The internal barriers of rotation for the 209 polychlorinated biphenyls

The internal barrier of rotation (Erot) was calculated for all 209 polychlorinated biphenyls (PCBs) by using a semi-empirical method, viz. the Austin Model 1 (AMI) Hamiltonian. The difference in total energy between a forced planar state and an optimised twisted structure was defined as Erot. The Erot values were in the range of 8.33 to 483 kj/mol, and were significantly influenced by the number of chlorine atoms inortho position. An additional structural characteristic of the PCBs influencing Erot ofortho substituted congeners was substitution by chlorine atoms in vicinalmeta positions, which is assumed to prevent outward bending ofortho substituents. This so-called buttressing effect contributed with 4 to 31 kj/mol per added chlorine atom. In conclusion, the internal barrier of rotation, calculated for all 209 PCBs, provides an important structure dependent physico-chemical parameter for multivariate modelling of future quantitative structure-activity and structure-property relationships (QSARs/QSPRs).     

Organochlorine residues in harbour porpoises from Southwest Greenland

During the 1995 hunting season, 75 harbour porpoises (Phocoena phocoena) were sampled in three locations in West Greenland: Maniitsoq, Nuuk, and Paamiut. Sex, age, morphometrics, reproductive condition, and organochlorine compound (OC) levels in blubber were determined for each individual. OC levels were extremely low and, therefore considered unlikely to affect the population adversely: mean blubber concentrations, expressed on lipid weight basis were 1.98 (S.D.=1.1) mg/kg for PCBs, 2.76 (S.D.=1.66) mg/kg for tDDT and 0.21 (S.D.=0.11) mg/kg for HCB. No statistical differences were observed among individuals caught in the various locations. OC concentrations showed statistically significant positive associations with age in males but negative in females; consequently, mature females presented lower pollutant loads than their male counterparts. Juveniles did not show differences between sexes. A higher proportion of less chlorinated and more metabolizable polychlorinated biphenyls (PCBs) compared to tPCBs was found in calves (age< or =1) than in mature females, indicating that the feeding habits of these two groups differ and that a greater transfer of less chlorinated compounds is passed from females to their pups through lactation and parturition. Harbour porpoises significantly contribute to the dietary intake of OCs by local Inuit populations. This contribution could be reduced if mature males were selectively avoided; however, current hunting procedures make this selection impracticable.     

A rule-based screening environmental risk assessment tool derived from EUSES

Within the context and scope of the forthcoming European Union chemical regulations (REACH), there is a need to be able to prioritise the chemicals for evaluation. Therefore, a simple, pragmatic and adequately conservative approach for the identification of substances of very low or no immediate concern at an early stage is presented. The fundamental principles and basic concepts are derived from the EU Technical Guidance Document and EUSES, and are translated into an easy-to-use rule-based system. For this development, the effect on risk characterisation ratios (RCRs) of the key environmental parameters in EUSES was quantified (taking into account several standardised chemical release scenarios). Using statistical analysis, ranges were identified for each key parameter, within which the end result of the assessment was not significantly affected. This information was then translated into a lookup table from which environmental risk characterisation ratios can be directly read as a function of a few parameters.     

Illuminating reactive microbial transport in saturated porous media: demonstration of a visualization method and conceptual transport model

We demonstrate a method to study reactive microbial transport in saturated translucent porous media using the bacteria Pseudomonas fluorescens 5RL genetically engineered to carry a plasmid with bioluminescence genes inducible by salicylate. Induced bacteria were injected into a cryolite grain filled chamber saturated with a sterile non-growth-promoting (phosphorus limited) chemical mixture containing salicylate as an aromatic hydrocarbon analogue. The amount of light produced by the bacteria serves as an estimator of the relative efficiency of aerobic biodegradation since bioluminescence is dependent on both salicylate and oxygen but only consumes oxygen. Bioluminescence was captured with a digital camera and analyzed to study the evolving spatial pattern of the bulk oxygen consuming reactions. As fluid flow transported the bacteria through the chamber, bioluminescence was observed to initially increase until an oxygen depletion zone developed behind the advective front. Bacterial transport was modeled with the advection dispersion equation and oxygen concentration was modeled assuming bacterial consumption via Monod kinetics with consideration of additional effects of rate-limited mass transfer from residual gas bubbles. Consistent with previous measurements, bioluminescence was considered proportional to oxygen consumed. Using the observed bioluminescence, model parameters were fit that were consistent with literature values and produced results in good agreement with the experimental data. These findings demonstrate potential for using this method to investigate the complex spatial and temporal dynamics of reactive microbial transport in saturated porous media.     

Laboratory shake flask batch tests can predict field biodegradation of aniline in the Rhine

The aim of this study was to compare degradation rates of aniline in laboratory shake flask simulation tests with field rates in the river Rhine. The combined events of a low flow situation in the Rhine and residual aniline concentrations in the effluent from the BASF treatment plant in Ludwigshafen temporarily higher than normal, made it possible to monitor aniline at trace concentrations in the river water downstream the wastewater outlet by means of a sensitive GC headspace analytical method. Aniline was analyzed along a downstream gradient and the dilution along the gradient was calculated from measurements of conductivity, sulfate and a non-readily biodegradable substance, 1,4-dioxane. Compensating dilution, field first-order degradation rate constants downstream the discharge of BASF were estimated at 1.8 day⁻¹ for two different dates with water temperatures of 21.9 and 14.7 °C, respectively. This field rate estimate was compared with results from 38 laboratory shake flask batch tests with Rhine water which averaged 1.5 day⁻¹ at 15 °C and 2.0 day⁻¹ at 20 °C. These results indicate that laboratory shake flask batch tests with low concentrations of test substance can be good predictors of degradation rates in natural water bodies––at least as ascertained here for short duration tests with readily degradable compounds among which aniline is a commonly used reference.     

Relating cadmium concentrations in three macrophyte-associated freshwater invertebrates to those in macrophytes,water and sediments

We found that Cd concentrations in three species of macrophyte-associated invertebrates (the gastropods Bithynia tentaculata and Physa gyrina, and the amphipod Gammarus fasciatus) collected at twenty sites along the St. Lawrence River were correlated with Cd concentrations in their main food source, i.e. macrophytes and associated periphyton. Cd in these invertebrates was not significantly correlated with Cd concentrations in the sediments (even when corrections for iron oxide or organic carbon content were applied) or to calculated free-cadmium concentrations in the water. Cd levels in juveniles of B. tentaculata were very tightly linked to Cd concentrations in macrophytes, which is consistent with the close relationship that these organisms have developed with macrophytes. Linear models predicting Cd levels in juveniles of B. tentaculata from Cd levels in different macrophyte species were strong (R2 = 0.69-0.90). Analysis of covariance on these models showed no statistical difference of slope or intercept for any of the macrophyte species, except Vallisneria americana. We suggest that the macrophyte-periphyton complex is a key link in the transfer of cadmium to some aquatic invertebrates in the littoral zone of the St. Lawrence River and that macrophytes and their associated epiphytes should also be used as biomonitors.     

KONRAD

Ohne Zusammenfassung     

COS,CS2 and SO2 in aluminium smelter exhaust

Measurements of carbonyl sulfide (COS) and carbondisulfide (CS₂) were carried out on samples drawn from a smoke stack of an aluminium smelter. Volume mixing ratios of 6 ppm COS and 0.1 ppm CS₂ were measured for gases from the electrolysis unit that had previously passed an Al₂O₃ fluid bed reactor and electrostatic precipitators. Specific emissions of 1.6 kg COS and 0.03 kg CS₂ per ton of primary aluminium were found. Extrapolating from this particular smelter’s conditions to a world mix specific COS emissions of about 4 kg/t(Al) are calculated resulting in emissions of annually 0.08 Tg COS into the atmosphere due to electrolytic aluminium production in 1995. Besides the photochemical conversion of anthropogenic CS₂ aluminium production is established to be the second major industrial source of COS probably exceeding automotive tire wear’s and coal combustion’s contributions.