In addition to being historically intentionally manufactured as commercial products, polychlorinated biphenyls (PCBs) can be unintentionally released as by-products from industrial processes. Recent studies have emphasized the importance of unintentionally produced PCBs (UP-PCBs) and have even identified them as major contributors to atmospheric PCBs. However, little is known about contributions of UP-PCBs in current soils. In this study, all 209 PCB congeners were analyzed in agricultural soils on a national scale to investigate the influence of unintentional sources on Chinese soil. The concentration of Σ₂₀₉PCBs in soils across China was in the range of 64.3–4358 pg/g. Four non-Aroclor congeners, i.e., PCB11, PCB44 + 47+65, PCB68, and PCB209, were dominant among all PCBs, averagely accounting for 26.3%, 8.83%, 3.03%, and 2.80% of total PCBs, respectively. PCB11 and PCB209 were found to be higher in East China, while PCB44 + 47+65 and PCB68 were higher in South China. Their spatial distributions were largely dependent on local sources. The results of source apportionment indicated that the legacy of historically produced and used commercial PCB mixtures was the dominant contributor to seven indicator PCBs in Chinese agricultural soils, especially high-chlorinated congeners. However, unintentional sources (i.e., pigment/paint, combustion-related sources, and polymer sealant), which contributed 57.4% of the total PCBs, are controlling PCB burdens in agricultural soils across China.

Fish Embryo Acute Toxicity (FET) test was proposed as an alternative to the traditional test methods using larval or adult fish. However, whether fathead minnow (Pimephales promelas) embryo is appropriate for FET remains uncertain. In the present study, ecological threshold of toxicological concern (ecoTTC) values and uncertainty factors (UFs) for each Verhaar et al. category in P. promelas were identified by employing probabilistic ecological risk assessment (PERA) approach with chemical toxicity distributions (CTDs). The sensitivity among different life stages and toxicity among different mode of actions (MOAs) classes were comprehensively compared by CTD comparisons. The results showed that embryo exhibited the less or similar sensitivity compared to larva or adult for Verhaar et al. MOA classes (1-4) while adults were more sensitive, followed by embryo than larval for non-classified chemicals. Considering growth effect as endpoint to class 1, class 3, and non-classified chemicals on P. promelas embryo and larva was more sensitive than mortality. Non-classified chemicals especially inorganic compounds were most toxic to P. promelas embryo for the four concerned Verharr et al. MOA-specific chemical classes. This study also derived uncertainty factors (UFs) as 26.5 (9.8, 109) for embryo-to-larva, 6.26 (3.94, 11.0) for embryo-to-adult, 15.6 (10.1, 36.1) for mortality-to-growth, and 3.03 (1.86, 7.08) for mortality-to-reproduction, which can be applied for extrapolations of life stage-to-life stage and effect-to-effect to reduce the underestimating and overestimating risk by the use of default UF such as 10, 100 or 1000. Our findings are vital for feasibility of FET test of P. promelas for ecotoxicity testing and ecological risk assessment for chemicals with different MOAs.

Bisphenol AF (BPAF) is an emerging environmental pollutant. Although BPAF is widely spread in the environment and human surroundings, its interference with ovarian function has not been fully elucidated. The aim of this study was to identify the mechanism underlying the effect of BPAF on the apoptosis of KGN cells, which maintain the physiological characteristics of ovarian granulosa cells. Our results indicated that BPAF induces KGN cell apoptosis in a concentration- and time-dependent manner. Meanwhile, BPAF exposure significantly promoted the expression of pro-apoptotic proteins, including Bax, Bid and Bak, while the expression of anti-apoptotic proteins, such as Bcl-2, Bcl-xL and Mcl-1, decreased significantly. We further detected a significant increase in intracellular ROS levels in response to high concentrations of BPAF exposure. After blocking the corresponding pathway, it was found that ROS mediates ASK1 and JNK activation. Furthermore, the role of Ca²⁺ overload and estrogen receptor β (ERβ) in BPAF-induced KGN cell apoptosis was also confirmed by using inhibitors. These results suggest that BPAF has potential reproductive toxicity for females, and ROS-ASK1-JNK axis may play a key role in BPAF-induced ovarian dysfunction. In addition, Ca²⁺ overload and ERβ pathway activation may also be an important mechanism of reproductive toxicity of BPAF.

The presence of microplastics in the various food web raised concerns on human health, but little is known about the target cells and mechanism of toxicity of microplastics. In this study, we evaluated the toxicity of microplastics using relevant cell lines to the oral route of exposure. Approximately 100 μm-sized fragment-type polypropylene (PP) and polystyrene (PS) particles were prepared by sieving after pulverization and further applied the accelerated weathering using ultraviolet and heat. Thus, the panel of microplastics includes fresh PP (f-PP), fresh PS (f-PS), weathered PP (w-PP), and weathered PS (w-PS). The spherical PS with a similar size was used as a reference particle. Treatment of all types of PP and PS did not show any toxic effects to the Caco-2 cells and HepG2 cells. However, the treatment of microplastics to THP-1 macrophages showed significant toxicity in the order of f-PS > f-PP > w-PS > w-PP. The weathering process significantly reduced the reactive oxygen species (ROS) generation potential of both microplastics because the weathered microplastics have an increased affinity to bind serum protein which acts as a ROS scavenger. The intrinsic ROS generation potential of microplastics showed a good correlation with the toxicity endpoints including cytotoxicity and pro-inflammatory cytokines in THP-1 macrophages. In conclusion, the results of this study suggest that the target cell type of microplastics via oral administration can be macrophages and the pathogenic factor to THP-1 macrophages is the intrinsic ROS generation potential of microplastics. Nevertheless, the toxic effect of microplastics tested in this study was much less than that of nano-sized particles.

Chlorinated paraffins (CPs), a type of toxic and persistent organic substances, can persist in environmental media for a long time and have adverse effects on human health. Thus, it is of great importance to investigate the accumulation and environmental behavior of CPs in industrial areas. In this study, farmland soil, water, and sediment core samples from abandoned oxidation ponds used by three chemical plants to treat wastewater over the past 38 years were investigated in detail. Results show that the concentration of CPs in sediments varied significantly with the water flow direction. The oxidation pond closest to a sewage outlet had the highest concentrations of short-chain chlorinated paraffin (SCCPs) and medium-chain chlorinated paraffin (MCCPs), within the ranges of 44.0–6.21 × 10⁴ ng/g dw (mean 9.32 × 10³ ng/g dw) and 143–1.30 × 10⁶ ng/g dw (mean 1.22 × 10⁵ ng/g dw), respectively. However, in the oxidation pond farthest from the sewage outlet, CP concentrations in sediments were significantly reduced, with ∑SCCPs and ∑MCCPs concentrations ranging from N.D.-249 ng/g dw (mean 66.8 ng/g dw) and N.D.-222 ng/g dw (mean 34.0 ng/g dw), respectively. Moreover, MCCP level in the water was below the detection limit, while the concentration of SCCP ranged from 41.0 to 1.53 × 10³ ng/L (mean 267 ng/L). Finally, a remarkable spatial trend and specific congener distribution were observed in the sediment test results. The horizontal and vertical distributions of the sediments indicate that short-chain (C₁₀₋₁₁) and low-chlorinated (Cl₆₋₇) homologs are more likely to migrate deeper or farther away from the pollution source.

Insecticidal Cry proteins from Bacillus thuringiensis (Bt) can be transferred from genetically engineered crops to herbivores to natural enemies. For the lady beetle Harmonia axyridis, we investigated potential uptake of Cry proteins from the gut to the body and intergenerational transfer. Third and fourth instar H. axyridis fed with pollen or spider mites from SmartStax maize contained substantial amounts of Cry1A.105, Cry1F, Cry2Ab2, Cry3Bb1, and Cry34Ab1. Cry protein concentrations in lady beetle larvae were typically one order of magnitude lower than in the food. When H. axyridis larvae were fed Bt maize pollen, median amounts of Cry protein in the non-feeding pupae were below the limit of detection except for small amounts of Cry34Ab1. No Cry protein was detected in pupae when spider mites were used as food. Cry protein concentrations decreased quickly after H. axyridis larvae were transferred from pollen or spider mites to Bt-free food. Aphids contained very low or no detectable Cry protein, and no Cry protein was found in H. axyridis larvae fed with aphids, and in pupae. When H. axyridis adults were fed with Bt maize pollen (mixed with Ephestia kuehniella eggs), the median concentrations of Cry proteins in lady beetle eggs were below the limit of detection except for Cry34Ab1 in eggs laid later in adult life. No Bt protein was detected in eggs laid by H. axyridis females fed with aphids from Bt maize. Our results confirm previous observations that Cry proteins are degraded and excreted quickly in the arthropod food web without evidence for bioaccumulation. Despite the fact that small amounts of Cry proteins were detected in some samples of the non-feeding pupal stage of H. axyridis as well as in eggs, we conclude that this route of exposure is unlikely to be significant for predators or parasitoids in a Bt maize field.

Nitrogen (N) addition and mowing can significantly influence micronutrient cycling in grassland ecosystems. It remains largely unknown about how different forms of added N affect micronutrient status in plant-soil systems. We examined the effects of different N compounds of (NH₄)₂SO₄, NH₄NO₃, and urea with and without mowing on micronutrient Fe, Mn, Cu, and Zn in soil-plant systems in a meadow steppe. The results showed that (NH₄)₂SO₄ addition had a stronger negative effect on soil pH compared with NH₄NO₃ and urea, resulting in higher increases in soil available Fe and Mn herein. Nitrogen addition decreased plant community-level biomass weighted (hereafter referred to as community-level) Fe concentration but increased Mn concentration, with a greater effect under (NH₄)₂SO₄ addition. Community-level Cu concentration increased with (NH₄)₂SO₄ and NH₄NO₃ addition only under mowing treatment. Mowing synergistically interacted with urea addition to increase community-level Mn and Zn concentrations even with decreased soil organic matter, possibly because of compensatory plant growth and thus higher plant nutrient uptake intensity under mowing treatment. Overall, responses of plant-soil micronutrients to N addition varied with mowing and different N compounds, which were mainly regulated by soil physicochemical properties and plant growth. Different magnitude of micronutrient responses in plants and soils shed light on the necessity to consider the role of various N compounds in biogeochemical models when projecting the effects of N enrichment on grassland ecosystems.

Soil and groundwater contamination with potentially toxic elements (PTEs) including cadmium (Cd) and copper (Cu) has become a serious problem for ecosystem functioning. Silicon (Si) may precipitate these metals as silicates, and may also form, at undersaturation of silicates, ‘Si-contaminant compounds’, i.e. particles of polymerized silica with PTEs incorporated or adsorbed by inner-sphere complexes. While the formation of these compounds in aqueous solution has been proven, their formation in soil remains unclear yet. Therefore, we conducted column experiments with a topsoil horizon artificially contaminated with Cd or Cu solutions (10 mM) in the presence (10 mM) and absence of monomeric Si, and monitored the elemental composition of the eluates during 12 irrigation steps with artificial rainwater by microwave-plasma atomic emission spectrometry, the size and charge of the particles eluted by dynamic light scattering and phase analysis light scattering, and determined the spatial distribution of total and exchangeable Cd and Cu in soil after the experiments. When Si was previously applied to soil, significantly larger particles (up to > 200 nm) in the eluates indicated Si polymerization and formation of Si-contaminant compounds. However, Cd and Cu concentrations were very low (<0.4 μM), pointing to efficient retardation in soil. In any variant, the particles formed were slightly negatively charged (−11 mV). The molar metal:Si ratios in the eluates and significant correlations between the amounts of Si and metals in soil extracted by NH₄NO₃ pointed to the formation of Si-contaminant compounds, too. More Cu than Cd was retained in soil, and significantly more in the presence of Si, but less Cu than Cd was in exchangeable form. While particularly Cu formed Si-contaminant compounds, which reduced the concentration of Cu ions, the Si-contaminant-compound particles in the eluates remained very small, thus potentially susceptible to particulate export from soil into the groundwater.

In this study, surface seawater, sediment and zooplankton samples were collected from three different sampling stations in Marseille Bay (NW Mediterranean Sea) and were analyzed for both microplastics and organic plastic additives including seven phthalates (PAEs) and nine organophosphate esters (OPEs). PAE concentrations ranged from 100 to 527 ng L⁻¹ (mean 191 ± 123 ng L⁻¹) in seawater, 12–610 ng g⁻¹ dw (mean 194 ± 193 ng g⁻¹ dw) in sediment and 0.9–47 μg g⁻¹ dw (mean 7.2 ± 10 μg g⁻¹ dw) in zooplankton, whereas OPE concentrations varied between 9 and 1013 ng L⁻¹ (mean 243 ± 327 ng L⁻¹) in seawater, 13–49 ng g⁻¹ dw (mean 25 ± 11 ng g⁻¹ dw) in sediment and 0.4–4.6 μg g⁻¹ dw (mean 1.6 ± 1.0 μg g⁻¹ dw) in zooplankton. Microplastic counts in seawater ranged from 0 to 0.3 items m⁻³ (mean 0.05 ± 0.05 items m⁻³). We observed high fluctuations in contaminant concentrations in zooplankton between different sampling events. However, the smallest zooplankton size class generally exhibited the highest PAE and OPE concentrations. Field-derived bioconcentration factors (BCFs) showed that certain compounds are prone to bioaccumulate in zooplankton, including some of the most widely used chlorinated OPEs, but with different intensity depending on the zooplankton size-class. The concentration of plastic additives in surface waters and the abundance of microplastic particles were not correlated, implying that they are not necessarily good indicators for each other in this compartment. This is the first comprehensive study on the occurrence and temporal variability of PAEs and OPEs in the coastal Mediterranean based on the parallel collection of water, sediment and differently sized zooplankton samples.

The incidence of thyroid cancer (TC) has increased rapidly worldwide in recent years. Exposure to endocrine disruptors can affect thyroid hormones and is probably carcinogenic to humans. The effects of polybrominated diphenyl ethers (PBDEs), some heavy metals (Cd, Pb, As and Hg) on risk of TC have been rarely reported. Hence, we aimed to examine the associations of TC risk with exposure to PBDEs and four heavy metals. This case-control study involved 308 TC cases and 308 age- and sex-matched controls. Plasma PBDEs concentrations were determined by gas chromatograph-mass spectrometry. Concentrations of heavy metals concentrations in urine specimens were detected by graphite furnace atomic absorption spectrometry or inductively coupled plasma optical emission spectrometry. Conditional logistic regression models were used to explore associations of PBDEs and 4 heavy metals exposures with TC risk. A joint-effect interaction term was inserted into the logistic regression models to assess the multiplicative interaction effects of PBDEs-heavy metals on TC risk. Some PBDE congeners (BDE-028, -047, −099, −183, −209) were positively correlated with TC risk. As and Hg were also associated with the increased TC risk. Compared with low exposure levels, participants with high exposure levels of As and Hg were 5.35 and 2.98 times more likely to have TC, respectively. Co-exposure to BDE-209 and Pb had a negative interaction effect on TC risk. Some PBDE congeners (e.g. BDE-028, -047, −209) and Hg had a significant positive interaction effect on the risk of TC. The joint exposure of BDE-183 and Hg showed a negative interaction effect on TC risk, but the corresponding OR value was still statistically significant. Exposure to PBDEs, As and Hg may be associated with TC development. Joint exposure to PBDEs and Pb or Hg has interaction effects on TC risk. Further prospective research with large sample is required to confirm these findings.