Occurrence of traffic related trace elements and organic micropollutants in tunnel wash water.

Substantially polluted tunnel wash water (TWW) is produced during road tunnel maintenance. Previous literature has reported the presence of trace elements and polycyclic aromatic hydrocarbons (PAHs). However, it was hypothesized that other organic pollutants are present, and more knowledge is needed to prevent environmental harm. This study reveals for the first time the presence of four short- and 17 long-chained per- and polyfluoroalkyl substances (PFASs), three benzothiazoles (BTHs), six benzotriazoles (BTRs), four bisphenols, and four benzophenones in TWW from a Norwegian road tunnel over a period of three years. Concentrations of PAHs, PFASs, BTHs, and BTRs were higher than previously reported in e.g., road runoff and municipal wastewater. Trace elements and PAHs were largely particulate matter associated, while PFASs, BTHs, BTRs, bisphenols, and benzophenones were predominantly dissolved. 26 of the determined contaminants were classified as persistent, mobile, and toxic (PMT) and are of special concern. It was recommended that regulations for TWW quality should be expanded to include PMT contaminants (such as PFPeA, PFBS, BTR, and 4-OH-BzP) and markers of pollution (like 2-M-BTH, 2-OH-BTH, and 2-S-BTH from tire wear particles). These findings highlight the need to treat TWW before discharge into the environment, addressing both, particulate matter associated and dissolved contaminants.

Per- and polyfluoroalkyl substance (PFAS) removal from soil washing water by coagulation and flocculation.

Soil washing is currently attracting attention as a promising remediation strategy for land contaminated with per- and polyfluoroalkyl substances (PFAS). In the soil washing process, the contaminant is transferred from the soil into the liquid phase, producing a PFAS contaminated process water. One way to treat such process water is to use coagulation and flocculation; however, few studies are available on the performance of coagulation and flocculation for removing PFAS from such process water. This study evaluated 6 coagulants and flocculants (polyaluminium chloride (PACl), zirconium oxychloride octahydrate, cationic and anionic polyacrylamide, Polyclay 685 and Perfluor Ad®), for the treatment of a proxy PFAS contaminated washing water, spiked with PFAS concentrations found at typical Aqueous Film Forming Foam (AFFF) contaminated sites. PFAS removal efficiencies (at constant pH) varied greatly depending on the coagulants and flocculants, as well as the dosage used and the targeted PFAS. All tested coagulants and flocculants reduced the turbidity by >95%, depending on the dosage. Perfluor Ad®, a specially designed coagulant, showed the highest removal efficiency for all longer chain (>99%) and shorter chain PFAS (>68%). The cationic polyacrylamide polymer removed longer chain PFAS up to an average of 80%, whereas average shorter chain PFAS removal was lower (<30%). The two metal-based coagulants tested, PACl and zirconium, removed longer chain PFAS by up to an average of 61% and shorter chain PFAS up to 48%. Polyclay 685, a mixture of powdered activated carbon (PAC) and aluminium sulphate, removed longer chain PFAS by 90% and shorter chain PFAS on average by 76%, when very high dosages of the coagulant were used (2,000 mg/L). PFAS removal efficiencies correlated with chain length and headgroup. Shorter chain PFAS removal was dependent on electrostatic interaction with the precipitating flocs, whereas for longer chain PFAS, hydrophobic interactions between apolar functional groups and flocs created by the coagulant/flocculant, dissolved organic matter and suspended solids played a major role. The results of this study showed that by selecting the most efficient coagulant and aqueous conditions, a greater amount of PFAS can be removed from process waters in soil washing facilities, and thus included as part of various treatment trains.

Influence of grain size, organic carbon and organic matter residue content on the sorption of per- and polyfluoroalkyl substances in aqueous film forming foam contaminated soils - Implications for remediation using soil washing.

A soil that was historically contaminated with Aqueous Film Forming Foam (AFFF) was dry sieved into size fractions representative of those produced during soil washing. Batch sorption tests were then conducted to investigate the effect of soil parameters on in situ per- and polyfluoroalkyl substances (PFAS) sorption of these different size fractions: < 0.063 mm, 0.063 to 0.5 mm, 0.5 to 2 mm, 2 to 4 mm, 4 to 8 mm, and soil organic matter residues (SOMR). PFOS (513 ng/g), 6:2 FTS (132 ng/g) and PFHxS (58 ng/g) were the most dominant PFAS in the AFFF contaminated soil. Non-spiked, in situ Kd values for 19 PFAS ranged from 0.2 to 138 L/Kg (log Kd -0.8 to 2.14) for the bulk soil and were dependant on the head group and perfluorinated chain length (spanning C4 to C13). The Kd values increased with decreasing grain size and increasing organic carbon content (OC), which were correlated to each other. For example, the PFOS Kd value for silt and clay (< 0.063 mm, 17.1 L/Kg, log Kd 1.23) were approximately 30 times higher compared to the gravel fraction (4 to 8 mm, 0.6 L/Kg, log Kd -0.25). The highest PFOS Kd value (116.6 L/Kg, log Kd 2.07) was found for the SOMR fraction, which had the highest OC content. Koc values for PFOS ranged from 6.9 L/Kg (log Koc 0.84) for the gravel fraction to 1906 L/Kg (log Koc 3.28) for the silt and clay, indicating that the mineral composition of the different size fractions also influenced sorption. The results here emphasize the need to separate coarse-grained fractions and fine-grained fractions, and in particular the SOMR, to optimize the soil washing process. Higher Kd values for the smaller size fractions indicate that coarser soils are better suited for soil washing.

The Determination of Polycyclic Aromatic Hydrocarbons (PAHs) with HPLC-DAD-FLD and GC-MS Techniques in the Dissolved and Particulate Phase of Road-Tunnel Wash Water: A Case Study for Cross-Array Comparisons and Applications.

Accelerated solvent extraction (ASE) and solid phase extraction (SPE) protocols tailored to either gas chromatography mass spectrometry (GC-MS) or high-performance liquid chromatography coupled to diode-array and fluorescence detection (HPLC-DAD-FLD) were developed for the determination of EPA 16 polycyclic aromatic hydrocarbons (PAHs) in the particulate and dissolved phase of road-tunnel wash water. An analytical approach was developed, assessed, and applied on environmental samples collected from five road tunnels in Norway. The absolute recoveries ranged from 57 to 104% for the particulates, and from 42 to 79% for the dissolved water phase. The target PAH compounds were separated in 34.75 min using the GC method and in 22.50 min by HPLC. In the particulate phases, higher molecular weight PAHs were detected in the range of 0.043 to 0.93 µg/g, and lower molecular weight PAHs were detected in the range of 0.020 to 1.0 µg/g, while the intermediate ones were present in the range of 0.075 to 2.0 µg/g. In contrast to the particulates, the dissolved phase mainly contained lower molecular weight PAHs in the range of 0.0098 to 0.50 µg/L. GC-MS demonstrated lower detection limits (LODs) than HPLC-DAD-FLD for 13 out of the 16 PAHs. A cross-array comparison of the two analytical techniques indicated that some target PAHs were detected solely or in higher concentrations with HPLC-DAD-FLD, indicating the occurrence of false positive peaks or/and co-eluting components. The resulting concentrations in the road tunnel wash water samples were used to calculate specific PAH forensic ratios to pinpoint the potential sources of PAH pollution. These ratios revealed that there are several potential sources for the origin of PAHs in tunnel wash water.

Inactivation of marine heterotrophic bacteria in ballast water by an Electrochemical Advanced Oxidation Process.

Seawater treatment is increasingly required due to industrial activities that use substantial volumes of seawater in their processes. The shipping industry and the associated management of a ship's ballast water are currently considered a global challenge for the seas. Related to that, the suitability of an Electrochemical Advanced Oxidation Process (EAOP) with Boron Doped Diamond (BDD) electrodes has been assessed on a laboratory scale for the disinfection of seawater. This technology can produce both reactive oxygen species and chlorine species (especially in seawater) that are responsible for inactivation. The EAOP was applied in a continuous-flow regime with real seawater. Natural marine heterotrophic bacteria (MHB) were used as an indicator of disinfection efficiency. A biphasic inactivation kinetic model was fitted on experimental points, achieving 4-Log reductions at 0.019 Ah L-1. By assessing regrowth after treatment, results suggest that higher bacterial damages result from the EAOP when it is compared to chlorination. Furthermore, several issues lacking fundamental understanding were investigated such as recolonization capacity or bacterial community dynamics. It was concluded that, despite disinfection processes being effective, there is not only a possibility for regrowth after treatment but also a change on bacterial population diversity produced by the treatment. Finally, energy consumption was estimated and indicated that 0.264 kWh·m-3 are needed for 4.8-Log reductions of MHB; otherwise, with 0.035 kWh·m-3, less disinfection efficiency can be obtained (2.2-Log red). However, with a residual oxidant in the solution, total inactivation can be achieved in three days.

Bacterial degradation of microcystin toxins within a biologically active sand filter.

Microcystin toxins are a problem for water authorities as they are recalcitrant to conventional water treatment. In this study, biological sand filtration was assessed in laboratory column experiments for its ability to remove two microcystin analogues, microcystin-LR and microcystin-LA. A lag period of 3 days was evident prior to the commencement of degradation. Contact times were varied during the experiment; however, no microcystin was detected in the effluent after 4 days, even under conditions similar to those of a rapid sand filter. Removals of microcystin through the sand filters were shown to be primarily through biological degradation processes. Using polymerase chain reaction (PCR), biofilm, extracted from one of the sand filters that had effectively removed the microcystins, was shown to contain bacteria with the mlrA gene. Detection of this gene provided additional evidence that biological degradation of microcystin was the primary removal mechanism.