Impact of sample acidification and extract storage on hormone receptor-mediated and oxidative stress activities in wastewater.

An underemphasized aspect of sampling strategies in effect-based in vitro testing is to determine suitable collection and preparation techniques. In the current study, the impact of sample acidification on bioactivities was assessed using in vitro bioassays for hormone receptor-mediated effects (estrogen receptor [ER] and androgen receptor [AR]) and the oxidative stress response (Nrf2 activity). Sampling was conducted at a recently upgraded Swedish wastewater treatment plant. Future plans for the treated wastewater include reuse for irrigation or as a potential drinking water source. In the AR and Nrf2 assays, acidification decreased bioactivities in the wastewater influent sample extracts, whereas acidification increased bioactivities following further treatment (disc filtration). In the ER assay, acidification had no impact on the observed bioactivities in the sample extracts. A secondary objective of the study was to assess the stability of the sample extracts over time. Lower activities were detected in the ER and AR assays in all extracts after storage for approximately 1 year. Nrf2 activities did not decrease over time, but rather increased in some of the acidified sample extracts. Overall, the findings suggest that sampling strategies involving acidification may need to be tailored depending on the selected bioassay(s) and the type of wastewater treatments being assessed.

Selective chlorination of natural organic matter: identification of previously unknown disinfection byproducts.

Natural organic matter (NOM) serve as precursors for disinfection byproducts (DBPs) in drinking water production making NOM removal essential in predisinfection treatment processes. We identified molecular formulas of chlorinated DBPs after chlorination and chloramination in four Swedish surface water treatment plants (WTPs) using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Chlorine-containing formulas were detected before and after disinfection and were therefore classified to identify DBPs. In total, 499 DBPs were detected, of which 230 have not been reported earlier. The byproducts had, as a group, significantly lower ratio of hydrogen to carbon (H/C) and significantly higher average carbon oxidation state (COS), double bond equivalents per carbon (DBE/C) and ratio of oxygen to carbon (O/C) compared to Cl-containing components present before disinfection and CHO formulas in samples taken both before and after disinfection. Electrophilic substitution, the proposed most significant reaction pathway for chlorination of NOM, results in carbon oxidation and decreased H/C while O/C and DBE/C is left unchanged. Because the identified DBPs had significantly higher DBE/C and O/C than the CHO formulas we concluded that chlorination of NOM during disinfection is selective toward components with relatively high double bond equivalency and number of oxygen atoms per carbon. Furthermore, choice of disinfectant, dose, and predisinfection treatment at the different WTPs resulted in distinct patterns in the occurrence of DBP formulas.

Artificial infiltration in drinking water production: Addressing chemical hazards using effect-based methods.

Artificial infiltration is an established managed aquifer recharge method that is commonly incorporated into drinking water processes. However, groundwater sourced from this type of purification method is prone to contamination with chemical hazards. Such an instance was previously shown at a Swedish DWTP where the river water was contaminated by hazardous chemicals during artificial infiltration. Further, there remains a paucity of research studying the quality of drinking water following this type of treatment from an effect-based bioanalytical perspective. In the current study, an effect-based assessment for chemical hazards was conducted for a Swedish drinking water system comprised of two DWTPs fed artificially-infiltrated river water. In this system, artificial infiltration of the river water takes approximately six to eight months. A sampling event was conducted in the autumn season and the samples were enriched by solid phase extraction. A panel of cell-based reporter gene assays representing several toxicity pathways was selected: oxidative stress response (Nrf2 activity), aryl hydrocarbon receptor (AhR) activation, and hormone receptor-mediated effects (estrogen receptor [ER], androgen receptor [AR]). AhR and ER bioactivities were detected in samples collected from the river intake and in the open-air infiltration basins prior to artificial infiltration. However, the AhR activity decreased and ER activity was effectively removed following artificial infiltration. In the Nrf2 and AR assays, no bioactivities above cut-off levels were detected in any samples collected along the entire treatment process of the drinking water production from source to tap. Using a suite of bioassays, the current study highlighted the effectiveness of artificial infiltration in reducing bioactive compounds in this raw river water. Although artificial infiltration is a common purification method in drinking water production, the limited number of effect-based studies evaluating the effectiveness of this method emphasizes the need for further research to better understand the risks and benefits of this water treatment process.

Innovative drinking water treatment techniques reduce the disinfection-induced oxidative stress and genotoxic activity.

Disinfection of drinking water using chlorine can lead to the formation of genotoxic by-products when chlorine reacts with natural organic matter (NOM). A vast number of such disinfection by-products (DBPs) have been identified, making it almost impossible to routinely monitor all DBPs with chemical analysis. In this study, a bioanalytical approach was used, measuring oxidative stress (Nrf2 activity), genotoxicity (micronucleus test), and aryl hydrocarbon receptor (AhR) activation to evaluate an innovative water treatment process, including suspended ion exchange, ozonation, in-line coagulation, ceramic microfiltration, and granular activated carbon. Chlorination was performed in laboratory scale after each step in the treatment process in order to investigate the effect of each treatment process to the formation of DBPs. Suspended ion exchange had a high capacity to remove dissolved organic carbon (DOC) and to decrease UV absorbance and Nrf2 activity in non-chlorinated water. High-dose chlorination (10 mg Cl2 L-1) of raw water caused a drastic induction of Nrf2 activity, which was decreased by 70% in water chlorinated after suspended ion exchange. Further reduction of Nrf2 activity following chlorination was achieved by ozonation and the concomitant treatment steps. The ozonation treatment resulted in decreased Nrf2 activity in spite of unchanged DOC levels. However, a strong correlation was found between UV absorbing compounds and Nrf2 activity, demonstrating that Nrf2 inducing DBPs were formed from pre-cursors of a specific NOM fraction, constituted of mainly aromatic compounds. Moreover, high-dose chlorination of raw water induced genotoxicity. In similarity to the DOC levels, UV absorbance and Nrf2 activity, the disinfection-induced genotoxicity was also reduced by each treatment step of the innovative water treatment technique. AhR activity was observed in the water produced by the conventional process and in the raw water, but the activity was clearly decreased by the ozonation step in the innovative water treatment process.

Integrity breaches in a hollow fiber nanofilter - Effects on natural organic matter and virus-like particle removal.

Ultrafiltration and nanofiltration have become common methods to treat surface water for drinking water purposes. Common aims of a membrane step are removal of natural organic matter (NOM), softening or adding an extra microbiological or chemical barrier. In most cases, the membrane is considered a good disinfection step; commonly the viral removal is at least 4-log. To ensure a working disinfection, reliable integrity tests are required. In the present pilot study with a hollow fiber nanofilter, the membrane achieved a high NOM reduction, and the difference in parameters related to NOM quality before and after treatment proved to be useful indicators of integrity breaches. Changes in total organic carbon (TOC) concentration, UV-absorbance at 254 nm (UVA254) and fluorescence derived parameters in the permeate flow were related to leaking fibers. On average, UVA254 in the permeate was 3 times higher for a membrane with compromised fibers (0.041 cm-1) compared to an intact membrane (0.013 cm-1), while TOC was less than 2 times as high on average. Thus, this membrane had a higher reduction of UVA254 than TOC and the sensitivity for changes from leakage was higher. Therefore, it is suggested that UVA254 could be used as an indicator for membrane integrity. Additionally, there is a significant (P < 0.01) difference in fluorescence derived parameters between a leaking and an intact fiber, showing that fluorescence also has potential to be applied for online monitoring of membrane processes. During fiber failure, around 2% of the permeate flow passes through one single leaking fiber. The transport depends on the distance between the inflow and the leak, which in most cases are similar and most likely close to the middle of the fiber.

Upgrading coagulation with hollow-fibre nanofiltration for improved organic matter removal during surface water treatment.

Rising organic matter concentrations in surface waters in many Nordic countries require current drinking water treatment processes to be adapted. Accordingly, the use of a novel nanofiltration (NF) membrane was studied during a nine month period in pilot scale at a large drinking water treatment plant in Stockholm, Sweden. A chemically resistant hollow-fibre NF membrane was fed with full scale process water from a rapid sand filter after aluminum sulfate coagulation. The combined coagulation and NF process removed more than 90% of the incoming lake water dissolved organic carbon (DOC) (8.7 mg C L(-1)), and 96% of the absorbance at 254 nm (A254) (0.28 cm(-1) incoming absorbance). Including granulated active carbon GAC) filter, the complete pilot plant treatment process we observed decreases in DOC concentration (8.7-0.5 mg C L(-1)), SUVA (3.1-1.7 mg(-1) L m(-1)), and the average nominal molecular mass (670-440 Da). Meanwhile, water hardness was practically unaffected (<20% reduction). Humic substances (HS) and biopolymers were almost completely eliminated (6510-140 and 260 to 10 µg C L(-1) respectively) and low molecular weight (LMW) neutrals decreased substantially (880-190 µg C L(-1)). Differential excitation emission matrices (EEMs), which illustrate the removal of fluorescing organic matter (FDOM) over a range of excitation and emission wavelengths, demonstrate that coagulation removed 35 ± 2% of protein-like material and 65 ± 2% of longer emission wavelength, humic-like FDOM. The subsequent NF treatment was somewhat less selective but still preferentially targeted humic-like FDOM (83 ± 1%) to a larger extent than protein-like material (66 ± 3%). The high selectivity of organic matter during coagulation compared to NF separation was confirmed from analyses with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), and liquid chromatography with organic carbon detection (LC-OCD), as coagulation exclusively targeted oxidized organic matter components while NF removed both chemically reduced and oxidized components. DOC removal and change in DOC character in the GAC filters showed marked differences with slower saturation and more pronounced shifts in DOC character using NF as pre-treatment. Fluorescence derived parameters showed a similar decrease over time of GAC performance for the first 150 days but also indicated ongoing change of DOM character in the post NF GAC filtrate over time even after LC-OCD indicated steady state with respect to outgoing carbon. During our trial iron concentrations were low (<30 ppb) and thus A254 could be directly related to the concentration of HS (R(2) = 0.9). The fluorescence derived freshness index (ß:α) proved to be an excellent variable for estimating the fraction of HS present in all samples. Given the recommended limit of 4 mg L(-1) for chemical oxygen demand (COD) for Swedish drinking water, coagulation will need to be supplemented with one or more treatment steps irrespective whether climate change will lead to drier or wetter conditions in order to maintain sufficient DOC removal with the current increasing concentrations in raw waters.