Soil bottles and soil slurry experiments were conducted to investigate the effect of some additives on the aerobic and anaerobic biodegradation of chlorinated aliphatic hydrocarbons; tetrachloroethylene (PCE), trichloroethylene (TCE) and dichloroethylene (DCE) in a contaminated soil from Startvätten AB Linköping Sweden. For the aerobic degradation study the soil sample was divided into two groups, one was fertilised. The two groups of soil in the experimental bottles were treated to varying amount of methane in pairs. DCE and TCE were added to all samples while PCE was found in the contaminated soil. Both aerobic and anaerobic experiments were conducted. For aerobic study air was added to all bottles to serve as electron acceptor (oxygen). It was observed that all the samples showed a very small amount of methane consumption while the fertilised soil samples showed more oxygen consumption. For the chlorinated compounds the expected degradation could not be ascertained since the control and experimental set up were more or less the same. For the anaerobic biodegradation study soil slurry was made with different media i.e. basic mineral medium (BM), BM and an organic compound (lactate), water and sulphide, phosphate buffer and sulphide and phosphate buffer, sulphide and ammonia. To assure anaerobic conditions, the headspace in the experimental bottles was changed to N2/CO2. As for the aerobic study all the samples were added DCE and TCE while PCE was found in the contaminated soil. The sample without the soil i.e. the control was also given PCE. It was observed that there was no clear decrease in the GC peak area of the pollutants in the different media. The decrease in GC peak area of the pollutants could not be seen, this may be so because more susceptible microorganisms are required, stringent addition of nutrients and to lower the risk of the high concentration of PCE and petroleum products in the soil from Startvätten AB.

Thallium is a highly toxic element that humans are exposed to mainly by consumption of drinking water and vegetables grown in soil with high thallium content but also through inhalation of particles in the air. Thallium is also present in fossil fuels, alloys, and in electronic utilities. The increasing use of the element and emissions from notably energy production has lead to a higher load on the surface of the Earth. This study aims at increasing the knowledge about the behaviour of thallium in aquatic environments. Focus has been on the redox chemistry of thallium in relation to its mobility, which is of great importance because Tl(I) and Tl(III) have very different properties in this respect. The relationship between Tl(I) and Tl(III) in surface waters from contaminated and uncontaminated environments was examined by ion chromatography connected on line to ICP-MS (inductively coupled plasma mass spectrometry). It was found in controlled systems that even though Tl(III) is thermodynamically unstable under fresh water conditions Tl(I) was oxidised in the presence of light and iron(III). This was also confirmed in field studies. When lake water samples were exposed to light, Tl(I) was oxidised and thallium was lost from the solution. The most likely explanation for this was adsorption of thallium to particle surfaces. The concentration of thallium in Swedish lakes and soil were measured. In unpolluted lakes the concentration ranges between 4.5-12 ng/l, the sediment concentration was 0.07-1.46 mg/kg. The anthropogenic load was found to have increased since the end of the Second World War although concentrations above background were found since the early industrialisation. In contaminated areas the concentration in soil ranges from 0.64-88 mg/kg, high concentrations were found in systems with alum shale and in soil exposed to runoff from a lead and zinc enrichment plant. The mobilisation of thallium from solid phases in contaminated areas was dependent on pH and about 50% of the leachable content was mobilised already at pH 5-6. Once it had been released to water it was highly mobile. These conditions suggest that in a large part of the Swedish environment a high mobility of thallium can be expected.

This thesis studied the viability of recycling filter substrates as soil amendments after being used in on-site systems for phosphorus (P) removal from wastewater. Focus was put on the materials Filtra P and Polonite, which are commercial products used in compact filters in Sweden. A prerequisite for this choice was to review filter materials and P sorption capacity. The filter substrates (Filtra P, Polonite and wollastonite tailings) were recycled from laboratory infiltration columns as soil amendments to a neutral agricultural soil and to an acid meadow soil to study their impacts on soil properties and yield of barley and ryegrass. The amendments tended to improve the yield and showed a liming effect, significantly increasing soil pH and the availability of P. In another experiment, samples of Filtra P and Polonite were equilibrated in batch experiments with the two soils in order to study the P dynamics in the soil-substrate system.  Batch equilibrations confirmed the liming potential of Filtra P and Polonite and showed that improved P availability in soils was strongly dependent on substrate P concentration, phase of sorbed P, and soil type. Finally, samples of Polonite used for household wastewater treatment were recycled as soil amendments to a mountain meadow and to an agricultural field for wheat cropping. The liming effect of Polonite was confirmed under field conditions and the results were similar to those of lime for the mountain meadow soil. However, the results were quite different for the agricultural field, where Polonite did not affect soil pH or any other chemical and physical soil properties investigated and had no impact on wheat yield and quality. The results from field experiments suggested that Polonite can be safely recycled to meadows and cropping fields at rates of 5-10 ton ha-1 but long-term studies are needed to forecast the effects of accumulation. / QC 20100708

In this thesis the oxidation of monoterpenes by O3 and NO2 and factors that influenced the oxidation were studied. In the environment both ozone (O3) and nitrogen dioxide (NO2) are present as oxidising gases, which causes sampling artefacts when using Tenax TA as an adsorbent to sample organic compounds in the air. A scrubber was developed to remove O3 and NO2 prior to the sampling tube, and artefacts during sampling were minimised when using the scrubber. The main organic compounds sampled in this thesis were two monoterpenes, alfa-pinene and delta-3-carene, due to their presence in both indoor and outdoor air. The recovery of the monoterpenes through the scrubber varied between 75-97% at relative humidities of 15-75%. The reactions of alfa-pinene and delta-3-carene with O 3, NO2 and nitric oxide (NO) at different relative humidities (RHs) and reaction times were studied in a dark reaction chamber. The experiments were planned and performed according to an experimental design were the factors influencing the reaction (O3, NO2, NO, RH and reaction times) were varied between high and low levels. In the experiments up to 13% of the monoterpenes reacted when O3, NO2, and reaction time were at high levels, and NO, and RH were at low levels. In the evaluation eight and seven factors (including both single and interaction factors) were found to influence the amount of alfa-pinene and delta-3-carene reacted, respectively. The three most influencing factors for both of the monoterpenes were the O 3 level, the reaction time, and the RH. Increased O3 level and reaction time increased the amount of monoterpene reacted, and increased RH decreased the amount reacted. A theoretical model of the reactions occurring in the reaction chamber was created. The amount of monoterpene reacted at different initial settings of O3, NO2, and NO were calculated, as well as the influence of different reaction pathways, and the concentrations of O3 and NO2, and NO at specific reaction times. The results of the theoretical model were that the reactivity of the gas mixture towards alfa-pinene and delta-3-carene was underestimated. But, the calculated concentrations of O3, NO2, and NO in the theoretical model were found to correspond to a high degree with experimental results performed under similar conditions. The possible associations between organic compounds in indoor air, building variables and the presence of sick building syndrome were studied using principal component analysis. The most complex model was able to separate 71% of the “sick” buildings from the “healthy” buildings. The most important variables that separated the “sick” buildings from the “healthy” buildings were a more frequent occurrence or a higher concentration of compounds with shorter retention times in the “sick” buildings. The outcome of this thesis could be summarised as follows; - - - -

<p>In this thesis the oxidation of monoterpenes by O3 and NO2 and factors that influenced the oxidation were studied. In the environment both ozone (O3) and nitrogen dioxide (NO2) are present as oxidising gases, which causes sampling artefacts when using Tenax TA as an adsorbent to sample organic compounds in the air. A scrubber was developed to remove O3 and NO2 prior to the sampling tube, and artefacts during sampling were minimised when using the scrubber. The main organic compounds sampled in this thesis were two monoterpenes, alfa-pinene and delta-3-carene, due to their presence in both indoor and outdoor air. The recovery of the monoterpenes through the scrubber varied between 75-97% at relative humidities of 15-75%.</p><p>The reactions of alfa-pinene and delta-3-carene with O 3, NO2 and nitric oxide (NO) at different relative humidities (RHs) and reaction times were studied in a dark reaction chamber. The experiments were planned and performed according to an experimental design were the factors influencing the reaction (O3, NO2, NO, RH and reaction times) were varied between high and low levels. In the experiments up to 13% of the monoterpenes reacted when O3, NO2, and reaction time were at high levels, and NO, and RH were at low levels. In the evaluation eight and seven factors (including both single and interaction factors) were found to influence the amount of alfa-pinene and delta-3-carene reacted, respectively. The three most influencing factors for both of the monoterpenes were the O 3 level, the reaction time, and the RH. Increased O3 level and reaction time increased the amount of monoterpene reacted, and increased RH decreased the amount reacted.</p><p>A theoretical model of the reactions occurring in the reaction chamber was created. The amount of monoterpene reacted at different initial settings of O3, NO2, and NO were calculated, as well as the influence of different reaction pathways, and the concentrations of O3 and NO2, and NO at specific reaction times. The results of the theoretical model were that the reactivity of the gas mixture towards alfa-pinene and delta-3-carene was underestimated. But, the calculated concentrations of O3, NO2, and NO in the theoretical model were found to correspond to a high degree with experimental results performed under similar conditions. The possible associations between organic compounds in indoor air, building variables and the presence of sick building syndrome were studied using principal component analysis. The most complex model was able to separate 71% of the “sick” buildings from the “healthy” buildings. The most important variables that separated the “sick” buildings from the “healthy” buildings were a more frequent occurrence or a higher concentration of compounds with shorter retention times in the “sick” buildings.</p><p>The outcome of this thesis could be summarised as follows;</p><p>-</p><p>-</p><p>-</p><p>-</p>

<p>Air pollutants pose a high risk for humans, and the environment, and this pollution is one of the major environmental problems facing modern society. Active air sampling is the technique that has been traditionally used to monitor nonpolar aromatic air pollutants. However, active high volume samplers (HiVols) require a power supply, maintenance and specialist operators, and the equipment is often expensive. Thus, there is a need to develop new, less complicated sampling techniques that can increase the monitoring frequency, the geographical distribution of the measurements, and the number of sites used in air monitoring programs. In the work underlying this thesis, the use of semipermeable membrane devices (SPMDs) as tools for monitoring gas phase concentrations of nonpolar aromatic compound was evaluated using the compound classes polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs (alkyl-PAHs) and nitrated PAHs (nitro-PAHs) as test compounds. </p><p>High wind-speeds increased the uptake and release in SPMDs of PAHs and PCBs with log K_OA values > 7.9, demonstrating that the uptake of most nonpolar aromatic compounds is controlled by the boundary layer at the membrane-air interface. The use of a metal umbrella to shelter the SPMDs decreased the uptake of PAHs and PCBs by 38 and 55 percent, respectively, at high wind/turbulence, and thus reduced the wind effect. Further, the use of performance reference compounds (PRCs) to assess the site effect of wind on the uptake in SPMDs reduced the between-site differences to less than 50 percent from as much as three times differences in uptake of PCBs and PAHs. However, analytical interferences reduced the precision of some PRCs, showing the importance of using robust analytical quality control.</p><p>SPMDs were shown to be efficient samplers of gas phase nonpolar aromatic compounds, and were able to determine local, continental and indoor spatial distributions of PAHs, alkyl- PAHs and nitro-PAHs. In addition, the use of the SPMDs, which do not require electricity, made sampling possible at remote/rural areas where the infrastructure was limited. SPMDs were also used to determine the source of PAH pollution, and different approaches were discussed. Finally, SPMDs were used to estimate the importance of the gas phase exposure route to the uptake of PAHs in plants. The results demonstrate that SPMDs have several advantages compared with HiVols, including integrative capacity over long times, reduced costs, and no need of special operators, maintenance or power supply for sampling. However, calibration data of SPMDs in air are limited, and spatial differences are often only semi-quantitatively determined by comparing amounts and profiles in the SPMDs, which have limited their use in air monitoring programs. In future work, it is therefore important that SPMDs are properly sheltered, PRCs are used in the sampling protocols, and that calibrated sampling rate data, or the SPMD-air partition data, of specific compounds are further developed to make determination of time weighted average (TWA) concentrations possible.</p>

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) have been assigned toxic equivalency factors (TEFs). These compounds are today routinely analysed with sophisticated analytical techniques. In a near future, there might be other dioxinlike compounds such as polychlorinated naphthalenes (PCNs), alkyl-polychlorodibenzofurans (R-PCDFs), and polychlorinated dibenzothiophenes (PCDTs) added to this list of toxic dioxin-like compounds. It is therefore important to have a readiness to analyse these new compounds in environmental samples. In this study, a multi-residue non-destructive analytical method for the analyses of these planar dioxin-like compound classes was developed. The use of HPLC PX-21 carbon column fractionation enabled the separation of interfering PCBs from coplanar PCBs and other planar dioxin-like compounds of interest. The obtained planar fraction containing the dioxin-like compounds was analysed using high-resolution GC-MS. Levels of PCNs in surface sediments and settling particulate matter in the northern Baltic Sea were determined. The concentrations of PCNs in background surface sediments were approximately 1 ng/g dw and the estimated PCN fluxes were similar to the pre-industrial levels determined in Europe. The PCN congener patterns in the surface sediments suggest that the PCNs deposited in the Baltic Sea originate from similar sources. Bioaccumulation of PCNs in a benthic food chain (sediment, amphipod, isopod, and four-horned sculpin) from the Gulf of Bothnia was studied. The results indicated that only a few PCN congeners biomagnified. The highest biomagnification factors (BMFs) were found for 2,3,6,7-substituted congeners and those lacking adjacent hydrogen-substituted carbon atoms. The calculated biota to sediment accumulation factors (BSAFs) showed that the tetra- and penta- CNs exhibited BSAF values higher than one, while BSAFs for the more chlorinated PCNs were less than one. A general difference between the northern and southern parts of the Gulf of Bothnia could be seen in the samples, with the lowest PCN and total PCB concentrations being found in the north and the highest in the south. This gradient is related to distance from the more industrialised and populated regions in the southern parts of Sweden and Finland, and central Europe. Analysis of R-PCDFs in crustacean samples from the Swedish west coast was performed using HRGC-MS/MS. The ΣR-PCDFs in these samples were present at concentrations up to 10 times higher than the ΣPCDFs. The relatively high concentrations of R-PCDFs in the crab samples demonstrate that these compounds bioaccumulate. The fate of a pollutant in the environment and the toxicity of a compound are governed by its physicochemical properties. The information found in a data set of properties can predict a compound’s mode of action. The following physicochemical properties for 87 PCDFs were measured: ultra-violetadsorption, relative retention times on two common gas chromatographic stationary phases, and relative mass spectrometric response factors using EI- and NCI- modes.

Air pollutants pose a high risk for humans, and the environment, and this pollution is one of the major environmental problems facing modern society. Active air sampling is the technique that has been traditionally used to monitor nonpolar aromatic air pollutants. However, active high volume samplers (HiVols) require a power supply, maintenance and specialist operators, and the equipment is often expensive. Thus, there is a need to develop new, less complicated sampling techniques that can increase the monitoring frequency, the geographical distribution of the measurements, and the number of sites used in air monitoring programs. In the work underlying this thesis, the use of semipermeable membrane devices (SPMDs) as tools for monitoring gas phase concentrations of nonpolar aromatic compound was evaluated using the compound classes polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs (alkyl-PAHs) and nitrated PAHs (nitro-PAHs) as test compounds. High wind-speeds increased the uptake and release in SPMDs of PAHs and PCBs with log KOA values &gt; 7.9, demonstrating that the uptake of most nonpolar aromatic compounds is controlled by the boundary layer at the membrane-air interface. The use of a metal umbrella to shelter the SPMDs decreased the uptake of PAHs and PCBs by 38 and 55 percent, respectively, at high wind/turbulence, and thus reduced the wind effect. Further, the use of performance reference compounds (PRCs) to assess the site effect of wind on the uptake in SPMDs reduced the between-site differences to less than 50 percent from as much as three times differences in uptake of PCBs and PAHs. However, analytical interferences reduced the precision of some PRCs, showing the importance of using robust analytical quality control. SPMDs were shown to be efficient samplers of gas phase nonpolar aromatic compounds, and were able to determine local, continental and indoor spatial distributions of PAHs, alkyl- PAHs and nitro-PAHs. In addition, the use of the SPMDs, which do not require electricity, made sampling possible at remote/rural areas where the infrastructure was limited. SPMDs were also used to determine the source of PAH pollution, and different approaches were discussed. Finally, SPMDs were used to estimate the importance of the gas phase exposure route to the uptake of PAHs in plants. The results demonstrate that SPMDs have several advantages compared with HiVols, including integrative capacity over long times, reduced costs, and no need of special operators, maintenance or power supply for sampling. However, calibration data of SPMDs in air are limited, and spatial differences are often only semi-quantitatively determined by comparing amounts and profiles in the SPMDs, which have limited their use in air monitoring programs. In future work, it is therefore important that SPMDs are properly sheltered, PRCs are used in the sampling protocols, and that calibrated sampling rate data, or the SPMD-air partition data, of specific compounds are further developed to make determination of time weighted average (TWA) concentrations possible.

Soil that is heavily contaminated with polycyclic aromatic hydrocarbons (PAHs) is often found at the sites of former gasworks and wood-impregnation plants. Since PAHs are toxic these sites represent a hazard to human health and the environment, and therefore they need to be treated, preferably by a method that destroys the contaminants, and thus eliminates the problem permanently. However, during biological and chemical degradation of PAHs other toxic compounds may be formed. If these transformation products are sufficiently persistent they could potentially accumulate during remedial processes. In the work underlying this thesis the degradation and transformation of PAHs were studied in three remedial processes: viz. a pilot-scale bioslurry reactor, microcosms with wood-rotting fungi and lab-scale treatments with Fenton's reagent. A group of transformation products referred to as oxygenated-PAHs (oxy-PAHs) was found to be particularly important, as these compounds are toxic and were shown to be relatively persistent in the environment. The oxy- PAHs were, for instance, found at significant concentrations in the gasworks soil used in most of the studies. This soil was highly weathered and had therefore been depleted of the more readily degradable compounds. In addition, experiments in which earthworms were exposed to the gasworks soil showed that the oxy-PAHs were more easily taken up in living organisms than PAHs. To facilitate the studies, new extraction and fractionation methods were developed. For instance, pressurized liquid extraction (PLE) was investigated for its reliability and efficiency to extract PAHs and oxy-PAHs from soil. Furthermore, a selective PLE-method was developed that can simultaneously extract and separate the PAHs and oxy-PAHs into two different fractions. This was accomplished by adding a chromatographic material (silica or Florisil) to the extraction cell. Under certain conditions all three remedial processes resulted in increasing amounts of oxy- PAHs in the soil. For example, 1-acenaphthenone and 4-oxapyrene-5-one accumulated in the bioslurry reactor. Similarly, in the soil inoculated with a white-rot fungus 9-fluorenone, benzo[a]anthracene-7,12-dione, 4-hydroxy-9-fluorenone and 4-oxapyrene-5-one accumulated. Finally, in an ethanol-Fenton treatment the concentration of some PAH-quinones increased in the soil. The results show that it might be necessary to monitor oxy-PAHs as well as PAHs during the remediation of PAH-contaminated sites. Otherwise, the soil may be considered detoxified too early in the process. In the long term it would be desirable to include analyses with sufficient marker compounds to follow the possible production and elimination of the oxy-PAHs. However, until such compounds can be identified it is suggested that contaminated soil should be screened for oxy-PAHs in general. The selective PLE-method presented in this thesis could be a useful tool for this.

<p>Polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzo-furans (PCDFs) belong to the most toxic compounds known to science and they are defined as Persistent Organic Pollutants (POPs) under the Stock-holm Convention. The general human exposure to PCDD/Fs is primarily through dietary intake. The importance of contaminated sites as secondary PCDD/F sources (i.e. sources that once received its contamination from a primary source) are getting increased attention. To be able to assess the risks for human exposure at PCDD/F contaminated sites, the environmen-tal distribution of PCDD/Fs and the potential mobilization between dif-ferent environmental media (e.g. food chain transfer) must be known. The primary aim of the work presented in this thesis was to investigate human exposure pathways associated with PCDD/F contaminated sites by combining field measurements and modeling. Site specific field measurements were made at a PCDD/F contaminated site in Sweden and multimedia modeling scenarios were evaluated against site specific data and national reference data.</p><p>The results show that the congener distributions in exposure media affected by contaminated soil may differ significantly from the distribu-tions found in media from reference locations. Higher chlorinated PCDD/Fs may be transferred into food chains where they contribute to a large fraction of the toxic equivalent concentration (TEQ). Ingestion of locally produced animal food may be an important exposure pathway al-ready at low or moderate PCDD/F soil concentrations. However, the con-gener composition of the source is critical for the exposure. The signifi-cance of the individual exposure routes varies depending on e.g. the spatial distribution and magnitude of the soil contamination, the pro-perties of the exposure media and the human behavior. Multimedia mo-deling can be used in risk assessments as long as model algorithms and model parameters are representative for the superhydrophobic properties of PCDD/Fs. However, selection of physical-chemical PCDD/F properties is a challenge due to large variation in reported values. For some proper-ties, data is scattered or completely lacking</p>