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.

This study examines size-resolved heavy metal data for particles sampled near an urban site affected by non-ferrous metal smelting in China with a focus on how particle sizes impact regional respiratory deposition behavior. Particles with aerodynamic diameters between 0.43 and 9 μm were collected during winter haze episodes from December 2011 to January 2012. The results showed that concentrations of individual trace elements ranged from ∼10⁻²–∼10⁴ ng/m³. Mass size distributions exhibit that Cu, Zn, As, Se, Ag, Cd, TI, and Pb have unimodal peak in fine particles range (<2.1 μm); Al, Ti, Fe, Sr, Cr, Co, Ni, Mo, and U have unimodal peak in coarse range (>2.1 μm), and Be, Na, Mg, Ca, Ba, Th, V, Mn, Sn, Sb, and K have bimodal profiles with a dominant peak in the fine range and a smaller peak in the coarse range. The total deposition fluxes of trace elements were estimated at 2.1 × 10⁻² – 4.1 × 10³ ng/h by the MPPD model, and the region with the highest contribution was the head region (42% ± 13%), followed by the tracheobronchial region (11% ± 3%) and pulmonary region (6% ± 1%). The daily intake of individual element for humans occurs via three main exposure pathways: ingestion (2.3 × 10⁻⁴ mg/kg/day), dermal contact (2.3 × 10⁻⁵ mg/kg/day), and inhalation (9.0 × 10⁻⁶ mg/kg/day). A further health risk assessment revealed that the risk values for humans were all above the guidelines of the hazard quotient (1) and cancer risk (10⁻⁶), indicating that there are potential non-cancer effects and cancer risks in this area.

In indoor air, terpene-ozone reactions can form secondary organic aerosols (SOA) in a transient process. ‘Real world’ measurements conducted in a furnished room without air conditioning were modelled involving the indoor background of airborne particulate matter, outdoor ozone infiltrated by natural ventilation, repeated transient limonene evaporations, and different subsequent ventilation regimes. For the given setup, we disentangled the development of nucleated, coagulated, and condensed SOA fractions in the indoor air and calculated the time dependence of the aerosol mass fraction (AMF) by means of a process model. The AMF varied significantly between 0.3 and 5.0 and was influenced by the ozone limonene ratio and the background particles which existed prior to SOA formation. Both influencing factors determine whether nucleation or adsorption processes are preferred; condensation is strongly intensified by particulate background. The results provide evidence that SOA levels in natural indoor environments can surpass those known from chamber measurements. An indicator for the SOA forming potential of limonene was found to be limona ketone. Multiplying its concentration (in μg/m³) by 450(±100) provides an estimate of the concentration of the reacted limonene. This can be used to detect a high particle formation potential due to limonene pollution, e.g. in epidemiological studies considering adverse health effects of indoor air pollutants.

To evaluate the ozone (O3) sensitivity among peach tree (Prunus persica) cultivars widely planted in Beijing region and explore the possible eco-physiological response mechanisms, thirteen cultivars of peach seedlings were exposed to either charcoal-filtered air or elevated O3 (E-O3, non-filtered ambient air plus 60 ppb) for one growing season in open-top chambers. Leaf structure, stomatal structure, gas exchange and chlorophyll a fluorescence, photosynthetic pigments, antioxidant defense system and lipid peroxidation were measured in three replicated chambers. Results showed that E-O3 significantly reduced abaxial epidemis thickness, but no effects on the thicknesses of adaxial epidemis, palisade parenchyma and spongy parenchyma. Stomatal area, density and conductance were not significantly affected by E-O3. E-O3 significantly accelerated leaf senescence, as indicated by increased lipid peroxidation and more declines in light-saturated photosynthetic rate and pigments contents. The reduced ascorbate content (ASC) was decreased but antioxidant enzyme activity (CAT, APX and SOD) and total antioxidant capacity (TAC) were significantly increased by E-O3 among cultivars. The cultivars with visible symptoms also had more reductions in net photosynthetic rate than those without visible symptoms. Ozone sensitivity among cultivars was strongly linked to leaf mass per area (LMA), antioxidant enzymes activity e.g. SOD, APX rather than stomatal parameters (stomatal area, density and conductance) and ASC. Results could provide a theoretical basis for selecting and breeding the ozone-resistant cultivars of peach trees grown in high O3-polluted regions.

We investigated whether local-scale decontamination (removal of the litter layer, superficial soil layer, and understory) in a secondary forest contaminated by the Fukushima nuclear power plant accident reduced 137Cs contamination of the soil and litter. We also measured 137Cs concentrations in plants and in the web-building spider Nephila clavata (Nephilidae: Arachnida), as an indicator species, to examine 137Cs contamination in arthropods. One month after decontamination, the total 137Cs contamination (soil + litter) was reduced by 20% (100 kBq·m−2) relative to that in an adjacent untreated (i.e., contaminated) area, which was however not statistically significant. Four months after decontamination, 137Cs in the decontaminated area had increased to a level similar to those in the untreated area, and the air radiation dose in the decontaminated area was about 2.1 μSv·h−1, significantly higher than that in the untreated area (1.9 μSv·h−1). This may have been attributed to a torrential rain event. Although no statistically significant reduction was observed, most spiders had a lower 137Cs contamination than that before the decontamination. This implied that the decontamination may have reduced 137Cs transfer from soil via litter to N. clavata through the detrital food chains, but may not have reduced the amount of 137Cs transfer through grazing food chains because the concentration of 137Cs in living tree leaves was not reduced by the decontamination. In autumn, about 2 kBq·m−2 of 137Cs was supplied from foliage to the ground by litterfall. The results suggested that removal of the litter and superficial soil layers in a contaminated forest may be ineffective. The present study suggests that the local-scale decontamination in a secondary forest had no effect on the reduction of 137Cs contamination in the treated area.

Three novel organic vermiculites (VER) modified by amphoteric surfactants (BS, SB and PBS) with different negatively charged groups (carboxylate, sulfonate and phosphate) were demonstrated and used for removal of bisphenol A (BPA) and tetrabromobisphenol A (TBBPA). The difference in the structure and surface properties of modified vermiculites were investigated using a series of characterization methods. BS and SB surfactant mainly adsorbed on the surface and hard to intercalate into the interlayer of VER, while both adsorption and intercalation occurred in PBS modification. This difference resulted in different packing density of surfactant and hydrophobicity according to the results of contact angle, and affect the adsorption capacities ultimately. The adsorption of two pollutants onto these modified vermiculites were very fast and well fitted with pseudo-second-order kinetic model and Langmuir isotherm. PBS-VER exhibited the highest adsorption capacity (92.67 and 88.87 mg g−1 for BPA and TBBPA, respectively) than other two modified vermiculites in this order PBS-VER > BS-VER > SB-VER. The ionic strength (Na+, Ca2+) and coexisting compounds (Pb2+, humic acid) have different effects on the adsorption. PBS-VER had a good reusability and could remove ionic (methylene blue and orange G) and molecular (BPA) pollutants simultaneously and effectively due to the function of amphoteric hydrophilic groups and alkyl chains. The results might provide novel information for developing low-cost and effective adsorbents for removal of neutral and charged organic pollutants.

Based on detailed data from Chengdu Plain (CP) from 6 January to 16 January, two typical haze episodes were analyzed to clarify the haze formation mechanism in winter. Weather conditions, chemical compositions, secondary pollutant transformation, optical properties of aerosols, the potential source contribution function (PSCF) and source apportionment were studied. The planetary boundary layer (PBL) height decreased distinctly during the haze episodes and restrained air pollutant vertical dispersion. As the haze worsened, the value of PBL × PM2.5 increased notably. The [NO3−]/[SO42−] ratio was 0.61, 0.76 and 0.88 during a non-haze period, episode 1 and episode 2, respectively, indicating that the mobile source of the air pollution is increasingly predominant in Chengdu. Water vapor also played a vital role in the formation of haze by accelerating the chemical transformation of secondary pollutants, leading to the hygroscopic growth of aerosols. The PSCF and backward trajectories of the air masses indicated that the pollution mainly came from the south. The secondary inorganic aerosols, vehicle emissions, coal combustion, biomass burning, industry, and dust contributed 34.1%, 24.1%, 12.7%, 12.3%, 7.6%, and 7.2% to PM2.5 masses in episode 1 and 28.9%, 23.1%, 9.4%, 9.5%, 20.3% and 7.5% in episode 2.

In spite of being a widespread activity causing the salinization of rivers worldwide, the impact of potash mining on river ecosystems is poorly understood. Here we used a mesocosm approach to test the effects of a salt effluent coming from a potash mine on algal and aquatic invertebrate communities at different concentrations and release modes (i.e. press versus pulse releases). Algal biomass was higher in salt treatments than in control (i.e. river water), with an increase in salt-tolerant diatom species. Salt addition had an effect on invertebrate community composition that was mainly related with changes in the abundance of certain taxa. Short (i.e. 48 h long) salt pulses had no significant effect on the algal and invertebrate communities. The biotic indices showed a weak response to treatment, with only the treatment with the highest salt concentration causing a consistent (i.e. according to all indices) reduction in the ecological quality of the streams and only by the end of the study. Overall, the treatment's effects were time-dependent, being more clear by the end of the study. Our results suggest that potash mining has the potential to significantly alter biological communities of surrounding rivers and streams, and that specific biotic indices to detect salt pollution should be developed.