Suitability of using diffusive gradients in thin films (DGT) to study metal bioavailability in mine tailings: possibilities and constraints

Background, aim, and scope: Diffusive gradients in thin films (DGT) have been recognized as a suitable tool to assess in situ metal bioavailability in soils. Mine tailings have some singular characteristics such as high heavy-metal concentrations, low pH, or absence of water retention capacity that may compromise the correct application of this technique whose applicability is known to be pH dependent. The goal of this study was to determine the response of DGT devices in heavy-metal-polluted mine tailings with different pH. In addition some experiments were performed in order to determine the effect of acidic pH and dissolved ions on the binding properties of the chelating resin. Materials and methods: We tested DGT devices on three different mine tailings: acid pH 3, acid tailing limed to pH 5.5, and neutral pH 7.2. The tailings showed high metal concentrations, e.g., 7,000mgkg−1 Pb, 9,000mgkg−1 Zn, and 380mgkg−1 Cu. Diffusive and Chelex resin gels were prepared according to previously published methods. Two chelating resins and diffusive gels thicknesses (0.4 and 0.7mm) were tested. Four DGT devices of each type were placed during 24h in pots (one device per pot) containing 1kg mine tailings in a climate chamber with humidity (50-90%) and controlled temperature conditions (night 16°C and day 23°C). Pots were irrigated with deionized water to field capacity, and then two different experiments were performed: (a) allowing free drainage and (b) maintaining the water saturation. In addition, we tested DGT devices in solutions at pH 3 with similar properties to the soil solution measured in the acid tailing. Eluted Zn, Cd, Pb, and Cu from the chelating resins were measured using inductively coupled plasma-optical emission spectrometer (ICP-OES; Vista-MPX Varian). Results and discussion: The metal concentrations taken up by the DGT devices were affected by the different pH values of the tailings. The highest metal concentrations measured with DGT (C DGT) were obtained in the pH 3 treatments (both saturated and free drainage). Significant differences for C DGT were observed between water-saturated and free drainage treatments in the acid pH 3 tailing. When limed pH 5.5 tailing and neutral pH 7 tailing were considered, these differences were lower and not significant. In pH 3 tailings low values for C DGT/C soil solution were obtained (<0.06), indicating that these soils have a low capacity to resupply depleted metals to the solution. The limed acid tailing and the neutral tailing showed values between 0.05 and 0.94 indicating a much more rapid resupply from the solid phase. Deployment under water-saturated conditions yielded much higher C DGT values than under free drainage, indicating the importance to adequately control the moisture content in these soils with poor water retention capacity. In solutions with pH 3 mimicking the soil solution composition of the tailings, a loss of the binding capacity of the resin of 50-60% and 60-80% for Zn in 0.7-mm DGT and 0.4-mm DGT devices, respectively, was observed. As a consequence, 0.7-mm DGT devices had better reliability to carry out in situ determinations in solutions with high metal concentrations and low pH. Conclusions: The use of DGT in mining soils can be a promising tool to study bioavailable metals concentrations in mine tailings but it has to be used carefully under acidic pH. Competition with other cations that are present at very high concentrations may hinder the accumulation of metals by the chelating resins, which should be tested under the conditions of the particular mine tailin

A Laboratory Study on Revegetation and Metal Uptake in Native Plant Species from Neutral Mine Tailings

Lygeum spartum, Zygophyllum fabago and Piptatherum miliaceum are typical plant species that grow in mine tailings in semiarid Mediterranean areas. The aim of this work was to investigate metal uptake of these species growing on neutral mine tailings under controlled conditions and their response to fertilizer additions. A neutral mine tailing (pH of soil solution of 7.1-7.2) with high total metal concentrations (9,100 and 5,200mg kg−1 Zn and Pb, respectively) from Southern Spain was used. Soluble Zn and Pb were low (0.5 and <0.1mg l−1, respectively) but the major cations and anions reached relatively high levels (e.g. 2,600 and 1,400mg l−1 Cl and Na). Fertilization caused a significant increase of the plant weight for the three species and decreased metal accumulation with the exception of Cd. Roots accumulated much higher metal concentrations for the three plants than shoots, except Cd in L. spartum. Shoot concentrations for the three plants were 3-14mg kg−1 Cd, 150-300mg kg−1 Zn, 4-11mg kg−1 Cu, and 1-10mg kg−1 As, and 6-110mg kg−1 Pb. The results indicate that neutral pH mine tailings present a suitable substrate for establishment of these native plants species and fertilizer favors this establishment. Metal accumulation in plants is relatively low despite high total soil concentration

Industrial production quantities and uses of ten engineered nanomaterials in Europe and the world

Not much is known so far about the amounts of engineered nanomaterials (ENM) that are produced but this information is crucial for environmental exposure assessment. This paper provides worldwide and Europe-wide estimates for the production and use of ten different ENM (TiO2, ZnO, FeO x , AlO x , SiO2, CeO2, Ag, quantum dots, CNT, and fullerenes) based on a survey sent to companies producing and using ENM. The companies were asked about their estimate of the worldwide or regional market and not about their company-specific production, information that they would be less likely to communicate. The study focused on the actual production quantities and not the production capacities. The survey also addressed information on distribution of the produced ENM to different product categories. The results reveal that some ENM are produced in Europe in small amounts (less than 10t/year for Ag, QDs and fullerenes). The most produced ENM is TiO2 with up to 10,000t of worldwide production. CeO2, FeO x , AlO x , ZnO, and CNT are produced between 100 and 1000t/year. The data for SiO2 cover the whole range from less than 10 to more than 10,000t/year, which is indicative of problems related to the definition of this material (is pyrogenic silica considered an ENM or not?). For seven ENM we have obtained the first estimates for their distribution to different product categories, information that also forms the base for life-cycle based exposure analysi

Sampling, defining, characterising and modeling the rhizosphere—the soil science tool box

We review methods and models that help to assess how root activity changes soil properties and affects the fluxes of matter in the soil. Subsections discuss (1) experimental systems including plant treatments in artificial media, studying the interaction of model root and microbial exudates with soil constituents, and microcosms to distinguish between soil compartments differing in root influence, (2) the sampling and characterization of rhizosphere soil and solution, focusing on the separation of soil at different distances from roots and the spatially resolved sampling of soil solution, (3) cutting-edge methodologies to study chemical effects in soil, including the estimation of bioavailable element or ion contents (biosensors, diffusive gradients in thin-films), studying the ultrastructure of soil components, localizing elements and determining their chemical form (microscopy, diffractometry, spectroscopy), tracing the compartmentalization of substances in soils (isotope probing, autoradiography), and imaging gradients in-situ with micro electrodes or gels or filter papers containing dye indicators, (4) spectroscopic and geophysical methods to study the plants influence on the distribution of water in soils, and (5) the modeling of rhizosphere processes. Macroscopic models with a rudimentary depiction of rhizosphere processes are used to predict water or nutrient requirements by crops and forests, to estimate biogeochemical element cycles, to calculate soil water transport on a profile scale, or to simulate the development of root systems. Microscopic or explanatory models are based on mechanistic or empirical relations that describe processes on a single root or root system scale and/or chemical reactions in soil solution. We conclude that in general we have the tools at hand to assess individual processes on the microscale under rather artificial conditions. Microscopic, spectroscopic and tracer methods to look at processes in small "aliquots” of naturally structured soil seem to step out of their infancy and have become promising tools to better understand the complex interactions between plant roots, soil and microorganisms. On the field scale, while there are promising first results on using non-invasive geophysical methods to assess the plant's influence on soil moisture, there are no such tools in the pipeline to assess the spatial heterogeneity of chemical properties and processes in the field. Here, macroscopic models have to be used, or model results on the microscopic level have to be scaled up to the whole plant or plot scale. Upscaling is recognized as a major challeng

Review of nanomaterial aging and transformations through the life cycle of nano-enhanced products

International audienceIn the context of assessing potential risks of engineered nanoparticles (ENPs), life cycle thinking can represent a holistic view on the impacts of ENPs through the entire value chain of nano-enhanced products from production, through use, and finally to disposal. Exposure to ENPs in consumer or environmental settings may either be to the original, pristine ENPs, or more likely, to ENPs that have been incorporated into products, released, aged and transformed. Here, key product-use related aging and transformation processes affecting ENPs are reviewed. The focus is on processes resulting in ENP release and on the transformation(s) the released particles undergo in the use and disposal phases of its product life cycle for several nanomaterials (Ag, ZnO, TiO 2 , carbon nanotubes, CeO 2 , SiO 2 etc.). These include photochemical transformations, oxidation and reduction, dissolution, precipitation , adsorption and desorption, combustion, abrasion and biotransformation, among other biogeochemical processes. To date, few studies have tried to establish what changes the ENPs undergo when they are incorporated into, and released from, products. As a result there is major uncertainty as to the state of many ENPs following their release because much of current testing on pristine ENPs may not be fully relevant for risk assessment purposes. The goal of this present review is therefore to use knowledge on the life cycle of nano-products to derive possible transformations common ENPs in nano-products may undergo based on how these products will be used by the consumer and eventually discarded. By determining specific gaps in knowledge of the ENP transformation process, this approach should prove useful in narrowing the number of physical experiments that need to be conducted and illuminate where more focused effort can be placed

Modified micro suction cup/rhizobox approach for the in-situ detection of organic acids in rhizosphere soil solution

Root-soil interactions can strongly influence the soil solution chemistry in the rhizosphere. In the present study we propose a modification of the classical rhizobox/micro suction cup system to make it suitable for the collection and analysis of organic acids in the rhizosphere. In order to show the potential of the method, we tested the modified system with Lupinus albus L. as a model plant known to exude large amounts of citrate. The suction cups were installed through the transparent front plate of the rhizoboxes just after the emergence of cluster roots in order to allow optimal localized collection of soil solution. A small dead-volume allowed almost immediate stabilisation with formaldehyde of the sampled soil solutions in the collection container to prevent microbial degradation. The concentrations of organic acids were significantly larger in the rhizosphere soil solution of active cluster roots of Lupinus albus L. than in the bulk soil solution (about 400µM of citrate versus <0.05µM). We were able to follow the exudation process in-situ, which occurred during 2-3days. Also the concentrations of other organic acids and inorganic anions differed between the bulk soil and the rhizosphere of cluster roots, normal roots, and nodule

The release of engineered nanomaterials to the environment

There is scientific agreement that engineered nanomaterial (ENM) production, use and disposal lead to environmental release of ENM. However, very little is known on emissions of ENM to the environment. Currently, techniques are lacking to quantitatively monitor ENM emissions to and concentrations in the environment, and hence data on emissions and environmental concentrations are scarce. One of the few available studies reports the detection of nano-TiO 2 in water leaching from exterior facades. Some experimental evidence is available on the release of nanosized materials from commercial textiles during washing. A handful of modeling studies have investigated ENM release to the environment. These studies modeled either the release of ENMs to the environment from ENM containing products during the consumer usage, or the release throughout the whole life cycle of ENM and ENM-containing products. Sewage sludge, wastewater, and waste incineration of products containing ENM were shown to be the major flows through which ENMs end up in the environment. However, reliable data are particularly lacking on release during ENM production and on the application amounts and empirical information on release coefficients for all life cycle stages and environmental compartments. Quantitative data linking occupational exposure measurements and ENM emission flows into the environment are almost completely missing. Besides knowing the amounts of ENM released into the environment, it is equally important to investigate in what form ENMs are released. First results show that much of the ENM released from products is present in matrix-bound form, but that also some fraction is released as single, dispersed nanoparticles

Application of nanoscale zero valent iron (NZVI) for groundwater remediation in Europe

Purpose: Nanoscale zero valent iron (NZVI) is emerging as a new option for the treatment of contaminated soil and groundwater targeting mainly chlorinated organic contaminants (e.g., solvents, pesticides) and inorganic anions or metals. The purpose of this article is to give a short overview of the practical experience with NZVI applications in Europe and to present a comparison to the situation in the USA. Furthermore, the reasons for the difference in technology use are discussed. Method: The results in this article are based on an extensive literature review and structured discussions in an expert workshop with experts from Europe and the USA. The evaluation of the experiences was based on a SWOT (strength, weakness, opportunity, threat) analysis. Result: There are significant differences in the extent and type of technology used between NZVI applications in Europe and the USA. In Europe, only three full-scale remediations with NZVI have been carried out so far, while NZVI is an established treatment method in the USA. Bimetallic particles and emulsified NZVI, which are extensively used in the USA, have not yet been applied in Europe. Economic constraints and the precautionary attitude in Europe raise questions regarding whether NZVI is a cost-effective method for aquifer remediation. Challenges to the commercialization of NZVI include mainly non-technical aspects such as the possibility of a public backlash, the fact that the technology is largely unknown to consultants, governments and site owners as well as the lack of long-term experiences. Conclusion: Despite these concerns, the results of the current field applications with respect to contaminant reduction are promising, and no major adverse impacts on the environment have been reported so far. It is thus expected that these trials will contribute to promoting the technology in Europ

Silver speciation and release in commercial antimicrobial textiles as influenced by washing

The use of nanoscale Ag in textiles is one the most often mentioned uses of nano-Ag. It has previously been shown that significant amounts of the Ag in the textiles are released upon washing. However, the form of Ag present in the textiles remains largely unknown as product labelling is insufficient. The aim of this study was therefore to investigate the solid phase speciation of Ag in original and washed silver textiles using XANES. The original Ag speciation in the textiles was found to vary greatly between different materials with Ag(0), AgCl, Ag2S, Ag–phosphate, ionic Ag and other species identified. Furthermore, within the same textile a number of different species were found to coexist. This is likely due to a combination of factors such as the synthesis processes at industrial scale and the possible reaction of Ag with atmospheric gases. Washing with two different detergents resulted in marked changes in Ag-speciation. For some textiles the two detergents induced similar transformation, in other textiles they resulted in very different Ag species. This study demonstrates that in functional Ag textiles a variety of different Ag species coexist before and after washing. These results have important implications for the risk assessment of Ag textiles because they show that the metallic Ag is only one of the many silver species that need to be considered

Influence of the initial state of carbon nanotubes on their colloidal stability under natural conditions

The colloidal stability of CNTs varies a lot depending on the initial state of the CNTs (dry vs. pre-dispersed), the applied dispersant for pre-suspension, and the composition of the medium. a r t i c l e i n f o Keywords: Carbon nanotubes Surfactants (anionic, non-ionic, cationic) Natural organic matter (humic/fulvic acid) Long-term colloidal stability a b s t r a c t The colloidal stability of dry and suspended carbon nanotubes (CNTs) in the presence of amphiphilic compounds (i.e. natural organic matter or surfactants) at environmentally realistic concentrations was investigated over several days. The suspensions were analyzed for CNT concentration (UVevis spectroscopy), particle size (nanoparticle tracking analysis), and CNT length and dispersion quality (TEM). When added in dry form, around 1% of the added CNTs remained suspended. Pre-dispersion in organic solvent or anionic detergent stabilized up to 65% of the added CNTs after 20 days of mild shaking and 5 days of settling. The initial state of the CNTs (dry vs. suspended) and the medium composition hence are critical determinants for the partitioning of CNTs between sediment and the water column. TEM analysis revealed that single suspended CNTs were present in all suspensions and that shaking and settling resulted in a fractionation of the CNTs with shorter CNTs remaining predominantly in suspension