RESUMEN
The pollution control of tetracycline antibiotics in the environment has become a hot topic, and biochar adsorption has become an important technology to remove organic pollutants. Pyrolytic biochars (BC400, BC500, and BC600) were prepared from corn straw and then were modified by KOH to obtain KBC400, KBC500, and KBC600. Among them, KBC400 was selected for secondary pyrolysis activation at 400-600â to obtain AKBC400, AKBC500, and AKBC600. The structure characteristics and surface properties of AKBC were also characterized. The adsorption kinetics and thermodynamic characteristics of oxytetracycline hydrochloride (OTC) in the solution by AKBC were investigated using batch experiments. Compared to that of BC400, the specific surface area and pore structure of AKBC were significantly improved, and the aromaticity was also enhanced, resulting in the notable enhancement of the adsorption capacities for OTC. The pseudo-second-order kinetics model could better fit the adsorption process, and AKBC500 had the largest adsorption rate constant and capacity. Both the intraparticle diffusion and film diffusion were the rate-limiting steps. The Langmuir, Freundlich, and Temkin models could fit the adsorption isotherms perfectly. The adsorption of OTC on AKBC was a spontaneous, endothermic, and entropy-increasing process by both physisorption and chemisorption. The pH values in the range of 3.0-7.0 were favorable for the adsorption of OTC by AKBC. The adsorption capacity decreased with the humic acid concentration over 10 mg·L-1. The adsorption mechanism of OTC by AKBC involved pore filling, hydrogen bonding, π-π conjugation, cation-π bond, and strong electrostatic effect. AKBC still had good reusability for OTC removal after five times of regeneration. The obtained AKBC is a potential adsorbent for OTC removal from water due to the good pore structure, high adsorption capacity, and stable adsorption effect.
Asunto(s)
Oxitetraciclina , Contaminantes Químicos del Agua , Zea mays , Agua , Adsorción , Antibacterianos , Carbón Orgánico/química , Cinética , Contaminantes Químicos del Agua/análisisRESUMEN
In sediments, wetlands, and flooded paddy soils, natural organic matter (DOM), such as humic acid (HA) and fulvic acid (FA), exist in a reduced state and mediate the reduction of Hg(â ¡) and affect the transformation of mercury and geochemical cycles. This study simulated a dark anaerobic environment to study the reduction of Hg(â ¡) by reduced HA and FA. Compared to oxidized HA and FA, the reduction capacity of the reduced HA and FA for Hg(â ¡) were higher. The optimal concentrations of reduced HA and FA to reduce Hg(â ¡) to Hg(0) were 0.2 mg·L-1 and 1.5 mg·L-1, respectively. The reduction quantity of Hg(â ¡) was enhanced with the increased concentration of reduced HA and FA at a lower than optimal concentration, whereas the reduction quantity of Hg(â ¡) decreased with increasing concentration of reduced HA and FA at a higher than optimal concentration due to the occurrence of thiol-competitive complexation. Hg(â ¡) was not reduced at a reduced HA concentration of 5 mg·L-1. The kinetics results of Hg(â ¡) reduction demonstrated that the reduction rates were IHSS-HA > FRC-HA > FRC-FA at a low molar ratio (dissolved organic carbon (DOC):Hg(â ¡)=400:1). The reduction of Hg(â ¡) by the reduced HA stopped or processed in the opposite direction at a high molar ratio (DOC:Hg(â ¡)=10000:1). The quantity of Hg(0) decreased with increasing HA concentration. Furthermore, as the concentrations of reduced HA and FA were increased to 5 mg·L-1 and 10 mg·L-1, respectively, no Hg(0) was detected in the samples. The experiment of the recovery confirmed that reduced HA and FA reacted with Hg(0). Additionally, reduced HA, FA, and Hg(0) induced oxidative complexation with sulfhydryl or disulfide bonds. Reduced DOM played a dual role in Hg redox reactions, affecting the availability of active Hg, which, in turn, affected the methylation of microbial Hg.
RESUMEN
In this study, composite extraction of hydroxypropyl-ß-cyclodextrin (HPCD) with rhamnolipid (RL) was selected to assess the bioavailability of polycyclic aromatic hydrocarbons (PAHs) to earthworms in red soil from Hainan, China, spiked with phenanthrene (Phe), pyrene (Pyr) and benzo (a) pyrene (BaP). The results showed that when RL was more than the critical micelle concentration, apparent solubility of PAHs increased due to micellar solubilization of RL. So more PAHs were desorbed from solid phase of soil. Real biological experiments showed that there was a good linear relationship between earthworm-accumulated PAHs and HPCD/RL-extracted PAHs (R2=0.98, n=15). However, earthworm-accumulated PAHs was 2.04 times higher than HPCD-extracted PAHs, but only 1.15 times higher than HPCD/RL-extracted PAHs. This indicated that HPCD/RL was more actual and reliable than HPCD in the assessment of PAHs bioavailability to earthworms. Therefore, the addition of RL, to some extent, enhanced the prediction ability of HPCD in PAHs bioavailability, which might provide a new direction and implications in risk assessment and bioremediation of organic contaminants.
Asunto(s)
2-Hidroxipropil-beta-Ciclodextrina/química , Disponibilidad Biológica , Glucolípidos/química , Oligoquetos/metabolismo , Hidrocarburos Policíclicos Aromáticos/análisis , Suelo/química , Animales , China , Contaminantes del Suelo/análisisRESUMEN
To evaluate the effect of aging on the availability of PAHs, chemical extraction by exhaustive ( ASE extraction) and nonexhaustive techniques (Tenax-TA extraction, hydroxypropyl-p-cyclodextrin ( HPCD ) extraction, n-butyl alcohol ( BuOH) extraction) as well as PAHs accumulation in earthworms (Eisenia fetida) were conducted in yellow soil from Baguazhou, Nanjing, China, and red soil from Hainan, China, spiked with phenanthrene, pryene and benzo(a) pyrene and aged 0, 7, 15, 30 and 60 days. The results showed that the concentration of PAHs extracted by ASE and three nonexhaustive techniques and accumulated by earthworms significantly decreased with aging time, except the ASE extracted concentration between 30-and 60-day aging time. Furthermore, the relationships were studied in this experiment between chemical extracted PAHs concentration and accumulated concentration in earthworms. PAHs accumulated concentration in earthworms was not significantly correlated with the exhaustive extracted concentration of PAHs in soil (R² 0.44-0.56), which indicated that ASE extraction techniques could not predict PAHs bioavailability to earthworms because it overestimated the risk of PAHs. However, the PAHs accumulated concentration in earthworms was significantly correlated with the three nonexhaustive extracted concentrations of PAHs in soil, which indicated that all the three nonexhaustive techniques could predict PAHs bioavailability to earthworm to some extent, among which, HPCD extraction (R² 0.94-0.99) was better than Tenax-TA extraction (R² 0.62-0.87) and BuOH extraction (R² 0.69-0.94). So HPCD extraction was a more appropriate and reliable technique to predict bioavailability of PAHs in soil.
Asunto(s)
Monitoreo del Ambiente , Oligoquetos , Hidrocarburos Policíclicos Aromáticos/análisis , Contaminantes del Suelo/análisis , 1-Butanol , Animales , Benzo(a)pireno , Biodegradación Ambiental , Disponibilidad Biológica , China , Fenantrenos , Suelo/químicaRESUMEN
A Gram-negative, aerobic, non-motile bacterial strain hun6(T) isolated from the polluted soil near a chemical factory in northern Nanjing, China was investigated to clarify its taxonomic position. Growth of strain hun6(T) occurred between 10 and 45 °C (optimum, 30 °C) and between pH 6.0 and 8.0 (optimum, pH 7.0). No growth occurred at NaCl concentrations greater than 5 % (w/v). The 16S rRNA gene sequence analysis indicated that strain hun6(T) belongs to the genus Aquamicrobium. The sequence similarities of strain hun6(T) to other type strains of Aquamicrobium genus were all below 98.5 %. The presence of ubiquinone-10, the predominant fatty acid summed feature 8 (C18:1 ω7c and/or C18:1 ω6c) and C19:0 cyclo ω8c, a polar lipid pattern with phosphatidylglycerol, phosphatidylcholine, diphosphatidylglycerol, phosphatidylethanolamine and phophatidylmonomethylethanoamine were in accord with the characteristics of the genus Aquamicrobium. The G+C content of the genomic DNA was determined to be 63.5 mol%. The results of DNA-DNA hybridization, physiological and biochemical tests and chemotaxonomic properties allowed genotypic and phenotypic differentiation of strain hun6(T) from all known Aquamicrobium species. Therefore, strain hun6(T) can be assigned to a new species of this genus for which the name Aquamicrobium terrae sp. nov. is proposed. The type strain is hun6(T) (= CICC 10733(T) = DSM 27865(T)).
Asunto(s)
Phyllobacteriaceae/clasificación , Phyllobacteriaceae/aislamiento & purificación , Microbiología del Suelo , Técnicas de Tipificación Bacteriana , Composición de Base , China , Análisis por Conglomerados , ADN Bacteriano/química , ADN Bacteriano/genética , ADN Ribosómico/química , ADN Ribosómico/genética , Contaminación Ambiental , Ácidos Grasos/análisis , Concentración de Iones de Hidrógeno , Datos de Secuencia Molecular , Hibridación de Ácido Nucleico , Fosfolípidos/análisis , Phyllobacteriaceae/genética , Phyllobacteriaceae/fisiología , Filogenia , Quinonas/análisis , ARN Ribosómico 16S/genética , Análisis de Secuencia de ADN , Cloruro de Sodio/metabolismo , TemperaturaRESUMEN
A laboratory experiment was conducted to study the influence of biochar on the residues of chlorobenzenes (CBs) in soil. Two treatments as the control and the addition of 1% wheat straw biochar were designed. Three chemical extractions as butanol, HPCD and Tenax extractions and earthworm accumulation were used to assess the changes of the bioavailability of CBs in soil. The results showed that the residues of HCB, PeCB and 1,2,4,5-TeCB in the control were 29.87%, 18.02% and 5.16% after 4 months incubation, however, the residues of HCB, PeCB and 1,2,4,5-TeCB in biochar amended soil were 68.25%, 61.32% and 58.02%, respectively, indicating that biochar amendment would inhibit the dissipation of CBs in soil. Butanol, HPCD and Tenax extraction as well as earthworm accumulation results demonstrated that the bioavailability of CBs in soil was significantly affected by biochar amendment (P < 0.05). With aging time increase, the biochar amendment significantly lowered the bioavailability of CBs. The extraction ratios differed among different chemical extraction methods. The extraction ratio was HCB > PeCB > 1,2,4,5-TeCB for butanol and Tenax extraction, while 1,2,4,5-TeCB > PeCB > HCB for HPCD extraction. The bioaccumulation factor of CBs by earthworm was significantly lower in biochar amended soil compared to the control (P < 0.05). This study showed that the biochar could reduce the bioavailability of organic pollutants, however, the high residues of the pollutants in soil showed potential environmental risk.
Asunto(s)
Carbón Orgánico/química , Clorobencenos/aislamiento & purificación , Contaminantes del Suelo/aislamiento & purificación , Animales , Disponibilidad Biológica , Butanoles/aislamiento & purificación , Butanoles/farmacocinética , Clorobencenos/farmacocinética , Oligoquetos/metabolismo , Tallos de la Planta/química , Polímeros/aislamiento & purificación , Polímeros/farmacocinética , Contaminantes del Suelo/farmacocinética , Triticum/químicaRESUMEN
Adsorption and degradation of three typical chlorinated benzenes (CBs) were evaluated using commercial nanoscale Fe (nFe) and synthesized palladized Fe (Pd/nFe) via batch experiments. The results showed that the adsorption capacity exhibited significant difference between various conditions, of which its maximum adsorption amount reached with Tris-buffered solution of pH = 6. 8. 1, 2, 4, 5-TeCB can be dechlorinated by Pd/nFe efficiently within 20 hours. The degradation rates were 75% and 92% in pure water system and Tris-buffered solution, respectively. However, nFe seemed to be inactive to 1, 2, 4, 5-TeCB with final degradation rate of about 25%. Meanwhile, Pd/nFe also only had slight degradation capacities to HCB and PeCB when compared to 1, 2, 4, 5-TeCB. 1, 2, 3, 4-TeCB, 1, 2, 3-TCB and 1, 2-DCB are the only products that were detected during the whole experiments, indicating that chlorine atoms of CBs with less steric effect were preferred to be dechlorinated. The degradation can be fitted by pseudo first order equations. The observed rate constants were ranged from 0. 14 4 h(-1) to 0.115 2 h(-1).
Asunto(s)
Clorobencenos/aislamiento & purificación , Hierro/química , Paladio/química , Contaminantes Químicos del Agua/aislamiento & purificación , Purificación del Agua/métodos , Adsorción , Clorobencenos/química , Nanopartículas del Metal/química , Oxidación-Reducción , Contaminantes Químicos del Agua/químicaRESUMEN
With computational method of density functional theory (DFT), quantified model study of equilibrium partitioning properties of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) between lipid phase of organism (Poecilia reticulata) and water phase was carried out based on quantum chemical and further calculated parameters, namely frontier orbital energies, entropies, traceless quadrupole moments as well as molecular absolute hardness, electronegativities and electrophilicity indices, which all were derived from full geometry optimization of PCDD/Fs. Through multiple linear regression (MLR) analyses, quantitative structure-property relationship (QSPR) was successfully proposed in the form of multi-parameter quadratic function: lgK(hw) = 5.343 - 0.001(S - 125.480)(2) - 0.355(omega - 3.239)(2) + 0.006( Q = - 2.950)(2) - 22.728(eta - 2.365)(2). It was shown that the obtained QSPR had higher goodness of fitting and robustness, determination coefficient and cross-validated correlation coefficient being 0.943 and 0.908 respectively, and it was also provided with ideal interior and exterior predictive abilities so that it could be used for prediction of unknown lipid-water partitioning properties. By comparison, QSPR in this research was superior to that from previous SOFA (solubility parameter for fate analysis) method on the whole. Lipid-water partitioning properties (coefficients) of PCDD/Fs should be mainly related to molecular volume and aryl hydrocarbon molecular interactions determined by charge distribution. To a certain degree, they also might be influenced by potential biotransformation and molecular reactivity.
Asunto(s)
Lípidos/química , Dibenzodioxinas Policloradas/análogos & derivados , Relación Estructura-Actividad Cuantitativa , Contaminantes Químicos del Agua/química , Agua/química , Benzofuranos/química , Química Física , Modelos Químicos , Dibenzodioxinas Policloradas/químicaRESUMEN
With DFT method of quantum chemistry, the electronic structures of all polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were fully optimized at the level of B3LYP/6-311G**, and the corresponding quantum parameters, viz. the mean polarizability(alpha), entropy(S) as well as the tensor components of polarizability and quadrupole moment (alpha(xx), alpha(yy), alpha(zz) and Q(xx), Q(yy), Q(zz)) and so on were used to the study on quantitative structure-property relationship (QSPR) of water solubility. And three QSPRs were successfully proposed on the basis of the internally consistent experimental values. The determination coefficients are 0.977, 0.968 and 0.961 respectively and the cross-validated correlation coefficients are 0.968, 0.959 and 0.946 respectively. It is indicated that water solubility of PCDD/Fs should mainly be related to the molecular volume, but much less influenced by the molecular interactions. And the differences of predicted values of QSPRs for the whole dioxins are probably related to the limited available experimental values and the characteristics of introduced variables. In comparison with the newly developed QSPR, the performance of QSPRs in this study is improved, which may attribute to both the precise calculations of electronic properties of PCDD/Fs by B3LYP/6-311G** and the introduction of tensor components of quadrupole moment into models.