Giant locally advanced and metastatic squamous cell skin carcinoma of head and neck region: case report.

INTRODUCTION: At the present time, the skin tumors are among the most common cancers. Optimal therapy is based on the extent of the disease and the age of the patient. The need for radiotherapy occurs for inoperable locally advanced tumors and in the event of failure, salvage surgery is applied. MATERIALS AND METHODS: We provided a case report of an older patient with giant squamous cell skin carcinoma and a review of published articles. RESULTS: We present a rare case of giant squamous cell skin carcinoma with metastatic satellite tumors that was primarily treated with curative radiotherapy. Five months after radiotherapy, a recurrent tumor was detected at the site of origin and the treatment was completed by salvage surgery. Full remission was achieved for four years. CONCLUSION: Despite the seemingly incurable finding it is always necessary to consider radical treatment regardless of the patient´s age. Curative treatment could achieve long term remission in the group of older patients.

Metal(loid)s behaviour in soils amended with nano zero-valent iron as a function of pH and time.

Nano zero-valent iron (nZVI) is currently investigated as a stabilising amendment for contaminated soils. The effect of pH (4-8) and time (48 and 192 h) on the behaviour of nZVI-treated Pb-Zn and As-contaminated soil samples was assessed. Additionally, soil leachates were subsequently used to study the direct interaction between soil solution components and nZVI particles in terms of mineralogical changes and contaminant retention. A typical U-shaped leaching trend as a function of pH was observed for Cd, Pb and Zn, while As was released predominantly under alkaline conditions. Oxidising conditions prevailed, so pH was the key controlling parameter rather than redox conditions. Generally, longer contact time resulted in increased soluble concentrations of metal(loid)s. However, the stabilisation effect of nZVI was only observed after the direct soil leachate-nZVI interactions, showing enhanced redox and sorption processes for the studied metals. A significant decrease of dissolved As concentrations was observed for both experimental soils, but with different efficiencies depending on neutralisation capacity, organic matter content or solid fractionation of As related to the origin of the soils. Scorodite (FeAsO4·2H2O) was predicted as a potential solubility-controlling mineral phase for As. Sorption of metal(loid)s onto secondary Fe- and Al-(oxyhydr)oxides (predicted to precipitate at pH > 5) represents an important scavenger mechanism. Moreover, transmission electron microscopy confirmed the retention of Zn and Pb under near-neutral and alkaline conditions by newly formed Fe oxides or aluminosilicates. This study shows that the efficiency of nZVI application strongly depends not only on soil pH-Eh conditions and contaminant type, but also on the presence of organic matter and other compounds such as Al/Fe/Mn oxyhydroxides and clay minerals.

Dust from Zambian smelters: mineralogy and contaminant bioaccessibility.

Metal smelting is often responsible for local contamination of environmental compartments. Dust materials escaping from the smelting facilities not only settle in the soil, but can also have direct effects on populations living close to these operations (by ingestion or inhalation). In this particular study, we investigate dusts from Cu-Co metal smelters in the Zambian Copperbelt, using a combination of mineralogical techniques (XRD, SEM/EDS, and TEM/EDS), in order to understand the solid speciation of the contaminants, as well as their bioaccessibility using in vitro tests in simulated gastric and lung fluids to assess the exposure risk for humans. The leaching of metals was mainly dependent on the contaminant mineralogy. Based on our results, a potential risk can be recognized, particularly from ingestion of the dust, with bioaccessible fractions ranging from 21 to 89% of the total contaminant concentrations. In contrast, relatively low bioaccessible fractions were observed for simulated lung fluid extracts, with values ranging from 0.01% (Pb) up to 16.5% (Co) of total contaminant concentrations. Daily intakes via oral exposure, calculated for an adult (70 kg, ingestion rate 50 mg dust per day), slightly exceeded the tolerable daily intake limits for Co (1.66× for fly ash and 1.19× for slag dust) and occasionally also for Pb (1.49×, fly ash) and As (1.64×, electrostatic precipitator dust). Cobalt has been suggested as the most important pollutant, and the direct pathways of the population's exposures to dust particles in the industrial parts of the Zambian Copperbelt should be further studied in interdisciplinary investigations.

Metal(loid)s in urban soil from historical municipal solid waste landfill: Geochemistry, source apportionment, bioaccessibility testing and human health risks.

Landfills, especially those poorly managed, can negatively affect the environment and human beings through chemical contamination of soils and waters. This study investigates the soils of a historical municipal solid waste (MSW) landfill situated in the heart of a residential zone in the capital of Slovakia, Bratislava, with an emphasis on metal (loid) contamination and its consequences. Regardless of the depth, many of the soils exhibited high metal (loid) concentrations, mainly Cd, Cu, Pb, Sb, Sn and Zn (up to 24, 2620, 2420, 134, 811 and 6220 mg/kg, respectively), classifying them as extremely contaminated based on the geo-accumulation index (Igeo >5). The stable lead isotopic ratios of the landfill topsoil varied widely (1.1679-1.2074 for 206Pb/207Pb and 2.0573-2.1111 for 208Pb/206Pb) and indicated that Pb contained a natural component and an anthropogenic component, likely municipal solid waste incineration (MSWI) ash and construction waste. Oral bioaccessibility of metal (loid)s in the topsoil was variable with Cd (73.2-106%) and Fe (0.98-2.10%) being the most and least bioaccessible, respectively. The variation of metal (loid) bioaccessibility among the soils could be explained by differences in their geochemical fractionation as shown by positive correlations of bioaccessibility values with the first two fractions of BCR (Community Bureau of Reference) sequential extraction for As, Cd, Mn, Ni, Pb, Sn and Zn. The results of geochemical fractionation coupled with the mineralogical characterisation of topsoil showed that the reservoir of bioaccessible metal (loid)s was calcite and Fe (hydr)oxides. Based on aqua regia metal (loid) concentrations, a non-carcinogenic risk was demonstrated for children (HI = 1.59) but no risk taking into account their bioaccessible concentrations (HI = 0.65). This study emphasises the need for detailed research of the geochemistry of wastes deposited in urban soils to assess the potentially hazardous sources and determine the actual bioaccessibility and human health risks of the accumulated metal (loid)s.

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.

Pyrolysed sewage sludge for metal(loid) removal and immobilisation in contrasting soils: Exploring variety of risk elements across contamination levels.

Efficient treatment of sewage sludge may transform waste into stable materials with minimised hazardous properties ready for secondary use. Pyrolysed sewage sludge, sludgechar, has multiple environmental benefits including contaminant sorption capacity and nutrient recycling. The properties of five sludgechars were tested firstly for adsorption efficiency in laboratory solutions before prospective application to soils. A wide variety of metal(loid)s (As, Cd, Co, Cr, Cu, Ni, Pb, Sb, and Zn) was involved. Secondly, the sludgechars (3 % v/v) were incubated in five soils differing in (multi)-metal(loid) presence and the level of contamination. The main aim was to evaluate the metal(loid) immobilisation potential of the sludgechars for soil remediation. Moreover, nutrient supply was investigated to comprehensively assess the material's benefits for soils. All sludgechars were efficient (up to 100 %) for the removal of metal cations while their efficiency for metal(loid) anions was limited in aqueous solutions. Phosphates and sulphates were identified crucial for metal(loid) capture, based on SEM/EDS, XRD and MINTEQ findings. In soils, important fluctuations were observed for Zn, being partially immobilised by the sludgechars in high-Zntot soils, while partially solubilised in moderate to low-Zntot soils. Moreover, pH showed to be crucial for material stability, metal(loid) adsorption ability and their immobilisation in soils. Although metal(loid) retention was generally low in soils, nutrient enrichment was significant after sludgechar application. Long-term evaluation of the material sorption efficiency, nutrient supply, and ageing in soil environments will be necessary in future studies.

Nano zerovalent Fe did not reduce metal(loid) leaching and ecotoxicity further than conventional Fe grit in contrasting smelter impacted soils: A 1-year field study.

The majority of the studies on nanoscale zero-valent iron (nZVI) are conducted at a laboratory-scale, while field-scale evidence is scarce. The objective of this study was to compare the metal(loid) immobilization efficiency of selected Fe-based materials under field conditions for a period of one year. Two contrasting metal(loid) (As, Cd, Pb, Zn) enriched soils from a smelter-contaminated area were amended with sulfidized nZVI (S-nZVI) solely or combined with thermally stabilized sewage sludge and compared to amendment with microscale iron grit. In the soil with higher pH (7.5) and organic matter content (TOC = 12.7 %), the application of amendments resulted in a moderate increase in pH and reduced As, Cd, Pb, and Zn leaching after 1-year, with S-nZVI and sludge combined being the most efficient, followed by iron grit and S-nZVI alone. However, the amendments had adverse impacts on microbial biomass quantity, S-nZVI being the least damaging. In the soil with a lower pH (6.0) and organic matter content (TOC = 2.3 %), the results were mixed; 0.01 M CaCl2 extraction data showed only S-nZVI with sludge as remaining effective in reducing extractable concentrations of metals; on the other hand, Cd and Zn concentrations were increased in the extracted soil pore water solutions, in contrast to the two conventional amendments. Despite that, S-nZVI with sludge enhanced the quantity of microbial biomass in this soil. Additional earthworm avoidance data indicated that they generally avoided soil treated with all Fe-based materials, but the presence of sludge impacted their preferences somewhat. In summary, no significant differences between S-nZVI and iron grit were observed for metal(loid) immobilization, though sludge significantly improved the performance of S-nZVI in terms of soil health indicators. Therefore, this study indicates that S-nZVI amendment of soils alone should be avoided, though further field evidence from a broader range of soils is now required.

Environmental and health impacts assessment of long-term naturally-weathered municipal solid waste incineration ashes deposited in soil-old burden in Bratislava city, Slovakia.

Municipal solid waste incineration (MSWI) is an effective method for reducing the volume/mass of waste. However, MSWI ashes contain high concentrations of many substances, including trace metal (loid)s, that could be released into the environment and contaminate soils and groundwater. In this study, attention was focused on the site near the municipal solid waste incinerator where MSWI ashes are deposited on the surface without any control. Here, combined results (chemical and mineralogical analyses, leaching tests, speciation modelling, groundwater chemistry and human health risk assessment) are presented to assess the impact of MSWI ash on the surrounding environment. The mineralogy of ∼forty years old MSWI ash was diverse, and quartz, calcite, mullite, apatite, hematite, goethite, amorphous glasses and several Cu-bearing minerals (e.g. malachite, brochantite) were commonly detected. In general, the total concentrations of metal (loid)s in MSWI ashes were high, following the order: Zn (6731 mg/kg) > Ba (1969 mg/kg) ≈ Mn (1824 mg/kg) > Cu (1697 mg/kg) > Pb (1453 mg/kg) > Cr (247 mg/kg) > Ni (132 mg/kg) > Sb (59.4 mg/kg) > As (22.9 mg/kg) ≈ Cd (20.6 mg/kg). Cadmium, Cr, Cu, Pb, Sb and Zn exceeded the indication or even intervention criteria for industrial soils defined by the Slovak legislation. Batch leaching experiments with diluted citric and oxalic acids that simulate the leaching of chemical elements under rhizosphere conditions documented low dissolved fractions of metals (0.00-2.48%) in MSWI ash samples, showing their high geochemical stability. Non-carcinogenic and carcinogenic risks were below the threshold values of 1.0 and 1 × 10-6, respectively, with soil ingestion being the most important exposure route for workers. The groundwater chemistry was unaffected by deposited MSWI ashes. This study may be useful in determining the environmental risks of trace metal (loid)s in weathered MSWI ashes that are loosely deposited on the soil surface.

Low-cost zeolite-based sorbents prepared from industrial perlite by-product material for Zn2+ and Ni2+ removal from aqueous solutions: synthesis, properties and sorption efficiency.

The conversion of waste/by-product materials into efficient sorbents is at the forefront of innovative remediation techniques. In the present study, the relationships among the synthesis conditions, physicochemical properties of synthesized sorbents and Zn2+ and Ni2+ removal efficiencies were studied in detail. Zeolite X, zeolite P, phillipsite, analcime, sodalite and cancrinite were synthesized from industrial perlite by-product material. The zeolite content in the synthesized sorbents and zeolite framework topology (dimensions, numbers and spatial configuration of channels) were the key factors affecting the removal of Zn2+ and Ni2+ from aqueous solutions. Zeolite X-based sorbent exhibited the best sorption performance mainly due to the large zeolite channel dimensions, low Si/Al ratio, high cation exchange capacity and high specific surface area. Nevertheless, the efficiency and stability of this sorbent need to be tested under field conditions prior to its application for remediation technologies.

Contaminated soils of different natural pH and industrial origin: The role of (nano) iron- and manganese-based amendments in As, Sb, Pb, and Zn leachability.

Soils containing a large proportion of industrial waste can pose a health risk due to high environmentally available concentrations of toxic metal(loid)s. Nano zero-valent iron (nZVI) and amorphous manganese oxide (AMO) were applied as immobilising amendments (1 wt%) to soils with different industrial origin of As and Sb, and leaching of As, Sb, Pb, and Zn was investigated using a single extraction with deionised water. The different industrial impact was reflected in the mineralogy, chemical composition and pH of these soils. Water-soluble As ratios positively correlated with pH in all experimental treatments. A significant decrease of water-soluble As ratios was observed in all nZVI-amended soils (~65-93% of the control) except for one sample with the lowest solution pH. Nano zero-valent iron was also successful in Sb immobilisation (~76-90% of the control). Highly variable results were obtained for AMO, which only led to a decrease of water-soluble As in soils with solution pH of ≥7 (~70-80% of the control), probably due to lower stability of AMO in acidic conditions. In each case, nZVI was more efficient at decreasing water-soluble As ratios than AMO. Dissolved Pb concentrations remained unchanged after the application of nZVI and AMO, and the decrease of Zn leaching using AMO was controlled mainly by soil pH increase induced by its application. According to the calculated saturation indices, tripuhyite (FeSbO4) was predicted to be the key mineral controlling Sb solubility in mine soils. Secondary Fe (hydr)oxides either originally present or newly formed due to nZVI oxidation were instrumentally identified at different stages of their transformation and metal(loid) retention. To conclude, nZVI is suitable for application to contaminated soils at a wide pH range, while the use of AMO for decreasing As leaching is limited to soils with pH ≥ 7.

Image-guided radiation therapy produces lower acute and chronic gastrointestinal and genitourinary toxicity in prostate cancer patients.

PURPOSE: This paper compares individual radiation therapy techniques used for prostate cancer and their benefits in clinical practice. METHODS: We retrospectively analyzed 921 patients with localized prostate tumors treated between 1997 and 2012. We divided the patients into four groups according to the selected treatment technique (conformal radiation therapy [3DCRT], intensity-modulated radiation therapy [IMRT], image-guided radiation therapy [IGRT], and volumetric-modulated arc therapy [VMAT]) and evaluated the incidence of acute and chronic gastrointestinal (GI) and genitourinary (GU) toxicity. RESULTS: The incidence of grade 2 or greater acute GU and GI toxicity was significantly higher among techniques other than IGRT (p˂0.001). We found the same results in the case of grade 3 or greater acute GU toxicity (p˂0.001). Grade 3 or higher acute GI toxicity occurred only in one patient treated by 3DCRT. Cumulative late GI toxicity of grade 2 or higher and grade 3 or higher was recorded over 3 years significantly more frequently among non-IGRT techniques as compared to IGRT (p˂0.001). As regards GU toxicity, we found significantly higher incidence only for grade 2 or higher (p˂0.001), not for grade 3 or higher. No occurrence of grade 4 toxicity was recorded. The greatest incidence of patients without acute and chronic GI/GU toxicity was recorded in connection with VMAT. CONCLUSION: IGRT demonstrated a pronounced reduction in acute and chronic GU and GI toxicity as compared to non-IGRT techniques in the treatment of localized prostate cancer.

Assessment of biochar and/or nano zero-valent iron for the stabilisation of Zn, Pb and Cd: A temporal study of solid phase geochemistry under changing soil conditions.

The remediation of a soil contaminated with Zn, Pb and Cd was tested by using biochar (BC), nano zero-valent iron (nZVI) and a combination of these two (BC + nZVI). Each amendment was individually applied to the soil at 2 wt%. We tested the influence of (i) the used amendments, (ii) time, and (iii) soil moisture conditions on the metal availability and soil physico-chemical parameters using various extraction methods, as well as soil pore water samplings. We found that metal availability was mainly affected by pH under the influence of time and water content. Among the tested treatments, BC was the most successful, resulting in the lowest amounts of the target metals in the pore water and the smallest temporal changes in metal concentrations and pH in the soil. The use of nZVI efficiently decreased water-extractable Pb in the short- and long-term. The BC + nZVI treatment also yielded promising results regarding the immobilisation of the studied metals. Time provoked a general decrease in pH, which occasionally increased the available metal concentrations. Raising the soil water content increased the pH and subsequently lowered the available metal concentrations in the pore water. The mechanisms of metal stabilisation were further investigated by SEM/EDS. The results indicated that the used soil amendments enhanced the binding of Zn, Pb, and Cd on Fe/Mn/Al oxides/hydroxides, which in turn resulted in the stabilisation of the target metals.

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).

Seasonal fluctuations of Zn, Pb, As and Cd contents in the biomass of selected grass species growing on contaminated soils: Implications for in situ phytostabilization.

Phytostabilization aims to immobilize contaminants at the rhizosphere level using the root system of adapted plants. In order to exploit wild grasses with potential for phytostabilization, a screening throughout the year was conducted at a site contaminated by Pb and Zn. Three plant species were chosen: Agrostis capillaris, Arrhenatherum elatius and Calamagrostis epigeios. Rhizospheric soil and biomass was used for chemical characterization. Above- and below-ground was analyzed. For each sample, arbuscular mycorrhiza fungi colonization was determined. The highest concentrations of Pb were found in the A. capillaris rhizosphere (3417 mg kg-1), and in A. elatius for Zn (3876 mg kg-1). CaCl2-extractable Zn in the rhizosphere of C. epigeios was the lowest and Pb was lower for A. elatius. CaCl2-extractable Cd was neither species-dependent nor time-dependent. Arsenic was not species-dependent. The fractionation of target elements did not show differences between separate sampling campaigns and Pb was the only element that showed differences during the year. A. capillaris showed the best capacity to take up elements. The colonization by AMF did not show significant differences for different sampling times, or interactions between time and species, however differences were found for different species, i.e., C. epigeios showed significantly lower colonization by arbuscular mycorrhiza fungi. Our results indicate that A. capillaris appears to be a good indigenous candidate for phytostabilization.

Nanoscale Zero-Valent Iron Has Minimum Toxicological Risk on the Germination and Early Growth of Two Grass Species with Potential for Phytostabilization.

Two Poaceae species, Agrostis capillaris and Festuca rubra, were selected for their potential as phytostabilizing plants in multicontaminated soils. These species are resistant to contamination and maintain high concentrations of contaminants at the root level. Nanoscale zero-valent iron (nZVI) is an engineered nanomaterial with the ability to stabilize metal(loid)s in soils; its potential toxicological effects in the selected species were studied in a germination test using: (i) control variant without soil; (ii) soil contaminated with Pb and Zn; and (iii) contaminated soil amended with 1% nZVI, as well as in an hydroponic experiment with the addition of nZVI 0, 25, 50 and 100 mg L-1. nZVI had no negative effects on seed germination or seedling growth, but was associated with an increase in shoot growth and reduction of the elongation inhibition rate (root-dependent) of F. rubra seedlings. However, applications of nZVI in the hydroponic solution had no effects on F. rubra but A. capillaris developed longer roots and more biomass. Increasing nZVI concentrations in the growing solution increased Mg and Fe uptake and reduced the Fe translocation factor. Our results indicate that nZVI has few toxic effects on the studied species.

Antimonate adsorption onto Mg-Fe layered double hydroxides in aqueous solutions at different pH values: Coupling surface complexation modeling with solid-state analyses.

In this study, the importance of Sb behavior under different pH conditions has been addressed with respect to its stabilization in aqueous solutions using Mg-Fe layered double hydroxides (LDHs). The Sb(V) adsorption onto Mg-Fe LDHs was performed at different initial Sb(V) concentrations and pH values (pH 5.5, 6.5 and 7.5). The removal rate and the maximal adsorbed amount increased with decreasing pH values. Moreover, the surface complexation modeling (SCM) predicted preferable formation of monodentate mononuclear and bidentate binuclear complexes on the Mg-Fe LDH surface. Spectroscopic (X-ray diffraction analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy) and microscopic (scanning electron microscopy and energy-dispersive X-ray spectroscopy) techniques were used to further specify the adsorption mechanisms. The influence of chemical adsorption, surface-induced precipitation of brandholzite Mg[Sb(OH)6]2·6H2O, formation of brandholzite-like phases and/or anion exchange was observed. Moreover, Sb(V) was nonhomogeneously distributed on the Mg-Fe LDH surface at all pH values. The surface complexation modeling supported by solid-state analyses provided a strong tool to investigate the binding arrangements of Sb(V) on the Mg-Fe LDH surface. Such a complex mechanistic/modeling approach has not previously been presented and enables prediction of the Sb(V) adsorption behavior onto Mg-Fe LDHs under different conditions, evaluating their possible use in actual applications.

Stability and stabilizing efficiency of Mg-Fe layered double hydroxides and mixed oxides in aqueous solutions and soils with elevated As(V), Pb(II) and Zn(II) contents.

Although the mechanisms of metal(loid) removal from aqueous solutions using LDHs (layered double hydroxides) and mixed oxides (thermally treated LDHs; CLDHs) have been studied, research dealing with their stability, stabilizing efficiency and remediation potential for contaminated soils remains scarce. We present a complex study investigating the stabilizing efficiency of Mg-Fe LDHs and CLDHs at different conditions, including aqueous solutions and real soils with highly elevated As(V), Pb(II) and Zn(II) concentrations. All studied materials showed excellent (ad)sorption efficiency for As(V), Pb(II) and Zn(II) in aqueous solutions. Additionally, the reconstruction ability of CLDHs at different conditions that could improve their adsorption properties was also evaluated, and the dependence on time, pH and the concentrations of metal(loid)s was shown. In general, CLDHs showed higher stability and stabilizing efficiency in aqueous and soil solutions; however, LDHs were more efficient in contaminated soils. Furthermore, solid state analyses coupled with geochemical modeling showed the formation of new phases corresponding to Mg­carbonates/silicates on the surfaces of LDH/CLDH after their incubation in soils. Both LDHs and CLDHs significantly decreased the bioavailable/labile fraction of As(V) and Zn(II) in the studied soils. In general, our work shows Mg-Fe LDHs and CLDHs as prospective materials for water and soil remediation.

Effect of nano zero-valent iron application on As, Cd, Pb, and Zn availability in the rhizosphere of metal(loid) contaminated soils.

Characterisation of geochemical transformations and processes in soils with special focus on the rhizosphere is crucial for assessing metal(loid) bioavailability to plants during in situ immobilisation and phytostabilisation. In this study, the effects of nano zero-valent iron (nZVI) were investigated in terms of the immobilisation of As, Zn, Pb and Cd in two soil types and their potential uptake by plants using rhizobox experiments. Such system allowed monitoring the behaviour of trace elements in rooted and bulk soil compartments separately. Sunflower (Helianthus annuus L.) and ryegrass (Lolium perenne L.) were tested for As-rich (15.9 g As kg-1) and Zn-rich (4.1 g Zn kg-1) soil samples, respectively. The application of nZVI effectively lowered the uptake of all target risk elements into plant tissues. Efficient immobilisation of As was determined in the As-soil without a significant difference between plant and bulk soil compartments. Similarly, a significant decrease was determined for CaCl2-available fractions of Zn, Pb and Cd in nZVI-treated Zn-soil. The behaviour of As corresponded to changes in Eh, while Zn and Cd showed to be mainly pH-dependent. However, despite the observed stabilisation effect of nZVI, high amounts of As and Zn still remained available for plants. Furthermore, the accumulation of the target risk elements in roots and the overall effect of nZVI transformations in the rhizosphere were verified and visualised by SEM/EDS. The following immobilising mechanisms were suggested: (i) sorption onto both existing and newly formed Fe (hydr)oxides, (ii) formation of secondary Fe-As phases, and (iii) sorption onto Mn (hydr)oxides.

AMOchar: Amorphous manganese oxide coating of biochar improves its efficiency at removing metal(loid)s from aqueous solutions.

A novel sorbent made from biochar modified with an amorphous Mn oxide (AMOchar) was compared with pure biochar, pure AMO, AMO+biochar mixtures and biochar+birnessite composite for the removal of various metal(loid)s from aqueous solutions using adsorption and solid-state analyses. In comparison with the pristine biochar, both Mn oxide-biochar composites were able to remove significantly greater quantities of various metal(loid)s from the aqueous solutions, especially at a ratio 2:1 (AMO:biochar). The AMOchar proved most efficient, removing almost 99, 91 and 51% of Pb, As and Cd, respectively. Additionally, AMOchar and AMO+biochar mixture exhibited reduced Mn leaching, compared to pure AMO. Therefore, it is concluded that the synthesis of AMO and biochar is able to produce a double acting sorbent ('dorbent') of enhanced efficiency, compared with the individual deployment of their component materials.

Tumor bed radiotherapy in women following breast conserving surgery for breast cancer-safety margin with/without image guidance.

Image guided radiation therapy (IGRT) enables the achievement of higher precision in radiation delivery, a reduction in safety margins and a reduced risk of toxicity in healthy tissues. The present study investigated the magnitude of safety margins for the radiation boost setup on skin marks or metal clips implanted into the tumor bed during breast cancer surgery. One hundred eighty-four patients after breast conserving surgery with implanted metal clips into tumor bed were analyzed. The present study investigated the difference in safety margin required for the treatment setup on skin marks and metal clips. The skin marks were created using a positioning laser system in the treatment room. Metal clips implanted in the tumor bed were registered using IGRT with kilovoltage X-rays in orthogonal projection. Treatment setup was performed during free breathing. The safety margin corresponding to the planning target volume (PTV) was calculated from the recorded data. Calculated safety margins for the treatment setup on skin marks were 9.4, 11.1 and 11.1 mm in the anteroposterior, craniocaudal, and laterolateral directions, respectively. Corresponding safety margins with the use of IGRT and metal clips registration were 4.7, 5.1 and 5.9 mm, respectively. The safe PTV margin was 12 mm using setup on skin marks without IGRT, whereas a 6-mm margin was sufficient with the use of metal clip-based IGRT with daily online correction. IGRT has been adopted as the standard treatment method within the Oncology Centre of Multiscan and Pardubice Hospital (Pardubice, Czech Republic).