Traceability of Croatian extra virgin olive oils to the provenance soils by multielement and carbon isotope composition and chemometrics.

A capacity to determine the provenance of high-value food products is of high scientific and economic interest. With the aim to develop a tool for geographical traceability of Croatian extra virgin olive oils (EVOO), multielement composition and 13C/12C isotope ratio in EVOO as well as the geochemistry of the associated soils were analysed in samples collected from three regions along the Croatian Adriatic coast. Soil geochemistry was shown to influence the transfer and elemental composition of EVOO. The most discriminating variables to distinguish EVOO from different regions were S, Mo, Rb, Mg, Pb, Mn, Sn, K, V and δ13C. The predictive models achieved high sensitivity and specificity, especially when carbon isotope composition was added. The results suggest that interregional geographical traceability of Croatian EVOO is possible based on matching their multielement composition with that of the soils in the provenance area.

Phosphorus Use Efficiency of Leafy Brassica sp. Grown in Three Contrasting Soils: Growth, Enzyme Activity and Phosphorus Fractionation.

Plant adaptations to low soil phosphorus (P) availability have been intensively studied in Brassica sp. in an attempt to identify the mechanisms involved in P uptake and utilization. The present pot experiment was conducted to evaluate the relationships between plant shoot and root growth, P uptake and use efficiency parameters, and P fractions and enzyme activity, in two species grown in three soil types. The aim of this study was to determine whether adaptation mechanisms are soil-dependent. Two kale species were grown in soils typical for coastal Croatia (terra rossa, rendzina, and fluvisol) with low P availability. Plants grown in fluvisol had the highest shoot biomass and accumulated most P, whereas plants developed the longest roots in terra rossa. Phosphatase activity differed among soils. P use efficiency differed among soils and species. Genotype IJK 17 showed better adaptation to low P availability, which was related to better uptake efficiency. In general, soils differed in inorganic and organic P fractions in rhizosphere soil, but no difference between genotypes was found. The activities of alkaline phosphatase and phosphodiesterase were negatively correlated with most organic P fractions, suggesting their function in the mineralization of soil organic P. Kale species activate different mechanisms of P uptake and utilization when grown in contrasting soil types, suggesting that specific responses to the soil type were more important than the genotypic difference.

Effect of olive-processing technology on the utilization of olive mill pomace as a soil amendment.

In the Mediterranean basin, the treatment and disposal of olive mill pomace (OMP) remain a salient environmental issue for the olive oil-producing industry. This study assesses the effects of olive-processing technology (three-phase and two-phase systems) on the potential use of OMP as a soil amendment. Samples from 12 Croatian olive mills were analyzed for their total phenolic content (TPC), residual oil fraction, and elemental concentration. The samples were profiled using Fourier transform infrared spectroscopy (FT-IR) and structurally characterized using scanning electron microscopy-energy-dispersive X-ray spectroscopy (EDS). Compared to three-phase samples, two-phase OMP was more acidic (pH 4.5 vs. 5.0), with a higher TPC (3835 vs. 1576 mg/kg fresh weight), oil content (11.7% vs. 7.5% d.w., where d.w. is dry weight), electrical conductivity (EC, 5.1 vs. 3.0 mS/cm), and levels of calcium (Ca, 1.34 vs. 1.20 g/kg d.w.) and copper (Cu, 10.4 vs. 7.0 mg/kg d.w.). Similar values of carbon/nitrogen (C/N; 61 vs. 72), N (10 vs. 8.1 g/kg d.w.), phosphorus (1040 vs. 691 mg/kg d.w.), and potassium (K, 13.7 vs. 8.1 g/kg d.w.) were observed. The amounts of chromium, copper, nickel, and zinc were below EC limits in both cases. The EDS mapping revealed that Ca was concentrated at sharp-edged OMP particles while K was evenly distributed, suggesting that pelletized OMP compost is preferable for amending soil to obtain a homogeneous distribution of nutrients. It was also possible to distinguish between OMPs based on oil and lignin absorption bands in their FT-IR spectra. According to the obtained results, composting is recommended for both types of OMP to produce a safe product for amendment purposes.

Effect of sewage sludge derived compost or biochar amendment on the phytoaccumulation of potentially toxic elements and radionuclides by Chinese cabbage.

This study set out to evaluate the effect of using sewage sludge-derived compost (SSC) or biochar (SSB) as a soil amendment on the phytoaccumulation of potentially toxic elements, PTE (Cd, Cr, Cu, Ni, Pb, Zn) and natural radionuclides (238U and 232Th) by Chinese cabbage (Brassica rapa L. subsp. pekinensis (Lour.) Hanelt) in terra rossa and rendzina soils, which are the two common soil types in Croatia. The experiment consisted of a greenhouse pot trial using a three-factor design where soil type, sludge post-stabilisation procedure and amendment rate (12 and 120 mgP/L) were the main factors. At harvest, the concentrations of analytes in the substrate, leaves and roots were measured, from which the edible tissue uptake (ETU) and concentration ratios (CR) were determined. Also, the average daily dose (ADD) and hazard quotient (HQ) were determined to assess the health risk, as well as soil contamination factor (CF). The results showed that neither adding SSC nor SSB affected the soil loading at the rates applied, suggesting a low risk of soil contamination (CF ≤ 1). The ETU of Cd, Cu, and Zn were 0.0061, 1.23, and 0.91 mg/plant from compost-amended soil and 0.0046, 0.78 and 0.65 mg/plant for biochar-amended soil, respectively. This difference suggests that their ETU was higher in compost-amended soils than in soils treated with biochar. The CR data indicate that the bioavailability of Cu (CR of 5.30) is highest at an amendment rate of 12 mgP/L, while for Zn (CR of 0.69), the highest bioaccumulation was observed with an amendment rate of 120 mgP/L. Translocation of Cr, Ni, Pb and 238U to the leaves was limited. Overall, the HQ (<1) for Cd, Cu and Zn in the edible parts confirmed that consuming Chinese cabbage does not threaten human health. Similarly, the daily intake of 232Th remained below the limit (3 µg) set by ICRP, suggesting no radiological risk. Finally, although the amendment rate, which was 10-times the amount stipulated in Croatian regulation and the CR ranged from 0.007 to 5.30, the precautionary principle is advised, and the long-term impact of sewage sludge derived compost or biochar on different plant groups (incl. root vegetables) at the field-scale is recommended.

Modelling spatial and temporal variability of water quality from different monitoring stations using mixed effects model theory.

Polder-type agricultural catchments within river deltas are specific land formations which management is highly demanding from several aspects. The close contact with the coastal sea may additionally affect the quality of adjacent marine environment. This study uses the case of the Lower Neretva Valley (LNV) to test the efficiency of applying Linear Mixed Effect (LME) theory in modelling spatial and temporal variations of surface and groundwater quality within a polder-type agricultural catchment. The methodology uses linear regressive techniques while taking into account spatial and temporal autocorrelation of residuals. The objective was to assess and model the spatial and temporal variability of the quality of surface- and ground-waters, in order to predict the impact of natural processes and human activities. A dataset of physicochemical properties of surface and groundwater quality of the LNV, recorded monthly in the period 2009-2017, was used to model the spatial and temporal variations of water salinity and nitrate concentrations. The network of water quality monitoring sites covers four polders on five thousand hectares of agricultural land, including the following types of water bodies: river streams, lateral canals, pumping stations, drainage canals and groundwater. The method of data analysis, based on LME theory with correlated spatial and temporal residuals, takes also into account the heteroscedasticity of the variance associated with each type of water quality monitoring station. The two Linear Mixed Effects models proposed for the prediction of electrical conductivity and nitrate concentration in the surface waters and groundwater, proved to be efficient at adequately reproducing the heterogeneity and complexity of the study area. However, the prediction of nitrate concentration in the water was not equally satisfactory of the one of electrical conductivity due to the large variation in nutrient concentrations. To improve spatial prediction, the density of monitoring network should be increased.

The effect of stabilization on the utilization of municipal sewage sludge as a soil amendment.

This study assesses the potential use of different types of stabilized sewage sludge as a soil amendment by considering their physicochemical characteristics, nutritional status, and their trace metal and radionuclide content. The concentrations of trace metals and radionuclides were determined using ICP-OES and gamma-ray spectrometry, respectively. For determining nutritional status and chemical characterization, this study followed standard ISO-recommended procedures. Data analysis revealed that anaerobic sludge contains higher concentrations of Cr, Hg, and Ni compared to aerobic and non-biologically stabilized sludge. A similar observation was observed in the case of 226Ra, 210Pb, 228Ra, and 228Th. Furthermore, the high levels of P and N in aerobic sludge suggest that biologically stabilized sludge has the potential to be a good fertilizer. In addition, the study finds strong evidence that nutrients are involved in the adsorption of metals and radionuclides onto sludge biomass. Overall, eight of the nine studied sludge samples are safe for agricultural use since the concentrations of trace metals fall well below the limits set by Croatian legislation (NN 38/08). In addition, the levels of radionuclides do not pose a radiological risk. This means that soil conditioning with sewage sludge remains a viable strategy for nutrient recovery from municipal waste, although long-term impact assessments of repeated applications are necessary.

Trace metals accumulation in soil irrigated with polluted water and assessment of human health risk from vegetable consumption in Bangladesh.

Trace metals accumulation in soil irrigated with polluted water and human health risk from vegetable consumption was assessed based on the data available in the literature on metals pollution of water, soil, sediment and vegetables from the cites of Bangladesh. The quantitative data on metal concentrations, their contamination levels and their pollution sources have not been systematically gathered and studied so far. The data on metal concentrations, sources, contamination levels, sample collection and analytical tools used were collected, compared and discussed. The USEPA-recommended method for health risk assessment was used to estimate human risk from vegetable consumption. Concentrations of metals in water were highly variable, and the mean concentrations of Cd, Cr, Cu and As in water were found to be higher than the FAO irrigation water quality standard. In most cases, mean concentrations of metals in soil were higher than the Bangladesh background value. Based on geoaccumulation index (I geo) values, soils of Dhaka city are considered as highly contaminated. The I geo shows Cd, As, Cu, Ni, Pb and Cr contamination of agricultural soils and sediments of the cities all over the Bangladesh. Polluted water irrigation and agrochemicals are identified as dominant sources of metals in agricultural soils. Vegetable contamination by metals poses both non-carcinogenic and carcinogenic risks to the public. Based on the results of the pollution and health risk assessments, Cd, As, Cr, Cu, Pb and Ni are identified as the priority control metals and the Dhaka city is recommended as the priority control city. This study provides quantitative evidence demonstrating the critical need for strengthened wastewater discharge regulations in order to protect residents from heavy metal discharges into the environment.

Organic matter and salinity modify cadmium soil (phyto)availability.

Although Cd availability depends on its total concentration in soil, it is ultimately defined by the processes which control its mobility, transformations and soil solution speciation. Cd mobility between different soil fractions can be significantly affected by certain pedovariables such as soil organic matter (SOM; over formation of metal-organic complexes) and/or soil salinity (over formation of metal-inorganic complexes). Phytoavailable Cd fraction may be described as the proportion of the available Cd in soil which is actually accessible by roots and available for plant uptake. Therefore, in a greenhouse pot experiment Cd availability was observed in the rhizosphere of faba bean exposed to different levels of SOM, NaCl salinity (50 and 100mM) and Cd contamination (5 and 10mgkg-1). Cd availability in soil does not linearly follow its total concentration. Still, increasing soil Cd concentration may lead to increased Cd phytoavailability if the proportion of Cd2+ pool in soil solution is enhanced. Reduced Cd (phyto)availability by raised SOM was found, along with increased proportion of Cd-DOC complexes in soil solution. Data suggest decreased Cd soil (phyto)availability with the application of salts. NaCl salinity affected Cd speciation in soil solution by promoting the formation of CdCln2-n complexes. Results possibly suggest that increased Cd mobility in soil does not result in its increased availability if soil adsorption capacity for Cd has not been exceeded. Accordingly, chloro-complex possibly operated just as a Cd carrier between different soil fractions and resulted only in transfer between solid phases and not in increased (phyto)availability.

Application of empirical model to predict background metal concentration in mixed carbonate-alumosilicate sediment (Adriatic Sea, Croatia).

A 96m long sediment core (S10-33) from the Mali Ston Channel (Adriatic Sea) showed large natural variation in carbonate share (between 1% and 95%) and concentration of elements. These variations indicate rather significant changes in fine-grained sediment that was deposited in this area during Younger Pleistocene and Holocene. Unaffected by anthropogenic influence, sediment in the core was used to determine background concentration of trace elements in sediment with various carbonate content. Here we propose a method of the normalization of trace elements to carbonate share, in order to assess natural/background concentration of metals in sediments consisting of carbonates and alumosilicates in various proportions. Six characteristic metals (Co, Cr, Cu, Ni, Pb, and Zn) that were normalized to carbonate share showed very good correlation, with much higher background concentrations in alumosilicate than in carbonate end member. Simple formulas were proposed to easily determine background concentration of these elements, in coastal and shelf depositional environments with mixed carbonate-alumosilicate sediments.

Soil organic matter and salinity affect copper bioavailability in root zone and uptake by Vicia faba L. plants.

Processes that control the mobility, transformation and toxicity of metals in soil are of special importance in the root-developing zone. For this reason, there is a considerable interest in understanding trace elements (TEs) behavior in soil, emphasising the processes by which plants take them up. Increased root-zone salinity can affect plant TEs uptake and accumulation in plant tissue. Furthermore, copper (Cu) complexation by soil organic matter (SOM) is an effective mechanism of Cu retention in soils, controlling thus its bioavailability. Therefore, a greenhouse pot experiment was conducted to study the effects of soil Cu contamination in a saline environment on faba bean (Vicia faba L.) element uptake. Treatment with NaCl salinity was applied (control, 50 mM NaCl and 100 mM NaCl) on faba bean plants grown in a control and in a soil spiked with Cu (250 and 500 mg kg(-1)). Low and high SOM content trial variants were studied. Cu accumulation occurred in faba bean leaf, pod and seed. Cu contamination affected plant element concentrations in leaves (Na, Ca, Mg, Mn), pod (Zn, Mn) and seed (Mn, Mo, Zn). Root-zone salinity also affected faba bean element concentrations. Furthermore, Cu contamination-salinity and salinity-SOM interactions were significant for pod Cu concentration, suggesting that Cu phytoavailability could be affected by these interactions. Future research will be focused on the mechanisms of Cu translocation in plant and adaptation aspects of abiotic stress.

Cadmium accumulation by muskmelon under salt stress in contaminated organic soil.

Human-induced salinization and trace element contamination are widespread and increasing rapidly, but their interactions and environmental consequences are poorly understood. Phytoaccumulation, as the crucial entry pathway for biotoxic Cd into the human foodstuffs, correlates positively with rhizosphere salinity. Hypothesising that organic matter decreases the bioavailable Cd(2+) pool and therefore restricts its phytoextraction, we assessed the effects of four salinity levels (0, 20, 40 and 60 mM NaCl) and three Cd levels (0.3, 5.5 and 10.4 mg kg(-1)) in peat soil on mineral accumulation/distribution as well as vegetative growth and fruit yield parameters of muskmelon (Cucumis melo L.) in a greenhouse. Salt stress reduced shoot biomass and fruit production, accompanied by increased Na and Cl and decreased K concentration in above-ground tissues. A 25- and 50-day exposure to salinity increased Cd accumulation in leaves up to 87% and 46%, respectively. Accumulation of Cd in the fruits was up to 43 times lower than in leaves and remained unaltered by salinity. Soil contamination by Cd enhanced its accumulation in muskmelon tissues by an order of magnitude compared with non-contaminated control. In the drainage solution, concentrations of Na and Cl slightly exceeded those in the irrigation solution, whereas Cd concentration in drainage solution was lower by 2-3 orders of magnitude than the total amount added. Chemical speciation and distribution modelling (NICA-Donnan) using Visual MINTEQ showed predominance of dissolved organic ligands in Cd chemisorption and complexation in all treatments; however, an increase in salt addition caused a decrease in organic Cd complexes from 99 to 71%, with free Cd(2+) increasing up to 6% and Cd-chlorocomplexes up to 23%. This work highlights the importance of soil organic reactive surfaces in reducing trace element bioavailability and phytoaccumulation. Chloride salinity increased Cd accumulation in leaves but not in fruit peel and pulp.

[High doses of immunoglobulin G in the therapy for severe forms of myasthenia gravis and Guillain-Barré syndrome].

BACKGROUND/AIM: High doses of immunoglobulin G (IVIG) have been recognized as a very important therapeutic modality in the treatment of neurological diseases. The aim of this report was to present our experience in the treatment of severe forms of myasthenia gravis (MG) and Guillain-Barré syndrome (GBS). METHODS: We analyzed the efficacy and safety of immunoglobulin G therapy in 53 patients with severe forms of myasthenia gravis, and 27 patients with very severe forms of Guillain-Barré syndrome. RESULTS: At the end of the follow-up period, a significant improvement was noticed in 47 out of 53 patients with myasthenia gravis (88.7%). In the group of 27 patients with severe forms of Guillain-Barré syndrome an improvement was registered in 19 patients (70.3%). The side effects of this therapy were mostly mild, manifested as headache, myalgia, skin rash, adynamia, and other clinically insignificant effects. No severe side effects were recognized. CONCLUSIONS: Our study clearly demonstrated the high efficacy of IVIG therapy in the treatment of severe forms of myastehnia gravis and Guillain-Barré syndome.