Application of Raney Al-Ni Alloy for Simple Hydrodehalogenation of Diclofenac and Other Halogenated Biocidal Contaminants in Alkaline Aqueous Solution under Ambient Conditions.

Raney Al-Ni contains 62% of Ni2Al3 and 38% NiAl3 crystalline phases. Its applicability has been studied within an effective hydrodehalogenation of hardly biodegradable anti-inflammatory drug diclofenac in model aqueous concentrates and, subsequently, even in real hospital wastewater with the aim of transforming them into easily biodegradable products. In model aqueous solution, complete hydrodechlorination of 2 mM aqueous diclofenac solution (0.59 g L-1) yielding the 2-anilinophenylacetate was achieved in less than 50 min at room temperature and ambient pressure using only 9.7 g L-1 of KOH and 1.65 g L-1 of Raney Al-Ni alloy. The dissolving of Al during the hydrodehalogenation process is accompanied by complete consumption of NiAl3 crystalline phase and partial depletion of Ni2Al3. A comparison of the hydrodehalogenation ability of a mixture of diclofenac and other widely used halogenated aromatic or heterocyclic biocides in model aqueous solution using Al-Ni was performed to verify the high hydrodehalogenation activity for each of the used halogenated contaminants. Remarkably, the robustness of Al-Ni-based hydrodehalogenation was demonstrated even for the removal of non-biodegradable diclofenac in real hospital wastewater with high chloride and nitrate content. After removal of the insoluble part of the Al-Ni for subsequent hydrometallurgical recycling, the low quantity of residual Ni was removed together with insoluble Al(OH)3 obtained after neutralization of aqueous filtrate by filtration.

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.

Concentrations of selected trace elements in surface soils near crossroads in the city of Bratislava (the Slovak Republic).

It is well known that road transport emits various trace elements into the environment, which are deposited in soils in the vicinity of roads, so-called roadside soils, and thus contributes to the deterioration of their chemical state. The aim of this work was to determine concentrations of some metals and metalloids (arsenic (As), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), lead (Pb), antimony (Sb), vanadium (V), and zinc (Zn)) in soils from crossroads with traffic signals, which are characterized by deceleration of vehicles and increased emissions of elements related mainly to brake and tyre wear. The results confirmed a moderate enrichment of soils with Cu, Pb, and Zn (enrichment factor (EF) values > 2) and significant enrichment for Sb (EF > 5), while the other elements showed no or minimal enrichment. The age of crossroads proved to have a positive influence on the accumulation of some elements in soils with the largest differences for Cu, Fe, Pb, Sb, and Zn (p < 0.001). Traffic volumes expressed as the average daily traffic intensity (ADTI) also positively influenced soil concentrations of Cr, Cu, Pb, Sb, and Zn, while distance to the crossroad had a significant negative effect on the soil concentration of Cu, Sb, and Zn (p < 0.001). The stable isotopic ratios of Pb, 206Pb/207Pb and 208Pb/206Pb, ranging from 1.1414 to 1.2046 and from 2.0375 to 2.1246, respectively, pointed to the mixed natural-anthropic origin of Pb in the soils of crossroads with a visible contribution of traffic-related sources. Based on the above findings combined with covariance among the studied elements using statistical methods applied to compositionally transformed data, it was possible to show that Cu, Pb, Sb, and Zn clearly originated from road traffic.

Sulfidated nano-scale zerovalent iron is able to effectively reduce in situ hexavalent chromium in a contaminated aquifer.

In a number of laboratory studies, sulfidated nanoscale zero-valent iron (S-nZVI) particles showed increased reactivity, reducing capacity, and electron selectivity for Cr(VI) removal from contaminated waters. In our study, core-shell S-nZVI particles were successfully injected into an aquifer contaminated with Cr(VI) at a former chrome plating facility. S-nZVI migrated towards monitoring wells, resulting in a rapid decrease in Cr(VI) and Crtot concentrations and a long-term decrease in groundwater redox potential observed even 35 m downstream the nearest injection well. Characterization of materials recovered from the injection and monitoring wells confirmed the presence of nZVI particles, together with iron corrosion products. Chromium was identified on the surface of the recovered iron particles as Cr(III), and its occurrence was linked to the formation of insoluble chromium-iron (oxyhydr)oxides such as CrxFe(1-x)(OH)3(s). Injected S-nZVI particles formed aggregates, which were slowly transformed into iron (oxyhydr)oxides and carbonate green rust. Elevated contents of Fe0 were detected even several months after injection, indicating good S-nZVI longevity. The sulfide shell was gradually disintegrated and/or dissolved. Geochemical modelling confirmed the overall stability of the resulting Cr(III) phase at field conditions. This study demonstrates the applicability of S-nZVI for the remediation of a Cr(VI)-contaminated aquifer.

Total mercury, chromium, nickel and other trace chemical element contents in soils at an old cinnabar mine site (Merník, Slovakia): anthropogenic versus natural sources of soil contamination.

The aims of this study were to investigate the occurrence and distribution of total mercury (Hg) and other trace elements of environmental concern, such as arsenic (As), copper (Cu), chromium (Cr), manganese (Mn), nickel (Ni), lead (Pb), zinc (Zn) and vanadium (V), in soils from the abandoned Merník cinnabar mine in eastern Slovakia. For this purpose, thirty soil samples from two depth intervals within the mine area (n = 60 soil samples) and additional sixteen soil samples from adjacent areas (n = 25 soil samples) were collected. Total Hg was measured by atomic absorption spectrometry, while As and other metals were analyzed using inductively coupled plasma atomic emission spectrometry. High mercury concentrations (> 100 mg/kg with a maximum of 951 mg/kg) were observed only in surface soils close to mine waste heaps and adits. Otherwise, Hg concentrations in the majority of surface soils were lower (0.14-19.7 mg/kg), however, higher than Hg in soils collected from sites outside the mine area (0.19-6.92 mg/kg) and even considerably higher than Hg in soils at sites not influenced by the Merník mine. Elevated Cr and Ni concentrations in soils regardless of their sampling sites (mean of 276 mg/kg and median of 132 mg/kg for Cr and 168 mg/kg and 81 mg/kg for Ni, respectively) were attributed to the lithology of the area; the soils are underlain by the sediments of the Central Carpathian Palaeogene, containing a detritus of ultrabasic rocks. As our geochemical data are compositional in nature, they were further treated by compositional data analysis (CoDA). Robust principal component analysis (RPCA) applied on centred (clr) log-ratio-transformed data and correlation analysis of compositional parts based on symmetric balances distinguished very well different sources of origin for the chemical elements. The following three element associations were identified: Hg association with the main source in mining/roasting, Cr-Ni association derived from bedrock and As-Cu-Mn-Pb-Zn-V association (natural background and minor sulphides/sulfosalts in mineralized rocks). The values of geoaccumulation index and enrichment factor suggested that concentrations of Hg in the soils were influenced by human industrial activities.

Use of the ferrates (FeIV-VI) in combination with hydrogen peroxide for rapid and effective remediation of water--laboratory and pilot study.

In recent years, particles of iron in higher oxidation states (Fe(IV-VI)), commonly called ferrates, have been presented theoretically as very effective oxidants. They can potentially be used for elimination of a wide range of organic and inorganic contaminants. However, so far the majority of applications have been carried out only as laboratory tests using model samples in many cases. The application of ferrates in remediation programs has so far proved to be more complicated with results failing to meet expectations. Therefore there is a necessity to consider the suitability of their use or consider their possible combination with other agents in order to reach required removal efficiencies in remediation. This study is focused on laboratory experiments using industrial groundwater leading to the proposal of a pilot field application realized as an ex-situ remediation. The combination of ferrates with hydrogen peroxide was used in this study in order to enhance the removal efficiency during pilot remediation of groundwater strongly contaminated by a wide range of organic contaminants. This combination has been shown to be very effective. During the 24-hour reaction time the majority of detected contaminants were removed by approximately 60-80%. Moreover, the unpleasant odor of the water was suppressed and suspended particles were removed by the flocculation effect of ferric sludge.

The Application of Nano-Sized Zero-Valent Iron for In Situ Remediation of Chlorinated Ethylenes in Groundwater: A Field Case Study.

In this paper, the authors present the pilot in situ application of nano zero-valent iron (nZVI) for effective remediation of groundwater in an industrial area contaminated by chlorinated ethylenes (CEs), which create a significant group of global environmental contaminants. This work covers the entire 1-year remediation process, including systematic laboratory tests and field application techniques for nZVI. The application was carried out in the area of a metal fabrication industrial facility in the Czech Republic. Contamination of CEs in this area is a consequence of old ecological loads. The entire remediation process contained the following steps: monitoring of the area, selection of the most relevant hot spot, selection of the most appropriate application borehole, systematic laboratory tests, application of nZVI, and postapplication monitoring. Ten kilograms of nZVI were applied as a water suspension into the selected borehole. Significant decreases in concentrations of selected contaminants were observed in the first month after application. The reaction in the borehole was completed within approximately 5 to 6 months after the application and during this period almost 50% elimination of contamination was achieved.

Application of comprehensive two-dimensional gas chromatography with mass spectrometric detection for the analysis of selected drug residues in wastewater and surface water.

Pharmaceutical residues have become tightly controlled environmental contaminants in recent years, due to their increasing concentration in environmental components. This is mainly caused by their high level of production and everyday consumption. Therefore there is a need to apply new and sufficiently sensitive analytical methods, which can detect the presence of these contaminants even in very low concentrations. This study is focused on the application of a reliable analytical method for the analysis of 10 selected drug residues, mainly from the group of non-steroidal anti-inflammatory drugs (salicylic acid, acetylsalicylic acid, clofibric acid, ibuprofen, acetaminophen, caffeine, naproxen, mefenamic acid, ketoprofen, and dicofenac), in wastewaters and surface waters. This analytical method is based on solid phase extraction, derivatization by N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) and finally analysis by comprehensive two-dimensional gas chromatography with Time-of-Flight mass spectrometric detection (GCxGC-TOF MS). Detection limits ranged from 0.18 to 5 ng/L depending on the compound and selected matrix. The method was successfully applied for detection of the presence of selected pharmaceuticals in the Svratka River and in wastewater from the wastewater treatment plant in Brno-Modrice, Czech Republic. The concentration of pharmaceuticals varied from one to several hundreds of ng/L in surface water and from one to several tens of isg/L in wastewater.