Drinking Water

Nutrient limitation is a biofouling control strategy in reverse osmosis (RO) membrane systems. In seawater, the assimilable organic carbon content available for bacterial growth ranges from about 50 to 400 μg C·L^-1, while the phosphorus concentration ranges from 3 to 11 μg P·L^-1. Several studies monitored biofouling development, limiting either carbon or phosphorus. The effect of carbon to phosphorus ratio and the restriction of both nutrients on membrane system performance have not yet been investigated.
This study examines the impact of reduced phosphorus concentration (from 25 μg P·L^-1 and 3 μg P·L^-1, to a low concentration of ≤0.3 μg P·L^-1), combined with two different carbon concentrations (250 C L^-1 and 30 μg C·L^-1), on biofilm development in an RO system. Feed channel pressure drop was measured to determine the effect of the developed biofilm on system performance. The morphology of the accumulated biomass for both carbon concentrations was characterized by optical coherence tomography (OCT) and the biomass amount and composition was quantified by measuring total organic carbon (TOC), adenosine triphosphate (ATP), total cell counts (TCC), and extracellular polymeric substances (EPS) concentration for the developed biofilms under phosphorus restricted (P-restricted) and dosed (P-dosed) conditions.
For both carbon concentrations, P-restricted conditions (≤0.3 μg P·L^-1) limited bacterial growth (lower values of ATP, TCC). A faster pressure drop increase was observed for P-restricted conditions compared to P-dosed conditions when 250 μg C·L^-1 was dosed. This faster pressure drop increase can be explained by a higher area covered by biofilm in the flow channel and a higher amount of produced EPS. Conversely, a slower pressure drop increase was observed for P-restricted conditions compared to P-dosed conditions when 30 μg C·L^-1 was dosed. Results of this study demonstrate that P-limitation delayed biofilm formation effectively when combined with low assimilable organic carbon concentration and thereby, lengthening the overall membrane system performance.

Chlorothalonil, a fungicide applied for decades worldwide, has recently been banned in the European Union (EU) and Switzerland due to its carcinogenicity and the presence of potentially toxic transformation products (TPs) in groundwater. The spread and concentration range of chlorothalonil TPs in different drinking water resources was examined (73 groundwater and four surface water samples mainly from Switzerland). The chlorothalonil sulfonic acid TPs (R471811, R419492, R417888) occurred more frequently and at higher concentrations (detected in 65-100% of the samples, ≤2200 ngL^-1) than the phenolic TPs (SYN507900, SYN548580, R611968; detected in 10-30% of the samples, ≤130 ngL^-1). The TP R471811 was found in all samples and even in 52% of the samples above 100 ngL^-1, the drinking water standard in Switzerland and other European countries. Therefore, the abatement of chlorothalonil TPs was investigated in laboratory and pilot-scale experiments and along the treatment train of various water works, comprising aquifer recharge, UV disinfection, ozonation, advanced oxidation processes (AOPs), activated carbon treatment, and reverse osmosis. The phenolic TPs can be abated during ozonation (second order rate constant k_O3 ∼10⁴ M^-1s^-1) and by reaction with hydroxyl radicals (OH) in AOPs (k_OH ∼10⁹ M^-1s^-1). In contrast, the sulfonic acid TPs, which occurred in higher concentrations in drinking water resources, react only very slowly with ozone (k_O3 <0.04 M^-1s^-1) and OH (k_OH <5.0 × 10⁷ M^-1s^-1) and therefore persist in ozonation and OH-based AOPs. Activated carbon retained the very polar TP R471811 only up to a specific throughput of 25 m³kg^-1 (20% breakthrough), similarly to the X-ray contrast agent diatrizoic acid. Reverse osmosis was capable of removing all chlorothalonil TPs by ≥98%.

Hypochlorous acid (HOCl) is typically assumed to be the primary reactive species in free available chlorine (FAC) solutions. Lately, it has been shown that less abundant chlorine species such as chlorine monoxide (Cl₂O) and chlorine (Cl₂) can also influence the kinetics of the abatement of certain organic compounds during chlorination. In this study, the chlorination as well as bromination kinetics and mechanisms of 12 olefins (including 3 aliphatic and 9 aromatic olefins) with different structures were explored. HOCl shows a low reactivity towards the selected olefins with species-specific second-order rate constants <1.0 M⁻¹s⁻¹, about 4-6 orders of magnitude lower than those of Cl₂O and Cl₂. HOCl is the dominant chlorine species during chlorination of olefins under typical drinking water conditions, while Cl₂O and Cl₂ are likely to play important roles at high FAC concentration near circum-neutral pH (for Cl₂O) or at high Cl⁻ concentration under acidic conditions (for Cl₂). Bromination of the 12 olefins suggests that HOBr and Br₂O are the major reactive species at pH 7.5 with species-specific second-order rate constants of Br₂O nearly 3-4 orders of magnitude higher than of HOBr (ranging from <0.01 to >10³ M⁻¹s⁻¹). The reactivities of chlorine and bromine species towards olefins follow the order of HOCl < HOBr < Br₂O < Cl₂O ≈ Cl₂. Generally, electron-donating groups (e.g., CH₂OH- and CH₃-) enhances the reactivities of olefins towards chlorine and bromine species by a factor of 3-10², while electron-withdrawing groups (e.g., Cl-, Br-, NO₂-, COOH-, CHO-, -COOR, and CN-) reduce the reactivities by a factor of 3-10⁴. A reasonable linear free energy relationship (LFER) between the species-specific second-order rate constants of Br₂O or Cl₂O reactions with aromatic olefins and their Hammett σ⁺ was established with a more negative ρ value for Br₂O than for Cl₂O, indicating that Br₂O is more sensitive to substitution effects. Chlorinated products including HOCl-adducts and decarboxylated Cl-adduct were identified during chlorination of cinnamic acid by high-performance liquid chromatography/high resolution mass spectrometry (HPLC/HRMS).

Pre-oxidation is often used before disinfection with chlorine to decrease the reactivity of the water matrix and mitigate the formation of regulated disinfection byproducts (DBPs). This study provides insights on the impact of oxidative pre-treatment with chlorine dioxide (ClO₂), ozone (O₃), ferrate (Fe(VI)) and permanganate (Mn(VII)) on Suwannee River Natural Organic Matter (SRNOM) properties characterized by the UV absorbance at 254 nm (UV₂₅₄) and the electron donating capacity (EDC). Changes in NOM reactivity and abatement of DBP precursors are also assessed. The impact of pre-oxidants (based on molar concentration) on UV₂₅₄ abatement ranked in the order O₃ > Mn(VII) > Fe(VI)/ClO₂, while the efficiency of pre-oxidation on EDC abatement followed the order Mn(VII) > ClO₂ > Fe(VI) > O₃ and two phases were observed. At low specific ClO₂, Fe(VI) and Mn(VII) doses corresponding to < 50% EDC abatement, a limited relative abatement of UV₂₅₄ compared to the EDC was observed (~ 8% EDC abatement per 1% UV₂₅₄ abatement). This suggests the oxidation of phenolic-type moieties to quinone-type moieties which absorb UV₂₅₄ and don't contribute to EDC. At higher oxidant doses (> 50% EDC abatement), a similar abatement of EDC and UV₂₅₄ (~ 0.9-1.2% EDC abatement per 1% UV₂₅₄ abatement) suggested aromatic ring cleavage. In comparison to the other oxidants, O₃ abated the relative UV₂₅₄ more effectively, due to a more efficient cleavage of aromatic rings. For a pre-oxidation with Mn(VII), ClO₂ and Fe(VI), similar correlations between the EDC abatement and the chlorine demand or the adsorbable organic halide (AOX) formation were obtained. In contrast, O₃ pre-treatment led to a lower chlorine demand and AOX formation for equivalent EDC abatement. For all oxidants_, trihalomethane formation was poorly correlated with both EDC and UV_254. The EDC abatement was found to be a pre-oxidant-independent surrogate for haloacetonitrile formation. These results emphasize the benefits of combining EDC and UV₂₅₄ measurement to understand and monitor oxidant-induced changes of NOM and assessing DBP formation.

In the present study, triplicate rings of 360° pipe surfaces of an operational drinking water distribution pipe were swabbed. Each ring was equally divided into 16 parts for swabbing. The collected swabs were grouped into 3 sections and compared with the biofilm samples sampled by sonication of specimens from the same pipe. The results showed that the biofilm is unevenly distributed over the 16 parts and the 3 sections of the pipe surface. Both the active biomass and the number of observed OTUs increased as the measurements proceeded from the top to the bottom of the pipe. The bacterial community was dominated in all sections by Proteobacteria. At the genus level, Nitrospira spp., Terrimonas spp., and Hyphomicrobium spp. were dominant in all sections. Gaiella spp. and Vicinamibacter spp. dominated in S-I, Blastopirellula spp. and Pirellula spp. dominated in S-II, while Holophaga spp. and Phaeodactylibacter spp. dominated in S-III. When swabbing and pipe specimen sonication were compared, the results showed that the sampling strategy significantly influences the obtained biofilm bacterial community. A consistent multisectional swabbing strategy is proposed for future biofilm sampling; it involves collecting swabs from all sections and comparing the swabs from the same position/section across locations.