Persistence of fluazinam in soil under boreal conditions.

Fluazinam, a widely used pesticide in conventional potato cultivation, is effective against epidemics of the fungal disease late blight. To assess fluazinam persistence in soil, laboratory experiments were conducted with fluazinam added to soil as a pure chemical or contained in the commercial product Shirlan®. In a follow-up experiment, the persistence was monitored under constant temperature and water content conditions during a maximum period of 1 year. In an annual climatic rotation experiment, fluazinam added to soil was exposed to the year-round temperature and water content conditions occurring in the boreal zone. A third experiment was undertaken to clarify the effect of soil organic matter (SOM) on the recovery of fluazinam. In the follow-up and annual climatic rotation experiments, more than half of the added fluazinam was recovered after 1 year of incubation. The estimated half-life of fluazinam ranged between 355 and 833 days. The degradation of fluazinam was enhanced by an abundance of SOM, a warm temperature, and wetness. Additionally, in over half of soil samples collected from fields where potato had been intensively cultivated for many years, varying concentrations of fluazinam were detected. Fluazinam can carry over to the next growing season in professional potato production.

Translocation of elements and sugars in wheat genotypes at vegetative and generative stages under continuous selenium exposure.

BACKGROUND: Biofortification with selenium (Se) elevates its concentration in feed and fodder plants and helps to prevent health problems in animals and humans. The aim of this study was to describe Se-induced modifications in the accumulation of elements important for the proper functioning of wheat, one of the most popular cereals. The presence of Se correlated with carbohydrate synthesis and electron paramagnetic resonance (EPR). This explained the mechanisms of Se's antioxidant activity. RESULTS: Selenium accumulation in vegetative and generative leaves, and in the grains of three wheat genotypes (cv. Parabola, cv. Raweta and cv. Manu), differing in their stress tolerance and grown hydroponically in the presence of 10 or 20 µM Na2 SeO4, , was proportional to its content in the medium. Stronger Se accumulation was typical of a stress-sensitive genotype. Selenium generally promoted the uptake of macronutrients and micronutrients but their distribution depended on tissue and genotype. Changes in the Se-induced EPR signals of paramagnetic metals and organic radicals corresponded with stress tolerance of the tested genotypes. CONCLUSIONS: Se application increased the accumulation of nutrients and carbohydrates that are vital for proper plant growth and development. Accelerated uptake of molybdenum (Mo), an element improving dietary properties of grains, may be an additional advantage of Se fertilization. The mechanisms of Se-induced changes in removing Mn and iron (Fe) ions from macromolecules may be one of the factors that differentiate plant tolerance to oxidative stress. © 2019 Society of Chemical Industry.

High-performance liquid chromatography (HPLC) as a tool for monitoring the fate of fluazinam in soil.

Fluazinam is a widely used pesticide employed against the fungal disease late blight in potato cultivation. A specific, repeatable, and rapid high-performance liquid chromatography (HPLC) method utilizing a diode array detector (DAD) was developed to determine the presence of fluazinam in soil. The method consists of acetonitrile (ACN) extraction, clean-up with solid-phase extraction (SPE), and separation using a mobile phase consisting of 70% ACN and 30% water (v/v), including 0.02% acetic acid. HPLC was performed with a C18 column and the detection wavelength was 240 nm. The method was successfully applied to an incubation experiment and to soil samples taken from potato fields where fluazinam had been applied two to three times during the on-going growing season. In the 90-day incubation experiment, analytical standard fluazinam and the commercial fungicide Shirlan(®) were added to soil samples that had never been treated with fluazinam, and were then extracted with ACN and 0.01 M calcium chloride (CaCl2). Fluazinam was not extractable with CaCl2, indicating that it does not leach to watercourses in the dissolved form. Recovery with ACN extraction for sandy soils was 72-95% immediately after application and 53-73% after 90 days of incubation. Out of the eight potato field soil samples, fluazinam was found in two samples at concentrations of 2.1 mg kg(-1) and 1.9 mg kg(-1), well above the limit of quantification (0.1 mg kg(-1)).

Protective effect of selenium in Broccoli (Brassica oleracea) plants subjected to cadmium exposure.

The protective effect of selenium against the cadmium-induced oxidative effect in broccoli ( Brassica oleracea) plants was studied. Plants grown in hydroponic culture were supplied with selenium [as Se(IV)] and cadmium [as Cd(II)], individually or simultaneously. Cadmium accumulation in roots was noticeably higher than in the aerial parts of the plants, and this effect was even more acute when selenium was simultaneously added. Cadmium phytotoxicity was evidenced by an increase in the malondialdehyde (MDA) concentration in the roots and a decrease of photosynthetic pigment and tocopherol concentration in the aerial parts of the plant. The simultaneous addition of selenium alleviated cadmium-induced stress in the roots after 40 days of exposition. In the leaves, a more remarkable decrease of tocopherol and chlorophyll concentration was observed in the cadmium-enriched plants after 10 days of exposure. The results provided evidence that selenium supplementation helps the plant to minimize the cadmium oxidant effect. Tocopherol concentration in broccoli fruit of cadmium-supplied plants was not affected in comparison to control. However, the proportion of alpha-tocopherol increases with the addition of selenium. This response is important not only for the protective effect against oxidative damage in the plant but also in terms of human nutrition.

Effects of soil phosphorus status on environmental risk assessment of glyphosate and glufosinate-ammonium.

The increased use of herbicides poses a risk to the aquatic environment. Easy and economical methods are needed to identify the fields where specific environment protection measures are needed. Phosphorus (P) and organophosphorus herbicides compete for the same adsorption sites in soil. In this study the relationship between P obtained in routine Finnish agronomic tests (acid ammonium acetate [P(AC)]) and adsorption of glyphosate and glufosinate-ammonium was investigated to determine whether P(AC) values could be used in the risk assessment. The adsorption of glyphosate ((N-(phosphonomethyl)glycine) and glufosinate-ammonium (2-amino-4-(hydroxymethylphosphinyl)butanoic acid) was studied in a clay and a sandy loam soil enriched with increasing amounts of P added as potassium dihydrogen phosphate. Desorption was also determined for some P-enriched soil samples. The adsorption of both herbicides diminished with increasing P(AC) value. The correlations between Freundlich adsorption coefficients obtained in the adsorption tests and P(AC) were nonlinear but significant (r > 0.98) in both soils. The exponential models of the relationship between soil P(AC) values and glyphosate adsorption were found to fit well to an independent Finnish soil data set (P < 0.1 for glyphosate and P < 0.01 for glufosinate-ammonium). The desorption results showed that glufosinate-ammonium sorption is not inversely related to soil P status, and the high correlation coefficients obtained in the test of the model were thus artifacts caused by an abnormal concentration of exchangeable potassium in soil. The solved equations are a useful tool in assessing the leaching risks of glyphosate, but their use for glufosinate-ammonium is questionable.

Retention of metal and sulphate ions from acidic mining water by anionic nanofibrillated cellulose.

We carried out an adsorption experiment to investigate the ability of anionic nanofibrillated cellulose (NFC) to retain metal and SO42- ions from authentic highly acidic (pH3.2) mining water. Anionic NFC gels of different consistencies (1.1-%, 1.4-% and 1.8-% w/w) were allowed to react for 10min with mining water, after which NFC-induced changes in the metal and SO42- concentrations of the mining water were determined. The sorption capacities of the NFC gels were calculated as the difference between the element concentrations in the untreated and NFC-treated mining water samples. All the NFCs efficiently co-adsorbed both metals and SO42-. The retention of metals was concluded to take place through formation of metal-ligand complexes. The reaction between the NFC ligand and the polyvalent cations renders the cellulose nanofibrils positively charged and, thus, able to retain SO42- electrostatically. Adsorption capacity of the NFC gels substantially increased upon decreasing DM content as a result of the dilution-induced weakening of the mutual interactions between individual cellulose nanofibrils. This outcome reveals that the dilution of the NFC gel not only increases its purification capacity but also reduces the demand for cellulosic raw material. These results suggest that anionic NFC made of renewable materials serves as an environmentally sound and multifunctional purification agent for acidic multimetal mining waters or AMDs of high ionic strength. Unlike industrial minerals traditionally used to precipitate valuable metals from acidic mining effluents before their permanent disposal from the material cycle, NFC neither requires mining of unrenewable raw materials nor produces inorganic sludges.

Distribution of selenium in different biochemical fractions and raw darkening degree of potato (Solanum tuberosum L.) tubers supplemented with selenate.

Effects of Se fertilization on potato processing quality, possible changes in Se concentration and form in tubers during storage, and retransfer of Se from seed tubers were examined. Potato plants were grown at five selenate (SeO4(2-)) concentrations. Tubers were harvested 16 weeks after planting and were stored at 3-4 degrees C prior to analysis. The results showed that the Se concentration did not decrease during storage for 1-12 months. In tubers, 49-65% of total Se was allocated in protein fraction, which is less than found in plant leaves in a previous study. The next-generation tubers produced by the Se-enriched seed tubers had increased Se concentrations, which evidenced the relocation of Se from the seed tubers. At low levels, Se improved the processing quality of potato tubers by diminishing and retarding their raw darkening. The value of Se-enriched potato tubers as a Se source in the human diet was discussed.

Effects of de-icing chemicals sodium chloride and potassium formate on cadmium solubility in a coarse mineral soil.

Excessive use of sodium chloride (NaCl) as de-icing chemical causes environmental problems, such as elevated chloride concentrations in groundwater. On vulnerable sites, this can be avoided by using alternative organic de-icing chemicals, such as potassium formate (KHCOO). The environmental impacts of KCHOO are, however, not well known. This study reports the potential effects of NaCl and KCHOO on mechanisms controlling the mobility of cadmium (Cd) in roadside soils as a result of vehicular traffic. Changes in the solubility of Cd in a coarse mineral soil treated with these two de-icing chemicals were studied in a 50-day incubation experiment under four different moisture and temperature combinations and an initial soil Cd concentration of 3 mg kg(-1). After incubation, the distribution of soil Cd into different fractions was analyzed using a sequential extraction method. Soil pH and soil redox potential were recorded and the occurrence of Cd-Cl complexes in the soil was estimated using published stability constants. During incubation, KCHOO lowered the soil redox potential, but this was not accompanied by a decrease in the sorption capacity of oxides and the release of oxide-bound Cd into soil solution. On the other hand, elevated pH (from 4.3 to 6.7-8.5) in the formate treatments increased the sorption of Cd onto the oxide surfaces (up to 80% of total sorbed Cd). In the NaCl treatments, cation competition and formation of Cd-Cl complexes increased the water-soluble Cd fraction. Consequently, the amount of bioavailable Cd was 3.5 times smaller in the KCHOO than in the NaCl treatments.

Impact of soil pH and organic matter on the chemical bioavailability of vanadium species: The underlying basis for risk assessment.

The main objective of this study was to unravel the chemical reactions and processes dictating the potential bioavailability of vanadium (V). In environmental solutions V exists in two stable oxidation states, +IV and +V, of which + V is considered to be more toxic. In this study, the effect of speciation and soil pH on the chemical accessibility of V was investigated with two soils: 1) field soil rather rich in soil organic matter (SOM) and 2) coarse mineral soil low in SOM. Fresh soil samples treated with V(+V) (added as NaVO3) or V(+IV) (added as VOSO4) (pH adjusted to the range 4.0-6.9) were incubated for 3 months at 22 °C. The adsorption tendency of V species was explored by water extraction (Milli-Q water, 1:50 dw/V) and by sequential extraction (0.25 M KCl; 0.1 M KH2/K2HPO4; 0.1 M NaOH; 0.25 M H2SO4, 1:10 dw/V). The potential bioavailability of V was found to be dictated by soil properties. SOM reduced V(+V) to V(+IV) and acted as a sorbent for both species, which lowered the bioaccessibility of V. A high pH, in turn, favored the predominance of the V(+V) species and thus increased the chemical accessibility of V.

Influence of Pb contamination in boreal forest soil on the growth and ligninolytic activity of litter-decomposing fungi.

Lignin mineralization activity of three basidiomycetous litter-decomposing fungi (LDF) was studied with humus layer samples taken from a boreal forest soil. The total Pb concentration in the samples was 32,000 mg kg(-1) and water soluble Pb 67 mg kg(-1). Synthetic lignin mineralization by Collybia dryophila and Clitocybe (Lepista) nebularis was strongly inhibited, whereas Stropharia coronilla was more tolerant to Pb stress in soil and liquid cultures. Purified laccases maintained their activity and purified MnPs remained partly active up to a concentration of 1450 mg Pb l(-1). High concentrations of Pb inhibited the growth of LDF and affected the activity of ligninolytic enzymes, but the extent of inhibition varied among different LDF species. In consequence, Pb contamination in soil may have a negative impact on recycling of organic carbon.

Biogeochemistry of selenium and its impact on food chain quality and human health.

In areas where soils are low in bioavailable selenium (Se), potential Se deficiencies cause health risks for humans. Though higher plants have been considered not to require this element, the experience with low-Se soils in Finland has provided evidence that the supplementation of commercial fertilizers with sodium selenate affects positively not only the nutritive value of the whole food chain from soil to plants, animals and humans but also the quantity of plant yields. The level of Se addition has been optimal, and no abnormally high concentrations in plants or in foods of animal origin have been observed. Se levels in serum and human milk indicate that the average daily intake has been within limits considered to be safe and adequate. In fact, plants act as effective buffers, because their growth is reduced at high Se levels. They also tend to synthesize volatile compounds in order to reduce excess Se. On the other hand, when added at low concentrations, Se exerts a beneficial effect on plant growth via several mechanisms. As in humans and animals, Se strengthens the capacity of plants to counteract oxidative stress caused by oxygen radicals produced by internal metabolic or external factors. At proper levels it also delays some of the effects of senescence and may improve the utilization of short-wavelength light by plants. High additions are toxic and may trigger pro-oxidative reactions. Thus, the present supplementation of fertilizers with Se can be considered a very effective and readily controlled way to increase the average daily Se intake nationwide.

Iron as a source of color in river waters.

Organic chromophores of total organic carbon (TOC) and those of iron (Fe) contribute to the color of water, but the relative contributions of colored organic carbon (COC%) and Fe (Fe%) are poorly known. In this study, we unraveled Fe% and COC% in 6128 unfiltered water samples collected from 94 Finnish river sites of contrasting catchment properties. According to regression analysis focusing on TOC alone, on average 84% of the mean TOC consisted of COC, while 16% was non-colored or below the color-detection limit. COC and Fe were much more important sources of color than phytoplankton (chlorophyll a as a proxy) or non-algal particles (suspended solids as a proxy). When COC and Fe were considered as the only two sources of color, COC% ranged from 16.8% to 99.5% (mean 71%) and Fe% from 0.5% to 83.2% (mean 29%). Similar Fe% and COC% values were obtained when color was estimated from the absorption coefficients of COC and Fe at 490 nm. Fe% increased as a function of the concentration of Fe and was well predicted by the TOC-to-Fe mass ratio. In 608 samples with TOC-to-Fe ratios of <4.5, Fe dominated the color. TOC-to-Fe ratios varied widely within most sites, but in relation to hydrology. In catchments with a peatland coverage of >30%, peak flow exported elevated amounts of TOC relative to Fe and resulted in a high COC%. Base flow, instead, mobilized elevated amounts Fe relative to TOC and resulted in a high Fe%. In a catchment covered with 31% of agricultural fields, peak flow transported eroded soil particles high in Fe and thus resulted in a high Fe%, while during base flow the water was high in COC%. This study demonstrated that Fe% and COC% vary widely in river water depending on the catchment properties and hydrology.

Effects of nationwide addition of selenium to fertilizers on foods, and animal and human health in Finland: From deficiency to optimal selenium status of the population.

Despite different geological features the Nordic countries are generally selenium-poor areas. In each country various factors such as food importation and life-style determine the selenium (Se) intake. Due to an extremely low Se intake in the 1970s in Finland, 0.025 mg/day, an official decision was made in 1984 to supplement multinutrient fertilizers with Se in the chemical form of sodium selenate. Almost all fertilizers used in Finland since 1985 have contained Se. Currently all crop fertilizers contain 15 mg Se/kg. Finland is still the only country to take this country-wide measure. In a national monitoring programme, sampling of cereals, basic foodstuffs, feeds, fertilizers, soils, and human tissues has been carried out annually since 1985 by four governmental research organizations. Sampling of foods has been done four times per year and human blood has been obtained annually from the same (n=60) adults. The accuracy of analyses has been verified by annual interlaboratory quality control. During this programme the selenium concentration of spring cereals has increased on average 15-fold compared with the level before the Se fertilization. The mean increase in the Se concentration in beef, pork and milk was 6-, 2- and 3-fold. In terms of Se, organically grown foods of plant origin are generally comparable to products produced before the Se supplementation of fertilizers. Milk from organically fed cows is 50% lower in Se than the usual milk. The average dietary human intake increased from 0.04 mg Se/day/10 MJ in 1985 to a present plateau of 0.08 mg Se/day/10 MJ, which is well above the current nutrition recommendations. Foods of animal origin contribute over 70% of the total daily Se intake. The mean human plasma Se concentration increased from 0.89 µmol/L to a general level of 1.40 µmol/L that can be considered to be an optimal status. The absence of Se deficiency diseases and a reference population have made conclusions on the impact on human health difficult. However, the rates of cardiovascular diseases and cancers have remained similar during the pre- and post-supplementation indicating medical and life-style factors to be much stronger determinants than Se. The nationwide supplementation of fertilizers with sodium selenate is shown to be effective and safe in increasing the Se intake of the whole population. Also, the health of animals has improved.

Effects of selenium treatments on potato (Solanum tuberosum L.) growth and concentrations of soluble sugars and starch.

The effect of selenium (Se) treatments on potato growth and Se, soluble sugar, and starch accumulation was investigated. Potato plants were cultivated in quartz sand without or with sodium selenate (0, 0.075, 0.3 mg Se kg(-1) sand). In young potato plants, Se treatment resulted in higher starch concentrations in upper leaves. The tuber yield of Se-treated potato plants was higher and composed of relatively few but large tubers. At harvest, the starch concentration in tubers did not differ significantly between treatments. The higher Se addition (0.3 mg Se kg(-1)) may have delayed the aging of stolons and roots, which was observed as high concentrations of soluble sugar and starch. Together with the earlier results showing elevated starch concentration in Se-treated lettuce, the findings of this research justify the conclusion that Se has positive effects also on potato carbohydrate accumulation and possibly on yield formation.

Effect of selenate supplementation on glycoalkaloid content of potato (Solanum tuberosum L.).

Potatoes (Solanum tuberosum L.) supplemented with increasing amounts of sodium selenate were analyzed for glycoalkaloid (GA) content. GAs were extracted with 5% acetic acid from freeze-dried tubers of two potato cultivars, Satu and Sini, harvested 10 weeks after planting as immature. The GAs alpha-solanine and alpha-chaconine were quantified by reverse-phase high-performance liquid chromatography (RP-HPLC) with diode array detection. Two independent experiments were performed. In the first experiment, the total GA concentration +/- standard error of the tubers ranged between 105 +/- 9 and 124 +/- 10 mg kg(-1) fresh weight in Satu and between 194 +/- 26 and 228 +/- 10 mg kg(-1) fresh weight in Sini. The ratio of alpha-solanine to alpha-chaconine was 0.2 in Satu and 0.5-0.6 in Sini. In the second experiment, the total GA concentration +/- standard error was 75 +/- 4 to 96 +/- 11 mg kg(-1) fresh weight, and the ratio of alpha-solanine to alpha-chaconine was 0.3-0.4 in Satu. A high sodium selenate supplementation (0.9 mg of Se kg(-1) quartz sand) slightly decreased the GA content in Satu, but this decrease was not statistically significant. Furthermore, at this addition level the Se concentration increased to a very high level of 20 microg g(-1) dry weight, which cannot be recommended for human consumption. In both experiments, the Se concentration in tubers increased with increasing sodium selenate application levels. Our results show that acceptable application levels of selenate did not have an effect on the GA concentration in immature potato tubers.

Germanium-68 as a tracer for silicon fluxes in freshwater sediment.

The sorption of Si may decisively influence the P dynamics in surface sediment through competitive ligand exchange mechanisms. Many aspects of the process, such as the impact of Si dissolving from diatoms, are both insufficiently known and difficult to monitor by quantitative analyses due to the ubiquitousness of Si in sediment. Since the radioactive isotopes of Si have impractical half-times, the applicability of 68Ge as a tracer for Si additions in both inorganic and biogenic form to freshwater sediment (Lake Vesijärvi, Southern Finland) was studied in a 24-h laboratory experiment. The 68Ge-label was added to the sediment with either inorganic Si (940mg l(-1)) or diatoms (3.2 x 10(6) cellsl(-1)), and the distributions of the 68Ge-label and the different forms of added Si between the interstitial water and sequentially extracted, solid-phase sediment pools were critically examined. The inorganic Si addition significantly increased the amount of Si in the interstitial water and in the reversibly bound fraction, while the diatom addition had no discernible effects. The relative distribution of Si and 68Ge between the various sediment pools indicated that the first sorption phase of the added inorganic Si was similar to that reported for P. The high concentration of diatom-derived 68Ge-labelled Si in the interstitial water and in the easily soluble, reversibly bound pool indicated rapid dissolution of the added diatoms. The comparable distributions of the diatom-derived and inorganic Si-derived 68Ge-label within the studied pools indicated that the sorption of Si dissolving from diatoms in surface sediment closely resembles that of an inorganic addition of Si. Caution about the chemical speciation of the 68Ge-label is, however, advisable in sediment environments. Fractionation procedures designed for e.g. P may also be of limited use when applied to a different element, such as Si.

Phosphorus removal in a wetland constructed on former arable land.

Phosphorus in surface runoff water may cause eutrophication of recipient water. This study clarifies the mechanisms of P removal in the wetland of Hovi, Finland, constructed on arable land in 1998. Before the construction, the surface soil (removed in the construction) and subsoil (the current wetland bottom) were analyzed for Al and Fe oxides (Al(ox) and Fe(ox)) reactive in P sorption, and for the distribution of P between various pools as well as for P exchange properties. Retention of P from runoff water within the wetland was studied from 1999 to 2001 in situ and factors affecting the P removal (O2 availability and P concentration in water) were investigated in a laboratory microcosm. The processes taking place in the wetland diminished by 68% the total P load and by 49% the dissolved reactive P load. Desorption-sorption tests indicated that without removal of the surface soil, there would have been a risk of the wetland being a source of P, since the equilibrium P concentration of the soil removed was high compared with the mean P concentration of the inflowing water. The subsoil contained less P and high amounts of reactive oxides, which could bind P. Evidently, the P sorption by Al(ox) played an important role in a first phase removal of P, since the wetland retained P efficiently even under anoxic conditions, where Fe tends to be reduced. Fine-textured, mineral soil on the bottom of the wetland (subsoil of the former arable land) seemed to be very efficient in retaining P from agricultural runoff.

Response of pore water Al, Fe and S concentrations to waterlogging in a boreal acid sulphate soil.

Environmental hazards caused by acid sulphate (AS) soils are of worldwide concern. Among various mitigation measures, waterlogging has mainly been studied in subtropical and tropical conditions. To assess the environmental relevance of waterlogging as a mitigation option in boreal AS soils, we arranged a 2.5-year experiment with monolithic lysimeters to monitor changes in the soil redox potential, pH and the concentrations of aluminium (Al), iron (Fe) and sulphur (S) in pore water in response to low and high groundwater levels in four AS soil horizons. The monoliths consisted of acidic oxidized B horizons and a reduced C horizon containing sulphidic material. Eight lysimeters were cropped (reed canary grass, Phalaris arundinacea) and two were bare without a crop. Waterlogging was conducive to reduction reactions causing a slight rise in pH, a substantial increase in Fe (Fepw) and a decrease in Al (Alpw) in the pore water. The increase in Fepw was decisively higher in the cropped waterlogged lysimeters than in the bare ones, which was attributable to the microbiologically catalysed reductive dissolution of poorly ordered iron oxides and secondary minerals. In contrast to warmer climates, Fepw concentrations remained high throughout the experiment, indicating that the reduction was poised in the iron range, while sulphate was not reduced to sulphide. Therefore, the precipitation of iron sulphide was negligible in the environment with a low pH and abundant with poorly ordered Fe oxides. Increased Fe in pore water counteracts the positive effects of waterlogging, when water is flushed from fields to watercourses, where re-oxidation of Fe causes acidity and oxygen depletion. However, waterlogging prevented further oxidation of sulphidic materials and decreased Alpw to one-tenth of the initial concentrations, and even to one-hundredth of the levels in the low water table lysimeters.

A multi-scale comparison of dissolved Al, Fe and S in a boreal acid sulphate soil.

Acid sulphate (AS) soils are most prevalent in the tropics, but the acidic discharge from cultivated AS soils also threatens water bodies under boreal conditions. Feasible options to reduce the acid load are needed. In this study, the groundwater of an AS field was monitored for 3.5 years, and the efficiency of waterlogging in mitigating the environmental risks caused by acidic discharge was investigated in a 2.5-year experiment with 10 monolithic lysimeters taken from the same field. In order to unravel the transferability of the results from lysimeters to the field scale, the Al, Fe and S concentrations in discharge water from the lysimeters were compared with those in the groundwater of the AS field (pedon and field scale), and in pore water (pedon and horizon scale). In the waterlogged bare lysimeters (HWB), the Al, Fe and S concentrations in discharge waters were broadly similar to those measured in the groundwater and followed the changes in the pore water. In the waterlogged cropped (reed canary grass, Phalaris arundinacea) lysimeters (HWC), in contrast, the discharge waters were markedly higher in Fe and lower in Al than the groundwater in the field. This outcome was attributable to the reduction of Fe(3+) to the more soluble Fe(2+) and the reduction-induced increase in pH, which enhanced the formation of Al(3+) hydroxy species. Lowering of the water table (LWC) caused soil ripening, which resulted in increased saturated hydraulic conductivity and porosity and enhanced the oxidation of sulphidic materials and acid formation. The responses of Al, Fe and S in drainage waters from HWC and LWC lysimeters resembled previous findings in AS soils. Based on this and the similarity between dissolved element concentrations in the discharge water of HWB lysimeters and groundwater in the field, we conclude that our monolithic lysimeters yielded realistic results concerning the efficiency of various methods in mitigating environmental risks related to cultivated AS soils.

Enhancement of phosphorus sorption onto light expanded clay aggregates by means of aluminum and iron oxide coatings.

Phosphorus (P) loading from non-point or point sources increases the eutrophication risk of natural waters. The functioning of constructed wetlands (CWs) used as natural water treatment systems can be improved by means of additional materials adsorbing soluble P. In this study, light expanded clay aggregates (LECA) and LECA coated with aluminum (Al) oxide (Al-LECA) or iron (Fe) oxide (Fe-LECA) were tested for their efficiency as P sorbents in the pH range 3-8. The oxide coatings duplicated the actual sorption capacity calculated from the sorption isotherms at the P concentration in the equilibrium solution of 20 µg L(-1), assumed to be the allowable P level in purified water. In the oxide-coated LECAs the sorption was fast and followed both the first- and second-order Lagergren kinetic models, suggesting that the formation of a binuclear surface complex was feasible. In LECA, sorption was markedly slower and followed the first-order kinetic model, indicating that retention occurred through a monodentate attachment. These findings were in harmony with the degree of P saturation (DPS) of the sorbent surfaces at the highest P addition level (200 µg L(-1)), DPS being decisively higher for LECA than for the oxide-coated sorbents. Accordingly, at higher pH values the competition by hydroxyl ions diminished the sorption in LECA relatively more than that in the coated sorbents. In agreement with the acidity of Al(3+) being 100 times lower than that of Fe(3+), at elevated pH the sorption by Al-LECA proved to be less reversible than that by Fe-LECA. The results provide evidence that in CWs Al-coated sorbents are superior to Fe-coated ones that are also redox-sensitive and may lose their sorption properties in anoxic conditions.