Evaluating microbial contaminations of alternative heating oils.

Since 2008, European and German legislative initiatives for climate protection and reduced dependency on fossil resources led to the introduction of biofuels as CO2-reduced alternatives in the heating oil sector. In the case of biodiesel, customers were confronted with accelerated microbial contaminations during storage. Since then, other fuel alternatives, like hydrogenated vegetable oils (HVOs), gas-to-liquid (GtL) products, or oxymethylene ether (OME) have been developed. In this study, we use online monitoring of microbial CO2 production and the simulation of onset of microbial contamination to investigate the contamination potential of fuel alternatives during storage. As references, fossil heating oil of German refineries are used. Biodiesel blends with fossil heating oils confirmed the promotion of microbial activity. In stark contrast, OMEs have an antimicrobial effect. The paraffinic Fischer-Tropsch products and biogenic hydrogenation products demonstrate to be at least as resistant to microbial contamination as fossil heating oils despite allowing a diversity of representative microbes. Through mass spectrometry, elemental analysis, and microbial sequencing, we can discuss fuel properties that affect microbial contaminations. In summary, novel, non-fossil heating oils show clear differences in microbial resistance during long-term storage. Designing blends with an intrinsic resistance against microbial contamination and hence reduced activity might be an option.

Freeze-thaw alternations accelerate plasticizers release and pose a risk for exposed organisms.

The application of plastic mulch films brings convenience to agricultural production, but also causes plastic waste that can be degraded into microplastics (MPs). However, little is known about the fate of plastic waste in agricultural ecosystem under freeze-thaw alternation in middle and high latitudes, as well as in highlands around the world. Whether the release of plasticizers, i.e. phthalate esters (PAEs), under such conditions would pose a potential risk to exposed organisms due to bioaccumulation is also unknown. To fill these data gaps, the agricultural fields in Liaoning of China with typical freeze-thaw alternation was selected as the study area. The transformation of plastic film was demonstrated by simulation freeze-thaw alternating from -30 to 20 â„ƒ. Soil samples were collected to investigate the patterns of MP composition, abundance, and distribution. Concurrently, the concentrations of two PAEs including bis(2-ethylhexyl) phthalate (DEHP) and diethyl phthalate (DEP) in soils were analyzed to provide information on the correlation between MPs abundance and PAEs concentrations as well as potential risks. The results showed that freeze-thaw alternating can accelerate the formation of MPs and release of PAEs from plastic waste. The abundance of MPs was positively correlated with the concentration of PAEs. Soil PAEs ranged from 3268 ± 213-6351 ± 110 µg/kg, indicating that over 40 % of the PAEs were transferred from plastic films to soils. Such residual amounts could pose risk for exposed organisms. Hence, the current study suggested that special concerns should be given to the release plasticizers in plastic waste of agricultural soils.

Toxicity of dodecylbenzene to algae, crustacean, and fish - Passive dosing of highly hydrophobic liquids at the solubility limit.

In the current study, improved exposure control and measurements were applied for the aquatic toxicity testing of a highly hydrophobic organic compound. The aim was to reliably determine the ecotoxicity of the model compound dodecylbenzene (DDB, Log KOW = 8.65) by applying passive dosing for aquatic toxicity testing exactly at the solubility limit. Methodologically, silicone O-rings were saturated by immersion in pure liquid DDB (i.e., "loading by swelling") and then used as passive dosing donors. Daphnia immobilization and fish embryo toxicity tests were successfully conducted and provide, together with recently reported algal growth inhibition data, a full base-set of ecotoxicological data according to REACH. All tests were conducted in closed test systems to avoid evaporative losses, and exposure concentrations were measured throughout test durations. The Daphnia test was optimized by placing the O-rings in cages to prevent direct contact between daphnids and the passive dosing donor. Toxicologically, Daphnia magna immobilization was 19.3 ± 8% (mean ± 95% CI; 6 tests) within 72 h, whereas Danio rerio fish embryos did not show any significant lethal or sublethal toxic responses within 96 h. Growth rate inhibition for the algae Raphidocelis subcapitata was previously reported to be 13 ± 5% in a first and 8 ± 3% in a repeated test. These results for aquatic organisms, spanning three trophic levels, demonstrate toxicity of a highly hydrophobic compound and suggest that improvements of the current ecotoxicological standard tests are needed for these "difficult-to-test" chemicals. Furthermore, the obtained toxicity results significantly question the existence of a generic Log KOW cut-off in baseline toxicity.

Improving the reliability of aquatic toxicity testing of hydrophobic chemicals via equilibrium passive dosing - A multiple trophic level case study on bromochlorophene.

The main objective of the present study was to improve the reliability and practicability of aquatic toxicity testing of hydrophobic chemicals based upon the model substance bromochlorophene (BCP). Therefore, we adapted a passive dosing format to test the toxicity of BCP at different concentrations and in multiple test systems with aquatic organisms of various trophic levels. At the same time, the method allowed for the accurate determination of exposure concentrations (i.e., in the presence of exposed organisms; Ctest) and freely dissolved concentrations (i.e., without organisms present; Cfree) of BCP in all tested media. We report on the joint adaptation of three ecotoxicity tests - algal growth inhibition, Daphnia magna immobilization, and fish-embryo toxicity - to a silicone O-ring based equilibrium passive dosing format. Effect concentrations derived by passive dosing methods were compared with corresponding effect concentrations derived by standard co-solvent setups. The passive dosing format led to EC50-values in the lower µgL-1 range for algae, daphnids, and fish embryos, whereas increased effect concentrations were measured in the co-solvent setups for algae and daphnids. This effect once more shows that passive dosing might offer advantages over standard methods like co-solvent setups when it comes to a reliable risk assessment of hydrophobic substances. The presented passive dosing setup offers a facilitated, practical, and repeatable way to test hydrophobic chemicals on their toxicity to aquatic organisms, and is an ideal basis for the detailed investigation of this important group of chemicals.

Aquatic toxicity testing of liquid hydrophobic chemicals - Passive dosing exactly at the saturation limit.

The aims of the present study were (1) to develop a passive dosing approach for aquatic toxicity testing of liquid substances with very high Kow values and (2) to apply this approach to the model substance dodecylbenzene (DDB, Log Kow = 8.65). The first step was to design a new passive dosing format for testing DDB exactly at its saturation limit. Silicone O-rings were saturated by direct immersion in pure liquid DDB, which resulted in swelling of >14%. These saturated O-rings were used to establish and maintain DDB exposure exactly at the saturation limit throughout 72-h algal growth inhibition tests with green algae Raphidocelis subcapitata. Growth rate inhibition at DDB solubility was 13 ± 5% (95% CI) in a first and 8 ± 3% (95% CI) in a repeated test, which demonstrated that improved exposure control can lead to good precision and repeatability of toxicity tests. This moderate toxicity at chemical activity of unity was higher than expected relative to a reported hydrophobicity cut-off in toxicity, but lower than expected relative to a reported chemical activity range for baseline toxicity. The present study introduces a new effective approach for toxicity testing of an important group of challenging chemicals, while providing a basis for investigating toxicity cut-off theories.

Accumulation and distribution of multiwalled carbon nanotubes in zebrafish (Danio rerio).

No data on the bioaccumulation and distribution of multiwalled carbon nanotubes (MWCNTs) in aquatic vertebrates is available until now. We quantified uptake and elimination of dispersed radiolabeled MWCNTs ((14)C-MWCNT; 1 mg/L) by zebrafish (Danio rerio) over time. The influences of the feeding regime and presence of dissolved organic carbon (DOC) on accumulation of the nanomaterial were determined. The partitioning of radioactivity to different organs and tissues was measured in all experiments. A bioaccumulation factor of 16 L/kg fish wet weight was derived. MWCNTs quickly associated with the fish, and steady state was reached within 1 day. After transfer to clear medium, MWCNTs were quickly released to the water phase, but on average 5 mg of MWCNTs/kg fish dry weight remained associated with the fish. The nanomaterial mainly accumulated in the gut of all fish. Feeding led to lower internal concentrations due to facilitated elimination via the digestive tract. In the presence of DOC, 10-fold less was taken up by the fish after 48 h of exposure compared to without DOC. Quick adhesion to and detachment from superficial tissues were observed. Remarkably, little fractions of the internalized radioactivity were detected in the blood and muscle tissue of exposed fish. The part accumulated in these fish compartments remained constant during the elimination phase. Hence, biomagnification of MWCNTs in the food chain is possible and should be a subject of further research.