Systematic analysis and overall toxicity evaluation of dioxins and hexachlorobenzene in human milk

A systematic method for analyzing dioxins (PCDDs, PCDFs and dioxin-like PCBs), hexachlorobenzene (HCB), heptachlor epoxide and beta-hexachlorocyclohexane (HCH) in human milk was developed to determine the residual amount of HCB in human milk and to evaluate the overall toxicity of both dioxins and HCB in human milk. The fractionation behavior of HCB on chromatography with silica gel, alumina, and activated carbon/silica gel, and the concentrated sulfuric acid decomposition method, which is widely used as a dioxin cleanup method, were studied in order to make the preprocessing operation for HCB measurement compatible with that for conventional dioxin measurement. HCB was found to be eluted in the 2% dichloromethane (DCM)/hexane 60 ml fraction from an alumina column. Heptachlor epoxide and a part of beta-HCH were eluted in the 10% DCM/hexane 50 ml fraction from a silica gel column, while the remaining beta-HCH was eluted in the 25% DCM/hexane 60 ml fraction from an activated carbon/silica gel column. Moreover, HCB showed significant correlation with dioxin congeners having high toxicity equivalence factors (TEFs). The results suggest that the exposure route to HCB and its accumulation behavior in the human body are similar to those of the dioxins.     

Human emotional stress, dioxin blood content and genetic damage in Chapaevsk town

Forty five women from Chapaevsk town (three groups of 14-16 persons aged 20-40 yr) with different exposures to dioxins and different dioxin levels in blood were tested by four standard psychological questionnaires to detect emotional stress. Results of psychological testing were compared with individual dioxin blood contents and chromosome aberration level in blood cells. Results of the investigation were the next: (1) three groups tested differed significantly (P < or = 0.05) in emotional stress level, thus that highest level of stress was detected within the group with the highest dioxin blood contents (group "Workers"); (2) high level of correlation between emotional stress and individual dioxins blood contents (up P < or = 0.001) as well as between emotional stress and individual chromosome aberration level (up P < or = 0.05) was revealed. These results are discussed from the position of desadaptation induced by dioxins, which led to chromosome aberration induction.     

Effects of dietary habits and CYP1A1 polymorphisms on blood dioxin concentrations in Japanese men

The major source of dioxin impurities in Japan in the past was agrochemical formulations; more recently, it has been exhaust from waste incinerators. To examine the environmental and genetic factors that influence blood dioxin concentration, we investigated the relationship among dioxin concentrations, dietary habits and cytochorome P450 1A1 (CYP1A1) polymorphisms (MspI type and Ile-Val type) in Japanese fishermen and farmers, including also a group of office workers as controls. The mean dioxin concentrations in the fishermen, the farmers and the controls were 161369, 79079 and 100500 pg/g fat, respectively. The elevated dioxin concentration with polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and coplanar-PCBs found in the fishermen may be due to the frequent consumption of fish; no such relationship was found both in the farmers and the controls. We found that the concentrations of congeners found as impurities in certain chemicals such as those previously used in agriculture showed no significant differences among the three groups; we consider it unlikely that the farmers would be directly exposed to dioxins from such chemicals. Thus, it is probable that the primary route of dioxin exposure in the Japanese population is through the food chain via fish consumption, regardless of occupation. No meaningful relationship between blood dioxin concentration and CYP1A1 polymorphisms was found in this study, although there was a significant difference between the concentration of total non-ortho-PCBs in genotypes A and B. Further studies on more subjects, including those of genotype C, are needed to confirm the relationship between blood dioxin concentrations and MspI polymorphisms.     

Abundance and sources of ambient dioxins in Hong Kong: a review of dioxin measurements from 1997 to 2001

Ambient measurements of seventeen 2,3,7,8-polychlorinated dibenzo-p-dioxin/dibenzofuran congeners (2,3,7,8-PCDD/Fs) have been taken in a number of monitoring programs or ad-hoc studies in Hong Kong. The longest monitoring program started at two locations in the territory in July 1997. The other monitoring efforts are ad-hoc studies, varying from a few coordinated sampling events at multiple sites to a year-long monitoring project that targeted suspected local dioxin sources. In this paper, we examined these measurements to understand the ambient levels, temporal and spatial variation, and possible sources of the 2,3,7,8-PCDD/Fs in Hong Kong. The territory-wide annual average concentration of the dioxins was 0.052 pg I-TEQ/m3 measured at the regular monitoring stations in the most recent annual cycle of 2000/2001. This level fell at the lower end of the range of dioxin concentrations measured at other urban locations around the world. The dioxin levels showed a clear seasonality in that elevated concentrations were observed in the winter and lower concentrations in the summer at all monitoring sites with one year or more regular measurements. The measurements indicated that the few known local dioxin sources, including a major chemical waste incinerator facility, landfill sites, and vehicular traffic, are not important contributors to ambient dioxins in Hong Kong. On days of high dioxin concentrations, the 2,3,7,8-PCDD/F congeners were observed to have almost identical compositions with a north-northwest to south-southeast spatial gradient in concentrations at different sampling locations in Hong Kong. This observation, along with other collaborative evidence, established a strong link between high dioxin concentration days in Hong Kong and regional transport of the polluted air masses from the north.     

Human exposure to dioxins through the diet in Catalonia,Spain: carcinogenic and non-carcinogenic risk

The main objectives of this study were to estimate the dietary intake of dioxins by the population of Catalonia, Spain, to determine which food groups showed the greatest contribution to this intake, and to assess the health risks potentially associated with the dietary dioxin intake. From June to August 2000, food samples were randomly acquired in seven cities of Catalonia. Dioxin concentrations were determined in 108 samples belonging to the following groups: vegetables, fruits, pulses, cereals, fish and shellfish, meats and meat products, eggs, milk and dairy products, and oils and fats. Estimates of average daily food consumption were obtained from recent studies. Total dietary intake of dioxins for the general population of Catalonia was estimated to be 95.4 pg WHO-TEQ/day (78.4 pg I-TEQ/day), with fish and shellfish (31%), diary products (25%), cereals (14%) and meat (13%) showing the greatest percentages of contribution to dioxin intake. The contribution of all the rest of food groups to the total dietary intake was under 20%. The non-carcinogenic risk index of dioxin intake through the diet was in the range 0.34-1.36, while the carcinogenic risk level was 1,360 excess cancer over a lifetime of 70 years. Our results corroborate the decreasing tendency in dietary intake of dioxins found in recent studies (2000-2001) from various countries.     

Characteristics of dioxin emissions at startup and shutdown of MSW incinerators

Dioxin concentrations from municipal waste incinerators in Japan and elsewhere often show low concentrations that comply with legal limits (in this paper, the term "dioxin" designates WHO-TEQ: PCDD/Fs+dioxin-like PCB). However, such data is usually generated under normal steady state operational conditions, and there has been little investigation of releases occurring during startup and shutdown. It is important, therefore, to ascertain quantitatively emissions in an unsteady state (startup and shutdown) in order to correctly evaluate the relationship between emissions from a facility and the surrounding environment. The present study aimed to examine dioxin emissions of a continuously operated incinerator at startup and shutdown, and estimating the time period of greatest emission, and the processes causing dioxin generation. The startup process was divided into five stages and the shutdown into two; at each stage, dioxins in the flue gas were measured at the boiler outlet and the stack. From the concentration of dioxins and the flue gas volume at each stage, the amount of dioxins at startup and shutdown were calculated, and these were compared with that under steady state conditions. Dioxin concentration at the stack under steady state conditions was a very low level, while those at startup and shutdown were higher. In the case where dioxin concentration under a steady state is a low level like in this study, it is indicated that the total annual dioxin emission from a facility could be attributed to the startup periods.     

Extraction and cleanup methods of dioxins in house dust from two cities in Japan using accelerated solvent extraction and a disposable multi-layer silica-gel cartridge

A simple and rapid method for the extraction and cleanup of dioxins from house dust was developed using an accelerated solvent extraction (ASE) method and a multi-layer silica-gel cartridge. It was found that the WHO-TEQ levels of dioxins extracted from the house dust obtained by both a conventional soxhlet extraction and the ASE were almost equal, when the data obtained by both methods were compared. As for the cleanup method, a multi-layer silica-gel cartridge yielded higher dioxin recoveries than the alkaline digestion method. The average values of the dioxins in house dust from Kumagaya city and Sendai city in Japan (Sendai city is bigger than Kumagaya city with respect to the population and industry), were 15.6 pg TEQ/g (8.6-26.0 pg TEQ/g, n=5, Kumagaya city) and 16.0 pg TEQ/g (5.9-30.5 pg TEQ/g, n=5, Sendai city), respectively.     

Effect of matrix on heterogeneous phase chlorine substitution reactions for dibenzo-p-dioxin and HCl in air

Five materials were used in gas-solid phase reactions between dibenzo-p- dioxin(DD) and HCl in order to determine the role of organic and inorganic components in fly ash on chlorine substitution reactions of chlorinated dioxins. The five solids were: granular activated carbon, silica gel, diatomaceous earth, Tenax-GC, and fly ash. Conditions for reactions were 10 min at 150°C with 5% HCl in air. Extent of chlorination was measured using GC/MS analyses of extracts of fly ash after treatment processes and was expressed as the ratio monochloroDD/original unreacted DD. These ratios were: fly ash, 1.082; silica gel, 0.059; activated carbon, 0.024; and Tenax-GC, 0.001. Measurement of similar behavior on diatomaceous earth was impossible since starting material and possible products were irreversibly adsorbed completely. The major chlorinated dioxin produced under these conditions was 2-chlorodibenzo-p- dioxin which is the isomer favored through an electrophilic substitution mechanism.     

Levels and tissue-dependent distribution of dioxin in Japanese domestic leafy vegetables--from the 1999 national investigation

In 1999, Japanese domestic leafy vegetables were successively investigated for levels of dioxins, including 17 dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), four non-ortho co-planar PCBs (co-PCBs) and eight mono-ortho co-PCBs, all of which had been assigned toxic equivalency factors (TEFs) by WHO in 1997. The mean levels of dioxins in the edible portions were 0.07 (0.09) pg TEQ/g in spinach, 0.13 (0.14) pgTEQ/g in garland chrysanthemum, 0.01 (0.04) pg TEQ/g in mitsuba (marsh parsley) and 0.01 (0.03) pg TEQ/g in chingentsuai (Brassica Campestris var. chinesis), when non-detects were set to zero (and set to half the limit of detection). In order to understand the dioxin pollution of leafy vegetables in detail, a further investigation of dioxin levels in the tissues of spinach was conducted. As a result, the dioxin levels in the leaves were found to be higher than those in the stem and red collar, but they were much lower than those found in the primary and secondary roots, which are considerably affected by the soil, which is recognized as a sink of airborne dioxins. The dioxin levels in edible portions (leaves, stem and red collar) were obviously lower than those in non-edible portions (primary and secondary roots). In addition, from the finding that several lower-chlorinated PCDD/Fs and co-PCBs, namely 2,3,7,8-TCDD/F, 1,2,3,7,8-PeCDD, 1,2,3,7,8/2,3,4,7,8-PeCDFs, 1,2,3,7,8,9-HxCDD, 1,2,3,4,7,8-/1,2,3,6,7,8-HxCDFs, 3,3',4,4'-TCB, 2,3,3',4,4'-/2,3',4,4',5-PeCBs, and 2,3',4,4',5,5'-HxCB, were more highly represented in the dioxins in the leaves than in those in the secondary roots, it was suggested that in leafy vegetables the deposition of gaseous, presumably moderately volatile dioxins in leaf wax is another pollution pathway in addition to the adhesion of dioxin-contaminated particles including soil.     

Dispersion modelling of dioxin releases from the waste incinerator at Avonmouth,Bristol, UK

A modified Gaussian atmospheric dispersion model, Industrial Source Complex (ISCST3), is used to estimate toxic equivalent ground level concentrations (GLC) of dioxins emitted from the Avonmouth municipal waste incinerator (MWI) in Bristol, UK. The sensitivity of the predicted GLC to various vapour and particle partitioning scenarios is reported. Predictions incorporating local terrain and actual emission data are used to estimate the mean incremental intake of dioxin due to MWI operation for local residents, through an existing multi-pathway human exposure model. Results are compared with predictions of incremental intake for a generalised MWI. The mean incremental dioxin intake for a hypothetical maximum exposed individual (HMEI) is shown to be up to 46.5% of the background intake compared to only 1.14% for the generalised MWI scenario. This indicates that the use of local terrain and emission data in MWI dispersion modelling is crucial for health risk assessments associated with human dioxin intake, especially in view of the current debate over the tolerable daily intake for dioxins.     

Comparison of the concentrations of polychlorinated biphenyls and dioxins in mothers affected by the Yusho incident and their children

Accumulated maternal dioxins are passed onto the fetus and neonate via the placenta and maternal milk. In Japan in 1968, an accidental human exposure to rice oil contaminated with polychlorinated biphenyls (PCBs) and other dioxin-related compounds, such as polychlorinated dibenzofurans (PCDFs), led to development of Yusho oil disease. We investigated differences in blood dioxin concentrations in mother-children pairs affected by the Yusho incident. From 2002 to 2008, blood samples were collected from 26 pairs of Yusho mothers and their children (19 mothers, 26 children). Specific congeners of seven polychlorinated dibenzo-p-dioxins (PCDDs), ten PCDFs, and four non-ortho PCBs were analyzed. The children had significantly lower TEQ concentrations of PCDDs, PCDFs, and coplanar PCBs compared to their mothers. The mother-child difference in blood concentrations varied with the congeners; the largest for 2,3,4,7,8-pentaCDF and the smallest for 1,2,3,4,6,7,8-heptaCDD. The level for 2,3,4,7,8-pentaCDF, which characterizes Yusho oil disease, was approximately 17-30 times higher in the mothers than in the general population, whereas there were no significant differences between children in the formula-fed group and the general population. In contrast, the mean level for 2,3,4,7,8-pentaCDF in the breast-fed group was approximately 1.5 times, (range 0.5-6.5 times) higher than that in the general population. Over 30 years after the Yusho incident, the mean blood dioxin levels in the offspring were only a fraction of the levels in their mothers. This is more consistent with exposure via breast milk than via transplacental transfer in the Yusho incident.     

Gas-phase mechanism for dioxin formation

We consider the formation of dioxin in the gas phase through the combination of phenoxy radicals in the context of a recently published scenario regarding the possibility of forming highly chlorinated benzenes in poorly mixed systems. It is demonstrated that the production of free chlorine in fuel lean combustion systems and subsequent mixing and quenching with fuel rich mixtures leads to chlorine atoms as the main reactive radicals. Under such conditions high concentrations of chlorinated phenoxy radicals can be formed. This leads to the formation of concentrations of dioxins that are consistent with recent measurements of Sidhu et al. [Combust. Flame 100 (1995) 11]. It suggests that there may be a gas-phase channel for the dioxin formation in addition to the usually assumed surface catalyzed process.     

Simulation of dioxin accumulation in human tissues and analysis of reproductive risk

Polychlorinated dibenzo-p-dioxin, polychlorinated dibenzofuran and dioxin-like polychlorinated biphenyl concentrations in human liver, kidney, fat, blood, muscle, richly perfused tissue (brain, lung etc.) and skin were simulated to assess the health risk for Japanese fetuses. A 40-year time course of dioxin accumulation via food ingestion was simulated using a physiologically based pharmacokinetic (PBPK) model. In richly perfused tissue, the concentration estimated by the PBPK model showed better agreement with measured concentrations than that calculated by the one-compartment model. Fetal dioxin concentration was simulated based on the assumption that the fetal concentration was almost equal to the concentration in the mother's richly perfused tissue. To assess the reproductive risk, the estimated concentration in human fetus was compared with that in rat fetus in which reproductive function showed signs of alteration by 2,3,7,8-TCDD in previous reports [Toxicol. Appl. Pharmacol. 114 (1992) 118; 146 (1997) 11; Toxicol. Sci. 53 (2000) 411; 57 (2000) 275]. The present daily intake of 2,3,7,8-TCDD is approximately 1/50 of the amount that leads to possible reproductive toxicity in the next generation. However, when 29 kinds of dioxin congeners are considered, the present level is 1/5 of the hazardous levels. For species extrapolation of dioxin risk, further study on tissue concentration versus toxicity is required.     

Convenient dioxin measuring method using an efficient sampling train, an efficient HPLC system and a highly sensitive HRGC/LRMS with a PTV injector

An efficient sampling method for dioxins from flue gas, an efficient automatic purification and fractionation method by a new HPLC system using a sulfuric acid-silica/silica column, a Nitro column and a PGC column, and sensitive determination method by an economical HRGC/LRMS using a programmable temperature vaporization (PTV) injector were developed. It was confirmed that the dioxins could be easily collected by the proposed simple sampling train consisting of only two bottles, and the extracted sample could be purified sufficiently and separated as mono-ortho PCBs, non-ortho PCBs and PCDDs/PCDFs completely with the proposed HPLC system. The peak areas of GC/MS were increased linearly with the injection volume up to 40 microl by the PTV technique, and the sensitivity could be increased to 20 times higher than usual. This convenient measuring method can drastically reduce operation time, consumption of hazardous solvent and cost.     

An assessment of dioxin contamination from the intermittent operation of a municipal waste incinerator in Japan and associated remediation

Significant dioxin (polychlorinated dibenzo-para-dioxins (PCDDs)/polychlorinated dibenzo-furans (PCDFs)) pollution from a municipal solid waste incinerator was discovered in 1997 in Osaka prefecture/Japan. The cause and mechanism of pollution was identified by a detailed assessment of the environment and incinerator plant. The primary sources of PCDD/PCDF pollution were high dioxin releases from an intermittently operated waste incinerator with PCDD/PCDF emissions of 150 ng-TEQ/Nm³. PCDD/PCDF also accumulated in the wet scrubber system (3,000 μg TEQ/L) by adsorption and water recirculation in the incinerator. Scrubber water was air-cooled with a cooling tower located on the roof of the incinerator. High concentrations of dioxins in the cooling water were released as aerosols into the surrounding and caused heavy soil pollution in the area near the plant. These emissions were considered as the major contamination pathway from the plant. Decontamination and soil remediation in and around the incinerator plant were conducted using a variety of destruction technologies (including incineration, photochemical degradation and GeoMelt technology). Although the soil remediation process was successfully finished in December 2006 about 3 % of the waste still remains. The case demonstrates that releases from incinerators which do not use best available technology or which are not operated according to best environmental practices can contaminate their operators and surrounding land. This significant pollution had a large impact on the Japanese government’s approach toward controlling dioxin pollution. Since this incident, a ministerial conference on dioxins has successfully strengthened control measures.     

Cytochrome p450 induction and gonadal status alteration in common carp (Cyprinus carpio) associated with the discharge of dioxin contaminated effluent to the Hikiji River,Kanagawa Prefecture,Japan

Accumulations of polychlorinated dibenzo-p-dioxins, dibenzofurans and coplanar polychlorinated biphenyls were analyzed in common carp (Cyprinus carpio) collected in the Hikiji River, Kanagawa Prefecture, Japan in which dioxin contaminated effluent was released during the period starting from November 1992 to March 2000. Higher levels of 2,3,7,8-tetrachlorinated dibenzo-p-dioxin toxic equivalents were observed in carps collected downstream to the dioxin release site (contaminated site) than the reference site. Modulations of cytochrome p450 (CYP) enzyme in liver, serum estrogen concentration and gonadal somatic index (GSI) were also measured as biomarkers for the contaminants. Total CYP content in livers was markedly higher in male and female carps from the contaminated site relative to the reference site fish. The expression level of the cytochrome p450 1A and Ethoxyresorufin O-deethylase activity were significantly higher in female carps from the contaminated site than from the reference site. A lower level of plasma estrogen was observed in carps from the contaminated site. The GSI in female carps from the contaminated site was smaller than that recorded at the reference site. The present study indicates that dioxins released to the Hikiji River might induce the CYP enzyme and inhibit the reproductive functions in common carps dwelling downstream from the release site.     

Maternal-fetal distribution and transfer of dioxins in pregnant women in Japan, and attempts to reduce maternal transfer with Chlorella (Chlorella pyrenoidosa) supplements

Dioxins can be transferred from mother to fetus via the placenta, or to nursing infants via breast milk, potentially causing developmental health problems in children. To assess pediatric health risks from dioxins, exposure of mothers and children to dioxins must be clarified. Methods of reducing maternal transfer of dioxins should also be investigated. Concentrations of 28 dioxin (polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and co-planar polychlorinated biphenyls) congeners in blood, adipose tissue, breast milk, cord blood and placenta collected from 44 pregnant Japanese women were measured. In addition, to investigate potential reductions in maternal transfer of dioxins, 23 pregnant women were instructed to take Chlorella pyrenoidosa supplements during pregnancy. Correlations were observed between dioxin total toxic equivalents (total TEQ) in blood and total TEQ in adipose tissue (r=0.913, P<0.0001), breast milk (r=0.695, P=0.0007), and cord blood (r=0.759, P<0.0001). Dioxin levels transferred to fetuses and nursing infants reflect cumulative maternal concentrations of dioxins. A linear regression equation was introduced to predict total TEQ in breast milk and cord blood from dioxin levels in maternal blood, which should prove useful in evaluating fetal and infant risk of dioxin exposure. Total TEQ in cord blood were approximately 26% lower than in maternal blood (P<0.0001). The results of this study suggest that transplacental transfer differs depending on the dioxin congener. Total TEQ in breast milk were approximately 30% lower in the Chlorella group than in controls (P=0.0113). This finding suggests that maternal transfer of dioxins can be reduced using dietary measures such as Chlorella supplements.     

Modified clean-up for PBDD,PBDF and PBDE with an active carbon column--its application to sediments

A clean-up method for polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs) and diphenyl ethers (PBDEs) was modified using combinations of multi-layered silica gel, Florisil and active carbon columns. By using active carbon column chromatography in the final procedure, PBDEs were well separated from PBDD/Fs in an elution test with reference standards. We report the application of this method to sediment samples taken from industrialized areas in Japan. These sediments contained PBDEs ranging in concentration from 13 to 2394 pg/g, dry wt. PBDEs did not interfere with the quantification of PBDD/Fs. In addition, PBDEs found in the PBDD/F fraction did not interfere with the identification of PBDFs using the HRGC/HRMS separation method. Some 2,3,7,8-tetra- to hexabrominated dioxins and furans were also detected in the sediment samples.     

The reduction of dioxin emissions from the processes of heat and power generation

The first reports that it is possible to emit dioxins from the heat and power generation sector are from the beginning of the 1980s. Detailed research proved that the emission of dioxins might occur during combustion of hard coal, brown coal, and furnace oil as well as coke-oven gas. The emission of dioxins occurs in wood incineration; wood that is clean and understood as biomass; or, in particular, wood waste (polluted). This paper thoroughly discusses the mechanism of dioxin formation in thermal processes, first and foremost in combustion processes. The parameters influencing the quantity of dioxins formed and the dependence of their quantity on the conditions of combustion are highlighted. Furthermore, the methods of reducing dioxin emissions from combustion processes (primary and secondary) are discussed. The most efficacious methods that may find application in the heat and power generation sector are proposed; this is relevant from the point of view of the implementation of the Stockholm Convention resolutions in Poland with regard to persistent organic pollutants.     

Memory effect on the dioxin emissions from municipal waste incinerator in Taiwan

Evaluation of the dioxin removal efficiency of the air pollution control device (APCD) at an existing municipal waste incinerator (MWI) located in Taiwan is conducted via stack sampling and analysis. The MWI investigated is equipped with cyclones, dry lime scrubbing systems and fabric filters as APCDs. Results indicate that the patterns of dioxin isomers at APCDs' inlet and stack are similar. During the first year of carbon injection, the concentrations of emitted dioxin decreased greatly. The dioxin removal efficiency increased from 26.9% to 96.6% after injecting 115 kg/day activated carbon (AC). At the second year, the dioxin removal efficiency reaches 98.7% after injecting the same rate of AC continuously. The lower efficiency achieved with activated carbon injection (ACI) during the first year can be attributed to the memory effect, i.e. the dioxin or precursor desorbs slowly to the flue gas and increases the dioxin concentration at stack, resulting in a lower dioxin removal efficiency than expected.