Zinc and cadmium mapping by NanoSIMS within the root apex after short-term exposure to metal contamination.

Zinc as a micronutrient and cadmium as a nonessential toxic element share similar pathways for entering plant tissues and thus may be antagonistic. In nutrient solution culture, 17-day-old radish (Raphanus sativus L) plants were exposed to short-term (24 h) equimolar metal contamination (2.2 µM of each 70Zn and total Cd) to investigate the in situ Zn/Cd distribution in the apical root tissues using high-resolution secondary ion mass spectrometry (NanoSIMS) imaging. Inductively-coupled plasma mass spectrometry analysis of bulk root tissue confirmed large root uptake of both metal elements. After 24-h exposure the total root concentration (in µg/g DW) of 70Zn was 180 ±â€¯24 (mean±SE) and of total Cd 352 ±â€¯11. NanoSIMS mapping was performed on the cross sections of the radish root apex as a crucial component in root growth and uptake of water and nutrients from soil. Elemental maps of 70Zn and 114Cd isotopes revealed greater enrichment of both metals in the outer epidermal root layer than in cortical tissues and especially stele, confirming the epidermal root cells as preferential sites of metal uptake, and indicating relatively slow and less-intensive metal transport into other parts (edible hypocotyl, shoot) of metal-sensitive radish. NanoSIMS has been confirmed as a powerful tool for spatial detection and visualisation of some ultra-trace metal isotopes (e.g. 70Zn) in the fast-growing root tips. However, precise (sub)cellular mapping of diffusible metallic ions (Cd, Zn) remains a technically-challenging task in plant specimens given an unavoidable compromise between optimising methodology for structural preservation vs. authentic in vivo ion localisation.

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.

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.

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.

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.

Humates mitigate Cd uptake in the absence of NaCl salinity, but combined application of humates and NaCl enhances Cd mobility & phyto-accumulation.

Cadmium is among the critical pollutants easily taken up from contaminated media by plants, which can be exploited in the phytoremediation of Cd-contaminated resources, but is also an obstacle in producing food with low Cd content. Crucial variables governing Cd biogeochemistry are complex humates (HA) and chlorides, but the underlying interactions are poorly understood. The aim was to determine the impacts of HA (0-60 mg/L) and NaCl (0-30 mM) on Cd biochemistry in contaminated (2.0 µM Cd) rhizosphere solution and Cd accumulation in various tissues of strawberry (Fragaria x ananassa). The results show that salinity (vs. non-saline NaCl0 control) suppressed vegetative and yield parameters, but increased dry matter and Na, Cl and Cd concentration/accumulation in most of the analysed tissues. The HA application in the NaCl0 treatment decreased tissue Cd content; however, at the highest application rates of NaCl and HA, there were increases in the tissue Cd concentration (by 70 %, 100 % and 120 % in crowns, leaves and fruits, respectively) and accumulation (by 110 %, 126 % and 148 % in roots, fruits and leaves, respectively) in comparison to the control (NaCl0HA0). Tissue Cd concentration/accumulation decreased in the order: roots>crowns>leaves>fruits; the same accumulation pattern was noted for Na and Cl, suggesting that Cd-Cl complexes may represent a major form of Cd taken up. Chemical speciation calculations revealed that the proportions of various Cd forms varied multi-fold across the treatments; in the control (without NaCl and HA), Cd2+ dominated (86 %), followed by CdHPO4 (6.5 %), CdSO4 (6.2 %) and CdNO3+. In other treatments the proportion of Cd2+ decreased with a corresponding increase of Cd-Cl (from 0.02 % in control to 57 % in Cd + NaCl30 treatment) and Cd-HA (from 0 % in control to 44 % in Cd + HA60 treatment), which was associated with higher Cd phytoaccumulation. The results represent a theoretical basis for phytoremediation studies and for producing low-Cd food in relatively complex matrices (contaminated soils, reused effluents); in the absence of salinity, amelioration with humates has a great potential to mitigate Cd contamination.

Irrigation of Young Olives Grown on Reclaimed Karst Soil Increases Fruit Size, Weight and Oil Yield and Balances the Sensory Oil Profile.

The influence of different irrigation regimes on olive fruit morphological parameters and on the quantity and quality (marketable indices, phenolic content, fatty acid composition, and sensory profile) of virgin olive oil (VOO) obtained from the Croatian cultivar Oblica, grown on an extremely rocky and dry reclaimed karst soil, was studied over three years. Four treatments were applied: rain-fed and three treatments calculated as 50%, 75%, and 100% of the crop's irrigation requirement (Irr). Principal component analysis separated growing seasons (GS) that differed in precipitation. In the 2016 season, which had a low number of fruits per kilogram and provided a higher amount of balanced VOO with medium to intense bitterness and pungency (rain-fed treatment), the oil yield increased by irrigation (Irr 75 and Irr 100) up to 18%, while unchanged phenolics, bitterness, and pungency were observed for the VOOs obtained. In the drier GS (2017), which under rain-fed conditions had high fruit per kg, smallest fruit sizes, and lowest oil yield, and in which the VOOs had high phenolic content and intense sensory taste attributes, fruit weight, fruit sizes, and oil yield increased by 35% in all irrigation treatments, while phenols, bitterness, and pungency decreased, balancing the sensory profile of the VOOs. The results obtained here led us to conclude that the irrigation of young olives resulted in a positive effect, with the indication that an abundant water supply is more effective in drought conditions.

Growth and Element Uptake by Salt-Sensitive Crops under Combined NaCl and Cd Stresses.

To test an assumption that organic soil can ameliorate nutritional disorders associated with metal and salinity stresses, we exposed salt-sensitive strawberry and lettuce to four salinity (0-60 mM NaCl) and three contamination (0.3-5 mg Cd/kg) rates in peat (pHH2O = 5.5). The results showed that, even at 20 mM NaCl, salinity stress exerted a dominant effect on rhizosphere biogeochemistry and physiological processes, inducing leaf-edge burns, chlorosis/necrosis, reducing vegetative growth in crops; at ≥40 mM, NaCl mortality was induced in strawberry. Signifiacntly decreased K/Na, Ca/Na and Mg/Na concentration ratios with raising salinity were confirmed in all tissues. The combined CdxNaCl stresses (vs. control) increased leaf Cd accumulation (up to 42-fold in lettuce and 23-fold in strawberry), whereas NaCl salinity increased the accumulation of Zn (>1.5-fold) and Cu (up to 1.2-fold) in leaves. Lettuce accumulated the toxic Cd concentration (up to 12.6 mg/kg) in leaves, suggesting the strong root-to-shoot transport of Cd. In strawberry Cd, concentration was similar (and sub-toxic) in fruits and leaves, 2.28 and 1.86 mg/kg, respectively, suggesting lower Cd root-to-shoot translocation, and similar Cd mobility in the xylem and phloem. Additionally, the accumulation of Cd in strawberry fruits was exacerbated at high NaCl exposure (60 mM) compared with lower NaCl concentrations. Thus, in salinized, slightly acidic and organically rich rhizosphere, pronounced organo- and/or chloro-complexation likely shifted metal biogeochemistry toward increased mobility and phytoavailability (with metal adsorption restricted due to Na+ oversaturation of the caton exchange complex in the substrate), confirming the importance of quality water and soils in avoiding abiotic stresses and producing non-contaminated food.

Interactions of humates and chlorides with cadmium drive soil cadmium chemistry and uptake by radish cultivars.

In contrast to some salts such as chlorides (Cl) that enhance cadmium (Cd) phyto-uptake, complex soil organics like humates (HA) potentially minimise Cd uptake, but are depleted in soils low in organic matter. Organically-depleted and salt-affected areas frequently coincide in (semi)arid agroecosystems where inappropriate management practices may load topsoils with Cd. We evaluated the impact of HA (0-100 mg/kg) and NaCl (0-60 mM) in Cd-contaminated (0-5 mg/kg) soil on the chemical changes in the rhizosphere and Cd uptake by two radish (Raphanus sativus L.) cultivars. In the rhizosphere solution the significant HAxCd interaction resulted in a decrease in Cd concentration with increasing HA rates, whereas the NaClxCd interaction was brought about by an increase in Cd concentration with NaCl rising. Also, the NaClxCd interaction increased Cd concentration in radish hypocotyl with increasing NaCl addition; in contrast, the HAxCd interaction reduced Cd concentration in hypocotyl, notably at the highest Cd rate, with increasing soil humification. The addition of HA acted as a biostimulant in both radish cultivars and decreased Cd accumulation (up to 44%), whereas NaCl stress reduced the root growth and enhanced total Cd accumulation (by almost 50%). Dose-dependent severity of Cd toxicity was confirmed in both cultivars by reduced growth and progressive (up to 2 orders of magnitude) Cd accumulation (vs. uncontaminated soil). Ion speciation modelling suggested that chemistry of deprotonated humates and chlorides is crucial for complexation of the most bioavailable Cd2+ species, thus driving Cd mobility within the soil matrix, including uptake by plants. Detected differences between the tested cultivars (e.g. lower Cd concentration in Sparkler vs. Cherry Belle) and their impacts on rhizosphere chemistry and Cd soil-plant acquisition/root-hypocotyl-shoot (re)distribution, suggest that genetic improvements (by developing and introducing salt- and/or metal-resistant varieties) should be exploited in phytoremediation of contaminated soils or for minimising metal accumulation in sustainable food production.

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.

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.

Zinc and Cadmium Mapping in the Apical Shoot and Hypocotyl Tissues of Radish by High-Resolution Secondary Ion Mass Spectrometry (NanoSIMS) after Short-Term Exposure to Metal Contamination.

Zinc (as an essential phytonutrient) and cadmium (as a toxic but readily bioavailable nonessential metal for plants) share similar routes for crossing plant biomembranes, although with a substantially different potential for translocation into above-ground tissues. The in situ distribution of these metals in plant cells and tissues (particularly intensively-dividing and fast-growing areas) is poorly understood. In this study, 17-day-old radish (Raphanus sativus L.) plants grown in nutrient solution were subjected to short-term (24 h) equimolar contamination (2.2 µM of each 70Zn and Cd) to investigate their accumulation and distribution in the shoot apex (leaf primordia) and edible fleshy hypocotyl tissues. After 24-h exposure, radish hypocotyl had similar concentration (in µg/g dry weight) of 70Zn (12.1 ± 1.1) and total Cd (12.9 ± 0.8), with relatively limited translocation of both metals to shoots (concentrations lower by 2.5-fold for 70Zn and 4.8-fold for Cd) as determined by inductively-coupled plasma mass spectrometry (ICP-MS). The in situ Zn/Cd distribution maps created by high-resolution secondary ion mass spectrometry (NanoSIMS, Cameca, Gennevilliers, France) imaging corresponded well with the ICP-MS data, confirming a similar pattern and uniform distribution of 70Zn and Cd across the examined areas. Both applied techniques can be powerful tools for quantification (ICP-MS) and localisation and visualisation (NanoSIMS) of some ultra-trace isotopes in the intensively-dividing cells and fast-growing tissues of non-metalophytes even after short-term metal exposure. The results emphasise the importance of the quality of (agro)ecosystem resources (growing media, metal-contaminated soils/waters) in the public health risk, given that, even under low contamination and short-term exposure, some of the most toxic metallic ions (e.g., Cd) can relatively rapidly enter the human food chain.

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.