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.     

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.     

Die Kristallstruktur des monoklinen α-Bi2O3

The Science of Nature -     

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.     

Liming of River Audna,Southern Norway: a large-scale experiment of benthic invertebrate recovery

This study describes the recovery of sensitive invertebrates after liming of the anadromous part of River Audna in 1985. The river lost its salmon population during 1960-1970. The aim of the liming was to produce a water quality with pH > 6.0 and ANC > 20 microg L(-1) and to reduce the content of labile aluminum. Highly sensitive invertebrates like the mayfly Baetis rhodani were not found in the river before liming. Two years after liming, several sensitive invertebrate species showed a positive response. B. rhodani was then recorded at 2 sites in the lower part of the river. In the following 5 years several species of sensitive invertebrates recolonized the whole limed reach of the river and became numerous. Ten years after liming the snail Lymnaea peregra was recorded in the river. The dispersa of this species was also very fast and after 5 years it was found at all investigated sites in the limed main river covering a reach of 40 km. Reduced sulfur deposition in the area also resulted in water-quality improvements in th unlimed stretches of River Audna. Comparisons between limed and unlimed localities indicated that the water quality and the critical limits of sensitive species are the ma factors determining the fauna composition in River Audna independent of the reason for the change in water quality.     

Release of sex pheromone and its precursors in the pine sawfly Diprion pini (Hym., Diprionidae)

Summary. The first identification of a sex pheromone of a pine sawfly (Hymenoptera, Diprionidae) dates back almost thirty years. Since then, female-produced pheromones of over twenty diprionid species have been investigated by solvent extraction followed by separation and identification. However, no study has shown what the females actually release. Collection of airborne compounds using absorbtion on charcoal filter as well as solid phase microextraction (SPME) followed by analysis employing gas chromatography combined with mass spectrometry (GC-MS), revealed an unusual system in Diprion pini, in which the pheromone precursor alcohol, 3,7-dimethyl-2-tridecanol, is released together with acetic, propionic, butyric and isobutyric acids. The corresponding acetate, propionate and butyrate esters of 3,7-dimethyl-2-tridecanol were also found in the samples. All esters were electrophysiologically active, and the propionate and isobutyrate were attractive in trapping experiments. Based on these and earlier reported results, it seems that at least in part of its range, the pheromone response of D. pini is not very specific with regard to the functional group, as long as this is an ester.     

Determination of airborne anhydrides using LC-MS monitoring negative ions of di-n-butylamine derivatives

An air sampling method for simultaneous determination of organic acid anhydrides and isocyanates is presented. Air samples are collected in impinger flasks filled with 0.01 M di-n-butylamine (DBA) in a mixture of toluene-acetonitrile (7:3, v/v) with a 13 millimetre glass fibre filter in series. The amount of anhydrides and isocyanates are determined as their amide and urea derivatives using LC-MS. Four anhydrides, maleic anhydride (MA), phthalic anhydride (PA), tetrahydrophthalic anhydride (TA) and cis-hexahydrophthalic anhydride (HA) and 11 isocyanates could be separated in 9 minutes using gradient elution. Anhydride-DBA derivatives in standard solutions were quantified using LC with chemiluminescent nitrogen detection (CLND). Anhydride-DBA derivatives were found to be stable for at least two months when stored in acetonitrile or toluene in the freezer. The yield of DBA derivatives of anhydrides in the 0.01 M DBA in toluene-acetonitrile (7:3, v/v) was in the range of 70->95%. Using MS and negative electrospray ionisation (ES-) linear calibrations curves were obtained for the anhydrides with correlation coefficients ranging from 0.9970-0.9997. The instrumental detection limit for the anhydrides ranged from 10-30 fmol, based on a signal to noise root mean square (RMS) ratio of 3. Monitoring positive and negative ions simultaneously, both isocyanates and anhydrides could be determined as their DBA derivatives in the same chromatographic run. When air samples were collected during thermal degradation of different coated metal sheets both anhydrides and isocyanates were present in the same samples and all the studied anhydrides were found.     

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.