Previous epidemiological and experimental studies have shown that legacy perfluoroalkyl acids (PFAAs) are immunotoxic. However, whether the immunosuppressive effects in PFAA alternatives which recently have been widely detected in the environment are unknown. To address this knowledge gap, we investigated the relationship of serum legacy PFAAs and PFAA alternatives with the antibody of hepatitis B virus in adults. We recruited 605 participants from a cross-sectional study, the Isomer of C8 Health Project in China. We measured two representative legacy PFAAs (perfluorooctane sulfonate, PFOS and perfluorooctanoic acid, PFOA), and three PFAA alternatives (two chlorinated polyfluorinated ether sulfonic acids, Cl-PFESAs and perfluorobutanoic acid, PFBA) in serum using ultra-performance liquid chromatograph-tandem mass spectrometry (UPLC-MS/MS). We applied linear and logistic regression models to analyze associations between serum PFAAs and hepatitis B surface antibody (HBsAb) with multivariable adjustments. We found negative associations between serum PFAAs concentrations and HBsAb. Lower serum HBsAb levels (log mIU/mL) were observed for each log-unit increase in linear PFOS (β = −0.31, 95% confidential interval: 0.84, −0.18), 6:2 PFESA (β = −0.81, 95% CI: 1.20, −0.42), 8:2 PFESA (β = −0.29, 95% CI: 0.43, −0.14) and PFBA (β = −0.18, 95% CI: 0.28, −0.08). The association between PFAAs and HBsAb seronegative seemed to be higher for 6:2 PFESA (odds ratio = 3.32, 95% CI: 2.16, 5.10) than its predecessors, linear PFOS (OR = 1.96, 95% CI: 1.37, 2.81) and branched PFOS isomers (OR = 1.64, 95% CI: 1.05, 2.56). We report new evidence that exposure to PFAA alternatives are associated with lower HBsAb in adults. This association seems to be stronger in 6:2 PFESA than PFOS. Our results suggest that more studies are needed to clarify the potential toxicity of PFAA alternatives in human which will facilitate better chemical regulations for PFAAs.

The surface organic horizons in forest soils have been affected by air and soil pollutants, including potentially toxic elements (PTEs). Monitoring of PTEs requires a large number of samples and adequate analysis. Visible–near infrared (vis–NIR: 350–2500 nm) spectroscopy provides an alternative method to conventional laboratory measurements, which are time-consuming and expensive. However, vis–NIR spectroscopy relies on an empirical calibration of the target attribute to the spectra. This study examined the capability of vis–NIR spectra coupled with machine learning (ML) techniques (partial least squares regression (PLSR), support vector machine regression (SVMR), and random forest (RF)) and a deep learning (DL) approach called fully connected neural network (FNN) to assess selected PTEs (Cr, Cu, Pb, Zn, and Al) in forest organic horizons. The dataset consists of 2160 samples from 1080 sites in the forests over all the Czech Republic. At each site, we collected two samples from the fragmented (F) and humus (H) organic layers. The content of all PTEs was higher in horizon H compared to F horizon. Our results indicate that the reflectance of samples tended to decrease with increased PTEs concentration. Cr was the most accurately predicted element, regardless of the algorithm used. SVMR provided the best results for assessing the H horizon (R² = 0.88 and RMSE = 3.01 mg/kg for Cr). FNN produced the best predictions of Cr in the combined F + H layers (R² = 0.89 and RMSE = 2.95 mg/kg) possibly due to the larger number of samples. In the F horizon, the PTEs were not predicted adequately. The study shows that PTEs in forest soils of the Czech Republic can be accurately estimated with vis–NIR spectra and ML approaches. Results hint in availability of a large sample size, FNN provides better results.

This study investigated the relationship between lead (Pb) speciation determined using Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy in <10 μm particulate matter (PM₁₀) from mining/smelting impacted Australian soils (PP, BHK5, BHK6, BHK10 and BHK11) and inhalation exposure using two simulated lung fluids [Hatch’s solution, pH 7.4 and artificial lysosomal fluid (ALF), pH 4.5]. Additionally, elemental composition of Pb rich regions in PP PM₁₀ and the post-bioaccessibility assay residuals were assessed using a combination of Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX) to provide insights into how extraction using simulated lung fluids may influence Pb speciation in vitro. Correlation between Pb speciation (weighted %) and bioaccessibility (%) was assessed using Pearson r (α = 0.1 and 0.05). Lead concentration in PM₁₀ samples ranged from 782 mg/kg (BHK6) to 7796 mg/kg (PP). Results of EXAFS analysis revealed that PP PM₁₀ was dominated by Pb adsorbed onto clay/oxide, while the four BHK PM₁₀ samples showed variability in the weighted % of Pb adsorbed onto clay/oxide and organic matter bound Pb, Pb phosphate, anglesite and galena. When bioaccessibility was assessed using different in vitro inhalation assays, results varied between samples and between assays, Pb bioaccessibility in Hatch’s solution ranged from 24.4 to 48.4%, while in ALF, values were significantly higher (72.9–96.3%; p < 0.05). When using Hatch’s solution, bioaccessibility outcomes positively correlated to anglesite (r:0.6246, p:0.0361) and negatively correlated to Pb phosphate (r: -0.9610, p:0.0041), organic bound Pb (r: -0.7079, p: 0.0578), Pb phosphate + galena + plumbojarosite (r: -0.9350, p: 0.0099). No correlation was observed between Pb bioaccessibility (%) using Hatch’s solution and weighted % of Pb adsorbed onto clay/oxide and between bioaccessibility (%) using ALF and any Pb species. SEM and EDX analysis revealed that a layer of O–Pb–Ca–P–Si–Al–Fe formed during the in vitro extraction using Hatch’s solution.

Traffic-generated ultrafine particles (UFPs) in the urban atmosphere have a high proportion of their composition comprised of semi-volatile compounds (SVOCs). The evaporation/condensation processes of these SVOCs can alter UFP number size distributions and play an important role in determining the fate of UFPs in urban areas. The neighbourhood-scale dispersion (over distances < 1 km) and evolution of traffic-generated UFPs for a real-world street network in central London was simulated by using the WRF-LES model (the large eddy simulation mode of the Weather Research and Forecasting modelling system) coupled with multicomponent microphysics. The neighbourhood scale dispersion of UFPs was significantly influenced by the spatial pattern of the real-world street emissions. Model output indicated the shrinkage of the peak diameter from the emitted profile to the downwind profile, due to an evaporation process during neighbourhood-scale dispersion. The dilution process and the aerosol microphysics interact with each other during the neighbourhood dispersion of UFPs, yielding model output that compares well with measurements made at a location downwind of an intense roadside source. The model captured the total SVOC concentrations well, with overestimations for gas concentrations and underestimations for particle concentrations, particularly of the lighter SVOCs. The contribution of the intense source, Marylebone Road (MR) in London, to concentrations at the downwind location (as estimated by a model scenario with emissions from MR only) is comparable with that of the rest of the street network (a scenario without emissions from MR), implying that both are important. An appreciable level of non-linearity is demonstrated for nucleation mode UFPs and medium range carbon SVOCs at the downwind receptor site.

Dissolved organic matter (DOM) is recognized as a good indicator of water quality as its concentration is influenced by land use, rainwater, windborne material and anthropogenic activities. Recent technological advances make it possible to characterize fluorescent dissolved organic matter (FDOM), the fraction of DOM that fluoresces. Among these advances, portable fluorometers and benchtop fluorescence excitation and emission spectroscopy coupled with a parallel factor analysis (EEM-PARAFAC) have shown to be reliable. Despite their rising popularity, there is still a need to evaluate the extent to which these techniques can assess DOM dynamics at the watershed scale. We compare the performance of in-situ measurements of FDOM with laboratory measurements of fluorescence spectroscopy within the context of two distinct glacierized watersheds in Peru. Glacierized watersheds represent unique testing environments with contrasting DOM conditions, flowing from pristine, vegetation-free headwaters through locations with obvious anthropogenic influences. We used an in-situ fluorometer and a portable multimeter to take 38 measurements of FDOM, pH and turbidity throughout the two catchments. Additionally, samples were analyzed in the laboratory using the EEM-PARAFAC method. Results were compared to dissolved organic carbon (DOC) measurements using standard high-temperature catalytic oxidation. Our results show that the three techniques together were able to capture the DOM dynamics for both studied watersheds. Taken individually, all three methods allowed detection of the watershed DOM main points of sources but in a more limited way. Due to the narrow bandwidth of the portable fluorometer used in the study, FDOM measurements were almost non-detectable to protein-like substances. Indeed, the more demanding EEM-PARAFAC was able to both differentiate between potential sources of DOM and provide an estimate of relative concentrations of different organic components. Finally, similar to FDOM but to a lesser extent, the DOC measurements showed some limits where protein-like substances make up most of the DOM composition.

This study was designed to investigate the seasonal characteristics and apportion the sources of organic carbon during non-haze days (<75 μg m⁻³) and haze (≥75 μg m⁻³) events at Pinggu, a rural Beijing site. Time-resolved concentrations of carbonaceous aerosols and organic molecular tracers were measured during the winter of 2016 and summer 2017, and a Chemical Mass Balance (CMB) model was applied to estimate the average source contributions. The concentration of OC in winter is comparable with previous studies, but relatively low during the summer. The CMB model apportioned seven separate primary sources, which explained on average 73.8% on haze days and 81.2% on non-haze days of the organic carbon in winter, including vegetative detritus, biomass burning, gasoline vehicles, diesel vehicles, industrial coal combustion, residential coal combustion and cooking. A slightly lower percentage of OC was apportioned in the summer campaign with 64.5% and 78.7% accounted for. The other unapportioned OC is considered to consist of secondary organic carbon (SOC). During haze episodes in winter, coal combustion and SOC were the dominant sources of organic carbon with 23.3% and 26.2%, respectively, followed by biomass burning emissions (20%), whereas in summer, industrial coal combustion and SOC were important contributors. Diurnal contribution cycles for coal combustion and biomass burning OC showed a peak at 6–9 pm, suggesting domestic heating and cooking were the main sources of organic aerosols in this rural area. Backward trajectory analysis showed that high OC concentrations were measured when the air mass was from the south, suggesting that the organic aerosols in Pinggu were affected by both local emissions and regional transport from central Beijing and Hebei province during haze episodes. The source apportionment by CMB is compared with the results of a Positive Matrix Factorization (PMF) analysis of ACSM data for non-refractory PM₁, showing generally good agreement.

In freshwater ecosystems with frequent cyanobacterial blooms, the cyanobacteria toxin pollution is becoming increasingly serious. Nodularin (NOD), which has strong biological toxicity, has emerged as a new pollutant and affects the normal growth, development and reproduction of aquatic organisms. However, little information is available regarding this toxin. In this study, a graphene oxide material modified by L-cysteine was synthesized and used to immobilize microcystin-LR (MC-LR)-degrading enzyme (MlrA) to form an immobilized enzyme nanocomposite, CysGO-MlrA. Free-MlrA was used as a control. The efficiency of NOD removal by CysGO-MlrA was investigated. Additionally, the effects of CysGO-MlrA and the NOD degradation product on zebrafish lymphocytes were detected to determine the biological toxicity of these two substances. The results showed the following: (1) There was no significant difference in the degradation efficiency of NOD between CysGO-MlrA and free-MlrA; the degradation rate of both was greater than 80% at 1 h (2) The degradation efficiency of the enzyme could retain greater than 81% of the initial degradation efficiency after the CysGO-MlrA had been reused 7 times. (3) CysGO-MlrA retained greater than 50% of its activity on the 8th day when preserved at 0 °C, while free-MlrA lost 50% of its activity on the 4th day. (4) CysGO-MlrA and the degradation product of NOD showed no obvious cytotoxicity to zebrafish lymphocytes. Therefore, CysGO-MlrA might be used as an efficient and ecologically safe degradation material for NOD.

The main objectives of the present study were to investigate urinary monohydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) in 77 primiparas who live in Shenzhen, Guangdong Province, China, and their association with 8-hydroxy-2′-deoxyguanosine (8-OHdG) and human health risks. High detection frequencies of OH-PAHs demonstrated the wide occurrence of chemicals in the human exposure to PAHs. The urinary concentrations of Σ₇OH-PAHs ranged from 1.37 to 45.5 ng/mL, and the median concentrations of 1-hydroxynaphthalene (1-OHN), 2-hydroxynaphthalene (2-OHN), 2-hydoxyfluorene (2-OHF), ΣOHPhe (the sum of 1-, 2+ 3-hydroxyphenanthrene), and 1-hydroxypyrene (1-OHP) were 3.00, 2.58, 0.31, 0.44, and 0.51 ng/mL, respectively. In the sum concentration of seven OH-PAHs, 1-OHN accounted for the largest proportion (43.7% of Σ₇OH-PAHs), followed by 2-OHN (37.1%), 2-OHF (4.94%), 1-OHP (8.01%), 1-OHPhe (4.79%), and 2+3-OHPhe (1.46%). The present results showed that vehicle exhaust and petrochemical emission are the main sources of PAHs in primiparas in Shenzhen, and inhalation is the most important exposure route. The living conditions have a significant influence on human exposure to PAHs. The concentrations of 8-OHdG were positively correlated with OH-PAH concentrations in urine because evidence suggested that urinary 8-OHdG levels can be considered as a biomarker of oxidative DNA damage. Hazard quotient was used to assess the human health risks from exposure to single compound, and hazard index was used to assess the cumulative risks of the compounds, which demonstrated that the exposure risks from PAHs in primiparas were relatively low.

In most cases, honey bees experience pesticide pollution in a long-term period through direct or indirect exposure, such as the development process from larvae to the pre-harvest stage. At present, little is known about how honey bees respond to pesticide stresses during the continuous development period. This study aims to examine effects of long-term acetamiprid exposure on the development and survival of honey bees, and further present the expression profile in larvae, 1-day-old, and 7-day-old adult worker bees that related to immune, detoxification, acetylcholinesterase (AChE) and memory. Honey bees from 2-day-old larvae to 14-day-old adults except the pupal stage were continuously fed with different acetamiprid solutions (0, 5, and 25 mg/L). We found that acetamiprid over 5 mg/L disturbed the development involving birth weight and emergence rate of newly emerged bees, and reduced the proportion of capped cells of larvae at 25 mg/L; gene expression related to immune and detoxification of worker bees exposed to acetamiprid was roughly activated, returned and then inhibited from larval to emerged and to the late adult stage, respectively. Moreover, lifespans of bees treated with acetamiprid at 25 mg/L were significantly reduced. The present study reflects the potential risk for honey bees continuously exposed to acetamiprid in the development stage.