Monitoring of heavy metals uptake and allocation in Pinus sylvestris organs in alkalised soil

The concentration of heavy metals in soil and in Scots pine (Pinus sylvestris) organs growing on a pH gradient from 4.0 to 7.9 of soil at different distances from a cement plant was monitored. Emission for over 40 years of alkaline dust (pH 12.3-12.6) into the atmosphere in North Estonia had resulted in alkalisation and elevated concentration of total heavy metals in upper layers of the soil (0-30 cm), which was considerable even 10 years after the dust pollution stopped. Monitoring showed that the accumulation and allocation of heavy metals varied between the stem, shoots and needles and differed from the trees in the unpolluted area, depending more on the mobility of elements and the pH than element concentrations in the alkaline soil. A strong negative correlation was found between the soil pH and Mn, Zn and Cd concentrations in different tree organs. Compared to the unpolluted area, Pb was present in relatively higher concentrations in all organs but Cr, Fe and Cu in needles and shoots. The concentrations of Mn and Cd were much lower than control in all organs of trees in alkalised soil. The height increment and density of needles on shoots were predominantly in negative correlation with the pH of soil.     

Long-range atmospheric transport of three toxaphene congeners across Europe. Modeling by chained single-box FATEMOD program

Background, aims, and scope  Since toxaphene (polychlorocamphene, polychloropinene, or strobane) mixtures were applied for massive insecticide use in the 1960s to replace the use of DDT, some of their congeners have been found at high latitudes far away from the usage areas. Especially polychlorinated bornanes have demonstrated dominating congeners transported by air up to the Arctic areas. Environmental fate modeling has been applied to monitor this phenomenon using parallel zones of atmosphere around the globe as interconnected environments. These zones, shown in many meteorological maps, however, may not be the best way to configure atmospheric transport in air trajectories. The latter could also be covered by connecting a chain of simple model boxes. We aim to study this alternative approach by modeling the trajectory chain using catchment boxes of our FATEMOD model. Polychlorobornanes analyzed in biota of the Barents Sea offered one case to study this modeling alternative, while toxaphene has been and partly still is used massively at southern East Europe and around rivers flowing to the Aral Sea. Materials and methods  Pure model substances of three polychlorobornanes (toxaphene congeners P26, P50, and P62) were synthesized, their environmentally important thermal properties measured by differential scanning calorimetry, as evaluated from literature data, and their temperature dependences estimated by the QSPR programs VPLEST, WATSOLU, and TDLKOW. The evaluated property parameters were used to model their atmospheric long-range transport from toxaphene heavy usage areas in Ukraine and Aral/SyrDarja/AmuDarja region areas, through East Europe and Northern Norway (Finnmarken) to the Barents Sea. The time period used for the emission model was June 1997. Usual weather conditions in June were applied in the model, which was constructed by chaining FATEMOD model boxes of the catchment’s areas along assumed maximal air flow trajectories. Analysis of the three chlorobornanes in toxaphene mixtures function as a basis for the estimates of emission levels caused by its usage. High estimate (A) was taken from contents in a Western product chlorocamphene and low estimate (B) from mean contents in Russian polychloroterpene products to achieve modeled water concentrations. Bioaccumulation to analyzed lipid of aquatic biota at the target region was estimated by using statistical calculation for persistent organic pollutants in literature. Results  The results from model runs A and B (high and low emission estimate) for levels in sea biota were compared to analysis results of samples taken in August 1997 at Barents Sea. The model results (ng g⁻¹ lw): 4–95 in lipid of planktovores and 7–150 in lipid of piscivores, were in fair agreement with the analysis results from August 1997: 21–31 in Themisto libellula (chatka), 26–42 in Boreocadus saida (Polar cod), and 5–27 in Gadus morhua (cod) liver. Discussion  The modeling results indicate that the application of chained simple multimedia catchment boxes on predicted trajectory is a useful method for estimation of volatile airborne persistent chemical exposures to biota in remote areas. For hazard assessment of these pollutants, their properties, especially temperature dependences, must be estimated by a reasonable accuracy. That can be achieved by using measurements in laboratory with pure model compounds and estimation of properties by thermodynamic QSPR methods. The property parameters can be validated by comparing their values at an environmental temperature range with measured or QSPR-estimated values derived by independent methods. The chained box method used for long-range air transport modeling can be more suitable than global parallel zones modeling used earlier, provided that the main airflow trajectories and properties of transported pollutants are predictable enough. Conclusions  Long-range air transport modeling of persistent, especially photo-resistant organic compounds using a chain of joint simple boxes of catchment’s environments is a feasible method to predict concentrations of pollutants at the target area. This is justified from model results compared with analytical measurements in Barents Sea biota in August 1997: three of six modeled values were high and the other three low compared to the analysis results. The order of magnitude level was similar in both modeled (planktovore and piscivore) and observed (chatka and polar cod) values of lipid samples. The obtained results were too limited to firm validation but are sufficient to justify feasibility of the method, which prompts one to perform more studies on this modeling system. Recommendations and perspectives  For assessment of the risk of environmental damages, chemical fate determination is an essential tool for chemical control, e.g., for EU following the REACH rules. The present conclusion of applicability of the chained single-box multimedia modeling can be validated by further studies using analyses of emissions and target biota in various other cases. To achieve useful results, fate models built with databases having automatic steps for most calculations and outputs accessible to all chemical control professionals are essential. Our FATEMOD program catchments at environments and compound properties listed in the database represent a feasible tool for local, regional, and, according our present test results, for global exposure predictions. As an extended use of model, emission estimates can be achieved by reversed modeling from analysis results of samples corresponding to the target area. This article is dedicated to the memory of Professor Alexander B Terentiev (who passed away in November 2006), our true friend. With his Institute of Organo-Element Compounds, Russian Academy of Science, Moscow, he was an important main organizer of the six joint Finnish–Russian seminars (every third year since 1989) on the field (‘Chemistry and Ecology of Organo-Element Compounds’). He prompted us especially to search properties and environmental fates for various polyhalogen compounds. We remember him for his friendly character and great sense of humor.     

Polyandry, multiple mating, and female fitness in a water strider Aquarius paludum

Contrary to Bateman’s principle, polyandry appears to be a common female mating strategy. Several hypotheses have been proposed to explain the evolution of polyandry. It is assumed that females gain either material or genetic benefits from multiple matings, or that they are coerced into mating by males. In water striders, mating is generally assumed to be costly to females, and they are thought to mate for reasons of convenience, adjusting their resistance to mating according to male harassment. Here, we tested the effect of number of matings (with the same male) and number of partners on female fitness in a water strider Aquarius paludum. In the first experiment, we regulated the time females spent with a male and found that females’ egg production increased with multiple matings up to a point. The result supports the existence of an optimal female mating frequency. In the second experiment, we tested how polyandry affects the number of eggs laid and egg hatching success. We conducted three different trials: females mated four times with either a single male, two different males, or with four different males. Females that mated with four different males laid the lowest number of eggs and had the lowest egg hatching success, suggesting that polyandry reduces females’ egg production and egg hatching success in A. paludum. We conclude that A. paludum females probably gain material benefits from mating but no genetic benefits were found in this study.     

Short-term responses of soil chemistry, needle macronutrients and tree growth to clinker dust and fertiliser in a stand of Scots pine

Waste management of clinker dust by spreading it on forest soil was studied in a 25-year-old Scots pine stand on acidic sandy soil. Clinker dust (0.5 kg m?2), fertiliser (N, P, K, Mg, 0.05 kg m?2; N 190 kg ha?1) and untreated soil were applied on 120-m2 plots in four replicates. The fertiliser was included to confirm the nutrient limitation in the stand. Clinker dust increased the soil pH by 1.2 units relative to the pH of 4.6 in the untreated soil by the second year. Soil K and Mg concentrations were larger in the dust and fertiliser treatments. Nutrient diagnostics indicated that needles of untreated trees were deficient in N and K. Fertiliser treatment indicated that the growth of trees was limited by N, since the fertiliser tended to increase needle K, N, N/P, needle dry mass and diameters of stem and shoots. By an auxiliary dataset, no effects of the dust and fertiliser on possible excess of the micronutrient Mn were observed. Clinker dust increased needle K concentration, but due to the N limitation, there was no increase in the growth of stems, branches, shoots and needles. It was concluded that in plots of 120 m2 application of clinker dust at a rate of 0.5 kg m?2 was safe for the 21-year-old Scots pine stand in this trial on an acid nutrient-poor sandy soil during 4 years after the treatment.     

Adsorption of sugar beet herbicides to Finnish soils

Three sugar beet herbicides, ethofumesate, phenmedipham and metamitron, are currently used on conventional sugar beet cultivation, while new varieties of herbicide resistant (HR) sugar beet, tolerant of glyphosate or glufosinate-ammonium, are under field testing in Finland. Little knowledge has so far been available on the adsorption of these herbicides to Finnish soils. The adsorption of these five herbicides was studied using the batch equilibrium method in 21 soil samples collected from different depths. Soil properties like organic carbon content, texture, pH and partly the phosphorus and oxide content of the soils were tested against the adsorption coefficients of the herbicides. In general, the herbicides studied could be arranged according to their adsorption coefficients as follows: glyphosate>phenmedipham>ethofumesate approximately glufosinate-ammonium>metamitron, metamitron meaning the highest risk of leaching. None of the measured soil parameters could alone explain the adsorption mechanism of these five herbicides. The results can be used in model assessments of risk for leaching to ground water resulting from weed control of sugar beet in Finland.     

Integrated Nitrogen Modeling in a Boreal Forestry Dominated River Basin: N Fluxes and Retention in Lakes and Peatlands

Two models, N_EXRET and INCA, were applied to the Simojoki river basin (3160 km²) in northern Finland in order to assess nitrogen retention in wetlands and lakes. N_EXRET is a spatial, export coefficient-based N export and retention model developed for large river basins. It utilizes remote sensing-based land use and forest classification, evaluated export coefficients, and data on areal N deposition and point sources of N. A new version (v1.7) of the Integrated Nitrogen in CAtchments model (INCA) is a semi-distributed, dynamic nitrogen process model, which simulates and predicts nitrogen transport and processes within catchments. Average retention of the gross total N load of 700 t a^-1 to the river system was estimated using N_EXRET model as 17 t N a^-1 to the wetlands and 77 t N a^-1 to the lakes. A good fit was found between modeled and measured values along the river. Inorganic N fluxes simulated by the INCA model were compared with measured fluxes along the river Simojoki, with a good fit between modeled and measured NH₄ ⁺-N fluxes, and an adequate fit for NO₃ ^--N fluxes. Both fluxes were overestimated at the first reach, below Lake Simojärvi. High percentage of peatlands led to high NH₄ ⁺-N/NO₃ ^--N ratios derived from data, indicating negligible nitrification in large river subbasins and particularly in small research catchments.     

The Radial Increment and Stemwood Element Concentrations of Scots Pine in the Area Influenced by the Narva Power Plants in Northeast Estonia

Soil is an important component of a watershed. Understanding soils and their interactions with the other components are, thus, considered to be critical and essential for conservation of resources and management of the watershed. Development of soil sampling and analysis programs are crucial for these purposes. Site-specific soil data are needed to identify current soil characteristics, as well as to validate datasets gathered for watershed-scale modelling of non-point sources (NPS) of pollutants arising from various land-use activities, hydrodynamics and water quality. The Koycegiz Lake–Dalyan Lagoon watershed, located in the southwest of Turkey along the Mediterranean Sea Coast, was selected as the study area for watershed modelling purposes. Development of soil sampling plans, their practical optimization, soil analyses and interpretation are presented in this article. The soil analyses conducted include physical, chemical and specific soil characteristics. Within the framework of this study, soil fertility parameters are presented and evaluated. Such an approach used is recommended for especially developing countries where up-to-date data sets are not fully available and/or centrally publicized.     

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.     

Assessment of growth and stemwood quality of Scots pine on territory influenced by alkaline industrial dust

Long-term influence of alkaline dust (pH 12.3–12.7) pollution emitted over 40 years from a cement plant in Estonia was the reason of alkalisation (pH 6.7–7.9) and high concentrations of K, Ca and Mg in the soil of affected territories. Although dust emission has diminished during the last 10 years, the disbalances in nutrition substrate and their influence on the growth of trees are notable up to now. The study of morphological and physical properties of 70–80-year-old Scots pine (Pinus sylvestris L.) crown, stems and stemwood from three different air pollution zones showed serious deviations in comparison with a relatively healthy forest in an unpolluted area. The specimens from polluted trees, if compared to reference site, showed significantly smaller height growth, radial increment and width of annual rings of sapwood. In heartwood wider annual rings were found in polluted areas. In the period of heartwood formation the dust pollution level emitted from the plant was relatively modest and cement dust, which contains elements necessary for mineral nutrition of trees, may have acted as fertiliser. The moisture content in sapwood and heartwood, especially in the upper layers of stems, was lower in the polluted area than in reference site trees. Regression analysis revealed a strong dependence between latewood percentage and sapwood or heartwood in stems of Scots pine in all sample plots.