) of the seven PARAFAC components and NOM fractions (humics, building blocks, neutrals, biopolymers and low molecular weight acids) of the same sample obtained using liquid chromatography with organic carbon detection (LC-OCD). There were significant correlations (p < 0.01) between sample DOC concentration, UVA₂₅₄, and F_max for the seven PARAFAC components and DOC concentrations of the LC-OCD fractions. Three of the humic-like components showed slightly better predictions of DOC and humic fraction concentrations than UVA_254. Tryptophan-like and tyrosine-like components correlated positively with the biopolymer fraction. These results demonstrate that fluorescent components extracted from F-EEMs using PARAFAC could be related to previously defined NOM fractions and that they could provide an alternative tool for evaluating the removal of NOM fractions of interest during water treatment.     

An innovative ultrasound, Fe and TiO2 photoassisted process for bisphenol a mineralization

This paper explores the degradation of a model pollutant, bisphenol A, by an advanced oxidation process that combines sonolysis, Fe²⁺, and TiO₂ in a photoassisted process. Experiments were done under saturated oxygen conditions. The effect of different Fe²⁺ (0.56 and 5.6 mg/L) and TiO₂ (10 and 50 mg/L) concentrations was investigated on both the elimination and mineralization of the pollutant. A pronounced synergistic effect that led to the complete and rapid elimination of dissolved organic carbon (DOC) was observed even at low catalyst loadings. In this system, almost a complete removal of DOC (93%) was observed after 4 h using 10 and 5.6 mg/L of TiO₂ and Fe²⁺, respectively, whereas at the same time, only 5, 6, and 22% of DOC was removed by an individual process alone (TiO₂ photocatalysis, ultrasound, and photo-Fenton, respectively). In this system, ultrasound has the principal role of eliminating the initial substrate and providing hydrogen peroxide for the photocatalytic systems, while photo-Fenton and TiO₂ photocatalysis are mainly responsible for the transformation of the intermediates in CO₂ and H₂O. The role of H₂O₂ generated from the sonochemical process is also discussed.     

Investigating dissolved air flotation performance with cyanobacterial cells and filaments

Dissolved air flotation (DAF) performance with two different naturally occurring cyanobacterial morphologies was investigated with respect to the biomass removal efficiency, the toxin release to water and the coagulant demand by different water background natural organic matter (NOM). Coagulation (C)/Flocculation (F)/DAF bench-scale experiments (2 min coagulation at 380 s⁻¹ with polyaluminium chloride (0.5-4 mg/L Al₂O₃, the dose depending on the water NOM content); 8 min flocculation at 70 s⁻¹; 8 min DAF with 5 bar relative pressure and 8% pressurised recycle) were performed with single cells of Microcystis aeruginosa and Planktothrix rubescens filaments spiked in synthetic waters with different NOM contents (hydrophobic vs. hydrophilic NOM; moderate (2-3 mgC/L) vs. moderate-high concentration (ca. 6 mgC/L)). For both morphologies, the results show no apparent cyanobacterial damage (since the water quality did not degrade in dissolved microcystins and the removal of intracellular microcystins matched the removal of chlorophyll a) and high biomass removal efficiencies (93-99% for cells and 92-98% for filaments) provided optimal coagulant dose for chlorophyll a removal was ensured. Charge neutralisation by the polyaluminium chloride was the main coagulation mechanism of the M. aeruginosa cells and most likely also of the P. rubescens filaments. The specific coagulant demand was severely affected by NOM hydrophobicity, hydrophobic NOM (with a specific UV_254nm absorbance, SUVA, above 4 L/(m mgC)) requiring ca. the triple of hydrophilic NOM (SUVA below 3 L/(m mgC)), i.e. 0.7 vs. 0.2-0.3 mg Al₂O₃/mg DOC.     

Heterotrophic microorganism Rhodotorula mucilaginosa R30 improves tannery sludge bioleaching through elevating dissolved CO2 and extracellular polymeric substances levels in bioleach solution as well as scavenging toxic DOM to Acidithiobacillus species

The introduction of acid-tolerant heterotrophic microorganisms into sludge bioleaching systems has been proven effective in improving sludge bioleaching processes, and such positive effect is mainly attributed to the biodegradation of low molecular weight organic acids or sludge dissolved organic matter (DOM) toxic to Acidithiobacillus species by the heterotrophic microorganisms introduced. Here we report that elevated dissolved CO₂ concentration and resulting extracellular polymeric substances (EPS) in bioleach solution due to the incorporation of heterotrophic microorganisms also play important roles in improving sludge bioleaching. It was found that in tannery sludge bioleaching system coinoculated with Rhodotorula mucilaginosa R30 and Acidithiobacillus species, dissolved CO₂ concentration in bioleach solution can be elevated from 0.23-0.54 mg/L to 0.76-1.01 mg/L compared to the control inoculated only with Acidithiobacillus species. Correspondingly, the distinct degradation of sludge DOM was also observed in this experiment. It was experimentally demonstrated that the accumulation of CO₂ did greatly enhance the growth of Acidithiobacillus thiooxidans and the decrease rate of pH in the medium. In addition, EPS derived from R. mucilaginosa R30 could bind readily Fe³⁺ in bioleach solution with maximum binding capacity (MBC) of 0.82 mg Fe³⁺ by per mg DOC of EPS secreted and the oxidization activity of EPS-bound Fe³⁺ was decreased but not totally inhibited, indicating that the formation of soluble EPS-Fe(III) complexes enhances, to a certain extent, bioleaching efficiency due to maintaining Fe³⁺ level in solution by inhibiting Fe precipitation occurrence.     

Changes in dissolved organic carbon during artificial recharge of groundwater in a forested esker in Southern Finland

Sprinkling infiltration in a forested esker leading to artificial recharge of groundwater was studied in Southern Finland. Changes in dissolved organic carbon (DOC) and the molecular size distribution and chemical properties of the organic carbon were investigated during the infiltration process. Artificial groundwater was produced using sprinkling infiltration directly onto the forest floor. One result of lake water infiltration through the organic horizon and 1 m thick mineral soil layer was a slight net increase in the DOC concentrations from 9.4 mg/L in the infiltration water to 13.2 mg/L in percolation water. This indicates that the forest soil represents a potential input of organic matter into infiltration water. However, the DOC concentrations decreased by 27–38% as the infiltration water percolated down through the unsaturated soil layer into the groundwater zone. At a distance of 1450 m from the infiltration area, the mean DOC concentration in the groundwater was below the recommended value for drinking water in Finland of 2.0 mg/L. There was a strong reduction in the concentrations of hydrophilic and hydrophobic acids, but only a slight decrease in hydrophilic neutral organic compounds during the infiltration process. The DOC in the production well consisted of low molecular size fractions. Larger molecular size fractions were removed effectively from the water during the infiltration process.     

Characterization of effluent water qualities from satellite membrane bioreactor facilities

Membrane bioreactors (MBRs) are often a preferred treatment technology for satellite water recycling facilities since they produce consistent effluent water quality with a small footprint and require little or no supervision. While the water quality produced from centralized MBRs has been widely reported, there is no study in the literature addressing the effluent quality from a broad range of satellite facilities. Thus, a study was conducted to characterize effluent water qualities produced by satellite MBRs with respect to organic, inorganic, physical and microbial parameters. Results from sampling 38 satellite MBR facilities across the U.S. demonstrated that 90% of these facilities produced nitrified (NH₄-N <0.4 mg/L-N) effluents that have low organic carbon (TOC <8.1 mg/L), turbidities of <0.7 NTU, total coliform bacterial concentrations <100 CFU/100 mL and indigenous MS-2 bacteriophage concentrations <21 PFU/100 mL. Multiple sampling events from selected satellite facilities demonstrated process capability to consistently produce effluent with low concentrations of ammonia, TOC and turbidity. UV-254 transmittance values varied substantially during multiple sampling events indicating a need for attention in designing downstream UV disinfection systems. Although enteroviruses, rotaviruses and hepatitis A viruses (HAV) were absent in all samples, adenoviruses were detected in effluents of all nine MBR facilities sampled. The presence of Giardia cysts in filtrate samples of two of nine MBR facilities sampled demonstrated the need for an appropriate disinfection process at these facilities.     

Occurrence and formation potential of N-nitrosodimethylamine in ground water and river water in Tokyo

N-nitrosodimethylamine (NDMA), a disinfection byproduct of water and wastewater treatment processes, is a potent carcinogen. We investigated its occurrence and the potential for its formation by chlorination (NDMA-FP_2Cl) and by chloramination (NDMA-FP_2NHCl) in ground water and river water in Tokyo. To characterize NDMA precursors, we revealed their molecular weight distributions in ground water and river water. We collected 23 ground water and 18 river water samples and analyzed NDMA by liquid chromatography-tandem mass spectrometry. NDMA-FP_2Cl was evaluated by chlorinating water samples with free chlorine for 24 h at pH 7.0 while residual free chlorine was kept at 1.0-2.0 mgCl₂/L. NDMA-FP_2NHCl was evaluated by dosing water samples with monochloramine at 140 mgCl₂/L for 10 days at pH 6.8. NDMA precursors and dissolved organic carbon (DOC) were fractionated by filtration through 30-, 3-, and 0.5 kDa membranes. NDMA concentrations were <0.5-5.2 ng/L (median: 0.9 ng/L) in ground water and <0.5-3.4 ng/L (2.2 ng/L) in river water. NDMA concentrations in ground water were slightly lower than or comparable to those in river water. Concentrations of NDMA-FP_2Cl were not much higher than concentrations of NDMA except in samples containing high concentrations of NH₃ and NDMA precursors. The increased NDMA was possibly caused by reactions between NDMA precursors and monochloramine unintentionally formed by the reaction between free chlorine and NH₃ in the samples. NDMA precursors ranged from 4 to 84 ng-NDMA eq./L in ground water and from 11 to 185 ng-NDMA eq./L in river water. Those in ground water were significantly lower than those in river water, suggesting that NDMA precursors were biodegraded, adsorbed, or volatilized during infiltration. The molecular weight of NDMA precursors in river water was dominant in the <0.5 kDa fraction, followed by 0.5-3 kDa. However, their distribution was inconsistent in ground water: one was dominant in the <0.5 kDa fraction, and the other in 0.5-3 kDa. Molecular weight distributions of NDMA precursors were very different from those of DOC. This is the first study to reveal the widespread occurrence and characterization of NDMA precursors in ground water.     

Electrochemical oxidation of trace organic contaminants in reverse osmosis concentrate using RuO2/IrO2-coated titanium anodes

During membrane treatment of secondary effluent from wastewater treatment plants, a reverse osmosis concentrate (ROC) containing trace organic contaminants is generated. As the latter are of concern, effective and economic treatment methods are required. Here, we investigated electrochemical oxidation of ROC using Ti/Ru_0.7Ir_0.3O₂ electrodes, focussing on the removal of dissolved organic carbon (DOC), specific ultra-violet absorbance at 254 nm (SUVA₂₅₄), and 28 pharmaceuticals and pesticides frequently encountered in secondary treated effluents. The experiments were conducted in a continuously fed reactor at current densities (J) ranging from 1 to 250 A m⁻² anode, and a batch reactor at J = 250 A m⁻². Higher mineralization efficiency was observed during batch oxidation (e.g. 25.1 ± 2.7% DOC removal vs 0% removal in the continuous reactor after applying specific electrical charge, Q = 437.0 A h m⁻³ ROC), indicating that DOC removal is depending on indirect oxidation by electrogenerated oxidants that accumulate in the bulk liquid. An initial increase and subsequent slow decrease in SUVA₂₅₄ during batch mode suggests the introduction of auxochrome substituents (e.g. -Cl, NH₂Cl, -Br, and -OH) into the aromatic compounds. Contrarily, in the continuous reactor ring-cleaving oxidation products were generated, and SUVA₂₅₄ removal correlated with applied charge. Furthermore, 20 of the target pharmaceuticals and pesticides completely disappeared in both the continuous and batch experiments when applying J ≥ 150 A m⁻² (i.e. Q ≥ 461.5 A h m⁻³) and 437.0 A h m⁻³ (J = 250 A m⁻²), respectively. Compounds that were more persistent during continuous oxidation were characterized by the presence of electrophilic groups on the aromatic ring (e.g. triclopyr) or by the absence of stronger nucleophilic substituents (e.g. ibuprofen). These pollutants were oxidized when applying higher specific electrical charge in batch mode (i.e. 1.45 kA h m⁻³ ROC). However, baseline toxicity as determined by Vibrio fischeri bioluminescence inhibition tests (Microtox) was increasing with higher applied charge during batch and continuous oxidation, indicating the formation of toxic oxidation products, possibly chlorinated and brominated organic compounds.     

Treating wastewater from a pharmaceutical formulation facility by biological process and ozone

Wastewater from a pharmaceutical formulation facility (TevaKS, Israel) was treated with a biological activated-sludge system followed by ozonation. The goal was to reduce the concentrations of the drugs carbamazepine (CBZ) and venlafaxine (VLX) before discharging the wastewater to the municipal wastewater treatment plant (WWTP). Both drugs were detected at extremely high concentrations in TevaKS raw wastewater ([VLX] = 11.72 ± 2.2 mg/L, [CBZ] = 0.84 ± 0.19 mg/L), and resisted the biological treatment. Ozone efficiently degraded CBZ: at an O₃ dose-to-dissolved organic carbon ratio of 0.55 (O₃/DOC), the concentration of CBZ was reduced by >99%. A lower removal rate was observed for VLX, which was decreased by ～98% at the higher O₃/DOC ratio of 0.87. Decreasing the pH of the biologically treated effluent from 7 to 5 significantly increased the ozone degradation rate of CBZ, while decreasing the degradation rate of VLX. Ozone treatment did not alter the concentration of the effluent's DOC and filtered chemical oxygen demand (COD_f). However, a significant increase was recorded (following ozonation) in the effluent's biological oxygen demand (BOD₅) and the BOD₅/COD_f ratio. This implies an increase in the effluent's biodegradability, which is highly desirable if ozonation is followed by a domestic biological treatment. Different organic byproducts were formed following ozone reaction with the target pharmaceuticals and with the effluent organic matter; however, these byproducts are expected to be removed during biological treatment in the municipal WWTP.     

Mechanisms of virus control during iron electrocoagulation--microfiltration of surface water

Results from a laboratory-scale study evaluating virus control by a hybrid iron electrocoagulation - microfiltration process revealed only 1.0-1.5 log MS2 bacteriophage reduction even at relatively high iron dosages (∼13 mg/L as Fe) for natural surface water containing moderate natural organic matter (NOM) concentrations (4.5 mg/L dissolved organic carbon, DOC). In contrast, much greater reductions were measured (6.5-log at pH 6.4 and 4-log at pH 7.5) at similar iron dosages for synthetic water that was devoid of NOM. Quantitative agreement with Faraday’s law with 2-electron transfer and speciation with phenanthroline demonstrated electrochemical generation of soluble ferrous iron. Near quantitative extraction of viruses by dissolving flocs formed in synthetic water provided direct evidence of their removal by sorption and enmeshment onto iron hydroxide flocs. In contrast, only approximately 1% of the viruses were associated with the flocs formed in natural water consistent with the measured poor removals. 1-2 logs of virus inactivation were also observed in the electrochemical cell for synthetic water (no NOM) but not for surface water (4.5 mg/L DOC). Sweep flocculation was the dominant destabilization mechanism since the ζ potential did not reach zero even when 6-log virus reductions were achieved. Charge neutralization only played a secondary role since ζ potential → 0 with increasing iron electrocoagulant dosage. Importantly, virus removal from synthetic water decreased when Suwanee River Humic Acid was added. Therefore, NOM present in natural waters appears to reduce the effectiveness of iron electrocoagulation pretreatment to microfiltration for virus control by complexing ferrous ions. This inhibits (i) Fe²⁺ oxidation, precipitation, and virus destabilization and (ii) virus inactivation through reactive oxygen species intermediates or by direct interactions with Fe²⁺ ions.     

Implications of land disturbance on drinking water treatability in a changing climate: Demonstrating the need for “source water supply and protection” strategies

Forests form the critical source water areas for downstream drinking water supplies in many parts of the world, including the Rocky Mountain regions of North America. Large scale natural disturbances from wildfire and severe insect infestation are more likely because of warming climate and can significantly impact water quality downstream of forested headwaters regions. To investigate potential implications of changing climate and wildfire on drinking water treatment, the 2003 Lost Creek Wildfire in Alberta, Canada was studied. Four years of comprehensive hydrology and water quality data from seven watersheds were evaluated and synthesized to assess the implications of wildfire and post-fire intervention (salvage-logging) on downstream drinking water treatment. The 95th percentile turbidity and DOC remained low in streams draining unburned watersheds (5.1 NTU, 3.8 mg/L), even during periods of potential treatment challenge (e.g., stormflows, spring freshet); in contrast, they were elevated in streams draining burned (15.3 NTU, 4.6 mg/L) and salvage-logged (18.8 NTU, 9.9 mg/L) watersheds. Persistent increases in these parameters and observed increases in other contaminants such as nutrients, heavy metals, and chlorophyll-a in discharge from burned and salvage-logged watersheds present important economic and operational challenges for water treatment; most notably, a potential increased dependence on solids and DOC removal processes. Many traditional source water protection strategies would fail to adequately identify and evaluate many of the significant wildfire- and post-fire management-associated implications to drinking water “treatability”; accordingly, it is proposed that “source water supply and protection strategies” should be developed to consider a suppliers’ ability to provide adequate quantities of potable water to meet demand by addressing all aspects of drinking water “supply” (i.e., quantity, timing of availability, and quality) and their relationship to “treatability” in response to land disturbance.     

Removal of bisphenol A and 17α-ethinyl estradiol from landfill leachate using single-walled carbon nanotubes

In this study, the adsorption of bisphenol A (BPA) and 17α-ethinyl estradiol (EE2) from landfill leachate onto single-walled carbon nanotubes (SWCNTs) was investigated. Different leachate solutions were prepared by altering the pH, ionic strength, and dissolved organic carbon (DOC) in the solutions to mimic the varying water conditions that occur in leachate during the various stages of waste decomposition. The youngest and oldest leachate solutions contained varying DOC and background chemistry and were represented by leachate Type A (pH = 5.0; DOC = 2500 mg/L; conductivity = 12,500 μS/cm; [Ca²⁺] = 1200 mg/L; [Mg²⁺] = 470 mg/L) and Type E (pH = 7.5; DOC = 250 mg/L; conductivity = 3250 μS/cm; [Ca²⁺] = 60 mg/L; [Mg²⁺] = 180 mg/L). These solutions were subsequently combined in different ratios to produce intermediate solutions, labeled B-D, to replicate time-dependent changes in leachate composition. Overall, a larger fraction of EE2 was removed as compared to BPA, consistent with its higher log K_OW value. The total removal of BPA and EE2 decreased in older leachate solutions, with the adsorptive capacity of SWCNTs decreasing in the order of leachate Type A > Type B > Type C > Type D > Type E. An increase in the pH from 3.5 to 11 decreased the adsorption of BPA by 22% in young leachate and by 10% in old leachate. The changes in pH did not affect the adsorption of EE2 in the young leachate, but did reduce adsorption by 32% in the old leachate. Adjusting the ionic strength using Na⁺ did not significantly impact adsorption, while increasing the concentration of Ca²⁺ resulted in a 12% increase in the adsorption of BPA and a 19% increase in the adsorption of EE2. DOC was revealed to be the most influential parameter in this study. In the presence of hydrophilic DOC, represented by glucose in this study, adsorption of the endocrine disrupting compounds (EDCs) onto the SWCNTs was not affected. In the absence of SWCNTs, hydrophobic DOC (i.e., humic acid) adsorbed 15-20% of BPA and EE2. However, when the humic acid and SWCNTs were both present, the overall adsorptive capacity of the SWCNTs was reduced. Hydrophobic (π-π electron donor-acceptor) interactions between the EDCs and the constituents in the leachate, as well as interactions between the SWCNTs and the EDCs, are proposed as potential adsorption mechanisms for BPA and EE2 onto SWCNTs.     

Characterization of intracellular & extracellular algae organic matters (AOM) of Microcystic aeruginosa and formation of AOM-associated disinfection byproducts and odor & taste compounds

Algae organic matters (AOM), including intracellular organic matters (IOM) and extracellular organic matters (EOM), are causing numerous water quality issues, among which formation of disinfection byproducts (DBPs) and odor & taste (O&T) compounds are of particular concern. In this study, physiochemical properties of IOM and EOM of Microcystic aeruginosa under an exponential growth phase (2.01 × 10¹¹/L) were comprehensively characterized. Moreover, the yields of DBPs during AOM disinfection and O&T-causing compounds were quantified. Hydrophilic organic matters accounted for 86% and 63% of DOC in IOM and EOM, respectively. Molecular weight (MW) fractions of IOM in <1 kDa, 40-800 kDa, and >800 kDa were 27%, 42%, and 31% of DOC, respectively, while EOM primarily contained 1-100 kDa molecules. Besides, a low SUVA (0.84 L/mg m) and the specific fluorescence spectra suggested that AOM (especially IOM) was principally comprised of protein-like substances, instead of humic-like matters. The formation potentials of chloroform, chloroacetic acid, and nitrosodimethylamine were 21.46, 68.29 and 0.0096 μg/mg C for IOM, and 32.44, 54.58 and 0.0189 μg/mg C for EOM, respectively. Furthermore, the dominant O&T compound produced from EOM and IOM were 2-MIB (68.75 ng/mg C) and β-cyclocitral (367.59 ng/mg C), respectively. Of note, dimethyltrisulfide became the prevailing O & T compound following anaerobic cultivation.     

Occurrence of polar organic contaminants in the dissolved water phase of the Danube River and its major tributaries using SPE-LC-MS analysis

Polar water-soluble organic contaminants were analysed in the dissolved liquid water phase of river water samples from the Danube River and its major tributaries (within the Joint Danube Survey 2). Analyses were performed by solid-phase extraction (SPE) followed by triple-quadrupole liquid chromatography mass spectrometry (LC-MS²). In total, 34 different polar organic compounds were screened. Focus was given on pharmaceutical compounds (such as ibuprofen, diclofenac, sulfamethoxazole, carbamazepine), pesticides and their degradation products (e.g. bentazone, 2,4-D, mecoprop, atrazine, terbutylazine, desethylterbutylazine), perfluorinated acids (PFOS; PFOA), and endocrine disrupting compounds (nonylphenol, NPE₁C, bisphenol A, estrone). The most relevant polar compounds identified in the Danube River basin in terms of frequency of detection, persistency, and concentration levels were 1H-benzotriazole (median concentration 185 ng/L), caffeine (87 ng/L), tolyltriazole (73 ng/L), nonylphenoxy acetic acid (49 ng/L), carbamazepine (33 ng/L), 4-nitrophenol (29 ng/L), 2,4-dinitrophenol (19 ng/L), PFOA (17 ng/L), sulfamethoxazole (16 ng/L), desethylatrazine (11 ng/L), and 2,4-D (10 ng/L). The highest contamination levels were found in the area around Budapest and in the tributary rivers Arges (Romania), Timok (Bulgaria), Rusenski Lom (Bulgaria), and Velika Morava (Serbia).     

The influence of disinfection on aquatic biodegradable organic carbon formation

The aim of this paper was to assess the extent of biodegradable dissolved organic carbon formation upon disinfection of water with chlorine dioxide. Wide diversity of natural waters has been subjected to reactions with various amounts of ClO₂. For comparison examined waters have also been treated with ozone and chlorine. The application of chlorine dioxide and ozone significantly changed the molecular weight distribution of aquatic organic matter. As a result significant amounts of biodegradable carboxylic acids and aldehydes were generated. The formic, acetic, oxalic and ketomalonic acids as well as formaldehyde, acetaldehyde, glyoxal, methylglyoxal were identified. The productivity of aldehydes calculated for all examined waters and disinfectants amounted 12.7-47.7 μg mg⁻¹ DOC in the case of ozonation, 1.3-8.1 μg mg⁻¹ DOC after chlorination and 1.7-9.4 μg mg⁻¹ DOC for ClO₂ treatment. The highest total concentration of carboxylic acids was determined after the ozonation processes. In this case the organic acids' formation potential was in the range 10.8-62.8 μg mg⁻¹ DOC. Relatively high formation potential (5.3-17.9 μg mg⁻¹ DOC) was determined after the oxidation with ClO₂ as well. In the case of chlorination, the productivity of organic acids was low and did not exceed 3.4 μg mg⁻¹ DOC. The relatively high correlation between BDOC formation and carboxylic acids' formation potential was observed. Thus, carboxylic acids' formation potential may be used as a measure of water potential to form BDOC.     

Effect of natural organic matter on toxicity and reactivity of nano-scale zero-valent iron

Nano-scale zero-valent iron (NZVI) particles are increasingly used to remediate aquifers contaminated with hazardous oxidized pollutants such as trichloroethylene (TCE). However, the high reduction potential of NZVI can result in toxicity to indigenous bacteria and hinder their participation in the cleanup process. Here, we report on the mitigation of the bactericidal activity of NZVI towards gram-negative Escherichia coli and gram-positive Bacillus subtilis in the presence of Suwannee River humic acids (SRHA), which were used as a model for natural organic matter (NOM). B. subtilis was more tolerant to NZVI (1 g/L) than E. coli in aerobic bicarbonate-buffered medium. SRHA (10 mg/L) significantly mitigated toxicity, and survival rates after 4 h exposure increased to similar levels observed for controls not exposed to NZVI. TEM images showed that the surface of NZVI and E. coli was surrounded by a visible floccus. This decreased the zeta potential of NZVI from −30 to −45 mV and apparently exerted electrosteric hindrance to minimize direct contact with bacteria, which mitigated toxicity. H₂ production during anaerobic NZVI corrosion was not significantly hindered by SRHA (p > 0.05), However, NZVI reactivity towards TCE (20 mg/L), assessed by the first-order dechlorination rate coefficient, decreased by 23%. Overall, these results suggest that the presence of NOM offers a tradeoff for NZVI-based remediation, with higher potential for concurrent or sequential bioremediation at the expense of partially inhibited abiotic reactivity with the target contaminant (TCE).     

Simultaneous degradation of disinfection byproducts and earthy-musty odorants by the UV/H2O2 advanced oxidation process

Advanced treatment technologies that control multiple contaminants are beneficial to drinking water treatment. This research applied UV/H₂O₂ for the simultaneous degradation of geosmin, 2-methylisoborneol, four trihalomethanes and six haloacetic acids. Experiments were conducted in de-ionized water at 24 ± 1.0 °C with ng/L amounts of odorants and μg/L amounts of disinfection byproducts. UV was applied with and without 6 mg/L H₂O_2. The results demonstrated that brominated trihalomethanes and brominated haloacetic acids were degraded to a greater extent than geosmin and 2-methylisoborneol. Tribromomethane and dibromochloromethane were degraded by 99% and 80% respectively at the UV dose of 1200 mJ/cm² with 6 mg/L H₂O₂, whereas 90% of the geosmin and 60% of the 2-methylisoborneol were removed. Tribromoacetic acid and dibromoacetic acid were degraded by 99% and 80% respectively under the same conditions. Concentrations of trichloromethane and chlorinated haloacetic acids were not substantially reduced under these conditions and were not effectively removed at doses designed to remove geosmin and 2-methylisoborneol. Brominated compounds were degraded primarily by direct photolysis and cleavage of the C-Br bond with pseudo first order rate constants ranging from 10⁻³ to 10⁻² s⁻¹. Geosmin and 2-methylisoborneol were primarily degraded by reaction with hydroxyl radical with direct photolysis as a minor factor. Perchlorinated disinfection byproducts were degraded by reaction with hydroxyl radicals. These results indicate that the UV/H₂O₂ can be applied to effectively control both odorants and brominated disinfection byproducts.