Residues of pyrethroid insecticides tend to accumulate in bed sediments due to their strong hydrophobicity. Rather than the total or bulk sediment concentration, it is the freely dissolved concentration (Cfᵣₑₑ) that drives toxicity to benthic invertebrates. In this study we developed thin film-based samplers for in situ ambient monitoring of pyrethroids at trace levels in sediment. Out of five common polymer materials, polyethylene (PE) and silicone rubber (SR), were identified to offer superior enrichment for pyrethroids from sediment. To circumvent the slow equilibrium process, ¹³C-permethrin and bifenthrin-d₅ were preloaded onto the films as performance reference compounds (PRCs). The PRC-preloaded film samplers were deployed at five sites in Southern California under field conditions for 7 d and retrieved for analysis. The sediment porewater Cfᵣₑₑ of eight pyrethroids derived from PRC-PE films ranged from 173 to 903 ng/L, accounting for 18.2–36.1% of the corresponding total porewater concentrations. The PRC-SR film samplers yielded Cfᵣₑₑ values closely mimicking those from the PRC-PE samplers, cross-validating the two sampling devices. Additionally, a significant positive association was found between the observed mortality from toxicity tests using Hyalella azteca and the Cfᵣₑₑ of bifenthrin (r = 0.628, p = 0.02). A significant linear correlation (R² = 0.99) between Cfᵣₑₑ derived from in situ monitoring and that of ex situ measurement under equilibrium conditions was also observed. Results from this study demonstrated that the film-based samplers may be used for in situ ambient monitoring to detect biologically relevant contamination of pyrethroids in bed sediments, which may contribute to improved risk assessment for this class of widely used insecticides.

The disturbance of the thyroid system and elimination of chiral pyrethroid pesticides with respect to enantioselectivity in reptiles have so far received limited attention by research. In this study, bioaccumulation, thyroid gland lesions, thyroid hormone levels, and hypothalamus-pituitary-thyroid axis-related gene expression in male Eremias argus were investigated after three weeks oral administration of lambda-cyhalothrin (LCT) enantiomers. In the lizard liver, the concentration of LCT was negatively correlated with the metabolite-3-phenoxybenzoic acid (PBA) level during 21 days of exposure. (+)-LCT exposure induced a higher thyroid follicular epithelium height than (−)-LCT exposure. The thyroxine levels were increased in both treated groups while only (+)-LCT exposure induced a significant change in the triiodothyronine (T3) level. In addition, the expressions of hypothalamus-pituitary-thyroid axis-related genes including thyroid hormone receptors (trs), deiodinases (dios), uridinediphosphate glucuronosyltransferase (udp), and sulfotransferase (sult) were up-regulated after exposure to the two enantiomers. (+)-LCT treatment resulted in higher expression of trs and (−)-LCT exposure led to greater stimulation of dios in the liver, which indicated PBA-induced antagonism on thyroid hormone receptors and LCT-induced disruption of thyroxine (T4) deiodination. The results suggest the (−)-LCT exposure causes higher residual level in lizard liver while induces less disruption on lizard thyroid activity than (+)-LCT.

Contamination of agricultural soils by pharmaceutical and personal care products (PPCPs) resulting from the application of treated wastewater, biosolids and animal wastes constitutes a potential environmental risk in many countries. To date a handful of studies have considered the phytotoxicity of individual PPCPs in crop plants, however, little is known about the effect of PPCPs as mixtures at environmentally relevant levels. This study investigated the uptake and transport, physiological responses and detoxification of a mixture of 17 PPCPs in cucumber seedlings. All PPCPs were detected at higher concentrations in roots compared to leaves, with root activity inhibited in a dose-dependent manner. At 5–50 μg/L, the mature leaves exhibited burnt edges as well as a reduction in photosynthesis pigments. Reactive oxygen species (ROS) production and lipid peroxidation increased with increasing PPCP concentrations; and their contents were greater in roots than in leaves for all PPCP treatments. Enzymes involved in various functions, including oxidative stress (superoxide dismutase and ascorbate peroxidase) and xenobiotic metabolism (peroxidase and glutathione S-transferase), were elevated to different levels depending on the PPCP concentration. Glutathione content gradually increased in leaves, while a maxima occurred at 0.5 μg L⁻¹ PPCPs in roots, followed by a decrease thereafter. This study illustrated the complexity of phytotoxicity after exposure to PPCP mixtures, and provided insights into the molecular mechanisms likely responsible for the detoxification of PPCPs in higher plants.

Feed intake, for non-smokers, is the first route of contamination to polycyclic aromatic hydrocarbons (PAHs), which are potentially toxic compounds via ingestion. Investigations are focused on the presence of PAHs in fruits and vegetables. Transfer of PAHs can occur from air and soil during cultivation. They can also appear prior to consumption during storage, transport or cooking processes.Rather low amounts of PAHs are usually detected in raw fruits and vegetables. Quantities are between 0.01 and 0.5 μg kg⁻¹ (wet weight) for compounds classified as priority pollutants by the US Environmental Protection Agency (EPA). However, several studies point out that concentrations of some PAHs can exceed 0.5 μg kg⁻¹ wet weight in diverse fruits and vegetables and even reach 5 μg kg⁻¹. Amounts can be very different depending on the surrounding area of the crops, the aromatic hydrocarbon, or even the product itself. PAHs content is usually higher for products grown near roadways or in urban regions than in rural areas. Trace level of compounds such as phenanthrene, fluoranthene and pyrene have been found in quite every raw fruit and vegetable. Relative high amounts of lighter PAHs such as naphthalene, acenaphthylene, and acenaphthene have been found in some of them.

The objective of this study is to investigate the qualitative contribution of internal and external factors of the area contaminated by polystyrene (PS) in coastal marine environments. This study is based on the extensive results of monitoring the styrene oligomers (SOs) present in sand and seawater samples along various coastlines of the Pacific Ocean. Here, anthropogenic SOs is derived from PS during manufacture and use, and can provide clues about the origin of SOs by PS pollution. The monitoring results showed that, if the concentration of SOs in water is higher than those concentrations in beach sand, this area could be affected by PS plastic caused by an external factor. On the other hand, if the concentration of SOs is higher in the beach sand, the region can be mainly influenced by PS plastic derived from its own area. Unlike the case of an external factor, in this case (internal influence), it is possible to take policy measures of the area itself for the PS plastic problem. Thus, this study is motivated by the need of policy measures to establish a specific alternative to the problems of PS plastic pollution in ocean environments.

Microbial methylmercury (MeHg) production in contaminated soil-rice systems and its accumulation in rice pose health risks to consumers, especially those in Asia. However, the mechanism responsible for microbial MeHg production in paddy soils is far from clear. While previous studies examined the effect of soil and microbial factors on soil MeHg levels, in this work we explored the impact of rice cultivation itself on microbial MeHg production, focusing on the root exudate organic matter as a potential source of electron donors for microbial methylators. Effects of the cultivation of two rice cultivars, Heigu246 (H-rice) and Neiwuyou8015 (N-rice), on MeHg production in soils were therefore investigated in pot and batch incubation experiments. Soil MeHg levels measured in H-rice treatment during the heading and harvest stages were 18–49% higher than in the control and 23–108% higher than in N-rice treatment. Consequently, MeHg levels in grain, straw, and root were 38%, 81%, and 40% higher in H-rice than those in N-rice, which was mainly attributed to cultivar-specific MeHg production in soils. Results of the batch experiments suggested that root exudate organic matter could be responsible for MeHg production in soils during rice cultivation, by increasing the abundances of potential microbial methylators. For instance, root exudate organic matter increased copy numbers of Hg methylation genes (hgcA) in soils 4.1-fold. Furthermore, the 211% higher concentration of acetate (a key electron donor for microbial methylators) in the root exudate of H-rice could account for the higher MeHg production under H-rice than N-rice cultivation. Our results suggest that root exudate organic matter, especially acetate, as its key component, contributes to the elevated soil MeHg concentrations during rice cultivation. The proposed mechanism provides new insights into the elevated risk of MeHg production in contaminated soil-rice systems, as well as cultivar-specific MeHg bioaccumulation.

Real-time analysis of volatile organic compounds (VOCs) in air is useful both for source identification and emissions compliance applications. In this work, two complementary triple quadrupole mass spectrometers, fitted with an atmospheric pressure chemical ionization (APCI) and a low pressure chemical ionization (LPCI) source, respectively, were deployed simultaneously to investigate emissions of VOCs associated with an Ontario-based chemical waste disposal facility. Mobile measurements performed upwind and downwind of the facility enabled selection of the best locations for stationary sampling. Seven separate field studies were undertaken between 2000 and 2016 to assess how emissions of VOCs have changed at the site as a function of time. Up to twenty-nine VOCs were successfully identified and quantified using MS/MS in each study. Simultaneous deployment of the two mass spectrometers enabled the detection of polar VOCs including alcohols, esters, amines and ketones as well as non-polar aromatic VOCs including benzene and naphthalene in real time. Concentrations of VOCs were found to decrease significantly in the vicinity of the facility over the sixteen year period, in particular since 2007. Concentration values for each year are compared with odour thresholds and provincial guidelines and implications of future expansion of on-site solid waste landfill volumes are also discussed.

Water diversion has been increasingly applied to improve water quality in many water bodies. However, little is known regarding pollution by organic micropollutants (OMPs) in water diversion projects, especially at the supplier, and this pollution may threaten the quality of transferred water. In the present study, a total of 110 OMPs belonging to seven classes were investigated in water and sediment collected from a supplier of the Yangtze River within four water diversion projects. A total of 69 and 58 target OMPs were detected in water and sediment, respectively, at total concentrations reaching 1041.78 ng/L and 5942.24 ng/g dry weight (dw). Polycyclic aromatic hydrocarbons (PAHs) and pharmaceuticals were the predominant pollutants identified. When preliminarily compared with the pollution in the receiving water, the Yangtze River generally exhibited mild OMPs pollution and good water quality parameters, implying a clean water source in the water diversion project. However, in Zongyang and Fenghuangjing, PAHs pollution was more abundant than that in the corresponding receiving water in Chaohu Lake. Ammonia nitrogen pollution in the Wangyu River was comparable to that in Taihu Lake. These findings imply that water diversion may threaten receiving waters in some cases. In addition, the risks of all detected pollutants in both water and sediment were assessed. PAHs in water, especially phenanthrene and high-molecular-weight PAHs, posed high risks to invertebrates, followed by the risks to fish and algae. Pharmaceuticals, such as antibiotics and antidepressants, may also pose risks to algae and fish at a number of locations. To the best of our knowledge, this report is the first to describe OMPs pollution in water diversion projects, and the results provide a new perspective regarding the security of water diversion projects.

Better understanding of the colloidal behaviors of nanomaterials impacted by aquatic chemistry parameters is needed for appropriate evaluation of the environmental risks posed by nanomaterials in natural waters. In the study, the colloidal stability of Fe3O4 magnetic nanoparticles (Fe-MNPs) was evaluated over a range of chemistry characteristics [e.g., pH, dissolved organic matter (DOM), salt types, cationic strength] in six synthetic water samples. The findings from the synthetic water samples were further examined with eight “real world” environmental water samples. Our results demonstrated that DOM fraction, humic acid (HA), promoted suspension of Fe-MNPs more by hydrophobic interactions in addition to ligand exchange and electrostatic effects compared with fulvic acid (FA). Capability of cations to increase aggregation of Fe-MNPs were in the order of Ca2+ > Mg2+ >> Na+ because of their different degrees of bridging complexation with DOM molecules on particle surfaces. As a key parameter for indicating Fe-MNPs colloidal stability, Zeta (ζ) potentials of Fe-MNPs in these waters samples were well correlated to (R2 = 0.880, P < 0.001) the contents, types and adsorption forms of DOM and cations. However, several other factors could also affect the hydrodynamic diameter (HDD) of Fe-MNPs in the “real world” environmental waters. It assumed that ampholytic-DOM molecules such as amino acid- and protein-like molecules caused great aggregation of Fe-MNPs. These findings would be helpful for better understanding and evaluating the colloidal behaviors of nanomaterials when they released into natural water environment, thus could shed light on developing relevant pollution control strategies.

Hypermethylation of СpG islands in the promoter regions of several genes with basic protective function in blood leukocytes of individuals exposed to ionizing radiation long time ago (2–46 years), and differential effects of age and radiation exposure on hypermethylation was reported in our previous work. To validate these results, epigenetic modifications were assessed in an independent series of 49 nuclear industry workers from the “Mayak” facility (67–84 years old at sampling) with documented individual accumulated doses from the prolonged external γ-radiation exposure (95.9–409.5 cGy, end of work with radiation:0.3–39 years ago), and in 50 non-exposed persons matched by age. In addition to the genes analyzed before (RASSF1A, p16/INK4A, p14/ARF, GSTP1), four additional loci were analyzed: TP53, ATM, SOD3, ESR1. The frequency of individuals displaying promoter methylation of at least one of the 8 genes (71.4%) was significantly higher in exposed group as compared to the control group (40%), p = .002, OR = 3.75. A significantly elevated frequency of individuals with hypermethylated СpG islands in GSTP1, TP53, SOD3 promoters was revealed among exposed subjects as compared to the control group (p = .012, OR = 8.41; p = .041, OR = 4.02 and p = .009, OR = 3.42, respectively). A similar trend (p = .12, OR = 3.06) was observed for the p16/INK4A gene. As a whole, p16/INK4A and GSTP1 promoter hypermethylation in irradiated subjects from both previously and currently analyzed groups was pronounced. Thus, the direction of the effects was fully confirmed, suggesting the result reproducibility. No statistically significant correlation between promoter methylation and individual radiation dose was found. Further studies are required to create an array of blood epigenetic markers of radiation exposure associating with premature aging and age-related diseases and to accurately evaluate radiation-added effect across the range of doses.The results of studies of epigenetic changes in two independent samples of irradiated subjects indicated the significance of radiation factor in the induction of hypermethylation of CpG islands in gene promoters that is revealed in blood cells years and decades after exposure.