An Electroanalytical Solution for the Determination of Pb2+ in Progressive Hair Dyes Using the Cork-Graphite Sensor.

Lead is one of the most toxic metals for living organisms: once absorbed by soft tissues, it is capable of triggering various pathologies, subsequently bioaccumulating in the bones. In consideration of this, its detection and quantification in products for human consumption and use is of great interest, especially if the procedure can be carried out in an easy, reproducible and economical way. This work presents the results of the electroanalytical determination of lead in three different commercial products used as progressive hair dyes. Analyses were performed by cyclic voltammetry (CV) and differential pulse stripping voltammetry (DPSV) using a composite cork-graphite sensor in 0.5M H2SO4 solution or 0.1M acetate buffer (pH 4.5), in the presence and absence of hair dye samples. The H2SO4 solution gave better results in terms of analyte sensitivity than the acetate buffer electrolyte. In both cases, well-defined signals for lead were obtained by DPSV analyses, enabling the calibration curve and figures of merit to be determined. The limits of detection (LOD) were found to be approximately 1.06 µM and 1.26 µM in H2SO4 and acetate buffer, respectively. The DPSV standard addition method was successfully applied to quantify the lead in hair dye samples, yielding values below 0.45% in Pb. All three analyzed samples were shown to comply with the limit set by the Brazilian Health Regulatory Agency, i.e., 0.6% lead in this type of product. The comparison of the electroanalytical results with those obtained by the reference method, based on the use of inductively coupled plasma optical emission spectrometry (ICP-OES), confirmed that the electroanalytical detection approach is potentially applicable as a strategy for quality control.

Dealing with complex contamination: A novel approach with a combined bio-phytoremediation strategy and effective analytical techniques.

Phytoremediation is a sustainable technology capable of efficiently removing low or moderate contamination. However, complex pollution conditions can drastically reduce efficiency, as plants can show themselves sensitive to organic contaminants, growing slowly and thus impairing metals' absorption. In cases where the action of indigenous bacteria degrading hydrocarbons and promoting plant growth is not sufficient, more sophisticated strategies are necessary. This investigation aims to evaluate the effectiveness of a train of technologies that sees advanced phytoremediation in combination with other biological approaches to remediate soil from a disused industrial area contaminated by N-containing compounds, alkyl aromatic hydrocarbons, copper, and nickel. In particular, a stepwise procedure was used with a pre-treatment (landfarming and bioaugmentation), significantly affecting the soil's fertility, increasing germinability up to 85%, and allowing the plants to extract the metals adequately. Furthermore, with EDTA as a mobilizing agent, nickel absorption has increased up to 36% in Helianthus annuus and up to 88% in Zea mays. For copper, an increase of up to 262% in Helianthus annuus and up to 202% in Zea Mays was obtained. Analysis through Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry highlighted the biodegradation of some of the N-containing compounds recording, after phytoremediation, a decrease of up to almost 90%. Metagenomic analysis of the soil showed a typical microbial population of oxidizing hydrocarbon strains with a prevalence of the Nocardiaceae family (43%). The results obtained appear to confirm the usefulness of the approach developed, and the employed cutting-edge analytical techniques allowed a top-notch characterization of the remediation scenario.

Enhancements in phytoremediation technology: Environmental assessment including different options of biomass disposal and comparison with a consolidated approach.

Phytoremediation represents a solution for treating soils contaminated by heavy metals, provided that appropriate plant species are selected and the proper strategy chosen. When dealing with soil contaminated with arsenic and/or lead, which are non-essential elements for plants but also among the most toxic metals, this task is particularly difficult to achieve. In a previous contribution we showed that metals accumulation by Lupinus albus, Brassica juncea and Helianthus annuus can be improved by dosing suitable chemicals (i.e. phosphate and EDTA), leading to a quicker and cheaper intervention. This study discusses the assisted phytoremediation of a real site contaminated by several metals, presenting an environmental assessment realized by using the GaBi LCA software. The environmental sustainability of the reclamation technology was analyzed in terms of Global Warming Potential (GWP-100 years), considering different destinations for the harvested biomass, and comparing its ecological footprint with the outcomes of a conventional treatment of excavation and landfill disposal. The comparison clearly shows the great advantage of the phytoremediation, in terms of environmental impact, highlighting the importance of correctly handling the disposal of contaminated biomass produced. In fact, its incineration (aimed at reducing the volumes to be disposed of) could be more onerous than a direct landfilling, but re-qualify as a more sustainable choice if combined with energy recovery. The same applies to fast pyrolysis, which seems to be the most sustainable approach to date, at least in terms of technological maturity, although this requires technical-economic considerations on the quality and use of biofuels produced.

Removal of Mn and As from drinking water by red mud and pyrolusite.

Due to limited economic resources, which impede access to specific advanced technologies, many developing countries are still facing the challenge of reducing human exposure to heavy metals, which is primarily associated with the consumption of water contaminated through the discharge of poorly treated wastewater. In wastewater treatment technology, adsorption is sometime preferred to other approaches because of its high efficiency, easy handling, availability of different substrates and cost effectiveness. Moreover, increasing emphasis has recently been given to the use of low-cost adsorbents (generally solid wastes) for the treatment of polluted water, with a resulting double benefit for the environment. In this paper, the use of red mud and pyrolusite has been investigated for the removal of As and Mn from drinking water. Adsorption equilibrium data have been examined through the application of constant temperature models (isotherms), while batch and dynamic tests have been used to clarify the effects of pH, initial metal ion concentration and temperature on the adsorption performance, aiming at identifying the best conditions for the treatment. The combined use of the two adsorbents allows exploiting their properties synergistically, maximizing efficacy and sustainability without affecting process design and costs. In particular, 'clean' water (i.e. water with heavy metals contents below law limits) has been obtained even after the passage of a volume of solution higher than 40 bed volumes, and considering initial unrealistically high concentrations for the metals.

Electrokinetic remediation of soils contaminated by potentially toxic metals: Dedicated analytical tools for assessing the contamination baseline in a complex scenario.

In order to assess the capabilities of a remediation technology, and to judge of its efficacy, it is necessary to evaluate the initial average contamination level of the soil, an operation that can be difficult because of the inhomogeneity of the contamination itself. The goal is even more challenging when different contaminants are present, greatly differing both in terms of nature and of concentration. By referring to an industrial site contaminated mainly by As, Cd, Cu, Pb, Sb, Tl and Zn, we present a new approach for the necessary processing of sampling data, in order to establish the pre-intervention baseline: an estimate of the average contamination has been obtained through a suitable integration of the volume underlying the distribution curve of each contaminating species. This information, otherwise not accessible by means of sampling of discrete points, is useful in evaluating the effectiveness of the remediation technology under investigation, and can also be considered for other reclamation approaches as well. Since "chemometrically acceptable" results are typically achieved by increasing the number of samples (with related analytical investments), the proposed approach can help keep low these ancillary costs, while providing results that are more reliable.

Assisted phytoremediation of a multi-contaminated soil: Investigation on arsenic and lead combined mobilization and removal.

The removal of contaminants from an earthy matrix by phytoremediation requires the selection of appropriate plant species and a suitable strategy to be effective. In order to set up an assisted phytoremediation intervention related to a disused industrial site affected by an arsenic and lead complex contamination, an extensive experimental investigation on micro and mesocosm scale has been conducted. Particular attention was given to the choice of plant species: using crop plants (Lupinus albus, Helianthus annuus and Brassica juncea) a series of parallel test campaigns have been realized to investigate different scenarios for the reclamation. With regard to the arsenic contamination, which is certainly the most worrying, the possibility of employing a hyper-accumulator species (Pteris vittata) has also been investigated, highlighting advantages and difficulties associated with such an approach. The application of various mobilizing agents in different concentrations was tested, in order to maximize the extraction efficiency of plants in respect of both contaminants, showing the necessity of a chemically assisted approach to promote their uptake and translocation in the shoots. Phosphate addition appears to produce the desired results, positively affecting As phyto-extraction for both hyper-accumulator and crop plants, while minimizing its toxic effects at the investigated concentrations. With regard to Pb, although tests with EDDS have been encouraging, EDTA should be preferred at present due to lower uncertainties about its effectiveness. The performed tests also improved the addition of mobilizing agents, allowing the simultaneous removal of the two metals despite their great diversity (which in general discourages such approach), with significant saving of time and an obvious improvement of the overall process.

A Novel Graphite-Based Sorbent for Oil Spill Cleanup.

The performance of an innovative material based on expanded graphite, Grafysorber® G+ (Directa Plus), has been tested through laboratory, tank, and confinement tests for oil removal in case of an oil spill and water treatment. In addition to the ability to retain oil, the possibility of reusing this material after regeneration via squeezing was also evaluated. As a comparison, the same experimental tests were conducted using polypropylene flakes (PP), the material currently most used to deal with spill accidents. Oils with different chemical and physical properties were used, namely kerosene, diesel, and crude oil. From the laboratory tests, the capacity of Grafysorber® G+ to retain oil was found to be directly proportional to the viscosity of the latter, with adsorption values ranging from 76.8 g/g for diesel to 50.8 g/g for kerosene, confirming the potential of the innovative material compared to the PP. Cyclical use tests have confirmed certain reusability of the material, even if its adsorbent capacity decreases significantly after the first cycle and continues to decrease in subsequent cycles, but a less marked manner. Finally, some considerations based on the adsorption capacities were found to suggest that the adoption of the new material is also economically preferable, resulting in savings of 20 to 40% per kg of hydrocarbon treated.

Nature-Based Solutions for Restoring an Agricultural Area Contaminated by an Oil Spill.

A feasibility study is presented for a bioremediation intervention to restore agricultural activity in a field hit by a diesel oil spill from an oil pipeline. The analysis of the real contaminated soil was conducted following two approaches. The first concerned the assessment of the biodegradative capacity of the indigenous microbial community through laboratory-scale experimentation with different treatments (natural attenuation, landfarming, landfarming + bioaugmentation). The second consisted of testing the effectiveness of phytoremediation with three plant species: Zea mays (corn), Lupinus albus (lupine) and Medicago sativa (alfalfa). With the first approach, after 180 days, the different treatments led to biodegradation percentages between 83 and 96% for linear hydrocarbons and between 76 and 83% for branched ones. In case of contamination by petroleum products, the main action of plants is to favor the degradation of hydrocarbons in the soil by stimulating microbial activity thanks to root exudates. The results obtained in this experiment confirm that the presence of plants favors a decrease in the hydrocarbon content, resulting in an improved degradation of up to 18% compared with non-vegetated soils. The addition of plant growth-promoting bacteria (PGPB) isolated from the contaminated soil also promoted the growth of the tested plants. In particular, an increase in biomass of over 50% was found for lupine. Finally, the metagenomic analysis of the contaminated soil allowed for evaluating the evolution of the composition of the microbial communities during the experimentation, with a focus on hydrocarbon- oxidizing bacteria.

Removal of polyethylene glycols from wastewater: A comparison of different approaches.

Physicochemical methods such as adsorption on activated carbon, oxidation with either ozone or Fenton reagent, and chemical precipitation (coagulation), were assessed for the removal of polyethylene glycol (PEG) from wastewater. This contaminant is rarely investigated due to its low toxicity, although its presence limits the use of large water resources. The experimental tests showed that adsorption on activated carbon is well approximated by a Langmuir isotherm, and influenced by contact time, PEG molecular weight, pH, temperature, and initial PEG concentration. Ozonation allowed fragmenting the polymeric chains but was unable to remove completely the PEG, while about 85% of the total organic carbon (TOC) was removed by Fenton oxidation reaction by using a ratio between H2O2 and FeII close to 4. Coagulation did not produce results worthy of note, most likely because the uncharged PEG molecule does not interact with the iron hydroxide flocs. However, when performed after the Fenton oxidation (i.e., by simply raising the pH to values > 8), it allowed a further reduction of the residual TOC, up to 96% of the total, in the best case. Based on the resources used by each process studied and in consideration of the effectiveness of each of them, a semi-quantitative comparison on the sustainability of the different approaches is proposed.

Nanoparticles Synthesis in Wet-Operating Stirred Media: Investigation on the Grinding Efficiency.

The use of nanomaterials, thanks to their peculiar properties and versatility, is becoming central in an increasing number of scientific and engineering applications. At the same time, the growing concern towards environmental issues drives the seeking of alternative strategies for a safer and more sustainable production of nanoparticles. Here we focus on a low-energy, magnetically-driven wet milling technique for the synthesis of metal nanoparticles starting from a bulky solid. The proposed approach is simple, economical, sustainable, and provides numerous advantages, including the minimization of the nanoparticles air dispersion and a greater control over the final product. This process is investigated by experiments and discrete element method simulations to reproduce the movement of the grinding beads and study the collision dynamics. The effect of several parameters is analyzed, including the stirring bar velocity, its inclination, and the grinding bead size, to quantify the actual frequency, energy, and angle of collisions. Experiments reveal a non-monotonous effect of the stirring velocity on the abrasion efficiency, whereas numerical simulations highlight the prevalent tangential nature of collisions, which is only weakly affected by the stirring velocity. On the other hand, the stirring velocity affects the collision frequency and relative kinetic energy, suggesting the existence of an optimal parameters combination. Although a small variation of the stirring bar length does not significantly affect the collision dynamics, the use of grinding beads of different dimensions offers several tuning opportunities.

Hydrogen Sulfide Adsorption by Iron Oxides and Their Polymer Composites: A Case-Study Application to Biogas Purification.

An experimental study of hydrogen sulfide adsorption on a fixed bed for biogas purification is proposed. The adsorbent investigated was powdered hematite, synthesized by a wet-chemical precipitation method and further activated with copper (II) oxide, used both as produced and after pelletization with polyvinyl alcohol as a binder. The pelletization procedure aims at optimizing the mechanical properties of the pellet without reducing the specific surface area. The active substrate has been characterized in its chemical composition and physical properties by X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), thermogravimetric analysis (TGA) and N2 physisorption/desorption for the determination of surface area. Both powders and pellets have been tested as sorbents for biogas purification in a fixed bed of a steady-state adsorption column and the relevant breakthrough curves were determined for different operating conditions. The performance was critically analyzed and compared with that typical of other commercial sorbents based on zinc oxide or relying upon specific compounds supported on a chemically inert matrix (SulfaTreat®). The technique proposed may represent a cost-effective and sustainable alternative to commercial sorbents in conventional desulphurization processes.

Green Synthesis of Silver Nanoparticles by Low-Energy Wet Bead Milling of Metal Spheres.

A low-energy, magnetically-driven milling technique for the synthesis of silver nanoparticles is proposed, where the grinding medium and the metal precursor consisting of silver spheres have the same shape and size, belonging to a millimetric scale. The process is carried out at room temperature in aqueous solvent, where different types of capping agents have been dissolved to damp particle agglomeration. The particle diameters, determined by dynamic light scattering and transmission electron microscopy, have been compared with those typical of conventional wet-chemical bottom-up synthesis processes. The use of milling spheres and metal precursor of the same initial shape and size allows to overcome some drawbacks and limitations distinctive of conventional bead-milling equipment, generally requiring complex operations of separation and recovery of milling media. The milling bead/nanoparticle diameter ratio obtained by this approach is lower than that typical of most previous wet bead milling techniques. The method described here represents a simple, one-pot, cost-effective, and eco-friendly process for the synthesis of metal nanoparticles starting from a bulky solid.

Improved arsenic phytoextraction by combined use of mobilizing chemicals and autochthonous soil bacteria.

Proper plant selection and application of suitable strategies are key factors to ensure the effectiveness of a reclamation via phytoremediation approach. In this study, micro- and meso-cosm scale experimentation has been realized to address a persistent contamination by arsenic on a disused industrial site through an assisted phytoremediation intervention. Three crop species, namely Brassica juncea, Helianthus annuus and Zea mays, have been considered and the addition of K2HPO4, a common mobilizing agent for As, or (NH4)S2O3, a promising additive for As mobilization in case of mercury co-presence, evaluated. The use of these additives significantly enhanced the bioavailability of the target contaminant and therefore its phytoextraction up to 80%. Furthermore, in order to maximize the extraction efficiency of the plants, the influence of five indigenous Plant Growth Promoting Bacteria (PGPB), in combination with the mobilizing agents, was measured. The addition of the microbial consortium led to a further increase in the total uptake of arsenic, especially in B. juncea (up to 140%). The combined strategy supports and enhances the arsenic phytoextraction together with an improvement of the soil quality, as shown by phytotoxicity tests.

Enhanced Oil Spill Remediation by Adsorption with Interlinked Multilayered Graphene.

The performances of an innovative material based on graphene multilayers in a 3D structure similar to expanded graphite, Grafysorber® G+ (Directa Plus), have been tested via in field applications on a real contaminated site. Several experimental tests were performed using Grafysorber® inside adsorbent devices (booms and pillows) to treat waters polluted by oil. The experimental campaign was carried out with the aim of comparing the performances of Grafysorber® with those of polypropylene (PP), which is the material used worldwide in case of water oil spill clean-up activities. The results achieved have confirmed a considerably higher selective adsorption capacity of Grafysorber® compared to PP, and configure the new material as a promising alternative to standard materials in enhancing oil spill remediation by selective adsorption.