Biochar-nanoparticle combinations enhance the biogeochemical recovery of a post-mining soil.

Here we addressed the capacity of distinct amendments to reduce arsenic (As), copper (Cu), selenium (Se) and zinc (Zn) associated risks and improve the biogeochemical functions of post-mining soil. To this, we examined nanoparticles (NPs) and/or biochar effects, combined with phytostabilization using Lolium perenne L. Soil samples were taken in a former metal mine surroundings. Ryegrass seeds were sown in pots containing different combinations of NPs (zero-valent iron (nZVI) or hydroxyapatite (nH)) (0 and 2 %), and biochar (0, 3 and 5 %). Plants were grown for 45 days and the plant yield and element accumulation were evaluated, also soil properties (element distribution within the soil fractions, fertility, and enzymatic activities associated with microbiota functionality and nutrient cycling) were determined. Results showed biochar-treated soil had a higher pH, and much higher organic carbon (C) content than control soil and NP-treated soils, and it revealed increased labile C, total N, and available P concentrations. Soil treatment with NP-biochar combinations increased exchangeable non-acid cation concentrations and reduced exchangeable Na%, improved soil fertility, reduced sodicity risk, and increased ryegrass biomass. Enzymatic activities, particularly dehydrogenase and glucosidase, increased upon the addition of biochar, and this effect was fostered by NPs. Most treatments led to a significant reduction of metal(loid)s contents in biomass, mitigating contamination risks. The two different NPs had similar effects in many parameters, nH outperformed nZVI in terms of increased nutrients, C content, and enzymatic activities. On the basis of our results, combined biochar-NP amendments use, specially nH, emerges as a potential post-mining soil restoration strategy.

Effectiveness of cork and pine bark powders as biosorbents for potentially toxic elements present in aqueous solution.

Cork oak and pine bark, two of the most prolific byproducts of the European forestry sector, were assessed as biosorbents for eliminating potentially toxic elements (PTEs) from water-based solutions. Our research suggests that bioadsorption stands out as a viable and environmental eco-friendly technology, presenting a sustainable method for the extraction of PTEs from polluted water sources. This study aimed to evaluate and compare the efficiency of cork powder and pine bark powder as biosorbents. Specifically, the adsorption of Fe, Cu, Zn, Cd, Ni, Pb and Sn at equilibrium were studied through batch experiments by varying PTEs concentrations, pH, and ionic strength. Results from adsorption-desorption experiments demonstrate the remarkable capacity of both materials to retain the studied PTE. Cork powder and pine bark powder exhibited the maximum retention capacity for Fe and Cd, while they performed poorly for Pb and Sn, respectively. Nevertheless, pine bark showed a slightly lower retention capacity than cork. Increasing the pH resulted in cork showing the highest adsorption for Zn and the lowest for Sn, while for pine bark, Cd was the most adsorbed, and Sn was the least adsorbed, respectively. The highest adsorption of both materials occurred at pH 3.5-5, depending on the PTE tested. The ionic strength also influenced the adsorption of the various PTEs for both materials, with decreased adsorption as ionic strength increased. The findings suggest that both materials could be effective for capturing and eliminating the examined PTEs, albeit with different efficiencies. Remarkably, pine bark demonstrated superior adsorption capabilities, which were observed to vary based on the specific element and the experimental conditions. These findings contribute to elucidating the bio-adsorption potential of these natural materials, specifically their suitability in mitigating PTEs pollution, and favoring the recycling and revalorization of byproducts that might otherwise be considered residue.

Use of metal nanoparticles in agriculture. A review on the effects on plant germination.

Agricultural nanotechnology has become a powerful tool to help crops and improve agricultural production in the context of a growing world population. However, its application can have some problems with the development of harvests, especially during germination. This review evaluates nanoparticles with essential (Cu, Fe, Ni and Zn) and non-essential (Ag and Ti) elements on plant germination. In general, the effect of nanoparticles depends on several factors (dose, treatment time, application method, type of nanoparticle and plant). In addition, pH and ionic strength are relevant when applying nanoparticles to the soil. In the case of essential element nanoparticles, Fe nanoparticles show better results in improving nutrient uptake, improving germination, and the possibility of magnetic properties could favor their use in the removal of pollutants. In the case of Cu and Zn nanoparticles, they can be beneficial at low concentrations, while their excess presents toxicity and negatively affects germination. About nanoparticles of non-essential elements, both Ti and Ag nanoparticles can be helpful for nutrient uptake. However, their potential effects depend highly on the crop type, particle size and concentration. Overall, nanotechnology in agriculture is still in its early stages of development, and more research is needed to understand potential environmental and public health impacts.

Use of Three Different Nanoparticles to Reduce Cd Availability in Soils: Effects on Germination and Early Growth of Sinapis alba L.

Globally, cadmium (Cd) is one of the metals that causes the most significant problems of contamination in agricultural soils and toxicity in living organisms. In this study, the ability of three different nanoparticles (dose 3% w/w) (hydroxyapatite (HANPs), maghemite (MNPs), or zero-valent iron (FeNPs)) to decrease the availability of Cd in artificially contaminated agricultural soil was investigated. The effect of Cd and nanoparticles on germination and early growth of Sinapis alba L. was also assessed by tolerance/toxicity bioassays. The available Cd contents in the contaminated soil decreased after treatment with the nanoparticles (available Cd decreased with HANPs: >96.9%, MNPs: >91.9%, FeNPs: >94%), indicating that these nanoparticles are highly efficient for the fixation of available Cd. The toxicity/tolerance bioassays showed different behavior for each nanoparticle. The HANPs negatively affected germination (G(%): 20% worsening compared to control soil), early root growth (Gindex: -27.7% compared to control soil), and aerial parts (Apindex: -12%) of S. alba, but showed positive effects compared to Cd-contaminated soils (Gindex: +8-11%; Apindex: +26-47%). MNP treatment in Cd-contaminated soils had a positive effect on germination (G(%): 6-10% improvement) and early growth of roots (Gindex: +16%) and aerial parts (Apindex: +16-19%). The FeNPs had a positive influence on germination (G(%): +10%) and growth of aerial parts (Apindex: +12-16%) but not on early growth of roots (Gindex: 0%). These nanoparticles can be used to reduce highly available Cd contents in contaminated soils, but MNPs and FeNPs showed the most favorable effects on the early growth and germination of S. alba.

Removal of emerging pollutants from the environment: From bioadsorbents to nanoparticle-based systems.

In the Call for Papers corresponding to this Virtual Special Issue (VSI), the Editors indicated that, as is well known, emerging pollutants include a variety of substances that pose remarkable risks for the environment and public health. In fact, emerging pollutants are considered a matter of concern deserving increasing efforts to elucidate their occurrence, fate, repercussions, and alternatives to their removal from the various environmental compartments where they can be found after spreading as contaminants. Also, the Editors commented that, among the various alternatives that can be considered for achieving their successful removal, some of them are based on the use of sorbent materials, and, specifically, bioadsorbents, which are attractive due to the efficacy and low cost associated with some of them. Another alternative is related to the utilization of nanoparticle-based systems, which may be considered a promising field of research in this way. In both cases, obtaining new research results, as well as designing and programming new ways of going steps ahead in the investigation of both kinds of materials, would be key objectives. According to the previous considerations, the Editors of the VSI invited researchers having new data concerning these aspects to submit manuscripts with experimental results, discussion, reflections and prospective related to their work. With the Special Issue closed, the number of submissions received was 83, with 40 high-quality works being accepted for publication, increasing the overall knowledge on this topic by providing results that we are sure will be of value for the scientific community and the society.

The Differences between the Effects of a Nanoformulation and a Conventional Form of Atrazine to Lettuce: Physiological Responses, Defense Mechanisms, and Nutrient Displacement.

The rapid development of nanotechnology influences the developments within the agro-sector. An example is provided by the production of nanoenabled pesticides with the intention to optimize the efficiency of the pesticides. At the same time, it is important to collect information on the unintended and unwanted adverse effects of emerging nanopesticides on nontarget plants. Currently, this information is limited. In the present study, we compared the effects of a nanoformulation of atrazine (NPATZ) and the nonencapsulated atrazine formulation (ATZ) on physiological responses, defense mechanisms, and nutrient displacement in lettuce over time with the applied concentrations ranging from 0.3 to 3 mg atrazine per kg soil. Our results revealed that both NPATZ and ATZ induced significant decreases in plant biomass, chlorophyll content, and protein content. Additionally, exposure to NPATZ and ATZ caused oxidative stress to the lettuce plant and significantly elevated the activities of the tested ROS scavenger enzymes in plant tissues. These results indicate that NPATZ and ATZ cause distinct adverse impacts on lettuce plants. When comparing the adverse effects in plants after exposure to NPATZ and ATZ, no obvious differences in plant biomass and chlorophyll content were observed between NPATZ and ATZ treatments at the same exposure concentration regardless of exposure duration. An enhanced efficiency of the active ingredient of the nanopesticide as compared to the conventional formulation was observed after long-term exposure to the high concentration of NPATZ, as it induced higher impacts on plants in terms of the end points of the contents of protein, superoxide anion (O2̇-), and MDA, and the activities of stress-related enzymes as compared to the same concentration of ATZ. Furthermore, exposure to both NPATZ and ATZ disrupted the uptake of mineral nutrients in plants, and the differences in the displacement of nutrients between the NPATZ and ATZ treatments depended on the element type, plant organ, exposure concentration, and time. Overall, the application dose of a nanopesticide should balance their increased herbicidal efficiency with the long-term adverse effects in order to maximize the desired impact while minimizing adverse impacts; only then will we be able to understand the potential impact of nanopesticides on the environment.

Compositional and functional responses of bacterial community to titanium dioxide nanoparticles varied with soil heterogeneity and exposure duration.

Titanium dioxide nanoparticles (TiO2 NPs) are widely used as nano-agrochemicals. In this study we investigated the influence of soil heterogeneity on bacterial communities exposed to TiO2 NPs over time. Clay and sandy soils with low- and high-organic matter contents were exposed to environmentally relevant concentration of TiO2 NPs (1 mg/kg) and soil bacterial communities were sampled after short-term (15 days) and long-term exposure (60 days). After short-term TiO2 NPs exposure, significant effects regarding the enzyme activity, bacterial community structure and composition, and community functioning were observed in the clay soils with high organic matter (clay-HOM) but not in other soil groups. Response alterations were observed to taxa belonging to Acidobacteria and Verrucomicrobia, and functional pathways related to carbohydrates degradation. These results indicated that soil heterogeneity play more important roles in shaping the bacterial community in soil with low clay fraction and less organic matter, while TiO2 NPs selection was the main driver in inducing the compositional and functional impacts on the soil bacterial community in the presence of clay soil with high organic matter content. As exposure time increased, the bacterial community recovered after a long-term exposure of 60 days, suggesting that the bacterial evolution and adaptation could overcome the TiO2 NPs selection after long-term exposure. Our results highlighted the importance of soil heterogeneity including clay fraction and organic matter and exposure duration in assessing the impact of nanoparticle on soil bacterial activity, community and function. By comprehensively evaluating the risks of nanoparticles on soil ecosystem and explicitly and explicitly include spatial and temporal variations, the benefit of nano-agrochemical products has the potential to be promoted in future applications.

Soils from abandoned shooting range facilities as contamination source of potentially toxic elements: distribution among soil geochemical fractions.

Civilian and military shooting range facilities cause environmental issues in several countries due to the accumulation of Potentially Toxic Elements; as a result of weathering of ammunitions accumulated into the soils. The contents and distribution of Cu, Ni, Pb and Zn were analyzed in 12 soils in an abandoned clay target shooting range at two different depths (0-15 and 15-30 cm). Single extractions (CaCl2 and DTPA) and Tessier sequential extraction were conducted to assess the PTE mobility and the PTE distribution in the different soil geochemical fractions at both depths. High total contents of Pb were found at both soil depths, while Cu, Ni and Zn showed lower significance levels. Copper, Ni and Zn are mainly associated with the residual fraction (> 95% of total content in all cases). However, Pb was highly associated with exchangeable fractions (21-52%), showing a high mobility at both depths. With moderate-high contents of organic matter (6-12%), the studied soils have acidic values and low levels of Al, Fe and Mn oxides that favors the migration of Pb through the soil profile and potential transformation to more mobile forms (Pb0 to Pb2+ and Pb4+). Although Pb reduced downward mobility in soils, due to the specific conditions of these facilities and the lead source (weathering of ammunition), risk assessment studies on clay-target shooting and firing range facilities should study the potential migration of Pb through the soil profile.

Particle number-based trophic transfer of gold nanomaterials in an aquatic food chain.

Analytical limitations considerably hinder our understanding of the impacts of the physicochemical properties of nanomaterials (NMs) on their biological fate in organisms. Here, using a fit-for-purpose analytical workflow, including dosing and emerging analytical techniques, NMs present in organisms are characterized and quantified across an aquatic food chain. The size and shape of gold (Au)-NMs are shown to control the number of Au-NMs attached to algae that were exposed to an equal initial concentration of 2.9 × 1011 particles mL-1. The Au-NMs undergo size/shape-dependent dissolution and agglomeration in the gut of the daphnids, which determines the size distribution of the NMs accumulated in fish. The biodistribution of NMs in fish tissues (intestine, liver, gills, and brain) also depends on NM size and shape, although the highest particle numbers per unit of mass are almost always present in the fish brain. The findings emphasize the importance of physicochemical properties of metallic NMs in their biotransformations and tropic transfers.

An environmental ecocorona influences the formation and evolution of the biological corona on the surface of single-walled carbon nanotubes.

Nanomaterials (NMs) taken up from the environment carry a complex ecocorona consisting of dissolved organic matter. An ecocorona is assumed to influence the interactions between NMs and endogenous biomolecules and consequently affects the formation of a biological corona (biocorona) and the biological fate of the NMs. This study shows that biomolecules in fish plasma attach immediately (within <5 min) to the surface of SWCNTs and the evolution of the biocorona is a size dependent phenomenon. Quantitative proteomics data revealed that the nanotube size also influences the plasma protein composition on the surface of SWCNTs. The presence of a pre-attached ecocorona on the surface of SWCNTs eliminated the influence of nanotube size on the formation and evolution of the biocorona. Over time, endogenous biomolecules from the plasma partially replaced the pre-attached ecocorona as measured using a fluorescently labelled ecocorona. The presence of an ecocorona offers a unique surface composition to each nanotube. This suggests that understanding the biological fate of NMs taken up from the environment by organisms to support the environmental risk assessment of NMs is a challenging task because each NM may have a unique surface composition in the body of an organism.

Influence of Seed Source and Soil Contamination on Ecophysiological Responses of Lavandula pedunculata in Rehabilitation of Mining Areas.

Mining activities have turned many areas of the Iberian Pyrite Belt (IPB) into extreme environments with high concentrations of metal(loid)s. These harsh conditions can inhibit or reduce the colonization and/or development of most vegetation. However, some species or populations have developed ecophysiological responses to tolerate stress factors and contaminated soils. The main objectives of this study are: (i) to assess the differences in germination, growth, development and physiological behaviour against oxidative stress caused by metal(loid)s in Lavandula pedunculata (Mill.) Cav. from two different origins (a contaminated area in São Domingos mine, SE of Portugal and an uncontaminated area from Serra do Caldeirão, S of Portugal) under controlled conditions; and (ii) to assess whether it is possible to use this species for the rehabilitation of mine areas of the IPB. After germination, seedlings from São Domingos (LC) and Caldeirão (L) were planted in pots with a contaminated soil developed on gossan (CS) and in pots with an uncontaminated soil (US) under controlled conditions. Multielemental concentrations were determined in soils (total and available fractions) and plants (shoots and roots). Germination rate, shoot height, dry biomass and leaf area were determined, and pigments, glutathione, ascorbate and H2O2 contents were measured in plant shoots. Total concentrations of As, Cr, Cu, Pb and Sb in CS, and As in US exceed the intervention and maximum limits for ecosystem protection and human health. The main results showed that L. pedunculata, regardless of the seed origin, activated defence mechanisms against oxidative stress caused by high concentrations of metal(loid)s. Plants grown from seeds of both origins increased the production of AsA to preserve its reduction levels and kept the contents of GSH stable to maintain the cell's redox state. Plants grown from seeds collected in non-contaminated areas showed a high capacity for adaptation to extreme conditions. This species showed a greater growth capacity when seeds from a contaminated area were sown in uncontaminated soils. Thus, L. pedunculata, mainly grown from seeds from contaminated areas, may be used in phytostabilization programmes in areas with soils with high contents of metal(loid)s.

Assessment of iron-based and calcium-phosphate nanomaterials for immobilisation of potentially toxic elements in soils from a shooting range berm.

Shooting range facilities in military areas have been indicated as a hotspot of land degradation with high contents of Potentially Toxic Elements (PTEs). Currently, based on the new nanomaterials with specific characteristics, nanoremediation technologies are used to immobilise and to reduce the availability of PTEs in field and laboratory conditions. In this study, the effects of nano-hydroxyapatite and/or hematite on PTEs immobilisation (As, Cd, Cu, Pb, Sb and Zn) in military shooting range soils were assessed through the measure of available and leachable forms with three single-extractions: calcium chloride (0.01M CaCl2), low molecular weight organic acids (10 mM LMWOAs) and toxicity characteristic leaching procedure (TCLP). A sequential chemical extraction was used to determine the distribution of the PTEs in the different geochemical phases of the soils before and after the nanomaterial treatments. Results showed that the availability of PTEs decreased, especially for Pb (40-95%) and Zn (50-99%) after nanomaterial treatments. When both nanomaterial (hydroxyapatite + hematite) were combined, the immobilisation rate improved. However, when each nanomaterial was added individually to the soils, some elements, such as, Cu or Sb, showed a slight increment of their mobilisation. The sequential chemical extraction showed that the highest percentage of PTEs were mainly in the residual fraction before and after adding nanomaterials, being even higher in soils after the nanomaterial treatments. Likewise, the mobile fractions decreased after the treatment with nanomaterials. Our findings suggest that nanoremediation techniques improve the soil conditions, but they should be used carefully to avoid mobilisation of non-target PTEs or unexpected potentially impacts for soil biota.

Chemical availability versus bioavailability of potentially toxic elements in mining and quarry soils.

Abandoned mining and quarry areas are sources of potentially toxic elements (PTEs), through lixiviates or transfer processes of bioavailable fractions from mining wastes and tailings. In this study, earthworms (Eisenia fetida Savigny, 1826) were exposed for 28 days to two mining soils from a lead/zinc mine and two quarry soils from an old serpentine quarry. Despite their pseudo total metal contents, a previous characterization of these soils pointed out for a low chemical availability of PTEs. Therefore, a multibiomarker approach was used and the response of E. fetida to soils was assessed through the analysis of neurotoxic, oxidative stress, energy metabolism and DNA damage biomarkers (acetylcholinesterase, catalase, glutathione-s-transferase, lactate dehydrogenase, lipid peroxidation and DNA strand breaks). Metal bioaccumulation was also assessed to evaluate bioavailability and organism's exposure. Results showed that high contents of PTEs were recorded in the whole body of earthworms exposed to lead/zinc mine. However, the bioaccumulation factors for worms exposed to soils from both sampling sites were <1 due to the high PTEs contents in soils. Earthworms exposed to both types of soils displayed neurotoxic and energy metabolism effects. However, significant levels of oxidative stress and DNA damage were recorded only for earthworms exposed to lead/zinc mine soils. This study demonstrated that despite the low availability of PTEs showed by previous sequential chemical extractions, the results obtained from the direct toxicity assessment performed in this study, highlight the importance of a multibiomarker approach using soil organisms to provide a better evaluation of soils pollution.

Do the joint effects of size, shape and ecocorona influence the attachment and physical eco(cyto)toxicity of nanoparticles to algae?

We systematically investigated how the combinations of size, shape and the natural organic matter (NOM)-ecocorona of gold (Au) engineered nanoparticles (ENPs) influence the attachment of the particles to algae and physical toxicity to the cells. Spherical (10, 60 and 100 nm), urchin-shaped (60 nm), rod-shaped (10 × 45, 40 × 60 and 50 × 100 nm), and wire-shaped (75 × 500, 75 × 3000 and 75 × 6000 nm) citrate-coated and NOM-coated Au-ENPs were used. Among the spherical particles only the spherical 10 nm Au-ENPs caused membrane damage to algae. Only the rod-shaped 10 × 45 nm induced membrane damage among the rod-shaped Au-ENPs. Wire-shaped Au-ENPs caused no membrane damage to the algae. NOM ecocorona decreased the membrane damage effects of spherical 10 nm and rod-shaped 10 × 45 nm ENPs. The spherical Au-ENPs were mostly loosely attached to the cells compared to other shapes, whereas the wire-shaped Au-ENPs were mostly strongly attached compared to particles with other shapes. NOM ecocorona determined the strength of Au-ENPs attachment to the cell wall, leading to the formation of loose rather than strong attachment of Au-ENPs to the cells. After removal of the loosely and strongly attached Au-ENPs, some particles remained anchored to the surface of the algae. The highest concentration was detected for spherical 10 nm Au-ENPs followed by rod-shaped 10 × 45 nm Au-ENPs, while the lowest concentration was observed for the wire-shaped Au-ENPs. The combined effect of shape, size, and ecocorona controls the Au-ENPs attachment and physical toxicity to cells.

Development of methods for extraction and analytical characterization of carbon-based nanomaterials (nanoplastics and carbon nanotubes) in biological and environmental matrices by asymmetrical flow field-flow fractionation.

Suitable methods and fit-for-purpose techniques are required to allow characterization of carbon-based nanomaterials (CB-NMs) in complex matrices. In this study, two methods were developed; a method for extraction and characterization of CB-NMs in biological media and a method for fractionation of natural organic matter (NOM) coated CB-NMs in environmental matrices. The former method was developed by extracting carbon nanotubes (CNTs: sized 0.75 × 3000 nm) and nanoplastics (sized 60, 200 and 600 nm) from eggshells and characterizing the extracted CB-NMs in terms of particle size distribution using asymmetrical flow field-flow fractionation (AF4) coupled with multi-angle light scattering (MALS). The latter method was developed using AF4-MALS to fraction NOM-coated CNT (sized 0.75 × 3000 nm) and nanoplastics (sized 60, 200 and 300 nm) in a simulated natural surface water and provide information about the size distribution of the CB-NM-NOM complexes. The developed AF4-MALS method successfully fractioned the CB-NM-NOM complexes based on hydrodynamic size and provided the size distribution of the complexes. The NOM corona did not shift significantly the median size of the CB-NMs. It influenced however the size distribution of the nanoplastics and CNTs. The sample preparation method failed to extract the CNTs (recovery < 20%) from the matrices of the eggshells while being successful for extracting the nanoplastics (recoveries > 60%). The AF4-MALS fractogram showed that the extraction method did not significantly influence the size distribution of the nanoplastics of 60 and 200 nm size, whereas the peak of 600 nm nanoplastics shifted towards a smaller hydrodynamic size. In conclusion, the developed sample preparation method followed by the developed AF4-MALS method can be applied for extraction, separation and characterization of CB-NMs in biological and environmental matrices. Thus, the methods have a high potential to be methods of choice to investigate CB-NMs in future studies.

Interaction of zero valent copper nanoparticles with algal cells under simulated natural conditions: Particle dissolution kinetics, uptake and heteroaggregation.

Some metal-based engineered nanoparticles (ENPs) undergo fast dissolution and/or aggregation when they are released in the environment. The underlying processes are controlled by psychochemical/biological parameters of the environment and the properties of the particles. In this study, we investigated the interaction between algal cells and zero valent copper nanoparticles (Cu0-ENPs) to elucidate how the cells influence the dissolution and aggregation kinetics of the particles and how these kinetics influence the cellular uptake of Cu. Our finding showed that the concentration of dissolved Cu ([Cu]dissolved) in the supernatant of the culture media without algal cells was higher than the [Cu]dissolved in the media with algal cells. In the absence of the cells, dissolved organic matter (DOC) increased the dissolution of the particle due to increasing the stability of the particles against aggregation, thus increasing the available surface area. In the presence of algae, Cu0-ENPs heteroaggregated with the cells. Thus, the available surface area decreased over time and this resulted in a low dissolution rate of the particles. The DOC corona on the surface of the particles increased the heteroaggregation of the particles with the cells and decreases the uptake of the particles. Our findings showed that microorganisms influence the fate of ENPs in the environment, and they do so by modifying the dissolution and aggregation kinetics of the Cu0-ENPs.

Dissolution and aggregation kinetics of zero valent copper nanoparticles in (simulated) natural surface waters: Simultaneous effects of pH, NOM and ionic strength.

The combined effects of pH, dissolved organic carbon (DOC) and Ca2+/Mg2+ on the dissolution and aggregation kinetics of zero valent copper engineered nanoparticles (Cu0 ENPs) were investigated. The dissolution and aggregation of the particles were studied in (a) synthetic aqueous media, similar in chemistry to natural surface waters, and (b) natural surface waters samples, for up to 32 or 24 h. The DOC stabilized the particles and prevented aggregation, and thus increased the available surface area. The higher available surface area in turn accelerated the dissolution of the particles. The presence of Ca2+/Mg2+, however, changed the aggregation and the dissolution of the DOC-stabilized particles. The influence of Ca2+/Mg2+ on DOC-stabilized particles was different at different pH's. In the absence of DOC, 10 mM of Ca2+/Mg2+ induced charge reversal on the particles and caused particle stability against aggregation. This subsequently increased particles dissolution. The results obtained with regard to dissolution and aggregation of the particles in natural surface waters were compared with those determined for the synthetic waters. This comparison showed that the behavior of the particles in the natural surface waters was mostly similar to the behavior determined for media at pH 9. Overall, the current study provides some novel insights into the simultaneous effects of physicochemical parameters of water on particle stability against aggregation and dissolution, and provides data about how the processes of aggregation and dissolution of Cu0 ENPs interact and jointly determine the overall particle fate.

Ability of Cytisus scoparius for phytoremediation of soils from a Pb/Zn mine: Assessment of metal bioavailability and bioaccumulation.

Abandoned mining areas are an environmental concern for aquatic and terrestrial ecosystems due to their unfavourable soil properties and high levels of potentially toxic elements. Despite this, some plant species may grow spontaneously and colonise these areas; being suitable in many cases for restoration practices, since they may accumulate metals in their tissues. This study aims to assess the effectiveness of 14 chemical soil extractants to predict the bioavailability of toxic elements (Cd, Pb and Zn) in soils from the abandoned Pb/Zn mine of Rubiais (NW Spain), based on root and shoot metal contents in Cytisus scoparius (L.) Link, which grows spontaneously in this area. Afterwards, its potential for phytoremediation activities was assessed. Mine soils showed high contents Cd (1.77-14.38 mg kg-1), Pb (850-2137 mg kg-1) and Zn (1754-12090 mg kg-1). Cytisus scoparius grows in spite of these high metal contents; accumulating Zn and Pb in its roots, Zn in the aerial part and excluding mostly Cd from its tissues. None of the extractants used to determine the bioavailable content of Pb allow predicting its availability for C. scoparius. However, LMWOA was the most effective extractant to determine the bioavailability of Cd and Zn for this species. Besides, NH4NO3 and Ca(NO3)2 are also good indicators for Zn bioavailability. The analysis of bioconcentration and translocation factors suggest that C. scoparius behaves like a Zn accumulator plant, whereas alternatively, it behaves like a Pb phytostabiliser and as a Cd excluder species. Thus, C. scoparius can be used as a species for mine soil restoration, decreasing the mobility of metals and preventing their dispersion to another ecosystem compartments.

Cistus monspeliensis L. as a potential species for rehabilitation of soils with multielemental contamination under Mediterranean conditions.

The Iberian Pyrite Belt (IPB; SW of the Iberian Peninsula) is one of the most important volcanogenic massive sulphide ore deposits in the world. Cistus monspeliensis L. is a native woody shrub that grows spontaneously in non-contaminated soils as well as in soils with multielemental contamination from the IPB. In this study, different ecophysiological parameters of C. monspeliensis growing in soils with different levels of metal(loid)s were evaluated to assess the potential of this species for revegetation of degraded areas. Composite samples of plants and rhizosphere soils were sampled in São Domingos and Lousal mines and in a reference area without soil contamination (Pomarão, Portugal) (Portuguese sector of IPB). Classical characterisation of the soils and quantification of their total and available metal(loid) concentrations were done. Multielemental concentration was determined in plants (shoots and roots). Ecophysiological parameters were also determined in shoots: concentrations of pigments (chlorophylls, anthocyanins and carotenoids), antioxidants (glutathione and ascorbate) and hydrogen peroxide as well as activities of several antioxidative enzymes. Although mining soils present high total concentrations of potentially hazardous elements, their available fractions were low and similar among studied areas. Soil pH as well as concentrations of extractable P, total concentrations of As, Cd and Ni and concentrations of Cu, Cr, Ni, Pb and Sb in the soil available fraction differentiate the studied areas. Only concentrations of Cd, Pb and Sb in roots and shoots were explained by the concentrations of the same elements in the soil available fraction. Although the majority of elements were translocated from roots to shoots, the shoots concentrations were below the toxic values for domestic animals and only As, Mn and Zn reached phytotoxic concentrations. Ecophysiological parameters were similar independently of the studied area. Due to its adaptability, tolerance and standard plant features, C. monspeliensis is a good choice for rehabilitation of soils with multielemental contamination under similar climatic characteristics.

The physiological mechanisms underlying the ability of Cistus monspeliensis L. from São Domingos mine to withstand high Zn concentrations in soils.

Cistus monspeliensis L. is a species that grows spontaneously in contaminated mining areas from the Iberian Pyrite Belt. This species can have high concentrations of Zn in the shoots without visible signs of phytotoxicity. In order to understand the physiological mechanisms underlying this tolerance, C. monspeliensis was grown at several concentrations of Zn(2+) (0, 500, 1000, 1500, 2000µM) and the effects of this metal on plant development and on the defence mechanisms against oxidative stress were evaluated. Independently of the treatment, Zn was mainly retained in the roots. The plants with the highest concentrations of Zn showed toxicity symptoms such as chlorosis, low leaf size and decrease in biomass production. At 2000µM of Zn, the dry biomass of the shoots decreased significantly. High concentrations of Zn in shoots did not induce deficiencies of other nutrients, except Cu. Plants with high concentrations of Zn had low amounts of chlorophyll, anthocyanins and glutathione and high contents of H2O2. The highest concentrations of Zn in shoots of C. monspeliensis triggered defence mechanisms against oxidative stress, namely by triggering antioxidative enzyme activity and by direct reactive oxygen species (ROS) scavenging through carotenoids, that are unaffected by stress due to stabilisation by ascorbic acid.