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. This article is dedicated to the memory of Professor Alexander B Terentiev (who passed away in November 2006), our true friend. With his Institute of Organo-Element Compounds, Russian Academy of Science, Moscow, he was an important main organizer of the six joint Finnish–Russian seminars (every third year since 1989) on the field (‘Chemistry and Ecology of Organo-Element Compounds’). He prompted us especially to search properties and environmental fates for various polyhalogen compounds. We remember him for his friendly character and great sense of humor.     

Study of organochlorine pollutants in snow at North Pole and comparison to the snow at north, central and south Finland

Organic pollutants, especially polychlorinated hydrocarbons, phenols, guaiacols and catechols have been studied by analyses of snow samples from North Pole, May 1984. All of these pollutants were below the limit of determination which was estimated to be as fallout 0.1–0.05 μg/m² for individual compounds. For comparison, snow samples from Central Finland and South Finland 1983–1985 also showed non-detectable levels of chlorinated hydrocarbons but well measurable levels of chlorophenol compounds which were significantly higher at urban (heavy traffic) than rural and higher at South than Central Finnish places, respectively. One sample from Lapland, North Finland 1985, however, had no measurable amounts of chlorophenols like the North Pole sample.     

Organic carbon causes interference with nitrate and nitrite measurements by UV/Vis spectrometers: the importance of local calibration

Compared with sporadic conventional water sampling, continuous water-quality monitoring with optical sensors has improved our understanding of freshwater dynamics. The basic principle in photometric measurements is the incident light at a given wavelength that is either reflected, scattered, or transmitted in the body of water. Here, we discuss the transmittance measurements. The amount of transmittance is inversely proportional to the concentration of the substance measured. However, the transmittance is subject to interference, because it can be affected by factors other than the substance targeted in the water. In this study, interference with the UV/Vis sensor nitrate plus nitrite measurements caused by organic carbon was evaluated. Total or dissolved organic carbon as well as nitrate plus nitrite concentrations were measured in various boreal waters with two UV/Vis sensors (5-mm and 35-mm pathlengths), using conventional laboratory analysis results as references. Organic carbon increased the sensor nitrate plus nitrite results, not only in waters with high organic carbon concentrations, but also at the lower concentrations (< 10 mg C L^?1) typical of boreal stream, river, and lake waters. Our results demonstrated that local calibration with multiple linear regression, including both nitrate plus nitrite and dissolved organic carbon, can correct the error caused by organic carbon. However, high-frequency optical sensors continue to be excellent tools for environmental monitoring when they are properly calibrated for the local water matrix.     

Identification of magnetic particulates in road dust accumulated on roadside snow using magnetic, geochemical and micro-morphological analyses

The aim of this study is to test the applicability of snow surveying in the collection and detailed characterization of vehicle-derived magnetic particles. Road dust extracted from snow, collected near a busy urban highway and a low traffic road in a rural environment (southern Finland), was studied using magnetic, geochemical and micro-morphological analyses. Significant differences in horizontal distribution of mass specific magnetic susceptibility (χ) were noticed for both roads. Multi-domain (MD) magnetite was identified as the primary magnetic mineral. Scanning electron microscope (SEM) analyses of road dust from both roads revealed: (1) angular-shaped particles (diameter ∼1-300 μm) mostly composed of Fe, Cr and Ni, derived from circulation of motor vehicles and (2) iron-rich spherules (d ∼ 2-70 μm). Tungsten-rich particles (d < 2 μm), derived from tyre stud abrasion were also identified. Additionally, a decreasing trend in χ and selected trace elements was observed with increasing distance from the road edge.     

Size-exclusion chromatographic study of ECF and TCF softwood kraft pulp bleaching liquors

Background, aims, and scope  

Currently, elemental chlorine-free (ECF) and totally chlorine-free (TCF) bleaching systems are widely used for pulp production. Low and medium molecular weight lignin break-down products are known to have harmful effects on the environment. According to some recent results, also high molecular weight (HMW) material consisting mainly of lignin and carbohydrates may cause toxic effects to the environment. For these reasons, toxicity and structure studies of HMW materials are of great importance. This investigation is a part of a larger project to obtain more structure information of HMW materials and toxicity of ECF and TCF bleaching effluents. Size-exclusion chromatography (SEC) has been commonly used for the characterization of organic macromolecules such as lignin, but to our knowledge, no reports have appeared dealing with the comparison of SEC of ECF and TCF bleaching liquors. The aim of the present study was to get more information about the molecular weight distribution (MWD) of HMW fractions of waste liquors from ECF and TCF bleaching sequences by SEC.     

Chlorohydrocarbons, PCB congeners, polychlorodioxins, furans and dibenzothiophenes in pine needles in the vicinity of a metal reclamation plant

Chlorohydrocarbons, PCB congeners, polychlorodioxins, furans and dibenzothiophenes in pine needles in the vicinity of a metal reclamation plant were analyzed by GC/ECD and GC/MS. Wax and the rest of the needles were analyzed separately. As a rule the concentrations of -HCH (0.5–13.6 ng/g), γ-HCH (0.4–7.3 ng/g), HCB (0.2–3.4 ng/g), PCB congeners (0.2–67 ng/g), PCDDs and PCDFs were higher in the older needles. The ratio of the concentration in the wax to the concentration in the rest of the needles was higher in the younger needles. The concentrations of PCB congeners, TeCDDs and TeCDFs were higher in the needles collected in the area nearest to the plant. The samples, obviously, contained tri- and tetrachlorodibenzothiophenes but these were not determined quantitatively due to interfering peaks in GC/MS.     

Defoliating insect immune defense interacts with induced plant defense during a population outbreak

During population outbreaks, top-down and bottom-up factors are unable to control defoliator numbers. To our knowledge, details of biotic interactions leading to increased population density have not been studied during real population outbreaks. We experimentally assessed the strength of plant defenses and of insect immunocompetence, assumed to contribute to active insect resistance against parasitoids and pathogens, in the geometrid Epirrita autumnata during a steep increase in population density. We demonstrated rapid (same-season) induced resistance in the foliage of its host, mountain birch. The response was systemic, spreading throughout the tree, and retarded larval growth rate by approximately 10%. On the other hand, no direct delayed carry-over effects were found in the next season in larval growth rate, mortality, or pupal mass. Larval damage to a tree during the previous year, however, significantly (by approximately 13%) accelerated the advance of the immune response (measured as melanization of an implant inserted into the pupal hemocoel). The encapsulation rate correlated positively with larval mortality in trees in which larvae had been introduced the previous year, but not in control trees. Both of these observations suggest that induced plant defense was associated with an increased insect immunocompetence during the population increase.     

Polychlorinated organic compounds in the Arctic cod liver: trends and profiles

Polychlorinated organic compounds (POCs) have been measured in Arctic cod liver from Vestertana Fjord for a period of 1987-1998. Significant decrease was observed for DDD (p = 0.043), alpha-HCH (p = 0.001), and gamma-HCH (lindane; p = 0.001). Contents of DDE, 2,3,7,8-tetrachlorodibenzofuran, PCBs, chlordanes, chloronaphthalenes, hexachlorobenzene and polychlorodiphenyl ethers had no significant trend. Contents of three hexa- and two heptachlorodibenzofurans and octachlorodibenzofuran increased slightly from 1987 to 1994, but then at very high rate from 1994 to 1998. Trends of HCHs, profiles of PCBs and levels of chlordanes are in accordance with atmospheric long range transport. The hexa-, hepta- and octachlorodibenzofurans observed are major impurities in chlorophenol formulation Ky-5, which has been used as wood preservative and as fungicide/slimicide in industrial processes. Their profile in Vestertana cod was similar to that observed in Ky-5 contaminated fish.     

Degradation half-life times of PCDDs, PCDFs and PCBs for environmental fate modeling

Literature search of the knowledge on the degradation of persistent organic pollutants (POPs) in environmental compartments air, water, soil and sediment was done in purpose to find properties of POPs of interest for modeling. One degradation process, hydrolysis (chemical degradation), was omitted as negligibly slow for POPs studied. The other two, photolysis and biodegradation processes, were considered separately in purpose to develop estimation procedures. The estimates can be given as pseudo first-order rate constants kP for photolysis and kB for biodegradation. For each compartment, an overall degradation rate is k(tot) = kP + kB and lifetime t(1/2) = ln 2/k(tot). The latter values, lifetimes in each compartment, will be used as input parameters to the Baltic Sea model.