Petroleum products and essential oils are complex mixtures of hydrophobic and volatile chemicals and are categorized as substances of unknown or variable composition, complex reaction products, or biological materials (UVCBs). In aquatic testing and research of such mixtures, it is challenging to establish initial concentrations without the addition of cosolvents, to maintain constant concentrations during the test, and to keep a constant mixture composition in dilution series and throughout test duration. Passive dosing was here designed to meet these challenges by maximizing the surface area (A donor /V medium = 3.8 cm 2 /mL) and volume (V donor /V medium > 0.1 L/L) of the passive dosing donor in order to ensure rapid mass transfer and avoid donor depletion for all mixture constituents. Cracked gas oil, cedarwood Virginia oil, and lavender oil served as model mixtures. This study advances the field by (i) showing accelerated passive dosing kinetics for 68 cracked gas oil constituents with typical equilibration times of 5−10 min and for 21 cederwood Virginia oil constituents with typical equilibration times < 1 h, (ii) demonstrating how to control mixture concentration and composition in aquatic tests, and (iii) discussing the fundamental differences between solvent spiking, water-accommodated fractions, and passive dosing.

The biodegradation kinetics of UVCB substances (Unknown or Variable composition, Complex reaction products or Biological materials) should be determined below the solubility limit to avoid experimental artefacts by the non-dissolved...

Petroleum products and essential oils are produced and used in large amounts and are categorized as "Substances of Unknown or Variable composition, Complex reaction products or Biological materials (UVCBs)." These UVCBs are notorious difficult-to-test substances, since they are complex mixtures of hydrophobic and volatile compounds. This study introduces two passive dosing (PD) approaches for whole UVCB toxicity testing:(1) headspace PD applies the UVCB and purified lipid oil as a donor to control exposure via the headspace and (2) silicone rod PD applies UVCB-loaded silicone rods to control exposure via an aqueous test medium and headspace. Headspace gas chromatography−mass spectrometry measurements were used to cross-validate the approaches at the saturation level and to confirm exposure and maintain mixture composition at varying donor concentration levels. Both approaches were applied to whole-mixture toxicity tests of petroleum and essential oil UVCBs with daphnia and algae. Finally, the observed toxicity was linked to concentrations in the donor and in lipid membranes at equilibrium with the donors. Dose−response curves were similar across the dosing approaches and tested species for petroleum products but differed by an order of magnitude between essential oils and PD systems. All observed toxic effects were consistent with baseline toxicity, and no excess mixture toxicity was observed.

Biodegradation kinetics data are keystone for evaluating the environmental persistence and risk of chemicals. Biodegradation kinetics depend highly on the prevailing temperature, which influences microbial community structures, metabolic rates, and chemical availability. There is a lack of high-quality comparative biodegradation kinetics data that are determined at different test temperatures but with the same microbial inoculum and chemical availability. The present study was designed to determine the effect of test temperature on the biodegradation kinetics of hydrocarbons while avoiding confounding factors. We used inocula from a Northern river (2.7 °C) and a Central European river (12.5 °C). Aqueous stock solutions containing 45 individual hydrocarbons were generated by passive dosing and added to river water containing the native microorganisms. Compound-specific biodegradation kinetics were then determined at 2.7, 12, and 20 °C based on substrate depletion. Main findings comprise the following: (1) Degradation half-times (DegT50) of 34 test chemicals were determined at different test temperatures and were largely consistent with the Arrhenius equation (activation energy, 65.4 kJ/mol). (2) Differences in biodegradation kinetics between tested isomers were rather limited. (3) The recent lowering of standard test temperature from 20 to 12 °C results typically in a doubling of DegT50 values and can lead to a stricter persistency assessment.

Experiments linked temperature, biodegradation kinetics and microbial composition. Biodegradation kinetics and microbial composition were similar for summer and winter inoculum but markedly affected by test incubation.