Alkylated Polycyclic Aromatic Compounds in Road Runoff Are an Environmental Risk and Should Be Included in Future Investigations.

Polycyclic aromatic compounds (PACs) and metals are important contaminants in road runoff. Vital mitigation measures against aquatic contamination from road runoff include the use of sedimentation ponds. However, it has been demonstrated that ecosystems in sedimentation ponds might be affected by road runoff. Sediments from six natural ponds and 27 sedimentation ponds were investigated to determine the environmental risk of contaminants. The amount of traffic on the respective roads associated with the sedimentation ponds was correlated with the environmental concentrations. Quantification included seven metals, the 16 US Environmental Protection Agency polycyclic aromatic hydrocarbons, alkylated PACs, dibenzothiophene, benzo[e]pyrene, and perylene. The environmental risk was assessed according to the European Union Water Framework Directive guidelines. Sedimentation ponds had a higher level of contaminants than natural ponds, and environmental risks were dominated by the concentration of PACs. Alkylated PACs contributed to the environmental risk posed by PACs and should be included in future monitoring. Only Cu and Zn were measured at concentrations above the environmental quality standards (EQSs), while 13 PACs exceeded the EQS. Sediment concentrations of Cu, Zn, and most PACs correlated significantly with the amount of traffic. The sources of PACs were determined by source apportionment ratios between PACs. Alkylation and pyrogenic indices showed that sources in natural ponds were of mostly pyrogenic origin, whereas in sedimentation ponds they were predominantly petrogenic. Asphalt was the probable main source of PACs. A hierarchical clustering technique was used to investigate both the environmental risks and the pattern of PACs in the ponds and revealed that a few sedimentation ponds were not protecting the environment as intended because the upper sediment layers had not been regularly dredged. Environ Toxicol Chem 2022;41:1838-1850. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Effects of simulated environmental discharges of the salmon lice pesticides deltamethrin and azamethiphos on the swimming behaviour and survival of adult Northern shrimp (Pandalus borealis).

Swimming behaviour was investigated in adult egg-carrying northern shrimp (Pandalus borealis) exposed to dilute concentrations of the pesticides Alpha Max® (active ingredient deltamethrin) and Salmosan® (active ingredient azamethiphos) used to control parasitic copepods in salmon aquaculture. These treatments are applied topically within fish nets or well boats. Following a short treatment period, the pesticides are directly discharged to sea, exposing non-target organisms such as P. borealis to diluted concentrations of these chemicals. Locomotor activity was measured continuously in individual shrimp over several days within which they were exposed to treatments of diluted AlphaMax® or Salmosan®. Dilutions were based on modelling and dispersion studies from the literature and were considered environmentally realistic for greater than 1 km from point of discharge. 24 h continuous flow treatments were delivered within a 3.5-day monitoring period to observe the timeline of events following the release of treatment water, addressing questions of temporal responses in locomotor activity, recognising key time points of significant events and assessing the survival capacity of the shrimp. Exposure of shrimp to 1 ng l-1 deltamethrin triggered an immediate increase in swimming activity which reduced in intensity over the following 22 h leaving all shrimp either moribund or dead. A further exposure trial exposing shrimp to 0.2 ng l-1 deltamethrin (nominal) showed an increase in activity at the start of exposure that continued throughout the 24 h delivery, returning to previous levels by the end of the 3.5-day monitoring period. All these shrimps survived for at least four weeks after exposure, putting the threshold concentration of deltamethrin leading to immobility or death in adult P. borealis within this study at greater than 0.2 ng l-1 (nominal) and less than 1 ng l - 1 (measured). Exposure of P. borealis to azamethiphos at 30 ng l-1 induced several periods of significantly increased activity within the first 10 h of exposure and an extended period of reduced activity during post exposure, though no morbidity was observed with this treatment. No significant increase in activity or morbidity was observed in shrimp during a water vehicle control assessment. Shrimps exposed to a combination of 30 ng l-1 azamethiphos and 1 ng l-1 deltamethrin broadly followed the response pattern shown by shrimp exposed to 1 ng l-1 deltamethrin alone. Pesticide residues were not detected in post exposure tissue analyses for either chemical. The potential ecological significance of increased swimming activity at the start of pesticide exposures is discussed.

Passive sampling and benchmarking to rank HOC levels in the aquatic environment.

The identification and prioritisation of water bodies presenting elevated levels of anthropogenic chemicals is a key aspect of environmental monitoring programmes. Albeit this is challenging owing to geographical scales, choice of indicator aquatic species used for chemical monitoring, and inherent need for an understanding of contaminant fate and distribution in the environment. Here, we propose an innovative methodology for identifying and ranking water bodies according to their levels of hydrophobic organic contaminants (HOCs) in water. This is based on a unique passive sampling dataset acquired over a 10-year period with silicone rubber exposures in surface water bodies across Europe. We show with these data that, far from point sources of contamination, levels of hexachlorobenzene (HCB) and pentachlorobenzene (PeCB) in water approach equilibrium with atmospheric concentrations near the air/water surface. This results in a relatively constant ratio of their concentrations in the water phase. This, in turn, allows us to (i) identify sites of contamination with either of the two chemicals when the HCB/PeCB ratio deviates from theory and (ii) define benchmark levels of other HOCs in surface water against those of HCB and/or PeCB. For two polychlorinated biphenyls (congener 28 and 52) used as model chemicals, differences in contamination levels between the more contaminated and pristine sites are wider than differences in HCB and PeCB concentrations endorsing the benchmarking procedure.

Occurrence and trophic transport of organic compounds in sedimentation ponds for road runoff.

Sedimentation ponds have been shown to accumulate several groups of contaminants, most importantly polycyclic aromatic compounds (PACs) and metals. But also, other urban organic pollutants have shown to be present, including polybrominated diphenyl ethers (PBDEs), organophosphate compounds (OPCs) and benzothiazoles (BTs). This investigation aimed at determining the occurrence of these four groups of contaminants in sedimentation ponds and determine their transport from water/sediment to organisms. PACs, including alkylated PACs, PBDEs; OPCs and BTs were determined in water, sediment, plants, dragonfly larvae and fish from two sedimentation ponds and one reference site. Fish were analysed for PAC metabolites. Overall, higher concentrations of all four pollutant groups were detected in water and sediment from sedimentation ponds compared to two natural lakes in rural environments (reference sites). The concentration difference was highest in sediments, and >20 higher concentration was measured in sedimentation ponds (3.6-4.4 ng/g ww) compared to reference (0.2 ng/g ww) for sum BDE6. For PACs and PBDEs a clear transport from water/sediment to organisms were observed. Fish were the highest trophic level organism (3.5-5) in our study, and all four pollutant groups were detected in fish. For PBDEs a trophic biomagnification (TMF) was found both in sedimentation ponds and reference, but higher concentrations in all matrices were measured in sedimentation ponds. TMF was not calculated for PACs since they are metabolised by vertebrates, but a transfer from water/sediment to organisms was seen. For BTs and OPCs, no consistent transfer to plants and dragonfly larvae could be seen. One OPC and two BTs were detected in fish, but only in fish from sedimentation ponds. It is therefore concluded that sedimentation ponds are hotspots for urban and traffic related contaminants, of which especially PACs and PBDEs are transferred to organisms living there.

Assessment of marine sediment remediation efficiency with SPME-based passive sampling measurement.

Passive sampling has been shown to be a suitable procedure to assess the risk of contaminated sediments through the measurement of freely dissolved concentrations (CFree) and remedial actions involving amendments such as activated carbon (AC). Here we report results of the application of simple, solvent-free solid phase micro extraction methodology (SPME) to assess the performance of different materials for the remediation of selected Norwegian harbour sediments contaminated with polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). AC amendments enabled a reduction of the availability of PAHs and/or PCBs by a factor of ten to over one hundred in Aker Brygge sediments (Oslo) and sediments from Elkembukta, impacted by industrial emissions of PAHs with/from coal tar pitch. Another material, anthracite, slightly less effective in this set of experiment than AC, showed nonetheless great promise as capping material. The SPME data are put in perspective with equilibrium measurements of CFree for PAHs and organochlorines with silicone rubber in other Elkembukta sediments collected in the vicinity of those used for the remediation experiments. A reduction of sediment Cfree for pyrene, benzo[a]pyrene and benzo[ghi]perylene in inner Elkembukta sediment from on average 407, 6.3 and 0.82 ng L-1 to values of/or below 1.3, 0.15 and 0.076 ng L-1, respectively can be expected upon remediation with AC. For the outer, less contaminated Elkembukta sediment, Cfree would reduce from 36, 0.81 and 0.13 ng L-1 to value of or below 0.06, 0.03 and 0.005 ng L-1 for these three compounds, respectively. Differences in pattern of PAH and organochlorine contamination of inner and outer Elkembukta sediments are discussed.

Effects of exposing shrimp larvae (Pandalus borealis) to aquaculture pesticides at field relevant concentrations, with and without food limitation.

Anti-parasitic drugs used in the aquaculture industry are discharged to the sea after treatment of salmon. In this study, the effects of azamethiphos (AZA) in the Salmosan® formulation and deltamethrin (DEL) in the Alpha Max® formulation, have been assessed in Northern shrimp larvae (Pandalus borealis) when administered both separately and in combination. The exposure concentrations were 100 ng/L for AZA and 2 ng/L for DEL, each representing a 1000-fold dilution of the prescribed concentrations for salmon. These two chemicals were combined at these concentrations to give a third treatment (AZA + DEL). When larvae were exposed for two hours on the first, second and third days post hatch (dph), significantly increased mortality and reduced swimming activity were observed for larvae from the DEL and combined AZA + DEL treatments 4 dph, though not in larvae from the AZA treatment. A single pulse exposure, delivered on the first day post hatch, caused similar effects on mortality and swimming activity 4 dph as the three-pulse exposure. Mortality was driven by the presence of DEL in both experiments, with no amplification or reduction of effects observed when DEL and AZA were combined. Larvae were observed for 13 days following the single pulse exposure, with food limitation introduced as an additional stressor on day 4. In the DEL and AZA + DEL treatments mortality continued to increase regardless of food level, with no larvae completing development to stage II. The overriding toxicity of DEL masked any potential effects the reduced food ration may have exerted. Swimming activity was lower for AZA treated larvae than Control larvae 13 dph, when both groups were fed daily, though no other significant changes to mortality, development to stage II, feeding rate or gene expression were observed. Food limited Control and AZA larvae had lower swimming activity and feeding rate than daily fed Control larvae, with expression of pyruvate kinase and myosin genes also downregulated. However, there was no negative effect on survival or successful development to stage II in these treatments. In addition, mesencephalic astrocyte-derived neurotropic factor was downregulated in food limited Control larvae when compared with the daily fed Controls. Results from this study together with reported estimates of dispersion plume concentrations of discharged pesticides indicate that toxic concentrations of deltamethrin could reach shrimp larvae several kilometers from a treated salmon farm.

Road related pollutants induced DNA damage in dragonfly nymphs (Odonata, Anisoptera) living in highway sedimentation ponds.

Nowadays, stormwater sedimentation ponds are popular in stormwater management because of their ability to mitigate flooding and treat polluted runoff from e.g. roads. In addition, they may provide other ecosystem services such as biodiversity. These man-made habitats will inevitably be polluted and the organisms living therein may be negatively affected by the chemical cocktail present in both the water and sediment compartments. The present study explored DNA damage in dragonfly nymphs (Odonata, Anisoptera) living in highway sedimentation ponds in comparison with natural ponds. The concentrations of Polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs and metals were also determined in sediment samples from the different ponds. The results showed that DNA damage was significantly higher in dragonfly nymphs living in sedimentation ponds compared to nymphs living in natural ponds. DNA damage was also highly and significantly correlated with the pollution levels in the sediment, i.e., PAH and Zinc. Finally, we report the concentrations of various alkylated PAHs which appeared to be very dominant in the sedimentation ponds. Our results show that there may be a conflict between the sedimentation ponds' primary function of protecting natural water bodies from polluted runoff and their secondary function as habitats for organisms. Overall, we suggest that this must be considered when planning and designing stormwater measures.

Early life stages of Northern shrimp (Pandalus borealis) are sensitive to fish feed containing the anti-parasitic drug diflubenzuron.

Increasing use of fish feed containing the chitin synthesis inhibiting anti-parasitic drug diflubenzuron (DFB) in salmon aquaculture has raised concerns over its impact on coastal ecosystems. Larvae of Northern shrimp (Pandalus borealis) were exposed to DFB medicated feed under Control conditions (7.0 °C, pH 8.0) and under Ocean Acidification and Warming conditions (OAW, 9.5 °C and pH 7.6). Two weeks' exposure to DFB medicated feed caused significantly increased mortality. The effect of OAW and DFB on mortality of shrimp larvae was additive; 10% mortality in Control, 35% in OAW, 66% in DFB and 92% in OAW + DFB. In OAW + DFB feeding and swimming activity were reduced for stage II larvae and none of the surviving larvae developed to stage IV. Two genes involved in feeding (GAPDH and PRLP) and one gene involved in moulting (DD9B) were significantly downregulated in larvae exposed to OAW + DFB relative to the Control. Due to a shorter intermoult period under OAW conditions, the OAW + DFB larvae were exposed throughout two instead of one critical pre-moult period. This may explain the more serious sub-lethal effects for OAW + DFB than DFB larvae. A single day exposure at 4 days after hatching did not affect DFB larvae, but high mortality was observed for OAW + DFB larvae, possibly because they were exposed closer to moulting. High mortality of shrimp larvae exposed to DFB medicated feed, indicates that the use of DFB in salmon aquaculture is a threat to crustacean zooplankton.

Exposing Northern shrimp (Pandalus borealis) to fish feed containing the antiparasitic drug diflubenzuron caused high mortality during molting.

Use of the chitin synthesis inhibitor diflubenzuron (DFB) as an antiparasitic drug in salmon aquaculture raises concern over its impact on marine ecosystems. Further, global drivers, such as ocean warming and acidification (OAW), may increase the toxicity of hazardous substances including DFB. The aim of the present study was to examine the combined effects of DFB-medicated salmon feed on ovigerous Northern shrimp (Pandalus borealis) under Control (pHNBS 8.0, 7.0ºC) and OAW conditions (pHNBS 7.6, 9.5ºC). DFB-exposed shrimp consumed on average 0.1-0.3 g medicated feed during the 2-week exposure period, and high mortality (61-73%) was documented at both environmental conditions. There was no significant interaction between OAW and DFB. Only 2-7% of DFB-exposed shrimp molted successfully compared to 65% in Control and 63% in OAW. The shrimp molted earlier (shorter intermolt period) and exhibited higher feeding rate at OAW compared to Control conditions. An additional experiment, where female shrimp were exposed to DFB closer to molting, noted increased mortality after only 4 d exposure, and successful molting for some shrimp after 2 to 3 weeks of depuration. High mortality of shrimp exposed to DFB-medicated feed indicates that the use of this feed in aquaculture could affect local shrimp populations.

Identification of non-regulated polycyclic aromatic compounds and other markers of urban pollution in road tunnel particulate matter.

A combination of silicone rubber extraction and non-target and suspect screening by gas chromatography coupled to high-resolution time-of flight mass spectrometry was used for the identification of compounds in particulate matter (PM). Tunnel PM is a proxy for local road pollution that constitutes a hazard to the urban environment and human health. The use of silicone rubber for the extraction of PM allowed the pre-concentration of a wide range of compounds for non-target analysis while minimising the effects of the sample matrix. As expected, polycyclic aromatic compounds (PACs) constituted the major group of compounds identified, but only 5 of 50 PACs identified were amongst those regularly monitored and many of them were alkylated or contained a heteroatom. Urban markers of contamination such as organophosphate flame-retardants, phthalates, benzothiazoles, musk compounds and a plasticiser were also identified. The level of confidence for the identifications was high based on accurate mass, the pattern of fragmentation and retention. The unequivocal identification of 16 compounds, from all groups, was confirmed by co-chromatography with standards and the compounds semi-quantified. Most of the PACs identified are not regularly monitored, and the hazards they pose are therefore unknown. Some of these PACs are known to be more persistent and mobile in the environment than the EPA PAH16.

Should silicone prostheses be considered for specimen banking? A pilot study into their use for human biomonitoring.

Persistent organic pollutant (POP) biomonitoring in humans is challenging and generally carried out using blood, breast milk or adipose tissue, with concentrations normalised to the lipid content of the sample matrix. The goal of this cross-sectional pilot study was to evaluate the validity and feasibility of explanted silicone prostheses as a matrix for persistent organic pollutant biomonitoring in humans. We postulate that pollutant concentrations in silicone prostheses inserted in the body will equilibrate with that in the body over time and provide a measure of the overall body burden. This study included silicone prostheses from 22 female patients of the Colosseum clinic (Oslo, Norway) collected between September 2010 and April 2012. Absorption of chlorinated and brominated POPs into silicone prostheses during implantation was observed. Relative levels of the different contaminants measured in prostheses were in agreement with those from serum and breast milk analyses from the general Norwegian population. The comparison of serum and breast milk-based literature data with prosthesis concentrations transposed into lipid-normalised concentrations supports the validity of the prosthesis measurements. The median of relative percent differences between measurements with replicate silicone prostheses from 11 patients was below 30%. Observed increases in prosthesis concentrations with patients' age were found to be very similar to literature data from studies of the Norwegian population. Silicone prostheses therefore represent a promising matrix for the biomonitoring of nonpolar and non-ionic pollutants in humans. Sample accessibility and body burden representativeness of the silicone prostheses suggest that specimen banking should be initiated.

Effect of sampler material on the uptake of PAHs into passive sampling devices.

Increasing demand for simple and reliable passive samplers for monitoring hydrophobic organic contaminants in water has led to increased frequency of use of single-phase polymeric sampling devices. In this study, we evaluate the effect of sampler material on the passive sampling of polycyclic aromatic hydrocarbons (PAHs) in two Norwegian rivers. Low density polyethylene membranes (LDPE), silicone strips and semipermeable membrane devices (SPMDs) with the exact same surface area and conformation were exposed in the Drammen River for overlapping exposures of 24 and 51 d, under identical hydrodynamic conditions. Dissipation rates of performance reference compounds (PRCs) spiked in all samplers were consistent and demonstrated no significant differences in sampler-water analyte exchange kinetics between the two exposures. The transition to fully boundary layer-controlled uptake shown by PRC dissipation rates was confirmed by investigating PAH masses absorbed by the samplers. Masses of analytes with log K(ow)>4.5 absorbed into the samplers were similar and independent of the sampler material used, generally indicating for these compounds that the boundary layer dominated the resistance to mass transfer. The very low variability in analyte masses absorbed across sampler types observed here indicates that much of the overall variability in dissolved contaminant concentrations seen in passive sampler intercomparison studies is likely the result of the uncertainty associated with sampler-water partition coefficients and PRC dissipation rates. PRC dissipation rates and ratios of masses absorbed over 51 and 24 d for these compounds demonstrated integrative sampling over 51 d and no major effects of biofouling on sampling. The equivalence of data obtained using silicone strips and SPMDs supports the use of single-phase polymeric passive sampling devices.