PCDD/DF in leachates from Korean MSW landfills

We analyzed levels of PCDD/DF in leachate liquid and solid from five Korean municipal solid waste landfills to investigate the relationship between PCDD/DF and dissolved organic carbon and suspended solids in raw leachate. The concentrations of PCDD/DF ranged from 173.2 to 1329.4 pg/l and 4.1 to 46.22 pg-TEQ/l. The range of PCDD/DF was 123.2-1161.3 pg/l in leachate solid and 50.0-383.3 pg/l in leachate liquid. Our results indicated that PCDD/DF in solid play a major role in determining their concentration levels, and the distribution of isomers in solid was almost the same as in liquid leachate. In addition, highly chlorinated PCDD/DF, such as HpCDD/DF and OCDD/DF, accounted for more than 70% of all isomers. Levels of PCDD/DF in liquid were strongly correlated with dissolved organic carbon concentrations, which increase the leachability (R2 = 0.92 in Korean leachate) of PCDD/DF from contaminant sources. Despite this high linearity between dissolved organic carbon and dissolved PCDD/DF, we observed no strong relationship between dissolved organic carbon and solid phase PCDD/DF (R2 = 0.001). Dissolved organic carbon scarcely affects dissolved PCDD/DF to be combined with solids. As a result, it is not appropriate for incinerated ash to be dumped with municipal solid wastes, as they have a large potential to result in high levels of organic matter, and therefore PCDD/DF, in leachate.     

PCDD/DF concentrations at the inlets and outlets of wet scrubbers in Korean waste incinerators

To further understand the effects of wet scrubbers on PCDD/DF levels, it was measured the concentrations of PCDD/DF, dust, and other gaseous pollutants at both the inlets and the outlets of seven wet scrubbers. As a result, the concentrations of PCDD/DF at the inlets and outlets of the wet scrubbers ranged from 0.2 to 37.4, and 0.8 to 6.0 ng TEQ N m-3, respectively. With the exceptions of wet scrubbers F and G, the PCDD/DF levels decreased by and large in most wet scrubbers. It was thought that their relatively high removal efficiencies were more increased with heavier loads of dust and particle-bound PCDD/DF. On the other hand, it was also surveyed the increase of gaseous PCDD/DF in wet scrubber, where the total level of PCDD/DF was decreased. However, it was not sure whether it had been resulted from the thermal adsorption/desorption phenomenon between packing materials and emission gases or not. At the very least, however, although there still remains an unexplained aspect for the increase of gaseous PCDD/DF, it is clear that wet scrubbers can be sufficiently applied to remove PCDD/DF to a certain extent, if only removal efficiencies for the particle loads are high, and if a significant part of the PCDD/DF at the inlets is particle associated.     

Chlorination of dibenzofuran and dibenzo-p-dioxin vapor by copper (II) chloride

Dibenzofuran (DF) is formed from phenol and benzene in combustion gas exhaust streams prior to particle collection equipment. Subsequent chlorination at lower temperatures on particle surfaces is a potential source of chlorinated dibenzofuran (CDF). Gas streams containing 8% O₂ and approximately 0.1% DF vapor were passed through particle beds containing copper (II) chloride (0.5% Cu, mass) at temperatures ranging from 200 to 400 °C to investigate the potential for CDF formation during particle collection. Experiment duration was sufficient to provide an excess amount of DF (DF/Cu=3). The efficiency of DF chlorination by CuCl₂ and the distribution of CDF products were measured, with effects of temperature, gas velocity, and experiment duration assessed. Results of a more limited investigation of dibenzo-p-dioxin (DD) chlorination by CuCl₂ to form chlorinated DD (CDD) products are also presented.

The efficiency of DF/DD chlorination by CuCl₂ was high, both in terms of CuCl₂ utilization and DF/DD conversion. Total yields of Cl on CDF/CDD products of up to 0.5 mole Cl per mole CuCl₂ were observed between 200 and 300 °C; this suggests that nearly 100% CuCl₂ was utilized, assuming a conversion of two moles of CuCl₂ to CuCl per mole Cl added to DD/DF. In a short duration experiment (DF/Cu=0.3), nearly 100% DF adsorption and conversion to CDF was achieved. The degree of CDF chlorination was strongly dependent on gas velocity. At high gas velocity, corresponding to a gas–particle contact time of 0.3 s, mono-CDF (MCDF) yield was largest, with yields decreasing with increasing CDF chlorination. At low gas velocity, corresponding to a gas–particle contact time of 5 s, octa-CDF yield was largest. DF/DD chlorination was strongly favored at lateral sites, with the predominant CDF/CDD isomers within each homologue group those containing Cl substituents at only the 2,3,7,8 positions. At the higher temperatures and lower gas velocities studied, however, broader isomer distributions, particularly of the less CDD/CDF products, were observed, likely due to preferential destruction of the 2,3,7,8 congeners.     

Chlorination of dibenzofuran and dibenzo-p-dioxin vapor by copper (II) chloride

Dibenzofuran (DF) is formed from phenol and benzene in combustion gas exhaust streams prior to particle collection equipment. Subsequent chlorination at lower temperatures on particle surfaces is a potential source of chlorinated dibenzofuran (CDF). Gas streams containing 8% O₂ and approximately 0.1% DF vapor were passed through particle beds containing copper (II) chloride (0.5% Cu, mass) at temperatures ranging from 200 to 400 °C to investigate the potential for CDF formation during particle collection. Experiment duration was sufficient to provide an excess amount of DF (DF/Cu=3). The efficiency of DF chlorination by CuCl₂ and the distribution of CDF products were measured, with effects of temperature, gas velocity, and experiment duration assessed. Results of a more limited investigation of dibenzo-p-dioxin (DD) chlorination by CuCl₂ to form chlorinated DD (CDD) products are also presented.The efficiency of DF/DD chlorination by CuCl₂ was high, both in terms of CuCl₂ utilization and DF/DD conversion. Total yields of Cl on CDF/CDD products of up to 0.5 mole Cl per mole CuCl₂ were observed between 200 and 300 °C; this suggests that nearly 100% CuCl₂ was utilized, assuming a conversion of two moles of CuCl₂ to CuCl per mole Cl added to DD/DF. In a short duration experiment (DF/Cu=0.3), nearly 100% DF adsorption and conversion to CDF was achieved. The degree of CDF chlorination was strongly dependent on gas velocity. At high gas velocity, corresponding to a gas–particle contact time of 0.3 s, mono-CDF (MCDF) yield was largest, with yields decreasing with increasing CDF chlorination. At low gas velocity, corresponding to a gas–particle contact time of 5 s, octa-CDF yield was largest. DF/DD chlorination was strongly favored at lateral sites, with the predominant CDF/CDD isomers within each homologue group those containing Cl substituents at only the 2,3,7,8 positions. At the higher temperatures and lower gas velocities studied, however, broader isomer distributions, particularly of the less CDD/CDF products, were observed, likely due to preferential destruction of the 2,3,7,8 congeners.     

A risk assessment tool for contaminated sites in low-permeability fractured media

A risk assessment tool for contaminated sites in low-permeability fractured media is developed, based on simple transient and steady-state analytical solutions. The discrete fracture (DF) tool, which explicitly accounts for the transport along fractures, covers different source geometries and history (including secondary sources) and can be applied to a wide range of compounds. The tool successfully simulates published data from short duration column and field experiments. The use for risk assessment is illustrated by three typical risk assessment case studies, involving pesticides, chlorinated solvents, benzene and MTBE. The model is compared with field data and with results from a simpler approach based on an Equivalent Porous Media (EPM). Risk assessment conclusions of the DF and EPM approaches are very different due to the early breakthrough, long term tailing, and lower attenuation due to degradation associated with fractured media. While the DF tool simulates the field data, it is difficult to conclude that the DF model is superior to an EPM model because of a lack of long term monitoring data. However, better agreement with existing field data by the DF model using observed physical fracture parameters favors the use of this model over the EPM model for risk assessments.     

The prediction of PCDD/DF levels in wet scrubbers associated with waste incinerators

Wet scrubber is one of the most conventional types of air pollutant control devices (APCDs), which is specially designed to treat dust and acidic gases in the flue gas simultaneously. In spite of its outstanding ability to control them, however, wet scrubbers have been considered as potential contaminant sources that may increase PCDD/DF concentrations in the flue gas. In this study, we investigated the change of PCDD/DF concentrations at the inlets and outlets of seven wet scrubbers, and compared them with other published data. With a multi-regression analysis of dust concentrations and temperature at the inlets and outlets of given wet scrubbers, we developed an empirical model to understand factors dominating the change of PCDD/DF concentrations. As a result, we confirmed that the changes of PCDD/DF concentrations in wet scrubbers are closely related to their concentrations at the inlets, which would usually be determined by the type of APCDs installed upstream of the wet scrubber.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in plywood combustion gas

Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/DF) levels in plywood combustion gas were investigated for the effects of ammonium chloride (NH4Cl) and paint. For combustion systems in which neither NH4Cl nor paint were present in the plywood samples, total amounts of PCDD/DFs in the combustion gas were in the order of 35-529 ng/Nm3, and were higher in the systems with softwood trees than broadleaf ones, depending on the Cl concentrations. For the systems with added NH4Cl and no paint, and those without NH4Cl but were painted, higher PCDD/ DF rates were observed at combustion temperatures of 270 degrees C and 500 degrees C, respectively. However, for the systems with both NH4Cl and paint, their amounts in the range of 0.6-13 ng/Nm3 were the lowest in all systems. The PCDD/DF abundance profiles were similar to their patterns in pentachlorophenol (PCP). Furthermore, it was found that the 2,3,7,8-chlorine substituted penta- and hexa-CDDs contributed more than other 2,3,7,8-chlorine substitutes to toxicity equivalency (TEQ).     

CuCl2-catalyzed PCDD/F formation and congener patterns from phenols

Homologue and isomer patterns of polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) in CuCl2-catalyzed formation were studied in an isothermal flow reactor using a distribution of 20 phenols as measured in municipal waste incinerator (MWI) exhaust gases. A mixture of 20 phenols was synthesized and used as reactants for this study because phenols are known to be key precursors in the formation of PCDD/F. Experiments were conducted at 400 degrees C. The 92% of nitrogen (N2) and 8% of oxygen (O2) were used as a carrier gas. PCDD/F homologue and isomer patterns with dibenzo-p-dioxin (DD) and dibenzofuran (DF) were obtained from a mixture of 20 phenols. DF+PCDF formation was favored over DD+PCDD formation. The major homologue groups formed were non-chlorinated DD and DF, and PCDD/F homologue fraction decreased with the degree of chlorination. PCDD/F homologue and isomer distributions were almost constant. Phenol and lower chlorinated phenols present in high amount played an important role in PCDD/F congener distributions. The results presented here can be used as characteristics or fingerprints for homologue and isomer patterns of PCDD/F formation attribution in CuCl2-catalyzed reaction from phenols.     

Road fugitive dust emission characteristics in Beijing during Olympics Game 2008 in Beijing,China

Eighty road dust-fall (DF) monitoring sites and 14 background monitoring sites were established in the Beijing metropolitan area, and monitoring was conducted from January 2006 to December 2008. The dust-fall attributable to roads (ΔDF) showed a clear decline from 2006 to 2008. Dust-fall levels decreased across different road types from freeway > major arterial roads > minor arterial roads > collector roads > background sites. The ΔDF showed declines of 65%, 55%, 65% and 84% respectively for freeways, major arterial, minor arterial and collector roads from August 2007 to August 2008, and declines of 77%, 76%, 82% and 82% between August 2006 and August 2008. The ΔDF declined by 80%, 79%, 82% and 69% for freeways, major arterial, minor arterial and collector roads respectively between September 2007 and September 2008, and declined by 84%, 88%, 80% and 81% between September 2006 and September 2008.Eighty samples were collected in August 2007 and August 2008 and analyzed for silt loading. PM₁₀ emission factors and emission strengths were calculated using the AP-42 model. The silt loading reduced by 77%, 35%, 61%, 59% and 75% for freeways, major arterial, minor arterial, collector and local roads respectively. The PM₁₀ emission factors were reduced by 57%, 15%, 36%, 51% and 61% and the PM₁₀ emission strength declined by 70%, 40%, 55%, 65% and 72% for freeways, major arterial, minor arterial, collector and local roads respectively between August 2007 and August 2008. The decline is consistent with the reduction in road dust-fall.     

Residual congener pattern of dioxins in human breast milk in southern Vietnam

This study evaluated residual congener patterns of dioxin/furan (=PCDD/DF) related to tactical herbicides aerially sprayed over the regions of southern Vietnam through Operation Ranch Hand. The study focused on Cam Chinh (CC) commune, Quang Tri province (an area sprayed with tactical herbicides), and the Cam Phuc (CP) commune, Ha Tinh province (a non-sprayed area). Breast milk samples for analysis were collected in September 2002 and July 2003 from lactating primiparous and multiparous mothers born after the war (<31 years old). We found the levels of each congener in the CC commune were higher than in the CP commune, and determined specificity in the PCDD/DF congener pattern in CC commune samples by cluster analysis. The congener pattern is characterized by higher (the hexa-, the hepta-, and the octa-) chlorinated PCDD/DFs; this appears to be the same profile as that presented by pentachlorophenol (PCP), rather than 2,4,5-trichlorophenoxy acid (2,4,5-T) contaminated with 2,3,7,8-TCDD. A GC/MS study in the 1970s detected the chlorophenols 2,4-di and 2,4,6-trichlorophenol in some Agent Orange samples, which contained, like PCP, a wide variety of PCDD/DF congeners. In this context, it may be expected that certain tactical herbicides contaminated with various chlorophenol impurities, have a unique congener pattern when compared with pure 2,4,5-T formulations.     

Geochemical processes of mercury in Wujiangdu and Dongfeng reservoirs, Guizhou, China

The geochemical processes of mercury in Dongfeng (DF) and Wujiangdu (WJD) reservoirs, which were constructed in 1992 and 1979, respectively in Wujiang River, which is the upper branch of Yangtze River were investigated. One sampling site was chosen upriver of 1 km from the dam for each reservoir. Three sampling campaigns were conducted at these sampling sites in December 2003, April 2004 and July 2004, respectively. The distributions of different mercury species in the water column, sediment, and sediment pore water were studied. We found that the sediment is the net source of both inorganic and MeHg to the water column for both reservoirs. The MeHg diffusion fluxes in WJD reservoir at all sampling campaigns were significantly higher than those in DF reservoir. Our study demonstrated that the high primary productivity in the reservoir produced elevated organic matter content that would favor the methylmercury production in sediment.     

Dengue fever awareness: effect of an educational intervention on nursing students,Tanta, Egypt

Environmental Science and Pollution Research - Dengue fever (DF) is one of the world’s most important vector-borne illnesses. In 2017, Egypt experienced a dengue outbreak. This study aimed to...     

Dechlorination/hydrogenation and destruction reactions of PCDDs in OCDD-added fly ash heated under vacuum

Octachlorodibenzo-p-dioxin (OCDD)-added, pretreated fly ash was heated under vacuum at sample temperatures ranging from T(s)=450 to 650 K. The fly ash and liquid nitrogen-cooled trap samples were analyzed for DD/DF through OCDD/DF. The total amounts of DD through OCDD decrease with increasing T(s), which indicates that dechlorination/hydrogenation (DCH) reactions are not the only reaction channels. Reduction of toxic equivalent (TEQ) for PCDDs by more than 99% was achieved in the fly ash by the vacuum heat treatment at T(s)=650 K for 4 h. The total amount of PCDDs and DD detected in the liquid nitrogen-cooled trap relative to that of added OCDD was about 17%, i.e., PCDDs and DD which were adsorbed to the fly ash surfaces can evaporate into the gaseous phase. The difference between the evaporation behavior of PCDDs in the present and the previous studies is discussed in the light of their states of existence.     

Mercury mass balance study in Wujiangdu and Dongfeng Reservoirs, Guizhou, China

From October 2003 to September 2004, we conducted a detailed study on the mass balance of total mercury (THg) and methylmercury (MeHg) of Dongfeng (DF) and Wujiangdu (WJD) reservoirs, which were constructed in 1992 and 1979, respectively. Both reservoirs were net sinks for THg on an annual scale, absorbing 3319.5 g km⁻² for DF Reservoir, and 489.2 g km⁻² for WJD Reservoirs, respectively. However, both reservoirs were net sources of MeHg to the downstream ecosystems. DF Reservoir provided a source of 32.9 g MeHg km⁻² yr⁻¹, yielding 10.3% of the amount of MeHg that entered the reservoir, and WJD Reservoir provided 140.9 g MeHg km⁻² yr⁻¹, yielding 82.5% of MeHg inputs. Our results implied that water residence time is an important variable affecting Hg methylation rate in the reservoirs. Our study shows that building a series of reservoirs in line along a river changes the riverine system into a natural Hg methylation factory which markedly increases the %MeHg in the downstream reservoirs; in effect magnifying the MeHg buildup problem in reservoirs.     

PCDD/DF formations by the heterogeneous thermal reactions of phenols and their TiO2 photocatalytic degradation by batch-recycle system

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) formation by the thermal reactions of phenols with CuCl2 under oxygen flux were carried out in relation to their formation mechanisms. To evaluate the effect of photocatalytic degradation of titanium dioxide (TiO2) thin film prepared by the sol-gel method, the photocatalysis of PCDD/DFs in acetonitrile/water solution by batch-recycle system was conducted. For the thermal reaction system of powder mixtures of 2,4,5-trichlorophenol (2,4,5-TCP) and CuCl2, the formation rates were 8.1 microg/g-2,4,5-TCP/min for total PCDD/DFs and 6.9 microg/g-2,4,5-TCP/min for PCDDs, and total PCDD/DF rate was higher by approximately 40 fold compared to phenol vapor/oxygen/CuCl2 powder system. For the system of 2,4,5-TCP, PCDDs were mainly formed via ortho-phenoxyphenols (POP) intermediate by the condensation of 2,4,5-trichlorophenate. For PCDD/DF photocatalytic degradations, most PCDD congeners photodecomposed rapidly and the rates presented more than 70% (as dechlorination rates of 76% for PCDDs) at 24 h after irradiation, using PCDD/DFs formed with 2,4,5-TCP. The rate constants were in the order of 4.8-6.1 x 10(-3) min(-1), assuming the pseudo-first-order reactions for their low levels.     

Formation and degradation of triademinol after the use of triadimefon in a wheat monoculture]

During two vegetation periods, the behaviour of the triadimefon metabolite, triadimenol, in different plant parts of winter wheat and in soil was investigated. The fungicide Bayleton DF (triadimefon + captafol) was applied at the beginning of earing. Different ratios of triadimenol-A/-B were found in individual plant parts. Triadimenol-A predominated in the two uppermost leaves, and triadimenol-B in the roots and in the soil. No residues of triadimenol were found in grain at harvest time (detection limit 0.01 mg/kg).     

Pesticide resistance from historical agricultural chemical exposure in Thamnocephalus platyurus (Crustacea: Anostraca)

Extensive pesticide usage in modern agriculture represents a considerable anthropogenic stressor to freshwater ecosystems throughout the United States. Acute toxicity of three of the most commonly used agricultural pesticides (Methyl Parathion^® 4ec, Tempo^® SC Ultra, Karmex^® DF, and DDT) was determined in two different wild-caught strains of the fairy shrimp Thamnocephalus platyurus. Fairy shrimp collected from playas surrounded by native grasslands were between 200% and 400% more sensitive than fairy shrimp derived from playas in agricultural watersheds for Methyl Parathion^® 4ec, Tempo^® SC Ultra, and Karmex^® DF, likely due to the development of resistance. Additionally, reduced sensitivity to DDT was observed among fairy shrimp from agriculturally-impacted playas as compared to those from native grassland-dominated playas. These data suggest that fairy shrimp inhabiting playas in agricultural regions have developed some degree of resistance to a variety of agrochemicals in response to historical usage.     

Behavior of captafol residues after prolonged application in a wheat monoculture

In a 4-year study, the behaviour of the residues of the fungicide captafol in different plant parts of winter wheat and in the soil was investigated. The fungicide Bayleton DF (captafol + triadimefon) was applied at the beginning of earing. Captafol residues clearly showed a high dependence on weather conditions in all examined aerial parts of the plant. After a 9-year application of captafol, there was no evidence of an enrichment of residues in the soil. At harvest, captafol residues in grains always were below the maximum residue limits of 0.5 mg/kg established in West Germany.     

Formation of PCDD/Fs from oxidation of 2-monochlorophenol over an Fe2O3/silica surface

The role of iron in surface-mediated formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from 2-chlorophenol (2-MCP) was investigated over the temperature range of 200-550 °C under oxidative conditions. In order to compare and contrast with previous work on copper and ferric oxide-mediated pyrolysis of 2-MCP, identical reaction conditions were maintained (50 ppm 2-MCP, model fly-ash particles containing 5% Fe₂O₃ on silica). Observed products included dibenzo-p-dioxin (DD), 1-monochlorodibenzo-p-dioxin (1-MCDD), dibenzofuran (DF), 4,6-dichlorodibenzofuran (4,6-DCDF), 2,4- and 2,6-dichlorophenol, 2,4,6-trichlorophenol, quinone, catechol, chloro-o-quinone, chlorocatechol and polychlorinated benzenes. Yields of DD and 1-MCDD were 2 and 5 times higher than under pyolysis conditions, respectively. Although 4,6-DCDF was the major PCDD/F product formed with a yield that was 2.5× greater than under pyrolysis, the yield of non-chlorinated DF, which was the dominant PCDD/F product under pyrolysis, decreased by a factor of 3. Furthermore, the ∼2× higher yield of PCDDs under oxidative conditions resulted in a PCDD to PCDF ratio of 0.75 compared to a relatively low ratio of 0.39 previously observed under pyrolytic conditions.     

Abbauverhalten von triadimefon und seinem metaboliten triadimenol in einer weizenmonokultur

Summary

In a 4‐year study, the behaviour of the residues of triadimefon and its metabolite triadimenol in different plant parts of winter wheat and in soil was investigated. The fungicide Bayleton DF (triadimefon + captafol) was applied at the beginning of earing. Triadimefon residues were quickly degraded in the great majority of the examined samples (more than 90% within the first 2 weeks after application in all aerial parts of the plant). Triadimenol residues were considerably more persistent. No residues either of triadimefon or triadimenol were found in grain at harvest time (detection limit 0.01 mg/kg).