Humans are exposed to chemical compounds in everyday life, both from the environment and from endogenous processes. Some compounds constitute a risk for cancer development. One such compound is glycidol, which is genotoxic and an animal carcinogen. It is the model compound of this work, partly due to its presence in food. Glycidol, often together with 3-monochloropropane-1,2-diol (3-MCPD), occurs in the form of esters particularly in refined cooking oils, which are used in a variety of food products. The esters are hydrolyzed in the gastrointestinal tract to form glycidol (and 3-MCPD).

The aim of the thesis has been to evaluate an approach for cancer risk estimation of genotoxic carcinogens based on a multiplicative (relative) risk model and genotoxic potency. Further, the aim was to estimate the cancer risk for exposure to glycidol via food. Measurement of the internal doses (concentration × time) of glycidol in the studied biological systems, including humans, has been crucial. Glycidol is electrophilic and forms adducts with nucleophilic sites in proteins and DNA. The doses of glycidol were quantified by mass spectrometry: in vivo from adduct levels to hemoglobin (Hb); in vitro from adducts to cob(I)alamin.

The first part of the thesis concerns the genotoxic potency (genotoxic response per internal dose) of glycidol, measured in vitro by mutation studies and in vivo by micronuclei as a biomarker for genotoxicity (short-term studies in mice). The results were compared to that of ionizing radiation, used as a standard, to estimate the relative genotoxic potency of glycidol: 10 and 15 rad-equ./mMh from mutations and micronuclei, respectively. No induction of micronuclei was observed for the related compound 3-MCPD.

Tumor incidence from published carcinogenicity studies of glycidol in mice and rats, together with the measured in vivo doses, was evaluated with the relative cancer risk model. A good agreement between predicted and observed tumor incidence was shown, and no significant difference of the obtained cancer risk coefficients (risk per dose) between mice (5.1 % per mMh) and rats (5.4 % per mMh) was observed. The overall results support that the relative risk coefficient (β) is independent of sex, tumor site, and species, and indicated that it can be transferred also to humans. The doubling dose, expressed as 1/β, is the dose that is required to double the background tumor incidence. The mean of the doubling doses from mice and rats (19 mMh) was assumed valid for risk estimation for humans. Transfer of β of glycidol to rad-equ. via its relative genotoxic potency showed a risk coefficient in agreement with the relative cancer risk coefficient of ionizing radiation.

In the final work, the lifetime (70 years) in vivo doses of glycidol were calculated from measured Hb adduct levels in blood from 50 children and 12 adults, and compared to the doubling dose. A fivefold variation was observed in the in vivo doses. The estimated lifetime excess cancer risk from glycidol exceeds 1/1000. This is much higher than what is considered as an acceptable risk.

To conclude, the multiplicative (relative) risk model together with relative genotoxic potency is promising to use in an approach for cancer risk estimation and in line with 3R (reduce-refine-replace) initiatives.

Glycidol is a genotoxic animal carcinogen that has raised concern due to its presence in food, as glycidyl fatty acid esters. Here we investigated the genotoxicity of glycidol in BalbC mice (0-120 mg/kg) by monitoring the induction of micronuclei in peripheral blood as a marker of chromosomal damage. The scoring of the micronuclei was assessed by flow cytometry. In the treated mice, the internal dose of glycidol, expressed as area under the concentration-time curve, AUC (mol x L-1 x h; Mh), was measured by dihydroxypropyl adducts to hemoglobin (Hb). The study showed that glycidol induced linear dose dependent increases of Hb adducts (20 pmol/g Hb per mg/kg) and of micronuclei frequencies (12 parts per thousand per mMh). Compared to calculations based on administered dose, an improved dose-response relationship was observed when considering internal dose, achieved through the applied combination of sensitive techniques used for the scoring of micronuclei and AUC estimation of glycidol in the same mice. By comparing with earlier studies on micronuclei induction in mice exposed to ionizing radiation we estimated the radiation dose equivalent (rad-eq.) of glycidol to be ca 15 rad-eq./mMh.

Here we evaluate a multiplicative (relative) risk model for improved cancer risk estimation of genotoxic compounds. According to this model, cancer risk is proportional to the background tumor incidence and to the internal dose of the genotoxic compound. Furthermore, the relative risk coefficient per internal dose is considered to be approximately the same across tumor sites, sex, and species. In the present study, we demonstrate that the relative risk model is valid for cancer risk estimation of glycidol, a common food contaminant. Published tumor data from glycidol carcinogenicity studies in mice and rats were evaluated in combination with internal dose estimates from hemoglobin adduct measurements in blood from mice and rats treated with glycidol in short-term studies. A good agreement between predicted and observed tumor incidence in responding sites was demonstrated in the animals, supporting a relative risk coefficient that is independent of tumor site, sex, and species. There was no significant difference between the risk coefficients for mice (5.1% per mMh) and rats (5.4% per mMh) when considering internal doses of glycidol. Altogether, this mechanism-based risk model gives a reliable risk coefficient, which then was extrapolated to humans considering internal dose, and background cancer incidence.

In this study 3-monochloropropane-1,2-diol (3-MCPD), a compound that appears as contaminant in refined cooking oils, has been studied with regard to genotoxicity in vivo (mice) with simultaneous measurement of internal dose using state-of-the-art methodologies. Genotoxicity (chromosomal aberrations) was measured by flow cytometry with dual lasers as the frequency of micronuclei in erythrocytes in peripheral blood from BalbC mice intraperitoneally exposed to 3-MCPD (0, 50, 75, 100, 125 mg/kg). The internal doses of 3-MCPD in the mice were calculated from N-(2,3-dihydroxypropyl)-valine adducts to hemoglobin (Hb), quantified at very low levels by high-resolution mass spectrometry.

Convincing evidence for absence of genotoxic potency in correlation to measured internal doses in the mice was demonstrated, despite relatively high administered doses of 3-MCPD. The results are discussed in relation to another food contaminant that is formed as ester in parallel to 3-MCPD esters in oil processing, i.e. glycidol, which has been studied previously by us in a similar experimental setup. Glycidol has been shown to be genotoxic, and in addition to have ca. 1000 times higher rate of adduct formation compared to that observed for 3-MCPD. The conclusion is that at simultaneous exposure to 3-MCPD and glycidol the concern about genotoxicity would be glycidol.

Here we evaluate a multiplicative (relative) risk model for more reliable cancer risk estimations of genotoxic compounds. According to this model, cancer risk is proportional to background tumor incidence and to internal dose of the genotoxic compound. A relative risk coefficient is considered to be common across species, sex, and tumor sites. The model has previously been shown to be successfully applied to rodent carcinogenicity data for a few genotoxic compounds. The aim of the present study was to evaluate this risk model for glycidol, a common food contaminant. Tumor data from published glycidol carcinogenicity studies in mice and rats were evaluated with the model, using internal doses estimated from hemoglobin adduct measurements in blood of B6C3F1 mice and Sprague Dawley rats treated with glycidol in short-term exposure studies.

The evaluation demonstrated that the relative risk model is valid for glycidol. A good agreement between predicted and observed tumor incidence was demonstrated in the animals, supporting a relative risk coefficient that is independent of species, sex, and tumor site. There was no significant difference of the risk coefficients between mice (5.1 % per mMh) and rats (7.1 % per mMh) when the internal doses of glycidol were considered. Altogether, this mechanism-based risk model gives a common and more reliable risk coefficient which could be extrapolated to humans via internal dose measurements, and by considering the background cancer incidence.

Glycidol (Gly) is an electrophilic low-molecular weight epoxide that is classified by IARC as probably carcinogenic to humans. Humans might be exposed to Gly from food, e.g. refined vegetable oils, where Gly has been found as a food process contaminant. It is therefore important to investigate and quantify the genotoxicity of Gly as a primary step towards cancer risk assessment of the human exposure. Here, quantification of the mutagenic potency expressed per dose (AUC: area under the concentration time curve) of Gly has been performed in Chinese hamster ovary (CHO) cells, using the HPRT assay. The dose of Gly was estimated in the cell exposure medium by trapping Gly with a strong nucleophile, cob(I)alamin, to form stable cobalamin adducts for analysis by LC-MS/MS. Gly was stable in the exposure medium during the time for cell treatment, and thus the dose in vitro is the initial concentration x cell treatment time. Gly induced mutations in the hprt-gene at ante of 0.08 +/- 0:01 mutations/10(5) cells/mMh. Through comparison with the effect of ionizing radiation in the same system a relative mutagenic potency of 9.5 rad-eq./mMh was obtained, which could be used for comparison of genotoxicity of chemicals and between test systems and also in procedures for quantitative cancer risk assessment. Gly was shown to induce strand breaks, that were repaired by base excision repair. Furthermore, Gly-induced lesions, present during replication, were found to delay the replication fork elongation. From experiments with repair deficient cells, homologous recombination repair and the ERCC1-XPF complex were indicated to be recruited to support in the repair of the damage related to the stalled replication elongation. The type of DNA damage responsible for the mutagenic effect of Gly could not be concluded from the present study.

Children are more susceptible to exposures to harmful compounds compared to adults. Monitoring of the actual exposures in vivo is important to enable risk mitigation actions. The general population, including children, is exposed to the carcinogen glycidol through food. A possible exposure source to glycidol is food containing refined cooking oils where it is present as a process-induced contaminant in the form of fatty acid esters.

In the present study internal (in vivo) doses of the genotoxic and carcinogenic compound glycidol have been determined in a cohort of 50 children and in a reference group of 12 adults (non-smokers and smokers). The lifetime in vivo doses of glycidol have been calculated from the levels of the hemoglobin (Hb) adduct N-(2,3-dihydroxypropyl)-valine in blood samples from the subjects, demonstrating about a 5-fold variation between the children (71–322 µMh). This variation is likely due to different dietary habits and/or different genotypes/phenotypes of the enzymes involved in the detoxification of glycidol. Data from the adults indicate that the non-smoking subjects are exposed to about the same level as the children, whereas the smoking subjects have about double levels, likely due to the presence of glycidol in tobacco smoke. The estimated exposure to glycidol in the children is higher than those estimated by European Food Safety Authority.

The calculated relative cancer risk increment due to glycidol exposure demonstrated an unacceptable risk for all subjects. The excess lifetime risk based on the estimated lifetime in vivo doses of glycidol exceeded 1/1000, which should be compared to a generally applied acceptable lifetime risk level of 1/100 000. A small contribution to the internal dose of glycidol from other precursors to the measured Hb adduct, and corresponding contribution to estimated risks from intake of glycidol from food cannot though be excluded.

The general population is exposed to the genotoxic carcinogen glycidol via food containing refined edible oils where glycidol is present in the form of fatty acid esters. In this study, internal (in vivo) doses of glycidol were determined in a cohort of 50 children and in a reference group of 12 adults (non-smokers and smokers). The lifetime in vivo doses and intakes of glycidol were calculated from the levels of the hemoglobin (Hb) adduct N-(2,3-dihydroxypropyl)valine in blood samples from the subjects, demonstrating a fivefold variation between the children. The estimated mean intake (1.4 mu g/kg/day) was about two times higher, compared to the estimated intake for children by the European Food Safety Authority. The data from adults indicate that the non-smoking and smoking subjects are exposed to about the same or higher levels compared to the children, respectively. The estimated lifetime cancer risk (200/10(5)) was calculated by a multiplicative risk model from the lifetime in vivo doses of glycidol in the children, and exceeds what is considered to be an acceptable cancer risk. The results emphasize the importance to further clarify exposure to glycidol and other possible precursors that could give a contribution to the observed adduct levels.

Activated carbon (AC) has been proven to be highly effective for the in-situ remediation of sediments contaminated with a wide range of hydrophobic organic contaminants (HOCs). However, adverse biological effects, especially to benthic organisms, can accompany this promising remediation potential. In this study, we compare both the remediation potential and the biological effects of several AC materials for two application methods: mixing with sediment (MIX) at doses of 0.1 and 1.0% based on sediment dw and thin layer capping (TLC) with 0.6 and 1.2 kg AC/m(2). Significant dose dependent reductions in PCB bioaccumulation in Lumbriculus variegatus of 35-93% in MIX treatments were observed. Contaminant uptake in TLC treatments was reduced by up to 78% and differences between the two applied doses were small. Correspondingly, significant adverse effects were observed for L. variegatus whenever AC was present in the sediment. The lowest application dose of 0.1% AC in the MIX system reduced L variegatus growth, and 1.0% AC led to a net loss of organism biomass. All TLC treatments let to a loss of biomass in the test organism. Furthermore, mortality was observed with 1.2 kg ACim(2) doses of pure AC for the TLC treatment. The addition of clay (Kaolinite) to the TLC treatments prevented mortality, but did not decrease the loss in biomass. While TLC treatments pose a less laborious alternative for AC amendments in the field, the results of this study show that it has lower remediation potential and could be more harmful to the benthic fauna.

A cascade of compounds is produced when foodstuffs are heated at high temperatures but only a few of these compounds have been identified and quantified. In this study data are evaluated regarding differences in the micronucleus frequency of human erythrocytes (fMNs) in peripheral blood (a known biomarker of genotoxicity) in individuals that consumed either high- or low-heated food during a 4-day period. Concomitantly, acrylamide (aa) levels were measured in the food that the participants consumed. The obtained fMNs in this human study are compared with the fMNs in mice after comparable exposure levels of pure aa. The results of this comparison showed several hundred times higher fMNs in humans compared with mice. With an assumed linear correlation between an increased genotoxic effect and cancer, our data suggest that aa only represents a fraction of all carcinogenic compounds produced in heated carbohydrate-rich food. Consequently, our daily intake of carbohydrate-rich food heated at high temperatures might be responsible for one-fifth of the rate of the total cancer risk. One sentence summary: A biomarker of genotoxicity indicates the risk of cancer to be some hundred-fold greater in heated carbohydrate-rich food than the risk calculated from animal studies on pure acrylamide.

Experiments with a climate model (NorESM1) were performed to isolate the effects of aerosol particles and greenhouse gases on surface temperature and precipitation in simulations of future climate. The simulations show that by 2025-2049, a reduction of aerosol emissions from fossil fuels following a maximum technically feasible reduction (MFR) scenario could lead to a global and Arctic warming of 0.26 K and 0.84 K, respectively; as compared with a simulation with fixed aerosol emissions at the level of 2005. If fossil fuel emissions of aerosols follow a current legislation emissions (CLE) scenario, the NorESM1 model simulations yield a non-significant change in global and Arctic average surface temperature as compared with aerosol emissions fixed at year 2005. The corresponding greenhouse gas effect following the RCP4.5 emission scenario leads to a global and Arctic warming of 0.35 K and 0.94 K, respectively.

The model yields a marked annual average northward shift in the inter-tropical convergence zone with decreasing aerosol emissions and subsequent warming of the northern hemisphere. The shift is most pronounced in the MFR scenario but also visible in the CLE scenario. The modeled temperature response to a change in greenhouse gas concentrations is relatively symmetric between the hemispheres and there is no marked shift in the annual average position of the inter-tropical convergence zone. The strong reduction in aerosol emissions in MFR also leads to a net southward cross-hemispheric energy transport anomaly both in the atmosphere and ocean, and enhanced monsoon circulation in Southeast and East Asia causing an increase in precipitation over a large part of this region.

Particulate matter suspended in air (i.e. aerosol particles) exerts a substantial influence on the climate of our planet and is responsible for causing severe public health problems in many regions across the globe. Human activities have altered the natural and anthropogenic emissions of aerosol particles through direct emissions or indirectly by modifying natural sources. The climate effects of the latter have been largely overlooked. Humans have dramatically altered the land surface of the planet causing changes in natural aerosol emissions from vegetated areas. Regulation on anthropogenic and natural aerosol emissions have the potential to affect the climate on regional to global scales. Furthermore, the regional climate effects of aerosol particles could potentially be very different than the ones caused by other climate forcers (e.g. well mixed greenhouse gases). The main objective of this work was to investigate the climatic effects of land use and air pollution via aerosol changes.

Using numerical model simulations it was found that land use changes in the past millennium have likely caused a positive radiative forcing via aerosol climate interactions. The forcing is an order of magnitude smaller and has an opposite sign than the radiative forcing caused by direct aerosol emissions changes from other human activities. The results also indicate that future reductions of fossil fuel aerosols via air quality regulations may lead to an additional warming of the planet by mid-21^st century and could also cause an important Arctic amplification of the warming. In addition, the mean position of the intertropical convergence zone and the Asian monsoon appear to be sensitive to aerosol emission reductions from air quality regulations. For these reasons, climate mitigation policies should take into consideration aerosol air pollution, which has not received sufficient attention in the past.

Human activities have lead to changes in the energy balance of the Earth and the global climate. Changes in atmospheric aerosols are the second largest contributor to climate change after greenhouse gases since 1750 A.D. Land-use practices and other environmental drivers have caused changes in the emission of biogenic volatile organic compounds (BVOCs) and secondary organic aerosol (SOA) well before 1750 A.D, possibly causing climate effects through aerosol-radiation and aerosol-cloud interactions. Two numerical emission models LPJ-GUESS and MEGAN were used to quantify the changes in aerosol forming BVOC emissions in the past millennium. A chemical transport model of the atmosphere (GEOS-Chem-TOMAS) was driven with those BVOC emissions to quantify the effects on radiation caused by millennial changes in SOA.

The specific objectives of this licentiate thesis are: 1) to understand what drove the changes in aerosol-forming BVOC emissions (i.e. isoprene, monoterpenes and sesquiterpenes) and to quantify these changes; 2) to calculate for the first time the combined historical aerosol direct and aerosol-cloud albedo effects on radiation from changing BVOC emissions through SOA formation; 3) to investigate how important the biological climate feedback associated to BVOC emissions and SOA formation is from a global climate perspective.

We find that global isoprene emissions decreased after 1800 A.D. by about 12% - 15%. This decrease was dominated by losses of natural vegetation, whereas monoterpene and sesquiterpene emissions increased by about 2% - 10%, driven mostly by rising surface air temperatures. From 1000 A.D. to 1800 A.D, isoprene, monoterpene and sesquiterpene emissions decline by 3% - 8% driven by both, natural vegetation losses, and the moderate global cooling between the medieval climate anomaly and the little ice age. The millennial reduction in BVOC emissions lead to a 0.5% to 2% reduction in climatically relevant aerosol particles (> 80 nm) and cause a direct radiative forcing between +0.02 W/m² and +0.07 W/m², and an indirect radiative forcing between -0.02 W/m² and +0.02 W/m². The suggested biological climate feedback seems to be too small to have observable consequences on the global climate in the recent past.

The Arctic region is warming considerably faster than the rest of the globe(1), with important consequences for the ecosystems(2) and human exploration of the region(3). However, the reasons behind this Arctic amplification are not entirely clear(4). As a result of measures to enhance air quality, anthropogenic emissions of particulate matter and its precursors have drastically decreased in parts of the Northern Hemisphere over the past three decades(5). Here we present simulations with an Earth system model with comprehensive aerosol physics and chemistry that show that the sulfate aerosol reductions in Europe since 1980 can potentially explain a significant fraction of Arctic warming over that period. Specifically, the Arctic region receives an additional 0.3Wm(-2) of energy, and warms by 0.5 degrees C on annual average in simulations with declining European sulfur emissions in line with historical observations, compared with a model simulation with fixed European emissions at 1980 levels. Arctic warming is amplified mainly in fall and winter, but the warming is initiated in summer by an increase in incoming solar radiation as well as an enhanced poleward oceanic and atmospheric heat transport. The simulated summertime energy surplus reduces sea-ice cover, which leads to a transfer of heat from the Arctic Ocean to the atmosphere. We conclude that air quality regulations in the Northern Hemisphere, the ocean and atmospheric circulation, and Arctic climate are inherently linked.

Boreal forests are ecosystems with low nitrogen (N) availability that store globally significant amounts of carbon (C), mainly in plant biomass and soil organic matter (SOM). Although crucial for future climate change predictions, the mechanisms controlling boreal C and N pools are not well understood. Here, using a three-year field experiment, we compare SOM decomposition and stabilization in the presence of roots, with exclusion of roots but presence of fungal hyphae and with exclusion of both roots and fungal hyphae. Roots accelerate SOM decomposition compared to the root exclusion treatments, but also promote a different soil N economy with higher concentrations of organic soil N compared to inorganic soil N accompanied with the build-up of stable SOM-N. In contrast, root exclusion leads to an inorganic soil N economy (i.e., high level of inorganic N) with reduced stable SOM-N buildup. Based on our findings, we provide a framework on how plant roots affect SOM decomposition and stabilization.

Dimethylamine (DMA) has a stabilizing effect on sulfuric acid (SA) clusters, and the SA and DMA molecules and clusters likely play important roles in both aerosol particle formation and growth in the atmosphere. We use the monodisperse particle growth model for acid-base chemistry in nanoparticle growth (MABNAG) together with direct and indirect observations from the CLOUD4 and CLOUD7 experiments in the cosmics leaving outdoor droplets (CLOUD) chamber at CERN to investigate the size and composition evolution of freshly formed particles consisting of SA, DMA, and water as they grow to 20nm in dry diameter. Hygroscopic growth factors are measured using a nano-hygroscopicity tandem differential mobility analyzer (nano-HTDMA), which combined with simulations of particle water uptake using the thermodynamic extended-aerosol inorganics model (E-AIM) constrain the chemical composition. MABNAG predicts a particle-phase ratio between DMA and SA molecules of 1.1-1.3 for a 2nm particle and DMA gas-phase mixing ratios between 3.5 and 80 pptv. These ratios agree well with observations by an atmospheric-pressure interface time-of-flight (APi-TOF) mass spectrometer. Simulations with MABNAG, direct observations of the composition of clusters <2nm, and indirect observations of the particle composition indicate that the acidity of the nucleated particles decreases as they grow from approximate to 1 to 20nm. However, MABNAG predicts less acidic particles than suggested by the indirect estimates at 10nm diameter using the nano-HTDMA measurements, and less acidic particles than observed by a thermal desorption chemical ionization mass spectrometer (TDCIMS) at 10-30nm. Possible explanations for these discrepancies are discussed.

Plant leaves play an important role in the fate of hydrophobic organic contaminants (HOCs) in theenvironment. Yet much remains unknown about the permeability of leaves by HOCs. In this pilot studywe measured (i) the kinetics of mass transfer of three polycyclic aromatic hydrocarbons (PAHs) and sixpolychlorinated biphenyls between a spiked and an unspiked sheet of polydimethylsiloxane (PDMS) indirect contact with each other for 24 h and (ii) kinetics of mass transfer of two PAHs through leaves andlow-density polyethylene (LDPE) in a passive dosing experiment by inserting these matrices between thetwo sheets of PDMS for 48 h. The kinetics of mass transfer of fluoranthene between PDMS sheets in directcontact were a factor of 12 slower than those reported in the literature. The kinetics of mass transfer offluorene and phenanthrene through leaves were within the range of those previously reported for 2,4-dichlorophenoxyacetic acid through isolated cuticles. Our results provide a proof-of-concept demon-stration that the passive dosing method applied in this study can be used to measure the mass transfercoefficients of organic chemicals through leaves. Key recommendations for future experiments are toload the PDMS at the highest feasible concentrations to avoid working at analyte levels close to the limitof detection, to keep the leaves moist and to minimize potential pathways for contamination of the PDMSsheets by exposure to laboratory air.

In recent years, application of nanomaterials as sorbent has gained the attention of researchers in bioanalysis. Different nanomaterials have been utilized as the sorbent in extraction techniques such as solid phase extraction, dispersive solid phase extraction, magnetic solid phase extraction, microextraction by packed sorbent, solid phase microextraction, dispersive pt-solid phase extraction, and stir bar sorptive extraction. In the present review, different nanomaterials which have recently been utilized as sorbent for bioanalysis are classified into six main groups, namely metallic, metallic and mixed oxide, magnetic, carbonaceous, silicon, and polymer-based nanomaterials. Application of these nanomaterials in different extraction techniques for bioanalysis has been reviewed. This study shows that magnetic nanomaterials have gained significant attention owing to their magnetic separation ability. In addition, the present review shows that there is a lack in the application of nanomaterials for on-line analysis procedures, most probably due to some intrinsic properties of nanomaterials such as spontaneous agglomeration.

The concentrations of 43 polycyclic aromatic hydrocarbons (PAHs) and 4 oxygenated PAHs (OPAHs) are reported for the first time in particulate matter (PM10) sampled in the air of the city of Sulaimaniyah in Iraq. The total PAH concentration at the different sampling sites varied between 9.3 and 114 ng/m(3). The corresponding values of the human carcinogen benzotalpyrene were between 0.3 and 6.9 ng/m(3), with most samples exceeding the EU annual target value of 1 ng/m(3). The highly carcinogenic dibenzopyrene isomers dibenzo[a,l]pyrene, dibenzo[a,e]pyrene, dibenzo[a,i]pyrene and dibenzo[a,h]pyrene constituted 0.1-0.4% of the total PAH concentration. However, when scaling for relative cancer potencies using toxic equivalency factors, a benzo[a]pyrene equivalent concentration of dibenzo[a,l]pyrene equal to that of benzo[a]pyrene was obtained, indicating that the contribution of dibenzo[a,l]pyrene to the carcinogenicity of the PAHs could be similar to that of benzo[a]pyrene. A high correlation between the determined concentrations of the dibenzopyrene isomers and benzo[a]pyrene was found, which supported the use of benzo[a]pyrene as an indicator for the carcinogenicity of PAHs in ambient air. The total concentrations of the four OPAHs, 9,10-anthraquinone, 4H-cyclopenta[def]phenanthren-4-one, benzanthrone, and 7,12-benz[a]anthraquinone, varied between 0.6 and 8.1 ng/m(3), with 9,10-anthraquinone being the most abundant OPAH in all of the samples.

Emission factors for oxygenated polycyclic aromatic hydrocarbons (OPAHs) and PAHs have been determined from two different fuel flexible light duty vehicles operated at -7 degrees C in the New European Driving Cycle (NEDC) and at +22 degrees C in the Artemis Driving Cycle (ADC). Three different gasoline/ethanol blends, commercially available in Sweden, were tested i.e., gasoline E5, with 5% v/v ethanol and ethanol fuel E85 with 85% v/v ethanol and winter time quality E70 with 70% v/v ethanol, respectively. The results showed greatly increased emissions of both OPAHs and PAHs at cold engine start conditions (-7 degrees C in the NEDC) compared to warm engine start (+ 22 degrees C in the ADC). For the OPAHs, higher average total emission factors were obtained when running on E85 compared to E5 at both cold 2.72 mu g/km vs 1.11 mu g/km and warm 0.19 mu g/km vs 0.11 mu g/km starting conditions with the highest emissions when using E70 at -7 degrees C 4.12 mu g/km. The same trend was found for the PAHs at cold engine start with higher average total emission factors when using ethanol fuel 71.5 mu g/km and 60.0 mu g/km for E70 and E85, respectively compared to gasoline E5 (20.2 mu g/km). Slightly higher average total PAH emissions were obtained when operating at + 22 degrees C with E5 compared to with E85 1.23 mu g/km vs 0.72 mu g/km.

The determination of total fluorine content using high-resolution graphite furnace continuum source molecular absorption spectrometry (HR- MAS) has been employed in a variety of samples for over 10 years. However, most of the samples analysed by HR-MAS are rich in fluoride, with negligible levels of organic fluorinated species. With an increase in concern surrounding per- and polyfluoroalkyl substances (PFASs), new methods to measure total fluorine of organofluorine using different techniques have been developed. However, no studies focused on PFASs behaviour in HR-MAS have been performed. As these compounds encompass a wide range of different structures, boiling points, decomposition temperatures and matrix interactions, a loss of accuracy can occur when an aqueous external calibration is performed using only one compound. To overcome this issue, an investigation into permanent modifiers for the graphite furnace was performed. After optimisation similar sensitivity for different PFCA was achieved when 400 mu g of W was used as a permanent modifier together with an optimised temperature program. The relative deviation between the different PFCA standard slopes relative to the PFOA slope was lower than 15%. The instrumental limit of detection and quantification (LOD and LOQ, respectively) of total fluorine as total PFCA was 0.1 mg L-1 and 0.3 mg L-1, respectively, while the method LOD and LOQ (using solid phase extraction) was 0.3 mu g L-1 and 1.0 mu g L-1, respectively. The developed method gave satisfactory recoveries for the spiked PFCA into seawater, river water and effluent using PFOA calibration standards. The optimised method is useful for measuring extractable organofluorines (EOF) when only ionic PFASs such as PFCA are expected. When other organofluorines are expected, the results using HR GF-MAS should be taken with caution.

Non-dioxin-like (NDL) polychlorinated biphenyls (PCBs) and their hydroxyl metabolites (OH-PCBs) are ubiquitous environmental contaminants in human tissues and blood. The toxicological impact of these metabolites is poorly understood. In this study rats were exposed to ultrapure PCB180 (10-1000 mg/kg bw) for 28 days and induction of genotoxic stress in liver was investigated. DNA damage signaling proteins (pChk1Ser317 and gamma H2AXSer319) were increased dose dependently in female rats. This increase was paralleled by increasing levels of the metabolite 3'-OH-PCB180. pChk1 was the most sensitive marker. In in vitro studies HepG2 cells were exposed to 1 mu M of PCB180 and 3'-OH-PCB180 or the positive control benzo[a]pyrene (BaP, 5 mu M). 3'-OH-PCB180, but not PCB180, induced CYP1A1 mRNA and gamma H2AX. CYP1A1 mRNA induction was seen at 1 h, and gamma H2AX at 3 h. The anti-oxidant N-Acetyl-L-Cysteine (NAC) completely prevented, and 17 beta-estradiol amplified the gamma H2AX induction by 3'-OH-PCB180. As 3'-OH-PCB180 induced CYP1A1, a major BaP-metabolizing and activating enzyme, interactions between 3'-OH-PCB180 and BaP was also studied. The metabolite amplified the DNA damage signaling response to BaP. In conclusion, metabolism of PCB180 to its hydroxyl metabolite and the subsequent induction of CYP1A1 seem important for DNA damage induced by PCB180 in vivo. Amplification of the response with estradiol may explain why DNA damage was only seen in female rats.

The third intensive measurement period (IMP) organised by the European Monitoring and Evaluation Programme (EMEP) under the UNECE CLTRAP took place in summer 2012 and winter 2013, with PM10 filter samples concurrently collected at 20 (16 EMEP) regional background sites across Europe for subsequent analysis of their mineral dust content. All samples were analysed by the same or a comparable methodology. Higher PM10 mineral dust loadings were observed at most sites in summer (0.5-10aEuro-A mu gaEuro-m(-3)) compared to winter (0.2-2aEuro-A mu gaEuro-m(-3)), with the most elevated concentrations in the southern- and easternmost countries, accounting for 20-40aEuro-% of PM10. Saharan dust outbreaks were responsible for the high summer dust loadings at western and central European sites, whereas regional or local sources explained the elevated concentrations observed at eastern sites. The eastern Mediterranean sites experienced elevated levels due to African dust outbreaks during both summer and winter. The mineral dust composition varied more in winter than in summer, with a higher relative contribution of anthropogenic dust during the former period. A relatively high contribution of K from non-mineral and non-sea-salt sources, such as biomass burning, was evident in winter at some of the central and eastern European sites. The spatial distribution of some components and metals reveals the influence of specific anthropogenic sources on a regional scale: shipping emissions (V, Ni, and SO42-) in the Mediterranean region, metallurgy (Cr, Ni, and Mn) in central and eastern Europe, high temperature processes (As, Pb, and SO42-) in eastern countries, and traffic (Cu) at sites affected by emissions from nearby cities.

Ocean acidification is caused by increasing amounts of carbon dioxide dissolving in the oceans leading to lower seawater pH. We studied the effects of lowered pH on the calanoid copepod Eurytemora affinis during a mesocosm experiment conducted in a coastal area of the Baltic Sea. We measured copepod reproductive success as a function of pH, chlorophyll a concentration, diatom and dinoflagellate biomass, carbon to nitrogen (C : N) ratio of suspended particulate organic matter, as well as copepod fatty acid composition. The laboratory-based experiment was repeated four times during 4 consecutive weeks, with water and copepods sampled from pelagic mesocosms enriched with different CO2 concentrations. In addition, oxygen radical absorbance capacity (ORAC) of animals from the mesocosms was measured weekly to test whether the copepod's defence against oxidative stress was affected by pH. We found no effect of pH on offspring production. Phytoplankton biomass, as indicated by chlorophyll a concentration and dinoflagellate biomass, had a positive effect. The concentration of polyunsaturated fatty acids in the females was reflected in the eggs and had a positive effect on offspring production, whereas monounsaturated fatty acids of the females were reflected in their eggs but had no significant effect. ORAC was not affected by pH. From these experiments we conclude that E. affinis seems robust against direct exposure to ocean acidification on a physiological level, for the variables covered in the study. E. affinis may not have faced acute pH stress in the treatments as the species naturally face large pH fluctuations.

Alternative plasticizers and flame retardants (FRs) have been introduced as replacements for banned or restricted chemicals, but much is still unknown about their metabolism and occurrence in humans. We identified the metabolites formed in vitro for four alternative plasticizers (acetyltributyl citrate (ATBC), bis(2-propylheptyl) phthalate (DPHP), bis(2-ethylhexyl) terephthalate (DEHTP), bis(2ethylhexyl) adipate (DEHA)), and one FR (2,2-bis (chloromethyl)-propane-1,3-diyltetrakis(2-chloroethyl) bisphosphate (V6)). Further, these compounds and their metabolites were investigated by LC/ESI-Orbitrap-MS in urine and finger nails collected from a Norwegian cohort. Primary and secondary ATBC metabolites had detection frequencies (% DF) in finger nails ranging from 46 to 95%. V6 was identified for the first time in finger nails, suggesting that this matrix may also indicate past exposure to FRs as well as alternative plasticizers. Two isomeric forms of DEHTP primary metabolite were highly detected in urine (97% DF) and identified in finger nails, while no DPHP metabolites were detected in vivo. Primary and secondary DEHA metabolites were identified in both matrices, and the relative proportion of the secondary metabolites was higher in urine than in finger nails; the opposite was observed for the primary metabolites. As many of the metabolites present in in vitro extracts were further identified in vivo in urine and finger nail samples, this suggests that in vitro assays can reliably mimic the in vivo processes. Finger nails may be a useful noninvasive matrix for human biomonitoring of specific organic contaminants, but further validation is needed.

The Siberian shelf seas are areas of extensive biogeochemical transformation of organic matter, both of marine and terrestrial origin. This in combination with brine production from sea ice formation results in a cold bottom water of relative high salinity and partial pressure of carbon dioxide (pCO(2)). Data from the SWERUS-C3 expedition compiled on the icebreaker Oden in July to September 2014 show the distribution of such waters at the outer shelf, as well as their export into the deep central Arctic basins. Very high pCO(2) water, up to similar to 1000 mu atm, was observed associated with high nutrients and low oxygen concentrations. Consequently, this water had low saturation state with respect to calcium carbonate down to less than 0.8 for calcite and 0.5 for aragonite. Waters undersaturated in aragonite were also observed in the surface in waters at equilibrium with atmospheric CO2; however, at these conditions the cause of undersaturation was low salinity from river runoff and/or sea ice melt. The calcium carbonate corrosive water was observed all along the continental margin and well out into the deep Makarov and Canada basins at a depth from about 50 m depth in the west to about 150 m in the east. These waters of low aragonite saturation state are traced in historic data to the Canada Basin and in the waters flowing out of the Arctic Ocean north of Greenland and in the western Fram Strait, thus potentially impacting the marine life in the North Atlantic Ocean.

Sympatric populations occur in many freshwater fish species; such populations are typically detected through morphological distinctions that are often coupled to food niche and genetic separations. In salmonids, trophic and genetically separate sympatric populations have been reported in landlocked Arctic char, whitefish and brown trout. In Arctic char and brown trout rare cases of sympatric, genetically distinct populations have been detected based on genetic data alone, with no apparent morphological differences, that is cryptic structuring. It remains unknown whether such cryptic, sympatric structuring can be coupled to food niche separation. Here, we perform an extensive screening for trophic divergence of two genetically divergent, seemingly cryptic, sympatric brown trout populations documented to remain in stable sympatry over several decades in two interconnected, tiny mountain lakes in a nature reserve in central Sweden. We investigate body shape, body length, gill raker metrics, breeding status and diet (stomach content analysis and stable isotopes) in these populations. We find small significant differences for body shape, body size and breeding status, and no evidence of food niche separation between these two populations. In contrast, fish in the two lakes differed in body shape, diet, and nitrogen and carbon isotope signatures despite no genetic difference between lakes. These genetically divergent populations apparently coexist using the same food resources and showing the same adaptive plasticity to the local food niches of the two separate lakes. Such observations have not been reported previously but may be more common than recognised as genetic screenings are necessary to detect the structures.

Detailed knowledge of protein changes in cerebrospinal fluid (CSF) across healthy and diseased individuals would provide a better understanding of the onset and progression of neurodegenerative disorders. In this study, we selected 20 brain-enriched proteins previously identified in CSF by antibody suspension bead arrays (SBA) to be potentially biomarkers for Alzheimer's disease (AD) and verified these using an orthogonal approach. We examined the same set of 94 CSF samples from patients affected by AD (including preclinical and prodromal), mild cognitive impairment (MCI), non-AD dementia and healthy individuals, which had previously been analyzed by SBA. Twenty-eight parallel reaction monitoring (PRM) assays were developed and 13 of them could be validated for protein quantification. Antibody profiles were verified by PRM. For seven proteins, the antibody profiles were highly correlated with the PRM results (r > 0.7) and GAP43, VCAM1 and PSAP were identified as potential markers of preclinical AD. In conclusion, we demonstrate the usefulness of targeted mass spectrometry as a tool for the orthogonal verification of antibody profiling data, suggesting that these complementary methods can be successfully applied for comprehensive exploration of CSF protein levels in neurodegenerative disorders.

Sunlight-absorbing aerosols, e.g., black and brown carbon (BC and BrC), have a potentially large, but highly uncertain contribution to climate warming. The spectral dependence of the aerosol absorption in the visible and near-UV regime is almost universally well-described with a heuristic power law, where the exponent is termed the absorption Angstrom exponent. However, the 2 underlying physicochemical causes for this relation are unknown. Here, a model is presented that predicts the emergence of the power law spectral dependence and unifies the absorption behavior of BC and BrC. Building on the theory of light absorption in amorphous materials, the interaction between multiple functional groups upon absorption is predicted to be a key feature for this broad spectral dependence. This aerosol amorphous absorption model is in agreement with recent empirical findings and provides a conceptual basis for the additional research needed to better constrain the optical properties of light-absorbing aerosols and their environmental impact.

Thick haze plagued northeastern China in January 2013, strongly affecting both regional climate and human respiratory health. Here, we present dual carbon isotope constrained (Delta C-14 and delta C-13) source apportionment for combustion-derived black carbon aerosol (BC) for three key hotspot regions (megacities): North China Plain (NCP, Beijing), the Yangtze River Delta (YRD, Shanghai), and the Pearl River Delta (PRD, Guangzhou) for January 2013. BC, here quantified as elemental carbon (EC), is one of the most health-detrimental components of PM2.5 and a strong climate warming agent. The results show that these severe haze events were equally affected (similar to 30%) by biomass combustion in all three regions, whereas the sources of the dominant fossil fuel component was dramatically different between north and south. In the NCP region, coal combustion accounted for 66% (46-74%, 95% C.I.) of the EC, whereas, in the YRD and PRD regions, liquid fossil fuel combustion (e.g., traffic) stood for 46% (18-66%) and 58% (38-68%), respectively. Taken together, these findings suggest the need for a regionally-specific description of BC sources in climate models and regionally-tailored mitigation to combat severe air pollution events in East Asia.

Stable isotope labeling is a standard technique for tracing material transfer in molecular, ecological and biogeochemical studies. The main assumption in this approach is that the enrichment with a heavy isotope has no effect on the organism metabolism and growth, which is not consistent with current theoretical and empirical knowledge on kinetic isotope effects. Here, we demonstrate profound changes in growth dynamics of the green alga Raphidocelis subcapitata grown in N-15-enriched media. With increasing N-15 concentration (0.37 to 50 at%), the lag phase increased, whereas maximal growth rate and total yield decreased; moreover, there was a negative relationship between the growth and the lag phase across the treatments. The latter suggests that a trade-off between growth rate and the ability to adapt to the high N-15 environment may exist. Remarkably, the lag-phase response at 3.5 at% N-15 was the shortest and deviated from the overall trend, thus providing partial support to the recently proposed Isotopic Resonance hypothesis, which predicts that certain isotopic composition is particularly favorable for living organisms. These findings confirm the occurrence of KIE in isotopically enriched algae and underline the importance of considering these effects when using stable isotope labeling in field and experimental studies.

beta-N-Methylamino-l-alanine (BMAA) is an important non-protein amino acid linked to neurodegenerative diseases, specifically amyotrophic lateral sclerosis (ALS). Because it can be transferred and bioaccumulated higher up the food chain, it poses significant public health concerns; thus, improved detection methods are of prime importance for the identification and management of these toxins. Here, we report the successful use of N-hydroxysuccinimide ester of N-butylnicotinic acid (C-4-NA-NHS) for the efficient separation of BMAA from its isomers and higher sensitivity in detecting BMAA compared to the current method of choice using 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) derivatization. Implementation of this efficient method allowed localization of BMAA in the non-visceral tissues of blue mussels, suggesting that more efficient depuration may be required to remove this toxin prior to consumption. This is a crucial method in establishing the absence or presence of the neurotoxic amino acid BMAA in food, environmental or biomedical samples.

Reference total nitrogen (TN) concentrations for the Gardsfjarden estuary in the central Bothnian Sea, which receives discharge from an industrial point-source, have been estimated from diatom assemblages using a transfer function. Sedimentological and diatom evidence imply a good ecological status before 1920 with an assemblage dominated by benthic taxa indicating excellent water transparency, high diatom species richness and less organic sedimentation resulting in homogeneous well oxygenated sediments. A change in the diatom assemblage starts between 1920 and 1935 when the species richness declines and the proportion of planktic taxa increases. Increased organic carbon sedimentation after 1920 led to hypoxic bottom waters, and the preservation of laminae in the sediments. The trend in the reconstructed TN-values agrees with the history of the discharge from the mill, reaching maximum impact during the high discharge between 1945 and 1990. The background condition for TN in Gardsfjarden is 260-300 mu L-1, reconstructed until 1920.

Methods involving polyoxymethylene (POM) as a passive sampler are increasing in popularity to assess contaminant freely dissolved porewater concentrations in soils and sediments. These methods require contaminant-specific POM-water partition coefficients, K-POM. Certain methods for determining K-POM perform reproducibly (within 0.2 log units). However, other methods can give highly varying K-POM values (up to 2 log units), especially for polycyclic aromatic hydrocarbons (PAHs). To account for this variation, the authors tested the influence of key methodological components in K-POM determinations, including POM thickness, extraction procedures, and environmental temperature and salinity, as well as uptake kinetics in mixed and static systems. All inconsistencies in the peer-reviewed literature can be accounted for by the likelihood that thick POM materials (500m or thicker) do not achieve equilibrium (causing negative biases up to 1 log unit), or that certain POM extraction procedures do not ensure quantitative extraction (causing negative biases up to 2 log units). Temperature can also influence K-POM, although all previous literature studies were carried out at room temperature. The present study found that K-POM values at room temperature are independent (within 0.2 log units) of POM manufacture method, of thickness between 17m and 80m, and of salinity between 0% and 10%. Regarding kinetics, monochloro- to hexachloro-polychlorinated biphenyls (PCBs) were within 0.2 log units of equilibrium after 28d in the mixed system, but only dichloro-PCBs achieved near equilibrium after 126d in the static system. Based on these insights, recommended methods and K-POM values to facilitate interlaboratory reproducibility are presented.

In July 2017 three research flights circumnavigating the megacity of London were conducted as a part of the STANCO training school for students and early career researchers organised by EUFAR (European Facility for Airborne Research). Measurements were made from the UK's Facility for Airborne Atmospheric Measurements (FAAM) BAe-146-301 atmospheric research aircraft with the aim to sample, characterise and quantify the impact of megacity outflow pollution on air quality in the surrounding region. Conditions were extremely favourable for airborne measurements, and all three flights were able to observe clear pollution events along the flight path. A small change in wind direction provided sufficiently different air mass origins over the 2 d such that a distinct pollution plume from London, attributable marine emissions and a double-peaked dispersed area of pollution resulting from a combination of local and transported emissions were measured. We were able to analyse the effect of London emissions on air quality in the wider region and the extent to which local sources contribute to pollution events. The background air upwind of London was relatively clean during both days; concentrations of CO were 88-95 ppbv, total (measured) volatile organic compounds (VOCs) were 1.6-1.8 ppbv and NOx was 0.7-0.8 ppbv. Downwind of London, we encountered elevations in all species with CO>100 ppbv, VOCs 2.8-3.8 ppbv, CH4> 2080 ppbv and NOx >4 ppbv, and peak concentrations in individual pollution events were higher still. Levels of O-3 were inversely correlated with NOx, during the first flight, with O-3 concentrations of 37 ppbv upwind falling to similar to 26 ppbv in the well-defined London plume. Total pollutant fluxes from London were estimated through a vertical plane downwind of the city. Our calculated CO2 fluxes are within the combined uncertainty of those estimated previously, but there was a greater disparity in our estimates of CH4 and CO. On the second day, winds were lighter and downwind O-3 concentrations were elevated to similar to 39-43 ppbv (from similar to 32 to 35 ppbv upwind), reflecting the contribution of more aged pollution to the regional background. Elevations in pollutant concentrations were dispersed over a wider area than the first day, although we also encountered a number of clear transient enhancements from local sources. This series of flights demonstrated that even in a region of megacity outflow, such as the south-east of the UK, local fresh emissions and more distant UK sources of pollution can all contribute substantially to pollution events. In the highly complex atmosphere around a megacity where a high background level of pollution mixes with a variety of local sources at a range of spatial and temporal scales and atmospheric dynamics are further complicated by the urban heat island, the use of pollutant ratios to track and determine the ageing of air masses may not be valid. The individual sources must therefore all be well-characterised and constrained to understand air quality around megacities such as London. Research aircraft offer that capability through targeted sampling of specific sources and longitudinal studies monitoring trends in emission strength and profiles over time.

The remoteness and low population in the Arctic allow us to study global environmental processes, where the analysis of indicators can provide useful information about local and distant pollution sources. Fresh snow represents a convenient indicator of regional and transboundary atmospheric contamination sources, entrapping aerosols, and particulates like a natural autosampler of the environment. Lead stable isotopes are widely used to trace and monitor local and distant pollution sources. However, the behavior of Pb within different snow components is still not thoroughly studied, and its significance could be underestimated if only larger particulates are accounted for. We collected snow and samples from potential sources (fuel, rocks, coal) in three Arctic localities: Nuuk (Greenland), Reykjavik (Iceland), and Longyearbyen (Svalbard). We separated the filtrate from the filter residue through 0.45 mu m nitrocellulose membranes to isolate the low-diameter particles associated with long-range transport from larger particles of mostly local natural origin. Filtrates yielded higher EFs (enrichment factor as the Pb/Al ratio relative to the upper crust) than filtration residues (80 +/- 104 and 2.1 +/- 1.1, respectively), and Pb isotope signals similar to fuel and coal (206Pb/207Pb are 1.199 +/- 0.028 in coal, 1.168 +/- 0.029 in filtrates, 1.163 +/- 0.013 in fuel, 1.137 +/- 0.045 in residues, and 0.985 +/- 0.020 in rocks). In contrast to filtrates, the filter residues present wider ranges of Pb isotope compositions and crustal contributions and lower EFs, so we suggest that filtrate contains Pb from fuel combustion more selectively, while the residue carries a more considerable contribution of local mineral dust that can mask the contribution of other anthropogenic or distant natural sources. These findings add weight to the notion that filtrates are a more selective measure of metal deposition from long-range anthropogenic emissions compared to analyzing bulk melted snow or only filter residues.

Adverse health effects have been linked to exposure to particulate matter, and wood combustion is considered as an important source of harmful particulate matter in the urban air and environment. Hydroxylated polycyclic aromatic hydrocarbons are a group of compounds with toxic, endocrine disrupting and carcinogenic properties. Sources of hydroxylated polycyclic aromatic hydrocarbons are different incomplete combustion processes, such as coal and wood combustion. They can also be formed by microbiological and/or photochemical degradation of polycyclic aromatic hydrocarbons in the environment.

This thesis describes analytical strategies and methods that have been developed and used for screening, tentative identification and determination of hydroxylated polycyclic aromatic hydrocarbons in wood combustion and urban air particles. Conventional targeted analytical methods have been developed for compounds with available reference standards, while suspect and non-target screening strategies have been used for the identification of suspects and unknown compounds lacking reference standards. Each step of the developed analytical methods is described and discussed: the choice of the analytical strategy, sampling of the matrices, extraction, clean-up, instrumental analysis, data processing and validation of the methods.

The influence of wood type (birch, spruce, pine and aspen) and burning conditions (nominal and high burn rate) on the hydroxylated polycyclic aromatic hydrocarbon emissions has been examined, showing that emissions from nominal burn rate combustion correspond on average to 14 % of the emissions from high burn rate combustion. It has been shown that spruce and pine have the highest emissions for nominal burn rate and high burn rate combustion, respectively.

The composition of wood combustion particles has been examined and 32 suspect hydroxylated polycyclic aromatic hydrocarbons have been tentatively identified together with 20 other oxygen-containing small molecular weight compounds. Furthermore, the presence of hydroxylated polycyclic aromatic hydrocarbons in airborne particles from an urban background and a car tunnel has been investigated, and nine target and 11 suspect hydroxylated polycyclic aromatic hydrocarbons have been determined and tentatively identified, respectively.

In summary, this thesis has shown that wood combustion is an important emission source of hydroxylated aromatic hydrocarbons and that the chemical composition of the emitted particles strongly depends on both burning conditions and wood type. Furthermore, the findings suggest that there might be other sources of these compounds in the urban environment than wood burning, such as the traffic. Thus, further investigations are required to fully understand the formation, sources and presence of hydroxylated polycyclic aromatic hydrocarbons in the atmosphere. The suitability of different analytical strategies and methods for identification and determination of hydroxylated polycyclic aromatic hydrocarbons is also discussed.

A simple and fast method for analysis of hydroxylated polycyclic aromatic hydrocarbons using pressurized liquid extraction and high performance liquid chromatography utilizing photoionization tandem mass spectrometry was developed. Simultaneous separation and determination of nine hydroxylated polycyclic aromatic hydrocarbons and two hydroxy biphenyls could be performed in negative mode with a run time of 12 min, including equilibration in 5 min. The calibration curves were in two concentration ranges; 1-50 ng/mL and 0.01-50 mu g/mL, with coefficients of correlation R (2) > 0.997. The limits of detection and method quantification limits were in the range of 9-56 pg and 5-38 ng/g, respectively. A two-level full factorial experimental design was used for screening of conditions with the highest impact on the extraction. The extraction procedure was automated and suitable for a large number of samples. The extraction recoveries ranged from 70 to 102 % and the matrix effects were between 92 and 104 %. The overall method was demonstrated on wood smoke particles and soil samples with good analytical performance, and five OH-PAHs were determined in the concentration range of 0.19-210 mu g/g. As far as we know, hydroxylated polycyclic aromatic hydrocarbons were determined in wood smoke and soil samples using photoionization mass spectrometry for the first time in this present study. Accordingly, this study shows that high performance liquid chromatography photoionization tandem mass spectrometry can be a good option for the determination of hydroxylated polycyclic aromatic hydrocarbons in complex environmental samples.

Hydroxylated polycyclic aromatic hydrocarbons are oxidation products of polycyclic aromatic hydrocarbons, but have not been studied as extensively as polycyclic aromatic hydrocarbons. Several studies have however shown that hydroxylated polycyclic aromatic hydrocarbons have toxic and carcinogenic properties. They have been detected in air samples in semi urban areas and combustion is assumed to be the primary source of those compounds. To better understand the formation and occurrence of particulate hydroxylated polycyclic aromatic hydrocarbons from residential wood log stove combustion, 9 hydroxylated polycyclic aromatic hydrocarbons and 2 hydroxy biphenyls were quantified in particles generated from four different types of wood logs (birch, spruce, pine, aspen) and two different combustion conditions (nominal and high burn rate). A previously developed method utilizing liquid chromatography photo ionization tandem mass spectrometry and pressurized liquid extraction was used. Polycyclic aromatic hydrocarbons were analyzed along with hydroxylated polycyclic aromatic hydrocarbons. The hydroxylated polycyclic aromatic hydrocarbon emissions varied significantly across different wood types and burning conditions; the highest emissions for nominal burn rate were from spruce and for high burn rate from pine burning. Emissions from nominal burn rate corresponded on average to 15% of the emissions from high burn rate, with average emissions of 218 mu g/MJ(fuel) and 32.5 mu g/MJ(fuel) for high burn rate and nominal burn rate, respectively. Emissions of the measured hydroxylated polycyclic aromatic hydrocarbons corresponded on average to 28% of polycyclic aromatic hydrocarbons emissions. This study shows that wood combustion is a large emission source of hydroxylated polycyclic aromatic hydrocarbons and that not only combustion conditions, but also wood type influences the emissions of hydroxylated polycyclic aromatic hydrocarbons and polycyclic aromatic hydrocarbons. There are few studies that have determined hydroxylated polycyclic aromatic hydrocarbons in emissions from wood combustion, and it is therefore necessary to further investigate the formation, occurrence and distribution of these compounds as they are present in significant amounts in wood smoke particles.

Up until now, the methods used for determination of hydroxylated polycyclic aromatic hydrocarbons in air particulate samples have been target methods, only determining compounds with available reference standards. In this present study, a combined target and suspect screening strategy for the analysis of hydroxylated polycyclic aromatic hydrocarbons was developed, utilizing liquid chromatography coupled to orbitrap high resolution mass spectrometry. The target screening included simultaneous determination of nine hydroxylated polycyclic aromatic hydrocarbons, while additional eight hydroxylated polycyclic aromatic hydrocarbon masses were screened for using the suspect screening. The target screening was validated with respect to linearity, limits of detection and quantification and matrix effects. The calibration curves ranged from 0.01 to 10 ng/mL, the method limits of detection and. quantification were in the rage of 0.001-0.018 pg/m(3) and 0.006-0.061 pg/m(3), respectively, while matrix effects ranged from 83% to 104%. For the suspect screening, a list with expected precursor ions created from suspect monoisotopic masses was used. The suspects were then identified by the accurate exact mass, with a mass accuracy threshold < 5 ppm, molecular formula, isotopic pattern, and mass spectra (fragments) and also semi-quantified in order to obtain information on their relative levels in different matrixes. The developed strategy was applied on five air particulate samples collected from an urban background and five samples from a car tunnel in Stockholm (Sweden). In total 20 hydroxylated polycyclic aromatic hydrocarbons were detected, of which nine compounds were determined using the target screening and 11 were tentatively identified and semi-quantified using the suspect screening strategy. The concentrations of the target compounds ranged from 20.7 to 96.9 pg/m(3), for most of the analytes the concentrations in particles from car tunnel were slightly higher than in urban air particles. The levels of most of the tentatively identified compounds were also slightly higher in particles from the car tunnel.

Wood combustion has been shown to contribute significantly to emissions of polycyclic aromatic hydrocarbons and hydroxylated polycyclic aromatic hydrocarbons, compounds with toxic and carcinogenic properties. However, only a small number of hydroxylated polycyclic aromatic hydrocarbons have been determined in particles from wood combustion, usually compounds with available reference standards. In this present study, suspect and non-target screening strategies were applied to characterize the wood smoke particles from four different wood types and two combustion conditions with respect to hydroxylated polycyclic aromatic hydrocarbons and other organic compounds. In the suspect screening, 32 peaks corresponding to 12 monohydroxylated masses were tentatively identified by elemental composition assignments and matching of isotopic pattern and fragments. More than one structure was suggested for most of the measured masses. Statistical analysis was performed on the non-target screening data in order to single out significant peaks having intensities that depend on the wood type and/or combustion condition. Significant peaks were found in both negative and positive ionization modes, with unique peaks for each wood type and combustion condition, as well as a combination of both factors. Furthermore, structural elucidation of some peaks was done by comparing the spectra in the samples with spectra found in the spectral databases. Six compounds were tentatively identified in positive ionization mode, and 19 in negative ionization mode. The results in this present study demonstrate that there are significant overall differences in the chemistry of wood smoke particles that depends on both the wood type and the combustion condition used.

A global vertically resolved aerosol data set covering more than 10 years of observations at more than 20 measurement sites distributed from 63 degrees N to 52 degrees S and 72 degrees W to 124 degrees E has been achieved within the Raman and polarization lidar network Polly(NET). This network consists of portable, remote-controlled multiwavelength-polarization-Raman lidars (Polly) for automated and continuous 24/7 observations of clouds and aerosols. Polly(NET) is an independent, voluntary, and scientific network. All Polly lidars feature a standardized instrument design with different capabilities ranging from single wavelength to multiwavelength systems, and now apply unified calibration, quality control, and data analysis. The observations are processed in near-real time without manual intervention, and are presented online at polly.tropos.de. The paper gives an overview of the observations on four continents and two research vessels obtained with eight Polly systems. The specific aerosol types at these locations (mineral dust, smoke, dust-smoke and other dusty mixtures, urban haze, and volcanic ash) are identified by their Angstrom exponent, lidar ratio, and depolarization ratio. The vertical aerosol distribution at the Polly(NET) locations is discussed on the basis of more than 55 000 automatically retrieved 30 min particle backscatter coefficient profiles at 532 nm as this operating wavelength is available for all Polly lidar systems. A seasonal analysis of measurements at selected sites revealed typical and extraordinary aerosol conditions as well as seasonal differences. These studies show the potential of Polly(NET) to support the establishment of a global aerosol climatology that covers the entire troposphere.

Several types of filter-based instruments are used to estimate aerosol light absorption coefficients. Two significant results are presented based on Aethalometer measurements at six Arctic stations from 2012 to 2014. First, an alternative method of post-processing the Aethalometer data is presented, which reduces measurement noise and lowers the detection limit of the instrument more effectively than box-car averaging. The biggest benefit of this approach can be achieved if instrument drift is minimised. Moreover, by using an attenuation threshold criterion for data post-processing, the relative uncertainty from the electronic noise of the instrument is kept constant. This approach results in a time series with a variable collection time (Delta t) but with a constant relative uncertainty with regard to electronic noise in the instrument. An additional advantage of this method is that the detection limit of the instrument will be lowered at small aerosol concentrations at the expense of temporal resolution, whereas there is little to no loss in temporal resolution at high aerosol concentrations (>2.1-6.7Mm(-1) as measured by the Aethalometers). At high aerosol concentrations, minimising the detection limit of the instrument is less critical. Additionally, utilising co-located filter-based absorption photometers, a correction factor is presented for the Arctic that can be used in Aethalometer corrections available in literature. The correction factor of 3.45 was calculated for low-elevation Arctic stations. This correction factor harmonises Aethalometer attenuation coefficients with light absorption coefficients as measured by the co-located light absorption photometers. Using one correction factor for Arctic Aethalometers has the advantage that measurements between stations become more inter-comparable.

This study reports the first investigation of atmospheric illicit drug concentrations in Northern Europe usingmeasurements of cocaine and cannabinoids in Amsterdam, London and Stockholm. Further, these measurements were compared to those made in Rome to explore the geographical and inter-city variability. Co-located measurements of atmospheric particulate mass and PAHs were used to help describe and interpret the illicit drug measurements with respect to atmospheric dispersion. Cocaine concentrations ranged from 0.03 to 0.14 ng/m(3) in Amsterdam, from 0.02 to 0.33 ng/m(3) in London and were below quantification limit (3pg/m(3)) in Stockholm. Cannabinol was the only cannabinoidmolecule detected in the three cities. During this campaign, London reported the highest concentrations of cocaine and meaningful differences were detected between the urban background and city centre London sites. Mean cocaine concentrations measured in Amsterdam during March 2011 were also compared with those measured simultaneously in eight Italian cities. The cocaine concentration inAmsterdamwas comparable to that measured at an urban background inMilan and at a densely populated site in Florence. Although correlating atmospheric concentrations directlywith drug prevalence is not possible using current data, links between concentrations of cocaine and estimates of abuse prevalence assessed by the more routinely usedwastewater analysiswere also examined. A statistically significant correlationwas found between the two sets of data (R-2= 0.66; p= 0.00131). Results confirmed that meteorology, population rate and habits of consumption influence the atmospheric concentrations of drugs. If these confounding factors were better controlled for, the techniques described here could became an easy and cost effective tool to index the impact of cocaine abuse in the area; especially where local hot spots need to be identified.

Adults are mainly exposed to per- and polyfluoroalkyl substances (PFASs) via ingestion of food, inhalation of air and ingestion of dust, whereas for children the exposure to PFASs is largely unknown. This study aimed to reconstruct the serum concentrations of perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS) and perfluorohexane sulfonic acid (PFHxS) in children after infancy up to 10.5 years of age and to test if dietary intake is the major exposure pathway for children to PFOA, PFOS and PFHxS after infancy. For this work, a dataset from a Finnish child cohort study was available, which comprised serum concentrations of the studied perfluoroalkyl acids (PFAAs) and PFAS concentration measurements in dust and air samples from the children's bedrooms. The calculated PFAA intakes were used in a pharmacokinetic model to reconstruct the PFAA serum concentrations from 1 to 10.5 years of age. The calculated PFOA and PFOS intakes were close to current regulatory intake thresholds and diet was the major exposure medium for the 10.5 year-olds. The one-compartment PK model reconstructed median PFOA and PFOS serum concentrations well compared to corresponding measured median serum concentrations, while the modelled PFHxS serum concentrations showed a constant underestimation. The results imply that children's exposure to PFOA and PFOS after breastfeeding and with increasing age resembles the exposure of adults. Further, the children in the Finnish cohort experienced a rather constant exposure to PFOA and PFOS between 1 and 10.5 years of age. The PFHxS exposure sources and respective pharmacokinetic parameter estimations need further investigation.