Formation of dioxins from triclosan with active chlorine: A potential risk assessment.
ABSTRACT: Triclosan, a widely used antimicrobial agent, can increase colitis-associated colon tumorigenesis, and induce liver fibrosis and cancer in mice through mechanisms which may be relevant in humans. In this study, an analytical method using gas chromatography-mass spectrometry (GC-MS) and high resolution gas chromatography-high resolution mass spectrometry (HRGC-HRMS) was developed to measure dioxins and chlorinated derivatives from triclosan in the presence of active chlorine in seawater matrix. Formation yields of dioxins and chlorinated triclosans were assessed at different initial precursor concentrations under dark and UV light irradiation conditions. Results showed that triclosan was rapidly transformed to its chlorinated derivatives, i.e. tetraclosans and pentaclosans, of which the formation yields peaked after 1?h of reaction. UV light was the key factor to promote the formation of dioxins. With the same initial triclosan/active chlorine ratio, the highest yield of dioxins was observed with lower initial concentrations of triclosan under UV irradiation. Five dioxins, including 2,8-DCDD, 1,2,8-TrCDD, 2,3,7-TrCDD, 1,2,3,8-TeCDD, and 2,3,7,8-TeCDD, were identified and quantified. 2,3,7,8-TeCDD, the most toxic dioxin, was firstly reported as the photo-transformation product of triclosan in aquatic solution. Results presented here are useful for a comprehensive understanding of the fate and toxicity of triclosan in contaminated waters.
Project description:The use of brominated flame retardants and incineration of bromine-containing materials has lead to an increase in polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in the environment. Measurable amounts of PBDD/Fs have been detected in soil, seafood, and human breast milk and serum. Studies indicate that the relative potencies of some PBDD/Fs based on enzyme induction are equivalent to those of some polychlorinated dibenzo-p-dioxins and dibenzofurans. To assess the humoral immunity relative potencies of PBDD/Fs and compare them to their chlorinated analogs, female B6C3F1/N mice received a single oral exposure to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), 2,3,7,8-tetrabromodibenzofuran (TBDF), 2,3,7,8-tetrachlorodibenzofuran (TCDF), 1,2,3,7,8-pentabromodibenzofuran (1PeBDF), 1,2,3,7,8-pentachlorodibenzofuran (1PeCDF), 2,3,4,7,8-pentabromodibenzofuran (4PeBDF), 2,3,4,7,8-pentachlorodibenzofuran (4PeCDF), 2,3-dibromo-7,8-dichlorodibenzo-p-dioxin (DBDCDD), or 2,3,7-tribromodibenzo-p-dioxin (TriBDD). Inhibition of the immunoglobulin M (IgM) antibody forming cell response was measured 4 days following immunization with sheep red blood cells. The data were fit to a Hill model to estimate the ED50 for inhibition. Expression of xenobiotic metabolizing enzyme (XME) and thyroxine transport protein (Ttr) genes in liver was measured by PCR to assess aryl hydrocarbon-mediated responses. TCDD, TBDF, TCDF, 1PeBDF, 4PeBDF, 4PeCDF, and DBDCDD suppressed the IgM antibody response and Ttr gene expression, and upregulated phase I XME genes. 1PeCDF suppressed the IgM antibody response but only upregulated phase I XME genes; TriBDD had no effect on antibody response. The rank order of potency (ED50) for these chemicals was TCDD>TBDF>4PeBDF>TCDF/4PeCDF/1PeBDF>1PeCDF. Whereas TCDD was the most potent compound tested, the brominated analogs were more potent than their chlorinated analogs, suggesting that these compounds should be considered in toxic equivalency factor evaluation and risk assessment.
Project description:Microcystin-LR (MC-LR), an algal toxin (cyanotoxin) common in sources of drinking water, poses a major human health hazard due to its high toxicity. In this study, UV/chlorine was evaluated as a potentially practical and effective process for the degradation of MC-LR. Via mass spectrometry analysis, fewer chlorinated-MC-LR products were detected with UV/chlorine treatment than with chlorination, and a transformation pathway for MC-LR by UV/chlorine was proposed. Different degrees of rapid degradation of MC-LR were observed with varying pH (6-10.4), oxidant dosage (0.5-3 mg L-1), natural organic matter (0-7 mg L-1), and natural water sources. In contrast to the formation of primarily chloroform and dichloroacetic acid in deionized water where MC-LR serves as the only carbon source, additional chlorinated disinfection byproducts were produced when sand filtered natural water was used as a background matrix. The UV/chlorine treated samples also showed quantitatively less cytotoxicity in vitro in HepaRG human liver cell line tests than chlorination treated samples. Following 16 min (96 mJ cm-2) of UV irradiation combined with 1.5 mg L-1 chlorine treatment, the cell viability of the samples increased from 80% after exposure to 1 mg L-1 MC-LR to 90%, while chlorination treatment evidenced no reduction in cytotoxicity with the same reaction time.
Project description:Polychlorinated naphthalenes (PCNs) are dioxins-like compounds and are formed along with polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in thermal and combustion procedures. Chlorophenols (CPs) are the most important forerunners of PCNs. A comprehensive comprehension of PCN formation procedure from CPs is a precondition for reducing the discharge of PCNs. Experiments on the formation of PCNs from CPs have been hindered by PCN toxicity and short of precise detection methods for active intermediate radicals. In this work, PCN formation mechanism in gas-phase condition from 2-chlorophenol (2-CP) as forerunner was studied by quantum chemistry calculations. Numbers of energetically advantaged formation routes were proposed. The rate constants of key elementary steps were calculated over 600-1200 K using canonical variational transition-state theory (CVT) with small curvature tunneling contribution (SCT) method. This study illustrates formation of PCNs with one chlorine atom loss from 2-CP is preferred over that without chlorine atom loss. In comparison with formation of PCDFs from 2-CP, PCN products are less chlorinated and have lower formation potential.
Project description:We evaluated electrochemical degradation (ECD) and photocatalytic degradation (PCD) technologies for saline water purification, with a focus on rate comparison and formation and degradation of chlorinated aromatic intermediates using the same non-chlorinated parent compound, 4-ethylphenol (4EP). At 15 mA·cm-2, and in the absence of chloride (0.6 mol·L-1 NaNO3 was used as supporting electrolyte), ECD resulted in an apparent zero-order rate of 30 ?mol L-1·h-1, whereas rates of ?300 ?mol L-1·h-1 and ?3750 ?mol L-1·h-1 were computed for low (0.03 mol·L-1) and high (0.6 mol·L-1) NaCl concentration, respectively. For PCD, initial rates of ?330 ?mol L-1·h-1 and 205 ?mol L-1·h-1 were found for low and high NaCl concentrations, at a photocatalyst (TiO2) concentration of 0.5 g·L-1, and illumination at ?max ? 375 nm, with an intensity ?0.32 mW·cm-2. In the chlorine mediated ECD approach, significant quantities of free chlorine (hypochlorite, Cl2) and chlorinated hydrocarbons were formed in solution, while photocatalytic degradation did not show the formation of free chlorine, nor chlorine-containing intermediates, and resulted in better removal of non-purgeable hydrocarbons than ECD. The origin of the minimal formation of free chlorine and chlorinated compounds in photocatalytic degradation is discussed based on photoelectrochemical results and existing literature, and explained by a chloride-mediated surface-charge recombination mechanism.
Project description:The inorganic metal oxides (IMOs), including titanium dioxide (TiO2) and tin dioxide (SnO2), inevitably induce decomposition of perovskite under UV illumination owing to their photocatalytic activity, and the use of a UV filter will add extra cost and reduce the effective power output. Here, we first reveal that the weak Pb-I bond in I-based perovskite is prone to breakage under UV photocatalysis, leading to serious degradation of the SnO2/perovskite interface. We introduced a chlorine-rich mixed-halide perovskite interlayer (ClMPI), which possesses an excellent tolerance to photocatalysis owing to the strong Pb-Cl bond, between the SnO2 and I-based perovskite. The ClMPI-based device achieves an enhanced efficiency of up to 21.01% (certified 20.17%). Most importantly, the resultant devices can maintain >94% of their initial performance after 180 h under outdoor solar irradiation, >80% after 500 h under UV irradiation, and 500 h under continuous full spectrum illumination at their maximum power points.
Project description:Food ingestion is a major route for human exposure and body burden to dioxins. We estimated the potential influence of changes in dietary patterns in Chinese population on human health risk to 2,3,7,8-TCDD (2,3,7,8-tetrachlorodibenzo-p-dioxin) over the last three decades. We performed multiple modeling scenario investigations to discriminate the contribution of 2,3,7,8-TCDD emissions and changes in dietary patterns to the cancer risks (CR) to dioxins. Results showed that changes in dietary patterns, featured by decreasing consumption of total grain (including all unprocessed grains) and vegetables and increasing intake of animal-derived foodstuffs, caused increasing CR from 7.3?×?10(-8) in 1980 to 1.1?×?10(-7) in 2009. Varying dietary patterns contributed 17% to the CR of Chinese population in 2009 under the fixed emission in 1980. The CR to 2,3,7,8-TCDD in urban and eastern China residents was higher considerably than those who lived in rural area and western China, attributable to higher emissions, household income, and greater intake of animal-derived foodstuffs in urban and eastern China inhabitants. On the other hand, more rapid increasing trend of the CR was found in rural residents due to their more rapid increase in the consumption of fat-dominated foods as compared with urban residents.
Project description:Residual chlorine is often required to remain present in public drinking water supplies during distribution to ensure water quality. It is essential to understand how bacteria respond to long-term chlorine exposure, especially with the presence of assimilable organic carbon (AOC). This study aimed to investigate the effects of chlorination on Pseudomonas aeruginosa in low AOC medium by both conventional plating and culture-independent methods including flow cytometry (FCM) and quantitative PCR (qPCR). In a simulated chlorinated system using a bioreactor, membrane damage and DNA damage were measured by FCM fluorescence fingerprint. The results indicated membrane permeability occurred prior to DNA damage in response to chlorination. A regrowth of P. aeruginosa was observed when the free chlorine concentration was below 0.3 mg/L. The bacterial response to long-term exposure to a constant low level of free chlorine (0.3 mg/L) was subsequently studied in detail. Both FCM and qPCR data showed a substantial reduction during initial exposure (0-16 h), followed by a plateau where the cell concentration remained stable (16-76 h), until finally all bacteria were inactivated with subsequent continuous chlorine exposure (76-124 h). The results showed three-stage inactivation kinetics for P. aeruginosa at a low chlorine level with extended exposure time: an initial fast inactivation stage, a relatively stable middle stage, and a final stage with a slower rate than the initial stage. A series of antibiotic resistance tests suggested long-term exposure to low chlorine level led to the selection of antibiotic-resistant P. aeruginosa. The combined results suggest that depletion of residual chlorine in low AOC medium systems could reactivate P. aeruginosa, leading to a possible threat to drinking water safety.
Project description:Chlorinated aromatics undergo surface-mediated reactions with metal oxides to form Environmentally Persistent Free Radicals (EPFRs) which can further react to produce polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Previous work using laboratory-made fly ash surrogates composed of transition metal oxides deposited on silica powder has confirmed their ability to mimic fly ash in the production of PCDD/Fs. However, little is known about the propensity of aluminas and aluminosilicates, other components of fly ash, to form PCDD/Fs. A fly ash sample containing both alumina and mullite, an aluminosilicate, was tested for PCDD/F formation ability and compared to PCDD/F yields from the thermal degradation of 2-monochlorophenol (2-MCP) precursor over ?-alumina, ?-alumina, and mullite. A packed-bed flow reactor was used to investigate the thermal degradation of 2-MCP over the various catalysts at 200-600 °C. Fly ash gave similar PCDD/F yields to surrogates made with similar transition metal content. ?-alumina, which is thermodynamically unfavorable, was very catalytically active and gave low PCDD/F yields despite a high destruction of 2-MCP. Mullite and ?-alumina, the thermodynamically favorable form of alumina, yielded higher concentrations of dioxins and products with a higher degree of chlorine substitution than ?-alumina. The data suggest that certain aluminas and aluminosilicates, commonly found in fly ash, are active catalytic surfaces in the formation of PCDD/Fs in the post-flame cool zones of combustion systems and should be considered as additional catalytic surfaces active in the process.
Project description:The correlation between the content and morphology of Fe2O3 and the yields of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) was studied in this work. Three fly ash surrogates containing 1%, 2.5%, and 4% of Fe2O3 were prepared and their effects on PCDD/Fs formation were investigated and compared to our previously studied 5% iron oxide sample using 2-monochlorophenol precursor model. As the intermediate of PCDD/Fs, environmentally persistent free radical formation propensity was correlated with the PCDD/Fs formation yields for different iron oxide samples. PCDD/Fs yield increases exponentially with the increasing iron content under pyrolytic conditions. On the contrary, low iron oxide content promotes oxidation and lowers yields of PCDD/Fs. Changing iron oxide clusters' morphology (crystallinity and cluster size) affects the mechanism of PCDD/Fs formation - on larger crystallites, a bidentate chemisorption of precursor is preferred leading to lower chlorinated congeners, while smaller clusters promote formation of PCDFs through mixed monodentate-bidentate surface species, resulting in formation of congeners with 1 chlorine more. This study further confirms the propensity of iron oxide to predominantly form PCDFs. The iron content also defines PCDDs:PCDFs ratio.
Project description:The World Health Organization recently proposed the inclusion of brominated congeners in addition to chlorinated congeners when computing the toxic equivalency (TEQ) of dioxin-like compounds (DLCs) in assessments of human health risks. In the present study, 12 polybrominated dibenzo-p-dioxins and furans (PBDD/Fs) were analyzed by gas chromatography/high resolution mass spectrometry in the composited, archived biosolids that were collected in 32 U.S. states and the District of Columbia from 94 wastewater treatment plants by the United States Environmental Protection Agency in its 2001 national sewage sludge survey. Two PBDDs and five PBDFs were detected in the biosolids composites at varying frequencies (40-100%) with a total mean concentration of 10,000 ng/kg dry weight (range: 630-42,800), of which 1,2,3,4,6,7,8-hepta-BDF constituted about 95% by mass. Relative to commercial polybrominated diphenyl ether (PBDE) formulations, the ratio of PBDD/Fs to PBDEs in biosolids was 55-times higher (? 0.002% vs ? 0.11%), which indicates potential PBDE transformation or possibly additional sources of PBDD/Fs in the environment. The TEQ contribution of PBDD/Fs was estimated at 162 ng/kg 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) (range: 15-672), which is equivalent to 75% (range: 12-96%) of the total TEQ in biosolids. The TEQ of DLCs released annually to U.S. soils as a result of the land application of biosolids was estimated at 720 g (range: 530-1600 g). Among all known DLCs determined in biosolids, brominated analogs contributed 370% more TEQ than did chlorinated congeners, which indicates the need to include brominated DLCs in the exposure and risk assessment of land-applied biosolids.