Fluoro‐mobilization of metals in a Slovak forest soil affected by the emissions of an aluminum smelter

Depositions originating from a central Slovak Al smelter may increase metal solubility in adjacent soils because they contain F (mainly HF). The reason for fluoro‐mobilization of metals may be the formation of soluble fluoro‐metal complexes or the mobilization of organic matter and subsequent formation of organo‐metal complexes. The objectives of our work were (1) to assess the extent of metal mobilization by fluoride in a Slovak Lithic Eutrochrept affected by the emissions of an Al smelter and (2) to model the dissolved metal species with the help of a chemical equilibrium model (MINEQL+). The O (Moder), A, and B horizons were equilibrated with solutions at F concentrations of 0, 0.9, 2.7, and 9.0 mmol l^—1. In the extracts, the concentrations of Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, Zn, dissolved organic carbon (DOC), free and complexed F, and the pH and electrical conductivity (EC) were determined. The heavy metal concentrations in the O horizon (Cd: 0.99, Cr: 18.0, Cu: 44, Ni: 26, Pb: 110, and Zn: 84 mg kg^—1) were 2.5 to 9 times larger than those in the A and B horizons. The concentrations of H₂O‐soluble F decreased from the O (261 mg kg^—1) to the A (103 mg kg^—1) and B horizon (92 mg kg^—1). In batch experiments increasing addition of F increased the equilibrium concentrations of Al, Cr, Cu, Fe, Ni, Pb, and DOC in all samples, of Cd in the A, and of K in the B horizon. At the same time the concentrations of complexed F and pH increased whereas EC decreased. Chemical equilibrium modelling indicated that the mobilizing effect of F resulted from the formation of fluoro‐Al complexes and organo‐complexes of all other metals.     

Propagating the errors of initial forest variables through stand- and tree-level growth simulators

Developments in the field of remote sensing have led to various cost-efficient forest inventory methods at different levels of detail. Remote-sensing techniques such as airborne laser scanning (ALS) and digital photogrammetry are becoming feasible alternatives for providing data for forest planning. Forest-planning systems are used to determine the future harvests and silvicultural operations. Input data errors affect the forest growth projections and these effects are dependent on the magnitude of the error. Our objective in this study was to determine how the errors typical to different inventory methods affect forest growth projections at individual stand level during a planning period of 30 years. Another objective was to examine how the errors in input data behave when different types of growth simulators are used. The inventory methods we compared in this study were stand-wise field inventory and single-tree ALS. To study the differences between growth models, we compared two forest simulators consisting of either distance-independent tree-level models or stand-level models. The data in this study covered a 2,000-ha forest area in southern Finland, including 240 sample plots with individually measured trees. The analysis was conducted with Monte Carlo simulations. The results show that the tree-level simulator is less sensitive to errors in the input data and that by using single-tree ALS data, more precise growth projections can be obtained than using stand-wise field inventory data.     

Rockfall and snow avalanche impacts leave different anatomical signatures in tree rings of juvenile Larix decidua

Rockfall and snow avalanche events often cause injury to European larch (Larix decidua Mill.) trees, giving rise to the formation of callus tissue and tangential rows of traumatic resin ducts (TRDs). We analyzed and quantified anatomical reactions of juvenile trees injured before the start of the growing season by snow avalanches (15 trees, 324 cross sections) or rockfalls (18 trees, 270 cross sections). Traumatic resin ducts were observed in the growth ring formed following injury in 94.3% of the rockfall samples and 87.3% of the snow avalanche samples. Traumatic resin ducts were formed at the beginning of the new annual ring around wounds caused by rockfalls. In contrast, in trees injured by snow avalanches, TRDs were not formed until after the formation of several rows of early earlywood (EE) tracheids (mean +/- SD = 4.19 +/- 2.56 rows). The dimensions of the EE tracheids observed in the snow avalanche samples were greatly reduced in the tissues bordering the wound, with radial width reaching an average of only 50% and lumen cross-sectional area an average of only 46% of pre-event values. It is therefore possible to differentiate injuries due to past snow avalanches from injuries due to rockfall based on anatomical growth reactions in the tissues bordering scars.     

Germination, genetics, and growth of an ancient date seed

An ancient date seed (Phoenix dactylifera L.) excavated from Masada and radiocarbon-dated to the first century Common Era was germinated. Climatic conditions at the Dead Sea may have contributed to the longevity of this oldest, directly dated, viable seed. Growth and development of the seedling over 26 months was compatible with normal date seedlings propagated from modern seeds. Preliminary molecular characterization demonstrated high levels of genetic variation in comparison to modern, elite date cultivars currently growing in Israel. As a representative of an extinct date palm population, this seedling can provide insights into the historic date culture of the Dead Sea region. It also has importance for seed banking and conservation and may be of relevance to modern date palm cultivation.     

Analysis of Mycosporine-Like Amino Acids in Selected Algae and Cyanobacteria by Hydrophilic Interaction Liquid Chromatography and a Novel MAA from the Red Alga Catenella repens

Mycosporine-like amino acids (MAAs), a group of small secondary metabolites found in algae, cyanobacteria, lichens and fungi, have become ecologically and pharmacologically relevant because of their pronounced UV-absorbing and photo-protective potential. Their analytical characterization is generally achieved by reversed phase HPLC and the compounds are often quantified based on molar extinction coefficients. As an alternative approach, in our study a fully validated hydrophilic interaction liquid chromatography (HILIC) method is presented. It enables the precise quantification of several analytes with adequate retention times in a single run, and can be coupled directly to MS. Excellent linear correlation coefficients (R² > 0.9991) were obtained, with limit of detection (LOD) values ranging from 0.16 to 0.43 µg/mL. Furthermore, the assay was found to be accurate (recovery rates from 89.8% to 104.1%) and precise (intra-day precision: 5.6%, inter-day precision ≤6.6%). Several algae were assayed for their content of known MAAs like porphyra-334, shinorine, and palythine. Liquid chromatography-mass spectrometry (LC-MS) data indicated a novel compound in some of them, which could be isolated from the marine species Catenella repens and structurally elucidated by nuclear magnetic resonance spectroscopy (NMR) as (E)-3-hydroxy-2-((5-hydroxy-5-(hydroxymethyl)-2-methoxy-3-((2-sulfoethyl)amino)cyclohex-2-en-1-ylidene)amino) propanoic acid, a novel MAA called catenelline.     

Partitioning of Hg Between Solid and Dissolved Organic Matter in the Humus Layer of Boreal Forests

The mobility of mercury (Hg) deposited on soils controls the concentration and toxicity of Hg within soils and in nearby streams and lakes, but has rarely been quantified under field conditions. We studied the in situ partitioning of Hg in the organic top layer (mor) of podsols at two boreal forest sites differing in Hg deposition and climatic regime (S. and N. Sweden, with pollution declining to the north). Soil solution leaching from the mor layer was repeatedly sampled using zero-tension lysimeters over 2 years, partly in parallel with tension lysimeters. Concentrations of Hg and dissolved organic carbon (DOC) were higher while pH was lower at the southern site (means ± SD: Hg?=?44?±?15 ng L^?1, DOC?=?63.0?±?31.3 mg L^?1, pH?=?4.05?±?0.53) than at the northern site (Hg?=?22?±?6 ng L^?1, DOC?=?41.8?±?12.1 mg L^?1, pH?=?4.28?±?0.43). There was a positive correlation over time between dissolved Hg and DOC at both sites, even though the DOC concentration peaked during autumn at both sites, while the Hg concentration remained more constant. This correlation is consistent with the expected strong association of Hg with organic matter and supports the use of Hg/C ratios in assessments of Hg mobility. In the solid phase of the overlying O_f layer, both Hg concentrations and Hg/C ratios were higher at the southern site (means ± SD: 0.34?±?0.06 μg g^?1 dw and 0.76?±?0.14 μg g^?1 C, respectively) than at the northern site (0.31?±?0.05 μg g^?1 dw and 0.70?±?0.12 μg g^?1 C, respectively). However, concentrations in the solid phase differed less than might be expected from the difference in current atmospheric input, suggesting that the fraction of natural Hg is still substantial. At both sites, Hg/C ratios in the upper half of the mor layer were only about two thirds of those in the lower half, suggesting that the recent decrease in anthropogenic Hg deposition onto the soil is offset by a natural downward enrichment of Hg due to soil decomposition or other processes. Most interestingly, comparison with soil leachate showed that the average Hg/C ratios in the dissolved phase of the mor layers at both sites did not differ from the average Hg/C ratios in the overlying solid organic matter. These results indicate a simple mobilisation with negligible fractionation, despite differences in Hg deposition patterns, soil chemistry and climatic regimes. Such a straight-forward linkage between Hg and organic matter greatly facilitates the parameterisation of watershed models for assessing the biogeochemical fate, toxic effect and critical level of atmospheric Hg input to forest soils.     

Trace elements bioavailability to <Emphasis Type="Italic">Triticum aestivum</Emphasis> and <Emphasis Type="Italic">Dendrobaena veneta</Emphasis> in a multielement-contaminated agricultural soil amended with drinking water treatment residues

Purpose

The in situ stabilization of multielement-contaminated agricultural soils has limited effectiveness when using common single amendments. This study examined the use of drinking water treatment residues (WTR), based on (hydr)oxides of Fe, Al, or Mn, as a cost-effective solution to optimize the immobilization of metals (Cd, Pb, Zn) and As.

Materials and methods

Trace elements (TE) bioavailability was assessed under semi-controlled conditions in a pot study cultivating winter wheat (Triticum aestivum L. cv. Tiger) until maturity. An Fe-based WTR and a Mn-based WTR, applied at rates of 0.5 and 1% (m/m), were related to effects of lime marl (LM) application. Additionally, a bioassay with earthworms (Dendrobaena veneta) was conducted. Both bioassays were compared with measurements of NH₄NO₃-soluble, diffusive gradients in thin film (DGT)-available and soil solution TE concentrations, representing well-established surrogates for mimicking the bioavailable element fractions in soil.

Results and discussion

The application of the Fe-based WTR reduced As accumulation in vegetative wheat tissues (by up to 75%) and earthworms (by up to 41%), which corresponded with the findings from soil chemical analyses and improved plant growth and earthworm body weight. However, As concentrations in cereal grains were not affected, Cd or Pb accumulation by wheat was not mitigated, and Zn uptake was enhanced. By contrast, the Mn-based WTR effected the greatest reduction in Pb uptake, and lowered Cd transfer to wheat grain (by up to 25%). Neither the NH₄NO₃-soluble nor DGT-available concentrations matched with Cd and Zn accumulation in plants or earthworms, indicating interferences due to competition for binding sites according to the biotic ligand model.

Conclusions

The results obtained in this study suggest that a bioassay with key species prior to field application should be mandatory when designing in situ stabilization options. The application of WTR to an agricultural soil strongly affected TE bioavailability to plants and earthworms. Low application rates tended to improve biomass production of biota. Higher application rates involved risks (e.g., P fixation, TE inputs), and none of the amendments tested could immobilize all targeted elements.

     

A data-driven fuzzy approach to simulate the critical shear stress of mixed cohesive/non-cohesive sediments

Purpose

The critical shear stress of cohesive and mixed cohesive/non-cohesive sediments is affected by multiple interacting physical, chemical and biological parameters. There are various mathematical approaches in the scientific literature for computing critical shear stress. However, processes that influence sediment stability are still not fully understood, and available formulas differ considerably. These discrepancies in the literature arise from random system behaviour (natural variability of the sediments), different definitions of the critical shear stress, different measurement techniques and different model frameworks (scope of the parameters, undisturbed versus artificial sediment samples). While analytical approaches fail to address the involved uncertainties, fuzzy logic-based models integrate uncertainty and imprecision.

Materials and methods

With this in mind, a data-driven neuro-fuzzy model (ANFIS) was used to determine the critical shear stress based on sediment characteristics such as wet bulk density and grain size distribution. In order to select model predictors systematically, an automated stepwise regression algorithm was applied. The database for this analysis consisted of 447 measurements of the critical shear stress originating from 64 undisturbed sediment samples.

Results and discussion

The study identified clay content as the primarily controlling variable for erosion resistance. Depending on the characteristics of the sampling location, the bulk density was also selected as a model predictor. In comparison to analytical models that are available in the scientific literature, the fuzzy model achieved higher correlation coefficients between measured and predicted data.

Conclusions

The neuro-fuzzy-model includes uncertainties of input variables and their interactions directly. Thus, it provides a reliable method for the prediction of erosion thresholds of cohesive/non-cohesive mixtures. It was also shown that this approach requires fewer measured variables as well as fewer assumptions than the models it was compared to.

     

Modeling temperature and moisture dependent emissions of carbon dioxide and methane from drying dairy cow manure

Greenhouse gas emissions due to biological degradation processes of animal wastes are significant sources of air pollution from agricultural areas. The major environmental controls on these microbe-induced gas fluxes are temperature and moisture content. The objective of this study was to model the effects of temperature and moisture content on emissions of CO₂ and CH₄ during the ambient drying process of dairy manure under controlled conditions. Gas emissions were continuously recorded over 15 d with paired fully automated closed dynamic chambers coupled with a Fourier Transformed Infrared gas analyzer. Water content and temperature were measured and monitored with capacitance sensors. In addition, on days 0, 3, 6, 9, 12 and 15, pH, moisture content, dissolved organic carbon and total carbon (TC) were determined. An empirical model derived from the Arrhenius equation confirmed high dependency of carbon emissions on temperature and moisture content. Results indicate that for the investigated dairy manure, 6.83% of TC was lost in the form of CO₂ and 0.047% of TC was emitted as CH₄. Neglecting the effect of temperature, the moisture contents associated with maximum gas emissions were estimated as 0.75 and 0.79 g·g⁻¹ for CO₂ and CH₄, respectively.