A wide variety of sampling techniques and strategies are needed to analyze polycyclic aromatic compounds (PACs) and interpret their distributions in various environmental media (i.e., air, water, snow, soils, sediments, peat and biological material). In this review, we provide a summary of commonly employed sampling methods and strategies, as well as a discussion of routine and innovative approaches used to quantify and characterize PACs in frequently targeted environmental samples, with specific examples and applications in Canadian investigations. The pros and cons of different analytical techniques, including gas chromatography – flame ionization detection (GC-FID), GC low-resolution mass spectrometry (GC-LRMS), high performance liquid chromatography (HPLC) with ultraviolet, fluorescence or MS detection, GC high-resolution MS (GC-HRMS) and compound-specific stable (δ¹³C, δ²H) and radiocarbon (Δ¹⁴C) isotope analysis are considered. Using as an example research carried out in Canada’s Athabasca oil sands region (AOSR), where alkylated polycyclic aromatic hydrocarbons and sulfur-containing dibenzothiophenes are frequently targeted, the need to move beyond the standard list of sixteen EPA priority PAHs and for adoption of an AOSR bitumen PAC reference standard are highlighted.

Bitumen recovery from oil sands in northeastern Alberta, Canada produces large volumes of tailings, which are deposited in mining areas that must be reclaimed upon mine closure. A new technology of non-segregated tailings (NST) developed by Canadian Natural Resources Limited (CNRL) was designed to accelerate the process of oil sands fine tailings consolidation. However, effects of these novel tailings on plants used for the reclamation of oil sands mining areas remain to be determined. In the present study, we investigated the effects of NST on seedlings of three species of plants commonly planted in oil sands reclamation sites including paper birch (Betula papyrifera), white spruce (Picea glauca) and green alder (Alnus viridis). In the controlled-environment study, we grew seedlings directly in NST and in the two types of reclamation soils with and without added NST and we measured seedling growth, gas exchange parameters, as well as tissue concentrations of selected elements and foliar chlorophyll. White spruce seedlings suffered from severe mortality when grown directly in NST and their needles contained high concentrations of Na. The growth and physiological processes were also inhibited by NST in green alder and paper birch. However, the addition of top soil and peat mineral soil mix to NST significantly improved the growth of plants, possibly due to a more balanced nutrient uptake. It appears that NST may offer some advantages in terms of site revegetation compared with the traditional oil sands tailings that were used in the past. The results also suggest that, white spruce may be less suitable for planting at reclamation sites containing NST compared with the two studied deciduous tree species.

Studies of the chemical composition of atmospheric aerosols, rain water and snow in various regions of the globe quite often show the presence of pyridine and a number of its low mass derivatives. Nevertheless, the sources of those compounds in the environment have not yet been established and definitely require elucidation, supported by reliable experimental results. In the present work the chemical composition of peat combustion products as one of the important sources of atmospheric aerosol emission is studied by two-dimensional gas chromatography – high-resolution mass spectrometry with a focus on the detection of pyridine derivatives. Twenty-five compounds of this class were reliably identified and quantified in laboratory experiments on peat burning. Among them 3-hydroxypyridine predominates, while the rest analytes are mostly represented by alkyl derivatives: pyridine, 2-methylpyridine, 3-methylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 2-ethylpyridine, lutidines (in order of decreasing concentration). The distribution of these combustion products coincides with that obtained earlier in environmental studies carried out in Arctic, Central Russia and France. The experiments on peat thermal decomposition by pyrolysis GC-MS demonstrated that the maximum concentrations as well as the number of detected analytes were found under conditions of oxygen lack and a temperature of about 500 °C, i.e. characteristic conditions of peat wildfires. The observed levels of pyridines’ emission recalculated on the peat dry weight exceeded 200 mg kg⁻¹. Considering hundreds of millions tons of peat burning in megafires over 20,000 tons of pyridines penetrate the Earth atmosphere annually. The obtained results allow concluding that peat burning may be the major and still underestimated source of pyridine and lower alkylpyridines in the Earth atmosphere.

The present work was done to explore the joint effect of Streptomyces pactum (Act12) and plant nutrients on phytoremediation of smelter-contaminated soils. The physiological indicators and phytoextraction indices of potherb mustard (Brassica juncea, Coss) grown in Act12 inoculated soil with or without Hoagland’s solution (H), humic acid (HA) and peat (PS) were evaluated. The results indicated that H, HA and PS acted synergistically with Act12, notably increasing chlorophyll and soluble protein contents and thereby promoting plant growth. Soil nutrient treatments reduced the antioxidant activities (PPO, CAT and POD) by 28.2–41.4%, 22.3–90.1% and 15.2–59.4% compared to control, respectively. Act12 and H treatments markedly facilitated plant to accumulate more cadmium (Cd) and zinc (Zn), but it was observed decreases when applied with HA and PS. Metal uptake (MU) values further indicated the differences in phytoextraction efficiency, i.e., H > PS > Control > HA. Taken together, Act12 combined with plant nutrients contributed to alleviating metal toxicity symptoms of plant. Hoagland’s solution and peat were highlighted in the present phytoextraction trial, and recommended as soil additives.

Mercury (Hg) is commonly extracted from solid phase samples using aqua regia for total Hg (tHg) analysis. However, uncertainties exist regarding the complete extraction of Hg by aqua regia, especially from carbonaceous materials. To investigate whether aqua regia can completely extract Hg from biochars, batch-style experiments were carried out to evaluate extraction efficiency of aqua regia with respect to Hg-loaded biochar and to characterize the residual Hg speciation and spatial distribution. Different types of biochars (raw, FeCl₃-modified, and FeSO₄-modified, prepared at different temperatures) were reacted with Hg-spiked solution before the digestion experiments. Adsorption analyses indicate the biochars were successfully loaded with Hg and that the Hg content was higher in biochars pyrolyzed at higher temperature (900 versus 300 or 600 °C). The results of digestion experiments indicate Hg could not be completely extracted from the biochars tested, with a greater percentage of residual Hg in biochars pyrolyzed at 600 (60 ± 15%) and 900 (75 ± 22%) than 300 °C (7 ± 2%). Furthermore, the fraction of residual Hg in FeSO₄-modified biochars after aqua regia digestion was significantly lower than in FeCl₃-modified and unmodified biochars. Confocal micro-X-ray fluorescence imaging (CMXRFI) showed residual Hg in biochars is concentrated on surfaces prior to digestion, but more homogeneously distributed after digestion, which indicates Hg on biochar surface is more easily digested. Hg extended X-ray absorption fine structure (EXAFS) spectra modelling showed residual Hg in biochars mainly exists as Hg(II)–Cl. These results indicate extra caution should be paid for tHg determinations using aqua regia digestion method in soil (especially in forest), sediment, and peat samples containing black carbon, activated carbon, or biochar.

We investigated the influence of sulfate (SO₄²⁻) deposition and concentrations on the net formation and solubility of methylmercury (MeHg) in peat soils. We used data from a natural sulfate deposition gradient running 300 km across southern Sweden to test the hypothesis posed by results from an experimental field study in northern Sweden: that increased loading of SO₄²⁻ both increases net MeHg formation and redistributes methylmercury (MeHg) from the peat soil to its porewater. Sulfur concentrations in peat soils correlated positively with MeHg concentrations in peat porewater, along the deposition gradient similar to the response to added SO₄²⁻ in the experimental field study. The combined results from the experimental field study and deposition gradient accentuate the multiple, distinct and interacting roles of SO₄²⁻ deposition in the formation and redistribution of MeHg in the environment.

Hematite nanoparticles (NPs) exist naturally and ubiquitously in soil, and they are always associated with soil organic matter by forming organic-inorganic complexes. In this work, hematite NPs coated with peat humic acid (HAₚₑₐₜ) and soil humic acid (HAₛₒᵢₗ) were chosen as sorbents for hydrophobic organic contaminants (HOCs) to simulate the sorption processes in soil. Ionizable pentachlorophenol (PCP) and non-ionizable phenanthrene (PHE) were selected as representative HOCs. Compared with sorption isotherms of uncoated hematite NPs, the coating of HA onto the surface of hematite NPs substantially increased its sorption affinity for PCP and PHE by about 1-2 orders of magnitude, and the increasing degree was positively correlated to the HA content. These phenomena emphasized the dominant role of HA in the sorption process. The reduced polarity and the introduction of functional groups contributed to the enhanced sorption of HOCs on HA-coated hematite NPs. Furthermore, HAₚₑₐₜ-hematite NPs showed higher sorption affinity for both PCP and PHE than HAₛₒᵢₗ-hematite NPs, which was mainly due to the lower polarity and higher hydrophobicity of HAₚₑₐₜ-hematite NPs. The sorption of PCP and PHE on HA-coated hematite NPs was inhibited obviously with increasing pH values and the pH effect on PCP sorption was more significant than that of PHE, due to the deprotonation of functional groups within adsorbed HA, the loose structure of adsorbed HA and the dissociation of PCP. Our findings elucidated the mechanisms involved in HOCs sorption processes by HA-hematite NPs and provided a theoretical basis for environmental remediation with natural NPs (e.g., hematite NPs).

Dissolved organic carbon (DOC) has a major influence upon sorption/desorption and transport of hydrophobic organic contaminants (HOCs) in soil environments. However, the molecular mechanisms of DOC sorption and its effects on aged HOC desorption in contaminated soils still remain largely unclear. Here, effects of three different DOC (one from commercial peat and two from biochars produced at 300 °C and 500 °C pyrolysis temperatures, respectively) and oxalate (as a reference) on abiotic desorption behavior of aged phenanthrene from three agricultural soils were investigated. Results showed that desorption of aged phenanthrene from soils was predominantly dependent on soil organic carbon content. The presence of DOC and oxalate resulted in higher desorption of phenanthrene compared to water alone, and the effects were positively related to soil organic carbon content and DOC/oxalate concentration. The facilitating effects of DOC were further increased during the second consecutive desorption, whereas oxalate had no such effect. Ultra-high-resolution Fourier transform-ion cyclotron resonance-mass spectrometry confirmed the molecular fractionation of DOC at the soil-water interface during DOC sorption. Specifically, the DOC molecules with O-rich moieties were preferentially adsorbed, whereas the molecules with phenolic and aromatic structures were selectively retained in the soil solutions through competitive displacement and co-sorption reactions during sorption. The enriched phenyl structures in the retained DOC facilitated its association with phenanthrene in the solutions and thus the release of phenanthrene from the soils. In contrast, oxalate replaced some organic carbon from the soils and thus released the associated phenanthrene into the solutions. Our findings highlight the importance of the molecular composition and structure of DOC for the desorption of phenanthrene in soil-water environments, which may help improve our understanding of the release and transport of organic compounds in the environments.