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.     

Halogenated organic contaminants in marine fish and mussels from southern Greenland--pilot study on relations to trophic levels and local sources

Mussels and marine fish (shorthorn sculpin and Greenland cod) were sampled at three locations with varying human activity. Fish livers and mussels were analysed for polychlorinated biphenyls (PCBs), polybrominated diphenylethers (PBDEs) and chlorinated pesticides including chlordane and toxaphene. Levels of chlorinated contaminants in shorthorn sculpins from the background location, [capital Sigma]PCB (217-224 ng g(-1) lw), [capital Sigma]DDT (180 ng g(-1) lw) and hexachlorobenzene (32-44 ng g(-1) lw), were in the same range as previously observed in eastern Greenland but exceeded the levels previously observed in southern and western Greenland. Multivariate analysis showed that pollutant concentrations were mainly explained by trophic levels of the species (cod > sculpins > mussels). A pooled sample of shorthorn sculpins from the harbour of Qaqortoq had significantly higher PCB and PBDE concentrations with a different congener pattern compared to the background site, while other contaminants were comparable. This points towards local pollution sources, possibly accumulated emissions from burning of waste.     

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.     

Liquid chromatographic aqueous product characterization of high-energy electron beam irradiated 2-chlorobiphenyl solutions

Polychlorinated biphenyls (PCBs) are of environmental concern due to their toxic nature. Ionizing radiation has been suggested as a means to remediate PCB-contaminated samples in complex matrices. A set of experiments was performed to qualitatively and quantitatively determine the aromatic degradation products of 2-monochlorobiphenyl (2-MCB) in an aqueous system exposed to ionizing radiation. The degradation of 2-MCB was observed in aqueous samples that were exposed to radiation from a linear accelerator electron beam source. Analytical measurements performed by liquid chromatography (LC) equipped with an ultraviolet (UV) detector revealed that biphenyl, o-hydroxybiphenyl, p-hydroxybiphenyl, phenol, chlorobenzene, and other unidentified products were created after 2-MCB irradiation. These results suggest that sensitive and selective analytical methods will be required to account for all degradation products during ionizing radiation of aqueous PCB-contaminated samples.     

Wet deposition of pesticides and nitrophenols at two sites in Denmark: measurements and contributions from regional sources

The concentrations of selected pesticides, of some of their degradation products and nitrophenols in rain were measured at two stations in Denmark in the period January 2000-July 2001. Forty compounds were quantified at least at one station during at least one sampling period. Additionally 17 compounds could be detected but not quantified, and 22 compounds could not be detected at all. The highest depositions of pesticides were observed for pendimethalin and desethylterbuthylazine, which is a degradation product of terbuthylazine. The deposition of the nitrophenols 2,4-dinitrophenol, DNOC, 3-methyl-4-nitrophenol was much higher than that of pesticides. The deposition of 2,4-dinitrophenol was e.g. up to a factor of 40 higher than that of pendimethalin. Atrazine, chloridazon, 2,4-D, dieldrin, disulfoton, fenitrothion, isoproturon, lenacil, metazachlor and propachlor were found in precipitation, although these pesticides are not allowed in Denmark. It can therefore be concluded that they came from abroad and have been transported over at least 60-80 km. For some of these compounds the transport distance is much longer.     

RDX and TNT residues from live-fire and blow-in-place detonations

Snow was used as a collection medium to examine 1,3,5-hexahydro-1,3,5-trinitrotriazine (RDX) and 2,4,6-trinitrotoluene (TNT) residues post-detonation of 60-, 81-, and 120-mm mortar rounds, 105- and 155-mm howitzer rounds, M67 hand grenades, 40-mm rifle grenades, and blocks of C4. Residue-covered snow samples were collected, processed, and analyzed for explosives without cross-contamination from previous detonations and other potential matrix interferences. Detonation trials were performed following standard military live-fire and blow-in-place techniques. When possible, replicate munitions were detonated under similar conditions to provide a more reliable estimation of the mass of unconsumed high explosive residues. Overall the amount of energetic residues deposited from live-fire detonations were considerably less than the energetic residues deposited by blow-in-place detonations.     

Testing the Norwegian phosphorus index at the field and subcatchment scale

Simple risk assessment tools for agricultural phosphorus (P) losses, like the P index, have been developed in the U.S.A. and in some European countries. Despite its popularity, there have been surprisingly few studies, which try to test the index close to the field scale. For Norway, the P index approach comprises the risk related to both the source of P (soil P status, amount of fertilizer and manure as well as method of application, plant P release by freezing and P balance) and the risk related to transport of P (erosion, flooding, surface runoff, contributing distance, modified connectivity, soil profile, subsurface drainage). In this paper, we have applied the Norwegian P index to farmer fields within a small agricultural catchment, the Skuterud catchment (450 ha), in southeastern Norway. The Norwegian P index was tested for two agricultural fields (0.3–0.4 ha) and nine subcatchments (6–65 ha). Total P concentrations in runoff from the 11 study areas were measured during the year from May 2001 to April 2002. Results from the testing showed that the Norwegian P index described 66% of the variation in measured relative total P concentration for fields and subcatchments included in this study. Additionally, the P index was able to detect fields and subcatchments with the highest measured P concentrations. Results also showed that the source factor contributed most to the variation between fields and hence were important for the identification of high-risk areas in Skuterud catchment. It was found that the soil P status described 66% of the variation in the source factor. Among the transport variables, it was found that both erosion risk and contributing distance had an important influence on the transport factor. Overall, the study illustrated the potential of the P index to detect areas with the highest risk of P loss.     

A pipette method for rapid karyotyping in prenatal diagnosis

The 'pipette method' is introduced as a method of prenatal diagnosis which is in competition with the 'in situ' and the 'trypsinization' technique. It is sufficiently standardized for routine diagnosis and the banding techniques currently used in prenatal diagnosis (G, Q, C-banding and NOR) have been adapted for it. In 180 cases from 27 different centres, the 'pipette method' was employed for chromosomal harvesting in order to save time. An average of 6·6 days was taken to achieve a result. There was a pathological karyotype in 28 cases (16·1 per cent) and this high proportion can be related to cases where ultrasound scan has led to a diagnosis of 'suspected chromosomal abnormality'. This technique is also of use in advanced stages of pregnancy. The early recognition of the fetal karyotype can contribute to the future management of the pregnancy. The 'pipette method' can also be used in chromosomal harvesting of tumour cells and fibroblast cultures.