Davor Romić

Representing soil pollution by heavy metals using continuous limitation scores

The paper suggests a methodology to represent overall soil pollution in a sampled area using continuous limitation scores. The interpolated heavy metal concentrations are first transformed to limitation scores using the exponential transfer function determined by using two threshold values: permissible concentration (0 limitation points) and seriously polluted soil (4 limitation points). The limitation scores can then be summed to produce the map of cumulative limitation scores and visualize the most critically polluted areas. The methodology was illustrated using the 784 soil samples analyzed for Cd, Cr, Cu, Ni, Pb and Zn in the central region of Croatia. The samples were taken at 1x1 and 2x2km grids and at fixed depths of 20cm. Heavy metal concentrations in soil were determined by ICP-OES after microwave assisted aqua regia digestion. The sampled concentrations were interpolated using block regression-kriging with geology and land cover maps, terrain parameters and industrialization parameters as auxiliary predictors. The results showed that the best auxiliary predictors are geological map, ground water depth, NDVI and slope map and distance to urban areas. The spatial prediction was satisfactory for Cd, Ni, Pb and Zn, and somewhat less satisfactory for Cu and Cr. The final map of cumulative limitation scores showed that 33.5% of the total area is suitable for organic agriculture and 7.2% of the total area is seriously polluted by one or more heavy metals. This procedure can be used to assess suitability of soils for agricultural production and as a basis for possible legal commitments to maintain the soil quality.

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 (Igeo) values, soils of Dhaka city are considered as highly contaminated. The Igeo 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.

Geochemistry of stream sediments within the reclaimed coastal floodplain as indicator of anthropogenic impact (River Neretva, Croatia)

PurposeThis study used multi-element signatures of stream sediments to assess both natural and human-induced impact on fluvial system in the River Neretva delta receiving environment over time. The river basin actually comprises several sub-catchments, and the geochemical features of major elements, trace metals radiometric and mineralogical characterisation of river bed sediments were used to assist the interpretation of the environment of deposition and its subsequent modifications caused by various anthropogenic pressures within the river basin.Materials and methodsFive sites were chosen for sediment sampling at key locations within the study area with assumed undisturbed, continuous sedimentation process. At each of the sites, three representative cores were taken by scuba divers. Sample sites were selected in order to reflect the influence of different sub-catchments they belong to and the land-use pattern of the surrounding area. Samples were analysed for pH, redox-potential, granulometry, mineralogy, thermogravimetry, major and trace element concentrations and radionuclide activities. The univariate and multivariate statistics were applied. The geochemical normalisation of data was done using Al, the procedure based on calculation of the regression line of the metal on the normaliser followed by testing the ratios metal/normaliser on all data-points.Results and discussionAll studied sediments are classified as silt, ranging from clayey silt to silt and sandy silt. Mineralogically, the sediments were dominated by carbonates and quartz. The chemical contaminant data are generally of good quality, mostly below guideline levels. Sedimentation rates were estimated using vertical distribution of 137Cs activities. Normalisation of TMs done by using Al shows strong R2adj values for the regressions of Al and V, Al and Cr, and Al and Ni. However, Al cannot fairly explain the fluctuation of the concentrations of Cd, Cu, Pb and Zn in sediment cores from all of the sampling sites. Generally, inorganic scavengers such as clay minerals followed by Fe and Mn oxides and S (pyrite and gypsum) seem to be dominant factors controlling TMs in studied sediments.ConclusionsAlthough the River Neretva delta occupies a rather small area, the geochemical features of major and trace elements and 137Cs activities show complex sediment provenances. Each of the sampling sites reflect exactly different effects of anthropogenic intervention that particularly refer to the changes in river morphology and ecology, along with the altered flow regimes within the catchment on sediment loads and quality.

Copper Accumulation in Vineyard Soils: Distribution, Fractionation and Bioavailability Assessment

The paper is focused on the following issues: why we need to study trace metals in soils, sources and behaviour of copper in soils ; anthropogenic inputs and copper contamination of cultivated soils, fractionation and bioavailability of copper in soils ; with a case study: Spatial distribution of copper concentrations in vineyard soils of Croatia: Wine– growing subregion of Plesivica

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.

Improvement of Vineyard Management of Vitis vinifera L. cv. Grk in the Lumbarda Vineyard Region (Croatia)

The vine-growing region of Lumbarda, located in the southeastern part of the island of Korcula, Croatia, has deep sandy soils (paleodunes) associated with the Mediterranean climate and provides optimal conditions for cultivating the autochthonous vine variety Vitis vinifera L. cv. Grk. Unfortunately, recently growers have noted declining yield and quality of grapes resulting from inadequate vineyard management (particularly unsustainable management of soil organic matter) and the occurrence of viral diseases. To revitalize and maintain the vineyards in the Lumbarda region, a detailed study was carried out involving intensive soil survey, analysis of grapevine nutrient status, positive clonal selection, and establishment of new vineyards with virus-free plant material. Preliminary soil survey results provided insight into the extent of variability in major physical and chemical soil characteristics. Based on these results, eight markedly different vineyards were selected for detailed analysis of grapevine nutrients [boron (B), calcium (Ca), copper (Cu), iron (Fe), potassium (K), magnesium (Mg), manganese (Mn), phosphorus (P), and zinc (Zn)] at key development stages to detect potential imbalances that may hamper vine growth and affect its production. Leaf blades and petioles were sampled at midflowering and midveraison stages during the 2007–8 growing season from each of the selected vineyards. The greatest variability in nutrient content between the study sites was recorded for Cu, and considerable variability was also determined for B, Mn, Mg, and P. Differences in fertilization practices are the most common reasons for this variability. The results point to B deficiency in some of the vineyards and suggest potentially toxic levels of Cu in others.

Humic acids decrease uptake and distribution of trace metals, but not the growth of radish exposed to cadmium toxicity

Naturally-occurring highly-complexed and polymerised organics such as humic acids (HA), due to their large negative charge, play a crucial role in biogeochemistry of trace metals (TM). Toxic (Cd) as well as essential (Zn, Cu, Mn) TM bind strongly to HA, but how these organo-metalic forms influence metal uptake by plants is poorly understood. A solution culture study was conducted to characterize the effects of different concentrations of HA (0-225mg/L) on the growth and element uptake/distribution in roots, shoots and hypocotyls of radish (Raphanus sativus L.) exposed to Cd (0.5mg/L) contamination. After 10-d-exposure to applied treatments, Cd induced phytotoxicity; in contrast, different concentrations of HA had no influence on biomass, but decreased concentration of most TM in examined tissues (Cu by 4.2-fold, Zn by 2.2-fold, Cd by 1.6-fold and Mn by 34%) and their total plant accumulation (Cu by 73%, Cd by 39%, Zn by 29% and Mn by 22%). HA influenced the transport/distribution of TM, decreasing accumulation in roots and increasing their translocation/deposition in shoots, with no effect on TM content in edible hypocotyls. Chemical speciation modelling of the rooting medium confirmed predominance of free metallic forms in the control (no HA) and the pronounced organo-metal complexation in the HA treatments. The results provide evidence of strong capacity of HA to decrease phytoavailability and uptake of Cd, Zn, Cu and Mn while being non-toxic even at relatively high concentration (225mg/L). Thus, HA, as naturally present soil components, control mobility and phyto-extraction of most TM as well as their phyto-accumulation.

Soil and Water Management for Sustained Agriculture in Alluvial Plains and Flood Plains Exposed to Salinity: A Case of Neretva River Valley

Salinisation, desertification and pollution are the biggest threat to soil fertility in costal river valleys around the Mediterranean basins. Risk of soil degradation in coastal river valleys is determined not only by the spatial characteristics of the area that can favour saltwater intrusions, but also by the physical and chemical properties of the soils, and the type of agricultural land use. The salinisation problem may also enhance trace metals mobilization, its bioavailability and phytoaccumulation. Hence, more holistic approach has to be applied in mitigation adverse effects of salinity on plant growth in saline environments. It is therefore particularly important to monitor and determine salinisation of soils and water in order to timely propose management measures which will slow down this process and/or reduce its adverse effects. This chapter present extensive field research on soil and water salinisation and experimental research on detrimental effects of soil and water salinity on crop production and metal phytoaccumulation. The represented research program was set out to develop and validate appropriate knowledge and technologies providing an important plank in achieving strategic objectives in environment protection and sustainable development.

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.

Hyperspectral imagery as a supporting tool in precision irrigation of karst landscapes

This research was carried out in an experimental vineyard grown in artificially transformed karst terrain (Croatia). The experimental design included four water treatments in three replicates: 1) fully watered or based on 100% evapotranspiration (ETc) application; 2) regulated deficit irrigation based on 75% and 50% ETc applications; and 3) non-watered. Hyperspectral images of grapevines were taken in the summer of 2016 using two spectral-radiance (W·sr −1 ·m −2 ) calibrated cameras, covering wavelengths from 409 to 988 nm and 950 to 2509 nm. The four treatments were grouped into two new sets: 1) drought (NO); and 2) watered (the remaining three treatments). The watered group was then split into two new sets: 1) 50% treatment; and 2) 75+100% treatment. The images were analyzed using Partial least squares – discriminant analysis (PLS-DA), and Single Vector Machines (SVM). The PLS-DA demonstrated the capability to determine levels of grapevine drought or watered groups with 70 - 80% accuracy. A similar success rate was achieved in distinguishing the 50% group from the 75+100% group.