[pMBRT: Principles and Design of Advanced Proton Radiotherapy Techniques].

The development history of pMBRT, the biological role of minibeam, the mechanism of minibeam protection of tissues, the generation of minibeam (collimator method and magnetic focusing method), and the analysis of advantages and disadvantages of proton minibeam matrix arrays is introduced with advanced proton minibeam arrays (pMBRT). It is proposed that the combination of proton minibeam arrays and magnetic resonance fields can help to exploit the normal tissue protective function of pMBRT, and improve the precision of proton therapy.

A ternary model of proton therapy based on boron medium radiosensitization and enhancement paths: a Monte Carlo simulation.

Background: To overcome proton therapy limitations [low linear energy transfer (LET) radiation with a relative biological effectiveness (RBE) typically ranging from 1.1 to 1.2], radiosensitization techniques can be employed to increase the radiosensitivity of tumor cells and improve the effectiveness of radiation therapy. In this study, we suggest using a boron-based medium to overcome the biological limitations of proton therapy. By inducing the hydrogen-boron fusion reaction (p + 11B → 3α) of incident protons and capturing thermal neutrons [10B + n → 7Li3+ (0.84 MeV) + 4He2+ (1.47 MeV) + γ (0.477 MeV)], high LET α particles can be released. We propose a "ternary" radiotherapy model to enhance the biological effect of proton therapy. Methods: Using Monte Carlo simulation, the possibility of interacting low-energy proton beams with 11B and thermal neutrons with 10B to produce α particles with higher RBE to enhance the biological effect of proton radiotherapy were investigated. And the number and location of α particles and thermal neutrons produced by the interaction of protons with natural boron had also been studied. Results: Under the basic principle of the "ternary" radiotherapy model, comparative analyses of neutrons and α particles produced by proton beams of different energies incident on the phantoms, which were composed of boron isotopes of different concentrations in proportion to the phantoms, have shown that the α particle yield decreased with decreasing boron doping concentration, whereas the neutron yield increased with decreasing boron doping concentration. The distribution of thermal neutrons and α particles in the longitudinal direction of the proton beam were also studied, and it was found that the number of α particles produced was high at high boron concentrations, and the locations of α and thermal neutrons were close to the treatment target. Conclusions: The proton therapy ternary model is theoretically feasible from the perspective of mathematical analysis and Monte Carlo simulation experiments.

Divergent Temporal Trends of Mercury in Arctic Char from Paired Lakes Influenced by Climate-Related Drivers.

Climate-driven changes including rising air temperatures, enhanced permafrost degradation, and altered precipitation patterns can have profound effects on contaminants, such as mercury (Hg), in High Arctic lakes. Two physically similar lakes, East Lake and West Lake at the Cape Bounty Arctic Watershed Observatory on Melville Island, Nunavut, Canada are being affected by climate change differently. Both lakes have experienced permafrost degradation in their catchments; however, West Lake has also undergone multiple underwater Mass Movement Events (MMEs; beginning in fall 2008), leading to a sustained 50-fold increase in turbidity. This provided the unique opportunity to understand the potential impacts of permafrost degradation and other climate-related effects on Hg concentrations and body condition of landlocked Arctic char (Salvelinus alpinus), an important sentinel species across the Circum-Arctic. Our objectives were to assess temporal trends in char Hg concentrations and to determine potential mechanisms driving the trends. There was a significant decrease in Hg concentrations in East Lake char, averaging 6.5%/year and 3.8%/year for length-adjusted and age-adjusted means, respectively, from 2008 to 2019. Conversely, in West Lake there was a significant increase, averaging 7.9%/year and 8.0%/year for length-adjusted and age-adjusted mean Hg concentrations, respectively, for 2009 to 2017 (the last year with sufficient sample size). The best predictors of length-adjusted Hg concentrations in West Lake were carbon and nitrogen stable isotope ratios, indicating a shift in diet including possible dietary starvation brought on by the profound increase in lake turbidity. Our study provides an example of how increasing lake turbidity, a likely consequence of climate warming in Arctic lakes, may influence fish condition and Hg concentrations. Environ Toxicol Chem 2023;42:2712-2725. © 2023 His Majesty the King in Right of Canada and The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. Reproduced with the permission of the Minister of Environment and Climate Change Canada.

Mercury at the top of the world: A 31-year record of mercury in Arctic char in the largest High Arctic lake, linked to atmospheric mercury concentrations and climate oscillations.

Lake Hazen, the largest lake north of the Arctic circle, is being impacted by mercury (Hg) pollution and climate change. The lake is inhabited by two morphotypes of land-locked Arctic char (Salvelinus alpinus), a sensitive indicator species for pollution and climatic impacts. The objectives of this study were to describe the trends in Hg concentration over time and to determine the relationship of climate to length-at-age and Hg concentrations in each char morphotype, as well as the relationship to atmospheric Hg measurements at a nearby monitoring station. Results for Hg in char muscle were available from 20 sampling years over the period 1990 to 2021. We found significant declines in Hg concentrations for both morphotypes during the 31-year study period. Increased rain and earlier freeze-up of lake ice during the summer growing season was linked to increased length-at-age in both char morphotypes. For the large morphotype, higher total gaseous Hg in the fall and winter seasons was related to higher concentrations of Hg in char, while increased glacial runoff was related to decreases in char Hg. For the small morphotype char, increased snow and snow accumulation in the fall season were linked to declines in char Hg concentration. The Atlantic Multidecadal Oscillation and Arctic Oscillation were positively related to the large char Hg trend and Arctic Oscillation was positively related to the small char Hg trend. Significant trend relationships between atmospheric Hg and Hg in biota in remote regions are rare and uniquely valuable for evaluation of the effectiveness of the Minamata Convention and related monitoring efforts.

Target and Nontarget Screening of Organic Chemicals and Metals in Recycled Plastic Materials.

Increased demand for recycling plastic has prompted concerns regarding potential introduction of hazardous chemicals into recycled goods. We present a broad screening of chemicals in 21 plastic flake and pellet samples from Canadian recycling companies. From target analysis, the organophosphorus ester flame retardants and plasticizers exhibited the highest detection frequencies (DFs) (5-100%) and concentrations (280 chemicals were detected in recycled plastic pellets and flakes, suggesting potential incorporation into recycled goods. Individual concentrations indicate unintentional trace contamination following European Union threshold limits for recycled granules (500 mg/kg) and waste plastic flakes (1,000 mg/kg), although do not reflect toxicological thresholds, if any. Our study highlights that while recycling addresses sustainability goals, additional screening of goods and products made from recycled plastics is needed to fully document potentially hazardous chemicals and exposure.

Nanoparticle radiosensitization: from extended local effect modeling to a survival modification framework of compound Poisson additive killing and its carbon dots validation.

Objective. To construct an analytical model instead of local effect modeling for the prediction of the biological effectiveness of nanoparticle radiosensitization.Approach. An extended local effects model is first proposed with a more comprehensive description of the nanoparticles mediated local killing enhancements, but meanwhile puts forward challenging issues that remain difficult and need to be further studied. As a novel method instead of local effect modeling, a survival modification framework of compound Poisson additive killing is proposed, as the consequence of an independent additive killing by the assumed equivalent uniform doses of individual nanoparticles per cell under the LQ model. A compound Poisson killing (CPK) model based on the framework is thus derived, giving a general expression of nanoparticle mediated LQ parameter modification. For practical use, a simplified form of the model is also derived, as a concentration dependent correction only to theαparameter, with the relative correction (α″/α) dominated by the mean number, and affected by the agglomeration of nanoparticles per cell. For different agglomeration state, a monodispersion model of the dispersity factorη = 1, and an agglomeration model of 2/3 < Î· < 1, are provided for practical prediction of (α″/α) value respectively.Main results. Initial validation by the radiosensitization of HepG2 cells by carbon dots showed a high accuracy of the CPK model. In a safe range of concentration (0.003-0.03µgµl-1) of the carbon dots, the prediction errors of the monodispersion and agglomeration models were both within 2%, relative to the clonogenic survival data of the sensitized HepG2 cells.Significance. The compound Poisson killing model provides a novel approach for analytical prediction of the biological effectiveness of nanoparticle radiosensitization, instead of local effect modeling.

Quantification of Spatial and Temporal Trends in Atmospheric Mercury Deposition across Canada over the Past 30 Years.

Mercury (Hg) is a pollutant of concern across Canada and transboundary anthropogenic Hg sources presently account for over 95% of national anthropogenic Hg deposition. This study applies novel statistical analyses of 82 high-resolution dated lake sediment cores collected from 19 regions across Canada, including nearby point sources and in remote regions and spanning a full west-east geographical range of ∼4900 km (south of 60°N and between 132 and 64°W) to quantify the recent (1990-2018) spatial and temporal trends in anthropogenic atmospheric Hg deposition. Temporal trend analysis shows significant synchronous decreasing trends in post-1990 anthropogenic Hg fluxes in western Canada in contrast to increasing trends in the east, with spatial patterns largely driven by longitude and proximity to known point source(s). Recent sediment-derived Hg fluxes agreed well with the available wet deposition monitoring. Sediment-derived atmospheric Hg deposition rates also compared well to the modeled values derived from the Hg model, when lake sites located nearby (<100 km) point sources were omitted due to difficulties in comparison between the sediment-derived and modeled values at deposition "hot spots". This highlights the applicability of multi-core approaches to quantify spatio-temporal changes in Hg deposition over broad geographic ranges and assess the effectiveness of regional and global Hg emission reductions to address global Hg pollution concerns.

The influence of a lost society, the Sadlermiut, on the environment in the Canadian Arctic.

High latitude freshwater ecosystems are sentinels of human activity and environmental change. The lakes and ponds that characterize Arctic landscapes have a low resilience to buffer variability in climate, especially with increasing global anthropogenic stressors in recent decades. Here, we show that a small freshwater pond in proximity of the archaeological site "Native Point" on Southampton Island (Nunavut, Arctic Canada) is a highly sensitive environmental recorder. The sediment analyses allowed for pinpointing the first arrival of Sadlermiut culture at Native Point to ~ 1250 CE, followed by a dietary shift likely in response to the onset of cooling in the region ~ 1400 CE. The influence of the Sadlermiut on the environment persisted long after the last of their population perished in 1903. Presently, the pond remains a distorted ecosystem that has experienced fundamental shifts in the benthic invertebrate assemblages and accumulated anthropogenic metals in the sediment. Our multi-proxy paleolimnological investigation using geochemical and biological indicators emphasizes that direct and indirect anthropogenic impacts have long-term environmental implications on high latitude ecosystems.

Dosimetric Deviations of Bragg-Peak Position Shifts in Uniform Magnetic Fields for Magnetic Resonance Imaging-Guiding Proton Radiotherapy: A Monte Carlo Study.

Objective: To investigate dosimetric deviations in scanning protons for Bragg-peak position shifts, which were caused by proton spiral tracks in an ideal uniform field of magnetic resonance (MRI) imaging-guided proton radiotherapy (MRI-IGPRT). Methods: The FLUKA Monte-Carlo (MC) code was used to simulate the spiral tracks of protons penetrating water with initial energies of 70-270 MeV under the influence of field strength of 0.0-3.0 Tesla in commercial MRI systems. Two indexes, lateral shift (marked as WD) perpendicular to the field and a penetration-depth shift (marked as ΔDD) along the beam path, were employed for the Bragg-peak position of spiral proton track analysis. A comparison was performed between MC and classical analytical model to check the simulation results. The shape of the 2D/3D dose distribution of proton spots at the depth of Bragg-Peak was also investigated. The ratio of Gaussian-fit value between longitudinal and transverse major axes was used to indicate the asymmetric index. The skewness of asymmetry was evaluated at various dose levels by the radius ratio of circumscribed and inscribed circles by fitting a semi-ellipse circle of 2D distribution. Results: The maximum of WD deflection is 2.82 cm while the maximum of shortening ΔDD is 0.44 cm for proton at 270 MeV/u under a magnetic field of 3.0 Tesla. The trend of WD and ΔDD from MC simulation was consistent with the analytical model, which means the reverse equation of the analytical model can be applied to determine the proper field strength of the magnet and the initial energy of the proton for the planned dose. The asymmetry of 2D/3D dose distribution under the influence of a magnetic field was increased with higher energy, and the skewness of asymmetry for one proton energy at various dose levels was also increased with a larger radius, i.e., a lower dose level. Conclusions: The trend of the spiral proton track under a uniform magnetic field was obtained in this study using either MC simulation or the analytical model, which can provide an optimized and planned dose of the proton beam in the clinical application of MRI-IGPRT.

Long-term spatial and temporal trends, and source apportionment of polycyclic aromatic compounds in the Athabasca Oil Sands Region.

We investigated the spatio-temporal trends of polycyclic aromatic compounds (PACs) deposition in the Athabasca Oil Sands Region (AOSR) between 2008 and 2017, and applied source apportionment tools to assess sources using snowpacks. Estimated PAC mass deposition was significantly correlated with crude oil production (R2 = 0.48, p = 0.03), and increased between 2008 and 2017. Loadings of alkylated PACs c1-, c2-fluorenes/pyrenes and c1-, c3-benzo[a]anthracenes/chrysenes/triphenylenes significantly increased at mid-field sites (25-50 km from central industrial reference site, AR6) (Mann-Kendall, p < 0.05) reflecting physical expansion of the AOSR. The distance from emission sources was important in the deposition of PACs, including the distance from AR6 (R2 = 0.69-0.91), nearest petcoke storage (R2 = 0.77-0.88), 0.89) and upgrader stack (R2 = 0.56-0.61). Source apportionment PAC distribution profiles of the source materials (petcokes, oil sand ores, road dust) did not show unique matching profiles with the snowpacks. However, the minimal presence of retene in petcokes and an abundance of benzo[ghi]fluoranthene in road dust was observed, and suggests potential for these compounds as chemical markers in distinguishing sources. Furthermore, correlations between PACs and selected metal(loid)s in the AOSR snowpacks were assessed to infer potential common sources. Significant positive (p < 0.05) correlations between metal(loid)s enriched in bitumen (vanadium, molybdenum, nickel) and PACs, at near to mid-field (0-50 km from AR6) sites suggests common sources or similar transfer and fate processes. The results of our study convey data necessary for monitoring studies in the constantly developing AOSR, advance our knowledge of PACs profiles in source materials (including the much less studied alkylated PACs and dibenzothiophenes), which will be valuable for other studies related to oil pollution, urban run-off and forest fires. PACs mass deposition increasing between 2008 and 2017 coincident with crude oil production, and retene and benzo[ghi]fluoranthene show potential in distinguishing AOSR sources.

[Analysis of Key Points of Radiation Sources in Proton and Carbon Ion Radiotherapy Facilities in Shanghai].

Compared with conventional high energy X-ray radiotherapy, proton/carbon ion has obvious advantages because of its Bragg peak dose distribution. However, proton heavy ion facility has complex structure, high energy and various radiation types due to various nuclear reaction processes, the radiation protection safety brought by the operation of facilities has gradually attracted attention. Taking the proton/carbon ion radiotherapy facility of Shanghai Proton and Heavy Ion Center as an example, the author mainly analyzed the operation principle of proton/carbon ion treatment facility, the basis of radiation protection, analysis of key radiation source points, etc., so as to provide theoretical support and experience for radiation protection.

Mercury in Ringed Seals (Pusa hispida) from the Canadian Arctic in Relation to Time and Climate Parameters.

Mercury is found in Arctic marine mammals that are important in the diet of northern Indigenous peoples. The objectives of the present long-term study, spanning a 45-yr period, were to 1) investigate the temporal trends of total mercury (THg; muscle and liver) and selenium (Se; liver) in ringed seals (Pusa hispida) from different regions of the Canadian Arctic; and 2) examine possible relationships with age, diet, and climate parameters such as air temperature, precipitation, climatic indices, and ice-coverage. Ringed seals were collected by hunters in northern communities in the Beaufort Sea, Central Arctic, Eastern Baffin Island, Hudson Bay, and Ungava/Nunatsiavut regions (Canada) between 1972 and 2017. Mercury levels did not change through time in seal liver, but THg levels in muscle decreased in seals from Hudson Bay (-0.91%/yr) and Ungava/Nunatsiavut (-1.30%/yr). Carbon stable isotope values in seal muscle decreased significantly through time in 4 regions. Selenium-to-THg ratios were found to be >1 for all years and regions. Variation partitioning analyses across regions indicated that THg trends in seals were mostly explained by age (7.3-21.7%), climate parameters (3.5-12.5%), and diet (up to 9%); climate indices (i.e., Arctic and North Atlantic Oscillations, Pacific/North American pattern) explained the majority of the climate portion. The THg levels had a positive relationship with Arctic Oscillation for multiple regions. Associations of THg with air temperature, total precipitation, and sea-ice coverage, as well as with North Atlantic Oscillation and Pacific/North American pattern were found to vary with tissue type and geographical area. Environ Toxicol Chem 2020;39:2462-2474. © 2020 Her Majesty the Queen in Right of Canada. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. Reproduced with the permission of the Minister of Fisheries and Oceans Canada.

A one-century sedimentary record of N- and S-polycyclic aromatic compounds in the Athabasca oil sands region in Canada.

The atmospheric deposition of polycyclic aromatic compounds (PACs) is considered a major pathway to isolated lakes and bogs in the Athabasca oil sands region (AOSR), Canada. However, the suite of PACs measured has been limited. We report the detailed depositional history of nitrogen and sulphur heterocyclic PACs using a 210Pb dated sediment core (1914-2015) near major developments in the AOSR. We observed (1) an exponential growth in the deposition of heterocyclic PACs to recent times with an average doubling time of 12 years, (2) significant breakpoints in PAC fluxes in the mid to late 1980s, and (3) a synchronous increase of PACs with crude oil production (r2 = 0.82, p = 0.001). NPACs were not detected prior to the 1960s in the sediment core studied, suggesting they may hold promise in serving as indicators for atmospheric PAC deposition of industrial origin. Furthermore, a change in heterocyclic PAC distribution profiles beginning in the 1970-1980s, after the onset of mining, resembling a petcoke signature, was also observed. Significant positive correlations (p < 0.05) were observed between heterocyclic PACs, and several metal(loid)s, including priority pollutant elements, chromium and beryllium, and rare earth elements, cerium, lanthanum and yttrium (r2 > 0.75), suggesting the potential of a common source or similar transport and fate mechanisms. Significant negative or no correlations were observed between heterocyclic PACs and other metal(loid)s, including vanadium, total mercury and lead, possibly reflecting the impact of broader regulatory controls introduced in the mid-1970s on some metal(loids) but not on PACs, including the installation of electrostatic precipitators in major upgrader stacks.

Sources of atmospheric metal(loid) pollution recorded in Thompson Manitoba lake sediment cores within the Canadian boreal biome.

Global atmospheric emissions and subsequent deposition of numerous metal(loid)s has increased markedly since the industrial revolution. Due to a paucity of long-term metal(loid) flux measurements, the magnitude and timing of change are largely unknown, resulting in limited ability to predict time-scales of ecosystem recovery in response to emission decreases. In the absence of long-term data, palaeo-reconstructions provide continuous records of atmospheric metal(loid) deposition on an ecosystem, and landscape, scale. Here, we use high-resolution dated lake sediment cores to reconstruct the last c. 100 years of atmospheric anthropogenic deposition of a full suite (40) of metal(loid)s near a large nickel (Ni) and copper (Cu) smelter in an other-wise largely "pristine" region of northern Canada (Thompson, Manitoba). Anthropogenic depositional fluxes were compared to other regions of Canada including Kejimkujik National Park in Nova Scotia, Experimental Lakes Area in Ontario, as well as the Flin Flon, Manitoba Cu and zinc (Zn) smelter, located ~200 km southwest of Thompson. Deposition of 12 metal(loid)s were enriched above baseline (pre-1915) levels: antimony (Sb) > palladium (Pd) > bismuth (Bi) > mercury (Hg) > cadmium (Cd) > Ni > lead (Pb) > arsenic (As) > strontium (Sr) > Cu > platinum (Pt) > Zn. Spatio-temporal patterns in depositional fluxes and inventories demonstrate that 6 of these metal(loid)s were sourced primarily from the smelter, while As, Hg, Pb, Pt, Sb and Zn were sourced primarily from global and/or regional sources. Comparison of anthropogenic fluxes and inventories to available emissions data showed that Cu and Ni deposition has plateaued since the late 1970s despite dramatic smelter emission decreases between 2005 and 2014. We hypothesize that this discrepancy is due to releases of terrestrial metal(loid)s by climate-driven permafrost degradation, which is widespread across the region and will likely continue to drive increased metal(loid) fluxes to northern Canadian lakes for unknown time-scales.

Temporal trends, lake-to-lake variation, and climate effects on Arctic char (Salvelinus alpinus) mercury concentrations from six High Arctic lakes in Nunavut, Canada.

Climate warming and mercury (Hg) are concurrently influencing Arctic ecosystems, altering their functioning and threatening food security. Non-anadromous Arctic char (Salvelinus alpinus) in small lakes were used to biomonitor these two anthropogenic stressors, because this iconic Arctic species is a long-lived top predator in relatively simple food webs, and yet population characteristics vary greatly, reflecting differences between lake systems. Mercury concentrations in six landlocked Arctic char populations on Cornwallis Island, Nunavut have been monitored as early as 1989, providing a novel dataset to examine differences in muscle [Hg] among char populations, temporal trends, and the relationship between climate patterns and Arctic char [Hg]. We found significant lake-to-lake differences in length-adjusted Arctic char muscle [Hg], which varied by up to 9-fold. Arctic char muscle [Hg] was significantly correlated to dissolved and particulate organic carbon concentrations in water; neither watershed area or vegetation cover explained differences. Three lakes exhibited significant temporal declines in length-adjusted [Hg] in Arctic char; the other three lakes had no significant trends. Though precipitation, temperature, wind speed, and sea ice duration were tested, no single climate variable was significantly correlated to length-adjusted [Hg] across populations. However, Arctic char Hg in Resolute Lake exhibited a significant correlation with sea ice duration, which is likely closely linked to lake ice duration, and which may impact Hg processing in lakes. Additionally, Arctic char [Hg] in Amituk Lake was significantly correlated to snow fall, which may be linked to Hg deposition. The lack of consistent temporal trends in neighboring char populations indicates that currently, within lake processes are the strongest drivers of [Hg] in char in the study lakes and potentially in other Arctic lakes, and that the influence of climate change will likely vary from lake to lake.

Charged particle radiobiology beamline using tandem accelerator-based MeV protons and carbon ions: a pilot study on the track-end radiation quality, variable biological effectiveness and Bayesian beam dosimetry.

For in vitro cell irradiation using tandem accelerator-based MeV protons and carbon ions, by TOPAS simulation, a pilot study of performance evaluation is presented on a collimation beamline for 3 MeV protons and 10 MeV carbon ions from a 2 × 3 MV tandem accelerator. Based on the elements and source parameters, a collimated beam of 2.8 MeV protons or 2.5 MeV carbon ions, with 5.175 mm or 5.166 mm full width tenth maximum (FWTM), respectively, can be delivered to the target cell dish. TOPAS simulations and/or deterministic algorithms present a Bragg curve of linear energy transfer (LET) (10-70 keV µm-1) along a 138 µm range of the proton beam, and a declining LET of the carbon beam (900-100 keV µm-1) within 4 µm range. Based on the biophysical models for relative biological effectiveness (RBE) of protons, TOPAS RBE scorers presents a set of depth-variation curves of the proton RBE (for V79 and DU145 cells), linearly related to the Bragg curve of the proton LET. Based on the microdosimetric-kinetic (MK) theory, in the 4 µm range for a monolayer cell thickness, the mean RBEα (V79 cells) of the carbon ion beam is estimated as 3.612 (late S phase) and 1.737 (G 1/S phase) for the mean LET of 492 keV µm-1. For practical irradiations, a tunable proton RBE can be acquired by changing the thickness of the cell dish. For the low-energy high-fluence (rate) beams, indirect beam measurements are proposed to detect the proton-beam induced scattering/recoil protons from a beam-intercepting Mylar film, and the carbon-beam induced backscattered electrons from a gold-deposited Havar-foil beam window. Statistical dosimetry for the indirect measurement is established, using a Bayesian model based on the preset number of detection counts, by which the mean value of the whole-dish dose can be prescribed and the uncertainty introduced in the survival data can be corrected.

Bioaccumulation of Selected Halogenated Organic Flame Retardants in Lake Ontario.

The trophic magnification of polybrominated diphenyl ethers (PBDEs) and selected nonlegacy halogenated organic compounds (HOCs) was determined in the food web of Lake Ontario (ON, Canada). In all, 28 Br3 -Br8 -PBDEs and 24 HOCs (10 of which had not been targeted previously) were analyzed. Average concentrations of Σ28 PBDEs in fish ranged between 79.7 ± 54.2 ng/g lipid weight in alewife (Alosa pseudoharengus) and 815 ± 695 ng/g lipid weight in lake trout (Salvelinus namaycush). For invertebrates, concentrations were between 13.4 ng/g lipid weight (net plankton; >110 µm) and 41.9 ng/g lipid weight in Diaporeia (Diaporeia hoyi). Detection frequency (DF) for HOCs was highest for anti-Dechlorane Plus (anti-DDC-CO), 1,3-diiodobenzene (1,3-DiiB), tribromo-methoxy-methylbenzene (ME-TBP), allyl 2,4,6-tribromophenyl ether (TBP-AE), pentabromocyclododecene (PBCYD), α+ß-tetrabromocylcooctane (TBCO), 2-bromoallyl 2,4,6-tribromophenyl ether (BATE), and pentabromotoluene (PBT; DF for all = 100% in lake trout). Tetrabromoxylene (TBX), dibromopropyl 2,4,6-tribromophenyl ether (TBP-DBPE), and syn-DDC-CO were also frequently detected in trout (DF = 70-78%), whereas 2,3,4,5,6-pentabromoethyl benzene (PBEB) was detected only in plankton. Several HOCs were reported in aquatic biota in the Great Lakes (USA/Canada) for the first time in the present study, including PBCYD, 1,3DiiB, BATE, TBP-DBPE, PBT, α + ß-TBCO, and ME-TBP. The Br4-6 -BDEs (-47, -85, -99, -100, -153, and -154) all had prey-weighted biomagnification factors (BMFPW ) values >6, whereas BMFPW values for Br7-8 -BDEs were <1. The highest BMFPW values of non-PBDEs were for TBP-DBPE (10.6 ± 1.34) and ME-TBP (4.88 ± 0.60), whereas TBP-AE had a BMFPW value of <1. Significant (p ≤ 0.05) trophic magnification factors (TMFs), both positive and negative, were found for Br4-8- BDEs (BDE 196 = 0.4; BDE 154 = 9.5) and for bis(2,4,6-tribromophenoxy)ethane (BTBPE; 0.53), PBCYD (1.8), 1,3-DiiB (0.33), and pentabromobenzene (PBB; 0.25). Food chain length was found to have a significant influence on the TMF values. Environ Toxicol Chem 2019;38:1198-1210. © 2019 SETAC.

Deposition and Source Identification of Nitrogen Heterocyclic Polycyclic Aromatic Compounds in Snow, Sediment, and Air Samples from the Athabasca Oil Sands Region.

Polycyclic aromatic compounds (PACs) can have multiple sources in the Athabasca Oil Sands Region (AOSR). The current study was designed to identify and explore the potential of nitrogen heterocyclic PACs (NPACs) as source indicators in snowpack, lake sediment and passive air samples from the AOSR during 2014-2015. Source samples including petroleum coke (petcoke), haul road dust, and unprocessed oil sands were also analyzed. Samples were analyzed using comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry, and liquid chromatography-high resolution Orbitrap mass spectrometry. Over 200 NPACs were identified and classified into at least 24 isomer groups, including alkylated carbazoles, benzocarbazoles, and indenoquinolines. Levels of NPACs in environmental samples decreased with distance from the main developments and with increasing depth in lake sediments but were detected within 50 km from the major developments. The composition profiles of several NPAC isomer classes, such as dimethylcarbazoles, showed that petcoke had a distinct distribution of NPACs compared to the haul road dust and unprocessed oil sands ores and was the most similar source material to near-field environmental samples. These results suggest that petcoke is a major contributing source for the identified NPACs and that these compounds have the potential to be used as source indicators for future research in the AOSR.

Legacy and Emerging Persistent Organic Pollutants (POPs) in Terrestrial Compartments in the High Arctic: Sorption and Secondary Sources.

Legacy persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and emerging perfluoroalkyl substances (PFASs) were measured in vegetation and soil samples collected at remote lakes in the Canadian High Arctic. Field studies were carried out in 2015 and 2016 to assess concentrations of POPs, study the relevant sorbing phases, and determine whether Arctic soils were sinks or sources of legacy POPs to the atmosphere and to neighboring lakes. The patterns of legacy POPs in vegetation and soils were dominated by low molecular weight PCB congeners along with OCPs, confirming the importance of long-range atmospheric transport. Lipid and non-lipid organic matter was a key determinant of legacy POPs in Arctic vegetation. Soil organic matter was the main descriptor of hydrophobic PCBs and OCPs in soils, while soil inorganic carbon content, was an important driver of the sorption of PFASs in soils. While contaminant concentrations were low in soil and vegetation, higher PCBs and PFOS organic and inorganic carbon-normalized concentrations were found at Resolute Lake indicating the presence of local sources of contamination. Comparison of fugacities of PCBs in soil and air from Resolute Lake indicated soils as net sources of PCBs to the atmosphere.

Climatic Influence on Temporal Trends of Polychlorinated Biphenyls and Organochlorine Pesticides in Landlocked Char from Lakes in the Canadian High Arctic.

Temporal trends and climate related parameters affecting the fate of legacy persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were examined in landlocked Arctic char from four lakes in the Canadian Arctic. Among biological parameters, lipid content was a key factor explaining the concentration of most POPs in Arctic char. Legacy PCBs and OCPs generally showed declining trends of concentrations in Arctic char, consistent with past restriction on uses and emissions of POPs. However, increases in lake primary productivity (measured as chlorophyll a) exerted a dilution effect on POPs concentrations in Arctic char. Concentrations of POPs in char from the last two decades were positively correlated with interannual variations of the North Atlantic Oscillation (NAO). Higher concentrations of POPs in Arctic char were observed in 3 of the 4 lakes during positive NAO phases. This, together with increasing local Arctic temperatures, could lead to increases on POPs concentrations in char from remote Arctic Lakes in future decades. Also, if there are nearby secondary sources as may be the case for Resolute Lake, located near an airport where increasing levels were found for hexachlorobenzene and toxaphene, probably due to the mobilization from secondary sources in soils.