Pollen and Chemical Content of Beebreads from Serpentine Areas in Albania and Bulgaria.

Beebread from serpentine localities in Albania and Bulgaria were characterized based on their pollen and chemical element content (macroelements K, Ca, Mg, P and microelements Cd, Co, Cr, Cu, Fe, Mn, Na, Ni, Pb, Zn) aiming to (1) evaluate the effect of serpentine soil on the quality of beebread; (2) compare elemental concentrations in samples from serpentine areas in Albania and Bulgaria; and (3) compare the differences in pollen spectra. Chemical element content was determined using microwave digestion of beebread samples followed by ICP-OES measurements. The analytical procedure developed was validated by added/found method. Analytical figures of merit of analytical method proposed were presented. The melissopalynological analysis was applied for pollen characterization. The results demonstrate clear difference in the pollen spectra between the two sets of samples, confirming differences in local serpentine flora in both countries, but specific pollen type is difficult to be suggested. The pollen content is related to the flowering period, climatic conditions, and bees forage preferences. The samples vary in their elemental concentrations depending on the pollen type and year of collection. The highest average concentrations found for K, Ca, Mg, and P are close to values reported in the literature. However, elevated concentrations observed for Ni, Cr, Mn, and Fe in beebread, especially from Albania, are in line with the serpentine characteristics of studied areas. The concentrations of Cd and Pb for all beebread samples are below permissible limits. The results should be taken into consideration in future specific food safety regulations at national and international level.

Can organic amendments replace chemical fertilizers in nickel agromining cropping systems in Albania?

In Albania, ultramafic outcrops cover 11% of the surface and have the potential to support nickel phytomining. In a large-scale in-situ experiment on an ultramafic Vertisols in Pojskë we are studying the influence of agronomical practices on Ni phytoextraction yield of Odontarrhena chalcidica (syn. Alyssum murale). Three cropping systems were compared in three plots in 2016-2017; POJ-1 Plot (0.3 ha) was established with plants that had germinated spontaneously without any treatments; POJ-2 plot (0.3 ha) was covered by plants that had germinated spontaneously and was treated with mineral fertilizer (N50P50K50 kg ha-1); and POJ-3 Plot (400 m2) was divided in four sub plots, where O. chalcidica was planted at a density of 4 plants m-2 on which, we neither applied fertilizer, nor NPK fertilizer (N65P65K65), pig (FPM; N260:P105:K260 + 15 kg ha-1N, P, K) or chicken manure (FCHM; N260:P390:K260 +15 kg ha-1 N, P, K. Irrigation and mechanical control of weeds was done on POJ-3. After 8 months, shoot Ni concentration, biomass, and Ni yields were higher in O. chalcidica treated with manure and the cost of biomass production was smaller. Nickel yield was more promising (145 kg ha-1) than in previous field trials. This study highlights that, using manure, the Ni yield increases Ni phytomining net values, thus agromining can become an economically justifiable agricultural cropping system.

Improving the Agronomy of Alyssum murale for Extensive Phytomining: A Five-Year Field Study.

Large ultramafic areas exist in Albania, which could be suitable for phytomining with native Alyssum murale. We undertook a five-year field experiment on an ultramafic Vertisol, aimed at optimizing a low-cost Ni-phytoextraction crop of A. murale which is adapted to the Balkans. The following aspects were studied on 18-m2 plots in natural conditions: the effect of (i) plant phenology and element distribution, (ii) plant nutrition and fertilization, (iii) plant cover and weed control and (iv), planting technique (natural cover vs. sown crop). The optimal harvest time was set at the mid-flowering stage when Ni concentration and biomass yield were highest. The application of N, P, and K fertilizers, and especially a split 100-kg ha(-1) N application, increased the density of A. murale against all other species. It significantly increased shoot yield, without reducing Ni concentration. In natural stands, the control of graminaceous weeds required the use of an anti-monocots herbicide. However, after the optimization of fertilization and harvest time, weed control procured little benefit. Finally, cropping sown A. murale was more efficient than enhancing native stands and gave higher biomass and phytoextraction yields; biomass yields progressively improved from 0.3 to 9.0 t ha(-1) and phytoextracted Ni increased from 1.7 to 105 kg ha(-1).

Selection and combustion of Ni-hyperaccumulators for the phytomining process.

Ni recovery from serpentine soils by phytomining has proved feasible. Phytomining involves the crop of hyperaccumulating plants with high Ni contents and the valorization of Ni by pyro or hydrometallurgical process. In order to evaluate the Ni content of different plants, we analyzed the organs of 14 hyperaccumulators from three genera: Alyssum, Leptoplax and Bornmuellera. The highest concentration was recorded in the leaves of Leptoplax (34.3 +/- 0.7 mg g(-1)DM). Additionally, we investigated biomass combustion which is the first step of the process we designed to obtain a nickel salt. We showed that temperature and duration were important parameters to ensure a good quality of ashes. At the bench scale, the best conditions were 550 degrees C and 3 h. In this way, we obtained ashes in which Ni could reach 20 wt%. Biomass ashes can be considered as a bio-ore for recovering metal value.

Pedogenesis and nickel biogeochemistry in a typical Albanian ultramafic toposequence.

This study aimed at relating the variability of Ni biogeochemistry along the ultramafic toposequence to pedogenesis and soil mineralogy. Hypereutric Cambisols dominate upslope; Cambic Vertisols and Fluvic Cambisols occur downslope. The soil mineralogy showed abundance of primary serpentine all over the sequence. It is predominant upslope but secondary smectites dominate in the Vertisols. Free Fe-oxides are abundant in all soils but slightly more abundant in the upslope soils. Whereas serpentines hold Ni in a similar and restricted range in every soil (approx. 0.3 %), Ni contents in smectites may vary a lot and Mg-rich and Al-poor smectites in the Vertisol could hold up to 4.9 % Ni. Ni was probably adsorbed onto amorphous Fe-oxides and was also exchangeable in secondary smectites. High availability of Ni in soils was confirmed by DTPA extractions. However, it varied significantly along the toposequence, being higher in upslope soils, where Ni-bearing amorphous Fe-oxides were abundant and total organic carbon higher and sensibly lower downslope on the Vertisols: NiDTPA varied from 285 mg kg(-1) in the surface of soil I (upslope) to 95.9 mg kg(-1) in the surface of Fluvic Cambisols. Concentration of Ni in Alyssum murale shoots varied from 0.7 % (Hypereutric Cambisols) to 1.4 % (Hypereutric Vertisol). Amazingly, Ni uptake by A. murale was not correlated to NiDTPA, suggesting the existence of specific edaphic conditions that affect the ecophysiology of A. murale upslope.