Mechanistic and predictive studies on the oxidation of furans by cytochrome P450: A DFT study.

Furan-containing compounds distribute widely in food, herbal medicines, industrial synthetic products, and environmental media. These compounds can undergo oxidative metabolism catalyzed by cytochrome P450 enzymes (CYP450) within organisms, which may produce reactive products, possibly reacting with biomolecules to induce toxic effects. In this work, we performed DFT calculations to investigate the CYP450-mediated metabolic mechanism of furan-ring oxidation using 2-methylfuran as a model substrate, meanwhile, we studied the regioselective competition of another hydroxylation reaction involving methyl group of 2-methylfuran. As a result, we found the toxicological-relevant cis-enedione product can be produced from O-addition directly via a concerted manner without formation of an epoxide intermediate as traditionally believed. Moreover, our calculations demonstrate the kinetic and thermodynamic feasibility of both furan-ring oxidation and methyl hydroxylation pathways, although the former pathway is a bit more favorable. We then constructed a linear model to predict the rate-limiting activation energies (ΔE*) of O-addition with 11 diverse furan substates based on their adiabatic ionization potentials (AIPs) and condensation Fukui functions (CFFs). The results show a good predictive ability (R2=0.94, Q2CV=0.87). Therefore, AIP and CFF with clear physichem meanings relevant to the mechanism, emerge as pivotal molecular descriptors to enable the fast prediction of furan-ring oxidation reactivities for quick insight into the toxicological risk of furans, using just ground-state calculations.

Experimental study on mine water purification mechanism for broken coal and rock masses in the underground reservoir of ecologically vulnerable mining area.

Water-rock interaction mechanism and water purification capacity of broken coal and rock masses are very important for the efficient operation of the underground reservoir. In this paper, a water purification simulation device for an underground mine reservoir was designed. The experimental study on the dynamic interaction between broken coal and rock masses and mine water was carried out. The water purification mechanism is analyzed from the changes in rock mineral composition and mine water quality before and after the test. The results show that after the broken coal and rock mass purification, the water turbidity and the concentration of chlorides and suspended solids decreased obviously. The water purification capacities of mudstone and sandstone are stronger than that of coal samples. After 60 days of reaction between the working face sewage and the broken samples (mudstone, sandstone, and coal), the turbidity, chromaticity, and residual chlorine decreased by > 90%, 90%, and 60%, respectively; and COD decreased by 35.29%, 30.59%, and 28.99%, respectively. While the TDS and the total hardness increased by about 40%, 30%, and 10% for the mudstone, sandstone, and coal, respectively. It shows that coal also has the worst degradation performance. The water purification effect of broken coal and rock masses has a significant time effect. The early stage of water-rock interaction is dominated by mineral dissolution, and the middle stage is dominated by precipitation and adsorption. The pH value of the solution has a certain influence on the ion change. In the later stage, the water-rock interaction is weak in a dynamic equilibrium state, and the change in the mine water quality index is not obvious. Considering the influence of rock lithology on water quality and the law of water-rock interaction time, the construction site selection and water storage time optimization of underground reservoirs in Jinjie Coal Mine were carried out, respectively.

Risk Assessment of Heavy Metals in Soils from Four Different Industrial Plants in a Medium-Sized City in North China.

Laboratory experiments were carried out to analyze 39 soil samples collected from four industrial areas in Xuzhou City using inductively coupled plasma mass spectrometry and atomic fluorescence spectrometry. The descriptive statistics of heavy metals (HMs) in the soil profiles showed that the HM content at three depths was highly variable, and most coefficients of variation (CVs) showed moderate variability. The enrichment of Cd at all depths exceeded the risk screening value, and Cd pollution occurred in four plants. The enrichment of the other HMs at three depths was mainly concentrated in the pharmaceutical plant A and chemical plant C. It was found that the different HMs had different vertical distribution characteristics. For the different industrial plants, the raw materials and products not only made the spatial distribution characteristics of the HMs different, but also caused the HM types and contents to differ. The average single pollution indices of Cd in plant A, iron-steel plant B, and plant C indicated a slight pollution level. The other seven HMs in A, B, and C and all HMs in chemical plant D belonged to the safe category. The mean values of the Nemerow pollution index in the four industrial plants belonged to the warning category. The analysis showed that none of the HMs posed potential noncarcinogenic health risks, and only the carcinogenic health risks of Cr in plants A and C were unacceptable. The carcinogenic effect of Cr through the inhalation intake of resuspended soil particulates and that of Cd, Ni, and As via direct oral ingestion were the main exposure pathways.

A constructed wetland system with aquatic macrophytes for cleaning contaminated runoff/storm water from urban area in Florida.

A community of aquatic macrophytes has an important role in reducing nutrient load and organic and inorganic contaminants in storm/runoff water. However, minimal information is available regarding the efficiency of constructed wetlands for cleaning runoff water from urban areas, especially in the tropical and subtropical regions. This study investigated the effectiveness of constructed wetland integrated with aquatic macrophytes for removal of chemical and microbial contaminants in the storm/runoff water from the urban areas. Water samples were monthly collected in the constructed wetland from the inlet of storm/runoff water, middle and outlet of discharge, and analyzed for physical and chemical properties, concentrations of nutrients, metals, and fecal coliform (FC) during the period of November, 2016 to April, 2018 in St. Lucie county, Florida, USA. The dominant plant species in the constructed wetland included cattail (Typha latifolia), waterthyme (Hydrilla verticillata) and water hyacinth (Eichhornia crassipes), and periphyton filamentous algae (Spirogyra). The improvement of pH and electrical conductivity (EC) was not obvious, but the concentration of total suspended solids was significantly reduced. This system was effective in the removal of fecal coliform (by 68%) and particulate phosphorus (P, 72%), followed by total P (42%) and N (35%). Concentrations of metallic pollutants including cadmium (Cd), lead (Pb), chromium (Cr), and copper (Cu) were mostly below the detection limit (<1 ppb) except for zinc (Zn), of which concentration was reduced by 23%. The removal of FC was consistently effective all the year round, whereas the removal of total N, P and particulate-P was effective in spring and summer, and less in autumn and winter. These results indicate that constructed wetland with a natural aquatic plant community can effectively reduce the loads of nutrients, metals, and fecal coliforms in water column. Regular harvest of aquatic macrophytes communities and collecting litters may further improve the system efficiency for cleaning storm water from urban areas.

Activated dolomite phosphate rock fertilizers to reduce leaching of phosphorus and trace metals as compared to superphosphate.

Use of water-soluble phosphorus (P) fertilizers such as superphosphates (SP) has been increasingly concerned due to the loss of P and trace metals such as cadmium (Cd) into the environment. Activated phosphate rock holds promising as an alternate due to non-destructive and slow release nature. The objective of this study was to assess the leaching potential of P and trace metals from newly developed activated dolomite phosphate rock (HA-DPR and SLS-DPR), as compared to water-soluble fertilizers, including superphosphate (SP), diammonium phosphate (DAP) and original dolomite phosphate rock (DPR). Two representative agricultural soils (Alfisol and Spodosol soil) were sampled at the 0-20 cm depth from two farms for the column leaching experiments. Seven leachings were conducted at day 1, 3, 7, 14, 21, 28, and 56, respectively, and a total of 1050 mL of deionized water (equivalent to half year's rainfall in the Indian River area) was applied for leaching. Leachates were collected from each leaching event and analyzed for water-soluble P and metals. Activated DPR application led to an increase in soil pH by 1.4-1.7 units, whereas SP resulted in a decrease in soil pH by 0.4-1.6 units. P leaching from activated DPR were 33-61 times less than that from SP or DAP. HA-DPR and SLS-DPR treatments reduced cumulative trace metals in leachate by 1.3-12.3 times for the Alfisol soil, and 1.4 to 8.4 times for the Spodosol soil, respectively. These results indicate that activated DPR fertilizers are more environmentally friendly than water-soluble fertilizers.

Release of Heavy Metals from Dolomite Phosphate Rock after Activation with Organic Agent.

As high-grade phosphate reserves begin to diminish worldwide, low-grade phosphate rock such as that containing dolomite [CaMg(CO)] needs to be explored as a potential fertilizer. Activation of dolomite phosphate rock with humic acid substantially increased P availability by chelating Ca and Mg. However, the release potential of heavy metals during the activation process should be evaluated. In this study, an orthogonal experiment was designed to investigate the effects of major activating factors on the release of Cd, Cr, Cu, Mn, Ni, Pb, and Zn in activated fertilizers using a batch-equilibrium technique. The release potential of heavy metals from activated fertilizers was further compared with single superphosphate fertilizers made from the same dolomite phosphate rock. The activation process increased water-soluble Cr, Ni, and Zn by 39.8 to 65.7, 26.5 to 35.6, and 6.9 to 14.6 times, respectively, as compared with the original dolomite phosphate rocks, but there was a decrease in water-soluble Cd, Mn, Ni, Pb, and Zn by 1.4 to 5.4, 5.4 to 8.6, 2.3 to 3.7, 0.7 to 2.8, and 2.6 to 5.0 times, respectively, as compared with single superphosphate fertilizers. The release of heavy metals was affected by activating factors including dolomite phosphate rock type, particle size, humic acid dosage, and moisture content. Similar results were obtained with Mehlich-3 extraction, but levels of Mehlich-3-extractable heavy metals were less in activated fertilizers than in the original dolomite phosphate rocks, except Cu. These results indicate that activated fertilizers contain less bioavailable heavy metals than single superphosphate fertilizers and, therefore, are more environmentally friendly for application in agriculture.

[Hyperspectral extraction of soil available nitrogen in Nan Mountain coal waste scenic spot of Jinhuagong Mine based on enter-PLSR].

Soil available nitrogen content is an important index reflecting soil fertility. It provides dynamic information for land reclamation and ecological restoration if soil available nitrogen can be monitored and evaluated using hyperspectral technology. Facing the study blank of soil available nitrogen in National Mine Park and the deficiency of poor computational efficiency of partial least squares regression (PLSR) method, the present paper presents the relationship between soil spectrum and soil available nitrogen based on spectrum curves (ranging from 350 to 2 500 nm) of 30 salinized chestnut soil samples, which were collected from southern mountain coal waste scenic spot, located in Jinhuagong mine in Datong city, Shanxi Province, China (one part of Jinhuagong national mine park). Soil reflection spectrum was mathematically manipulated into first derivative and inverse-log spectral curves, then a corresponding estimation model was built and examined by PLSR and Enter-partial least squares regression (Enter-PLSR) based on characteristic absorption. The result indicated that Enter-PLSR corresponding estimation model greatly increased the computation efficiency by reducing the number of independent variables to 12 from 122 in case of a close accuracy of PLS corresponding estimation model. By using hyperspectral technology and Enter-PLSR method, the study blank of soil available nitrogen in National Mine Park was filled. At the same time, the computation efficiency problem of PLSR was resolved.

Phosphorus removal from secondary effluents through integrated constructed treatment system.

The treatment capacity of an integrated constructed treatment system (CTS) was explored which was designed to reduce phosphorus (P) from secondary effluents. The integrated CTS was combined with vertical-flow constructed wetland, floating bed and sand filter. The vertical wetland was filled from the bottom to the top with gravels, steel slag and peat. Vetiverzizanioides (L.) Nash was selected to grow in the vertical constructed wetland while Coixlacrymajobi L. was grown in floating bed. The results suggested that integrated CTS displayed excellent removal efficiency for chemical oxygen demand (COD), dissolved phosphorus (DP), and total phosphorus (TP). The average COD removal efficiency of the integrated CTS was 90.45% after 40 days of operation, the average DP and TP removal efficiencies of the integrated CTS were 97.43% and 96.40%, respectively. The integrated CTS has good potential in removing COD as well as P from secondary effluents.

The role of bacteria in the heavy metals removal and growth of Sedum alfredii Hance in an aqueous medium.

This study was the first attempt to examine the possible role of the naturally occurring rhizospheric bacteria in heavy metal removal by Sedum alfredii Hance, a terrestrial Zn/Cd hyperaccumuluator, from Zn, Cd, Cu and Pb contaminated water using antibiotic ampicillin. Moreover, the toxicity symptom in plants under heavy metal stress expressed as total chlorophyll, chlorophyll a and b content, growth inhibition, root length, and N, P contents were studied, and the possible relationship among them were also discussed. These results indicate that rhizospheric bacteria may play an important role in the uptake of N and P by S. alfredii, and consequently result in the increase of Chlorophyll content in the leaves and plant biomass due to improved photosynthesis. At the same time, root length significantly decreased under the treatment with ampicillin, which suggested that rhizospheric bacteria appeared to protect the roots against heavy metal toxicity. The Pb, Zn, Cu and Cd concentrations in the roots, stems and leaves of S. alfredii were much higher than those exposed to ampicillin. Accordingly, metal concentrations in the contaminated water without ampicillin treatment were lower than those treated with ampicillin. These results suggest that the rhizospheric bacteria may be useful in plant tolerance to heavy metal toxicity, and also accelerate the metal removal from contaminated water.

Phosphate removal from solution using steel slag through magnetic separation.

Steel slag with magnetic separation was used to remove phosphate from aqueous solutions. The influence of adsorbent dose, pH, and temperature on phosphate removal was investigated in a series of batch experiments. Phosphate removal increased with the increasing temperature, adsorbent dose and decreased with increasing initial phosphate concentrations, while it was at its peak at pH of 5.5. The phosphate removal predominantly occurred through ion exchange. The specific surface area of the steel slag was 2.09m2/g. The adsorption of phosphate followed both Langmuir and Freundlich isotherms. The maximum adsorption capacity of the steel slag was 5.3mgP/g. The removal rates of total phosphorus (TP) and dissolved phosphorus (DP) from secondary effluents were 62-79% and 71-82%, respectively. Due to their low cost and high capability, it was concluded that the steel slag may be an efficient adsorbent to remove phosphate both from solution and wastewater.