Occurrence and properties of steryl ferulates and glycosides in wheat and rye

Cereal kernels are known to contain a number of minor components that possess beneficial health attributes. In this thesis rye and wheat were studied as sources of steryl ferulates and steryl glycosides and their behaviour in processing were evaluated. Further, enzymatic hydrolysis of these conjugates was studied, as well as the capacity of steryl ferulates to inhibit lipid oxidation at different temperatures. Steryl ferulates were shown to have a strong positive correlation with dietary fibre contents in milling fractions from the outer parts of the kernels obtained from a commercial scale mill. Highest contents of steryl ferulates were found in the bran in both cereals, with the content decreasing once moving towards the inner parts of the kernel. Variation in the contents of steryl ferulates was higher in wheat fractions than rye fractions. Steryl glycosides, on the other hand, had either negative or no correlation with dietary fibre, and the range of the steryl glycoside contents was much narrower than that of steryl ferulates in both cereals. There were significant differences in the sterol compositions of these steryl conjugates when compared with each other or with the total plant sterols in the corresponding fractions. Properties of steryl ferulates and steryl glycosides were evaluated after common processing methods and in enzymatic hydrolysis. Thermal and mechanical processing had only minor or no effects on the contents of steryl conjugates from rye and wheat bran. Enzymatic treatments on the other hand caused some changes, especially in the contents of glycosylated sterols. When steryl ferulates extracted from rye or wheat bran were subjected to enzymatic treatments by steryl esterase, significant differences in the rates of hydrolysis were observed between steryl ferulates from different sources with differing sterol compositions. Further, differences were also observed between enzymes from different sources. Steryl glycosides were shown to be hydrolysed by β-glucosidase (cellobiase) from A. niger, but less with β-glucosidases from other sources. Steryl ferulates showed good antioxidant activity at both moderate and high temperatures. In bulk and emulsion systems of methyl linoleate at 40°C steryl ferulates extracted from rye and wheat bran inhibited hydroperoxide formation much more effectively than synthetic steryl ferulates or those extracted from rice (γ-oryzanol), demonstrating that the sterol composition has an effect on the activity. At cooking (100°C) and frying temperatures (180°C) sitostanyl ferulate was shown to inhibit polymer formation significantly and, especially at 100°C, comparably to α-tocopherol. The rate of antioxidant degradation was slower for sitostanyl ferulate, showing higher heat stability than α-tocopherol. When evaluated as a mixture, no synergistic effect was observed between these two antioxidants. The data presented in this thesis provides information that may henceforth be applied when evaluating the intakes of steryl conjugates from cereal sources, as well as their possible influences as minor bioactive components. Wheat and rye both are good sources of steryl ferulates and steryl glycosides and, especially with steryl ferulates, what may be lost out to some other cereals on quantity is compensated with quality of the sterol composition.

What kind of data would ascertain real periodicity in the terrestrial impact crater record

Maan törmäyskraaterien ikäjakauman mahdollinen ajallinen jaksollisuus on herättänyt laajaa keskustelua sen jälkeen, kun ilmiö ensimmäistä kertaa raportoitiin joukossa arvostettuja tieteellisiä artikkeleita vuonna 1984. Vaikka nykytiedon valossa on kyseenalaista perustuuko havaittu jaksollisuus todelliseen fysikaaliseen ilmiöön, on kuitenkin mahdollista, että jaksollisuus on todella olemassa ja se voitaisiin havaita laajemmalla ja tarkemmalla törmäyskraateriaineistolla. Tutkimuksessa luotiin simuloidut kraaterien ajalliset tiheys- ja kertymäfunktiot tapauksille, jossa kraaterit syntyvät joko täysin jaksollisella tai satunnaisella prosessilla. Näiden kahden ääritapauksen lisäksi luotiin jakaumat myös kahdelle niiden yhdistelmälle. Nämä mallit mahdollistavat myös erilaisten kraaterien iänmäärityksen epätarkkuuksien huomioonottamisen. Näistä jakaumista luotiin eri pituisia simuloituja kraaterien ikien aikasarjoja. Lopulta simuloiduista aikasarjoista pyrittiin Rayleigh'n menetelmän avulla etsimään jakaumassa ollutta jaksollisuutta. Tutkimuksemme perusteella ajallisen jaksollisuuden havaitseminen kraateriaikasarjoista on lähes mahdotonta mikäli vain yksi kolmasosa kraatereista on jaksollisen ilmiön aiheuttamia, vaikka nykyistä kraateriaineistoa laajempi ja tarkempi aineisto olisi tulevaisuudessa saatavilla. Mikäli kaksi kolmasosaa meteoriittitörmäyksistä on jaksollisia, sen havaitseminen on mahdollista, mutta vaatii huomattavasti tämän hetkistä kattavamman kraateriaineiston. Tutkimuksen perusteella on syytä epäillä, että havaittu kraaterien ajallinen jaksollisuus ei ole todellinen ilmiö.

Organic contaminants - occurrence and biological effects in the Baltic Sea

The Baltic Sea was studied with respect to selected organic contaminants and their ecotoxicology. The research consisted of analyses of total hydrocarbons, polycyclic aromatic hydrocarbons, bile metabolites, hepatic ethoxyresorufin-O-deethylase (EROD) activity, polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). The contaminants were measured from various matrices, such as seawater, sediment and biota. The methods of analysis were evaluated and refined to comparability of the results. Polyaromatic hydrocarbons, originating from petroleum, are known to be among the most harmful substances to the marine environment. In Baltic subsurface water, seasonal dependence of the total hydrocarbon concentrations (THCs) was seen. Although concentrations of parent polycyclic aromatic hydrocarbons (PAHs) in sediment surface varied between 64 and 5161 ug kg-1 (dw), concentrations above 860 ug kg-1 (dw) were found in all the studied sub-basins of the Baltic Sea. Concentrations commonly considered to substantially increase the risk of liver disease and reproductive impairment in fish, as well as potential effects on growth (above 1000 ug kg-1 dw), were found in all the studied sub-basins of the Baltic Sea except Kattegat. Thus, considerable pollution in sediments was indicated. In bivalves, the sums of 12 PAHs varied on a wet weight basis between 44 and 298 ug kg-1 (ww). The predominant PAHs were high molecular weight and the PAH profiles of M. balthica differed from those found in sediment from the same area. The PAHs were both pyrolytic and petrogenic in origin, and a contribution from diesel engines was found, which indicates pollution of the Baltic Sea, most likely caused by the steadily increasing shipping in the area. The HPLC methods developed for hepatic EROD activity and bile metabolite measurements proved to be fast and suitable for the study of biological effects. A mixed function oxygenase enzyme system in Baltic Sea perch collected from the Gulf of Finland was induced slightly: EROD activity in perch varied from 0.30 14 pmol min-1 mg-1 protein. This range can be considered to be comparable to background values. Recent PAH exposure was also indicated by enhanced levels (213 and 1149 ug kg-1) of the bile metabolite 1-hydroxypyrene. No correlation was indicated between hepatic EROD activity and concentration of 1-hydroxypyrene in bile. PCBs and OCPs were observed in Baltic Sea sediment, bivalves and herring. Sums of seven CBs in surface sediment (0 5 cm) ranged from 0.04 to 6.2 ug kg-1 (dw) and sums of three DDTs from 0.13 to 5.0 ug kg-1 (dw). The highest levels of contaminants were found in the most eastern area of the Gulf of Finland where the highest total carbon and nitrogen content was found and where the lowest percentage proportion of p,p -DDT was found. The highest concentrations of CBs and the lowest concentration of DDTs were found in M. balthica from the Gulf of Finland. The highest levels of DDTs were found in M. balthica from the Hanö Bight, which is the outer part of the Bornholm Basin close to the Swedish mainland. In bivalves, the sums of seven CBs were 72 108 ug kg-1 (lw) and the sums of three DDTs were 66 139 ug kg-1 (lw). Results from temporal trend monitoring showed, that during the period 1985 2002, the concentrations of seven CBs in two-year-old female Baltic herring were clearly decreased, from 9 16 to 2 6 ug kg-1 (ww) in the northern Baltic Sea. At the same time, concentrations of three DDTs declined from 8 15 to 1 5 ug kg-1 (ww). The total concentration of the fat-soluble CBs and DDTs in Baltic herring muscle was shown to be age-dependent; the average concentrations in ten-year-old Baltic herring were three to five-fold higher than in two-year-old herring. In Baltic herring and bivalves, as well as in surface sediments, CB 138 and CB153 were predominant among CBs, whereas among DDTs p,p'-DDD predominated in sediment and p,p'-DDE in bivalves and Baltic herring muscle. Baltic Sea sediments are potential sources of contaminants that may become available for bioaccumulation. Based on ecotoxicological assessment criteria, cause for concern regarding CBs in sediments was indicated for the Gulf of Finland and the northern Baltic Proper, and for the northern Baltic Sea regarding CBs in Baltic herring more than two years old. Statistical classification of selected organic contaminants indicated high-level contamination for p,p'-DDT, p,p'-DDD, p,p'-DDE, total DDTs, HCB, CB118 and CB153 in muscle of Baltic herring in age groups two to ten years; in contrast, concentrations of a-HCH and g-HCH were found to be moderate. The concentrations of DDTs and CBs in bivalves is sufficient to cause biological effects, and demonstrates that long-term biological effects are still possible in the case of DDTs in the Hanö Bight.

Environmental factors affecting the occurrence of periglacial landforms in Finnish Lapland: a numerical approach

Determination of the environmental factors controlling earth surface processes and landform patterns is one of the central themes in physical geography. However, the identification of the main drivers of the geomorphological phenomena is often challenging. Novel spatial analysis and modelling methods could provide new insights into the process-environment relationships. The objective of this research was to map and quantitatively analyse the occurrence of cryogenic phenomena in subarctic Finland. More precisely, utilising a grid-based approach the distribution and abundance of periglacial landforms were modelled to identify important landscape scale environmental factors. The study was performed using a comprehensive empirical data set of periglacial landforms from an area of 600 km2 at a 25-ha resolution. The utilised statistical methods were generalized linear modelling (GLM) and hierarchical partitioning (HP). GLMs were used to produce distribution and abundance models and HP to reveal independently the most likely causal variables. The GLM models were assessed utilising statistical evaluation measures, prediction maps, field observations and the results of HP analyses. A total of 40 different landform types and subtypes were identified. Topographical, soil property and vegetation variables were the primary correlates for the occurrence and cover of active periglacial landforms on the landscape scale. In the model evaluation, most of the GLMs were shown to be robust although the explanation power, prediction ability as well as the selected explanatory variables varied between the models. The great potential of the combination of a spatial grid system, terrain data and novel statistical techniques to map the occurrence of periglacial landforms was demonstrated in this study. GLM proved to be a useful modelling framework for testing the shapes of the response functions and significances of the environmental variables and the HP method helped to make better deductions of the important factors of earth surface processes. Hence, the numerical approach presented in this study can be a useful addition to the current range of techniques available to researchers to map and monitor different geographical phenomena.

Ballistic Trauma in Finland : An Epidemiologic and Clinical Study of Firearm and Explosion Injuries

The occurrence and nature of civilian firearm- and explosion-injuries in Finland, and the nature of severe gunshot injuries of the extremities were described in seven original articles. The main data sources used were the National Hospital Discharge Register, the Cause-of-Death Register, and the Archive of Death Certificates at Statistics Finland. The present study was population based. Epidemiologic methods were used in six and clinical analyses in five papers. In these clinical studies, every original hospital record and death certificate was critically analyzed. The trend of hospitalized firearm injuries has slightly declined in Finland from the late 1980s to the early 2000s. The occurrence decreased from 5.1 per 100 000 person-years in 1990 to 2.6 in 2003. The decline was found in the unintentional firearm injuries. A high incidence of unintentional injuries by firearms was characteristic of the country, while violence and homicides by firearms represented a minor problem. The incidence of fatal non-suicidal firearm injuries has been stable, 1.8 cases per 100 000 person-years. Suicides using firearms were eight times more common during the period studied. This is contrary to corresponding reports from many other countries. However, the use of alcohol and illegal drugs or substances was detected in as many as one-third of the injuries studied. The median length of hospitalization was three days and it was significantly associated (p<0.001) with the type of injury. The mean length of hospital stay has decreased from the 1980s to the early 2000s. In this study, there was a special interest in gunshot injuries of the extremities. From a clinical point of view, the nature of severe extremital gunshot wounds, as well as the primary operative approach in their management, varied. The patients with severe injuries of this kind were managed at university and central hospital emergency departments, by general surgeons in smaller hospitals and by cardiothoracic or vascular surgeons in larger hospitals. Injuries were rarities and as such challenges for surgeons on call. Some noteworthy aspects of the management were noticed and these should be focused on in the future. On the other hand, the small population density and the relatively large geographic area of Finland do not favor high volume, centralized trauma management systems. However, experimental war surgery has been increasingly taught in the country from the 1990s, and excellent results could be expected during the present decade. Epidemiologically, explosion injuries can be considered a minor problem in Finland at present, but their significance should not be underestimated. Fatal explosion injuries showed up sporadically. An increase occurred from 2002 to 2004 for no obvius reason. However, in view of the historical facts, a possibility for another rare major explosion involving several people might become likely within the next decade. The national control system of firearms is mainly based on the new legislations from 1998 and 2002. However, as shown in this study, there is no reason to assume that the national hospitalization policies, or the political climate, or the legislation might have changed over the study period and influenced the declining development, at least not directly. Indeed, the reason for the decline to appear in the incidence of unintentional injuries only remains unclear. It may derive from many practical steps, e.g. locked firearm cases, or from the stability of the community itself. For effective reduction of firearm-related injuries, preventive measures, such as education and counseling, should be targeted at recreational firearm users. To sum up, this study showed that the often reported increasing trend in firearm as well as explosion-related injuries has not manifested in Finland. Consequently, it can be recognized that, overall, the Finnish legislation together with the various strategies have succeeded in preventing firearm- and explosion-related injuries in the country.

Cereal alkylresorcinols as dietary biomarkers-absorption and occurrence in biological membranes

Several studies link the consumption of whole-grain products to a lowered risk of chronic diseases, such as certain types of cancer, type II diabetes, and cardiovascular diseases. However, the final conclusions of the exact protective mechanisms remain unclear, partly due to a lack of a suitable biomarker for the whole-grain cereals intake. Alkylresorcinols (AR) are phenolic lipids abundant in the outer parts of wheat and rye grains usually with homologues of C15:0- C25:0 alkyl chains, and are suggested to function as whole-grain biomarkers. Mammalian lignan enterolactone has also previously been studied as a potential whole-grain biomarker. In the present work a quantified gas chromatography-mass spectrometry method for the analysis of AR in plasma, erythrocytes, and lipoproteins was developed. The method was used to determine human and pig plasma AR concentrations after the intake of whole-grain wheat and rye products compared to low-fibre wheat bread diets to assess the usability of AR as biomarkers of whole-grain intake. AR plasma concentrations were compared to serum ENL concentrations. AR absorption and elimination kinetics were investigated in a pig model. AR occurrence in human erythrocyte membranes and plasma lipoproteins were determined, and the distribution of AR in blood was evaluated. Plasma AR seem to be absorbed via the lymphatic system from the small intestine, like many other lipophilic compounds. Their apparent elimination half-life is relatively short and is similar to that of tocopherols, which have a similar chemical structure. Plasma AR concentrations increased significantly after a one- to eight-week intake of whole-grain wheat and further on with whole-grain rye bread. The concentrations were also higher after habitual Finnish diet compared to diet with low-fibre bread. Inter-individual variation after a one-week intake of the same amount of bread was high, but the mean plasma AR concentrations increased with increasing AR intake. AR are incorporated into erythrocyte membranes and plasma lipoproteins, and VLDL and HDL were the main AR carriers in human plasma. Based on these studies, plasma AR could function as specific biomarkers of dietary whole-grain products. AR are exclusively found in whole-grains and are more suitable as specific biomarkers of whole-grain intake than previously investigated mammalian lignan enterolactone, that is formed from several plants other than cereals in the diet. Plasma AR C17:0/C21:0 -ratio could distinguish whether whole-grain products in the diet are mainly wheat or rye. AR could be used in epidemiological studies to determine whole-grain intake and to better assess the role of whole-grains in disease prevention.

Primary Fallopian tube carcinoma:occurrence, risk and prognostic factors

The aim of the study was to clarify the occurrence, and etiological and prognostic factors of primary fallopian tube carcinoma (PFTC). We studied the sociodemographic determinants of the incidence of PFTC in Finland and the role of chlamydial infections and human papillomavirus infections as risk factors for PFTC. Serum tumor markers were studied as prognostic factors for PFTC. We also evaluated selected reproductive factors (parity, sterilization and hysterectomy) as risk or protective factors of PFTC. The risks of second primary cancers after PFTC were also studied. The age-adjusted incidence of PFTC in Finland increased to 5.4 / 1,000,000 in 1993 97. The incidence rate was higher in the cities, but the relative rise was higher in rural areas. Women in the two highest social classes showed a 1.8 fold incidence compared with those in the lowest. Women in agriculture and those not working outside the home showed only half the PFTC incidence of those in higher socioeconomic occupations. Pretreatment serum concentrations of hCGβ, CA125 and TATI were evaluated as prognostic markers for PFTC. Elevated hCGβ values (above the 75th percentile, 3.5 pmol/L; OR 2.49, 95% CI 1.22 5.09), stage and histology were strong independent prognostic factors for PFTC. The effects of parity, sterilization and hysterectomy on the risk of PFTC were studied in a case control-study with 573 PFTC cases from the Finnish Cancer Registry. In multivariate analysis parity was the only significant protective factor as regards PFTC, with increasing protection associated with increasing number of deliveries. In univariate analysis sterilization gave borderline protection against PFTC and the protective effect increased with time since the operation. In multivariate analysis the protection did not reach statistical significance. Chlamydial and human papillomavirus (HPV) infections were studied in two separate seroepidemiological case-control studies with 78 PFTC patients. The incidence of women with positive HPV or chlamydial serology was the same in PFTC patients and in the control group and was not found to be a risk factor for PFTC. Finally, the possible risk of a second primary cancer after diagnosis and treatment of PFTC in a cohort of 2084 cases from 13 cancer registries followed for second primary cancers within the period 1943 2000 was studied. In PFTC patients, second primary cancers were 36% more common than expected (SIR 1.36, 95% CI 1.13 1.63). In conclusion, the incidence of PFTC has increased in Finland, especially in higher social classes and among those in certain occupations. Elevated serum hCGβ reflect a worsened prognosis. Parity is a clear protective factor, as is previous sterilization. After PFTC there is a risk of second primary cancers, especially colorectal, breast, lung and bladder cancers and non-lymphoid leukemia. The excess of colorectal and breast cancers after PFTC may indicate common effects of earlier treatments, or they could reflect common effects of lifestyle or genetic, immunological or environmental background.

Iron and manganese in groundwater in Finland : Occurrence in glacifluvial aquifers and removal by biofiltration

Yhteenveto: Rauta ja mangaani Suomen glasifluviaalisten akviferien pohjavedessä ja poisto biosuodatuksella

Assessment of insect occurrence in boreal forests based on satellite imagery and field measurements.

The presence/absence data of twenty-seven forest insect taxa (e.g. Retinia resinella, Formica spp., Pissodes spp., several scolytids) and recorded environmental variation were used to investigate the applicability of modelling insect occurrence based on satellite imagery. The sampling was based on 1800 sample plots (25 m by 25 m) placed along the sides of 30 equilateral triangles (side 1 km) in a fragmented forest area (approximately 100 km2) in Evo, S Finland. The triangles were overlaid on land use maps interpreted from satellite images (Landsat TM 30 m multispectral scanner imagery 1991) and digitized geological maps. Insect occurrence was explained using either environmental variables measured in the field or those interpreted from the land use and geological maps. The fit of logistic regression models varied between species, possibly because some species may be associated with the characteristics of single trees while other species with stand characteristics. The occurrence of certain insect species at least, especially those associated with Scots pine, could be relatively accurately assessed indirectly on the basis of satellite imagery and geological maps. Models based on both remotely sensed and geological data better predicted the distribution of forest insects except in the case of Xylechinus pilosus, Dryocoetes sp. and Trypodendron lineatum, where the differences were relatively small in favour of the models based on field measurements. The number of species was related to habitat compartment size and distance from the habitat edge calculated from the land use maps, but logistic regressions suggested that other environmental variables in general masked the effect of these variables in species occurrence at the present scale.