Determination of technical grade isocyanates used in the production of polyurethane plastics

A method for determination of technical grade isocyanates used in the production of polyurethane (PUR) is presented. The isocyanates in technical grade products were characterised as di-n-butylamine (DBA) derivatives using LC-MS and LC-chemiluminescent nitrogen detection (CLND) and the total isocyanate content was compared to a titration assay. For collection of isocyanates in air, an impinger-filter sampling technique with DBA as derivatisation reagent was used. Characterised DBA and nonadeuterium labelled DBA derivatives of isocyanates in technical products were used as calibration standards and internal standards, respectively, in the analysis of air samples. Three workplaces were studied where PUR products were produced either by spraying or by moulding. In both technical products and in air samples, a number of monomeric, oligomeric and prepolymeric isocyanates of e.g. methylenebisphenyl diisocyanate (MDI) and hexamethylene diisocyanate (HDI) were characterised. Several of these have not previously been described in workplace atmospheres. In the technical isocyanate products, between 69 and 102% of the NCO content determined by titration was accounted for by LC-CLND. Quantifications of a wide range of isocyanates in air samples were performed with correlation coefficients in the range 0.988-0.999 (n= 8) and the instrumental detection limits were 0.7-25 pg. At the two workplaces where MDI- and HDI isocyanurate-based products were sprayed, the isocyanate composition in the air reflected the composition in the technical product. At the workplace where a MDI-based product was used in a moulding process, only the monomeric isocyanates were found in the air. The advantage of using characterised technical grade isocyanates as analytical standards was clearly demonstrated and the possibility of using index compounds when monitoring isocyanate exposure is discussed.     

Determination of isocyanates, aminoisocyanates and amines in air formed during the thermal degradation of polyurethane

An air sampling method for the determination of isocyanates, aminoisocyanates and amines formed during the thermal degradation of polyurethane (PUR) is presented. The method is based on the collection of air samples using impinger flasks containing di-n-butylamine (DBA) in toluene with a glass fibre filter in series. Isocyanates are derivatized with DBA to urea derivatives, and amines are derivatized in a subsequent work-up procedure with ethyl chloroformate (ET) to carbamate esters. Amine, aminoisocyanate and isocyanate derivatives were characterized using liquid chromatography-time of flight mass spectrometry (LC-TOFMS) and liquid chromatography-chemiluminescent nitrogen detection (LC-CLND). Quantification was performed by LC-MS, monitoring molecular ions [MH]+ in the electrospray mode. The instrumental detection limits for amines, aminoisocyanates and isocyanates were in the ranges 30-40, 2-3 and 3-70 fmol, respectively. Thermal degradation products of PUR were observed in high concentrations during welding in district heating pipes and PUR-coated metal sheets. Eleven isocyanates, three amines and five aminoisocyanates were identified. The concentrations of isocyanates, aminoisocyanates and amines in samples collected in the smoke close to the welding spot were in the ranges 150-650, 4-290 and 1-70 ppb, respectively. In samples collected in the breathing zone, isocyanates and aminoisocyanates were observed in the ranges 9-120 and 4-19 ppb, respectively. The compounds were present in both gas and particle phases. Volatile compounds dominated in the gas phase, whereas less volatile compounds dominated in the particle phase. The method presented makes it possible to sample and determine amines and aminoisocyanates, in addition to isocyanates. The need to monitor these compounds is clearly illustrated by the high concentrations found during the thermal degradation of PUR.     

Tracing recovery from acidification in the western Norwegian Nausta watershed

A novel method, redundancy analysis (RDA), has been used to examine whether chemical recovery from acidification in the western Norwegian Nausta watershed produces detectable recovery within the community structure of the macro-zoobenthos. The RDA results have been compared with measures of recovery based on the changes detected using highly specialized and regionally defined biological acidity indices. We found that the beginning of biological recovery in the Nausta watershed was recognizable during the period 1989-1998. Recovery occurred in the upper reaches and in the tributaries. The multivariate approach proved to complement the acidity indices approach, and much biological information can be gained by their combined use. The RDA method is conservative, i.e. does not overestimate biological recovery, and it is not geographically constrained as are the acidity indices. We also found that seasonal climatic factors strongly influence the benthic community, and may confound the detection of the biological recovery process.     

Die Kristallstruktur des monoklinen α-Bi2O3

The Science of Nature -     

Molecular effects and bioaccumulation of levonorgestrel in the non-target organism Dreissena polymorpha

Bioaccumulation and effects of the contraceptive hormone levonorgestrel were examined in the non-target organism Dreissena polymorpha. Molecular biomarkers of biotransformation, elimination, antioxidant defence and protein damage were analyzed after exposure to increasing concentrations of levonorgestrel in a flow-through system. The lowest concentration (0.312 μg L⁻¹) was 100-fold bioconcentrated within four days. A decrease of the bioconcentration factor was observed within one week for the highest test concentrations (3.12 and 6.24 μg L⁻¹) suggesting enhanced excretory processes. The immediate mRNA up-regulation of pi class glutathione S-transferase proved that phase II biotransformation processes were induced. Disturbance of fundamental cell functions was assumed since the aryl hydrocarbon receptor has been permanently down-regulated. mRNA up-regulation of P-glycoprotein, superoxide dismutase and metallothioneine suggested enhanced elimination processes and ongoing oxidative stress. mRNA up-regulation of heat shock protein 70 in mussels exposed to the two highest concentrations clearly indicated impacts on protein damage.     

Some heterocyclic aromatic compounds are Ah receptor agonists in the DR-CALUX assay and the EROD assay with RTL-W1 cells

Purpose  

Heterocyclic aromatic compounds containing nitrogen, sulfur, or oxygen heteroatoms (NSO-HET) have been detected in air, soil, marine, and freshwater systems. However, only few publications are available investigating NSO-HET using in vitro bioassays. To support better characterization of environmental samples, selected NSO-HET were screened for dioxin-like activity in two bioassays.     

Abundances and flux estimates of volatile organic compounds from a dairy cowshed in Germany

Animal husbandry and manure treatment have been specifically documented as significant sources of methane, ammonia, nitrous oxide, and particulate matter. Although volatile organic compounds (VOCs) are also produced, much less information exists concerning their impact. We report on chemical ionization mass spectrometry and photo-acoustic spectroscopy measurements of mixing ratios of VOCs over a 2-wk measurement period in a large cowshed at the Federal Agricultural Research Centre (FAL) in Mariensee, Germany. The high time resolution of these measurements enables insight into the sources of the emissions in a typical livestock management setting. During feeding hours and solid manure removal, large mixing ratio spikes of several VOCs were observed and correlated with simultaneous methane, carbon dioxide, and ammonia level enhancements. The subsequent decay of cowshed concentration due to passive cowshed ventilation was used to model emission rates, which were dominated by ethanol and acetic acid, followed by methanol. Correlations of VOC mixing ratios with methane or ammonia were also used to calculate cowshed emission factors and to estimate potential nationwide VOC emissions from dairy cows. The results ranged from around 0.1 Gg carbon per year (1 Gg = 10(9) g) for nonanal and dimethylsulfide, several Gg carbon per year for volatile fatty acids and methanol, to over 10 Gg carbon per year of emitted ethanol. While some estimates were not consistent between the two extrapolation methods, the results indicate that animal husbandry VOC emissions are dominated by oxygenated compounds and may be a nationally but not globally significant emission to the atmosphere.     

From agricultural use of sewage sludge to nutrient extraction: A soil science outlook

The composition of municipal wastewater and sewage sludge reflects the use and proliferation of elements and contaminants within society. In Sweden, official statistics show that concentrations of toxic metals in municipal sewage sludge have steadily decreased, by up to 90 %, since the 1970s, due to environmental programmes and statutory limits on metals in sludge and soil. Results from long-term field experiments show that reduced metal pollution during repeated sewage sludge application has reversed negative trends in soil biology. Despite this Swedish success story, organic waste recycling from Swedish towns and cities to arable land is still limited to only about 20 % of the total amount produced. Resistance among industries and consumers to products grown on land treated with sewage sludge may not always be scientifically grounded; however, there are rational obstacles to application of sewage sludge to land based on its inherent properties rather than its content of pollutants. We argue that application of urban organic wastes to soil is an efficient form of recycling for small municipalities, but that organic waste treatment from large cities requires other solutions. The large volumes of sewage sludge collected in towns and cities are not equitably distributed back to arable land because of the following: (i) The high water and low nutrient content in sewage sludge make long-distance transportation too expensive; and (ii) the low plant availability of nutrients in sewage sludge results in small yield increases even after many years of repeated sludge addition. Therefore, nutrient extraction from urban wastes instead of direct organic waste recycling is a possible way forward. The trend for increased combustion of urban wastes will make ash a key waste type in future. Combustion not only concentrates the nutrients in the ash but also leads to metal enrichment; hence, direct application of the ash to land is most often not possible. However, inorganic fertiliser (e.g. mono-ammonium phosphate fertiliser, MAP) can be produced from metal-contaminated sewage sludge ash in a process whereby the metals are removed. We argue that the view on organic waste recycling needs to be diversified in order to improve the urban–rural nutrient cycle, since only recycling urban organic wastes directly is not a viable option to close the urban–rural nutrient cycle. Recovery and recycling of nutrients from organic wastes are a possible solution. When organic waste recycling is complemented by nutrient extraction, some nutrient loops within society can be closed, enabling more sustainable agricultural production in future.