Isocyanates and Amines – Sampling and Analytical Procedures

This thesis covers sampling and analytical procedures for isocyanates (R-NCO) and amines (R-NH2), two kinds of chemicals frequently used in association with the polymeric material polyurethane (PUR). Exposure to isocyanates may result in respiratory disorders and dermal sensitisation, and they are one of the main causes of occupational asthma. Several of the aromatic diamines associated with PUR production are classified as suspected carcinogens. Hence, the presence of these chemicals in different exposure situations must be monitored. In the context of determining isocyanates in air, the methodologies included derivatisation with the reagent di-n-butylamine (DBA) upon collection and subsequent determination using liquid chromatography (LC) and mass spectrometric detection (MS). A user-friendly solvent-free sampler for collection of airborne isocyanates was developed as an alternative to a more cumbersome impinger-filter sampling technique. The combination of the DBA reagent together with MS detection techniques revealed several new exposure situations for isocyanates, such as isocyanic acid during thermal degradation of PUR and urea-based resins. Further, a method for characterising isocyanates in technical products used in the production of PUR was developed. This enabled determination of isocyanates in air for which pure analytical standards are missing. Tandem MS (MS/MS) determination of isocyanates in air below 10-6 of the threshold limit values was achieved. As for the determination of amines, the analytical methods included derivatisation into pentafluoropropionic amide or ethyl carbamate ester derivatives and subsequent MS analysis. Several amines in biological fluids, as markers of exposure for either the amines themselves or the corresponding isocyanates, were determined by LC-MS/MS at amol level. In aqueous extraction solutions of flexible PUR foam products, toluene diamine and related compounds were found. In conclusion, this thesis demonstrates the usefulness of well characterised analytical procedures and techniques for determination of hazardous compounds. Without reliable and robust methodologies there is a risk that exposure levels will be underestimated or, even worse, that relevant compounds will be completely missed.

Spatial distribution and morphometric analysis of thermokarst lakes and other water bodies : Case study from the sporadic permafrost region, Tavvavuoma, Sweden

Projected air and ground temperatures are expected to be higher in Arctic and sub-Arcticlatitudes and with temperatures already close to the limit where permafrost can exist,resistance against degradation is low. With thawing permafrost, the landscape is modifiedwith depression in which thermokarst lakes emerge. In permafrost soils a considerableamount of soil organic carbon is stored, with the potential of altering climate even furtherif expansion and formation of new thermokarst lakes emerge, as decay releasesgreenhouse gases (C02 and CH4) to the atmosphere. Analyzing the spatial distribution andmorphometry over time of thermokarst lakes and other water bodies, is of importance inaccurately predict carbon budget and feedback mechanisms, as well as to assess futurelandscape layout and these features interaction. Different types of high-spatial resolutionaerial and satellite imageries from 1963, 1975, 2003, 2010 and 2015, were used in bothpre- and post-classification change detection analyses. Using object oriented segmentationin eCognition combined with manual adjustments, resulted in digitalized water bodies>28m2 from which direction of change and morphometric values were extracted. Thequantity of thermokarst lakes and other water bodies was in 1963 n=92, with succeedingyears as a trend decreased in numbers, until 2010-2015 when eleven water bodies wereadded in 2015 (n=74 to n=85). In 1963-2003, area of these water bodies decreased with50 651m2 (189 446-138 795m2) and continued to decrease in 2003-2015 ending at 129337m2. Limnicity decreased from 19.9% in 1963 to 14.6% in 2003 (-5.3%). In 2010 and2015 13.7-13.6%. The late increase in water bodies differs from an earlier hypothesis thatsporadic permafrost regions experience decrease in both area and quantity of thermokarstlakes and water bodies. During 1963-2015, land gain has been in dominance of the ratiobetween the two competing processes of expansion and drainage. In 1963-1975, 55/45%,followed by 90/10% in 1975-2003. After major drainage events, land loss increased to62/38% in 2010-2015. Drainage and infilling rates, calculated for 15 shorelines werevaried across both landscape and parts of shorelines, with in average 0.17/0.15/0.14m/yr.Except for 1963-1975 when rate of change in average was in opposite direction (-0.09m/yr.), likely due to evident expansion of a large thermokarst lake. Using a squaregrid, distribution of water bodies was determined, with an indistinct cluster located in NEand central parts. Especially for water bodies <250m2, which is the dominant area classthroughout 1963-2015 ranging from n=39-51. With a heterogeneous composition of bothsmall and large thermokarst lakes, and with both expansion and drainage altering thelandscape in Tavvavuoma, both positive and negative climate feedback mechanisms are inplay - given that sporadic permafrost still exist.