Metal-mediated chlorinated dibenzo-p-dioxin (CDD) and dibenzofuran (CDF) formation from phenols

Heterogeneous formation of chlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs) on CuCl2 from three phenols without ortho chlorine and one phenol with two ortho chlorines was studied in a flow reactor over a temperature range of 325-450 degrees C. Heated nitrogen gas streams containing 8% oxygen, 1.5% benzene vapor, and equal amounts of phenol, 3-chlorophenol, 3,4-dichlorophenol and 2,4,6-trichlorophenol vapor (700 ppmv, each) were passed through a 1 g particle bed of silica and 0.5% (Cu mass) CuCl2. Maximum product yields of greater than 1.4% phenol conversion to CDD and 5.7% phenol conversion to CDF were observed between 400 and 450 degrees C. CDDs formed with loss of one chlorine atom were favored. While total CDD/F yield varied with temperature, CDD/F homologue and isomer distributions did not vary significantly with temperature. Based on the results of experiments with single phenol precursors, phenol precursors could be assigned to all PCDD/F products. Of the chlorinated phenols without ortho chlorine that were studied, 3,4-dichlorophenol was found to have the greatest propensity to form CDFs.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran in urban air of an Andean city

Particle-bound polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in ambient air were monitored together with particulate matter less than 10 μm (PM₁₀) at three sampling sites of the Andean city of Manizales, Colombia; during September 2009 and July 2010. PCDD/Fs ambient air emissions ranged from 1 fg WHO-TEQ m⁻³ to 52 fg WHO-TEQ m⁻³ in particulate fraction. The PM₁₀ concentrations ranged from 23 μg m⁻³ to 54 μg m⁻³. Concentrations of PM₁₀ and PCDD/Fs in ambient air observed for Manizales - a medium sized city with a population of 380 000 - were comparable to concentrations in larger cities. The highest concentrations of PCDD/Fs and PM₁₀ found in this study were determined at the central zone of the city, characterized by public transportation density, where diesel as principal fuel is used. In addition, hypothetical gas fractions of PCDD/Fs were calculated from theoretical K_p data. Congener profiles of PCDD/Fs exhibited ratios associated with different combustion sources at the different sampling locations, ranging from steel recycling to gasoline and diesel engines. Taking into account particle and gas hypothetical fraction of PCDD/Fs, Manizales exhibited values of PCDD/Fs equivalent to rural and urban-industrial sites in the southeast and center of the city respectively. Poor correlation of PCDDs with PM₁₀ (r = −0.55 and r = 0.52) suggests ambient air PCDDs were derived from various combustion sources. Stronger correlation was observed of PCDFs with PM₁₀. Poor correlation between precipitation and reduced PM₁₀ concentration in ambient air (r = −0.45) suggested low PM₁₀ removal by rainfall.     

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

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

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

Fast extraction of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran in sewage sludge and soil samples

The current environmental legislations recommend monitoring chemical contaminants such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans before the use of sewage sludge on the agricultural land. In this study, a solid–liquid extraction with low-temperature purification (SLE-LTP) was optimized and validated to determine 2,3,7,8-tetrachlorodibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzofuran in sewage sludge and soil samples. The analyses were performed by gas chromatography-mass spectrometry operating in the selective ion mode (GC-MS-SIM). Acetonitrile:ethyl acetate 6.5:1.5 (v/v) was the best extraction phase, and the recoveries percentages were close to 100%. The linearity was demonstrated in the range of 1.25–25 µg L^?1 of 1.25–20 µg L^?1 for sewage sludge and soil, respectively. Matrix effect was proved for the two compounds and in the two matrices studied. Extraction percentages were between 78 and 109% and relative standard deviations ≤ 19%. The proposed method is faster than methods described in the literature because showed a few steps. The quantification limits (LOQ) in sewage sludge were 6.4 and 32 ng TEQ kg^?1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. In soil, LOQs were 0.8 and 8.0 ng TEQ kg^?1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. These values are lower than the maximum residue limits established by European Legislation. The method was applied to 22 agricultural soil samples from different Brazilian cities and 2,3,7,8-TCDF was detected in one of these samples.     

Polychlorinated dibenzofuran (PCDF) and dibenzo-p-dioxin (PCDD) levels in organisms and sediments from the frierfjord, southern Norway

The contamination of a fjord region by PCDD and PCDF produced from a Mg-production plant has been studied. Levels in organisms (fish, crustacea, mussels) and sediments were determined. The results allowed an estimate of the spreading of PCDD/PCDF by coastal currents. The present situation is compared with available information from other contaminated areas and with data for other contaminants in the recipient area such as hexachlorobenzene and octachlorostyrene.     

Kinetics of OH radical reactions with dibenzo-p-dioxin and selected chlorinated dibenzo-p-dioxins

The pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique has been applied to obtain rate coefficients for OH + dioxin (DD) (k1), OH + 2-chlorodibenzo-p-dioxin (2-CDD) (k2), OH + 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD) (k3), OH + 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) (k4), OH + 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) (k5), OH + 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) (k6), and OH + octachlorodibenzo-p-dioxin (OCDD) (k7) over an extended range of temperature. The atmospheric pressure (740 +/- 10 Torr) rate measurements are characterized by the following Arrhenius parameters (in units of cm3 molecule(-1) s(-1), error limits are 1 omega): k1(326-907 K) = (1.70+/-0.22) x 10(-12)exp(979+/-55)/T, k2(346-905 K) = (2.79+/-0.27) x 10(-12)exp(784+/-54)/T, k3(400-927 K) = 10(-12)exp(742+/-67)/T, k4(390-769 K) = (1.10+/-0.10) x 10(-12)exp(569+/-53)/T, k5(379-931 K) = (1.02+/-0.10) x 10(-12)exp(580+/-68)/T, k6(409-936 K) = (1.66+/-0.38) x 10(-12)exp(713+/-114)/T, k7(514-928 K) = (3.18+/-0.54) x 10(-12)exp(-667+/-115)/T. The overall uncertainty in the measurements, taking into account systematic errors dominated by uncertainty in the substrate reactor concentration, range from a factor of 2 for DD, 2-CDD, 2,3-DCDD, 2,7-DCDD, and 2,8-DCDD to +/- a factor of 4 for 1,2,3,4-TCDD and OCDD. Negative activation energies characteristic of an OH addition mechanism were observed for k1-k6. k7 exhibited a positive activation energy. Cl substitution was found to reduce OH reactivity, as observed in prior studies at lower temperatures. At elevated temperatures (500 K < T < 500 K), there was no experimental evidence for a change in reaction mechanism from OH addition to H abstraction. Theoretical calculations suggest that H abstraction will dominate OH reactivity for most if not all dioxins (excluding OCDD) at combustion temperatures (>1000 K). For OCDD, the dominant reaction mechanism at all temperatures is OH addition followed by Cl elimination.     

The effect of metal catalysts on the formation of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran precursors

The catalytic effects of copper and iron compounds were examined for their behavior in promoting formation of chlorine (Cl₂), the major chlorinating agent of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), in an environment simulating that of municipal waste fly ash. Formation of Cl₂ occurred as a result of a metal-catalyzed reaction of HCl with O₂. Catalytic activity was greatest at a temperature of approximately 400 °C, supporting a theory of de novo synthesis of PCDDs and PCDFs on fly ash particles downstream of waste combustion.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran concentrations in common fish species in the Pearl River Delta area, China

Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) concentrations in 31 fish samples from 19 commonly consumed freshwater and saltwater species from the Pearl River Delta Area were analyzed. The PCDD/Fs dietary intake from fish for the local population was evaluated to provide a database for setting the national PCDD/F limits in fish for the People's Republic of China. The median concentration from the 31 fish samples was 1.27 pg/g wet weight for the total of PCDD/Fs, and the median WHO-TEQ was 0.26 pg/g wet weight, and ranged from 0.063 to 1.30 pg WHO-TEQ/g wet weight. The dominant contributors to the WHO-TEQ were 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF, which accounted for 38% and 28%, respectively. The dietary intake of PCDD/Fs from fish for local people was estimated to be 0.47 pg WHO-TEQ/kg bw x day. In view of the findings, the dietary of PCDD/Fs from other foods of animal origins in China should be studied in more detail as soon as possible in order that standards can be put forward to protect human health.     

Assessment of polychlorinated dibenzo-p-dioxin and dibenzofuran emissions from a hazardous waste incineration plant using long-term sampling equipment

The aim of this work is to evaluate the performance of a continuous monitoring system for the analysis of the mass concentration of PCDD/Fs from stationary sources. Data was acquired from a modern, state of the art, hazardous waste thermal treatment plant for a period of more than 2 years using a commercial available continuous monitoring system. The study consisted of a total of 16 samples, collected in periods from 1 week to 2 months resulting in an average of 360 m³ sampled flue gas per sample. The study showed the system was able to confirm that for a period of more than 2 years the plant was complying with the limit of 0.1 ng I-TEQ/Nm³. In addition, the data showed the typical fingerprint of such installations which is useful for example in impact studies. Long-term samples were compared to five short-term samples (6 h) collected every 6 months during the study period. Principal component analysis was applied to PCDD/Fs obtained data as useful statistical tool to find out trends and similarities between different samples. Improvement in terms of representativeness of data was achieved through continuous assessment since the starts of the project. The obtained data was further used to determine the emission factor for this activity and the total annual PCDD/Fs release to the atmosphere.     

Effects of burnings of wax apple stubble and rice straw on polychlorinated dibenzo-p-dioxin and dibenzofuran concentrations in air and soil

Measurements of the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were made in ambient air, ash, and soil impacted by the open burning of wax apple and rice straw residues. Measurements showed that the mean PCDD/F concentration (0.458 pg I-TEQ/Nm3; international toxicity equivalence) in air at two wax apple orchards during open burning increased markedly, -8.1 times higher than that (0.057 pg I-TEQ/Nm3); before open burning. In addition, the mean PCDD/F concentration (0.409 pg I-TEQ/Nm3) in ambient air at a rice straw field was 4.6 times higher than that (0.089 pg I-TEQ/Nm3) before open burning. After burning the residues of wax apple stubble and rice straw, the contents of PCDD/F in ashes were 1.393 and 1.568 ng I-TEQ/kg-ash, respectively, and the contents of PCDD/F in soil were 2.258 and 2.890 ng I-TEQ/kg-soil, respectively. Therefore, the turnover of soil with the ash after open burning over years will result in the accumulation of PCDD/Fs in farm soils.     

Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) isomer patterns from municipal waste combustion: formation mechanism fingerprints

Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) byproducts can be formed in combustion systems by a variety of mechanisms. While total PCDD/F emissions and, to a lesser extent, homologue distributions from incinerators have been found to vary widely depending on combustion conditions, PCDD/F isomer distributions do not. Formation mechanisms can be grouped into two general categories: condensation of precursors, such as chlorinated phenols, and formation from particulate carbon, termed de novo synthesis. In addition to these mechanisms, chlorination and dechlorination reactions may affect isomer patterns. In this work, isomer patterns from field and laboratory municipal waste combustion samples are compared with computed thermodynamic distributions and those from the following experimental investigations: both gas-phase and metal-catalyzed condensation of chlorinated phenols, chlorination of dibenzo-p-dioxin and dibenzofuran, and dechlorination of octachlorodibenzo-p-dioxin and octachlorodibenzofuran. PCDD/F isomer patterns produced by different formation mechanisms in controlled experiments are distinct and robust, largely unaffected by combustion conditions. PCDD isomer patterns from municipal waste combustion are most similar to those produced by CuCl(2)-catalyzed phenol condensation from 10 chlorinated phenols. PCDF isomer patterns are most similar to those produced by chlorination and dechlorination.     

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.     

Inclusion of 13C12-labelled mono-, di-, and tri-chlorinated dibenzo-p-dioxin and dibenzofuran standards in US EPA methods 0023A/8290

13C12-Labelled mono-, di-, and tri-chlorinated dibenzo-p-dioxin (CDD) and chlorinated dibenzofuran (CDF) standards have been tested for their applicability to standard EPA sampling and analytical Methods 0023A/8290. These methods target for analysis only the tetra- through octa-CDD/CDF homologues. Extension of the isotope dilution method to include those lower chlorinated homologues is important toward obtaining reliable species concentration data on the complete, mono- to octa-chlorinated homologue profile. These data will improve our ability to model poly-CDD/CDF concentrations through understanding mechanisms of poly-CDD/CDF formation, chlorination, and dechlorination.     

Thermodynamic considerations in dibenzodioxin and dibenzofuran formation: Concentrations of chlorinated dioxins and furans in model fuel-rich combustion gases

A database for chlorinated dioxins (DBDs), with heats of formation derived by analogy with chlorination of quinone and benzene, has already been shown to predict relative isomer distributions nearer to those observed, and those predicted using MOPAC, than an earlier database due to Shaub. The model has been extended to obtain a similar database for chlorinated dibenzofurans (DBF's), and comparisons with observed isomer concentration distributions are illustrated. Calculations are carried out using the NPL MTDATA suite of programs. Isomer group values for the properties of the original compounds and each degree of chlorination have been derived, and the use of these values leads to a reduction in the data obtained in computations to more manageable proportions. The reduced database obtained is combined with other databases to carry out computer predictions for simulated chlorine-containing combustion gases. Data for inorganics substances and the simplest organic substances (methane. ethane and related species) are obtained from the SGTE database. More extensive data for aliphatic and aromatic hydrocarbons from various standard sources have been incorporated in an additional computational database. In order to examine the relative concentrations of DBFs and DBDs a database for chlorinated hydrocarbons has been established. Predictions for simulated fuel rich combustion products for the C, H, O, Cl system are presented.     

The impact of production type and region on polychlorinated biphenyl (PCB), polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) concentrations in Canadian chicken egg yolks

Chicken eggs from five different production types (conventional, omega-3 enriched, free range, organic and free run) were collected, when available, from three regions (west, central and east) of Canada to determine persistent organic pollutant (POP) concentrations. Total polychlorinated biphenyl (PCB) concentrations (∑37 congeners) in yolks from the eggs ranged from 0.162 ng g⁻¹ lipid to 24.8 ng g⁻¹ lipid (median 1.25 ng g⁻¹ lipid) while the concentration of the sum of the 6 indicator PCBs ranged from 0.100 ng g⁻¹ lipid to 9.33 ng g⁻¹ lipid (median 0.495 ng g⁻¹ lipid). Total polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F) concentrations ranged from 2.37 pg g⁻¹ lipid to 382 pg g⁻¹ lipid (median 9.53 pg g⁻¹ lipid). The 2005 WHO toxic equivalency (TEQ) ranged from 0.089 pg TEQ_{PCDD/F+dioxin-like[DL]-PCB} g⁻¹ lipid to 12.8 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid (median 0.342 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid). PCB and PCDD/F concentrations were significantly different (p < 0.001) in egg yolks from different regions of collection. In contrast to observations in Europe, PCB and PCDD/F concentrations in Canadian egg yolks were not impacted solely by the production type (e.g., conventional, free range, organic, etc.) used to maintain the laying chickens. Additionally, only one Canadian free range yolk from western Canada (12.8 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid) exceeded the European toxic equivalent concentration limits for eggs (5 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid). This differs from observations in Europe where free range/home produced eggs frequently have higher POP concentrations than eggs from other production types. Median PCB dietary intake estimates based on consumption of eggs were less than 10 ng d⁻¹ while median PCDD/F intakes were less than 45 pg d⁻¹.     

Comparison of instrumental methods for chlorinated dibenzo-p-dioxin (CDD) determination - interim results of a round-robin study involving GC-MS, MS-MS, and high resolution MS

A study was designed to determine the feasibility of using GC-MS-MS techniques for the determination of chlorinated dibenzo-p-dioxins (CDD) and dibenzofurans (CDF) in difficult environmental samples with reduced cleanup. Three fish and three sediment extracts were provided to six different laboratories with GC-MS-MS capability for analysis. In addition, extracts were analysed by GC-low reduction MS (LRMS) and GC-high resolution MS (HRMS). At the time of this report, all participating GC-MS-MS laboratories had not completed their analysis of the supplied samples. All reporting laboratories found the analysis of these very complex samples difficult without extensive cleanup. GC-HRMS determination of some samples was possible with reduced cleanup compared to GC-LRMS.     

An occupational exposure assessment of polychlorinated dibenzo-p-dioxin and dibenzofurans in firefighters

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are unintentional byproducts of combustion and industrial processes. Firefighters face the risk of occupational exposure to PCDD/Fs. Congener-specific analyses of 17 PCDD/Fs were performed on 20 serum samples collected from firefighters and fire scene investigators, and four soot samples that had deposited on the surfaces of the fire helmets and were collected after the firefighters had fought fires. The PCDD/F concentrations on the helmets that were contaminated by being worn at the fire scenes were 63-285 times higher than those on a clean helmet. The median serum PCDD/F concentration of the 16 firefighters (12 pg WHO₂₀₀₅-TEQ g⁻¹ lipid) was not different from those of the males from the general Taiwanese population (9.4 pg WHO₂₀₀₅-TEQ g⁻¹ lipid). However, the median PCDD/F level in the four fire scene investigators (15 pg WHO₂₀₀₅-TEQ g⁻¹ lipid) was higher than those in the male from the general Taiwanese population (Mann-Whitney U test, p < 0.01). Furthermore, the serum samples from the firefighters and fire scene investigators, and the soot samples from the fire scenes presented similarly distinctive PCDD/F profiles that had elevated proportions for 10 PCDF congeners. Limited data indicated that the fire scene investigators were occupationally exposed to PCDD/Fs at the fire scenes. We suggested that the firefighters were not occupationally exposed to PCDD/Fs at the fire scenes due to appropriate protection. However, the fire scene investigators may have had more occupational exposure to PCDD/Fs due to poor protection, and further research must be performed to confirm this.     

Temporal changes in some chlorinated hydrocarbon residue levels of Canadian breast milk and infant exposure

Between 1967 and 1986, five national surveys were carried out to determine organochlorine residues in Canadian breast milk. In these surveys the number of samples, their geographic sampling distribution and fat content changed over the years. In addition, the number of samples obtained from younger mothers decreased, while those from older mothers (31-40 years) increased. Total DDTs showed the most consistent decline of all declining residues, while PCBs only decreased after 1982. Levels of oxychlordane and trans-nonachlor remained constant. Ratios of p,p'-DDE/p,p'-DDT gradually increased from 3.1 to 10.0 over the same period of time. With few exceptions, regional trends in residue levels followed those observed for the whole country. Although the number of reported chemicals increased since 1967, this was not necessarily reflected in the total accumulated residues in breast milk. By 1986, the daily intakes of all compounds at 8 weeks of nursing were well below the established acceptable daily intakes.     

Trends in the levels of some chlorinated hydrocarbon residues in adipose tissue of Canadians

Trends in the levels of hexachlorobenzene, hexachlorocyclohexanes, oxychlordane, t-nonachlor, heptachlor epoxide, dieldrin, DDTs and polychlorinated biphenyls in adipose tissue of the Canadian population were followed from 1969 to 1985. Residues of lindane, dieldrin and p,p'-DDT continuously and significantly (P<0.025) decreased during that time, coinciding with restrictions on their use. Other residues also decreased significantly between 1969 and 1985, although not always continuously, while t-nonachlor levels did not change significantly since 1972. In general no consistent and/or significant differences were observed between the sexes, but in some instances differences were found for a particular residue in a given year. Three arbitrarily chosen age groups (0-25; 26-50 and > or =51 years) showed a downward trend in residue levels with time. The results of the surveys also indicate an increase in adipose tissue burden of chlorinated hydrocarbons with age, but this increase became apparently less significant with increasing age.     

Incidence of chlorinated benzenes and chlorinated ethylenes in Lake Ontario Herring Gulls

Great Lakes Herring Gulls (Larus argentatus) and their eggs have proven to be useful integrators on a lakewide basis of high molecular weight, relatively involatile organochlorine pollutants such as PCRs. A search for relatively volatile organochlorine compounds by GC/MS also revealed the presence of tri- and tetrachloroethylene, and isomers of di-, tri-, tetra-, penta- and hexachlorobenzene in the body lipid of adult Herring Gulls from Lake Ontario. Analysis of pooled eggs from colonies throughout the Great Lakes in 1978 showed that pentachlorobenzene and hexachlorobenzene were ubiquitous contaminants at levels from 14–50 ng/kg and 90–350 ng/kg, respectively. Hexachlorobenzene levels were 2–3 times higher in Lake Ontario than the other lakes, whereas pentachlorobenzene was more evenly distributed geographically. Levels of 1,2,3,4-tetra-, 1,2,4,5-tetra- and 1,2,4-trichlorobenzene near the detection limit of 10–20 ng/kg were found in a few samples.