Dissolved humic acid (HA) is ubiquitous in natural waters. Its presence significantly changes the photo-and bio-degradation of some organic pollutants in natural waters. The effects of photobleaching on the composition, photosensitizing property and bioavailability of HA were investigated here along with the subsequent influence on its photochemical and biological reactivity in mediating 17α-ethynylestradiol (EE2) degradation. Photobleaching transformed the refractory HA into some small molecules, including organic acids and aliphatics. Along with composition alteration, the photochemical reactivity of HA towards EE2 was slightly depressed, with 9% of the removal rate inhibited by a 70-h photobleaching. Contrarily, the reactivity of HA in mediating EE2 biodegradation by E. coli was significantly promoted by a short-term photobleaching. Compared to the biodegradation of EE2 in the pristine HA, the 10-h photobleached HA increased the biodegradation removal rate of EE2 by 25%, reaching its peak value of about 60%. However, the EE2 biodegradation was inhibited by further irradiation, and the removal rate of EE2 decreased to that in the pristine HA systems. Because no substrate competition was found between EE2 and formate or glucose, EE2 biodegradation mediated by HA in natural waters may not be affected by coexistent organics. Photodegradation and biodegradation of EE2 mediated by HA thus can be combined together by photobleaching to remove pollutants from natural waters. The results reported here could assist environmental risk assessment with respect to EE2 in natural aquatic systems.

This study investigated the effects of particle-bound polycyclic aromatic hydrocarbons (PAHs) produced from burning three incense types on and their bioreactivity in the RAW 264.7 murine macrophage cell line. Gas chromatography/mass spectrometry was used to determine the levels of 16 identified PAHs. Macrophages were exposed to incense particle extracts at concentrations of 0, 3.125, 6.25, 12.5, 25, 50, and 100 μg/mL for 24 h. After exposure, cell viability and nitric oxide (NO) and inflammatory mediator [tumor necrosis factor (TNF)-α] production of the cells were examined. The mean atomic hydrogen (H) to carbon (C) ratios in the environmentally friendly, binchotan charcoal, and lao shan incenses were 0.69, 1.13, and 1.71, respectively. PAH and total toxic equivalent (TEQ) mass fraction in the incenses ranged from 137.84 to 231.00 and 6.73–26.30 pg/μg, respectively. The exposure of RAW 264.7 macrophages to incense particles significantly increased TNF-α and NO production and reduced cell viability. The cells treated with particles collected from smoldering the environmentally friendly incense produced more NO and TNF-α compared to other incenses. Additionally, the TEQ of fluoranthene (FL), pyrene (Pyr), benzo[a]anthracene (BaA), chrysene (Chr), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), indeno[1,2,3-cd]pyrene (INP), dibenz[a,h]anthracene (DBA), and benzo[g,h,i]perylene [B(ghi)P] had a significant correlation (R2 = 0.64–0.98, P < 0.05) with NO and TNF-α production. The current findings indicate that incense particle-bound PAHs are biologically active and that burning an incense with a lower H/C ratio caused higher bioreactivity. The stimulatory effect of PAH-containing particles on molecular mechanisms of inflammation are critical for future study.

This study assessed and monitored 40 consecutive reproduction tests - multigenerational (MG) - of continuous exposure to Cd (at 2 reproduction Effect Concentrations (EC): EC10 and EC50) using the standard soil invertebrate Folsomia candida, in total 3.5 years of data were collected. Endpoints included survival, reproduction, size and metallothionein (MTc) gene expression. Further, to investigate adaptation to the toxicant, additional standard toxicity experiments were performed with the MG organisms of F6, F10, F26, F34 and F40 generations of exposure. Exposure to Cd EC10 caused population extinction after one year, whereas populations survived exposure to Cd EC50. Cd induced the up-regulation of the MTc gene, this being higher for the higher Cd concentration, which may have promoted the increased tolerance at the EC50. Moreover, EC10 induced a shift towards organisms of smaller size (positive skew), whereas EC50 induced a shift towards larger size (negative skew). Size distribution shifts could be an effect predictor. Sensitivity increased up to F10, but this was reverted to values similar to F0 in the next generations. The maximum Cd tolerance limits of F. candida increased for Cd EC50 MG. The consequences for risk assessment are discussed.

Radical measures for controlling ambient air pollution sources were employed by the Chinese government during the Asia-Pacific Economic Cooperation (APEC) meeting in 2014, providing a unique case to evaluate the health effect benefits from such measures. To examine the cancer risk reduction from the source control measures during the APEC meeting, we estimated the reduction in population exposure to PM2.5 and PAHs and the reduction in PAHs-associated cancer risk if the control measures were sustained over time. We determined the population exposure to PM2.5 and PM2.5-bound PAHs for the 21.52 million Beijing residents using a Land Use Regression model to determine the spatial distribution of PM2.5 and a Monte Carlo approach to revise indoor/outdoor infiltration factor and time activity patterns. Into the model and approach, we incorporated the spatial variance and indoor/outdoor differences in the PM2.5 and PM2.5-bound PAHs concentrations, based on measurements. We then estimated lung cancer risk using the population attributable fraction (PAF), assuming the control measures were sustained over time. The mean PM2.5 exposure concentration decreased from 37.5 μg/m3 (CI:17.1–74.9 μg/m3) to 24.0 μg/m3 (CI:10.2–47.7 μg/m3), whereas the mean PM2.5-bound equivalent benzo[a]pyrene (BaPeq) exposure concentration decreased from 7.1 ng/m3 (CI:3.3–14.2 ng/m3) to 4.2 ng/m3 (CI:1.8–7.7 ng/m3), resulting in a reduction in the lung cancer PAF from 0.75% to 0.45%, if the measures were sustained over time.

The xenobiotic nature and lack of degradability of polymeric materials has resulted in vast levels of environmental pollution and numerous health hazards. Different strategies have been developed and still more research is being in progress to reduce the impact of these polymeric materials. This work aimed to isolate and characterize polyester polyurethane (PU) degrading fungi from the soil of a general city waste disposal site in Islamabad, Pakistan. A novel PU degrading fungus was isolated from soil and identified as Aspergillus tubingensis on the basis of colony morphology, macro- and micro-morphology, molecular and phylogenetic analyses. The PU degrading ability of the fungus was tested in three different ways in the presence of 2% glucose: (a) on SDA agar plate, (b) in liquid MSM, and (c) after burial in soil. Our results indicated that this strain of A. tubingensis was capable of degrading PU. Using scanning electron microscopy (SEM), we were able to visually confirm that the mycelium of A. tubingensis colonized the PU material, causing surface degradation and scarring. The formation or breakage of chemical bonds during the biodegradation process of PU was confirmed using Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy. The biodegradation of PU was higher when plate culture method was employed, followed by the liquid culture method and soil burial technique. Notably, after two months in liquid medium, the PU film was totally degraded into smaller pieces. Based on a comprehensive literature search, it can be stated that this is the first report showing A. tubingensis capable of degrading PU. This work provides insight into the role of A. tubingensis towards solving the dilemma of PU wastes through biodegradation.

In this study, we demonstrated an assay with turn-on fluorescence for monitoring cerebrospinal acetylcholinesterase (AChE) fluctuation as a biomarker for organophosphorus pesticides (OPs) poisoning and management based on single layer MnO2 nanosheets with graphene quantum dots (GQDs) as signal readout. Initially, the fluorescence of GQDs was quenched by MnO2 nanosheets mainly due to the inner filter effect (IFE). However, with the presence of reductive thiocholine (TCh), the enzymatic product, hydrolyzed from acetylthiocholine (ATCh) by AChE, the redox reaction between MnO2 and TCh occurred, leading to the destruction of the MnO2 nanosheets, and thereby IFE was diminished gradually. As a consequence, the turn-on fluorescence of GQDs with the changes in the spectrum of the dispersion constituted a new mechanism for sensing of cerebrospinal AChE. With the method developed here, we could monitor cerebrospinal AChE fluctuation of rats exposed to OPs before and after therapy, and could thereby open up the pathway to a new sensing platform for better understanding the mechanism of brain dysfunctions associate with OPs poisoning.

Fate and toxicity of manufactured nanoparticles (NPs) in the living organisms and the environment are highly related to their transformation. In the present study, the effect of phosphate on the phytotoxicity and transformation of CeO2 NPs was investigated in an agar medium using head lettuce plants that are sensitive to Ce³⁺ ions. Plants were treated by CeO2 NPs with or without phosphate for 10 days. Results suggest that the treatments of P deficiency (P(-)) and CeO2 NPs (P(+)&Ce) could separately induce significant inhibition on the growth of lettuce seedlings and cause oxidative stress, but the inhibition was the most serious when the two conditions were combined (P(-)&Ce). In the absence of phosphate, more CeO2 NPs were transformed to Ce(III) in the roots and more Ce³⁺ ions were translocated to the shoots, which induced higher toxicity to head lettuce. Phosphates could alleviate the phytotoxic effect of CeO2 NPs through the precipitation of dissociated Ce³⁺ ions. Considering the wide existence of phosphate in the environment, phosphate-related transformation may be a critical factor in evaluating the toxicity and fate of many other metal-based NPs.

With the phaseout of perfluorooctane sulfonate (PFOS) production in most countries and its well known recalcitrance, there is a need to quantify the potential release of PFOS from precursors previously or currently being emitted into the environment. Aerobic biodegradation of N-ethyl perfluorooctane sulfonamidoethanol (EtFOSE) was monitored in two soils from Indiana, USA: an acidic forest silt loam (FRST-48, pH = 5.5) and a high pH agricultural loam (PSF-49, pH = 7.8) with similar organic carbon contents (2.4 and 2.6%) for 210 d and 180 d, respectively. At designated times, triplicate samples were sacrificed for which headspace samples were taken followed by three sequential extractions. Extracts were analyzed using HPLC-tandem mass spectrometry. Measured profiles of EtFOSE degradation and generation/degradation of subsequent metabolites were fitted to the Indiana soils data as well as to a previously published data set for a Canadian soil using an R-based model (KinGUII) to explore pathways and estimate half-lives (t1/2) for EtFOSE and metabolites. EtFOSE degradation ranged from a few days to up to a month. PFOS yields ranged form 1.06–5.49 mol% with the alkaline soils being four to five times higher than the acidic soil. In addition, a direct pathway to PFOS had to be invoked to describe the early generation of PFOS in the Canadian soil. Of all metabolites, the sulfonamidoacetic acids were the most persistent (t1/2 ≥ 3 months) in all soils. We hypothesized that while pH-pKa dependent speciation may have impacted rates, differences in microbial communities between the 3 soils arising from varied soil properties including pH, nutrient levels, soil management, and climatic regions are likely the major factors affecting pathways, rates, and PFOS yields.

Cacao from South America is especially used to produce premium quality chocolate. Although the European Food Safety Authority has not established a limit for cadmium (Cd) in chocolate raw material, recent studies demonstrate that Cd concentrations in cacao beans can reach levels higher than the legal limits for dark chocolate (0.8 mg kg−1, effective January 1st, 2019). Despite the fact that the presence of Cd in agricultural soils is related to contamination by fertilizers, other potential sources must be considered in Ecuador. This field study was conducted to investigate Cd content in soils and cacao cultivated on Ecuadorian farms in areas impacted by oil activities. Soils, cacao leaves, and pod husks were collected from 31 farms in the northern Amazon and Pacific coastal regions exposed to oil production and refining and compared to two control areas. Human gastric bioaccessibility was determined in raw cacao beans and cacao liquor samples in order to assess potential health risks involved. Our results show that topsoils (0–20 cm) have higher Cd concentrations than deeper layers, exceeding the Ecuadorian legislation limit in 39% of the sampling sites. Cacao leaves accumulate more Cd than pod husks or beans but, nevertheless, 50% of the sampled beans have Cd contents above 0.8 mg kg−1. Root-to-cacao transfer seems to be the main pathway of Cd uptake, which is not only regulated by physico-chemical soil properties but also agricultural practices. Additionally, natural Cd enrichment by volcanic inputs must not be neglected. Finally, Cd in cacao trees cannot be considered as a tracer of oil activities. Assuming that total Cd content and its bioaccessible fraction (up to 90%) in cacao beans and liquor is directly linked to those in chocolate, the health risk associated with Cd exposure varies from low to moderate.

The effects of humic acid (HA) and heavy metals (Cu²⁺ and Ag⁺) on the sorption of polar and apolar organic pollutants onto biochars that were produced at temperatures of 200 °C (BC200) and 700 °C (BC700) were studied. Due to the plentiful polar functional groups on BC200, cationic propranolol exhibited higher levels of sorption than naphthalene on BC200 while naphthalene and propranolol showed similar sorption capacities on BC700. HA changed the characteristics of biochars and generally inhibited the sorption of target organic pollutants on biochars; however, enhancement occurred in some cases depending on the pollutants involved and their concentrations, biochars used and the addition sequences and concentrations of HA. On BC200, HA modifications mainly influenced sorption by decreasing its polarity and increasing its aromaticity, while on BC700, the surface area and pore volume greatly decreased due to the pore-blocking effects of HA. Residue dissolved HA in solution may also contribute to sorption inhibition. Complexation between polar functional groups on BC200 and heavy metals slightly enhanced the sorption of neutral naphthalene and significantly enhanced that of anionic 4-nitro-1-naphtol, while limited the sorption of cationic propranolol. Heavy metals together with their associated water molecules decreased the sorption of target chemicals on BC700 via pore-filling or pore-mouth-covering. Inhibition of heavy metals for 4-nitro-1-naphthol was found to be the weakest due to the bridge effects of heavy metals between 4-nitro-1-naphtol and BC700. The higher polarizability of Ag⁺ led to the increase of its sorption on biochars in the presence of organic aromatic pollutants. The results of the present study shed light on the sorption mechanisms of bi-solute systems and enable us to select suitable biochar sorbents when chemicals co-exist.