Quadrupole ion storage tandem mass spectrometry and high-resolution mass spectrometry: complementary application in the measurement of 2,3,7,8-chlorine substituted dibenzo-p-dioxins and dibenzofurans in US foods

The US Food and Drug Administration has simultaneously utilized both high-resolution mass spectrometry (HRMS) and quadrupole ion storage tandem mass spectrometry (QISTMS) in the measurement of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in 147 food samples collected in 1998 and 1999 in the US. In 1998, 20 egg samples, six scallop, 10 blue crab, eight American lobster, 10 pollack, 15 striped bass, five rockfish, 10 crawfish, seven aqua-cultured and 13 wild-caught salmon, along with 19 cream and 18 mozzarella cheese samples were measured for PCDD/Fs. QISTMS provided limits of detection (LODs) close to those produced using HRMS for many congeners in 56 samples analyzed by both techniques in 1998 and three salmon and three striped bass collected in 1999. The I-TEQs of the mean levels for measured congeners in 40 samples of fish and shellfish and 16 cheese and eggs from 1998 analyzed by HRMS and QISTMS were 0.99 and 1.1 ng/kg wet weight, respectively. The I-TEQ for mean congener levels in the 40 fish and shellfish measured by HRMS was 1.4 ng/kg wet weight. A higher sample throughput with greater data quality at a lower cost is achievable by using both QISTMS and HRMS.     

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。     

Isomeric analysis of PCDD/PCDF in waste incinerator fly ash by GC-MS/MS

The development of an analytical method for the analysis of PCDD/PCDF in flyash using a bench analytical system comprising of a gas chromatograph fitted with an ion trap detector operated in the tandem MS mode is described. The optimum settings for the most important MS/MS parameters are given, including those for the less reported mono- to tri-chlorinated dioxin and furan congener groups. Flyash samples from three waste incineration plants representing a decommissioned 1970s plant design, an upgraded and still operating plant originally designed in the 1970s, and a modern 1990s design operating plant have been analysed for PCDD/PCDF. The flyash samples were analysed for PCDD/PCDF using the methods developed and the total PCDD/PCDF, I-TEQ values and isomeric profiles are reported. The flyash from the older decommissioned incinerator had very significantly higher concentrations of PCDD/PCDF compared to the modern incinerator flyash.     

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.     

Quantification of PCDD/F concentrations in animal manure and comparison of the effects of the application of cattle manure and sewage sludge to agricultural land on human exposure to PCDD/Fs

PCDD/Fs were quantified in samples of cattle, pig, sheep and chicken manure. TEQs ranged from 0.19 ng TEQ/kg dw for the pig manure to 20 ng TEQ/kg dw for one cattle manure sample. Exposure assessments were carried out to compare the effect of various sewage sludge and cattle manure land application scenarios on human PCDD/F exposure. Background exposure was estimated at 4.9 pg TEQ/kg bw/day and it was found that land application of sewage sludge and cattle manure at contemporary rates did not increase PCDD/F TEQ background exposure. It was concluded that the application of sewage sludge, under the new UK guidelines, and cattle manure to agricultural land, do not make a significant contribution to human exposure to PCDD/Fs.     

Analysis of dioxins and furans in environmental samples by GC-ion-trap MS/MS

The work aims to characterise PCDDs/Fs in environmental matrices by high resolution gas chromatography coupled to low resolution quadrupole ion-trap mass spectrometry (GC-QITMS/MS). In particular, the study was mainly focused in different environmental samples such as sewage sludge, soils, and sediments and in combustion residues as fly ashes. Previous experiences have already detected and quantified PCDDs/PCDFs in all matrices studied. Moreover, isomer-specific analysis of 2,3,7,8-PCDDs/Fs compounds corroborated good correlation between GC-QITMS/MS and a well-established technique such as high resolution mass spectrometry (HRMS). Finally, QC measures included the participation in intercalibration exercises. Successful results were achieved using GC-QITMS/MS in the analysis of fly ashes, soils and sediment materials. In general, GC-QITMS/MS constitutes an interesting alternative for routine analysis of dioxins in such as matrices.     

Levels of PCDD/FS in ambient air and soil in the vicinity of a municipal solid waste incinerator in Hsinchu

Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were determined in twenty-one ambient air samples, eight soil samples and two stack gas samples, collected near or in a municipal solid waste incinerator (MSWI) in Hsinchu, Taiwan. A systematic decrease of PCDD/Fs in the ambient air from the northeastern area was observed. PCDD/Fs levels measured in the ambient air range from 0.058 to 0.127 pg-TEQ/m3. Higher PCDD/Fs levels in the ambient air were found during winter. In addition, PCDD/Fs levels measured in the soil range from 0.524 to 5.02 pg-TEQ/g d.m. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) did not provide sufficient evidence that the environmental PCDD/Fs contamination was caused by emissions from the Hsinchu MSWI. An unknown PCDD/Fs source was proposed using congener profile analysis and supported by both PCA and HCA.     

A study of the influence of sewage sludge fertilization on the concentrations of PCDD/F and PCB in soil and milk

The influence of the agricultural use of sewage sludge on the concentrations of PCBs and PCDD/Fs in soil, feed and milk was investigated on four dairy farms. Evidence of contaminant accumulation in the soil was found on both farms that fertilized with sewage sludge. The concentrations in feed and milk from one of these farms were similar to the concentrations in the matched control, while the concentrations in the samples from the second sludge user were elevated. The study demonstrates that the agricultural use of sewage sludge does under some conditions lead to higher levels of PCBs and PCDD/Fs in food products.     

Polychlorinated biphenyl, polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran residues in sediments and fish of the River Nile in the Cairo region

The levels of organohalogenated contaminants, i.e. PCBs, PCDDs and PCDFs were determined in sediment and fish samples collected from different locations in the River Nile, Egypt. Thirty-six sediment and eighteen fish samples were carried out during a period of 12 months from February 2003 to February 2004. Determination of PCBs and dioxins was carried out using a high resolution GC mass spectrometer. The results indicated that the PCB and PCDD/F mean concentrations in sediment samples ranged from 1461 to 2244 and from 240 to 775pgg(-1) dry wt basis, respectively. The mean concentration of PCBs and PCDD/Fs in fish samples were found to be in the range from 695 to 853pgg(-1) fresh wt for PCB congeners and from 27.7 to 121pgg(-1) lipid for total PCDD/Fs. Moreover, the concentrations of both PCBs and PCDD/Fs were found to be different at different locations along the River Nile. It could be concluded that the contamination of the River Nile is within the permissible limits set by the FDA and the Egyptian Standards for fish and shellfish.     

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.     

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).     

Polychlorinated dibenzo-p-dioxins/furans and polychlorinated biphenyls in fresh fishes from Qiantangjiang River, China

Muscles of two species of fish collected in Qiangtangjiang River were analyzed for polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). Average concentrations of total PCDD/Fs in Crucian carp and White Amur bream were 1.14-7.88 pg g(-1)ww and 1.02-8.18 pg g(-1)ww respectively. Corresponding values for PCBs were 469.36-10972 pg g(-1)ww and 364.79-4948.0 pg g(-1)ww. Average total WHO-TEQ of Crucian carp and White Amur bream from five areas ranged from 0.25 to 2.33 pg g(-1)ww and 0.30 to 1.70 pg g(-1)ww. The contamination level was compared with other studies and risk assessment was discussed.     

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.     

Distribution characteristics and source analysis of dioxins in sediments and mussels from Qingdao coastal sea

Seven of surface sediments, one sediment core and two mussel samples were collected from the Qingdao coastal sea of the western Yellow Sea and analyzed to determine the horizontal distribution, deposition flux, and toxicity equivalency (TEQs) of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The total PCDD/Fs concentrations in the surface sediments ranged between 10.7 and 428 ng kg(-1) dry wt. The horizontal distribution of PCDD/F congeners in the sediments was characterized by elevated concentrations at the locations in the east of Jiaozhou Bay with the highest concentration occurring near the Haibo River mouth. Physical parameters (total organic carbon contents and sediment types) and the current circulation systems in Jiaozhou Bay can be important factors controlling the horizontal distribution pattern of PCDD/Fs in the bay. The influence of the Haibo River as a source of pollution was evidenced by PCDD/F homologue profiles, indicating a contribution from sewage sludge in addition to other possible sources. Records from the sediment core revealed that the total PCDD/Fs in the Qingdao coastal sea were nearly constant since 1951 till 1980s and increased remarkably after 1980s. The total 2,3,7,8-substituted PCDD/Fs and total TEQs of PCDD/Fs on the lipid basis in the mussel sample inside the bay were significantly higher than in the adjacent sediment. The homologue profiles of PCDD/Fs in the mussels were quite different from those of the sediments, characterized by high TCDF (50% of the total PCDD/Fs).     

Identifying source regions for the atmospheric input of PCDD/Fs to the Baltic Sea

PCDD/F contamination of the Baltic Sea has resulted in the European Union imposing restrictions on the marketing of several fish species. Atmospheric deposition is the major source of PCDD/Fs to the Baltic Sea, and hence there is a need to identify the source regions of the PCDD/Fs in ambient air over the Baltic Sea. A novel monitoring strategy was employed to address this question. During the winter of 2006–2007 air samples were collected in Aspvreten (southern Sweden) and Pallas (northern Finland). Short sampling times (24 h) were employed and only samples with stable air mass back trajectories were selected for analysis of the 2,3,7,8-substituted PCDD/F congeners. The range in the PCDD/F concentrations from 40 samples collected at Aspvreten was a factor of almost 50 (range 0.6–29 fg TEQ/m³). When the samples were grouped according to air mass origin into seven compass sectors, the variability was much lower (typically less than a factor of 3). This indicates that air mass origin was the primary source of the variability. The contribution of each sector to the PCDD/F contamination over the Baltic Sea during the winter half year of 2006/2007 was calculated from the average PCDD/F concentration for each sector and the frequency with which the air over the Baltic Sea came from that sector. Air masses originating from the south–southwest, south–southeast and east segments contributed 65% of the PCDDs and 75% of the PCDFs. Strong correlations were obtained between the concentrations of most of the PCDD/F congeners and the concentration of soot. These correlations can be used to predict the PCDD/F concentrations during the winter half year from inexpensive soot measurements.     

Study of PCDD/Fs distribution in fly ash,ash deposits,and bottom ash from a medical waste incinerator in China

Over the past decades in China, the number of medical waste incinerators (MWIs) has been rising rapidly, causing emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). In this study, samples of fly ash, ash deposits, and bottom ash from typical MWIs were analyzed for PCDD/Fs and their distribution characteristics. Results showed international toxic equivalent (I-TEQ) values in the range of 6.9–67 ng I-TEQ/g in fly ash and ash deposits, whereas the concentration in bottom ash was extremely low (only 1.33 pg I-TEQ/g), yet the generation of PCDD/Fs was mostly de novo synthesis in fly ash and ash deposits according to the ratio of PCDFs to PCDDs; the major distribution differences of PCDD/Fs in fly ash was manifested by the content of toxic furan 2,3,7,8-TCDF, but other toxic PCDD/Fs showed similar distribution. Other findings are that 2,3,4,7,8-PeCDF had the most contribution to TEQ concentration, and that the most abundant toxic furan congener is 1,2,3,4,6,7,8-HpCDF. Correlation analysis showed that there was no significant correlation between PCDD/Fs concentration and several other physical and chemical parameters.

Implications: This paper is of interest because it presents the emission performances of PCDD/Fs in ash from medical waste incineration in China. PCDD/F contents in fly ash and ash deposits vary between 6.9 and 67.3 ng I-TEQ/g. However, the concentration in bottom ash was extremely low (only 1.33?×?10^?3 ng I-TEQ/g). The fingerprints of PCDD/Fs in fly ash are almost similar, except for 2,3,7,8-TCDF. There is no marked correlation between PCDD/Fs and other physicochemical properties.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.     

Analysis of polychlorinated dibenzo-p-dioxins and furans in various aqueous samples in Taiwan

Twenty-one fresh water samples were taken from reservoirs, wells and drinking water treatment plants in Taiwan for measurement of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) concentrations. Due to low concentration of PCDD/Fs, water samples (400-1000 L) were collected by using the on-site large volume pre-concentration system and analyzed by high resolution gas chromatography (HRGC)/high resolution mass spectrometer (HRMS). Different characteristics of dioxin profiles in surface water and groundwater are observed. The PCDD/F concentrations in fresh water samples varied from 0.001 to 0.265 pg WHO₉₈-TEQ/L which are lower than the standard (12 pg WHO₉₈-TEQ/L) set by the Taiwan Environmental Protection Administration (TEPA) for drinking water. Only a small fraction (<5%) of the total PCDD/F concentration in fresh water samples was water-soluble. As a result of their hydrophobicity, PCDD/Fs are effectively removed along with suspended solid via the water treatment process (average 98% removal efficiency).     

PCDDs and PCDFs in sewage sludges from two wastewater treatment plants in Beijing, China

The levels of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were analyzed by an isotope-dilution high-resolution mass spectrometric in 16 sewage sludges, sampled from 2004 to 2009, from two municipal wastewater treatment plants (WWTPs) in Beijing. Total toxicity equivalent (TEQ) values were evaluated using the toxicity equivalent factors proposed by International for PCDD/Fs. The I-TEQs for these sewage sludges were from 0.97 to 15.0 pg g⁻¹ dry weight (dw) with a mean value 4.43 pg g⁻¹ dw, indicating that all I-TEQs were below Chinese legislation limit value regulated for agricultural use in soils.The results from limited samples (16 samples) showed that the levels of PCDD/Fs might be correlated with the sludge age. Meanwhile, the temporal trends of PCD/Fs suggested that the I-TEQs may correlate with rainfall in the present study.     

Influence of a municipal solid waste incinerator on ambient air and soil PCDD/Fs levels

To examine the influence of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) emissions from a municipal solid waste incinerator (MSWI) on the environment, we measured the levels of PCDD/Fs in ambient air and soil samples collected near a MSWI in Bucheon, Korea. The PCDD/Fs concentrations in the ambient air samples ranged from 0.22 to 1.16 pg I-TEQm(-3) (13.39-75.16 pg m(-3)), with an average of 0.66 pg I-TEQ m(-3) (35.62 pg m(-3)). The soil samples contained between 1.25 and 74.98 pg I-TEQ g(-1) (38.15-3,303.33 pg g(-1)), with an average of 19.06 pg I-TEQ g(-1) (1,077.11 pg g(-1)). These levels were higher than those previously reported by other investigators in a number of surveys. The furan homologues predominated in the air samples and some soil samples, and the soil PCDD/Fs levels decreased with increasing distance from the MSWI. Comparison of the homologue patterns and a multivariate statistical analysis showed that PCDD/Fs emission from the MSWI directly affected the pattern of PCDD/Fs in air, while the PCDD/Fs patterns in soil differed according to the location relative to the MSWI, roads, and construction sites. These results collectively indicate that the MSWI was the major PCDD/Fs emission source in this area, but that unidentified combustion sources and vehicles might influence the environment to some extent.     

Survey of PCDD/Fs and non-ortho PCBs in UK sewage sludges

A survey of PCDD/F and non-ortho PCB concentrations in the mesophilic, anaerobically digested sludge of 14 UK wastewater treatment works was carried out. The range of total Cl1-Cl8DD/F concentrations in the sludges was 8880-428000 pg/g dw with a median of 23300 pg/g dw. The concentrations of the three non-ortho PCBs were in the range 272-63000 pg/g dw with a median of 695 pg/g dw. The PCDD/F I-TEQs of the sludges studied were comparable to those published in the literature with a range of 20-225 pg I-TEQ/g dw and a median of 40.4 pg/g dw. The non-ortho PCBs usually added 2-7 pg/g to the total TEQ with one notable exception which increased the TEQ value 20-fold. With three exceptions, the PCDD/F content of the sludges fell well below the draft EU limit values proposed on 27 April 2000. The homologue group pattern of the PCDD/Fs is dominated by the HpCDDs and OCDD and is consistent with that found in most sewage sludges. There appears to be no correlation between the degree of industrial input and the PCDD/F concentration. This suggests that trade effluent is not always the most significant source of PCDD/Fs to wastewater in the UK.