Search Results (21)

Copper nanoparticles (CuNPs) are increasingly used in agriculture either alone or in combination with pesticides. Recognizing the potential hazards of CuNPs in soil environments, our study evaluated their effects on the metabolic activity of Nitrobacter winogradskyi ATCC 2539, a chemolithoautotrophic bacterium crucial for the nitrification process, which involves the oxidation of nitrite to nitrate in soil ecosystems. This study evaluated the effects of concentration ranges of CuNPs (2.5 to 162.7 mg L⁻¹), CuONPs (3.2 to 203.6 mg L⁻¹), and various pesticides (iprodione, carbendazim, and 2,4-D) and their derivatives (3,5-dichloroaniline, catechol, and 2,4-dichlorophenol) at concentrations ranging from 0.04 to 2.56 mM. CuSO₄ was also used as a control for comparative purposes. Our findings indicated that the CuNPs significantly inhibited the metabolic activity of N. winogradskyi, resulting in a reduction of up to 95% at concentrations of ≥2.5 mg L⁻¹. The CuONPs were less toxic, while the pesticides and their derivatives generally showed lower toxicity. Notably, combinations of CuNPs with pesticides or their derivatives maintained high toxicity levels comparable to those of the CuNPs alone. According to the Loewe additivity model, these effects were largely additive and primarily associated with CuNPs or CuONPs. Protein profiling using matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF)/TOF mass spectrometry (MS) revealed that carbendazim induced noticeable changes in protein profiles. These findings underscore the detrimental impacts of CuNPs and CuONPs on the metabolic activity of N. winogradskyi, posing a considerable risk to the health of agricultural soils. Overall, this research provides crucial insights into the risks associated with using CuNPs in agriculture, particularly regarding their potential threat to nitrifying microorganisms in soils. Full article

The use of cellular energy allocation (CEA) as a physiological energetic biomarker is useful for detecting the sublethal effects of environmental contaminants. The CEA assesses the health and energy status of organisms, serving as a reliable indicator for monitoring the health of aquatic ecosystems. This study aimed to evaluate the impact of emerging contaminants already listed as a priority for monitoring in freshwater ecosystems, namely sulfamethoxazole (0.156–2.50 mg/L), trimethoprim (25.0–400 mg/L), 4-chloroaniline (5.21–20.0 mg/L), and 3,4-dichloroaniline (0.38–4.00 mg/L), on the CEA of D. rerio embryos. A standard fish embryo toxicity test was conducted, and an adaptation of the allometric scaling approach was developed through the relationship between the size and the fresh weight of the embryos. All the compounds affected the fractions of the energy reserves (total carbohydrate, lipid, and protein contents) differently, with carbohydrates being the predominant energy fraction and the most responsive indicator. Although the energy consumed showed no significant changes, the CEA was notably altered after exposure to all the contaminants, indicating a direct connection to shifts in the available energy. The CEA alterations may indicate a reallocation of energy toward detoxification, combating the stress of contaminant exposure. Energy allocation biomarkers provide a comprehensive assessment of an organism’s physiological state, which is essential for evaluating emerging contaminants’ impacts, safeguarding aquatic ecosystems, and shaping effective environmental policies. Full article

In this study, carbon materials with different dimensions, including the typical one-dimensional (1D) carbon nanotube (CNT), two-dimensional (2D) graphene (GF), and three-dimensional (3D) activated carbon (AC), were investigated as a support for Pt catalysts for the selective hydrogenation of 3,4-dichloronitrobenzene (3,4-DCNB) to 3,4-dichloroaniline (3,4-DCAN). Notably, the Pt/CNT catalyst with the lowest dimension exhibited the best conversion of 3,4-DCNB under mild reaction conditions, followed by Pt/GF. Comprehensive characterizations, including XRD, TEM, XPS, and in situ CO DRIFTS, reveal that the dimension of carbon supports plays an important role in the particle size and electronic properties of Pt species, consequently affecting the catalytic performances of Pt catalysts. According to the results, electron-deficient Pt particles with small sizes are more favorable for the hydrogenation of 3,4-DCNB to 3,4-DCAN. In addition, dynamic tests and in situ DRIFTS of 3,4-DCNB indicated that the carbonaceous supports will largely influence the adsorption and activation capacity of the Pt catalysts, so that Pt loaded on CNT and GF are superior to that on the AC. We believe this study will provide good guidance for designing efficient carbon-supported metal catalysts for selective hydrogenation. Full article

3,4-Dichloroaniline (34DCA), a major metabolite of phenylurea herbicides, causes environmental contamination owing to its toxicity and recalcitrant properties. Acinetobacter soli strain GFJ2, isolated from soil potentially contaminated with herbicides, can degrade 34DCA. This study aimed to identify and characterize the 34DCA degradation gene cluster responsible for the conversion of 34DCA to 4,5-dichlorocatechol in the strain GFJ2. Genome analysis revealed one chromosome and seven plasmids in GFJ2, comprising 21, 75, and 3309 copies of rRNA, 75 tRNA, and protein-encoding genes, respectively. A gene cluster responsible for 34DCA degradation was identified, comprising dcdA, dcdB, and dcdC, which encode dioxygenase, flavin reductase, and aldehyde dehydrogenase, respectively. Transcriptional analysis indicated that this gene cluster is constructed as an operon, induced during 34DCA utilization. The heterologous expression of dcdA and dcdB in Escherichia coli confirmed their activity in degrading 34DCA to an intermediate metabolite, converted to 4,5-dichlorocatechol via a reaction involving the dcdC gene product, suggesting their involvement in 34DCA conversion to 4,5-dichlorocatechol. Deletion mutants of dcdA and dcdB lost 34DCA degradation ability, confirming their importance in 34DCA utilization in GFJ2. This study provides insights into the genetic mechanisms of 34DCA degradation by GFJ2, with potential applications in the bioremediation of environments contaminated by phenylurea herbicides. Full article

The growing concern over the environmental impacts of industrial chemicals on aquatic ecosystems has prompted increased attention and regulation. Aromatic amines have drawn scrutiny due to their potential to disturb aquatic ecosystems. 4-chloroaniline and 3,4-dichloroaniline are chlorinated derivatives of aniline used as intermediates in the synthesis of pharmaceuticals, dyes, pesticides, cosmetics, and laboratory chemicals. While industrial applications are crucial, these compounds represent significant risks to aquatic environments. This article aims to shed light on aromatic amines’ ecological and ecotoxicological impacts on aquatic ecosystems, given as examples 4-chloroaniline and 3,4-dichloroaniline, highlighting the need for stringent regulation and management to safeguard water resources. Moreover, these compounds are not included in the current Watch List of the Water Framework Directive, though there is already some information about aquatic ecotoxicity, which raises some concerns. This paper primarily focuses on the inherent environmental problem related to the proliferation and persistence of aromatic amines, particularly 4-chloroaniline and 3,4-dichloroaniline, in aquatic ecosystems. Although significant research underscores the hazardous effects of these compounds, the urgency of addressing this issue appears to be underestimated. As such, we underscore the necessity of advancing detection and mitigation efforts and implementing improved regulatory measures to safeguard the water bodies against these potential threats. Full article

3,4-dichloroaniline (3,4-DCA) and 3,5-dichloroaniline (3,5-DCA) are, respectively, the primary metabolites deriving from the breakdown of phenylurea herbicides and dicarboximide fungicides in both soils and plants, whose residues in vegetable products have a heightened concern considering their higher health risks to humans and greater toxicity than the parent compounds in the environment. In this study, a sensitive high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was developed for the simultaneous determination of 3,4-DCA and 3,5-DCA residues in chive products based on the optimization of HPLC-MS/MS chromatographic and mass-spectrometric conditions using the standard substances and the modified QuEChERS preparation technique. The preparation efficiency of 3,4-DCA and 3,5-DCA from chive samples showed that acetonitrile was the best extractant. The combination of the purification agent graphite carbon black + primary secondary amine and the eluting agent acetonitrile + toluene (4:1, v/v) had a satisfactory purification effect. The linear correlation coefficients (R²) were more than 0.996 with the six concentration range of 0.001–1.000 mg/L for 3,4-DCA and 3,5-DCA. The limit of detection and limit of quantitation of this method was 0.6 and 2.0 µg/kg for 3,4-DCA, as well as 1.0 and 3.0 µg/kg for 3,5-DCA, respectively. The matrix effect range of 3,4-DCA and 3,5-DCA in chive tissues was from −9.0% to −2.6% and from −4.4% to 2.3%, respectively. The fortified recovery of 3,4-DCA and 3,5-DCA in chive samples at four spiked levels of 0.001–1.000 mg/kg was 75.3–86.0% and 78.2–98.1%, with the relative standard deviation of 2.1–8.5% and 1.4–11.9%, respectively. The limit of detection (LOD) and limit of quantification (LOQ) of the method were 0.6, 2.0, and 1.0, 3.03 for 4-DCA and 3,5-DCA, respectively. This study highlights that the analytical method established here can efficiently and sensitively detect residues of 3,4-DCA and 3,5-DCA residues for monitoring chive products. The method was successfully applied to 60 batches of actual vegetable samples from different regions. Full article

The assessment and prediction of the toxicity of engineered nanomaterials (NMs) present in mixtures is a challenging research issue. Herein, the toxicity of three advanced two-dimensional nanomaterials (TDNMs), in combination with an organic chemical (3,4-dichloroaniline, DCA) to two freshwater microalgae (Scenedesmus obliquus and Chlorella pyrenoidosa), was assessed and predicted not only from classical mixture theory but also from structure-activity relationships. The TDNMs included two layered double hydroxides (Mg-Al-LDH and Zn-Al-LDH) and a graphene nanoplatelet (GNP). The toxicity of DCA varied with the type and concentration of TDNMs, as well as the species. The combination of DCA and TDNMs exhibited additive, antagonistic, and synergistic effects. There is a linear relationship between the different levels (10, 50, and 90%) of effect concentrations and a Freundlich adsorption coefficient (K_F) calculated by isotherm models and adsorption energy (E_a) obtained in molecular simulations, respectively. The prediction model incorporating both parameters K_F and E_a had a higher predictive power for the combined toxicity than the classical mixture model. Our findings provide new insights for the development of strategies aimed at evaluating the ecotoxicological risk of NMs towards combined pollution situations. Full article

This work provides the basis for implementing a continuous treatment system using a bacterial consortium for wastewater containing a pesticide mixture of iprodione (IPR) and chlorpyrifos (CHL). Two bacterial strains (Achromobacter spanius C1 and Pseudomonas rhodesiae C4) isolated from the biomixture of a biopurification system were able to efficiently remove pesticides IPR and CHL at different concentrations (10 to 100 mg L⁻¹) from the liquid medium as individual strains and free consortium. The half-life time (T_1/2) for IPR and CHL was determined for individual strains and a free bacterial consortium. However, when the free bacterial consortium was used, a lower T_1/2 was obtained, especially for CHL. Based on these results, an immobilized bacterial consortium was formulated with each bacterial strain encapsulated individually in alginate beads. Then, different inoculum concentrations (5, 10, and 15% w/v) of the immobilized consortium were evaluated in batch experiments for IPR and CHL removal. The inoculum concentration of 15% w/v demonstrated the highest pesticide removal. Using this inoculum concentration, the packed-bed bioreactor with an immobilized bacterial consortium was operated in continuous mode at different flow rates (30, 60, and 90 mL h⁻¹) at a pesticide concentration of 50 mg L⁻¹ each. The performance in the bioreactor demonstrated that it is possible to efficiently remove a pesticide mixture of IPR and CHL in a continuous system. The metabolites 3,5-dichloroaniline (3,5-DCA) and 3,5,6-trichloro-2-pyridinol (TCP) were produced, and a slight accumulation of TCP was observed. The bioreactor was influenced by TCP accumulation but was able to recover performance quickly. Finally, after 60 days of operation, the removal efficiency was 96% for IPR and 82% for CHL. The findings of this study demonstrate that it is possible to remove IPR and CHL from pesticide-containing wastewater in a continuous system. Full article

For the detection of Cd(II) in aquatic media, a novel dicyanomethylene dihydrofuran hydrazone(DCDHFH)-based colorimetric chemosensor was developed. DCDHFH was prepared by an azo-coupling process involving the diazonium chloride of 2, 4-dichloroaniline and a dicyanomethylene dihydrofuran heterocyclic moiety bearing an active methyl group. The DCDHFH chromophore showed strong solvatochromism depending on solvent polarity due to electronic delocalization. The pH sensory effects of the DCDHFH chromophore were also explored. DCDHFH could be used to identify Cd(II) in the presence of other competitive metals, as indicated by variations in color and absorbance spectra. In the presence of cadmium ions, the synthesized DCDHFH probe with hydrazone recognition moiety exhibited a significant sensitivity and selectivity to cadmium ions at the ppm concentration level (10–250 ppm). A DCDHFH-immobilized paper test strip was also prepared and effectively used for the detection of cadmium in aqueous media at various concentrations. According to CIE Lab’s criteria, colorimetric strength (K/S), and the UV–Vis absorbance spectra, the cadmium detection abilities of the DCDHFH-immobilized paper strips were evaluated. The optimal pH range for the determination of Cd(II) was monitored in the area of 5.5–6.3, with a fast chromogenic change from yellow to red relying on the Cd(II) concentration. The deposition of dicyanomethylene dihydrofuran hydrazone onto the paper strip’s surface was studied by scanning electron microscopy (SEM). Full article

Dichloroanilines and phthalic acid esters (phthalates) are food contaminants, stable in solution even at high temperatures, which exhibit considerable toxic effects, while acting as endocrine disruptors. In the present study, a quick and easy UHPLC-MS/MS method for simultaneously analyzing two dichloroanilines (3,4-DCA and 3,5-DCA) and six phthalates (DMP, DnBP, BBP, DnOP, DEHP, and mBP) in commercial rice samples was developed, validated, and applied. For the cleanup process, the methodology of quick, easy, cheap, effective, rugged, and safe (QuEChERS) was applied, whereas different dispersants (GCB, C18, and PSA) were tested. What was developed and presented had limits of detection ranging from 0.017 up to 0.12 mg/kg, recoveries (trueness) below 120%, and relative standard deviations (RSD; precision) <15% for all target analytes, whilst no significant matrix effects occurred for all analytes. It was determined that the rice samples analyzed using this developed technique did not contain any of the two dichloroaniline compounds (3,4-DCA and 3,5-DCA) nor two of the six phthalate (DMP and mBP) compounds analyzed, while the levels of other phthalates (DEHP, BBP, DnBP and DnOP) were within the legal limits. The current method ensures a fast and easy approach for the high-throughput quantification of the selected food contaminants in rice. Full article

The phenylurea herbicides are persistent in soil and water, making necessary the de-velopment of techniques for their removal from the environment. To identify new options in this regard, bacterial strains were isolated from a soil historically managed with pesticides. Ochrobactrum anthropi CD3 showed the ability to remove completely herbicides such as diuron, linuron, chlorotoluron and fluometuron from aqueous solution, and up to 89% of isoproturon. In the case of diuron and linuron, their main metabolite, 3,4-dichloroaniline (3,4-DCA), which has a higher toxicity than the parent compounds, was formed, but remained in solution without further degradation. O. anthropi CD3 was also tested for bioremediation of two different agricultural soils artificially contaminated with diuron, employing bioremediation techniques: (i) biostimulation, using a nutrient solution (NS), (ii) bioaugmentation, using O. anthropi CD3, and iii) bioavailability enhancement using 2-hydroxypropyl-β-cyclodextrin (HPBCD). When bioaugmentation and HPBCD were jointly applied, 50% of the diuron initially added to the soil was biodegraded in a range from 4.7 to 0.7 d. Also, 3,4-DCA was degraded in soil after the strain was inoculated. At the end of the soil biodegradation assay an ecotoxicity test confirmed that after inoculating O. anthropi CD3 the toxicity was drastically reduced. Full article

The kinetics of photocatalytic degradation of aniline, 2-chloroaniline, and 2,6-dichloroaniline in the presence of halloysite-TiO₂ and halloysite-Fe₂O₃ nanocomposites, halloysite containing naturally dispersed TiO_2, Fe₂O₃, commercial TiO₂, P25, and α-Fe₂O₃ photocatalysts, were investigated with two approaches: the Langmuir–Hinshelwood and first-order equations. Adsorption equilibrium constants and adsorption enthalpies, photodegradation rate constants, and activation energies for photocatalytic degradation were calculated for all studied amines photodegradation. The photodegradation mechanism was proposed according to organic intermediates identified by mass spectrometry and electrophoresis methods. Based on experimental results, it can be concluded that after 300 min of irradiation, aniline, 2-chloro-, and 2,6-dichloroaniline were completely degraded in the presence of used photocatalysts. Research results allowed us to conclude that higher adsorption capacity and immobilization of TiO₂ and Fe₂O₃ on the halloysite surface in the case of halloysite-TiO₂ and halloysite-Fe₂O₃ nanocomposites significantly increases photocatalytic activity of these materials in comparison to the commercial photocatalyst: TiO₂, Fe₂O₃, and P25. Full article

Supported nickel catalysts represent a class of important catalytic materials in selective hydrogenations, but applications are frequently limited by metal agglomeration or active-site blocking induced by the presence of hydrogen halides. Herein, we report a novel pre-coking strategy, exposing the nickel nanoparticles under methane dry reforming conditions to manipulate performance in the continuous-flow hydrogenation of 1,2-dichloro-4-nitrobenzene. Compared with the pristine nickel catalyst, the nanotube-like coke-modified nickel catalyst showed weakened hydrogenating ability, but much improved stability and slightly better selectivity to the target product, 3,4-dichloroaniline. Characterization results revealed that the strengthened stability performance can be mainly linked to the reduced propensity to retain chlorine species, which seems to block the access of the substrate molecules to the active sites, and thus is a major cause of catalyst deactivation on the pristine nickel catalyst. Coke deposition can occur on the pre-coked nickel catalyst but not on the pristine analog; however, the impact on the stability performance is much milder compared with that on chlorine uptake. In addition, the presence of coke is also beneficial in restraining the growth of the nickel nanoparticles. Generally, the developed method might provide an alternative perspective on the design of novel transition-metal-based catalytic materials for other hydrogenation applications under harsh conditions. Full article

This study provides the basis for implementing a continuous treatment system for wastewater containing a pesticide mixture formed by atrazine, iprodione, and chlorpyrifos. Two fungal strains (Verticilium sp. H5 and Metacordyceps sp. H12) isolated from a biomixture of a biopurification system were able to remove different pesticide concentrations (10 to 50 mg L⁻¹) efficiently from the liquid medium; however, the half-life of the pesticides was reduced and characterized by a T_1/2 of 5.4 to 9.2 d for atrazine, 3.7 to 5.8 d for iprodione, and 2.6 to 2.9 d for chlorpyrifos using the fungal consortium. The immobilization of the fungal consortium in alginate bead was effective, with the highest pesticide removal observed using an inoculum concentration of 30% wv⁻¹. The packed-bed reactor with the immobilized fungal consortium, which was operated in the continuous mode at different flow rates (30, 60, and 90 mL h⁻¹), required approximately 10 d to achieve removal efficiency (atrazine: 59%; iprodione: 96%; chlorpyrifos: ~85%). The bioreactor was sensitive to flow rate fluctuations but was able to recover performance quickly. The pesticide metabolites hydroxyatrazine, 3,5-dichloroaniline, and 3,5,6-trichloro-2-pyridinol were produced, and a slight accumulation of 3,5,6-trichloro-2-pyridinol was observed. Nevertheless, reactor removal efficiency was maintained until the study ended (60 d). Full article

Compound 3,4-dichloroaniline (3,4-DCA) is a metabolite of several urea herbicides and intermediate chemical of several industrial products. Moreover, 3,4-DCA has been frequently detected in aquatic ecosystems around the world. This aniline is more toxic than the parent chemicals, and it affects non-target organisms. This study evaluated a 21-day reproductive response of an emerging aquatic vertebrate model, Javanese medaka (Oryzias javanicus), exposed to 3,4-DCA. Fecundity and gonads histopathology were observed. The spawning rate and fertilisation reduced significantly in the highest exposed-group (250 µg/L). Gonadosomatic index (GSI) was significantly low in females exposed to 250 µg/L. No substantial structural alteration of male gonads. However, oocyte development and ovarian cell structure were disrupted in 250 µg/L exposed females. The gonadal developmental was not affected in the males; however, a significant reduction in the developmental of female gonads was observed at 250 µg/L. These results show that 3,4-DCA interfere with the reproduction of Javanese medaka through fecundity and alteration of gonadal tissues. Full article