Long-range atmospheric transport of three toxaphene congeners across Europe. Modeling by chained single-box FATEMOD program.

BACKGROUND, AIMS, AND SCOPE: Since toxaphene (polychlorocamphene, polychloropinene, or strobane) mixtures were applied for massive insecticide use in the 1960s to replace the use of DDT, some of their congeners have been found at high latitudes far away from the usage areas. Especially polychlorinated bornanes have demonstrated dominating congeners transported by air up to the Arctic areas. Environmental fate modeling has been applied to monitor this phenomenon using parallel zones of atmosphere around the globe as interconnected environments. These zones, shown in many meteorological maps, however, may not be the best way to configure atmospheric transport in air trajectories. The latter could also be covered by connecting a chain of simple model boxes. We aim to study this alternative approach by modeling the trajectory chain using catchment boxes of our FATEMOD model. Polychlorobornanes analyzed in biota of the Barents Sea offered one case to study this modeling alternative, while toxaphene has been and partly still is used massively at southern East Europe and around rivers flowing to the Aral Sea. MATERIALS AND METHODS: Pure model substances of three polychlorobornanes (toxaphene congeners P26, P50, and P62) were synthesized, their environmentally important thermal properties measured by differential scanning calorimetry, as evaluated from literature data, and their temperature dependences estimated by the QSPR programs VPLEST, WATSOLU, and TDLKOW. The evaluated property parameters were used to model their atmospheric long-range transport from toxaphene heavy usage areas in Ukraine and Aral/SyrDarja/AmuDarja region areas, through East Europe and Northern Norway (Finnmarken) to the Barents Sea. The time period used for the emission model was June 1997. Usual weather conditions in June were applied in the model, which was constructed by chaining FATEMOD model boxes of the catchment's areas along assumed maximal air flow trajectories. Analysis of the three chlorobornanes in toxaphene mixtures function as a basis for the estimates of emission levels caused by its usage. High estimate (A) was taken from contents in a Western product chlorocamphene and low estimate (B) from mean contents in Russian polychloroterpene products to achieve modeled water concentrations. Bioaccumulation to analyzed lipid of aquatic biota at the target region was estimated by using statistical calculation for persistent organic pollutants in literature. RESULTS: The results from model runs A and B (high and low emission estimate) for levels in sea biota were compared to analysis results of samples taken in August 1997 at Barents Sea. The model results (ng g(-1) lw): 4-95 in lipid of planktovores and 7-150 in lipid of piscivores, were in fair agreement with the analysis results from August 1997: 21-31 in Themisto libellula (chatka), 26-42 in Boreocadus saida (Polar cod), and 5-27 in Gadus morhua (cod) liver. DISCUSSION: The modeling results indicate that the application of chained simple multimedia catchment boxes on predicted trajectory is a useful method for estimation of volatile airborne persistent chemical exposures to biota in remote areas. For hazard assessment of these pollutants, their properties, especially temperature dependences, must be estimated by a reasonable accuracy. That can be achieved by using measurements in laboratory with pure model compounds and estimation of properties by thermodynamic QSPR methods. The property parameters can be validated by comparing their values at an environmental temperature range with measured or QSPR-estimated values derived by independent methods. The chained box method used for long-range air transport modeling can be more suitable than global parallel zones modeling used earlier, provided that the main airflow trajectories and properties of transported pollutants are predictable enough. CONCLUSIONS: Long-range air transport modeling of persistent, especially photo-resistant organic compounds using a chain of joint simple boxes of catchment's environments is a feasible method to predict concentrations of pollutants at the target area. This is justified from model results compared with analytical measurements in Barents Sea biota in August 1997: three of six modeled values were high and the other three low compared to the analysis results. The order of magnitude level was similar in both modeled (planktovore and piscivore) and observed (chatka and polar cod) values of lipid samples. The obtained results were too limited to firm validation but are sufficient to justify feasibility of the method, which prompts one to perform more studies on this modeling system. RECOMMENDATIONS AND PERSPECTIVES: For assessment of the risk of environmental damages, chemical fate determination is an essential tool for chemical control, e.g., for EU following the REACH rules. The present conclusion of applicability of the chained single-box multimedia modeling can be validated by further studies using analyses of emissions and target biota in various other cases. To achieve useful results, fate models built with databases having automatic steps for most calculations and outputs accessible to all chemical control professionals are essential. Our FATEMOD program catchments at environments and compound properties listed in the database represent a feasible tool for local, regional, and, according our present test results, for global exposure predictions. As an extended use of model, emission estimates can be achieved by reversed modeling from analysis results of samples corresponding to the target area.

A wood preservative metabolite in river water.

A previously unknown pollutant in river water was identified to be 2-mercaptobenzothiazole (2-MBT) by interpretation and simulation of its GC/LRMS spectrum. Further GC/HRMS measurement of the isotope composition of the molecular ion verified this structure. 2-MBT is a well-known agent for corrosion inhibition and a stable metabolite of several other benzothiazoles. The present 2-MBT trace was most probably a metabolite of the wood preservative TCMTB which leaked from an upstream sawmill. The metabolite had been detected earlier in urine of the sawmill workers, but now was identified in the recipient water environment for the first time.

Polybrominated methoxy diphenyl ethers (MeO-PBDEs) in fish and guillemot of Baltic, Atlantic and Arctic environments.

Arctic cod liver samples from Vestertana Fjord at the Arctic coast of Norway, salmon and guillemot samples from the Baltic Sea and the Atlantic Ocean, and salmon and lamprey larva samples from Kymijoki River in southern Finland were analysed for the occurrence of tri-, tetra- and pentabromomethoxy diphenyl ethers and their concentration levels were estimated. These compounds have previously been identified by other research groups in salmon, seal and dolphin samples. The aim of this study was to find out a possible temporal trend in the concentrations of these compounds in the cod liver samples from years 1987-1998 and to investigate the possible spatial differences in the concentrations in biota samples from the Baltic Sea, Atlantic Ocean, Arctic Sea and contaminated freshwater river. Two most abundant methoxy-tetrabromo diphenyl ether congeners occurred in the same statistically significant ratio in 14 sea biota samples. Levels in lamprey larvae were below detection limit. The origin of these methoxylated bromodiphenyl ethers in biota samples remained unknown. They may be metabolites of polybrominated diphenyl ethers used as flame retardants or compounds of natural origin.

Screening of halogenated aromatic compounds in some raw material lots for an aluminium recycling plant.

Four samples of scrap raw materials for an aluminium recycling plant were screened for the occurrence of persistent halogenated aromatic compounds. The samples contained waste from handling of electric and electronic plastics, filter dust from electronic crusher, cyclone dust from electronic crusher and light fluff from car shredder. In our screening analyses, brominated flame retardants were observed in all samples. Polybrominated diphenyl ethers (PBDE) were identified in all samples in amounts of 245-67450 ng/g. The major PBDE congeners found were decabromo- and pentabromodiphenyl ethers. 1,1-bis(2,4,6-tribromophenoxy)ethane, hexabromobenzene, ethyl-pentabromobenzene, tetrabromobisphenol-A, pentabromotoluene and dimethyl tetrabromobenzene were observed in all scrap samples. The concentrations of PCBs, PCNs (polychlorinated naphthalenes) and nona- to undecachlorinated terphenyls in some of these scrap samples were remarkably high.

Analyses of known and new types of polyhalogenated aromatic substances in oven ash from recycled aluminium production.

Persistent aromatic bromine, chlorine and mixed chlorine-bromine compounds were analysed from recycled aluminium smelter (ALS) ashes to explore the impact of brominated flame retardants (BFR) on their formation. Polybrominated diphenyl ethers (PBDE) were the most abundant original BFRs found. Induction furnace ash contained tetra- to octa-BDEs about 2000ng g(-1) in similar congener ratios as the original scrap, but contents of nona- and deca-BDEs were only 25 and 5ng g(-1) indicating their significant degradation in ALS process. In the most non-polar fraction, PCB levels and profiles were similar as earlier ALS ash samples in 1990s. The highest PCB level measured was that of deca-CB (450ng g(-1)) in the induction furnace ash. In this fraction, bromo compounds were non-detectable (<5ng g(-1)). Fraction of the most polar compounds (from reversed toluene elution of carbon column ("dioxin fraction") contained PCDDs, PCDFs and polychlorinated dibenzothiophenes (PCDTs) in similar amounts and congener profiles as earlier investigated ALS ash samples. Bromine-containing dioxin and furan congeners were not detected. From individual PCDDs and PCDFs, octaCDF was the most abundant (205ng g(-1)) in induction furnace ash. In this fraction, the original BFR, tetrabromo-bisphenol-A, was identified. Its level in the induction furnace ash was approximated to be 388ng g(-1). In addition, 12 novel brominated and chlorinated compounds were found as abundant (8-441ng g(-1) in the induction furnace ash) contaminants from the fraction. Four of them were bisphenol derivatives, five biphenylols, then octachlorofluorenone (OCFL) and octachlorobiphenylene (OCBP). Their structures or structure types were deduced from total low-resolution EI mass spectra by theoretical isotope cluster simulation (ICLU) and through known fragmentation rules.

Temperature dependent properties of environmentally important synthetic musks.

Environmental fate determining physical properties including their temperature dependence for five nitro musks and for seven polycyclic musks were estimated. The properties evaluated were vapor pressure in a solid and liquid state (PS and PL), solubility in water (S), Henry's law coefficient (H = PL/S) and log octanol-water partition coefficient (log KOW). Gas chromatography for starting values of vapor pressure estimation and HPLC experiments at 5-20 degrees C for comparison of the theoretical versus experimental solubilities in water were performed. The values of temperature (T) dependence coefficients (Ai and Bi) in equations: log (Property)i = Ai - Bi/T were determined. Values of properties were compared with literature-based data, and an example of their use in environmental hazard estimation by fate modeling was given.