Development and applications of a mass spectrometry/mass spectrometry method for the quantification of polychlorinated dibenzo-p-dioxins and dibenzofurans

Mass spectrometry/mass spectrometry (MS/MS) has been demonstrated to be a valuable technique in the analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs, PCDFs). In this study, we demonstrate both the value and limitations of high-resolution mass spectrometry (HRMS) and MS/MS in the analysis of PCDDs and PCDFs. We have found that in certain cases, MS/MS can solve analytical problems that cannot be solved by high-resolution mass spectrometry and we demonstrate the reliability and reproducibility of MS/MS in the analysis of PCDDs and PCDFs in environmental matrices.     

Evaluation of GC-ion trap-MS/MS methodology for monitoring PCDD/Fs in infant formulas

The application of high resolution gas chromatography in combination with low resolution mass spectrometry with electron ionization and MS/MS detection (HRGC-MS/MS) is tested for its use in the analysis of PCDD/Fs in infant formulas. Development of the analytical method was based upon EPA directrices and international recommendations. Calibration linearity was tested and average relative response for any native and labelled compound over the five-point calibration range below 14% was found. The precision and accuracy of the proposed analytical procedure are also presented. Results obtained are in agreement with EPA criteria. The method is applied to the analysis of a number of initial and follow-on milk based infant formulas. In general, HRGC-MS/MS constitutes an interesting method for the analysis of dioxins in such matrices.     

流化床垃圾焚烧炉产生的有毒二噁英同类物分布研究

测定了流化床垃圾焚烧炉焚烧产生的飞灰、烟尘和烟气中的2，3，7，8位氯取代二噁英同类物的含量及其毒性当量。结果表明，产生的二噁英主要存在于飞灰中，烟气中的含量很少。飞灰中二噁英总浓度和毒性当量分别为8.44ng／g和0．80ng／g，经过布袋除尘器后的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为0．34ng／m^3和0．02ng／m^3，而布袋除尘器前的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为40．78ng／m^3和3．0ng／m^3。飞灰和烟尘中2，3，7，8位氯取代二噁英同类物的分布相似，但是与烟气中2，3，7，8位氯取代二噁英同类物的分布差别较大。通过了解有毒二噁英同类物的分布，可以进一步优化流化床垃圾焚烧炉的焚烧条件，降低二噁英的排放量，减少垃圾焚烧对环境的污染。     

Concentration of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and dioxin-like PCBs in human adipose tissue from Turkish men

There is no previous report from Turkey on chemically determined polychlorinated dibenzo-para-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) in human tissues expressed as World Health Organization (WHO) toxic equivalents (TEQs). The objective of this study was to determine the occurrence of PCDDs/Fs, and dioxin-like PCBs in the general adult Turkish population. For this reason we measured adipose tissue concentrations of PCDDs/Fs and dioxin-like PCBs in 23 Turkish men living in Ankara,Turkey in 2004. PCDD/F concentrations ranged between 3.2 and 19.7 pg WHO-TEQ/g fat (5.34 and 42.7 WHO-TEQ/g fat, respectively, including dioxin-like PCBs). The mean concentrations of WHO(PCDD/F)-TEQ and WHO(PCB)-TEQ were 9.2 and 6.67 pg/g on a lipid basis , respectively. Samples were analyzed for PCDD/F and twelve dioxin-like PCB congeners using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). This study is very important since it is the first report on PCDDs/Fs and dioxin-like PCB contamination in human adipose tissue from Turkey.     

Baseline levels of PCDD/Fs in soil and herbage samples collected in the vicinity of a new hazardous waste incinerator in Catalonia,Spain

The construction in Constantí (Catalonia, Spain) of a new hazardous waste incinerator (HWI), which is the first one in Spain, finished in 1999. In order to determine the temporal variation (1996–1998) in the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in the vicinity of the new HWI, 40 soil and 40 herbage samples were collected (1998) at the same sampling points in which samples had been taken two years before (1996). Each sample was analyzed for PCDDs and PCDFs by high resolution gas chromatography/high resolution mass spectrometry. In the 1996 survey, PCDD/F concentrations in soils ranged from 0.13 to 24.20 ng I-TEQ/kg (d.m.), with median and mean values of 0.67 and 1.68 ng I-TEQ/kg (d.m.), respectively. In the present study, PCDD/F concentrations ranged from 0.12 to 17.20 ng I-TEQ/kg (d.m.), with a median value of 0.75 ng I-TEQ/kg (d.m.) and a mean value of 1.59 ng I-TEQ/kg (d.m.). In turn, in the present study PCDD/F concentrations in vegetation ranged from 0.14 to 2.01 ng I-TEQ/kg (d.m.) (median and mean values: 0.23 and 0.31 ng I-TEQ/kg, respectively), while in the 1996 survey PCDD/F concentrations ranged from 0.24 to 1.22 ng I-TEQ/kg (d.m.) (median and mean values: 0.53 and 0.61 ng I-TEQ/kg, respectively). According to the present (1998) and the previous (1996) levels of PCDD/Fs found in soils and vegetation, the area under potential influence of the new facility shows a rather low contamination by these compounds. The current results should be useful to establish the environmental impact of the HWI.     

Application of GC-MS/MS for the analysis of PCDD/Fs in sewage effluents

The application of high resolution gas chromatography in combination with tandem mass spectrometry in an ion trap was tested to substitute the expensive high resolution mass spectrometry in analysing polychlorinated dibenzo-p-dioxins and furans in sewage effluents. In tandem mass spectrometry, a set of parameters has to be optimised in order to attain the required sensitivity. To the best of our knowledge, this is the first time a method development for analysing PCDD/Fs with GC-MS/MS in an ion trap is described in this detail. Nine parameters are varied, including isolation window, collision induced dissociation (CID) amplitude, CID time, acquisition mass range, broadband amplitude, CID bandwidth, modulation range, filament current and ion trap temperature. This technique can be adapted to other analytes. By this optimisation, limits of detection of 0.01-0.05 ng/l are obtained. With its selectivity and sensitivity, tandem mass spectrometry is a powerful tool for the determination of PCDD/Fs in water samples. 55 sewage effluent samples from Germany were analysed.     

Dechlorination and destruction of PCDDs/PCDFs in fly ashes from municipal solid waste incinerators by low temperature thermal treatment

Dechlorination and destruction characteristics of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs) in fly ashes from commercial-scale municipal solid waste incinerators by low temperature thermal treatment using a laboratory-scale heating system were investigated. Experiments were carried out in reducing atmosphere at temperatures of 300 degrees C, 450 degrees C and 600 degrees C respectively, for the treatment time of 1h and 3h. Concentrations of PCDDs/PCDFs in raw fly ashes ranged from 35.5 to 107.3 microg kg(-1) (1.5-3.4 microg TEQ kg(-1)) and treated fly ashes ranged from 0.34 to 45.3 microg kg(-1) (0.012-1.63 microg TEQ kg(-1)). Concentrations of PCDDs/PCDFs in fly ashes treated at the different temperatures and times were observed to decrease with increase of treatment temperature and time by dechlorination or destruction. The distribution of octa- and hepta-chlorinated congeners were decreased and tetra-, penta- and hexa-chlorinated congeners were increased at 300 degrees C and 450 degrees C, but the distribution of octa- and hepta-chlorinated congeners were increased and tetra-, penta- and hexa-chlorinated congeners were again decreased at 600 degrees C. Total destruction efficiencies of PCDDs/PCDFs in fly ashes showed above 95% at the treatment temperature of 450 degrees C for 3h. However, removal efficiency of each congener in fly ashes varied, especially, 2,3,7,8-TeCDD and 1,2,3,7,8-PeCDD in fly ash A increased. And the dechlorination and destruction characteristics of PCDDs/PCDFs in fly ash A and B was different due to difference in contents of Ca-compounds and metal oxides such as CuO and PbO in fly ashes.     

Assessment of human exposure to PCDDs,PCDFs and Co-PCBs using hair as a human pollution indicator sample I: Development of analytical method for human hair and evaluation for exposure assessment

Dioxins including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and co-planar polychlorinated biphenyls (Co-PCBs) are highly toxic. Even at environmental pollution levels, they cause hormonal damage in women, and they have been shown to induce immunosuppression and genital function damage in humans. In this study, a new method using isotope dilution was established to detect PCDDs, PCDFs and Co-PCBs in human hair. This method, comprised of washing and cutting of hair, alkaline decomposition, hexane extraction, multilayer silica gel column chromatography, high performance liquid chromatography with a porous graphite carbon column and analysis by high resolution gas chromatography/high resolution mass spectrometry, enabled us to analyze PCDDs, PCDFs and Co-PCBs at trace levels of less than pg/g with good reproducibility. In addition, there was a correlation between some isomers in human hair and blood collected from identical donors. Human hair analysis is useful to evaluate human risk assessment including that due to environmental pollution.     

Distribution of polybrominated diphenyl ethers (PBDEs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in municipal solid waste incinerators

The stack flue gases and the ashes in different units of two municipal solid waste incinerators (MSWIs) are sampled to investigate the characteristics of polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Bottom ashes (BA) exhibited much higher PBDD/F (8.11-52.2 pg TEQ/g) and PBDE contents (20.4-186 ng/g) than those of fly ashes (0.0932-2.02 pg TEQ/g and 0.332-25.5 ng/g), revealing that the PBDD/Fs and PBDEs in the feeding waste may not be completely destroyed. The PBDE concentrations/contents in the stack flue gases (26.1-109 ng/Nm³) and in the BA (20.4-186 ng/g) of the MSWIs could reach three orders higher than those in the atmosphere and reference soils. PBDE contributions to the environment from the stack flue gases or the reutilization of BA of MSWIs should not be ignored from the developing PBDE inventory.     

Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI FT-ICR MS): Characterization of Complex Environmental Mixtures

Structural and chemical characterization of compounds within complex environmental mixtures provides unique insights into the roles of these compounds in different environmental processes. Here, an emerging technique in environmental chemistry, electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS), is described and its applications to the molecular characterization of humic acids and petroleum products are reviewed and examined. ESI is a low-fragmentation ionization technique that preferentially ionizes polar functional groups prior to mass spectrometric analysis. This technique allows the characterization of intact polar macromolecules that are inaccessible to standard chromatographic techniques. ICR MS is an ultrahigh resolution and mass accuracy MS technique based on the detection of ion cyclotron motion within a magnetic field. The combination of ESI FT-ICR MS with other structural techniques such as nuclear magnetic resonance (NMR) allows the unprecedented identification and characterization of polar macromolecules in environmental mixtures and will find numerous applications within environmental chemistry and forensics.     

Measures to prevent emissions of PCDDS/DFs and co-planar PCBs from crematories in Japan

In this study, PCDDs/DFs and co-planar PCBs concentrations in flue gases from 17 crematories and in fly ashes and bottom ashes (mainly bone) from several crematories were measured to grasp the present state of PCDDs/DFs emissions from crematories. The effects of several factors were discussed to prevent PCDDs/DFs emissions from crematories. Total concentration (normalized by 12% O2) of PCDDs/DFs was ranged from 4.9 to 1200 ng/m3 N, and toxic equivalent concentration was ranged from 0.064 to 24 ng TEQ/m3 N. As the results obtained in this research, the following measures to reduce PCDDs/DFs emission are recommended for existing crematories: (1) keeping the temperature at 800 degrees C in main/secondary chambers during a whole cremation, and (2) lowering the temperature in the dust collector. For newly installed crematories, following measures to prevent PCDDs/DFs emission including the measures for existing ones are recommended: (1) connecting one secondary chamber to one main chamber, (2) installing the high efficiency dust collector and reducing dust concentration to less than 0.01 g/m3 N, and (3) installing the sampling point for monitoring of PCDDs/DFs.     

Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI FT-ICR MS): Characterization of Complex Environmental Mixtures

Structural and chemical characterization of compounds within complex environmental mixtures provides unique insights into the roles of these compounds in different environmental processes. Here, an emerging technique in environmental chemistry, electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS), is described and its applications to the molecular characterization of humic acids and petroleum products are reviewed and examined. ESI is a low-fragmentation ionization technique that preferentially ionizes polar functional groups prior to mass spectrometric analysis. This technique allows the characterization of intact polar macromolecules that are inaccessible to standard chromatographic techniques. ICR MS is an ultrahigh resolution and mass accuracy MS technique based on the detection of ion cyclotron motion within a magnetic field. The combination of ESI FT-ICR MS with other structural techniques such as nuclear magnetic resonance (NMR) allows the unprecedented identification and characterization of polar macromolecules in environmental mixtures and will find numerous applications within environmental chemistry and forensics.     

Formation and transport of PCDD/Fs in the packed bed of soil containing organic chloride during a thermal remediation process

The authors previously proposed the concept of a new thermal remediation process for particulate/powder materials contaminated by polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and experimentally verified its validity on the basis of process efficiency. However, contaminees such as soils and fly ashes from waste incinerators often contain a considerable amount of other chlorides, which may act as a main source of chlorine in the formation of PCDD/Fs via thermal processes. The present study aims to examine the formation and transport of PCDD/Fs in the packed bed of soil containing a chloride during the process. Polyvinyl chloride (PVC) polymer was mixed with soil sample as an organic chloride model. A laboratory-scale apparatus was employed as a process simulator. Further, a technique to quench the process was applied to observe the concentration distribution of PCDD/Fs in the solid bed in the vertical direction. The result shows that the PCDFs tend to form dominantly in the high temperature (calcination and/or combustion) zone and are successively trapped in the low temperature (wet) zone. Especially, TeCDF is the most dominant homologue contained in the wet zone and outlet gas. Although PCDD/Fs are once trapped at the wet zone, the concentration of the remediated materials gives fairly low value (1.9 pg/g-dry, 0.04 pg-TEQ/g-dry). It signifies that organic chlorides mingled in the solid contaminee not affect the removal efficiency of PCDD/Fs in the process. Nevertheless, attention should be paid to the potential emission of PCDD/Fs in the outlet gas due to the presence of organic chloride in the soil.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans and polychlorinated biphenyls levels in human breast milk from different regions of Turkey

Human breast milk offers the optimal nutrition for all infants and have been widely used in biomonitoring programs to assess human exposure to lipophylic environmental contaminants such as polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and polychlorinated biphenyls (PCB). There are no previous reports from Turkey on chemically determined levels of PCDDs, PCDFs, and PCBs in human breast milk expressed as World Health Organization (WHO) toxic equivalents (TEQ). To get an overview of the levels of these contaminants in Turkish human milk, samples from 51 Turkish women living in the Ankara, İstanbul, Antalya, Kahramanmaraş, and Afyon provinces were analyzed by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) throughout 2007. The mean concentrations of WHO_PCDD/F-TEQ and WHO_PCB-TEQ of all samples from the five regions were 7.5 and 3.1 pg g⁻¹ on a lipid basis, respectively. PCDD/F concentrations ranged between 0.78 and 29.3 pg WHO-TEQ g⁻¹ fat (1.7 and 36.2 pg WHO-TEQ g⁻¹ fat, respectively, including PCB). Of the five studied locations, the lowest levels of ∑TEQs (PCDD/F + PCB) were found in the Afyon (6.8 pg WHO-TEQ g⁻¹ fat) and the highest in the Antalya (15.6 pg WHO-TEQ g⁻¹ fat) province. The results have been discussed in terms of regions and PCDD/F and PCBs for which analyses had been made. The mean levels of PCDD/Fs and PCBs in Turkish human milk are comparable to that found in other countries.     

Formation of aromatic chlorinated compounds catalyzed by copper and iron

This study shows the catalyzing effects of iron and copper on the formation of chlorinated compounds such as chlorobenzenes (ClBzs), chlorophenols (CIPhs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Both total concentrations and congener distributions have been studied. The parameters and conditions varied during the combustion tests were the complete and incomplete combustion and the metal and chlorine addition. The incomplete combustion promoted the formation of organic chlorinated compounds in flue gas particles. Highly chlorinated congeners of PCDD/F were dominant in the flue gas particles, whereas the importance of lower chlorinated congener were increased in the gas phase. In the complete combustion conditions the concentrations of PCDD/Fs increased when the degree of chlorination were high, nevertheless the concentrations of tetra and penta PCDD/Fs were higher in the gas phase than the concentrations in the fly ash particles. Organic chlorine promoted the formation of chlorinated compounds more effectively than inorganic chlorine, which instead promoted the formation of PCDD/Fs in the gas phase, especially with copper catalyst. Different concentration levels of chlorinated compounds were observed in the gas phase and in particles when the chlorine source and combustion conditions were varied from incomplete to optimum conditions. Both copper and iron seem to have a catalytic effect on PCDD/F formation.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans from food salt samples processed by heat treatment in Korea

Eight samples of processed food salt collected from five plants in Korea were analyzed for 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) using liquid-liquid extraction, clean-up procedures, and high resolution gas chromatography-high resolution mass spectrometry. The study included the analyses of two kinds of salt product sample: bamboo-salt and parched salt. The levels of toxic PCDD/Fs found in the salt product samples were extremely low: the results revealed TEQ levels ranging between the sub pg TEQ/g and sub fg TEQ/g. The differences in the TEQ values of toxic PCDD/F were observed between the salt product samples, which were treated with different frequency of baking using four different fuels (firewood, pine wood, pine resin, and indirect heating by gas) at temperatures from 300 to 2000 degrees C. In bamboo-salt samples, the concentrations and TEQ values of toxic PCDD/Fs ranged between 0.57-66 pg/g and 5.7x10(-5)-0.64 pg TEQ/g, respectively. PCDD/Fs levels in bamboo-salts baked by firewood were found to be higher than those baked by pinewood or pine resin. In parched salt samples, the concentrations and TEQ values of toxic PCDD/Fs ranged between 0.97-3.7 pg/g and 0.0097-0.017 pg TEQ/g, respectively. The data was discussed regarding the concentration and the distribution pattern of congeners.     

Matrix effects on the de novo synthesis of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes

The formation of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes in de novo synthesis experiments have been studied on model fly ashes with a wide range of matrices. The model fly ash consisted of 18 selected matrices with the addition of CuCl(2) x 2H(2)O, activated charcoal and NaCl. The studied matrices were not restricted to the commonly investigated matrices with defined chemical composition (silica gel, alumina, florisil) and industrially produced adsorbents with silicate structures (diatomaceous earths), but also included natural occurring matrices (clays, kaolin, bentonite and feldspars). In addition fly ashes from a hazardous waste incinerator were included in the study for comparison. Differences in the isomer composition (homologue profiles and isomer patterns) of the substances formed by de novo synthesis experiments are discussed in dependence on the chemical composition of the studied matrices. The de novo synthesis experiments on matrices with silicate structures resulted in high concentration of mainly perchlorinated aromatic compounds while for other matrices in particular alkaline matrices a homologue shift to lower chlorinated homologues and lower formation rates were found. The paper discusses the resulting PCDD/PCDF pattern and compares them to the PCDD/PCDF profile found in naturally occurring kaolin and ball clay (illite).     

Development and validation of a method for analysis of "dioxin-like" PCBs in environmental samples from the steel industry

A method, previously used for determination of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), has been modified for quantitative analysis of "dioxin-like" polychlorobiphenyls (PCBs) in environmental samples from the steel industry. The existing sample clean-up procedure, involving liquid chromatography on multi-layered silica and Florisil columns, has been extended to include a third chromatography stage on a basic alumina stationary phase. The additional clean-up stage is required for PCB analysis in order to eliminate interferences from relatively large concentrations of saturated cyclic and aliphatic hydrocarbons. Samples were analysed for WHO-12 congeners using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) and standard solutions of the method US EPA 1668A. Replicate analysis of method blanks revealed background contamination for PCBs 118, 105 and 77, which are generally abundant in ambient air. These contaminants were taken into account using a subtraction method. The entire procedure was validated by replicate analysis (N = 3) of a certified reference sediment. The RSD for each WHO-12 congener was below 15%, 13C12-labelled PCB internal standard recoveries were in the range 70-95%. A waste dust sample collected in the electrostatic precipitator of a UK sinter plant was analysed for determination of PCDD/Fs and WHO-12 PCBs and exhibited a PCDD/F I-TEQ of 148.5 +/- 21.2 ngkg(-1) and a WHO-TEQ of 7.2 +/- 1.5 ngkg(-1). WHO-12 congeners contributed only 4.6% to the overall TEQ and PCB 126 was the major congener contributing to the WHO-TEQ (96%). The contribution to the overall TEQ of the waste dust sample was mainly attributed to PCDF followed by PCDD, which accounted for 86.6% and 8.7% to the overall TEQ, respectively.     

Polychlorinated dibenzodioxins and polychlorinated dibenzofurans in sewage sludges

A municipal sewage sludge from Syracuse, New York and a largely domestic sludge from Sodus, New York were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) using combined gas chromatography and high resolution mass spectrometry (GC/HRMS). Concentrations in ppt of the following PCDDs were found in the syracuse sludge: tetrachlorodibenzo-p-dioxins (TCDDs), 150, hexachlorodibenzo-p-dioxins (HxCDDs), 2100, heptachlorodibenzo-p-dioxins (HCDDs), 6300, octachlorodibenzo-p-dioxins (OCDDs), greater than 60,000. The following ppt concentrations were found in the Sodus sludge: TCDDs, 7200, HxCDDs, 300, HCDDs, 900, OCDDs 7500. The TCDD was a single but not the highly toxic 2,3,7,8-isomer. PCDFs were mostly nondetectable in the sludges. The toxicology and potential for environmental contamination by these compounds are discussed.     

Rapid PCDD/PCDF screening method for fly ash with ion trap MS/MS

A rapid screening method for the polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) in fly ash has been developed. The screening is done in two steps: (a) the extraction by the accelerated solvent extraction and (b) the quantitative measurement by ion trap tandem mass spectrometer (MS/MS). Anhydrous sodium sulfate was added to the fly ash containing activated carbon in order to increase the extraction efficiency. The selectivity of the ion trap MS/MS was confirmed with 13C-labelled internal standard. Then the results of the screening method were compared with those obtained by the conventional analytical method using high-resolution mass spectrometer (HRMS).