Chemical characteristics and behaviour of sediment phosphorus in the northeastern Baltic Sea.

Chemical characteristics and behaviour of sediment phosphorus in the northeastern Baltic Sea Eutrophication is a severe environmental problem in the Baltic Sea, especially in the Gulf of Finland and the Archipelago Sea, and it is enhanced by the release of phosphorus (P) from bottom sediments. The release of P from sediment reserves largely depends on the occurrence of P in different chemical forms and on the prevailing conditions, especially on the presence of oxygen. This study examines the chemical character and the vertical distribution of sediment P in two shallow estuaries, in shallow coastal sediments overlain by oxic near-bottom water, and in poorly oxygenated open sea sediments in the northeastern Baltic Sea. The objective was to evaluate how much of the sediment P is buried and removed from the nutrient cycle, and how much of it is in forms that can be released from the sediment to the overlaying water over time. Relationships between the distribution of the different P forms and the chemical and physical properties of the sediment, sediment pore water, and near-bottom water were determined in order to examine the behaviour of P at the sediment-water interface. The results show that the chemical character of sediment P varied in the different areas. Generally, in the outer estuaries and in the organic-rich coastal areas in the eastern Gulf of Finland, the sediments were higher in P than the sediments in the poorly oxygenated open sea areas in the central and western Gulf. The estuary sediments that received erosion-transported material were characterised by P bound to hydrated oxides of iron and aluminum. Iron-bound P is sensitive to changes in redox-conditions, but part of it was buried in the estuaries, possibly because of high sedimentation rates and incomplete reduction of iron. The open sea sediments in the central and western Gulf of Finland were dominated by apatite-P, which was also abundant in the areas strongly affected by sediment transportation. The burial of sediment P was most effective in the areas rich in apatite-P, which is a relatively stable form of P in sediment. In the eastern Gulf of Finland, organic P forms predominated in the organic-rich sediments. A part of these P forms will be buried, while part will be degraded in the long term, releasing soluble P to the pore water. In the poorly oxygenated areas, iron compounds at the sediment surface are not able to retain P released during mineralisation of organic matter or reduction-induced dissolution of iron-compounds in deep sediment layers. However, in the shallow coastal areas overlain by oxic near-bottom water, the organic-rich surface sediment can also become temporarily reduced and release P from the sediment to the overlaying water. The considerable variation in the chemical composition of sediment P reserves in the northeastern Baltic Sea proved that it is an important factor and should be taken into account when evaluating the release of sediment P and the role of P reserves in bottom sediments in eutrophication.

Phosphorus in agricultural soils of Finland - characterization of reserves and retention in mineral soil profiles

An overwhelming majority of all the research on soil phosphorus (P) has been carried out with soil samples taken from the surface soils only, and our understanding of the forms and the reactions of P at a soil profile scale is based on few observations. In Finland, the interest in studying the P in complete soil profiles has been particularly small because of the lack of tradition in studying soil genesis, morphology, or classification. In this thesis, the P reserves and the retention of orthophosphate phosphorus (PO4-P) were examined in four cultivated mineral soil profiles in Finland (three Inceptisols and one Spodosol). The soils were classified according to the U.S. Soil Taxonomy and soil samples were taken from the genetic horizons in the profiles. The samples were analyzed for total P concentration, Chang and Jackson P fractions, P sorption properties, concentrations of water-extractable P, and for concentrations of oxalate-extractable Al and Fe. Theoretical P sorption capacities and degrees of P saturation were calculated with the data from the oxalate-extractions and the P fractionations. The studied profiles can be divided into sections with clearly differing P characteristics by their master horizons Ap, B and C. The C (or transitional BC) horizons below an approximate depth of 70 cm were dominated by, assumingly apatitic, H2SO4-soluble P. The concentration of total P in the C horizons ranged from 729 to 810 mg kg-1. In the B horizons between the depths of 30 and 70 cm, a significant part of the primary acid-soluble P has been weathered and transformed to secondary P forms. A mean weathering rate of the primary P in the soils was estimated to vary between 230 and 290 g ha-1 year-1. The degrees of P saturation in the B and C horizons were smaller than 7%, and the solubility of PO4-P was negligible. The P conditions in the Ap horizons differed drastically from those in the subsurface horizons. The high concentrations of total P (689-1870 mg kg-1) in the Ap horizons are most likely attributable to long-term cultivation with positive P balances. A significant proportion of the P in the Ap horizons occurred in the NH4F- and NaOH-extractable forms and as organic P. These three P pools, together with the concentrations of oxalate-extractable Al and Fe, seem to control the dynamics of PO4-P in the soils. The degrees of P saturation in the Ap horizons were greater (8-36%) than in the subsurface horizons. This was also reflected in the sorption experiments: Only the Ap horizons were able to maintain elevated PO4-P concentrations in the solution phase − all the subsoil horizons acted as sinks for PO4-P. Most of the available sorption capacity in the soils is located in the B horizons. The results suggest that this capacity could be utilized in reducing the losses of soluble P from excessively fertilized soils by mixing highly sorptive material from the B horizons with the P-enriched surface soil. The drastic differences in the P characteristics observed between adjoining horizons have to be taken into consideration when conducting soil sampling. Sampling of subsoils has to be made according to the genetic horizons or at small depth increments. Otherwise, contrasting materials are likely to be mixed in the same sample; and the results of such samples are not representative of any material present in the studied profile. Air-drying of soil samples was found to alter the results of the sorption experiments and the water extractions. This indicates that the studies on the most labile P forms in soil should be carried out with moist samples.

Extraction methods in soil phosphorus characterisation : Limitations and applications

The quantification and characterisation of soil phosphorus (P) is of agricultural and environmental importance and different extraction methods are widely used to asses the bioavailability of P and to characterize soil P reserves. However, the large variety of extractants, pre-treatments and sample preparation procedures complicate the comparison of published results. In order to improve our understanding of the behaviour and cycling of P in soil, it is crucial to know the scientific relevance of the methods used for various purposes. The knowledge of the factors affecting the analytical outcome is a prerequisite for justified interpretation of the results. The aim of this thesis was to study the effects of sample preparation procedures on soil P and to determine the dependence of the recovered P pool on the chemical nature of extractants. Sampling is a critical step in soil testing and sampling strategy is dependent on the land-use history and the purpose of sampling. This study revealed that pre-treatments changed soil properties and air-drying was found to affect soil P, particularly extractable organic P, by disrupting organic matter. This was evidenced by an increase in the water-extractable small-sized (<0.2 µm) P that, at least partly, took place at the expense of the large-sized (>0.2 µm) P. However, freezing induced only insignificant changes and thus, freezing can be taken to be a suitable method for storing soils from the boreal zone that naturally undergo periodic freezing. The results demonstrated that chemical nature of the extractant affects its sensitivity to detect changes in soil P solubility. Buffered extractants obscured the alterations in P solubility induced by pH changes; however, water extraction, though sensitive to physicochemical changes, can be used to reveal short term changes in soil P solubility. As for the organic P, the analysis was found to be sensitive to the sample preparation procedures: filtering may leave a large proportion of extractable organic P undetected, whereas the outcome of centrifugation was found to be affected by the ionic strength of the extractant. Widely used sequential fractionation procedures proved to be able to detect land-use -derived differences in the distribution of P among fractions of different solubilities. However, interpretation of the results from extraction experiments requires better understanding of the biogeochemical function of the recovered P fraction in the P cycle in differently managed soils under dissimilar climatic conditions.

Om naturens förvandlingar : Vetenskap, kunskap och frihet i Rudolf Steiners tidiga tänkande. Idéhistoriska perspektiv på Waldorfpedagogiken

TRANSFORMATIONS OF NATURE Science, Knowledge and Freedom in the Early Thinking of Rudolf Steiner. Perspectives on Waldorf Education in the light of the History of Ideas Waldorf Education is based on the worldview that Rudolf Steiner (1861-1925) developed to a wide-ranging anthroposophical movement in the first decades of the 20th century. This thesis takes as its departure the early thinking of Rudolf Steiner that precedes anthroposophy, and its main purpose is to uncover the tradition of ideas represented in Steiner´s early life and which, in different ways, have emerged in the practice of Waldorf Education. Through systematic analysis I attempt to bring to light different aspects of Steiner’s early thinking: his concept of science, his epistemological startingpoints and his philosophy of freedom. By departing from J. W. Goethe’s qualitative concept of science, Steiner strove in his early works to formulate a monistic worldview which appears to be closely related to the Romantic Movement and its philosophy of nature. Characteristic traits of his thinking are, on the one hand, a critique of a one-sided enlightenment and, on the other hand, an aspiration to see the world as a living organic unity. Human beings can, by developing our intuitive faculties, get a deeper understanding of the indissoluble relationship between man and nature. Against this background Steiner´s early thinking can be read as a special kind of romantic development narrative. Steiner’s early thinking also opens the way for romantic perspectives on Waldorf Education. It appears that many central aims and conceptions in Waldorf Education can be illuminated by the epistemological perspective upon which Steiner elaborated early in his life. An organic curriculum, phenomenological didactics and high ideal of freedom can be considered seen as educational applications of conceptions that played an important role in Goethe and his age. Thus, Waldorf Education provides in our contemporary society an exceptional set of educational values: a holistic education with romantic undertones.

Agronomic challenges for organic crop husbandry

With respect to resource management and environmental impact, organic farming offers rationales for agricultural sustainability. However, agronomic productivity is usually higher with conventional farming. This work aimed at investigating two factors of major importance for the agronomic productivity of organic crop husbandry, nitrogen (N) supply through symbiotic N fixation (SNF) and weed occurrence. Perennial red clover-grass leys and spring cereal crops subjected to regular agricultural practices were studied on 34 organic farms located in the southern and the north-western coastal regions of Finland. Herbage growth, clover content as a proportion of the ley and extent of SNF in perennial leys, and the occurrence of weed species and weed-crop competition in spring cereal stands were related to climate conditions, soil properties, and management measures. The herbage accumulated from the first and the second cut of one- and two-year-old leys averaged 7.5 t DM ha-1 (SD ± 1.7 t DM ha-1); the clover content averaged 43.9% (SD ± 18.8%). Along with the clover content, herbage production decreased with ley age. Radiation use efficiency (RUE) correlated positively with clover proportion but despite low clover contents, three-year-old leys were still productive with regard to RUE. SNF in the accumulated annual growth of one- and two-year-old leys averaged 247.5 kg N ha-1 yr-1 (SD ± 114.4 kg N ha-1 yr-1). It was supposed that if red clover-grass leys constituted 40% of the rotation, then the mean N supply by SNF would be able to sustain two or three succeeding cereal crops (green manure and forage ley, respectively), yielding 3.0 to 4.0 t grain ha-1. Being a function of clover biomass, the SNF increased from the first to the second cut and thereafter declined with ley age. Coefficients of variation of clover contents (and SNF) between and within fields were around 50%, which was about twice as high as those of herbage production. The lower were the clover contents, the higher were the within-field variations of clover as a proportion of the ley. Low clover contents in one-year-old leys and increasing variability with ley age suggested that red clover growth was limited by poor establishment and poor overwintering. The proportions of clover in leys were lower and their variability was higher in the northwest than in the south. Soil properties, primarily texture and structure, had a major impact on clover proportion and herbage production, which largely explained regional differences in ley growth. Within-field variability of soil properties can be amended through site-specific measures, including drainage, liming, and applications of organic manures and mineral fertilizers. Overwintering and the persistence of leys can be improved by the choice of winter-hardy varieties, careful establishment and the appropriate harvest regime. Mean grain yields of spring cereal crops amounted to 3.2 t ha-1 in the south and 3.6 t ha-1 in the northwest. At 570 and 565 m-2 for the south and northwest respectively, mean weed densities did not differ between the regions, whereas the respective mean weed biomass of 697 and 1594 kg dry weight ha-1, respectively did differ. Weed abundance varied remarkably between single fields. The number of weed species was higher in the south than in the northwest. For example, Fumaria officinalis and Lamium spp. were found only in the south. Frequencies and abundances of Lapsana communis, Myosotis arvensis, Polygonum aviculare, Tripleurospermum inodorum, and Vicia spp. were higher in the south, whereas those of Elymus repens, Persicaria spp. and Spergula arvensis were higher in the northwest. The number of years since conversion to organic farming, i.e. long-term management, was one of the variables that explained the abundance of single weed species. E. repens was the weed species whose biomass increased most with the duration of organic farming. Another significant variable was crop biomass, which was affected by short-term management. The presence of different weed species was related to the duration of organic farming and to low crop yield. This finding demonstrated that it was not the organic farming regime per se, which resulted in high weed infestation and low yielding crops, but failures in the understanding and the management of organic farming systems. Successful weed control relies on farm- and field-specific long- and short-term management approaches. The agronomic productivity of ley and spring cereal crops managed by full-time farmers with an interest in organic farming was on the same level as of the mean for conventional farming. Given the many options for further improvements of the agronomic performance of organic arable systems, organic farming offers foundations for the development of sustainable agriculture. The main threat to the sustainability of farming in Finland, both conventional and organic, is the spatial separation of crop production and animal husbandry by region, along with the simplification of associated crop rotations.

Intensity, productivity and efficiency in agriculture in Finland and implications for N and P fertiliser management

The purpose of this study was to evaluate intensity, productivity and efficiency in agriculture in Finland and show implications for N and P fertiliser management. Environmental concerns relating to agricultural production have been and still are focused on arguments about policies that affect agriculture. These policies constrain production while demand for agricultural products such as food, fibre and energy continuously increase. Therefore the importance of increasing productivity is a great challenge to agriculture. Over the last decades producers have experienced several large changes in the production environment such as the policy reform when Finland joined the EU 1995. Other and market changes occurred with the further EU enlargement with neighbouring countries in 2005 and with the decoupling of supports over the 2006-2007 period. Decreasing prices a decreased number of farmers and decreased profitability in agricultural production have resulted from these changes and constraints and of technological development. It is known that the accession to the EU 1995 would herald changes in agriculture. Especially of interest was how the sudden changes in prices of commodities on especially those of cereals, decreased by 60%, would influence agricultural production. The knowledge of properties of the production function increased in importance as a consequence of price changes. A research on the economic instruments to regulate productions was carried out and combined with earlier studies in paper V. In paper I the objective was to compare two different technologies, the conventional farming and the organic farming, determine differences in productivity and technical efficiency. In addition input specific or environmental efficiencies were analysed. The heterogeneity of agricultural soils and its implications were analysed in article II. In study III the determinants of technical inefficiency were analysed. The aspects and possible effects of the instability in policies due to a partial decoupling of production factors and products were studied in paper IV. Consequently connection between technical efficiency based on the turnover and the sales return was analysed in this study. Simple economic instruments such as fertiliser taxes have a direct effect on fertiliser consumption and indirectly increase the value of organic fertilisers. However, fertiliser taxes, do not fully address the N and P management problems adequately and are therefore not suitable for nutrient management improvements in general. Productivity of organic farms is lower on average than conventional farms and the difference increases when looking at selling returns only. The organic sector needs more research and development on productivity. Livestock density in organic farming increases productivity, however, there is an upper limit to livestock densities on organic farms and therefore nutrient on organic farms are also limited. Soil factors affects phosphorous and nitrogen efficiency. Soils like sand and silt have lower input specific overall efficiency for nutrients N and P. Special attention is needed for the management on these soils. Clay soils and soils with moderate clay content have higher efficiency. Soil heterogeneity is cause for an unavoidable inefficiency in agriculture.

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.

The effects of organic environmental toxicants on hard tissue formation in developing tooth : An in vitro study in mice

Dioxins are organic toxicants that are known to impair tooth development, especially dental hard tissue formation. The most toxic dioxin congener is 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). Further, clinical studies suggest that maternal smoking during pregnancy can affect child s tooth development. One of the main components of tobacco smoke is the group of non-halogenated polycyclic aromatic hydrocarbons (PAHs), a representative of which is 7,12-dimethylbenz[a]anthracene (DMBA). Tributyltin (TBT), an organic tin compound, has been shown to impair bone mineralization in experimental animals. In addition to exposure to organic toxicants, a well-established cause for enamel hypomineralization is excess fluoride intake. The principal aim of this thesis project was to examine in vitro if, in addition to dioxins, other organic environmental toxicants, like PAHs and organic tin compounds, have adverse effects on tooth development, specifically on formation and mineralization of the major dental hard tissues, the dentin and the enamel. The second aim was to investigate in vitro if fluoride could intensify the manifestation of the detrimental developmental dental effects elicited by TCDD. The study was conducted by culturing mandibular first and second molar tooth germs of E18 NMRI mouse embryos in a Trowell-type organ culture and exposing them to DMBA, TBT, and sodium fluoride (NaF) and/or TCDD at various concentrations during the secretory and mineralization stages of development. Specific methods used were HE-staining for studying cell and tissue morphology, BrdU-staining for cell proliferation, TUNEL-staining for apoptosis, and QPCR, in situ hybridization and immunohistochemistry for the expressions of selected genes associated with mineralization. This thesis work showed that DMBA, TBT, TCDD and NaF interfere with dentin and enamel formation of embryonic mouse tooth in vitro, and that fluoride can potentiate the harmful effect of TCDD. The results suggested that adverse effects of TBT involve altered expression of genes associated with mineralization, and that DMBA and TBT as well as NaF and TCDD together primarily affect dentin mineralization. Since amelogenesis does not start until mineralization of dentin begins, impaired enamel matrix secretion could be a secondary effect. Dioxins, PAHs and organotins are all liposoluble and can be transferred to the infant by breast-feeding. Since doses are usually very low, developmental toxicity on most of the organs is difficult to indentify clinically. However, tooth may act as an indicator of exposure, since the major dental hard tissues, the dentin and the enamel, are not replaced once they have been formed. Thus, disturbed dental hard tissue formation raises the question of more extensive developmental toxicity.