The effects of soil processes, related to the oxidation of sulphide sediments, on heavy metal concentrations in the soil and soil solution were investigated in a Norway spruce stand on a fine-textured, acidic soil rich in sulphates located on the isostatic land-uplift western coast of Finland. The age of the soil is ca. 300–400 years, and the soil texture is silt and till. The chemical properties of the soil and soil solution clearly reflected the formation of acid sulphate (AS) soil. Compared to background reference values for podzolic coniferous forest soil, the pH of the soil solution in the mineral soil (20–40 cm depth) was very low, and the Al, Fe and S concentrations extremely high. The Zn and Ni concentrations in the soil solution were also strongly elevated, and similar to the concentrations reported close to anthropogenic heavy-metal emission sources. The concentrations of Cd and Cu were also frequently elevated. In contrast, the acidity and metal concentrations of the soil solution sampled in the organic layer were not elevated. Similarly, exchangeable Zn and Ni concentrations were also elevated in the mineral soil, but not in the organic layer. Because Norway spruce has a very superficial rooting system and the zone with exceptionally high metal concentrations did not extend up to the topmost soil layers, sulphide-oxidation derived soil acidification is not likely to pose a serious threat to forest ecosystems growing on this type of site. Despite the elevated concentrations of protons and many metals in the mineral soil and soil solution (20–40 cm), the nutrient status of the spruce stand was satisfactory and the general health of the stand has been reported to be relatively good.

On the coastal plains of Finland there are approximately 3,000 km² of acid sulfate soils developed as a result of intensive agricultural drainage of waterlogged sulfide-bearing sediments. The runoff from these soils contains very high amounts of acidity and metals that have severely deteriorated the aquaculture in several downstream rivers and estuaries. Therefore, there is an urgent need to develop and test more environmental friendly ways of draining landscapes underlain with these nasty soils. In this study, over a 3-year monitoring period the effect of excess surface liming, controlled drainage and lime filter drainage of acid sulfate soils on runoff water quality (pH, sulfate, metals) was determined and assessed. The results showed that (1) the liming measures had not prevented severely acidic and metal-rich waters from forming and discharging from the soils, (2) the controlled drainage system might have reduced discharge peaks but its potential effects on the discharged water quality were nondetectable due to its small effect on the groundwater level and naturally inherited heterogeneities, and (3) the spatial and temporal variations identified for the various hydrochemical determinants were not caused by the kind of treatment applied. Therefore, on acid sulfate soil fields, like the one studied here, the short-term hydrochemical effects of the treatments tested are minor (or nonexistent) at least as long as the controlled drainage systems are not technically improved or better maintained.

The sampling and analysis properties of 1-stage and 2-stage filter-pack methods were studied in detail in monitoring of sulphur and nitrogen containing inorganic gases and particles (sulphur dioxide, sulphate, sum of nitric acid and nitrate and total ammonium). The limit of detection and the limit of quantitation for 24-h samples were estimated using the results of a short-term field experiment completed with available data from long-term monitoring and internal quality assurance. Furthermore, the combined expanded measurement uncertainty including sampling and analysis (Uₜₒₜ) was estimated for filter-pack methods in order to give a tool for distinguishing long-term trends in air quality from the measurement variability. Uₜₒₜ was found to be very near the analytical uncertainty when measuring higher air concentration levels, being ± 4.0% for sulphur concentrations > 1.0 μg m⁻³, ± 3.0% for sulphate concentrations > 0.5 μg m⁻³, ± 3.5% for the sum of nitrate and nitric acid concentrations > 0.3 μg m⁻³ and ± 4.5% for total ammonium concentrations > 0.8 μg m⁻³. At the lower air concentration range Uₜₒₜ increases significantly due to the field blank values. The precision of the 24-h filter-pack sample results expressed by means of modified median absolute difference (M.MAD) and coefficient of variance (CoV) gave 8.3% for sulphur dioxide and 5.4% for particulate sulphate. For the sum of gaseous nitric acid and particulate nitrate the CoV was 5.5% and for total ammonium 4.3%. In addition the suitability of the 24-h filter-pack methods in weekly sampling was proved.

BACKGROUND AND AIM: In non-eutrophicated freshwaters, humic substances (HS) pose chemical stresses on aquatic organisms and, hence, separating sensitive from less sensitive or even tolerant species. One of the stresses, identified so far, is the reduction of photosynthetic oxygen production and reduction in growth in freshwater macrophytes and algae. In a previous paper, it has been shown that even closely related coccal green algae responded differently upon identical stress by HS, which is consistent with the hypothesis above. Due to their much simpler cellular ultrastructure, cyanobacteria are supposed to be more sensitive to HS exposure than eukaryote should be. One coccal green algal species (Desmodesmus communis) and one cyanobacterium (Chroococcus minutus) were exposed to four natural organic matter (NOM) isolates. One NOM has been isolated from a brown water lake (Schwarzer See) in Brandenburg State; three were obtained from a comprehensive Scandinavian NOM research project and originated from Norway (Birkenes), Finland (Hietajärvi), and Sweden (Svartberget). METHODS: Cultures of D. communis and C. minutus were obtained from the Culture Collection of Algae, Göttingen, and maintained in a common medium. The cultures were non-axenic. The algae and cyanobacteria were exposed under identical conditions to environmentally realistic NOM concentrations. Cell numbers were counted microscopically in Neugebauer cuvettes in triplicates. To avoid limitation by nutrient depletion, the experiments were terminated after 14 to 15 days. Until culture day 12, no growth limitation has been observed in the controls. RESULTS: All NOM isolates modulated the growth of the algae and cyanobacteria. During the early culture days, there was a slight growth promotion with the coccal green alga and to a much lesser degree with the cyanobacterium. Yet, the major effect were significant reductions in cell yield in both primary producer cultures. C. minutus was much more affected than D. communis. This applies particularly to the three tested Scandinavian NOM isolates, which were effective at concentrations even below 1 mg L-1 DOC. DISCUSSION: The growth promoting effect may be due to an increase in bioavailability of some trace nutrients in the presence of NOM, the release of some growth promoting substances by microbial or photochemical processing of the NOM, and/or a hormetic effect. The growth reducing effect can be explained as a herbicide-like mode of action that affects the photosystem II most prevalent by blocking the electron transport chain, absorption of electrons, or production of an internal oxidative stress after processing the bioconcentrated HS. Furthermore, it may be postulated that also phototoxicity of these HS in the algal cells contributes to the overall toxicity; however, experimental evidence is lacking so far. CONCLUSIONS: Upon exposure to HS, cyanobacteria appear to be much more sensitive than coccal green algae and respond in growth reduction. This high sensitivity of cyanobacteria to HS may explain phytoplankton patterns in the field. Eutrophic, humic-rich lakes do not support the cyanobacterial blooms characteristic of eutrophic, but humic-poor lakes. In the humic-rich systems, raphidophytes or, less frequent, specific coccal greens are more common. Obviously, cyanobacteria appear to be unable to make advantage of their accessory pigments (phycocyanin) to exploit the reddish light prevailing in humic-rich lakes. RECOMMENDATION: At present, no effective structure can be figured out which may be responsible for the adverse effect on the cyanobacterial species. It is reserved to future research whether or not HS may be applied more specifically (for instance, with elevated moieties of the effective structures) as a natural geochemical to combat cyanobacterial blooms.