Penetration pathways, influencing factors and predictive models for dermal absorption of exobiotic molecules: A critical review.

This review provides a comprehensive summary of the skin penetration pathways of xenobiotics, including metals, organic pollutants, and nanoparticles (NPs), with a particular focus on the methodologies employed to elucidate these penetration routes. The impacts of the physicochemical properties of exogenous substances and the properties of solvent carriers on the penetration efficiencies were discussed. Furthermore, the review outlines the steady-state and transient models for predicting the skin permeability of xenobiotics, emphasizing the models which enable realistic visualization of pharmaco-kinetic phenomena via detailed geometric representations of the skin microstructure, such as stratum corneum (SC) (bricks and mortar) and skin appendages (hair follicles and sebaceous gland units). Limitations of published research, gaps in current knowledge, and recommendations for future research are highlighted, providing insight for a better understanding of the skin penetration behavior of xenobiotics and associated health risks in practical application contexts.

Remediation of neonicotinoid-contaminated soils using peanut shell biochar and composted chicken manure: Transformation mechanisms of geochemical fractions.

Soil remediation techniques are promising approaches to relieve the adverse environmental impacts in soils caused by neonicotinoids application. This study systematically investigated the remediation mechanisms for peanut shell biochar (PSB) and composted chicken manure (CCM) on neonicotinoid-contaminated soils from the perspective of transformation of geochemical fractions by combining a 3-step sequential extraction procedure and non-steady state model. The neonicotinoid geochemical fractions were divided into labile, moderate-adsorbed, stable-adsorbed, bound, and degradable fractions. The PSB and CCM addition stimulated the neonicotinoid transformation in soils from labile fraction to moderate-adsorbed and stable-adsorbed fractions. Compared with unamended soils, the labile fractions decreased from 47.6% ± 11.8% of the initial concentrations to 12.1 ± 9.3% in PSB-amended soils, and 7.1 ± 4.9% in PSB and CCM-amended soils, while the proportions of moderate-adsorbed and stable-adsorbed fractions correspondingly increased by 1.8-2.4 times and 2.3-4.8 times, respectively. A small proportion (<4.8%) in bound fractions suggested there were rather limited bound-residues after 48 days incubation. The PSB stimulated the -NO2-containing neonicotinoid-degraders, which promoted the degradable fractions of corresponding neonicotinoids by 8.2 ± 6.3%. Degradable fraction of neonicotinoids was the dominant fate in soils, which accounted for 58.3 ± 16.7%. The findings made beneficial theoretical supplements and provided valuable empirical evidence for the remediation of neonicotinoid-contaminated soils.

Nutrient recovery from wastewater for hydroponic systems: A comparative analysis of fertilizer demand, recovery products, and supply potential of WWTPs.

Nutrient recovery from wastewater treatment plants (WWTPs) for hydroponic cultivation holds promise for closing the nutrient loop and meeting rising food demands. However, most studies focus on solid products for soil-based agriculture, thus raising questions about their suitability for hydroponics. In this study, we address these questions by performing the first in-depth assessment of the extent to which state-of-the-art nutrient recovery processes can generate useful products for hydroponic application. Our results indicate that less than 11.5% of the required nutrients for crops grown hydroponically can currently be recovered. Potassium nitrate (KNO3), calcium nitrate (Ca(NO3)2), and magnesium sulfate (MgSO4), constituting over 75% of the total nutrient demand for hydroponics, cannot be recovered in appropriate form due to their high solubility, hindering their separated recovery from wastewater. To overcome this challenge, we outline a novel nutrient recovery approach that emphasizes the generation of multi-nutrient concentrates specifically designed to meet the requirements of hydroponic cultivation. Based on a theoretical assessment of nutrient and contaminant flows in a typical municipal WWTP, utilizing a steady-state model, we estimated that this novel approach could potentially supply up to 56% of the nutrient requirements of hydroponic systems. Finally, we outline fundamental design requirements for nutrient recovery systems based on this new approach. Achieving these nutrient recovery potentials could be technically feasible through a combination of activated sludge processes for nitrification, membrane-based desalination processes, and selective removal of interfering NaCl. However, given the limited investigation into such treatment trains, further research is essential to explore viable system designs for effective nutrient recovery for hydroponics.

Land-Ocean Exchange Mechanism of Chlorinated Paraffins and Polycyclic Aromatic Hydrocarbons with Diverse Sources in a Coastal Zone Boundary Area, North China: The Role of Regional Atmospheric Transmission.

The marine environment is regarded as a crucial "sink" of numerous land-origin pollutants. As typical boundary regions, the coastal and offshore areas are used to evaluate the dominating transfer process and land-ocean exchange mechanism of semivolatile organic compounds. In air samples collected from a coastal area in North China over a whole year, chlorinated paraffins (CPs), including short-chain CPs and medium-chain CPs, and prior control 16 polycyclic aromatic hydrocarbons (PAHs) were determined, with mean concentrations of 25.8 and 94.7 ng/m3, respectively. Results of different gas-particle partitioning models indicated that the steady-state hypothesis provides a better description of the possible land-ocean exchange molecular mechanism. The source-sink influences for CPs and PAHs were affected by the predominant atmospheric motion, which alternated between gaseous diffusion and particulate sedimentation in different seasons. Source apportionment results indicated that different transfer characteristics contributed to the source divergence of ambient CPs and PAHs within 12 nautical miles in the same area. Coal/biomass combustion and diesel/natural gas combustion were the main PAH sources in the coast site (43.1%) and sea site (35.3%), respectively. Similar industrial sources CP-52 and CP-42 were the main CP sources in the coast site (41.4%) and sea site (40.8%), respectively.

Evidence of stockpile contamination for legacy polychlorinated biphenyls and organochlorine pesticides in the urban environment of Cyprus (Eastern Mediterranean): Influence of meteorology on air level variability and gas/particle partitioning based on equilibrium and steady-state models.

The present study investigated comprehensively the atmospheric occurrence and fate of an extensive range of polychlorinated biphenyls (PCBs; forty-two congeners), organochlorine pesticides (OCPs; twenty-seven emerging and legacy agrochemicals) and polycyclic aromatic hydrocarbons (PAHs; fifty parent and alkylated members, including the non USEPA-16 listed toxic ones), in both gas and particulate phase of the scarcely monitored atmosphere over Cyprus for the first time. Parent-metabolite concentration ratios suggested fresh application for dichlorodiphenyl-trichloroethanes (DDTs), dicofol, hexachlorocyclohexanes, endosulfan and chlorothalonil, particularly during spring (April-May). Regressions of logarithms of partial pressure against ambient temperature revealed that secondary recycling from contaminated terrestrial surfaces regulates the atmospheric level variability of PCBs, DDTs, aldrin, chlordane, dicofol, heptachlor and endosulfan. Enthalpies of surface-air exchange (∆HSA) calculated from Clausius-Clapeyron equations were significantly correlated to vaporization enthalpies (∆HV) determined by chromatographic techniques, corroborating presence of potential stockpile-contaminated sites around the study area. The Harner-Bidleman equilibrium model simulating urban areas, and the Li-Jia empirical model, predicted better the partitioning behavior of PAHs (

Prediction of the gas/particle partitioning quotient of PAHs based on ambient temperature.

Gas/particle (G/P) partitioning is an important influencing factor for the environmental fate of semi-volatile organic compounds (SVOCs). The G/P partitioning of polycyclic aromatic hydrocarbons (PAHs) is an integrated complex process due to its formation and growth concurrently with particles. Based on the large dataset of gaseous and particulate samples in a wide ambient temperature range of 50 °C, the simple empirical equations based on ambient temperature were established to predict the G/P partitioning quotient (KP) of PAHs at the temperature range from 252 K to 307 K (-21 °C to 34 °C). The performance of the empirical equations was validated by comparison with the monitoring KP of PAHs worldwide. The empirical equations exhibited good performance for the prediction of KP of PAHs based on ambient temperature. Two deviations with the prediction lines of the previous G/P partitioning models from the monitoring data of KP were observed. It was found that the deviations might be attributed to some non-considered influencing factors with the previous G/P partitioning prediction models. Therefore, further research should be conducted to study the mechanism of the G/P partitioning of PAHs, and more influencing factors should be introduced into the establishment of G/P partitioning models of PAHs. In summary, the result of the present study provided a convenient method for the prediction of KP of PAHs, which should be useful for the study of environmental fate of PAHs in atmosphere.

An Approach to Steady-State Power Transformer Modeling Considering Direct Current Resistance Test Measurements.

Measurements obtained in transformer tests are routinely used for computing associated steady-state model parameters, which can then be used for load flow simulation and other modeling applications. The short circuit and open circuit tests are most commonly performed with this purpose, allowing estimation of series and parallel branch transformer parameters. In this study, an extended model is proposed which does not employ the usually assumed cantilever circuit approximation and explicitly accounts for transformer connection resistance. An estimation of the proposed model parameters is enabled by usage of additional measurements yielded by the direct current (DC) resistance test. The proposed approach is validated by means of an experiment carried out on a real distribution power transformer, whose results demonstrate that the proposed model and parameter computation approach effectively decompose total transformer resistance into winding and contact components. Furthermore, the numerical results show that contact resistance is not negligible especially for low voltage windings, which reinforces the usefulness of the proposed model in providing detailed modeling of transformer resistances.

Degradation kinetics of target compounds and correlations with spectral indices during UV/H2O2 post-treatment of biologically treated acrylonitrile wastewater.

In this study, the post-treatment of biologically treated acrylonitrile wastewater was investigated during UV/H2O2 process. Five contaminants in the effluent were selected as target compounds, including Furmaronitrile (FMN), 3-Pyridinecarbonitrile (3PCN), 1,3-Dicyanobenzene (1,3-DCB), 5-Methyl-1H-benzotriazole (5MBT), and 7-Azaindole (7AID). Under optimal reaction conditions, the UV/H2O2 post-treatment exhibited good performances in destruction of organic compounds and toxicity. The photo-chemical parameters of the target compounds were measured and it was found that 5MBT and 3PCN had fast degradation rate constants under direct UV photolysis. The second-order rate constants of the target compounds with hydroxyl radicals were determined to be in the range of (1.0-5.0) × 109 M-1 s-1 at pH 3.0 and 25 °C. A simplified pseudo-first-order steady state (Sim-PSS) model, which considered direct UV photolysis and radical oxidation simultaneously, agreed well with the experimental data from the post-treatment of a biologically treated effluent. High-performance size exclusion chromatography (HPSEC) coupled with diode-array detector (DAD) and fluorescence detector (FLD) analysis revealed that humic-like sub-peak signals from different molecular weights of fluorescent organic matter decreased consistently during the oxidation process, which made humic-like fluorescence exhibit higher correlation with the target compounds' degradation than the spectral indices of UV absorbance at 254 nm (UVA254) and protein-like fluorescence.

Post-treatment of bio-treated acrylonitrile wastewater using UV/Fenton process: degradation kinetics of target compounds.

In this study, post-treatment of bio-treated acrylonitrile wastewater was performed using the UV/Fenton process. Five target compounds (furmaronitrile, 3-pyridinecarbonitrile, 1,3-dicyanobenzene, 5-methyl-1H-benzotriazole, and 7-azaindole) were selected as target compounds and their degradation kinetics were examined. Under optimal reaction conditions (H2O2 dosage 3.0 mM, Fe2+ dosage 0.3 mM, and initial pH 3.0), more than 85% of total organic carbon (TOC) was eliminated in 30 min when a 10-W UV lamp was employed, and the electrical energy per order of magnitude for TOC removal was as low as 2.96 kWh m-3. Furthermore, the target compounds and the toxicity were largely removed from the bio-treated effluent. Size exclusion chromatography with organic carbon detector analysis revealed that organic components with a wide range of molecular weights were greatly reduced after the UV/Fenton process. A simplified pseudo steady-state (SPSS) model was applied to predict the degradation of target compounds during the UV/Fenton process. The concentrations of generated hydroxyl radicals were estimated to be 3.06 × 10-12 M, 6.37 × 10-12 M, and 10.9 × 10-12 M under 5-, 10-, and 15-W UV lamps, respectively. These results demonstrate that the proposed SPSS model fitted well with experimental data on the post-treatment of real wastewater, and consequently indicate that this model can be a useful tool in the prediction of degradation of target compounds during the UV/Fenton process.