Terbuthylazine (TBA) has replaced atrazine in many EU countries, becoming one of the most frequently detected pesticides in natural waters. TBA is a compound of emerging concern, due to its persistence, toxicity and proven endocrine disruption activity to wildlife and humans. Techniques applied in water treatment plants remove only partially this herbicide and poor attention is given to the generation and fate of by-products, although some of them have demonstrated an estrogenic activity comparable to atrazine. This paper summarizes the environmental occurrence of TBA and its main metabolite desethylterbuthylazine and reports the performance of an innovative electrochemical cell equipped with a solid polymer electrolyte (SPE) sandwiched between a Ti/RuO₂ cathode and a Boron-Doped Diamond anode, operating at constant current, in the treatment of an aqueous solution of TBA. The herbicide removal in the first 30 min of treatment increases from 42% to 92% as the applied current is increased from 100 to 500 mA. The rate of degradation at 500 mA decreases between 30 and 60 min, with a final abatement of 97%. An 89% removal was reached at 100 mA when the initial TBA concentration was raised from 0.1 to 4 mg L⁻¹ and less than 1% of the herbicide was converted in desethylterbuthylazine and minor metabolites. No chemicals are needed, no sludge is produced. Further research is encouraged, as this technology may be promising for the achievement of a zero-discharge removal of different emerging pollutants as pesticides, pharmaceuticals and personal care products.

The objective of the present study was to evaluate the contamination of sewage sludge produced by municipal waste treatment plants in Poland by viable eggs of intestinal parasites of the genera Ascaris, Toxocara and Trichuris (ATT). Ninety-two municipal, mechanical-biological sewage treatment plants located within Poland were selected. These plants belonged to types of agglomerations: group 0 (large), group 1 (medium), group 2 (smaller) and group 3 (small). Samples were collected at the final stage of sewage treatment after the addition of flocculent to sludge, followed by dehydration. The samples were examined by a method adjusted to examine sewage sludge dehydrated using polyelectrolytes. The viability of the isolated eggs was evaluated based on incubation in a moist chamber. Live eggs of intestinal nematodes were found in 99% of samples. Most samples were contaminated by the eggs of Ascaris spp. (95%) and Toxocara spp. (96%). However, Trichuris spp. eggs were detected in 60% of samples. The mean number of eggs in 1 kg of dry mass (eggs/kg d.m.) was 5600 for Ascaris, 3700 for Toxocara and 1100 for Trichuris. The highest number of ATT eggs was detected in samples from sewage treatment plants located in south-eastern and central Poland. The highest number of ATT eggs was found in sewage sludge produced in large sewage treatment plants (agglomeration Groups 0 and 1), with mean values of 15,000 and 8900 eggs/kg d.m. The present study is the first parasitological investigation conducted on a large number of samples (92 samples) taken from various types of municipal sewage treatment plants located throughout Poland (16 regions) after the common introduction of polyelectrolytes during sewage sludge dehydration. The results of this study indicate that sludge produced in municipal sewage treatment plants is highly contaminated with parasite eggs.

In the present study, the electrocatalytic degradation of triazine herbicide metamitron using Ti/PbO₂-CeO₂ composite anode was studied in detail. The effects of the current density, initial metamitron concentration, supporting electrolyte concentration, and initial pH value were investigated and optimized. The results revealed that an electrocatalytic approach possessed a high capability of metamitron removal in aqueous solution. After 120 min, the removal ratio of metamitron could reach 99.0% in 0.2 mol L⁻¹ Na₂SO₄ solution containing 45 mg L⁻¹ metamitron with the current density at 90 mA cm⁻² and pH value at 5.0. The reaction followed the pseudo-first-order kinetics model. HPLC and HPLC-MS were employed to analyze the degradation by-products in the metamitron oxidization process, and the degradation pathway was also proposed, which was divided into two sub-routes according to the different initial attacking positions on metamitron by hydroxyl radicals. Therefore, the electrocatalytic approach was considered as a very promising technology in practical application for herbicide wastewater treatment.

The aim of the present experimental study was to perform a technical-economic evaluation of a combined treatment system, consisting of coagulation-flocculation or rapid sand filtration as pre-treatment followed by column adsorption, for reducing the arsenic concentration from approximately 1 mg/L to below the limit set for groundwater remediation and drinking water, i.e., 0.01 mg/L, according to the legislation in force. A wide number of operating conditions were experimentally evaluated in the different tests. In the coagulation-flocculation study, it was initially investigated if the iron contained in a mining drainage co-mixed with the groundwater would be able to achieve a better As content reduction by adsorption/precipitation, thus avoiding fresh coagulant addition. Then, different polyelectrolyte dosages were tested varying the mixing ratio. None of the tested conditions allowed to improve the arsenic removal so significantly to warrant the consequent incremental costs. Therefore, the optimal condition was considered any mixing with a different liquid stream and any polyelectrolyte dosage. The iron content naturally present in the groundwater and contact with air was capable alone of reducing As concentration of about 80%. Sand filtration reached approximately the same removal efficiency (about 80%) at the lower surface loading rate among the values tested. Between coagulation and sand filtration, in terms of costs, the latter showed to be more convenient than coagulation-flocculation, at the same removal efficiency: therefore, it was considered the optimal pre-treatment. The following adsorption column plant was capable of further reducing As concentration up to the required value of 0.01 mg/L. Among the two iron-based commercial adsorbents applied in the adsorption column tests, the hybrid media consisting of an exchange resin with iron oxides showed to be preferable under the selected operating conditions: it offered higher adsorption capacity at breakthrough and, after exhaustion, could be regenerated for a number of cycles. The influent pH showed to have a great influence on the duration of the adsorbent media, and values around neutrality were considered preferable. The estimated cost of the full treatment was computed to be about 0.50 €/m³ of purified water. Therefore, the capacity of achieving the required remediation goal, the limited cost, and simplicity of operation make the proposed combined treatment being potentially suitable for real application.

A growing number of electrochemical oxidation system was employed for the degradation of refractory contaminants. In this study, a boron-doped diamond (BDD) anode/Ti cathode equipped in the differential column batch reactor (DCBR) was utilized for electrochemical oxidation of ciprofloxacin (CIP). The feed solution within the DCBR system was confirmed as a uniform flow state through a computational fluid dynamics (CFD) simulation analysis. The results showed that the BDD anode/Ti cathode electrochemical system was with a high efficiency oxidation performance when treating the CIP contaminant. The CIP was completely degraded within 20 min, and over 50% DOC removed after 120 min. Therefore, two-stage electrochemical oxidation mechanism was proposed. Four major factors, the initial concentration, current density, pH, and electrolyte concentration, on the CIP degradation efficiency were systematically investigated. The CIP degradation curve followed pseudo first-order degradation kinetics. The electric efficiency per order (EE/O) of the electrochemical oxidation system was calculated to determine an optimal operation condition. Moreover, the oxidation intermediates were identified with a mass spectrometry (LC/MS/MS) and the degradation pathways were proposed in this study. The destruction of quinolone moiety and piperazine ring and fluorine substitution were the three possible degradation pathways during BDD anode oxidation process.

Drinking water containing environmental endocrine disruptor compounds (EDCs) endangers human health, and researching the purification process of drinking water for the effective removal of EDCs is vitally important. Filtering plays a crucial role in the bio-adsorption of EDCs, but the adsorption mechanism that occurs between the EDCs and filters remains unclear. In this study, a quartz crystal microbalance (QCM) was employed to elucidate the adsorption mechanism because QCM is a label-free method that possesses high selectivity, high stability, and high sensitivity. The results indicated that a pseudo-first-order kinetic model best fits the adsorption process of four different EDCs, which included bisphenol A (BPA), estrone (E1), estradiol (E2), and sulfamethoxazole (SMZ), on silica (quartz sand), a typical filter material surface. The order of the amount of individual EDCs absorbed on the silica surface was qE₂ > qE₁ > qSMZ > qBPA and related to their molecular structure, polarity, and chargeability. As the initial EDC concentration increased, the adsorbed amount of the four EDCs on the silica surface increased; however, the initial concentration had little effect on removal efficiency. The calculated Freundlich exponent (1/n) demonstrated SMZ and BPA showed a greater tendency for adsorption than E1 and E2. The mass response time on the surface of the silica gradually increased as the pH increased (from 5.5 to 8.5), indicating the adsorption rate was inhibited by the increase in pH. The addition of electrolytes shortened the mass response time of EDCs on the QCM chip. The pH and ionic strength produced no significant effects on adsorption because hydrophobicity was the primary contributor to adsorption. This study facilitated a better understanding of the interaction between EDCs and filters in water treatment.

Atrazine, one of the most widespread herbicides in the world, is considered as an environmental estrogen and has potential carcinogenicity. In this study, atrazine was degraded on boron-fluorine co-doped TiO₂ nanotube arrays (B, F-TiO₂ NTAs), which had similar morphology with the pristine TiO₂ NTAs. The structure and morphology of TiO₂ nanotube samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and UV-visible diffuse reflectance spectroscopy (DRS). It showed that the decoration of fluorine and boron made both the absorption in the visible region enhanced and the band edge absorption shifted. The efficiency of atrazine degradation by B, F-TiO₂ NTAs through photoelectrocatalysis was investigated by current, solution pH, and electrolyte concentration, respectively. The atrazine removal rate reached 76% through photoelectrocatalytic reaction by B, F-TiO₂ NTAs, which was 46% higher than that under the photocatalysis process. Moreover, the maximum degradation rate was achieved at pH of 6 in 0.01 M of Na₂SO₄ electrolyte solution under a current of 0.02 A and visible light for 2 h in the presence of B, F-TiO₂ NTAs. These results showed that B, F-TiO₂ NTAs exhibit remarkable photoelectrocatalytic activity in degradation of atrazine.

Uranium-contaminated wastewater associated with uranium (U) mining and processing inevitably releases into soil environment. In order to assess the risk of U wastewater contamination to groundwater through percolation, U adsorption and transport behavior in a typical red soil in South China was investigated through batch adsorption and column experiments, and initial pH and carbonate concentration were considered of the high-sulfate background electrolyte solution. Results demonstrated that U adsorption isotherms followed the Freundlich model. The adsorption of U to red soil significantly decreased with the decrease of the initial pH from 7 to 3 in the absence of carbonate, protonation-deprotonation reactions controlled the adsorption capacity, and lnCₛ had a linear relationship with the equilibrium pH (pHₑq). In the presence of carbonate, the adsorption was much greater than that in the absence of carbonate owing to the pHₑq values buffered by carbonate, but the adsorption decreased with the increase of the carbonate concentration from 3.5 to 6.5 mM. Additionally, the breakthrough curves (BTCs) obtained by column experiments showed that large numbers of H⁺ and CO₃²⁻ competed with the U species for adsorption sites, which resulted in BTC overshoot (C/C₀ > 1). Numerical simulation results indicated that the BTCs at initial pH 4 and 5 could be well simulated by two-site chemical non-equilibrium model (CNEM), whereas the BTCs of varying initial carbonate concentrations were suitable for one-site CNEM. The fractions of equilibrium adsorption sites (f) seemed to correlate with the fractions of positively charged complexes of U species in solution. The values of partition coefficients (kd′) were lower than those measured in batch adsorption experiments, but they had the same variation trend. The values of first-order rate coefficient (ω) for all BTCs were low, representing a relatively slow equilibrium between U in the liquid and solid phases. In conclusion, the mobility of U in the red soil increased with the decrease of the initial pH and with the increase of the initial carbonate concentrations.

This study examined the electrocatalytic activity of multi-walled carbon nanotube (CNT) filters for remediation of aqueous phenol in a sodium sulfate electrolyte. CNT filters were loaded with antimony-doped tin oxide (Sb-SnO₂; SS) and bismuth- and antimony-codoped tin oxide (Bi-Sb-SnO₂; BSS) via electrosorption at 2 V for 1 h and then assembled into a flow-through batch reactor as anode–cathode couples with perforated titanium foils. The as-synthesized pristine CNT filters were composed of 50–60-nm-thick tubular carbons with smooth surfaces, whereas the tubes composing the SS-CNT and BSS-CNT filters were slightly thicker and bumpy, because they were coated with SS and BSS particles ~50 nm in size. Electrochemical characterization of the samples indicated a positive shift in the onset potential and a decrease in the current magnitude in the modified CNT filters due to passivation and oxidation inhibition of the bare CNT filters. These filters exhibited a similar adsorption capacity for phenol (5–8%), whereas loadings of SS and BSS enhanced the degradation rate of phenol by ~1.5 and 2.1 times, respectively. In particular, the total organic carbon removal performance and mineralization efficiency of the BSS-CNT filters were approximately twice those of the bare CNT filters. The BSS-CNT filters also exhibited an enhanced oxidation of ferrocyanide [Feᴵᴵ(CN)₆⁴⁻], which was not adsorbed onto the CNT filters. The enhanced electrocatalytic performance of the modified CNT filters was attributed to an effective generation of OH radicals. The surfaces of the filters were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy.

Waste printed circuit boards (WPCBs) are usually dismantled, crushed, and sorted to WPCB metal-enriched scraps, still containing an amount of non-metallic materials. This research used slurry electrolysis to refine these WPCB metal-enriched scraps and to examine if a standard ionic liquid, [MIm]HSO₄, can replace H₂SO₄ in the system. The impact of the refinement process on metal migration and transformation is discussed in detail. The results demonstrated that metals in WPCB metal-enriched scraps could be successfully refined using slurry electrolysis, and [MIm]HSO₄ can be used to replace H₂SO₄ in the system. When 80% of H₂SO₄ was replaced by [MIm]HSO₄ (electrolyte of 200 mL, 30 g/L CuSO₄·5H₂O, 60 g/L NaCl, 130 g/L H₂SO₄, and 1.624 A for 4 h), the total metal recovery rate is 85%, and the purity, current efficiency, and particle size of cathode metal powder were 89%, 52%, and 3.77 μm, respectively. Moreover, the microstructure of the cathode metal powder was dendritic in the H₂SO₄-CuSO₄-NaCl slurry electrolysis system, whereas at an 80% [MIm]HSO₄ substitution rate slurry electrolysis system, the cathode metal powder was irregular and accumulated as small-sized spherical particles. Thus, replacing inorganic leaching solvents with ionic liquids may provide a potential choice for the resources in WPCB metal-enriched scraps.