Sustainable use of composted sewage sludge: Metal(loid) leaching behaviour and material suitability for application on degraded soils.

Composted sewage sludge was investigated as a promising material for the reclamation or remediation of degraded sites. Using sewage sludge as soil amendment provides environmental benefits and risks while supporting circularity and waste minimisation. This study aims to comprehensively assess the suitability of locally available low-cost sludge treatment for sustainable and environmentally safe topsoil disposal in a brownfield area affected by coal mining. A nine-month composting was conducted before field application to the soil environment. The objectives were to assess: (i) composting time-dependent and pH-dependent metal(loid) leachability from composted sludges, (ii) the effect of sludges on metal(loid) leachability from soil over the first six months, and (iii) metal(loid) plant uptake during the first vegetation season as well as the bioaccumulation and translocation factors. The set of standardised leaching experiments confirmed the positive effect of compost maturity, i.e. despite some fluctuations over time, metal(loid) availability from the final composts was very low. Some metals showed unusual pH-dependent behaviour with the highest leachability at pH 8 due to excessive release of dissolved organic matter from the not-yet-stabilised matrix. Ecotoxicity testing confirmed the safety of the final composts for further soil application. The sludge-amended plots displayed similar metal(loid) leaching and pH evolution in time compared to the control biomass-amended plot. However, plant species (Artemisia vulgaris L.) that formed the natural vegetation cover of the experimental plots showed cumulative metal(loid) uptake. Cadmium and zinc were identified as the critical metals possibly related to the applied sludges, yielding high bioaccumulation and translocation factors. Yet, the quality of the compost feedstock, heterogeneity, and background values of the brownfield site need to be considered. Nevertheless, soil respiration indicated no adverse effects on soil health six months after sludge application. Overall, the composted material demonstrated potential suitability for remediation application in the studied area.

Innovative in situ remediation of mine waters using a layered double hydroxide-biochar composite.

The current demand for alternative water sources requires the incorporation of low-cost composites in remediation technologies. These represent a sustainable alternative to more expensive, commercially used adsorbents. The main objective of this comprehensive field-scale study was to incorporate the layered double hydroxides (LDHs) into the hybrid biochar-based composites and apply an innovative material to remediate As/Sb-rich mine waters. The presence of hydrous Fe oxides (HFOs) within the composite enhanced the total adsorption efficiency of the composite for As(V) and Sb(V). The kinetic data fitted a pseudo-second order model. Equilibrium experiments confirmed that the composite had a stronger interaction with As(V) than with Sb(V). The efficient removal of As(V) from mine water was achieved in both batch and continuous flow column systems, reaching up to 98% and 80%, respectively. Sb(V) showed different behavior to As(V) during mine water treatment, reaching adsorption efficiencies of up to 39% and 26% in batch and column experiments, respectively. The migration of Sb(V) in mine water was mostly attributed to its dispersion before it was able to show affinity to the composite. In general, the proposed column technology is suitable for the field remediation of small volumes of contaminated water, and thus has significant commercial potential.

Health risk assessment of metal(loid)s in soil and particulate matter from industrialized regions: A multidisciplinary approach.

In this study, samples of soil and particulate matter obtained from the highly industrialized region of Ostrava, Czech Republic, are used for the toxicity evaluation of the selected metal(loid)s (Cd, Cr, Cu, Ni, Pb, Zn, As). We investigated the samples from sites supposedly affected the most by the local pollution sources using mineralogical techniques (XRD, SEM/EDS) to understand the solid speciation of the contaminants as the crucial factor affecting their release. Although the bulk composition was defined by common silicates and oxides that are rather resistant to leaching, the presence of tiny Ni, Pb, and/or Zn sulfate-like droplets indicated a potential increase of the solubility of these metals. In vitro tests simulating gastric and lung fluids were used to assess the exposure risk for humans, as well as metal(loid) bioaccessibility. Based on the results, the potential risk for the observed age group (3-year-old children) could be recognized, particularly in the cases of As, Pb and Cd for both oral and inhalation exposure. Arsenic exhibits high bioaccessibility (7.13-79.7%, with the median values of 10.6 and 15.6 for SGL and SLF, respectively), high daily intake (1.4- to 8.5-fold higher than the tolerable daily intake) and high concentrations in atmospheric PM10 (2.5 times the tolerable concentration in air). In contrast, Ni exceeded tolerable concentrations in the atmosphere up to 20-fold, but its bioaccessibility remained relatively low (0.1-22%), and Ni did not pose a major threat to human health. Cadmium, Pb and As originating from industrial activities and domestic heating have been suggested to be the most important pollutants (tolerable daily intake was exceeded by up to 74-, 34- and 8-fold for Cd, Pb and As, respectively).

The role of soil components in synthetic mixtures during the adsorption and speciation changes of Cr(VI): Conjunction of the modeling approach with spectroscopic and isotopic investigations.

This study investigates redox transitions associated with the adsorption of Cr(VI) on commonly occurring soil components (silicates, oxides and humic acids) and their synthetic mixtures by coupling the mechanistic surface complexation modeling with spectroscopic and isotopic analyses. The mixtures of soil components were prepared to reflect the composition of the real anthroposol sample, determined by X-ray Powder Diffraction (XRD), total organic carbon (TOC) measurement and extraction methods. The effect of different initial Cr(VI) concentrations (2×10-2, 5×10-4, 10-4, 10-5, and 10-6M), background electrolyte (10-3, 10-2, and 10-1M KNO3), pH values (3-9), and sorbate/sorbent ratios (2g/L - 20g/L) were investigated. Maghemite and ferrihydrite were confirmed to be the main phases controlling Cr(VI) adsorption with increasing Cr(VI) concentration. Humic acids were primarily responsible for Cr(VI) reduction, especially at low pH values. The reduction of Cr(VI) was also proved in case of illite and kaolinite by XAS and isotopic analyses. Illite revealed higher reduction capacity in comparison with kaolinite based on XAS measurements. Chromium isotopic fractionation, resulting from Cr(VI) reduction, was the highest in the case of humic acids, followed by kaolinite and illite. However, a dissolution of intrinsic Cr originally present within kaolinite and illite might affect the final Cr isotopic composition of the supernatants due to its different Cr isotopic signature. In general, the combination of three different approaches was confirmed to offer more comprehensive information about Cr(VI) adsorption and/or reduction in soils. Detailed studies using soil mixtures can help to predict how the soil components affect Cr(VI) behavior in natural soils and possibly could improve the environmental remediation processes.

Unleaded gasoline as a significant source of Pb emissions in the Subarctic.

After the phasing out of leaded gasoline, Pb emissions to the atmosphere dramatically decreased, and other sources became more significant. The contribution of unleaded gasoline has not been sufficiently recognized; therefore, we evaluated the impact of Pb from unleaded gasoline in a relatively pristine area in Subarctic NE Norway. The influence of different endmembers (Ni slag and concentrate from the Nikel smelter in Russia, PM10 filters, and traffic) on the overall Pb emissions was determined using various environmental samples (snow, lichens, and topsoils) and Pb isotope tracing. We found a strong relationship between Pb in snow and the Ni smelter. However, lichen samples and most of the topsoils were contaminated by Pb originating from the current use of unleaded gasoline originating from Russia. Historical leaded and recent unleaded gasoline are fully distinguishable using Pb isotopes, as unleaded gasoline is characterized by a low radiogenic composition (206Pb/207Pb = 1.098 and 208Pb/206Pb = 2.060) and remains an unneglectable source of Pb in the region.

Suitability of selected bioindicators of atmospheric pollution in the industrialised region of Ostrava, Upper Silesia, Czech Republic.

This study is a continuation of our preceding research identifying suitable environmental samples for the tracing of atmospheric pollution in industrial areas. Three additional types of environmental samples were used to characterise contamination sources in the industrial area of Ostrava city, Czech Republic. The region is known for its extensive metallurgical and mining activities. Fingerprinting of stable Pb isotopes was applied to distinguish individual sources of anthropogenic Pb. A wide range of 206Pb/207Pb ratios was observed in the investigated samples: 206Pb/207Pb = 1.168-1.198 in mosses; 206Pb/207Pb = 1.167-1.215 in soils and 206Pb/207Pb = 1.158-1.184 in tree cores. Black and brown coal combustion, as well as metallurgical activities, is the two main sources of pollution in the area. Fossil fuel burning in industry and households seems to be a stronger source of Pb emissions than from the metallurgical industry. Concentration analyses of tree rings showed that a significant increase in As concentrations occurred between 1999 and 2016 (from 0.38 mg kg-1 to 13.8 mg kg-1). This shift corresponds to the use of brown coal from Bílina, Czech Republic, with an increased As concentration. The burning of low-quality fuels in households remains a problem in the area, as small ground sources have a greater influence on the air quality than do industrial sources.

Stable isotope tracing of Ni and Cu pollution in North-East Norway: Potentials and drawbacks.

The use of Ni and Cu isotopes for tracing contamination sources in the environment remains a challenging task due to the limited information about the influence of various biogeochemical processes influencing stable isotope fractionation. This work focuses on a relatively simple system in north-east Norway with two possible endmembers (smelter-bedrock) and various environmental samples (snow, soil, lichens, PM10). In general, the whole area is enriched in heavy Ni and Cu isotopes highlighting the impact of the smelting activity. However, the environmental samples exhibit a large range of δ60Ni (-0.01 ± 0.03‰ to 1.71 ± 0.02‰) and δ65Cu (-0.06 ± 0.06‰ to -3.94 ± 0.3‰) values which exceeds the range of δ60Ni and δ65Cu values determined in the smelter, i.e. in feeding material and slag (δ60Ni from 0.56 ± 0.06‰ to 1.00 ± 0.06‰ and δ65Cu from -1.67 ± 0.04‰ to -1.68 ± 0.15‰). The shift toward heavier Ni and Cu δ values was the most significant in organic rich topsoil samples in the case of Ni (δ60Ni up to 1.71 ± 0.02‰) and in lichens and snow in the case of Cu (δ65Cu up to -0.06 ± 0.06‰ and -0.24 ± 0.04‰, respectively). These data suggest an important biological and biochemical fractionation (microorganisms and/or metal uptake by higher plants, organo-complexation etc.) of Ni and Cu isotopes, which should be quantified separately for each process and taken into account when using the stable isotopes for tracing contamination in the environment.

Evaluating the suitability of different environmental samples for tracing atmospheric pollution in industrial areas.

Samples of lichens, snow and particulate matter (PM10, 24 h) are used for the source identification of air pollution in the heavily industrialized region of Ostrava, Upper Silesia, Czech Republic. An integrated approach that uses different environmental samples for metal concentration and Pb isotope analyses was applied. The broad range of isotope ratios in the samples indicates a combination of different pollution sources, the strongest among them being the metallurgical industry, bituminous coal combustion and traffic. Snow samples are proven as the most relevant indicator for tracing metal(loid)s and recent local contamination in the atmosphere. Lichens can be successfully used as tracers of the long-term activity of local and remote sources of contamination. The combination of PM10 with snow can provide very useful information for evaluation of current pollution sources.

Metal(loid) distribution and Pb isotopic signatures in the urban environment of Athens, Greece.

Lead concentrations and isotopic compositions of contaminated urban soils and house dusts from Athens, Greece, have been determined to identify possible sources of Pb contamination and examine relationships between these two environmental media. Different soil particle sizes (<2000 µm, <200 µm, <100 µm, <70 µm, <32 µm) and chemical fractions (total, EDTA-extractable and acetic acid-extractable (HAc)) were analyzed for their Pb content and isotopic composition. Metal(loid)s (Pb, Zn, Cu, As, Ni, Cr, Mn, Fe) are significantly enriched in the finest fraction. The Pb isotopic compositions were similar for the different soil particle size fractions and different chemical extractions. The HAc extraction proved to be a useful procedure for tracing anthropogenic Pb in urban soil. The range of (206)Pb/(207)Pb ratios (1.140-1.180) in Athens soil suggests that the Pb content represents an accumulated mixture of Pb deposited from past vehicular emissions and local natural sources. The contribution of anthropogenic Pb to total soil Pb ranged from 36% to 95%. The Pb isotopic composition of vacuum house dusts ((206)Pb/(207)Pb = 1.1.38-1.167) from Athens residents is mostly comparable to that of urban soil suggesting that exterior soil particles are transferred into homes. As a result, anthropogenic Pb in house dust from Athens urban environment principally originated from soil particles containing Pb from automobile emissions (former use of leaded gasoline).

Biosorbent encapsulation in calcium alginate: Effects of process variables on Cr(VI) removal from solutions.

Selected biosorbents, brewers draff and grape waste, have been encapsulated in calcium alginate beads and used for the removal of Cr(VI) from aqueous solutions. The effects of encapsulation variables, including the type of waste, the percentage of waste in the beads and the curing time of the beads in CaCl2, on the diameters of the beads and Cr(VI) sorption kinetics have been evaluated. In total, 21 different types of beads were produced. The diameters of the beads increased with increasing amounts of encapsulated biomaterial. Beads that contained grape waste were larger than those containing brewers draff. The most efficient beads for Cr(VI) removal were beads that contained 4% (w/w) of grape waste. No significant differences in the kinetics of Cr(VI) sorption were found with respect to the curing time variable in the case of grape waste calcium alginate beads. Statistical analysis confirmed that the type and percentage of waste are the critical parameters influencing the diameters of the beads and Cr(VI) removal. It was proven that the sorption efficiencies of the beads containing draff and grape waste encapsulated under the optimum conditions were much higher than the efficiencies obtained when using both wastes in their native states.

Interactions of nano-oxides with low-molecular-weight organic acids in a contaminated soil.

Various low-molecular-weight organic acids (LMWOAs) play an important role in the mobilisation of contaminants and their subsequent uptake by plants. Nano-maghemite (NM) and an amorphous Mn oxide (AMO) were investigated for their stabilisation potential under simulated rhizosphere conditions in terms of their use during chemical stabilisation and aided phytostabilisation of metal(loid)s in contaminated soils. In order to understand the reactivity of these potential sorbents of contaminants in soils and subsequent mobility of metal(loid)s, a set of time-dependent batch leaching experiments was performed using a mix of acetic, lactic, citric, malic and formic acids simulating root exudates. Despite being relatively unstable under given conditions, the AMO proved to be an efficient amendment for rapid stabilisation of both metals and As compared to NM. Generally, low pH (∼ 4) and the presence of citrate complexes resulted in higher mobility of metals in the non- and NM-amended soil. In contrast, the presence of AMO in the soil accelerated the neutralisation reactions related to pH increase and (co-) precipitation of secondary Fe/Mn/Al oxyhydroxides. Mineralogical transformations of the AMO showed to be crucial for contaminant immobilisation.

Evaluating the potential of three Fe- and Mn-(nano)oxides for the stabilization of Cd, Cu and Pb in contaminated soils.

The potential of three Fe- and Mn-(nano)oxides for stabilizing Cd, Cu and Pb in contaminated soils was investigated using batch and column experiments, adsorption tests and tests of soil microbial activity. A novel synthetic amorphous Mn oxide (AMO), which was recently proposed as a stabilizing amendment, proved to be the most efficient in decreasing the mobility of the studied metals compared to nano-maghemite and nano-magnetite. Its application resulted in significant decreases of exchangeable metal fractions (92%, 92% and 93% decreases of Cd, Cu and Pb concentrations, respectively). The adsorption capacity of the AMO was an order of magnitude higher than those recorded for the other amendments. It was also the most efficient treatment for reducing Cu concentrations in the soil solution. No negative effects on soil microorganisms were recorded. On the other hand, the AMO was able to dissolve soil organic matter to some extent.

Isotope fractionation and spectroscopic analysis as an evidence of Cr(VI) reduction during biosorption.

This work investigates the mechanisms behind Cr(VI) biosorption/reduction on three biomaterials (brewers draff, grape waste and synthetic humic acid). Coupled Cr isotope analysis with ICP-OES, XPS and SEM was tested as a novel approach to study the reduction of Cr(VI) by the biomaterials. The Cr(VI) biosorption process was accompanied with heavier Cr isotopes enrichment in the remaining Cr(VI) fraction. A significant fractionation of Cr stable isotopes was observed with no significant pH effect; δ(53)Cr of the remaining fraction ranged from 0.2‰ to 1.9‰ while δ(53)Cr of the product (sorbed Cr) ranged from -1.2‰ to -2.8‰. The Rayleigh fractionation model fitted well the measured data and Cr isotope analysis provides thus an efficient tool to quantify Cr(VI) reduction by different biomaterials. In general, the sorption/reduction potential of the three studied biomaterials decreased in the following order: grape waste>humic acids>brewers draff.

Brewers draff as a new low-cost sorbent for chromium (VI): comparison with other biosorbents.

In this study, used brewers draff was investigated as a novel sorbent for Cr(VI) and compared with other biosorbents (grape waste, peat moss, and sawdust). FTIR-ATR, BET analysis, and pHPZC determination were used to characterize the sorbents. Kinetic and equilibrium experiments were performed, and two empirical models, Langmuir and Freundlich, were used to describe Cr adsorption. Additionally, packed bed column experiments were also performed. In order to identify possible reduction processes, ion exchange separation on the AG1-X8 resin was used to separate the anionic Cr(VI) and the reduced cationic Cr(III) from the aqueous phase after biosorption. Cr(VI) removal was pH-dependent and fitted well both the Langmuir and the Freundlich isotherm models. The ion exchange separation showed that Cr(VI) reduction had occurred in the solution during biosorption. The efficiency of draff as a biosorbent was comparable (or even higher) to highly organic materials (e.g., composted peat), showing its potential application for Cr(VI) decontamination.