Levels and characteristic homologue patterns of polychlorinated dibenzo-p-dioxins and dibenzofurans in various incinerator emissions and in air collected near an incinerator

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were monitored in stack gas and fly ash of various Korean incinerators and in air samples collected near the facilities. Concentrations of PCDD/Fs in emissions were investigated, and characteristic PCDD/F homologue patterns were classified using statistical analyses. The PCDD/F emission levels in stack gas and fly ash samples from small incinerators (SIs) were higher than those from municipal solid waste incinerators (MSWIs). The PCDD/F concentrations ranged between 0.38 and 1.16 pg I-TEQ/m3 (21.2-75.2 pg/m3) in ambient air samples. The lower-chlorinated furans were the dominant components in most of the stack gas and fly ash samples from SIs, although this was not the case for fly ash from MSWIs. This homologue pattern is consistent with other studies reporting a high fraction of lower-chlorinated furans in most environmental samples affected by incinerator emissions, and it can be used as an indicator to assess the impact of such facilities on the surrounding environment.     

Partitioning and removal of dioxin-like congeners in flue gases treated with activated carbon adsorption

Activated carbon adsorption is commonly used to control dioxin-like congener (PCDD/Fs and PCBs) emissions. Partitioning of PCDD/Fs and PCBs between vapor and solid phases and their removal efficiencies achieved with existing air pollution control devices (APCDs) at a large-scale municipal waste incinerator (MWI) and an industrial waste incinerator (IWI) are evaluated via intensive stack sampling and analysis. Those two facilities investigated are equipped with activated carbon injection (ACI) with bag filter (BF) and fixed activated carbon bed (FACB) as major PCDD/F control devices, respectively. Average PCDD/F and PCB concentrations of stack gas with ACI+BF as APCDs are 0.031 and 0.006ng-TEQ/Nm(3), and that achieved with FACB are 1.74 and 0.19ng-TEQ/Nm(3) in MWI and IWI, respectively. The results show that FACB could reduce vapor-phase PCDD/Fs and PCBs concentrations in flue gas, while the ACI+BF can effectively adsorb the vapor-phase dioxin-like congener and collect the solid-phase PCDD/Fs and PCBs in the meantime. Additionally, the results of the pilot-scale adsorption system (PAS) experimentation indicate that each gram activated carbon adsorbs 105-115ng-PCDD/Fs and each surface area (m(2)) of activated carbon adsorbs 10-25ng-PCDD/Fs. Based on the results of PAS experimentation, this study confirms that the surface area of mesopore+macropore (20-200A) of the activated carbon is a critical factor affecting PCDD/F adsorption capacity.     

Baseline soil levels of PCDD/Fs established prior to the construction of municipal solid waste incinerators in China

In order to determine the baseline contamination by polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in different areas in China, prior to the construction of municipal solid waste incinerators (MSWIs), a total of 32 representative soil samples was collected near 16 incinerators and analyzed for their PCDD/F concentrations. The PCDD/F baseline concentrations in the soil samples ranged from 0.32 to 11.4 ng I-TEQ kg⁻¹ (dry matter), with average and median value of 2.73 and 2.24 ng I-TEQ kg⁻¹ (dry matter), respectively, and a span between maximum and minimum recorded value of 36. The PCDD homologues predominated in 26 out of 32 soil samples, with the ratio (PCDDs)/(PCDFs) ranging from 1.1 to 164; however in the other 6 samples, PCDF homologues were larger, with the same ratio varying from 0.04 to 0.8. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were used to examine PCDD/F amount and profile in these soil samples, and their possible associations with known emission sources: in this process 6 really distinct isomer fingerprints were identified. Background PCDD/F levels and profiles were comparable to those found in soils from China and other countries and indicate a rather low baseline PCDD/F contamination of soils. The present data provide the tools for future assessment of a possible impact of these MSWIs.     

Congener-specific approach to human PCB concentrations by serum analysis

The objective of this study was to evaluate all congeners of polychlorinated biphenyls (PCBs) in human serum samples. Concentrations of all PCB congeners in the serum of 87 volunteers were determined by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). The participants consisted of 47 males and 40 females, including 25 men working at municipal solid waste incinerators (MSWIs). The mean concentrations of total PCBs and dioxin-like PCBs were 242.77ng/g lipid (median: 180.17ng/g lipid) and 18.57ng/g lipid (median: 15.34ng/g lipid), respectively. Penta-, hexa-, and heptachlorinated biphenyls contributed more than 80% of the total PCBs detected in human serum. Congener-specific analysis indicated that PCB153, PCB138, PCB180, PCB187, and PCB118 contributed 57.3% of the total PCBs detected in human serum samples. A statistical analysis was performed to determine whether there were significant correlations between PCB concentrations and specific variables such as age, gender, smoking habits, occupation, and body mass index (BMI). However, serum PCB concentrations correlated only with age. In addition, we found that total PCBs and dioxin-like PCBs highly correlated with PCB153 (correlation coefficient r=0.93, p<0.01) and PCB118 (correlation coefficient r=0.98, p<0.01), respectively. Thus these two congeners could be satisfactory indicators for total PCBs and dioxin-like PCBs in human serum.     

Air and soil dioxin levels at three sites in Italy in proximity to MSW incineration plants

Levels of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in both air and soil samples were measured at three different sites in Italy, in proximity to three municipal solid waste incinerators (MSWIs) to determine baseline contamination and the contributory role of incinerator emissions. At the first site, located in an agricultural, cattle-breeding, typically flattish area of the Po Valley, the dioxin concentrations had already been measured before the start-up of the new MSWI. These dioxin concentrations were then again measured after two years of continual operation of the incinerator. Despite the presence of the plant, the PCDD/Fs concentrations appear not to have been affected and were found to be in a range of 22-125 fg I-TEQ m(-3) in the air samples and 0.7-1.5 pg I-TEQ g(-1) in the soil samples. The second site is located in an industrial district of the Veneto Region, in the surroundings of an old MSWI that is not equipped with Best Available Technology (BAT) dioxin removal system. The PCDD/Fs concentrations in the air samples were between 144 and 337 fg I-TEQ m(-3). This is a typical range of values for industrial areas, while the soil samples showed contamination levels between 1.1 and 1.4 pg I-TEQ g(-1). The third site lies in the Adige Valley, near a MSWI that has been equipped with BAT for flue gas cleaning. The observed values ranged from 10 to 67 fg I-TEQ m(-3) for the air samples and 0.08-1.2 pg I-TEQ g(-1) for the soil samples. The contributory factors of the varying characteristics of the different areas together with the types of technology adopted at each MSWI plant are discussed. The PCDD/Fs levels are subsequently compared with established values from previous studies.     

The influence of soil contamination on the concentrations of PCBs in milk in Siberia

Although atmospheric deposition is generally the dominant pathway of PCBs into agricultural food chains, soil ingestion by livestock can be important in some cases. The relationship between PCB levels in cow's milk and in pasture soil was studied in the Irkutsk region in Siberia where an historical atmospheric source(s) of PCBs has led to widespread contamination of soil. Milk samples were collected in spring and again in autumn from 18 different farms and analyzed for PCBs. Pasture soil samples were also collected and analyzed. The PCB concentrations in both milk and soil ranged over more than an order of magnitude between the farms. A good correlation was obtained between PCB levels in autumn milk and in soil. This together with a range of other evidence suggested that ingestion of pasture soil was the dominant source of the PCB contamination in the milk. The average soil ingestion rate was estimated to be 1700 g/d, which is at the upper end of values reported in the literature. This may be due to the arid summer climate or the animal husbandry practices in Siberia.     

Occurrence of polybrominated diphenylethers, polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls in coastal sediments from Spain

Fifteen sediment samples were analysed in order to determine their content of polybrominated diphenylethers (PBDEs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs). Samples were collected from several hot spots on the Spanish coast, such as the harbours of Almeria and Tarragona, and the mouths of the Besos and Llobregat rivers in Barcelona. A generic analytical procedure based on Soxhlet extraction followed by an automated cleanup system and gas chromatography-ion trap-mass spectrometry was employed for determining the toxic congeners of PCDDs and PCDFs, as well as dioxin-like PCBs. As regards PBDE determinations, a rapid method based on the use of selective pressurized liquid extraction followed by gas chromatography-negative ion chemical ionization-mass spectrometry was applied. Total toxicity equivalent (WHO-TEQ) values were calculated using the toxicity equivalent factors proposed by WHO for dioxin-like PCBs, PCDDs and PCDFs. WHO-TEQ values ranged from 0.3 to 75 pg/g dry weight (dw), with PCB contribution on the toxicity of the samples between 1 and 84%. Total PBDE levels ranged from 2.7 to 134 ng/g dw, with BDE-209 contribution on the total PBDE contamination between 50 and 99%.     

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.     

Assessment of PCDD/F risk after implementation of emission reduction at a MSWI

Municipal solid waste incinerators (MSWIs) have been shown to be important sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The emission of PCDD/Fs by MSWIs is a controversial subject in human health risk assessment. In this study the effect of a MSWI on a residential area was assessed before and after the installation of an additional treatment system for flue gas. This additional treatment system resulted in a dramatic decrease in PCDD/F concentrations in stack flue gas samples by 99.98%, while the concentrations in air decreased by approximately 50% (36,500 and 0.75 pg I-TEQ m(-3) for air in 1999; 3.5 and 0.38 pg I-TEQ m(-3) in 2002; 1.6 and 0.076 pg I-TEQ m(-3) in 2005 for stack gas and air, respectively). Considering the congener distributions of PCDD/Fs between stack flue gas and air samples, the study area seemed to have been contaminated by other urban sources as well as the MSWI. ISC3 model results support the conclusion that this incinerator became only a minor contributor to the study area after installation of the supplementary systems. This resulted from both proper MSWI operation using modern technology and additional sources of contaminants in this region. Finally, PCDD/F uptake by humans through inhalation of contaminated air was estimated. Assuming that inhalation exposure contributes 10% of total exposure, total exposure was lower than WHO guidelines. These results confirm that proper operation and maintenance of the incinerator led to a reduction in emissions and potential health impacts of PCDD/Fs.     

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.     

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.     

Evaluation of dioxin-like chemicals in pooled human milk samples collected in Australia

DESIGN: Human milk samples were collected and analysed for the levels of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and selected dioxin-like polychlorinated biphenyls (PCBs). In total, 157 individual samples collected during 2002 and 2003 as well as 24 samples collected in 1993 were analysed as 20 pools. RESULTS: PCDDs, PCDFs and dioxin-like PCBs were detected in all pooled samples. For samples collected during 2002/2003, the TEQ(DFP) ranged from 6.0 to 15.2 pg TEQ g(-1) lipid with an average of 9.0 pg TEQ g(-1) lipid. The average lipid content was 3.7+/-0.5%. No systematic differences were observed in the levels of PCDDs, PCDFs and PCBs in human milk samples collected from different regions of Australia during 2002/2003. For samples collected in 1993 and analysed as pools, the mean level, expressed as TEQ(DFP) was 16+/-1.4 pg TEQ g(-1) lipid. The average lipid content was 3.9+/-0.7%. CONCLUSION: The levels of PCDDs, PCDFs and dioxin-like PCBs in the human milk of Australian women are both low compared to international levels and similar across all regions of Australia. Consistent with world-wide trends, the levels of PCDDs, PCDFs and dioxin-like PCBs have decreased over a 10 year period from 1993 to 2003 by approximately 40%.     

Occurrence of polychlorinated naphthalenes, polychlorinated biphenyls and short-chain chlorinated paraffins in marine sediments from Barcelona (Spain)

Polychlorinated naphthalenes (PCNs), short-chain chlorinated paraffins (SCCPs) and polychlorinated biphenyls (PCBs) were analysed in marine sediment samples collected from the coastal area of Barcelona (Spain) and near of a submarine emissary coming from a waste water treatment plant located at the mouth of the Besòs River (Barcelona). An integrated sample treatment based on Soxhlet extraction followed by a simple clean-up with Florisil and graphitized carbon cartridge was employed. Gas chromatography coupled to ion-trap tandem mass spectrometry (GC-MS/MS) and gas chromatography-mass spectrometry in electron capture negative ionization mode, were used for PCN and SCCP determinations, respectively, while for PCB analysis gas chromatography with electron capture detection (GC-ECD) was used. The method developed provided low limits of detection (0.001-0.003 ng g(-1) dry weight (dw) for PCNs, 1.8 ng g(-1) for SCCPs and 0.006-0.014 ng g(-1)dw for PCBs) and good run-to-run precisions (lower than RSD 8%) for the analysis of sediment samples. Concentration levels ranging from 0.17 to 3.27 ng g(-1)dw for PCNs, between 0.21 and 1.17 microg g(-1)dw for SCCPs, and from 2.33 to 44.00 ng g(-1) (dw) for PCBs, were found in the coastal sediments, while for samples collected near to the submarine emissary higher levels (from 2.02 to 6.56 ng g(-1)dw for PCNs, between 1.25 and 2.09 microg g(-1)dw for SCCPs and from 22.34 to 37.74 ng g(-1)dw for PCBs) were obtained. The results obtained provide new data about the occurrence of PCN and SCCP in the coastal area of Barcelona.     

PCDDs, PCDFs and dioxin-like PCBs in food of animal origin (Slovakia)

The levels of 17 toxic polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and 12 non-ortho and mono-ortho polychlorinated biphenyls (PCBs) in 73 foodstuff samples of animal origin collected from shops and small farms in selected districts of Slovak Republic are presented in this paper. The concentrations expressed as WHO-TEQ in analysed samples ranged for PCDDs/PCDFs from 0.25 pg/g fat in pork to 75 pg/g fat in cod liver. The TEQ concentrations of non-ortho PCBs were between 0.007 and 181 pg/g fat and mono-ortho PCBs between 0.0083 and 66.5 pg/g fat. The mean concentrations in freshwater fish and imported species of marine fish were 0.089 pg TEQ/g fresh weight for PCDDs/PCDFs, 0.17 pg TEQ/g fresh weight for non-ortho PCBs and 0.034 pg TEQ/g fresh weight for mono-ortho PCBs. The mean total concentration of PCDDs/PCDFs and dioxin-like PCBs in samples of infant milk formula imported from EU countries was 0.98 pg TEQ/g fat.     

Monitoring of polychlorinated dibenzo-p-dioxins and dibenzofurans, dioxin-like PCBs and polycyclic aromatic hydrocarbons in food and feed samples from Ismailia city, Egypt

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyl (PCBs) and polycyclic aromatic hydrocarbons (PAHs) have been determined using GC/HRMS in food (butter, seafood and meat) and feed samples (chicken, cattle and fish) purchased from Ismailia city, Egypt. PCDD/F concentrations in food samples ranged between 0.12 and 3.35 pg WHO TEQ/g wet w, while those in feed samples were between 0.08 and 0.2 pg WHO TEQ/g dry w. Levels of PCB TEQ ranged from 0.14 to 3.2 pg/g wet w in the food samples. The feed samples have an average of 0.35 pg PCB TEQ /g dry w. In this study, butter samples showed the highest contamination levels of PCDD/Fs and PCBs. The PCBs contribution to the total TEQ was on average 63% in seafood and on average 49% for meat and butter. The highest contamination levels of PCDD/Fs and PCBs were found in butter samples. The butter TEQ content is several times higher than that reported in all EU countries and exceeded the EU limits, while the PCDD/F levels in seafood and the feed samples is far below the current EU limit. Generally, congener profiles in the food samples reflect the non-industrialized nature of the city and suggest solid waste burning as a significant source of emission. Nevertheless, the profiles for butter suggest an impact from various sources. In the case of the sum of 16 PAH contamination levels in food samples were in the range of 11.7-154.3 ng/g wet w and feed samples had a range of 116-393 ng/g dry w. Benzo(a)pyrene (BaP) has been detected in the range of 0.05-3.29 ng/g wet w in the food samples; butter showed the highest contamination which exceeded the EU standard set for fats and oil. Fingerprints of PAHs suggested both petrogenic and pyrolytic sources of contamination.     

Long-term monitoring and modeling of polychlorinated dibenzo-p-dioxins and dibenzofurans from municipal solid waste incinerators and surrounding area in northern Taiwan

Municipal solid waste incinerators (MSWIs) have long been the major contributors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) to ambient air in Taiwan. After stringent MSWI emission standards were introduced in 2001, the long-term continuous monitoring of flue gas and ambient air quality became necessary to ensure the effectiveness of the related control strategies. Three MSWIs and the surrounding ambient air were investigated in the current study for PCDD/F characteristics during 2006 to 2011. The average concentrations in the flue gas ranged from 0.008?~?0.0488 ng I-TEQ/Nm³, which is much less than the emission standard in Taiwan (0.1 ng I-TEQ/Nm³) (I-TEQ is the abbreviation of International Toxic Equivalent). This led to extremely low levels in the ambient air, 0.0255 pg I-TEQ/Nm³, much less than the levels seen in most urban areas around the world. Additionally, the results obtained using the Industrial Source Complex Short-Term Dispersion Model (ISCST3) indicate that the PCDD/F contributions from the three MSWIs to the ambient air were only in the range from 0.164?~?0.723 %. Principal component analysis (PCA) showed that the PCDD/Fs in the air samples had very similar characteristics to those from mobile sources. The results thus show that stringent regulations have been an effective control strategy, especially for urban areas, such as Taipei City.     

Environmental contamination with polychlorinated biphenyls in the area of their former manufacture in Slovakia

Evidently increased environmental pollution as a consequence of the 25-year manufacture of polychlorinated biphenyls (PCBs) in eastern Slovakia was observed. PCB levels determined in ambient air, soil, surface water, bottom sediment, wildlife (fish and game) samples collected in a potentially contaminated area of about 250 km2 (a part of the Michalovce district) were compared with those determined in a control area (Stropkov district). Up to 1700 ng/m3 were found in ambient air in a village close to a manufacturer's dumping site and a highly contaminated manufacturer's effluent canal whereas PCB concentrations in ambient air samples taken in villages in the control area were about 80 ng/m3 only. While soil samples taken from the agricultural fields of the polluted area contained PCBs at levels comparable with soil samples from the control area (about 0.008 mg/kg) much higher values (from 0.4 to 53,000 mg/kg) were determined in soil taken in the vicinity of manufacturer's landfill and storage sites and especially plants preparing asphalted gravel using formerly PCBs in their heat-exchanging systems. The contamination of the Laborec river and large Zemplinska Sirava reservoir is caused by the manufacturer's effluent canal since PCB levels in the canal sediment are still to be found about 3000 mg/kg. While PCB levels in sediment samples from Michalovce watercourses ranged between 1.7 and 6 mg/kg, sediment samples from the control Stropkov district ranged between 0.007 and 0.052 mg/kg only. Fish living in contaminated Michalovce waters contained about hundred times higher PCB levels than those caught in Stropkov ones. Similarly, game animals shot in Michalovce forests contained several times higher levels than those shot in Stropkov ones.     

Atmospheric deposition of PCDD/Fs near an old municipal solid waste incinerator: levels in soil and vegetation

The levels of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were determined in soil and vegetation samples taken from 24 sites in the vicinity of an old municipal solid waste incinerator (San Adrià del Besòs, Barcelona, Spain). Duplicate samples were collected within a radius of 3 km from the stack. PCDD/F concentrations in soils ranged from 1.22 to 34.28 ng I-TEQ/kg (d.m.) with median and mean values of 9.06 and 12.24 ng I-TEQ/kg, respectively. In turn, the levels of PCDD/Fs in vegetation samples ranged from 0.33 to 1.98 ng I-TEQ/kg (d.m.), with median and mean values of 0.58 and 0.70 ng I-TEQ/kg, respectively. Although the present PCDD/F concentrations in soil samples were higher than those recently found in soils taken near other incinerators from Catalonia, they are of the same order of magnitude than the levels of these pollutants found in incinerators from other countries. By contrast, the concentrations of PCDD/Fs in herbage samples were comparable to those found in recent surveys carried out in Catalonia.     

Spatial distribution of organochlorine contaminants in soil, sediment, and fish in Bikini and Enewetak Atolls of the Marshall Islands, Pacific Ocean

Several nuclear tests were performed at Enewetak and Bikini Atolls in the Marshall Islands between 1946 and 1958. The events at Bikini Atoll involved several ships that were tested for durability during nuclear explosions, and 24 vessels now rest on the bottom of the Bikini lagoon. Nine soil samples were collected from different areas on the two islands of the atoll, and eighteen sediment, nine fish, and one lobster were collected in the vicinity of the sunken ships. Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polychlorinated terphenyls (PCTs) in these samples were analyzed using gas chromatography/ion trap mass spectrometry (GC/ITMS). The average recoveries ranged from 78% to 104% for the different PCB congeners. The limits of detection (LOD) for PCBs, PCTs, DDE, DDT, and dieldrin ranged 10-50 pg g⁻¹. Some fish from Enewetak contained PCBs at a concentration range of 37-137 ng g⁻¹, dry weight (dw), and most of the soils from Enewetak showed evidence of PCBs (22-392 ng g⁻¹ dw). Most of the Bikini lagoon sediment samples contained PCBs, and the highest was the one collected from around the Saratoga, an aircraft carrier (1555 ng g⁻¹ dw). Some of the fish samples, most of the soil samples, and only one of the sediment samples contained 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (DDE) and PCBs. In addition to PCBs, the soils from Enewetak Atoll contained PCTs. PCTs were not detected in the sediment samples from Bikini Atoll. The results suggest local pollution sources of PCBs, PCTs, and OCPs.     

Polychlorinated biphenyls in contaminated soil samples evaluated by GC-ECD with dual-column and GC-HRMS

We present and compare results obtained from the analysis of polychlorinated biphenyls (PCBs) of a limited number of contaminated soil samples collected in three areas of Basilicata region (south of Italy). The levels of PCBs were evaluated by using two analytical methods: (i) parallel dual-column gas-chromatography with dual electron capture detectors (GC-ECD) and (ii) gas-chromatography coupled to high-resolution mass spectrometry (GC-HRMS) via electron impact ionization (EI) in the multiple ion monitoring mode (MIM, two ions per compound). Two extraction methods prior to sample cleanup were also examined: microwave-assisted extraction (MAE) and ultrasonic-assisted extraction (UAE). The MAE was the extraction procedure adopted using acetone/n-hexane (1:1, v/v) as it is mainly characterized by higher sample throughput and allowed reduced consumption of organic solvents. While extraction and analysis of spiked soil samples showed the applicability of both methods, systematic differences between the results were obtained for the sum of PCBs as a result of some non-detected congeners by GC-ECD compared with GC-HRMS. Indeed, high resolution MS using EI mode (electron energy 40eV) with a resolving power of 10,000 provides additional information about the contamination pattern. The GC-ECD screening of 11 soil samples led to just one sample non-compliant to as it was close to the guide value for soils fixed by the Italian legislation (i.e., 60ppb for private or urban soil). Using GC-HRMS, the amount of all PCBs found ranged from 5.4 to 127ppb with five soil samples non-compliant to the guide value. The number of identified congeners ranged from 1 to 9 and 9 to 18 using dual-column GC-ECD and GC-HRMS, respectively.