Chlorinated aromatic organic compounds are extremely toxic to the environment and cause cancer to the human body. Pentachlorophenol (PCP) is a hydrophobic and ionic organic compound that is employed as a production material in various industries. Although the Taiwanese government has banned the use of PCP for years, large PCP-contaminated areas remain in Southern Taiwan. Chemical oxidation, which has been proposed as a viable method for restoring PCP-contaminated areas, involves the use of micronanosize birnessite (δ-MnO₂), which is a type of manganese oxide and a natural mineral in soil environments. The goal of this study was to simulate the decontamination of the underlying soil of the PCP-contaminated areas, which is situated in anaerobic and lightless environment. Through the use of a self-developed gas release and absorption reaction flask, the oxidative mineral decarboxylation and dechlorination effects of δ-MnO₂ on PCP in aerobic and anaerobic (with oxygen removed through the use of nitrogen) environments without light were investigated. Results indicated that adding δ-MnO₂ facilitated the oxidative decarboxylation and dechlorination of PCP and the release of Cl⁻ in an aerobic, lightless environment without microbial activity. In the anaerobic environment, the oxidative decarboxylation effect of δ-MnO₂ on PCP decreased significantly, and the dechlorination effect was the primary reaction. Accordingly, adding δ-MnO₂ inorganically destroys aromatic benzene and releases CO₂ and Cl⁻. The molar ratio between CO₂ and Cl⁻ was calculated to assess the mechanisms of the distinct reaction systems. The parameters and data acquired from the experiment, which involved simulating the conditions of the contaminated areas, can be used in planning the on-site management of the PCP contamination; in particular, these parameters and data provide a reference for eliminating PCP from underlying soil—including groundwater-saturated layers.

The increased use of heavy metals in process industries often results in the generation of large quantities of wastewater (WW) and aqueous waste (AW) containing mixtures of heavy metals such as copper and nickel. This research focuses on the electrochemical recovery of copper and nickel from acid pickling solutions used to treat metal surfaces. Using hull cells, beaker plating, and electrolytic cells in pilot scale (capacity 30 L), the most important parameters influencing the process have been identified (temperature, contact time, and current density). In total, about 60 tests were carried out on AW containing nickel and copper. The results of the tests carried out with copper-containing AW shows that removal yields are often higher than 50%; while the energy consumption is less than 15 kWh kg⁻¹ of metal deposited. The best removal efficiency (100%) was achieved by applying a current density of 6 A dm⁻² and the energy consumption was 2 kWh kg⁻¹. The tests carried out with AW containing nickel point out very low removal yields (< 20%) and very high energy consumption (even exceeding 300 kWh kg⁻¹). The best removal yield obtained, applying a current density of 3 A dm⁻², is 6.7% with an energy consumption of 40 kWh kg⁻¹ of metal removed. A costs analysis based on Metal Exchange value was carried out. The cost analysis suggests that the results, in terms of removal and recovery, obtained for these metals, in particular for copper, are very promising for an industrial application.

Application of fungicides on grapevines is the main source of soil contamination by copper and zinc. Studies on this issue in relatively young grapevines are common; however, studies that elucidate the metal transfer in a soil-plant-food production system in a centenarian vineyard are scarce. The present work was aimed at tracing the copper and zinc accumulation in three different compartments—soil, plant, and vine products—in young and centenarian vineyards. Soil samples were collected in the middle plant row and rhizosphere positions of the vineyards; samples of root and leaf tissue and of grape juice and wine from these vineyards were also collected. In the centenarian vineyard, the soil available copper, regardless of vineyard position, reached 1100 mg kg⁻¹. Copper in root and leaf tissues reached 12,300 mg kg⁻¹ and 6800 mg kg⁻¹, respectively. In grape juice and wine, copper was 9.08 mg L⁻¹ and 0.78 mg L⁻¹, respectively. The roots retained most part of the metals reducing their transfer through the system. However, Cu levels in the grape juice from the centenarian vineyard exceeded by 908% the limit established by Brazilian and international norms. Zinc concentrations in soil and vine products were within the permitted level. Finally, the magnitude of metal transfer and accumulation is due to decades of cupric fungicide application and varies according to the compartment evaluated. The findings will provide information to rethink the vineyard agricultural practices in order to avoid environmental contamination by metals and compromising the whole food chain.

The synthetic hormone sodium levothyroxine (LTX) is one of the most prescribed drugs in the world and the most effective in hypothyroidism treatment. The presence of LTX in the environment has become a matter of major concern due to the widespread use of this hormone and by the fact that it is only partially removed in conventional water and sewage treatment plants. However, information regarding the photochemical fate of this hormone in environmental or engineered systems is scarce in the literature. In this work, the sunlight-driven direct and indirect LTX degradation was investigated by determining the photolysis quantum yield, ΦLTX = 3.80 (± 0.02) × 10⁻⁵, as well as the second-order kinetic constants of the reactions with hydroxyl radicals, kLTX,•OH = 1.50 (± 0.01) × 10¹⁰ L mol⁻¹ s⁻¹ and singlet oxygen, kLTX,₁O₂ = 1.47 (± 0.66) × 10⁸ L mol⁻¹ s⁻¹. Mathematical simulations indicate that LTX photodegradation is favored in shallow, nitrite-rich, and dissolved organic matter (DOM)-poor environments, with LTX half-life times varying from less than 10 days to about 80 days. LTX removals of 85 and 95% were achieved by UVC photolysis and UVC/H₂O₂ after 120 min, respectively. Three transformation products, triiodothyronine, diiodothyronine, and diiodotyrosine, were identified during LTX degradation by the UVC-based processes studied. The results herein regarding photo-induced kinetics coupled with environmental fate simulations may help evaluate LTX persistence and also the design of water and wastewater treatment processes.

Perfluorinated and polyfluorinated substances (PFASs) are widely found in freshwater ecosystems because of their resistance to degradation and their ability to accumulate in aquatic organisms. While water temperature controls many physiological processes in fish, knowledge of the effects of this factor on PFAS toxicokinetic is still limited. This study presents experimental results of internal distribution and elimination rates of two perfluorinated acid compounds, namely perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS) in adult rainbow trout (Oncorhynchus mykiss) exposed to three temperatures. Dietary exposure experiments were conducted at 7 °C, 11 °C, and 19 °C and liver, blood, muscle, brain, and kidney were sampled for analysis. PFOS concentrations were comparable to or exceeded those of PFHxS, while PFHxS was eliminated faster than PFOS, whatever the temperature. Internal distribution changed significantly for both substances when fish were exposed to a range of temperatures from 7 to 19 °C. Indeed, PFOS and PFHxS relative distribution increased in blood, liver, and brain while they decreased in muscle when the water temperature rose. The water temperature variation affected the elimination half-lives, depending on the substances and organs.

A new adsorbent poly-3-hydroxybutyrate-2-(dodecylthiocarbonothioylthio)-2-methylpropionate triester (PH-DTT-MPT) was first time loaded in a micropipette tip for speciation of chromium in different water samples. Total chromium (Cr), trivalent chromium (Crᴵᴵᴵ), and hexavalent chromium (Crⱽᴵ) in different natural water samples were determined by electrothermal atomic absorption spectrometry. Known concentration of Crᴵᴵᴵ and Crⱽᴵ was passed through a biodegradable polymer for investigation of the behavior of the newly used adsorbent. The newly used copolymer absorbed the Crᴵᴵᴵ on surface of the PH-DTT-MPT at pH 7.0, while Crⱽᴵ was not adsorbed in desired pH value. After passing the real and standard solutions through the micropipette, then 2.0 mol L⁻¹ HCl was used for elution of Crᴵᴵᴵ from the biodegradable polymer. Total Cr was calculated after reducing Crⱽᴵ into Crᴵᴵᴵ by specific concentration of hydroxy ammonium chloride (HONH₂·HCl). The concentration of Crⱽᴵ in different natural water samples was estimated after back calculation of Crᴵᴵᴵ from total chromium. Effect of analytical parameters like adsorbent, pH, eluent, sample volume, flow rates, and interfering ions was also studied. The LOD, LOQ, RSD, and EF of the developed method were calculated as 6.1 ng L⁻¹, 20 ng L⁻¹, 1.17%, and 90, respectively. Validation of developed method was checked by certified reference materials and spiking addition method. The developed method was successfully applied for determination of total Cr, Crᴵᴵᴵ, and Crⱽᴵ in various natural water ecosystems.

In this study, organoclay and clay-biopolymer composites were evaluated for the adsorption process of an anionic red dye, Allura Red (AR), in aqueous solution. For this purpose, the cationic exchange capacity (CEC) of a natural bentonite was calculated, and it was modified with the cationic surfactant hexadecyltrimethylammonium bromide (OB). Furthermore, a commercial montmorillonite modified with dimethyldialkyl ammonium (OM) was also employed. These organo-modified clays were used for the synthesis of two series of composites, with alginate as the polymer matrix, and were identified as OBC and OMC, respectively; composites were obtained in the wet (W) and dry (D) states. The adsorbent materials were characterized by means of infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and dispersive energy spectroscopy (EDS). Afterwards, kinetics and isotherms studies were performed in batch systems, with dye solutions of different concentrations, without pH adjustment. Some parameters were evaluated, such as the variation of the pH value of the solution and the concentration of the dye with the organoclays and composites. Chemisorption was considered as the main mechanism that follows the adsorption processes of AR. Results demonstrated that the pseudo-second order was the kinetics model that best described the adsorption process of the AR dye, with both, hydrated and dry composites. Finally, the Freundlich and the Langmuir–Freundlich isotherms were the best models that described the hydrated and dry composites behavior, respectively.

The residue concentrations and congener profiles of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) were examined in fly ash and bottom ash released from different thermal industrial processes in Vietnam. PCDD/F concentrations and toxic equivalents (TEQs) in the ash samples varied greatly and decreased in the following order: steel making > aluminum recycling > medical waste incinerator > boilers > municipal waste incinerator > tin production > brick production > coal-fired power plant. Both the precursor and de novo synthesis were estimated as possible formation mechanisms of dioxins in the ash, but the latter pathway was more prevalent. The highest emission factors were estimated for the ash released from some steel-making plants, aluminum-recycling facilities, and a medical waste incinerator. The emission factors of PCDD/Fs in ash released from some steel plants of this study were two to six times higher than the UNEP Toolkit default value. The annual emission amount of ash-bound dioxins produced by 15 facilities in our study was estimated to be 26.2 to 28.4 g TEQ year⁻¹, which mainly contributed by 3 steel plants. Health risk related to the dioxin-containing ash was evaluated for workers at the studied facilities, indicating acceptable risk levels for almost all individuals. More comprehensive studies on the occurrence and impacts of dioxins in waste streams from incineration and industrial processes and receiving environments should be conducted, in order to promote effective waste management and health protection scheme for dioxins and related compounds in this rapidly industrializing country.

Nowadays, widespread application of engineered nanoparticles (ENPs) inevitably leads to their release into the environment. Soils are regarded as the ultimate sink for ENPs. The study on mobility of ENPs in soils is important in the assessment of potential risks related to their toxicity. The behavior of ENPs is dependent not only on parameters of soil but also on exposure scenarios, namely, the amount of ENPs trapped in soil. In the present work, the mobility of cerium dioxide nanoparticles (nCeO₂) in soils at different exposure scenarios has been studied. The relationship between mobility of nCeO₂ and their concentration in soil in the range from 1 to 1000 μg g⁻¹ is evaluated. It is shown that the mobility of nCeO₂ decreases with decreasing their concentration in soil and attains the minimum value at the concentration of nCeO₂ below 10 μg g⁻¹. In relative terms, only about 0.1–0.2% of nCeO₂ at their concentration in soil 10–1000 μg g⁻¹ are mobile and can migrate in soil profile under saturated conditions. The major portion of nCeO₂ (about 99.8%) remains immobile in soil. Evidently, the vertical transport of nCeO₂ in soil profile should depend on volume of released suspensions. In the case of small or moderate wet deposition, nanoparticles will accumulate in upper soil horizons, where biological activity is highest, and affect the soil inhabitants (plant roots, earthworms, insects, microorganisms, etc.).

High temperature poses a severe extortion to productivity of many crops like wheat. Therefore, well documented roles of brassinosteroid (BR) and silicon (Si) in terms of abiotic stress tolerance, the current study was designed to evaluate the response of wheat (Triticum aestivum L. Var. PBW-343) to 24-epibrassinolide (EBL) mediated by silicon grown under high temperature stress. At 10- and 12-day stage after sowing, the seedlings were administered Si (0.8 mM) through the sand, and the plants at 20, 22, or 24 days after sowing (DAS) were given EBL (0.01μM) through foliage. Plants were treated to high-temperature stress (35/28 or 40/35 °C), for 24 h with 12-h photoperiod in plant growth chamber at 25- and 26-day stage of growth. High temperatures cause significant reduction in growth performance and photosynthesis-related attributes at 35 days after sowing. However, antioxidant enzymes and proline content also augmented substantially with increasing temperature. BR and Si enhanced antioxidant activity and proline content, which was earlier increased by the high temperature. It is established that interaction of EBL and Si considerably improved the growth features, photosynthetic efficacy, and several biochemical traits under high-temperature stress through elevated antioxidant system and osmoprotectant.