Organic Compounds in Cloud Water and their Deposition at a Remote Continental Site

Some organic compounds (alkylbenzene, chlorinated hydrocarbons and poiycyclic aromatic hydrocarbons) in clouds have been determined from samples collected above the canopy of a coniferous forest. The cloud samples were collected during 1987 and 1988 at Mt. Mitchell State Park, North Carolina, a remote high elevation (～2006 m MSL) continental site. Concentrations of the organic chemicals in clouds were in the range of 0.2 to ～200 ng mL^-1; and their estimated deposition rates via clouds were found to range from 1.58 * 10⁴ to 4.67 * 10⁶ ng m^-2 yr^-1. Great variations in concentrations were found which can best be explained, based on 72 hour back trajectory analysis, by different source locales and moving air masses. The concentration of these chemicals exceeded their water solubility as predicted by Henry's Law, suggesting that clouds are an excellent scavenger of organic chemicals in the ambient environment.     

Fat solubility — A property of environmental relevance?

Solubilities in fats ranging from 0.88 g l^?1 to completely miscible are reported for twelve organic chemicals. Comparison of these and other literature values with bioconcentration factors and octanol: water partition coefficients indicate that fat solubility is not a reliable predictor for either parameter. The results for the solubilities of seven chemicals in eight different fats cover a restricted range, indicating that the composition of the fat is not a critical parameter in determining the solubility.     

Systematic development of reactive tracer technology to determine hydroxyl radical concentrations in the troposphere

In recent years, it has become possible to release controlled quantities of inert tracers to study transport and dispersion over 1000 km distances. On the basis of the successes and proven technology of these studies, we have conceptualized that by simultaneously releasing an inert tracer and a tracer that reacts exclusively or predominantly with hydroxyl (OH) radicals, it would be possible to determine OH concentrations over similar transport distances. Such an OH tracer must react exclusively with OH radicals at a relatively fast but known rate (5 × 10⁻¹²to 3 × 10⁻¹¹ cm³ molec⁻¹s⁻¹). The OH reactive tracer should also have a negligible background and be detectable at 10⁻¹⁴ to 10⁻¹⁵ V/V concentrations. While the reactive OH-tracer application is simple to conceptualize, no chemicals are known that would satisfy all the properties that a reactive tracer must possess. The effort discussed here seeks to define these properties, and to design and develop a reactive OH tracer that can be applied in the field. Theoretical techniques are used to estimate the properties of designed chemicals. Most of the chemicals suitable for the purpose are not commercially available. From nearly 100 chemicals initially considered, a list of 10 finalists have been selected. Laboratory tests are underway to experimentally verify the properties of these tracers. When successful, the reactive/inert tracer method could be used to determine OH radical concentrations with a sensitivity of ⩽ 5 × 10⁵ molec cm⁻³.     

QSAR modeling for predicting mutagenic toxicity of diverse chemicals for regulatory purposes

The safety assessment process of chemicals requires information on their mutagenic potential. The experimental determination of mutagenicity of a large number of chemicals is tedious and time and cost intensive, thus compelling for alternative methods. We have established local and global QSAR models for discriminating low and high mutagenic compounds and predicting their mutagenic activity in a quantitative manner in Salmonella typhimurium (TA) bacterial strains (TA98 and TA100). The decision treeboost (DTB)-based classification QSAR models discriminated among two categories with accuracies of >96% and the regression QSAR models precisely predicted the mutagenic activity of diverse chemicals yielding high correlations (R ²) between the experimental and model-predicted values in the respective training (>0.96) and test (>0.94) sets. The test set root mean squared error (RMSE) and mean absolute error (MAE) values emphasized the usefulness of the developed models for predicting new compounds. Relevant structural features of diverse chemicals that were responsible and influence the mutagenic activity were identified. The applicability domains of the developed models were defined. The developed models can be used as tools for screening new chemicals for their mutagenicity assessment for regulatory purpose.

     

15N Metabolic test for the determination of phytotoxic effects of chemicals and contaminated environmental samples

A stable isotope¹⁵N-nitrogen test (ESIMA = Ecotoxicological Stable Isotope Metabolic Assay) was developed to assess biological effects and the potential toxicological hazard of chemicals and contaminated environmental samples on plant metabolism. The assay measures the effect of toxicants on the incorporation of a¹⁵N labelled tracer into the total nitrogen fraction (both the nonprotein and protein fraction) of plants. Segments ofPisum arvense epicotyls are used as test substrates because of their high metabolic activity. The plant material is incubated under standardised conditions for two hours; subsequently¹⁵N incorporation is analysed by determining the¹⁵N abundance (¹⁵N atom-%) in the epicotyl segments. The effects of toxicants are evaluated by comparing the¹⁵N incorporation rates of control tissue and epicotyl segments exposed to individual chemicals or complex environmental samples. The specificity and sensitivity of effects as indicated by ESIMA were compared with effects as measured by two established ecotoxicological bioassays, the pollen tube growth test using pollen ofNicotiana sylvestris and the bacterial luminescence inhibition test using pollen ofPhotobacterium phosphoreum. The results of the study clearly indicate the suitability of ESIMA for assessing toxic impacts on plant nitrogen metabolism. Prof. Dr. habil. Hans Faust dedicated to his 70^th birthday.     

An object-oriented software for fate and exposure assessments

The model system CemoS¹ (Chemical Exposure Model System) was developed for the exposure prediction of hazardous chemicals released to the environment. Eight different models were implemented involving chemicals fate simulation in air, water, soil and plants after continuous or single emissions from point and diffuse sources. Scenario studies are supported by a substance and an environmental data base. All input data are checked on their plausibility. Substance and environmental process estimation functions facilitate generic model calculations. CemoS is implemented in a modular structure using object-oriented programming. e-mail: cemos@aphrodite.mathematik.uni-osnabrueck.de     

Sorption and desorption of glyphosate,MCPA and tetracycline and their mixtures in soil as influenced by phosphate

Phosphate fertilizers and herbicides such as glyphosate and MCPA are commonly applied to agricultural land, and antibiotics such as tetracycline have been detected in soils following the application of livestock manures and biosolids to agricultural land. Utilizing a range of batch equilibrium experiments, this research examined the competitive sorption interactions of these chemicals in soil. Soil samples (0-15 cm) collected from long-term experimental plots contained Olsen P concentrations in the typical (13 to 20 mg kg^?1) and elevated (81 to 99 mg kg^?1) range of build-up phosphate in agricultural soils. The elevated Olsen P concentrations in field soils significantly reduced glyphosate sorption up to 50%, but had no significant impact on MCPA and tetracycline sorption. Fresh phosphate additions in the laboratory, introduced to soil prior to, or at the same time with the other chemical applications, had a greater impact on reducing glyphosate sorption (up to 45%) than on reducing tetracycline (up to 13%) and MCPA (up to 8%) sorption. The impact of fresh phosphate additions on the desorption of these three chemicals was also statistically significant, but numerically very small namely < 1% for glyphosate and tetracycline and 3% for MCPA. The presence of MCPA significantly reduced sorption and increased desorption of glyphosate, but only when MCPA was present at concentrations much greater than environmentally relevant and there was no phosphate added to the MCPA solution. Tetracycline addition had no significant effect on glyphosate sorption and desorption in soil. For the four chemicals studied, we conclude that when mixtures of phosphate, herbicides and antibiotics are present in soil, the greatest influence of their competitive interactions is phosphate decreasing glyphosate sorption and the presence of phosphate in solution lessens the potential impact of MCPA on glyphosate sorption. The presence of chemical mixtures in soil solution has an overall greater impact on the sorption than desorption of individual organic chemicals in soil.     

Biomineralization rates of 14C-labelled organic chemicals in aerobic and anaerobic suspended soil

The formation of ¹⁴CO₂ from 13 ¹⁴C-labelled organic chemicals in aerobic and anaerobic suspended soil was determined. After 5 days at 35°C, ¹⁴CO₂ was between 70.1% (urea, anaerobic) and < 0.1% (2,6-dichlorobenzonitrile and hexachlorobenzene, aerobic and anaerobic) of the ¹⁴C initially applied.     

Accumulation and elimination kinetics of di-, tri- and tetra chlorobiphenyls by goldfish after dietary and aqueous exposure

Bioaccumulation kinetics of five di-, tri- and tetrachlorobiphenyls from water and food were studied in laboratory experiments with goldfish (Carassius auratus). First order rate constants for uptake from water and clearance were determined after simultaneous administration of the five compounds in constant concentration, and were related to bioconcentration factors obtained in a static fish-water equilibration system. Biomagnification by retention of the PCB's from food was studied in a separate experiment.The difference in clearance rates for the chlorobiphenyls is the main reason for the different bioconcentration and biomagnification factors.Absorption efficiencies from water and food are higher than 40%. Clearance half lives vary from 10 days for 2,5-dichlorobiphenyl to 60 days for 2,3′,4′5-tetrachlorobiphenyl, which is correlalated with the decreasing aqueous solubilities of the compounds. Bioconcentration factors are between 0.4 × 10⁶ and 1.5 × 10⁶, biomagnification factors between 0.2 and 1.7, based on extractable lipids. Substitution of chlorine in the position para to the phenyl-phenyl bond influences hydrophobicity and bioaccumulation of the PCB's more strongly than substitution in ortho position.A kinetic model is developed which accounts for the influence of the lipid content of the fish on the clearance rate of a chemical. Reproducible determination of the bioconcentration potential of environmental chemicals is possible by use of an “internal bioaccumulation standard” in a kinetic test system. Food chain accumulation in fish is likely to be an important process only for persistent chemicals with extremely low water solubility.     

Degradation of the herbicides bromacil,diuron and chlortoluron in soil

In laboratory studies, the rate of degradation of ¹⁴C-labeled diuron, chlortoluron, and bromacil in soil was determined by monitoring ¹⁴CO₂ evolution at 25, 30, and 35°C. Degradation of the three herbicides was slow and followed the first-order rate law. The rate of ¹⁴CO₂ evolution from the treated soil was nearly tripled by a 10°C rise in temperature from 25 to 35°C. The half-lives as well as the activation energies of degradation for the three chemicals were determined and discussed.     

Inhibition of animal acetyl-coenzyme a carboxylase by 2-(p-chlorophenoxy)-2-methylpropionic acid and 2-ethylhexanoic acid

Peroxisome proliferators are generally known as activators of fatty acid β-oxidation which is one of degradation pathways. However, since it is unknown whether peroxisome proliferators have an effect on biosynthesis of fatty acid or not, we commenced to study if acetyl-CoA carboxylase, the rate-limiting enzyme of fatty acid biosynthesis, is inhibited by 2-(p-chlorophenoxy)-2-methylpropionic acid or 2-ethylhexanoic acid which is a typical peroxisome proliferator. Acetyl-CoA carboxylase(s) from rat, mouse, hamster, rabbit, dog and monkey were completely inhibited by 2-(p-chlorophenoxy)-2-methylpropionic acid or 2-ethylhexanoic acid at the concentration of 10⁻³M. For both compounds, there was not a large species difference in the inhibition. However, there was only several times difference between I₅₀ values for the two compounds. The findings imply that inhibition of acetyl-CoA carboxylase by the chemicals leads to reduction of fatty acid biosynthesis when the chemicals are administered to the animals at high dose levels.     

Effects of selected chemicals to photoluminescent bacteria and their correlations with acute and sublethal effects on other organisms

Microtox^R1 test toxicity values for twenty chlorophenols, twelve chlorobenzenes and thirteen para-substituted phenols have been determined and correlated with the acute and sublethal effects of these chemicals on several species of fish, bacteria and shrimp. The results indicate that the Microtox^R test provides good estimates of the toxicities to the various biota, as shown by the linear correlation equations presented, and that it is useful for the calculation of structure-activity correlations with physico-chemical parameters, such as the octanol/water partition coefficient.     

Canine toys and training devices as sources of exposure to phthalates and bisphenol A: Quantitation of chemicals in leachate and in vitro screening for endocrine activity

Chewing and mouthing behaviors exhibited by pet dogs are likely to lead to oral exposures to a variety of environmental chemicals. Products intended for chewing and mouthing uses include toys and training devices that are often made of plastics. The goal of the current study was to determine if a subset of phthalates and bisphenol A (BPA), endocrine disrupting chemicals commonly found in plastics, leach out of dog toys and training devices (bumpers) into synthetic canine saliva. In vitro assays were used to screen leachates for endocrine activity. Bumper leachates were dominated by di-2-ethylhexyl phthalate (DEHP) and BPA, with concentrations reaching low μg mL⁻¹ following short immersions in synthetic saliva. Simulated chewing of bumpers during immersion in synthetic saliva increased concentrations of phthalates and BPA as compared to new bumpers, while outdoor storage had variable effects on concentrations (increased DEHP; decreased BPA). Toys leached substantially lower concentrations of phthalates and BPA, with the exception of one toy which leached considerable amounts of diethyl phthalate. In vitro assays indicated anti-androgenic activity of bumper leachates, and estrogenic activity of both bumper and toy leachates. These results confirm that toys and training devices are potential sources of exposure to endocrine disrupting chemicals in pet dogs.     

Combined toxic impacts of thiamethoxam and four pesticides on the rare minnow (Gobiocypris rarus)

To examine pesticide mixture toxicity to aqueous organisms, we assessed the single and combined toxicities of thiamethoxam and other four pesticides (chlorpyrifos, beta-cypermethrin, tetraconazole, and azoxystrobin) to the rare minnow (Gobiocypris rarus). Data from 96-h semi-static toxicity assays of various developmental phases (embryonic, larval, juvenile, and adult phases) showed that beta-cypermethrin, chlorpyrifos, and azoxystrobin had the highest toxicities to G. rarus, and their LC₅₀ values ranged from 0.0031 to 0.86 mg a.i. L^?1, from 0.016 to 6.38 mg a.i. L^?1, and from 0.39 to 1.08 mg a.i. L^?1, respectively. Tetraconazole displayed a comparatively high toxicity, and its LC₅₀ values ranged from 3.48 to 16.73 mg a.i. L^?1. By contrast, thiamethoxam exhibited the lowest toxic effect with LC₅₀ values ranging from 37.85 to 351.9 mg a.i. L^?1. Rare minnow larvae were more sensitive than embryos to all the pesticides tested. Our data showed that a pesticide mixture of thiamethoxam–tetraconazole elicited synergetic toxicity to G. rarus. Moreover, pesticide mixtures containing beta-cypermethrin in combination with chlorpyrifos or tetraconazole also had synergetic toxicities to fish. The majority of pesticides are presumed to have additive toxicity, while our data emphasized that the concurrent existence of some chemicals in the aqueous circumstance could cause synergetic toxic effect, leading to severe loss to the aqueous environments in comparison with their single toxicities. Thence, the synergetic impacts of chemical mixtures should be considered when assessing the ecological risk of chemicals.

     

Environmental hazard profile of organic chemicals: An experimental method for the assessment of the behaviour of organic chemicals in the ecosphere by means of simple laboratory tests with 14C labelled chemicals

The concept of “Environmental Hazard Profile” developed at this institute has been tested with 100 ¹⁴C-labelled organic compounds. Concentration factors in activated sludge, in algae and fish were determined. The microbial degradation of the chemicals to CO₂ in activated sludge and the decomposition to CO₂ under artificial light were determined. Ranking of compounds is given in the order of falling concentration factors and accumulation in rats respectively, and decreasing rates of decomposition. Relationship between chemical structure and accumulative and degradative behaviours is demonstrated using some selected groups of chemicals, such as benzenes, phenols, biphenyls and polyaromatic hydrocarbons. Correlations between the octanol/water partition coefficient, concentration factors and rates of decomposition could be established. Evaluation of test compounds was possible using hazard profiles obtained by the sum of single test results.     

Diquat associated with copper sources for algae control: Efficacy and ecotoxicology

The aims of this research were to evaluate the efficacy of copper oxychloride (CuCl₂.3Cu(OH)₂), copper hydroxide (Cu(OH)₂) and diquat (1.1′-ethylene-2.2′-bipyridyldiylium dibromide), isolated and in association with 0.1% of both copper sources, in the control of the unicellular algae Ankistrodesmus gracilis and the filamentous algae Pithophora kewesis, and to determine the acute toxicity of the tested chemicals in Hyphressobrycon eques, Pomacea canaliculata, Lemna minor and Azolla caroliniana. The efficacy was estimated by the methods of chlorophyll a and pheophytin a readings, changed into growth inhibition percentage. Both algae were exposed to the following concentrations: 0.2; 0.4; 0.8; 1.2 mg L^?1 of diquat and its association with the copper sources; and 0.1; 0.3; 0.5; 0.7; 1.0 and 1.5 mg L^?1 in the isolated applications of copper hydroxide and copper oxychloride. An untreated control was kept. The acute toxicity was estimatedby 50% lethal concentration (LC50). The copper sources were effective for A. gracilis control, at rates as high as 0.1 mg L^?1 (>95% efficacy). Isolated diquat and its association with copper hydroxide were both effective at rates as high as 0.4 mg L^?1, with 95 and 88% control efficacy, respectively. The copper oxychloride was effective at 0.2 mg L^?1, with 93% efficacy. None of the tested chemicals and associations was effective on P. kewesis control. The most sensitive non target organism to the tested chemicals was L. minor; the less sensitive was H. eques.     

Relationship between bioconcentration in fish and steric factors of hydrophobic chemicals

Most polychlorinated naphthalones (PCN) accumulate rapidly according to their hydrophobicity. The uptake and ellmination rate constants are comparable to those of chlorinated benzenes and biphenyls.For most PCN-congeners the resulting bioaccumulation factors show an increase with increasing hydrophobicity. For higher K_d,oct-values (>10⁵) however, no further increase of K_c is observed (K_c. max. = 3.5.10⁴).For the two hepta- and the octachloronaphthalenes no detectable concentrations are found in the fishes, although no restricted blo-availability could be expected. Based on these observations and on data obtained from the literature. a loss of membrane permeation is suggested for hydrophobic molecules with widths over 9.5 Å.In addition a membrane permeation model, as part of the accumulation process of hydrophobic chemicals. Is proposed, which is based on diffusion and partition processes.     

Endocrine disrupting nonyl- and octylphenol in infant food in Germany: considerable daily intake of nonylphenol for babies

Nonylphenol and octylphenol are persistent endocrine disrupters that are priority substances of the European Union Water Framework Directive. Their presence in the environment has caused increasing concern about their impact to human health. Infants are more sensitive to hormonal impacts of environmental chemicals than adults. The results of the present study indicate that nonylphenol is ubiquitous in foodstuffs for babies and toddlers commercially available in Germany, while octylphenol could only be determined in 80% of all food samples. The daily intakes based on consumption studies in μg nonylphenol kg⁻¹ body weight per day for high consumers in the baby category (0.23-0.65 μg kg⁻¹ bw d⁻¹) were relatively high. This could lead to a higher risk especially for babies.