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.

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.

Impact of various aeration strategies on the removal of micropollutants and biological effects in aerated horizontal flow treatment wetlands.

Two aerated horizontal subsurface flow treatment wetlands were studied over two years for the removal efficacy with respect of conventional wastewater parameters, micropollutants and effect-based methods. One wetland served as control and was aerated 24 h d-1 across 100% of the fractional length of the system. The second aerated horizontal flow treatment wetland was investigated under several aeration modes: first year with a zone of 85% aeration, followed by five months with a zone of 50% aeration and six months with a zone of 35% aeration. With 85% aeration, no significant difference in the removal efficacy as compared to the fully aerated control could be observed, except for E. coli, which were removed four times better in the control. No significant difference in removal efficacy for Total Organic Carbon, 5-day Carbonaceous Biochemical Oxygen Demand, caffeine, and naproxen were observed. A 50% non-aerated zone reduced the overall removal efficacy of biological effects. The highest removal efficacy for the moderately biodegradable micropollutants benzotriazole and diclofenac was observed in the system with 50% aeration. This could be due to the sharp increase of dissolved oxygen (DO) and oxidation reduction potential at the passage from the non-aerated to the aerated zone (at 75% of the fractional length). The internal concentration profiles of caffeine, ibuprofen and naproxen varied from 12.5%, 25%, 50% to 75% fractional length due to redox shift, DO variations and other conditions. A reduction of the aerated zone to 35% of the fractional length results in reduced treatment efficacy for benzotriazole, diclofenac, acesulfame and biological effects but 50% aeration yielded as much degradation as the fully aerated control. These results indicate that less aeration could provide similar effluent water quality, depending on the pollutants of interest. E. coli and biological effects were removed best in the fully aerated system.

Removal of micropollutants and biological effects by conventional and intensified constructed wetlands treating municipal wastewater.

Seven treatment wetlands and a municipal wastewater treatment plant (WWTP) were weekly monitored over the course of one year for removal of conventional wastewater parameters, selected micropollutants (caffeine, ibuprofen, naproxen, benzotriazole, diclofenac, acesulfame, and carbamazepine) and biological effects. The treatment wetland designs investigated include a horizontal subsurface flow (HF) wetland and a variety of wetlands with intensification (aeration, two-stages, or reciprocating flow). Complementary to the common approach of analyzing individual chemicals, in vitro bioassays can detect the toxicity of a mixture of known and unknown components given in a water sample. A panel of five in vitro cell-based reporter gene bioassays was selected to cover environmentally relevant endpoints (AhR: indicative of activation of the aryl hydrocarbon receptor; PPARγ: binding to the peroxisome proliferator-activated receptor gamma; ERα: activation of the estrogen receptor alpha; GR: activation of the glucocorticoid receptor; oxidative stress response). While carbamazepine was persistent in the intensified treatment wetlands, mean monthly mass removal of up to 51% was achieved in the HF wetland. The two-stage wetland system showed highest removal efficacy for all biological effects (91% to >99%). The removal efficacy for biological effects ranged from 56% to 77% for the HF wetland and 60% to 99% for the WWTP. Bioanalytical equivalent concentrations (BEQs) for AhR, PPARγ, and oxidative stress response were often below the recommended effect-based trigger (EBT) values for surface water, indicating the great benefit for using nature-based solutions for water treatment. Intensified treatment wetlands remove both individual micropollutants and mixture effects more efficiently than conventional (non-aerated) HF wetlands, and in some cases, the WWTP.