Advancements in Heavy Metal Stabilization: A Comparative Study on Zinc Immobilization in Glass-Portland Cement Binders.

Recent literature has exhibited a growing interest in the utilization of ground glass powder (GP) as a supplementary cementitious material (SCM). Yet, the application of SCMs in stabilizing heavy metallic and metalloid elements remains underexplored. This research zeroes in on zinc stabilization using a binder amalgam of GP and ordinary Portland cement (OPC). This study juxtaposes the stability of zinc in a recomposed binder consisting of 30% GP and 70% OPC (denoted as 30GP-M) against a reference binder of 100% CEM I 52.5 N (labeled reference mortar, RM) across curing intervals of 1, 28, and 90 days. Remarkably, the findings indicate a heightened kinetic immobilization of Zn at 90 days in the presence of GP-surging up to 40% in contrast to RM. Advanced microstructural analyses delineate the stabilization locales for Zn, including on the periphery of hydrated C3S particles (Zn-C3S), within GP-reactive sites (Si*-O-Zn), and amid C-S-H gel structures, i.e., (C/Zn)-S-H. A matrix with 30% GP bolsters the hydration process of C3S vis-à-vis the RM matrix. Probing deeper, the microstructural characterization underscores GP's prowess in Zn immobilization, particularly at the interaction zone with the paste. In the Zn milieu, it was discerning a transmutation-some products born from the GP-Portlandite reaction morph into GP-calcium-zincate.

Assessment of Dynamic Surface Leaching of Monolithic Polymer Mortars Comprised of Wastes.

Today, the reuse of waste in building materials occupies an important place in the approach to the circularity of materials. National and European environmental regulations require ensuring the environmental safety of material-incorporating waste. For this, there are specific tests to verify that there is no health risk when using these materials. Concretely, to check the environmental acceptability of construction materials, including wastes, the release of hazardous substances into water must be assessed. In this research, we performed a diffusion test with the sequential renewal of water during a 64-day period according to the NF EN 15863 specifications on polymer mortar monoliths, common construction products used in floor-covering applications and incorporating sediments. Polymer mortars were prepared at a laboratory scale by incorporating 30 or 50% of polluted sediment for various polymer concentrations (12, 14, 16, 18, 20 and 25%). It was shown that the release of inorganic substances is limited in these hydrodynamic conditions. Among trace elements, As, Cd, Cr, Ni, Pb and Zn are lower than quantification limits in most leachates, whereas Ba, Co, Cu and V are systematically quantified at low concentration levels. This is particularly true for samples displaying the highest polymer concentration (25%) and the lowest sediment incorporation rate (30%). This is because of the low water absorption level and low porosity of polymer mortar matrices. No adverse effect is to be expected for environmental health from the leachates of these construction materials, including waterways sediments, because all the measured parameters were below the Soil Quality Decree limits applied in the Netherlands for environmental assessment of construction products.

Storage facilities reclamation using dredged sediments from waterways: Growing media formulation for plants according to the EU Ecolabel requirements.

Dredged sediments display a great potential for growing media applications; however, there are few studies about their beneficial reuse for the waste storage reclamation. This research study aims at checking the agronomic values and environmental impacts of three growing media based on waterways sediments (WSs) and green waste (GW) according ecolabel requirements. For this purpose, three growing media named GW0, GW25, and GW50 were prepared at field pilot scale by co-composting WS and GWs during 12 months. Samples were submitted to ecolabel analyses package. Following to the ecolabel requirements, the growing media comply with criteria like pH, electrical conductivity, trace elements and polycyclic aromatic hydrocarbon contents, chlorides, and pathogens, whereas they are not in compliance with the EU Ecolabel guidelines for propagules, organic matter, and zinc contents. Results of laboratory leaching tests performed according to NF EN 12457-2 for GW0, GW25, and GW50 have shown that sulfates, soluble fraction exceed limit for inert waste storage. Lysimeter tests at pilot scale were performed during 6 months to check the leaching potential of pollutants from growing media under real field conditions, including a European ecolabel product. Results demonstrate that Ba, Mo, Sb, Zn, Se, and Sb are higher in GW0, GW25, and GW50 than in the European ecolabel. As, Cd, Cr, Ni, and F- are more soluble in the commercial product compared to other growing media. This study allowed to demonstrate that main characteristics are fulfilling for reusing these growing media in the specific field of waste storage reclamation.

Investigation of a biosurfactant-enhanced electrokinetic method and its effect on the potentially toxic trace elements in waterways sediments.

In this study, the biosurfactant-enhanced electrokinetic method was investigated for the removal of potentially toxic trace elements (As, Ba, Cd, Cr, Cu, Mo, Ni, Pb, Sb, Se and Zn) in waterways sediments. The effect of this method was compared to the removal capacities of deionized water in the same conditions in order to assess its efficiency. After treatment, batch leaching tests have shown that almost toxic elements (As: 81.3%; Ba: 80%; Cr: 97.3%; Cu: 82%; Zn: 94.5%; Mo: 13.8%; Ni: 62.7%; Se: 66.8% and Sb: 9.3%) were less released in waters. On the whole sediment samples, Ba and Cd displayed the highest removal rates (Ba: 71.2% and Cd: 77.5%). The use of biosurfactant enhanced the electrokinetic method by improving the trace elements migration and altering pH and Eh locally generated by the system. Overall, the application of this new approach dredged sediments seems to be promising but needed further investigations for industrial applications.

Over-sulfated soils and sediments treatment: A brief discussion on performance disparities of biological and non-biological methods throughout the literature.

High sulfate concentrations in industrial effluents as well as solid materials (excavated soils, dredged sediments, etc.) are a major hindrance for circular economy outlooks. SO42- acceptability standards are indeed increasingly restrictive, given the potential outcomes for public health and ecosystems. This literature review deals with the treatment pathways relying on precipitation, adsorption and microbial redox principles. Although satisfactory removal performances can be achieved with each of them, significant yield differences are displayed throughout the bibliography. The challenge here was to identify the parameters leading to this variability and to assess their impact. The precipitation pathway is based on the formation of two main minerals (ettringite and barite). It can lead to total sulfate removal but can also be limited by aqueous wastes chemistry. Stabilizer kinetics of formation and equilibrium are highly constrained by background properties such as pH, Eh, SO42- saturation state and inhibiting metal occurrences. Regarding the adsorption route, sorbents' intrinsic features such as the qmax parameter govern removal yields. Concerning the microbial pathway, the chemical oxygen demand/SO42- ratio and the hydraulic retention time, which are classically evoked as yield variation factors, appear here to be weakly influential. The effect of these parameters seems to be overridden by the influence of electron donors, which constitute a first order factor of variability. A second order variability can be read according to the nature of these electron donors. Approaches using simple monomers (ethanol lactates, etc.) perform better than those using predominantly ligneous organic matter.

An eco-friendly epoxy polymer binder for the treatment of Tunisian harbor sediments: Laboratory investigations for beneficial reuse.

The management of dredged sediments poses serious environmental and economic problems because of their geochemical properties and in particular their pollutant content. In this research, marine sediments from Tunisian harbors were collected to study their beneficial reuse as construction materials using an eco-friendly polymer binder. Experimental investigations include the determination of physicochemical, mineralogical, and environmental parameters of sediments from the Sidi Mansour and Sidi Youssef areas in Tunisia. Prismatic mortar samples (4 × 4 × 16 cm) were prepared at laboratory scale using normalized sand and epoxy resin. Then their composition was modified by including a sediment fraction in the substitution of sand at rates ranging from 10 to 50% in dry mass. After a 7-day curing period, mortar samples were submitted to mechanical, physicochemical, and environmental analyses. Mortar samples including sediment fractions displayed lower strength than sand mortar used as control. This result is explained by the increase of porosity values in the mortar samples when sediment samples were incorporated. A positive relationship between porosity and compressive strength values was evidenced, suggesting that the compactness of granular skeleton could play an important role in the preparation of materials. From an environmental point of view, the mortar samples containing sediment fractions showed relatively low leaching levels, which confirms their suitability for the manufacturing of construction materials.

Environmental availability and oral bioaccessibility of Cd and Pb in anthroposols from dredged river sediments.

Dredging and disposal of sediments onto land sites is a common practice in urban and industrial areas that can present environmental and health risks when the sediments contain metallic elements. The aim of this study was to characterise and study the environmental and toxicological availability of Cd and Pb in anthroposols from dredged river sediments. To do this, 67 surface samples spread over 12 sediment disposal sites in northern France were studied. The results showed substantial heterogeneity for this matrix in terms of physicochemical parameters and contamination degree; however, ascending hierarchical clustering made it possible to classify the samples into eight groups. For each group, the mobile fraction of Cd and Pb was studied using single EDTA extraction, solid-phase distribution was analysed with sequential extractions and toxicological availability was assessed with the oral bioaccessibility test. The results showed that (i) Cd had a higher environmental and toxicological availability than Pb; (ii) this availability depends on the physicochemical characteristics of the matrix; and (iii) it is necessary to take into account the environmental and toxicological availability of contaminants when requalifying these sites in order to propose appropriate management measures. In the first years after sediment disposal, it would appear that the environmental and toxicological availability of Cd and Pb increased (from 52.5 to 71.8% and from 28.9 to 48.9%, respectively, by using EDTA and from 50.2 to 68.5% for Cd with the bioaccessibility test). Further studies would therefore be required to confirm this trend and understand the mechanisms involved.

Use of hydraulic binders for reducing sulphate leaching: application to gypsiferous soil sampled in Ile-de-France region (France).

Polluted soils are a serious environmental risk worldwide and consist of millions of tons of mineral waste to be treated. In order to ensure their sustainable management, various remediation options must be considered. Hydraulic binder treatment is one option that may allow a stabilisation of pollution and thus offer a valorisation as secondary raw materials rather than considering them as waste. In this study, we focused on sulphate-polluted soil and tested the effectiveness of several experimental hydraulic binders. The aim was to transform gypsum into ettringite, a much less soluble sulphate, and therefore to restrict the potential for sulphate pollutant release. The environmental assessment of five formulations using hydraulic binders was compared to the gypsiferous soil before treatment (contaminated in sulphate). The approach was to combine leaching tests with mineralogical quantifications using among others thermogravimetric and XRD methods. In the original soil and in the five formulations, leaching tests indicate sulphate release above environmental standards. However, hydraulic binders promote ettringite formation, as well as a gypsum content reduction as observed by SEM. The stabilisation of sulphates is, however, insufficient, probably as a result of the very high content of gypsum in the unusual soil used. The mineralogical reactions highlighted during the hydration of hydraulic binders are promising; they could pave the way for the development of new industrial mixtures that would have a positive environmental impact by allowing reuse of soils that would otherwise be classified as waste.

Beneficial reuse of Brest-Harbor (France)-dredged sediment as alternative material in road building: laboratory investigations.

The scarcity of natural aggregates promotes waste reuse as secondary raw material in the field of civil engineering. This article focuses on the beneficial reuse of marine-dredged sediments in road building. Thus, mixtures of raw sediments and dredged sand collected from Brest Harbur (Bretagne, France) were treated with road hydraulic binders. Formulation were prepared and characterized as recommended by the French Technical Guidelines for soil treatment with lime and/or hydraulic binders. Mechanical resistance results are quite similar for both the hydraulic binders, suggesting a similar reactivity with the studied sediment sample. However, some discrepancies can be noted on sustainability parameters. Indeed, water resistance after immersion at 40°C is significantly better for the mixtures treated with cement containing more glass-forming oxides (SiO2 + Al2O3) and fluxing (Fe2O3+CaO + MgO + K2O + Na2O). Moreover, the both hydraulic binders can lead to swelling in the road materials as observed in scanning electron microscopy analyses. Indeed, microscopic observations indicated volumetric swelling of treated samples, which is greatly influenced on the one side by ettringite quantity and on the other hand by the presence of water in pores material.

Relationship between the water-exchangeable fraction of PAH and the organic matter composition of sediments.

The sorption of PAH on 12 different sediments was investigated and was correlated to their corresponding organic matter (OM) content and quality. For this purpose, the OM was precisely characterized using thermal analysis consisting in the successive combustion and quantification of the increasingly thermostable fractions of the OM. Simultaneously, the water-exchangeable fraction of the sorbed PAH defined as the amount of PAH freely exchanged between the water and the sediment (by opposition to the PAH harshly sorbed to the sediments particles) was determined using a passive sampler methodology recently developed. The water concentrations, when the sediment-water system is equilibrated, were also assessed which allows the determination of the sediment-water distribution coefficients without artifacts introduced by the non water-exchangeable fraction of PAH. Hence, the present study provides the distribution coefficients of PAH between the water and 4 different OM fractions combusted at a specific temperature range. The calculated distribution coefficients demonstrate that the sedimentary OM combusted at the intermediate temperature range (between 300 °C and 450 °C) drives the reversible sorption of PAH while the inferred sorption to the OM combusted at a lower and higher temperature range does not dominate the partitioning process.

Simulation of aromatic polycyclic hydrocarbons remobilization from a river sediment using laboratory experiments supported by passive sampling techniques.

Resuspension of bedded sediments was simulated under laboratory-controlled conditions in order to assess the amount of polycyclic aromatic hydrocarbons (PAH) remobilized in the dissolved fraction during one short and vigorous mixing. The desorbed amount of PAH was compared to the exchangeable fraction, the total amount of PAH sorbed on the sediment particles, and the dissolved PAH amount contained in the interstitial pore waters in order to evaluate the contribution of each fraction to the total amount of PAH released. To monitor the desorption of PAH and measure low trace level concentrations, passive samplers were used in an experimental open flow through exposure simulator. Results show that for the selected sediment, a substantial fraction of sorbed PAH (69 % of the total amount) is not available for remobilization in a depleted medium. Obtained data pinpoint that over 9 days, only 0.007 % of PAH are desorbed by passive diffusion through a water-sediment interface area of 415 cm(2) and that an intense resuspension event of 15 min induces desorption of 0.015 % of PAH during the following 9 days. Results also highlight that during resuspension simulation, modifications of the sediment and the water body occurred since partitioning constants of some pollutants between sediment and water have significantly decreased.

Thickness and material selection of polymeric passive samplers for polycyclic aromatic hydrocarbons in water: Which more strongly affects sampler properties?

Three configurations of single-phase polymer passive samplers made of polyoxymethylene (POM), silicone rubber, and polyethylene (PE) were simultaneously calibrated in laboratory experiments by determining their partitioning coefficients and the POM diffusion coefficients and by validating a kinetic accumulation model. In addition, the performance of each device was evaluated under field conditions. With the support of the developed model, the device properties are discussed with regard to material selection and polymer thickness. The results show that a sampler's properties, such as its concentration-averaging period and ability to sample a large amount of polycyclic aromatic hydrocarbons, are widely affected by material selection. Sampler thickness also allows modulation of the properties of the device but with a much lower magnitude. Selection of the appropriate polymer and/or thickness allows samplers to be adapted either for quick equilibration or for the kinetic accumulation regime and promotes either membrane or water boundary layer control of the kinetic accumulation. In addition, membrane-controlled or equilibrated compounds are quantified with greater accuracy because they are not corrected by the performance reference compounds approach. However, the averaged concentrations cannot be assessed when compounds reach equilibrium in the sampler, whereas membrane-controlled devices remaining in the kinetic accumulation regime provide averaged concentrations without requiring performance reference compound correction; detection limits are then increased because of the higher mass transfer resistance of the membrane. Environ Toxicol Chem 2016;35:1708-1717. © 2015 SETAC.

Copper, nickel and zinc speciation in a biosolid-amended soil: pH adsorption edge, µ-XRF and µ-XANES investigations.

Metal solid phase speciation plays an important role in the control of the long-term stability of metals in biosolid-amended soils. The present work used pH-adsorption edge experiments and synchrotron-based spectroscopy techniques to understand the solid phase speciation of copper, nickel and zinc in a biosolid-amended soil. Comparison of metal adsorption edges on the biosolid-amended soil and the soil sample showed that Cu, Ni, and Zn can be retained by both soil and biosolid components such as amorphous iron phases, organic matter and clay minerals. These data are combined with microscopic results to obtain structural information about the surface complexes formed. Linear combination fitting of K-edge XANES spectra of metal hot-spots indicated consistent differences in metal speciation between metals. While organic matter plays a dominant role in Ni binding in the biosolid-amended soil, it was of lesser importance for Cu and Zn. This study suggests that even if the metals can be associated with soil components (clay minerals and organic matter), biosolid application will increase metals retention in the biosolid-amended soil by providing reactive organic matter and iron oxide fractions. Among the studied metals, the long-term mobility of Ni could be affected by organic matter degradation while Cu and Zn are strongly associated with iron oxides.

Fate of nickel in a lime-stabilized biosolid, a calcareous soil and soil-biosolid mixtures.

Soil contamination with anthropogenic metals resulting from biosolid application is widespread around the world. To better predict the environmental fate and mobility of contaminants, it is critical to study the capacity of biosolid-amended soils to retain and release metals. In this paper, nickel adsorption onto a calcareous soil, a lime-stabilized biosolid, and soil-biosolid mixtures (30, 75, and 150 t biosolid/ha) was studied in batch experiments. Sorption experiments showed that (1) Ni adsorption was higher onto the biosolid than the calcareous soil, and (2) biosolid acted as an adsorbent in the biosolid-soil mixtures by increasing Ni retention capacity. The sorption tests were complemented with the estimation of Ni adsorption reversibility by successive applications of extraction solutions with water, calcium (100 mg/L), and oxalic acid (equivalent to 100 mg carbon/L). It has been shown that Ni desorption rates in soil and biosolid-amended soils were lower than 30 % whatever the chemical reagent, indicating that Ni was strongly adsorbed on the different systems. This adsorption/desorption hysteresis effect was particularly significant at the highest biosolid concentration (150 t/ha). Finally, an adsorption empirical model was used to estimate the maximum permissible biosolid application rate using French national guideline. It has been shown that desorption effects should be quantitatively considered to estimate relevant biosolid loadings.

Impact of lime-stabilized biosolid application on Cu, Ni, Pb and Zn mobility in an acidic soil.

A soil column leaching study was conducted on an acidic soil in order to assess the impact of lime-stabilized biosolid on the mobility of metallic pollutants (Cu, Ni, Pb and Zn). Column leaching experiments were conducted by injecting successively CaCl2, oxalic acid and ethylenediaminetetraacetic acid (EDTA) solutions through soil and biosolid-amended soil columns. The comparison of leaching curves showed that the transport of metals is mainly related to the dissolved organic carbon, pH and the nature of extractants. Metal mobility in the soil and biosolid-amended soils is higher with EDTA than with CaCl2 and oxalic acid extractions, indicating that metals are strongly bound to solid-phase components. The single application of lime-stabilized biosolid at a rate ranging from 15 to 30 t/ha tends to decrease the mobility of metals, while repeated applications (2 × 15 t/ha) increase metal leaching from soil. This result highlights the importance of monitoring the movement and concentrations of metals, especially in acid and sandy soils with shallow and smaller water bodies.

Comparison of mineral-based amendments for ex-situ stabilization of trace elements (As, Cd, Cu, Mo, Ni, Zn) in marine dredged sediments: a pilot-scale experiment.

Trace element pollution of marine dredged sediments is an emerging problem all over the world. Comparing to other wastes, trace elements stabilization is more difficult both due to the wide range of contaminants present in the marine sediments and their inherent physicochemical properties. In this study, a pilot-scale experiment was performed to stabilize As, Cd, Cu, Mo, Ni, and Zn in a multi-contaminated sediment sample using hematite, zero-valent iron and zeolite. Results showed that iron-based amendments were able to reduce the leaching and the bioavailability of trace elements in the sediment sample, while zeolite was unsuitable. Chemical stabilization through iron-based amendments seems to be a promising approach as a low-cost alternative to traditional stabilization methods involving chemical reagents.

Batch and column studies of the stabilization of toxic heavy metals in dredged marine sediments by hematite after bioremediation.

The management of dredged sediments is an important issue in coastal regions where the marine sediments are highly polluted by metals and organic pollutants. In this paper, mineral-based amendments (hematite, zero-valent iron and zeolite) were used to stabilize metallic pollutants (As, Cd, Cu, Mo, Ni, Pb, and Zn) in a contaminated marine sediment sample. Mineral-based amendments were tested at three application rates (5 %, 10 %, and 15 %) in batch experiments in order to select the best amendment to perform column experiments. Batch tests have shown that hematite was the most efficient amendment to stabilize inorganic pollutants (As, Cd, Cu, Mo, Ni, Pb, and Zn) in the studied sediment. Based on batch tests, hematite was used at one application rate equal to 5 % to conduct column experiments. Column tests confirmed that hematite was able to decrease metal concentrations in leachates from stabilized sediment. The stabilization rates were particularly high for Cd (67 %), Mo (80 %), and Pb (90 %). The Microtox solid phase test showed that hematite could decrease significantly the toxicity of stabilized sediment. Based on batch and column experiments, it emerged that hematite could be a suitable adsorbent to stabilize metals in dredged marine sediment.

Arsenic in marine sediments from French Mediterranean ports: geochemical partitioning, bioavailability and ecotoxicology.

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 Lkg(-1)) than in EST (55 Lkg(-1)), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.

Impact of sewage sludge spreading on nickel mobility in a calcareous soil: adsorption-desorption through column experiments.

A soil column adsorption-desorption study was performed on an agricultural calcareous soil to determine the impact of sewage sludge spreading on nickel mobility. Ni adsorption experiments were followed by desorption tests involving the following liquid extractants: water, calcium (100 mg/L), oxalic acid (525 mg/L equivalent to 100 mg carbon/L), and sludge extracts (0.5 and 2.5 g/L). Desorption tests were also conducted after sewage sludge spreading at three application rates (30, 75, and 150 t/ha). According to the breakthrough curve, Ni adsorption was irreversible and occurred mainly through interactions with calcite surface sites. Nickel desorption from the soil column was promoted in presence of significant dissolved organic carbon (DOC) concentration as observed with oxalic acid elution and sludge extract at 2.5 g/L. In sludge-amended soil columns, the maximum Ni levels occurred in first pore volumes, and they were positively correlated to the sludge application rate. The presence of DOC in leaching waters was the main factor controlling Ni desorption from the sludge-amended soil columns. This finding implies that DOC generated by sludge applied on calcareous soils might facilitate the leaching of Ni due to the formation of soluble Ni-organic complexes. Thus, sludge application can have potential environmental impacts in calcareous soils, since it promotes nickel transport by decreasing Ni retention by soil components.

Ex situ remediation of contaminated sediments using mineral additives: assessment of pollutant bioavailability with the Microtox solid phase test.

The aim of this work is to assess the potential ecotoxicological effects of contaminated sediments treated with mineral additives. The Microtox solid phase test was used to evaluate the effect of mineral additives on the toxicity of sediment suspensions. Four Mediterranean port sediments were studied after dredging and bioremediation: Sample A from navy harbor, sample B from commercial port and samples C and D from pleasure ports. Sediment samples were stabilized with three mineral additives: hematite, zero-valent iron and zeolite. Results show that all studied mineral additives can act as stabilizer agent in highly contaminated sediments (A and C) by decreasing dissolved metal concentrations and sediment toxicity level. On the contrary, for the less contaminated samples (B and D) hematite and zeolite can provoke toxic effect towards Vibrio fischeri since additive particles can favor bacteria retention and decrease bioluminescence emission.