The two forage species used in New Zealand pastoral agricultural systems, chicory (Cichorium intybus) and plantain (Plantago lanceolata) show differential ability to absorb and translocate cadmium (Cd) from roots to shoots. Chicory can accumulate Cd from even low Cd soils to levels that might exceed regulatory guidelines for Cd in fodder crops and food. Chicory and plantain were grown in soil-filled rhizocolumns under increasing Cd levels (0 (Control), 0.4, 0.8 and 1.6 mg Cd/kg soil) for 60 days and showed variable secretion of oxalic, fumaric, malic and acetic acids as a function of Cd treatment. Plant roots secrete such Low Molecular Weight Organic Acids into the rhizosphere soil, which can influence Cd uptake. Chicory showed significantly (P < 0.05) lower secretion of fumaric acid, and higher secretion of acetic acid than plantain at all Cd treatments. We propose that the significant secretion differences between the two species can explain the significantly (P < 0.05) higher shoot Cd concentration in chicory for all Cd treatments. Understanding the mechanism for increased uptake in chicory may lead to breeding or genetic modification which yield low Cd uptake cultivars needed to mitigate the risk of Cd accumulation in pastoral agricultural food chains from this increasingly important fodder crop.

This research apportioned size-resolved particulate matter (PM) contributions in a megacity in northern China based on a full year of measurements of both inorganic and organic markers. Ions, elements, carbon fractions, n-alkanes, polycyclic aromatic hydrocarbons (PAHs), hopanes and steranes in 9 p.m. size fractions were analyzed. High molecular weight PAHs concentrated in fine PM, while most other organic compounds showed two peaks. Both two-way and three-way receptor models were used for source apportionment of PM in different size ranges. The three-way receptor model gave a clearer separation of factors than the two-way model, because it uses a combination of chemical composition and size distributions, so that factors with similar composition but distinct size distributions (like more mature and less mature coal combustion) can be resolved. The three-way model resolved six primary and three secondary factors. Gasoline vehicles and coal and biomass combustion, nitrate and high relative humidity related secondary aerosol, and resuspended dust and diesel vehicles (exhaust and non-exhaust) are the top two contributors to pseudo-ultrafine (<0.43 μm), fine (0.43–2.1 μm) and coarse mode (>2.1 μm) PM, respectively. Mass concentration of PM from coal and biomass combustion, industrial emissions, and diesel vehicle sources showed a bimodal size distribution, but gasoline vehicles and resuspended dust exhibited a peak in the fine and coarse mode, separately. Mass concentration of sulphate, nitrate and secondary organic aerosol exhibited a bimodal distribution and were correlated with temperature, indicating strong photochemical processing and repartitioning. High relative humidity related secondary aerosol was strongly associated with size shifts of PM, NO₃⁻ and SO₄²⁻ from the usual 0.43–0.65 μm to 1.1–2.1 μm. Our results demonstrated the dominance of primary combustion sources in the <0.43 μm particle mass, in contrast to that of secondary aerosol in fine particle mass, and dust in coarse particle mass in the Northern China megacity.

Sodium percarbonate (SPC, 2Na₂CO₃∙3H₂O₂), is a compound that can be used under multiple environmental applications. In this work, SPC was employed as oxidant in the treatment of soil contaminated with diesel oil. The soil samples were collected during the earthmoving stage of RNEST Oil Refinery (Petrobras), Brazil. Then, the samples were air-dried, mixed and characterized. Subsequently, raw soil was contaminated with diesel and treated by photo-Fenton reaction (H₂O₂/Fe²⁺/UV). SPC played a significant role in the generation of hydroxyl radicals under the catalytic effect of ferrous ions (Fe²⁺), hydrogen peroxide (H₂O₂) and radiation. These radicals provoked the photodegradation of polycyclic aromatic hydrocarbons (PAHs), in the soil remediation. A factorial design 3³ was carried out to assess the variables which most influenced the decrease in total organic carbon (TOC). The study was performed with the following variables: initial concentration of [H₂O₂] and [Fe²⁺], between 190.0 and 950.0 mmol L⁻¹ and 0.0–14.4 mmol L⁻¹, respectively. UV radiation was supplied from sunlight, blacklight lamps, and system without radiation. All experiments were performed with 5.0 g of contaminated soil in 50.0 mL of solution. The initial concentration of Fe²⁺ showed the statistically most significant effect. The oxidation efficiency evaluated in the best condition showed a decrease from 34,765 mg kg⁻¹ to 15,801 mg kg⁻¹ in TOC and from 85.750 mg kg⁻¹ to 20.770 mg kg⁻¹ in PAHs content. Moreover, the sums of low and high molecular weight polycyclic aromatic hydrocarbons (LMW-PAHs and HMW-PAHs) were 19.537 mg kg⁻¹ and 1.233 mg kg⁻¹, respectively. Both values are within the limits recommended by the United Sates Environmental Protection Agency (USEPA) and evidenced the satisfactory removal of PAHs from contaminated soil, being an alternative to classic oxidation protocols.

Membrane concentrated landfill leachate (MCLL) contains large amounts of recalcitrant organic matter that cause potential hazards to the environment. Knowledge on the compositional variation of MCLL during treatment is important for a better understanding on the degradation pathway of organic pollutants. In this work, the structural change of MCLL during Fenton oxidation process was examined using spectroscopic techniques. The removal rates of COD, TOC and UV254 reached 78.9 ± 1.3%, 70.2 ± 1.4% and 90.64 ± 1.6%, respectively, under the optimal condition (i.e., dosage of H2O2 = 9.0 mL/200 mL, H2O2/Fe(II) molar ratio = 3.0, pH = 3.0, time = 40 min). Spectral analyses suggested that aromatic/CC structure and CO bonds in MCLL can be successfully destroyed by Fenton oxidation, resulting in a decrease in molecular weight. One fulvic-like and one humic-like components were identified in MCLL, both of which can be removed by Fenton treatment. In addition, two-dimensional correlation spectroscopic analyses suggested the oxidative changes of MCLL structure in the order of fulvic-like component/unsaturated conjugated bond > aromatic structure > humic-like component. The results may provide a new insight to the understanding on the structure variation of MCLL during treatment, which is beneficial for the design of cost-effective treatment strategies.

Humic acid (HA) plays vital roles in regulating the environmental behaviors of metals and thus their toxicity to biota. However, the inner relation between metal bioavailability to soil organisms and the presence of HA with different molecular weight (Mw) is not well documented. In this study, we separated HAs into four fractions with Mw range of 5-30k Da, and discussed their ability to alleviating the toxicity of Cd and Pb to earthworm. The bioaccumulation capacities (Cₘₐₓ) increased in order of: UF1<UF2<UF3<UF4, which is in line with the variations of bioavailable concentrations of Cd and Pb in soil. Variations of Mw and binding capacities of HA determine the accumulation behavior in soil solution. The unsatisfactory of biotic ligand model fitting and the differences in fractions of the total biotic ligand sites (f) in earthworm bound by Cd and Pb suggested that only free species of Cd could be considered as biological available to earthworm, while the Pb–HAs complexes have potential ability to interact with earthworm membrane. Antioxidant enzymes are effective biomarkers, and HA with lower Mw play more important roles in restricting the toxicity of soil Cd and Pb to earthworm. These results reveal the different mechanism for HA controlling metal bioavailability between Cd and Pb in soil environment.

Numerous studies have focused on assessing the risk of human exposure to polycyclic aromatic hydrocarbons (PAHs) in indoor dust via dermal contact. However, the dermal bioaccessibility and dermal absorption of PAHs in indoor dust have seldom been reported. In the present study, the effects of temperature, sweat ratio, solid-liquid ratio and incubation time on the dermal bioaccessibility of PAHs were examined. Naphthalene, phenanthrene, pyrene and benzo[a]pyrenewere selected for examination in an absorption assay with keratinocyte cells. The results showed the release of PAHs from indoor dust fitted a first-order one-compartment model. Naphthalene had the highest rate of release, which was consistent with the bioaccessibility assay results. In addition, the absorption rate of naphthalene and phenanthrene by keratinocytes was higher than that of pyrene and benzo[a]pyrene, with the latter being of higher molecular weight. These results indicated that low molecular weight PAHs were much more easily absorbed via dermal contact than were high molecular weight PAHs. The dermal bioavailability of PAHs in indoor dust was estimated by multiplying the bioaccessibility of PAHs in indoor dust by the ratio of dermal absorption by skin cells, and ranged from 0.12 to 51.0%. These data will be useful in risk assessments.

Marine deposit feeders are of ecological significance in transferring sedimentary Cd along aquatic food chains. A key process for this transfer is these organisms’ dietary uptake of Cd via solubilization of Cd present in ingested contaminated sediment. To better understand the bioavailability of sedimentary Cd to deposit feeders, the present study used in vitro extraction experiments to explore the contribution of different digestive agents (proteins, amino acids and surfactants) to the solubilization of Cd from sediment collected in a highly-contaminated Chinese bay. This was done for various commercially-available mimetic digestive agents (the protein BSA, a mixture of amino acids, and the surfactants rhamnolipid and SDS), and for proteins and surfactants collected from the gut juice of a sipunculan worm. The Cd mobilization capacity of BSA was significantly higher than that of the amino acids and the commercial surfactants. In the presence of BSA, > 70% of the released Cd became associated with this protein. In contrast, the digestive proteins from the sipunculan had a lower Cd mobilization capacity than was the case for the other digestive agents and the majority of the released Cd (∼80%) was associated with small molecular weight fractions. The differences in Cd mobilization between the BSA and the digestive proteins were attributed to differences in their sediment-adsorption tendencies and their Cd-complexing capacities. While the digestive surfactants had minor effects on the release of sedimentary Cd, they significantly enhanced Cd mobilization by the digestive proteins when both were present simultaneously. Our results suggest that the characteristics of proteins should be considered when using commercially-available mimetic digestive agents to explore Cd bioavailability in sediments. Furthermore, digestive surfactants seem to have important effects on the solubilization of Cd during gut passage by reducing the adsorption of the digestive proteins to the sediments.

Whereas non-extractable residue (NER) formation is recognized as an important process affecting the ecological risk of organic contaminants in soils, it is commonly neglected in regional-scale multi-media models assessing chemical environmental fate and risk. We used a combined field and modeling study to elucidate the relative importance of NER formation to the reduction in available organic contaminants compared with fate processes commonly considered in risk assessment models (volatilization, leaching, and biodegradation). Specifically, four polycyclic aromatic hydrocarbons (PAHs), i.e., phenanthrene (Phe), pyrene (Pyr), benzo[a]pyrene (BaP), and benzo[ghi]perylene (BghiP), were spiked and measured in a one-year field pot experiment at four sites with diverse environmental conditions on the eastern Tibetan Plateau. The rate of NER formation was derived as the difference between the overall rate of decline in total-extractable PAH concentrations, obtained by fitting a biphasic first-order model to the measured concentrations, and the sum of the calculated rates of volatilization, leaching, and biodegradation. Our work shows that the total-extractable PAH concentration undergoes a rapid decline and a slow decline, with shorter overall half-lives (especially for BaP and BghiP) than those observed in earlier studies. Generally, NER formation was assessed to be the dominant contributor (64 ± 33%) to the overall decline of PAHs, followed by biodegradation (35 ± 32%); volatilization and leaching were the smallest contributors. In particular, heavier PAHs (i.e. BaP and BghiP) tend to have shorter half-lives in the rapid and the overall decline phase, indicating that the erroneous estimation of environmental fate and risks might be more pronounced for organic contaminants with a large molecular size. The trend of overall decline rates of PAHs displayed a combined effect of NER formation and biodegradation. This work indicates the need to consider NER formation as a process in multi-media models of chemical fate and risk.

Following the 16TAN Husky oil spill along the North Saskatchewan River (NSR), the occurrence and natural attenuation of the petroleum hydrocarbons were assessed by analyzing the littoral zone sediments/oil debris collected from July 2016 to October 2017. Husky oil-free, mixed sediment-Husky oil, and Husky oil debris samples were identified for all the collected samples. Shoreline sediments were contaminated by mixed biogenic, pyrogenic and petrogenic inputs prior to the spill. Oil stranded on the shoreline of NSR was moved or buried due to the very dynamic conditions of the shoreline, or cleaned through a series of cleanup activities after the spill. Most normal alkanes were naturally weathered, whereas most of the branched alkanes and all of the saturated petroleum biomarkers remained. Some lighter molecular weight (e.g., 2 to 3-ring) polycyclic aromatic hydrocarbons (PAHs) were lost rapidly after the spill, whereas sulfur containing components, e.g., dibenzothiophenes and benzonaphthothiiophenes, and those having a heavier molecular weight did not change markedly even 15 months post-spill. Similarly, some light hydrocarbons (e.g., <C₁₀) were lost over the first kilometers from the point of entry (POE), while heavier hydrocarbons did not show any major differences away from the POE. Very large inter-site and inter-survey discrepancies were found for samples. Evaporation into the air and dissolution into water, combined with biodegradation, were together or independently the main contributors to the loss of the light molecular hydrocarbons.

Atmospheric dry deposition is a major pathway for removal of polycyclic aromatic hydrocarbons (PAHs) from the atmosphere. Despite its significance in the atmospheric environment, measurements of the dry deposition velocity (VDD) and deposition fluxes (FDD) of PAHs are relatively limited. In this study, a passive dry deposition (PAS-DD) collector was co-deployed with passive air sampler polyurethane foam (PAS-PUF) from November 2015 to November 2016 in two major cities (Kathmandu and Pokhara), Nepal, to investigate the VDD and FDD of PAHs. The VDD of PAHs ranged from 0.25 to 0.5 cm s⁻¹ and the annual average was recorded as 0.37 ± 0.08 cm s⁻¹. On the basis of measured VDD, the FDD of ∑15PAHs in Kathmandu and Pokhara were estimated as 66 and 5 kg yr⁻¹ respectively. According to the measured VDD of Kathmandu and Pokhara in this study, and the previously published VDD data of Toronto, Canada, where the same PAS-DD collector was used, a significant multi-linear correlation (r² = 0.79, p < 0.05) was found between VDD of higher molecular weight (HMW with MW ≥ 228.3 and ≥ 4 rings) PAHs and meteorological parameters (precipitation and wind speed) and vapor pressure of PAHs. To the best of our knowledge, this enabled the development of an empirical model that can exhibit the combined effects of meteorological conditions on the VDD of HMW PAHs. The model was used to estimate the VDD values for major cities in the Indo-Gangetic Plain (IGP) region and the maximum estimated proportion of HMW PAHs deposited by dry deposition reached up to 60% of total emissions. Although PAH emissions in the IGP region pose global risks, the results of this study highlight the considerable risk for local IGP residents, due to the large dry deposition proportion of HMW PAHs.