Environmental assessment of ester-based lubricants after application

GOAL, SCOPE AND BACKGROUND: Lubricants based on renewable resources are an environmentally friendly alternative to petrochemical products due to their better ecotoxicological performance and their excellent biodegradability. To improve the technical performance of lubricants, and to reduce friction and wear, the use of additives is nowadays obligatory. The collaborative research center SFB 442 aims at developing environmentally acceptable lubricants that facilitate the avoidance of these additives by transferring their function to suitable coatings. For a complete assessment of the ecological performance of these newly developed lubricants, the whole life cycle including production, application as well as disposal and fate in the environment is studied. In the following study the focus was on the application and its influence on the environmental behavior of the lubricant. The application of lubricants leads, among other things, to the intake of metals due to abrasion from tools, work pieces or mechanical components. Previous examinations indicated a possible influence of metals on the toxicity of eluates prepared from used lubricants (Erlenkaemper et al. 2005). To clarify if the apparent toxicity of used lubricants solely results from the intake of metals, the extractability of these metals from the oil matrix is determined. By combining chemical analyses with bioassays, the bioavailability of metals that are present in the extract is estimated. To further investigate the relevance of metals on toxicity, toxic units (TU) were calculated and related to the results of the bioassays. Interactions between the metals were investigated with aqueous mixtures of metal chlorides and calculations based on the concept of concentration addition and independent action. METHODS: A lubricant mixture was applied to a tribological test bench that simulates real conditions of use and extremely short time load, respectively. Samples were taken at particular times, water soluble fractions (WSF) of these fluids were prepared and dilution series were investigated in several bioassays. Concentration of metals and total organic carbon (TOC) were determined in the eluates. TUs were calculated according to Sprague (1970) and mixture toxicity was calculated according to the concept of concentration addition (Loewe and Muischnek 1926) and independent action (Bliss 1939). RESULTS: Analyses of the metal content of the lubricant and the eluates clearly revealed the availability of the metals in the aqueous extracts. Especially copper, zinc, nickel and chromium were found and their concentrations increased during the time of use. The water extractable fraction, e.g., of copper, rose from 8.8% to 45.3% of the total content in the lubricant after 33.5 hours of use. Tests performed with the algal growth inhibition assay and the luminescence inhibition assay revealed the uptake or absorption by the organisms and, thus, the bioavailability of the metals. The calculation of TUs partly indicated a possible influence of the metals on ecotoxicity of the eluates. Copper reached concentrations equal to or higher than the EC50 value of copper chloride in the growth inhibition assays with algae and Ps. putida as well in the immobilization assay with daphnids. TUs for copper are also larger than 1 for the algal growth inhibition assay. The EL50 values indicated that the luminescence inhibition assay was the most sensitive test system, with values between 4.7% and 9.6%. While the toxicity towards algae and V. fischeri in the growth inhibition assay decreased until both organisms were no longer influenced by the exposure, the EL50 values for the D. magna immobilization assay and the Ps. putida growth inhibition assay decreased with the progressing use of the lubricant. The tested metal salt mixtures showed that Ps. putida, algae and daphnids are the most sensitive organisms with EC50 values below 1 mg/l. DISCUSSION: Although the intake of metals mainly occurred via abrasion of particles, the results revealed the availability of these metals in water. The availability varied for each of the four metals. For both the algal growth inhibition assay and the luminescence inhibition assay, an uptake or absorption of the metals could be demonstrated. The calculated TUs indicated an effect in some bioassays that was not verified in the test itself. The influence of copper on V. fischeri, for example, was not confirmed while the EL50 values for the daphnid bioassay decreased, meaning that the eluates became more toxic with progressing use of the lubricant. The calculations of mixture toxicity based on the concept of concentration addition demonstrated good correlations with the tested metal mixtures, but also a different sensitivity of the organisms. CONCLUSIONS: The results presented here reveal the availability of those metals in water that were taken in during the use of the lubricant in a tribological test bench and, thus, have the possibility of interacting with the organisms. The availability of the metals in the bioassays was proven by chemical analyses. The calculation of TUs and the corresponding EL50 values, however, indicate different availabilities of the metals. The results of the metal salt mixtures show good correlations with calculations of mixture toxicity based on concentration addition. Moreover, the varying sensitivity of the organisms when exposed to eluates or metal mixtures indicates a different bioavailability of the metals and/or the presence of other compounds that exert toxic action. RECOMMENDATIONS AND PERSPECTIVES: For further investigations, the organic oil matrix and its influence on the toxicity have to be taken into account. The toxicity of the eluates may not only be due to metals; additional effects could arise from changes in the lubricant itself.     

Characterization and application of the enzyme peroxidase to the degradation of the mycotoxin DON

Deoxynivalenol (DON), one of the main mycotoxins found in food matrices, has high level of toxicity. This study aimed to characterize the peroxidase enzyme extracted from rice bran to be applied to the biodegradation of DON in order to evaluate the potential peroxidase (PO) from rice bran (RB) has to degrade DON in optimal conditions. Purification and recovery factors of PO extracted from RB and purified by three-phase partitioning were 5.7% and 50%, respectively. PO had the highest level of activity in the phosphate buffer 5 mM pH 5.5 in both crude and purified forms, whose reaction temperatures were 25°C and 10°C. At the end of production, purification and characterization steps, specific activities of the bran were 115.79 U mg^?1 and 4363 U g^?1. Reduction in the mycotoxin DON in optimal conditions determined for PO from RB was 20.3%, a promising result when the aim is to adequate mycotoxicological levels to foods.     

Phenol tolerance, changes of antioxidative enzymes and cellular damage in transgenic tobacco hairy roots colonized by arbuscular mycorrhizal fungi

Phytoremediation has been recognized as a cheap and eco-friendly technology which could be used for the remediation of organic pollutants, such as phenolic compounds. Besides, the extent to which plants react to environmental pollution might depend on rhizosphere processes such as mycorrhizal symbiosis. In the present work, phenol tolerance of transgenic tobacco hairy roots (HR), namely TPX1, colonized with an arbuscular mycorrhizal fungus (AMF) was studied. However, the question is whether AMF symbiosis can moderate adverse effects of phenol to the plant tissues. Thus, the antioxidative response as well as parameters of oxidative damage, like malondialdehyde (MDA) content, were determined. Antioxidative enzymes such as peroxidase, superoxide dismutase, ascorbate peroxidase were higher in TPX1 HR colonized with AMF, compared to wild type HR colonized by AMF, in the presence of increasing concentrations of the pollutant. Besides, MDA levels remained unaltered in TPX1 HR associated with AMF treated with the xenobiotic. These results, suggested that this culture could tolerate phenol and moreover, it has an efficient protective mechanism against phenol-induced oxidative damage, which is of great importance in the selection of species with remediation capacities. Thus, transgenic HR colonized with AMF could be considered as an interesting model system to study different processes which play a key role in the phytoremediation of organic pollutants.     

A screening model for fate and transport of biodegradable polyesters in soil

A numerical model for predicting the fate and transport of biodegradable polyester residues in soil, following successive applications of mulch film, was developed and applied. The polymer, applied on surface soil, was assumed to be converted into by-products (monomers), according to a first order kinetics with constant K(1deg). The monomers released were assumed to sorb on soil organic matter (according to a first-order kinetics with constant K(s)), to be leached with the seepage water, through vertical advection and hydrodynamic dispersion, and biodegraded (according to a first-order kinetics with constant K(b)). Results suggested that, to assess a possible build-up of mulch film (as a polymer) on the surface soil, the degradation constant K(1deg) relating the polymer conversion to by-products should be known, whereas the biodegradation constant K(b) indicates there is no danger of groundwater pollution. Likewise, on the basis of by-product concentration in deep soil, soil pollution should not occur.     

Photolysis of fluometuron in the presence of natural water constituents

Phototransformation of the herbicide fluometuron (1 microM) in natural sunlight was investigated in neutral Milli-Q water and in synthetic waters containing either fulvic acids, nitrate ions or both in order to mimic reactions taking place in aquatic environments. Fluometuron degradation followed a pseudo-first order kinetics. The reaction was faster in synthetic than in Milli-Q water. Fulvic acids (10 mg l(-1)) increased the rate of fluometuron photolysis by a factor 2.5 and nitrates (25 mg l(-1)) by a factor 15. Identification of major photoproducts was conducted under laboratory conditions using LC-ESI-MS. Numerous photoproducts were detected and tentatively characterized. In the presence of nitrates, hydroxylation of the aromatic ring with or without hydrolysis of CF(3) into CO(2)H and oxidation of the urea chain leading to demethylation were observed. In the presence of fulvic acids, hydroxylation of the aromatic ring was the major reaction route.     

Production of zeolitic materials in pilot scale based on coal ash for phosphate and potassium adsorption in order to obtain fertilizer

Environmental Science and Pollution Research - The use of different types of zeolites (X, Na-P1, and 4A) synthesized by different methods and scales were tested in this work to adsorb nutrients...     

Irrigation water intensity and climate variability: an agricultural crops analysis of Italian regions

Environmental Science and Pollution Research - This paper examines the relationship between the requirement of water resources for irrigation and climate variability and analyses the ranking of the...     

Trace metals in estuarine organisms from a port region in southern Brazil: consumption risk to the local population

Environmental Science and Pollution Research - Metal contamination is a threat to estuarine environments. They can accumulate in the food chain and cause toxic effects on aquatic organisms and...     

Effects of learning and adaptation on population viability

Cultural adaptation is one means by which conservationists may help populations adapt to threats. A learned behavior may protect an individual from a threat, and the behavior can be transmitted horizontally (within generations) and vertically (between generations), rapidly conferring population-level protection. Although possible in theory, it remains unclear whether such manipulations work in a conservation setting; what conditions are required for them to work; and how they might affect the evolutionary process. We examined models in which a population can adapt through both genetic and cultural mechanisms. Our work was motivated by the invasion of highly toxic cane toads (Rhinella marina) across northern Australia and the resultant declines of endangered northern quolls (Dasyurus hallucatus), which attack and are fatally poisoned by the toxic toads. We examined whether a novel management strategy in which wild quolls are trained to avoid toads can reduce extinction probability. We used a simulation model tailored to quoll life history. Within simulations, individuals were trained and a continuous evolving trait determined innate tendency to attack toads. We applied this model in a population viability setting. The strategy reduced extinction probability only when heritability of innate aversion was low (<20%) and when trained mothers trained >70% of their young to avoid toads. When these conditions were met, genetic adaptation was slower, but rapid cultural adaptation kept the population extant while genetic adaptation was completed. To gain insight into the evolutionary dynamics (in which we saw a transitory peak in cultural adaptation over time), we also developed a simple analytical model of evolutionary dynamics. This model showed that the strength of natural selection declined as the cultural transmission rate increased and that adaptation proceeded only when the rate of cultural transmission was below a critical value determined by the relative levels of protection conferred by genetic versus cultural mechanisms. Together, our models showed that cultural adaptation can play a powerful role in preventing extinction, but that rates of cultural transmission need to be high for this to occur.