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Biomonitoring of chlorophenols in human urine from several Asian countries, Greece and the United States
2018
Honda, Masato | Kannan, Kurunthachalam
Chlorophenols (CPs) are used in the production of pesticides and preservatives. Although human exposure to CPs has been known for years, current exposure levels to these chemicals in Asian countries are not known. In this study, we analyzed concentrations of eight CPs in 300 human urine samples collected from nine countries. Of these CPs, 2,5-dichlorophenol and 2,4-dichlorophenol were found at the highest median concentrations (median for all nine countries: 1.78 and 0.34 ng/mL, respectively). Pentachlorophenol was found in 59% of the samples analyzed at a median concentration of 0.07 ng/mL. Urine samples from Japan had the highest concentration of total CPs (median: 16.7 ng/mL) with 2,5-dichlorophenol accounting for 93.1% of the total concentration. The estimated daily intake (DI) for precursors of dichlorophenols varied widely, but several samples showed values higher than the acceptable DI recommended by the United States Environmental Protection Agency (EPA). These results suggest that CP exposure, especially to dichlorophenols, is prevalent in several countries, particularly in Asia, suggesting a pressing need for further assessment of the global sources and potential health effects of these chemicals.
Mostrar más [+] Menos [-]Assessment of PCDD/Fs levels in soil at a contaminated sawmill site in Sweden – A GIS and PCA approach to interpret the contamination pattern and distribution
2013
Henriksson, S. | Hagberg, J. | Bäckström, M. | Persson, I. | Lindström, G.
Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzo-p-furans (PCDD/Fs) were analysed in soil from a Swedish sawmill site where chlorophenols (CPs) had been used more than 40 years ago. The most contaminated area at the site was the preservation subarea where the PCDD/F WHO2005-TEQ level was 3450 times higher than the current Swedish guideline value of 200 ng TEQ/kg soil for land for industrial use. It was also shown that a fire which destroyed the sawmill might have affected the congener distribution at the concerned areas. To get a broader picture of the contamination both GIS (spatial interpolation analysis) and multivariate data analysis (PCA) were applied to visualize and compare PCDD/F levels as well as congener distributions at different areas at the site. It is shown that GIS and PCA are powerful tools in decisions on future investigations, risk assessments and remediation of contaminated sites.
Mostrar más [+] Menos [-]Sorption of apolar and polar organic contaminants by waste tire rubber and its chars in single- and bi-solute systems
2011
Lian, Fei | Huang, Fang | Chen, Wei | Xing, Baoshan | Zhu, Lingyan
Single- and bi-solute sorption of organic compounds [1,3-dichlorbenzene (DCB), 1,3-dinitrobenzene (DNB) and 2,4-dichlorophenol (DCP)] on ground tire rubber and its chars was studied. The chars were prepared by pyrolyzing tire rubber at different temperatures (200–800 °C). Their surface area, aromaticity and hydrophobicity increase greatly with pyrolytic temperature, and the polymeric phase is partly converted into a condensed phase. The sorption of DNB and DCP increases with pyrolytic temperature and is characterized by a transition from a partition dominant to an adsorption dominant process. However, the sorption of DCB linearly decreases with the pyrolytic temperature. The enhanced adsorption of DNB and DCP on carbonized phase is primarily attributed to nonhydrophobic interactions such as π–π electron-donor–acceptor interactions and/or H bonding. The higher partition of DCB to polymeric phase is attributed to its high hydrophobicity. Competitive sorption between DCB and DCP on the tire chars is highly dependent on dissociation of the latter.
Mostrar más [+] Menos [-]Adsorption of chlorophenols on polyethylene terephthalate microplastics from aqueous environments: Kinetics, mechanisms and influencing factors
2020
Liu, Zheming | Qin, Qingdong | Hu, Zhixian | Yan, Lu | Ieong, Un-Io | Xu, Yan
Microplastics have received growing attention as carriers of organic pollutants in the water environment. To better understand the contribution of hydrophobic interaction, hydrogen-bonding interaction, π-π interaction and electrostatic interaction on the adsorption of hydrophilic compounds on microplastics and their adsorption behavior in natural waters, polyethylene terephthalate (PET, <150 μm) was used as an adsorbent and 4-chlorophenol (MCP), 2,4-dichlorophenol (DCP) and 2,4,6-trichlorophenol (TCP) were used as adsorbates. The results of batch adsorption experiments showed that chlorophenols (CPs) reached adsorption sites of PET through film diffusion and intra-particle diffusion. pH greatly affected the adsorption capacity. Hydrophobic interaction was the main adsorption mechanism of undissociated CPs on PET. Hydrogen-bonding interaction was also an adsorption mechanism between undissociated CPs and PET, and the contribution of hydrogen-bonding interaction to adsorption decreased with the increase of chlorine content. Meanwhile, the increase of chlorine content was favorable to the hydrophobic interaction between undissociated CPs and PET. However, higher chlorine content CPs with lower pKₐ values tended to dissociate at neutral pH condition and resulted in stronger electrostatic repulsion with PET. The increase of solution ionic strength and fulvic acid content negatively affected the adsorption of DCP and TCP on PET, but did not show significant impacts on MCP adsorption. Similarly, the adsorption capacity obtained using Taihu lake water and Bohai seawater as matrices was much lower than that using laboratory water for both DCP and TCP, while the adsorption coefficient (Kd) of MCP remained at approximately 10.6 L/kg to 11.4 L/kg in the three different solution matrices. The Kd values exhibited using natural water matrices consistently followed the order of DCP > MCP > TCP. This study provides insights into the fate of CPs in the presence of microplastics and suggests that the potential risks posed by CPs and microplastics to aqueous ecosystems merit further investigation.
Mostrar más [+] Menos [-]Associations of prenatal exposure to five chlorophenols with adverse birth outcomes
2016
Guo, Jianqiu | Wu, Chunhua | Lv, Shenliang | Lu, Keng | Feng, Chao | Qi, Xiaojuan | Liang, Weijiu | Chang, Xiuli | Xu, Hao | Wang, Guoquan | Zhou, Zhijun
Exposures to chlorophenols (CPs) have been linked with adverse health effects on wildlife and humans. This study aimed to evaluate prenatal exposure to five CP compounds using maternal urinary concentrations during pregnancy and the potential associations with birth outcomes of their infants at birth. A total of 1100 mother-newborn pairs were recruited during June 2009 to January 2010 in an agricultural region, China. Urinary concentrations of five CPs from dichlorophenol (DCP) to pentachlorophenol (PCP), namely, 2,5-DCP, 2,4-DCP, 2,4,5-trichlorophenol (2,4,5-TCP), 2,4,6-TCP and PCP, were measured using large-volume-injection gas chromatography-tandem mass spectrometry (LVI-GC-MS-MS), and associations between CP levels and weight, length as well as head circumference at birth were examined. Median urinary creatinine-adjusted concentrations of 2,5-DCP, 2,4-DCP, 2,4,5-TCP, 2,4,6-TCP and PCP were 3.34 μg/g, 1.03 μg/g, < LOD, 1.78 μg/g and 0.39 μg/g creatinine, respectively. We found lower birth weight 30 g [95% confidence interval (CI): −57, −3; p = 0.03] for per SD increase in log10-transformed concentrations of 2,4,6-TCP and lower birth weight 37 g (95% CI: −64, −10; p = 0.04) for PCP, respectively. Similarly, head circumference decrease in associations with creatinine-corrected 2,4,6-TCP and PCP concentrations were also achieved. Considering sex difference, the associations of lower birth weight were only found among male neonates, while head circumference was associated with 2,4-DCP and 2,5-DCP only found among female neonates. This study showed significant negative associations between CPs exposure and reduction in neonatal anthropometric measures. The biological mechanisms concerning CPs exposure on fetal growth deserved further investigations.
Mostrar más [+] Menos [-]Effect of lead on the sorption of 2,4,6-trichlorophenol on soil and peat
2007
Pei, Z.G. | Shan, X.Q. | Li︠u︡, T. | Xie, Y.N. | Wen, B. | Zhang, S. | Khan, S.U.
The effect of lead on the sorption of 2,4,6-trichlorophenol (2,4,6-TCP) on soil and peat was investigated using a batch equilibration method. Lead markedly diminished the sorption of 2,4,6-TCP, and 2,4,6-TCP had little effect on lead sorption. Peat was a more effective adsorbent for 2,4,6-TCP than soil. The desorption hysteresis of 2,4,6-TCP verified the presence of high-energy sorption sites. Mechanisms of lead suppression effect on the 2,4,6-TCP sorption included the following: Firstly, lead accelerated the aggregation of colloids, the aggregates covered the surface in part and shrunk the pore sizes of the adsorbents, hence decreased the sorption of 2,4,6-TCP. Secondly, X-ray absorption and Fourier transform infrared spectroscopy study suggested that lead competed with 2,4,6-TCP for carboxylic, phenolic and Si-OH groups of organic matter and clay minerals. Such competition was partly responsible for the overall suppression effect of lead on the sorption of 2,4,6-TCP. Lead diminished the sorption of 2,4,6-trichlorophenol onto soil and peat.
Mostrar más [+] Menos [-]Microbial degradation kinetics and molecular mechanism of 2,6-dichloro-4-nitrophenol by a Cupriavidus strain
2020
Min, Jun | Xu, Lingxue | Fang, Suyun | Chen, Weiwei | Hu, Xiaoke
2,6-Dichloro-4-nitrophenol (2,6-DCNP) is an emerging chlorinated nitroaromatic pollutant, and its fate in the environment is an important question. However, microorganisms with the ability to utilize 2,6-DCNP have not been reported. In this study, Cupriavidus sp. CNP-8 having been previously reported to degrade various halogenated nitrophenols, was verified to be also capable of degrading 2,6-DCNP. Biodegradation kinetics assay showed that it degraded 2,6-DCNP with the specific growth rate of 0.124 h⁻¹, half saturation constant of 0.038 mM and inhibition constant of 0.42 mM. Real-time quantitative PCR analyses indicated that the hnp gene cluster was involved in the catabolism of 2,6-DCNP. The hnpA and hnpB gene products were purified to homogeneity by Ni-NTA chromatography. Enzymatic assays showed that HnpAB, a FAD-dependent two-component monooxygenase, converted 2,6-DCNP to 6-chlorohydroxyquinol with a Kₘ of 3.9 ± 1.4 μM and a kcₐₜ/Kₘ of 0.12 ± 0.04 μΜ⁻¹ min⁻¹. As the oxygenase component encoding gene, hnpA is necessary for CNP-8 to grow on 2,6-DCNP by gene knockout and complementation. The phylogenetic analysis showed that the hnp cluster originated from the cluster involved in the catabolism of chlorophenols rather than nitrophenols. To our knowledge, CNP-8 is the first bacterium with the ability to utilize 2,6-DCNP, and this study fills a gap in the microbial degradation mechanism of this pollutant at the molecular, biochemical and genetic levels. Moreover, strain CNP-8 could degrade three chlorinated nitrophenols rapidly from the synthetic wastewater, indicating its potential in the bioremediation of chlorinated nitrophenols polluted environments.
Mostrar más [+] Menos [-]Oxidative degradation of chlorophenolic compounds with pyrite-Fenton process
2019
Kantar, Cetin | Oral, Ozlem | Urken, Ozge | Oz, Nilgun Ayman | Keskin, Selda
Batch experiments, in conjunction with chromatographic and spectroscopic measurements, were performed to comparatively investigate the degradation of various chlorophenolic (CP) compounds (e.g., 2-CP, 4-CP, 2,3-DCP, 2,4-DCP, 2,4,6-TCP, 2,3,4,6-TeCP) by a modified Fenton process using pyrite as the catalyst. The batch results show that the CP removal by pyrite-Fenton process was highly dependent on chemical conditions (e.g., pH, CP and pyrite concentration), CP type, number and location of chlorine atoms on the aromatic ring. With the exception of 2,3,4,6-TeCP and 2,3-DCP, the CP removal decreased with increasing the number of chlorine constituents. While the main mechanism responsible for monochlorophenol removal (e.g., 2-CP and 4-CP) was the hydroxyl radical attack on aromatic rings, the CP removal for multichlorophenolic compounds (e.g., 2,3,4,6-TeCP) was driven by both: (1) hydroxyl radical attack on aromatic rings by both solution and surface-bound hydroxyl radicals and (2) adsorption onto pyrite surface sites. The adsorption affinity increased with increasing the number of Cl atoms on the aromatic ring due to enhanced hydrophobic effect. The TOC removal was not 100% complete for all CPs investigated due to formation of chemically less degradable chlorinated intermediate organic compounds as well as low molecular weight organic acids such as formic and acetic acid. Spectroscopic measurements with SEM-EDS, zeta potential and XPS provided evidence for the partial oxidation of pyrite surface Fe(II) and disulfide groups under acidic conditions.
Mostrar más [+] Menos [-]Comparison of competitive and synergetic adsorption of three phenolic compounds on river sediment
2011
Gao, Peng | Feng, Yujie | Zhang, Zhaohan | Liu, Junfeng | Ren, Nanqi
Knowledge of toxic chemical sorption by soil/sediment is critical for environmental risk assessment of toxic chemicals, especially for the multi-sorbate system in river ecosystem. Sorption characteristics of 2, 4-Dichlorophenol, 2, 4-Dinitrophenol and 2, 4-Dimethyphenol on sediment were investigated. Adsorption isotherms in single- and multi-sorbate systems fitted well the Freundlich model. The adsorption effects were different among three selected phenolic compounds in single- and multi-sorbate systems. The synergetic affect that 2, 4-Dinitrophenol and 2, 4-Dimethyphenol bring to 2, 4-Dichlorophenol can be explained by the compression of double electronic layer and the charge neutrality. Adsorption kinetic results showed that pseudo-second-order model can be used to describe the experimental data and the adsorption affinity of phenolic compounds influenced greatly by the adsorption velocity. The present study suggests that the fate and transport of emerging pollutants such as phenolic compounds could be affected in the presence of different hydrophobic pollutants in aquatic systems.
Mostrar más [+] Menos [-]An adsorption diffusion model for removal of para-chlorophenol by activated carbon derived from bituminous coal
2010
Sze, M.F.F. | McKay, G.
Batch adsorption experiments were carried out to study the adsorptive removal and diffusion mechanism of para-chlorophenol (p-CP) onto Calgon Filtrasorb 400 (F400) activated carbon. The external mass transfer resistance is negligible in the adsorption process carried out under different conditions in batch operation. Intraparticle diffusion model plots were used to correlate the batch p-CP adsorption data; three distinct linear sections were obtained for every batch operation. The textural properties of F400 activated carbon showed that it has a large portion of supermicropores, which is comparable to the size of the p-CP molecules. Due to the stronger interactions between p-CP molecules and F400 micropores, p-CP molecules predominantly diffused and occupied active sites in micropore region by hopping mechanism, and eventually followed by a slow filling of mesopores and micropores. This hypothesis is proven by the excellent agreement of the intraparticle diffusion model plots and the textural properties of F400 activated carbon.
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