Background, Aims and Scope Releasing agents, applied in the aluminium diecasting process, usually consist of water, oils, waxes, polysiloxanes, as well
as of a set of additives like emulsifiers, corrosion inhibitors, and biocides. During spray application and part release,
gases and aerosols are emitted into workplace air. The chemical compositions of these emissions are determined by the components
of the releasing agents and their reaction products formed during thermal stress of more than 700 °C. In the frame of the
joint project, the analytical tasks were to develop an appropriate sampling strategy for this production environment, to draw
conclusions about the occurrence of hazardous chemicals from production plant studies and from laboratory-scale thermolysis
experiments, and to determine the biodegradability of customary releasing agents.
Methods During realistic test production, active air sampling was performed in a production hall using different adsorption materials.
Cotton fabric sheets were positioned in the production area as passive samplers. Thermolysis experiments were performed at
600 °C with sealed quartz ampoules. The biodegradability of different releasing agents was determined according to German
industry standard DIN 51828 (2000). For analyses, GC/MS (headspace), FTIR, HPLC, IC, and ICP-OES techniques were applied.
Results and Discussion The substance spectrum, which was found in workplace air, was dominated by saturated and non-saturated aliphatic hydrocarbons.
Besides these, alcohols, alkyl phenols, xylenes and other benzene derivatives, aldehydes, glycols, carboxylic acid esters,
and amides were present. The German limiting value of 40 mg/m3 of complex hydrocarbon mixtures in a diecasting workplace atmosphere
was clearly under-run. Total hydrocarbon contents ranged between 2.7 and 6.3 mg/m3. Five different PAH were found in the air
close to the diecasting machine, with maximum concentrations between 0.05 and 3.06 μg/m3. Concentrations of nonylphenols ranged
from 10 to 200 μg/m3, and those of triethanolamine from 20 to 30 μg/m3. From 17 elements analyzed, only B, Fe, P, S, Si, and
Ti were emitted in small amounts. It was striking that the PAH patterns resulting from thermolysis experiments were quite
the same compared to those determined during the diecasting process. An influence of water and of Fe/Al on the composition
of the thermolysis products could mostly be shown. The degrees of biodegradation of three releasing agent extracts after 21
days were 21%, 29%, and 55%, respectively.
Conclusion A sampling strategy was developed, which allows an emission assessment for the industrial process of aluminium diecasting.
It enabled one to control limiting values, to characterise a wide variety of compounds emitted, and to identify and quantify
relevant pollutants. Only a few hazardous substances could be detected during the exemplary use of one releasing agent within
the compounds emitted into workplace air. Indications were found, that the prediction of the formation of harmful substances
from releasing agent components should be possible via thermolysis experiments. The biodegradability test can serve to assess
the expenditure of disposal of the usual leakage run-off of excess agent during production.
Recommendation and Outlook Investigations on further differently composed releasing agents, e.g. powders, would be desirable. A substitution of nonylphenol
ethoxylates by less harmful components would surely be an improvement of a releasing agent with regard to work safety and
health care, because of avoiding the emission of toxic and endocrine active nonylphenols. The surprisingly wide range of biodegradability
of the investigated releasing agents points to an optimization potential, that has obviously not yet been considered. 相似文献
The purpose of this study was to evaluate photodegradabilities of the following new low-nitrogen chelating agents: N-bis[(carboxymethoxy)ethyl]glycine (compound 1), N-bis[(1,2-dicarboxyethoxy)ethyl]glycine (compound 2) and N-bis[(1,2-dicarboxyethoxy)ethyl]aspartic acid (compound 3). At first photodegradation of these chelating agents as uncomplexed Na-compound 1–3 and Cu(II) complexes were tested, both in lake and distilled water, by exposing them to near-UV region radiation at the range of 315–400 nm. Uncomplexed Na-compounds 2 and 3 were selected to sunlight exposure experiments carried out in lake and distilled water. Compound 3 was also tested in sunlight as Cu and Ca complexes in both solutions. Photodegradation of Na6-compound 3 in distilled water was studied by exposing it to radiation at the wavelength of 253.7 nm. Photodegradation products were analysed by means of GC-MS (gas chromatography with mass selective detector).
The results demonstrated that compound 1 was quite photostable even as Cu complex while compounds 2 and 3 were found to be photodegradable. Over 90% reduction of compound 3 was achieved during one week and 80% reduction of compound 2 in two weeks' time when they were added as Na salt to lake water and exposed to sunlight. Compound 3 as Cu complex degraded totally in the sunlight in less than one week. In the case of compound 3, the degradation rate decreased depending on the counter cation in the order Cu > Na Ca. The study demonstrated that photodegradation of Na6-compound 3 does not result in total mineralization of the compound. A photodegradation pathway for Na6-compound 3 is proposed. 相似文献