A Deep Insight into Perfluorooctanoic Acid Photodegradation Using Metal Ion-Exchanged Zeolites.

Treating perfluorooctanoic acid (PFOA) in an aqueous environment is problematic due to its low concentration and its high resistance to biological and chemical degradation. To tackle this challenge, combinations of pre-enrichment and photodegradation processes are promising solutions. In this work, we investigated metal ion-exchanged zeolites as adsorbents and photocatalysts for PFOA treatment. Among various transition metal ion-exchanged BEA zeolites, Fe-exchanged BEA (Fe-BEA) zeolites showed significant activity for the photodegradation of PFOA. The isolated iron species in Fe-BEA zeolite are responsible for PFOA photodegradation, whereas other iron species present from excess iron loading in the zeolite will lower its photocatalytic activity. Furthermore, it was proved via size exclusion tests using branched PFOA isomers that the photodegradation of PFOA took place on the internal surface rather than the external surface of Fe-BEA zeolite. Photodegradation of PFOA was also tested to be effective with Fe-exchanged BEA-type zeolites having various SiO2/Al2O3 ratios, but ineffective with FAU-type zeolites. The optimal Fe-BEA zeolite showed a sorption coefficient Kd of 6.0 × 105 L kg-1 at an aqueous phase PFOA concentration of 0.7 µg L-1 and a PFOA half-life of 1.8 h under UV-A irradiation. The presented study offers a deeper understanding of the use of metal ion-exchanged zeolites for photodegradation of PFOA.

Fe-zeolites for the adsorption and oxidative degradation of nitroaromatic compounds in water.

Nitroaromatic compounds (NACs) are prominent explosives. In this context, these toxic substances were released into the environment and cause long-lasting groundwater contamination. In preparation of a possible in-situ remediation, colloidal Fe-zeolites were investigated for their capabilities as adsorbents and oxidation catalysts. It was shown that the Fe-zeolites FeBEA35 and FeFAU55 are potent inorganic adsorbents for NACs and simultaneously capable of activating H2O2 as Fenton-like oxidation catalysts. Adsorption isotherms of 15 NACs on both zeolites were measured to evaluate the option of coupling adsorptive contaminant enrichment with oxidative degradation. The faujasite-type zeolite FeFAU55 showed a distinct S-type adsorption behaviour and reached significantly higher NAC loadings of > 20 wt%. For FeBEA35, L-type adsorption isotherms and maximum loadings qmax of about 4 wt% were obtained. Degradation of all NACs, monitored by nitrate formation, was observed. Apparent rate constants of the NACs with hydroxyl radicals in a homogeneous, stoichiometric Fenton reaction were related to the heterogeneous system to examine the role of adsorption on the oxidative degradation. Beneficial influence of the adsorption on the oxidation rates was identified. The results of this work open up promising prospects for future application of Fe-zeolites for the in-situ remediation of NAC-contaminated groundwater.

Bottom-Up Synthesis of De-Functionalized and Dispersible Carbon Spheres as Colloidal Adsorbent.

Recent innovative adsorption technologies for water purification rely on micrometer-sized activated carbon (AC) for ultrafast adsorption or in situ remediation. In this study, the bottom-up synthesis of tailored activated carbon spheres (aCS) from sucrose as renewable feedstock is demonstrated. The synthesis is based on a hydrothermal carbonization step followed by a targeted thermal activation of the raw material. This preserves its excellent colloid properties, i.e., narrow particle size distribution around 1 µm, ideal spherical shape and excellent aqueous dispersibility. We investigated the ageing of the freshly synthesized, highly de-functionalized AC surface in air and aqueous media under conditions relevant to the practice. A slow but significant ageing due to hydrolysis and oxidation reactions was observed for all carbon samples, leading to an increase of the oxygen contents with storage time. In this study, a tailored aCS product was generated within a single pyrolysis step with 3 vol.-% H2O in N2 in order to obtain the desired pore diameters and surface properties. Adsorption characteristics, including sorption isotherms and kinetics, were investigated with monochlorobenzene (MCB) and perfluorooctanoic acid (PFOA) as adsorbates. The product showed high sorption affinities up to log (KD/[L/kg]) of 7.3 ± 0.1 for MCB and 6.2 ± 0.1 for PFOA, respectively.

Recent developments in microplastic contaminated water treatment: Progress and prospects of carbon-based two-dimensional materials for membranes separation.

Micro (nano)plastics pollution is a noxious menace not only for mankind but also for marine life, as removing microplastics (MPs) is challenging due to their physiochemical properties, composition, and response toward salinity and pH. This review provides a detailed assessment of the MPs pollution in different water types, environmental implications, and corresponding treatment strategies. With the advancement in nanotechnology, mitigation strategies for aqueous pollution are seen, especially due to the fabrication of nanosheets/membranes mostly utilized as a filtration process. Two-dimensional (2D) materials are increasingly used for membranes due to their diverse structure, affinity, cost-effectiveness, and, most importantly, removal efficiency. The popular 2D materials used for membrane-based organic and inorganic pollutants from water mainly include graphene and MXenes however their effectiveness for MPs removal is still in its infancy. Albeit, the available literature asserts a 70- 99% success rate in micro/nano plastics removal achieved through membranes fabricated via graphene oxide (GO), reduced graphene oxide (rGO) and MXene membranes. This review examined existing membrane separation strategies for MPs removal, focusing on the structural properties of 2D materials, composite, and how they adsorb pollutants and underlying physicochemical mechanisms. Since MPs and other contaminants commonly coexist in the natural environment, a brief examination of the response of 2D membranes to MPs removal was also conducted. In addition, the influencing factors regulate MPs removal performance of membranes by impacting their two main operating routes (filtration and adsorption). Finally, significant limitations, research gaps, and future prospects of 2D material-based membranes for effectively removing MPs are also proposed. The conclusion is that the success of 2D material is strongly linked to the types, size of MPs, and characteristics of aqueous media. Future perspectives talk about the problems that need to be solved to get 2D material-based membranes out of the lab and onto the market.

Uniform and dispersible carbonaceous microspheres as quasi-liquid sorbent.

Functional colloidal carbon materials find various applications, including the remediation of contaminated water and soil in so-called particle-based in-situ remediation processes. In this study, uniform and highly dispersible micro-sized carbonaceous spheres (CS) were generated by hydrothermal carbonization (HTC) of sucrose in the presence of carboxymethyl cellulose (CMC) as environmentally friendly polyelectrolyte stabilizer. In order to ensure their optimal subsurface delivery and formation of a self-contained treatment zone, a narrow size distribution and low agglomeration tendency of the particles is desired. Therefore, the obtained CS were thoroughly characterized and optimized with respect to their colloidal properties which are a crucial factor for their application as quasi-liquid sorbent. The as-prepared uniform CS are readily dispersible into single particles in water as confirmed by digital microscopy and form stable suspensions. Due to their perfectly spherical shape, particle sedimentation in aqueous suspensions is well predicted by Stokes' law. High sorption coefficients on the synthesized CS KD,CS were determined for phenanthrene (up to log (KD,CS/[L kg-1]) = 5) and other hydrophobic groundwater contaminants. This confirms the application potential of the CS, which were prepared by an economic low-temperature process using sucrose as bio-based precursor, for generating in-situ sorption barriers for groundwater and soil remediation.

Phylogeny and potential virulence of cryptic clade Escherichia coli species complex isolates derived from an arable field trial.

Analysis of Escherichia coli taxonomy has expanded into a species-complex with the identification of divergent cryptic clades. A key question is the evolutionary trajectory of these clades and their relationship to isolates of clinical or veterinary importance. Since they have some environmental association, we screened a collection of E. coli isolated from a long-term spring barley field trial for their presence. While most isolates clustered into the enteric-clade, four of them clustered into Clade-V, and one in Clade-IV. The Clade -V isolates shared >96% intra-clade average nucleotide sequence identity but <91% with other clades. Although pan-genomics analysis confirmed their taxonomy as Clade -V (E. marmotae), retrospective phylogroup PCR did not discriminate them correctly. Differences in metabolic and adherence gene alleles occurred in the Clade -V isolates compared to E. coli sensu scricto. They also encoded the bacteriophage phage-associated cyto-lethal distending toxin (CDT) and antimicrobial resistance (AMR) genes, including an ESBL, blaOXA-453. Thus, the isolate collection encompassed a genetic diversity, and included cryptic clade isolates that encode potential virulence factors. The analysis has determined the phylogenetic relationship of cryptic clade isolates with E. coli sensu scricto and indicates a potential for horizontal transfer of virulence factors.

Borohydride and metallic copper as a robust dehalogenation system: Selectivity assessment and system optimization.

Hydrodechlorination (HDC) using noble-metal catalysts in the presence of H-donors is a promising tool for the treatment of water contaminated by halogenated organic compounds (HOCs). Cu is an attractive alternative catalyst to noble metals since it is cheaper than Pd, Rh, or Pt and more stable against deactivation. Cu with borohydride (BH4-) as reductant (copper-borohydride reduction system; CBRS) was applied here for the treatment of saturated aliphatic HOCs. The HDC ability of CBRS was evaluated based upon product selectivities during reduction of CCl3-R compounds (R = H, F, Cl, Br, and CH3). For CHCl3, CH2Cl2, and CHCl2-CH3, the dechlorination reaction proceeds predominantly via α-elimination with initial product selectivities to CH4 and C2H6 of 84-85 mol-% and 70-72 mol-%. For CCl4, CBrCl3, CFCl3, and CCl3-CH3, stepwise hydrogenolysis dominates. CH2Cl-R compounds are formed as recalcitrant intermediates with initial selectivities of 50-72 mol-%, whereas CH4 and C2H6 are minor products with 16-35 mol-% and 30-35 mol-%. The effect of reaction conditions on product selectivities were investigated for CHCl3 as target. Solution composition, variation of reducing agents (BH4-, H* from H2) and increase of electron pressure (electric potential at Cu electrode and Fe0 as support) did not have marked influence on the selectivities (ratio of CH4 : CH2Cl2). Product selectivities for reduction of CCl3-R compounds were found to be substrate-specific rather than reductant-specific. Since the formation of halogenated by-products could not be avoided, transformation via a second reduction step was optimized by higher catalyst dose, addition of Ag, and vitamin B12 to the CBRS. Comparison between Pd and Cu based on costs, catalyst activities, selectivities, metal stability, and fate of halogenated by-products shows that the CBRS is a potent alternative to conventional HDC catalysts and can be recommended as 'agent of choice' for treatment of α-substituted haloalkanes in heavily contaminated waters.

Genetic variability of Arthurdendyus triangulatus (Dendy, 1894), a non-native invasive land planarian.

Arthurdendyus triangulatus (Dendy, 1894) is a land planarian native to New Zealand which has become established in the United Kingdom and the Faroe Islands during the last 60 years. The species has become prevalent and widely established in Scotland mediated by human activity mostly through the exchange of plants and associated soil. As a predator of earthworms, concerns regarding both the direct impact on earthworm abundance and diversity and the indirect impact on those birds and mammals that have earthworms as a primary dietary component led to A. triangulatus being the subject of both national and EU regulation. Whilst much is known regarding the ecology of A. triangulatus there is a significant knowledge gap regarding the genetic variability of the species. Using four DNA target regions cytochrome oxidase (CoI), elongation factor (EF), internal transcribed spacer region (ITS-1) and large subunit (LSU), we characterised the genetic variability of A. triangulatus populations across its full geographic range in Scotland and included a few populations from New Zealand, England and Northern Ireland.                Two DNA regions, ITS-1 and CoI, revealed inter-population variability yielding well supported genetic structure in predominantly Scottish populations. We also identified considerable intra-specific and intra-individual heterogeneity in both ribosomal and mitochondrial regions, including the prevalence of pseudo-gene nuclear encoded mitochondrial DNA (Numt), the latter not previously reported for Platyhelminthes. Furthermore, given the presence of multiple ITS-1 haplotypes in individual specimens of A. triangulatus it is not possible to make definitive comment to support previously published findings that A. triangulatus was subjected to multiple introductions into the UK.

Interaction of zero-valent iron and carbonaceous materials for reduction of DDT.

Dechlorination of dichlorodiphenyltrichloroethane (DDT) as a model compound was performed with zero-valent iron (micro-ZVI and nano-ZVI) as reductant and carbonaceous adsorbents as sink and catalyst in water. DDT is rapidly converted to dichlorodiphenyldichloroethane (DDD) in direct contact with ZVI. However, up to 90% of the DDD is transformed into non-identified, most likely oligomeric products. There is no indication of dechlorination at the aromatic rings. DDT is still rapidly dechlorinated when it is adsorbed on carbonaceous adsorbents, even though ZVI particles have no direct access to the adsorbed DDT. The carbonaceous materials function as adsorbent and catalyst for the dechlorination reaction at once. From electrochemical experiments, we deduced that direct physical contact between ZVI particles and the adsorbent is essential for enabling a chemical reaction. Electron conduction alone does not effect any dechlorination reaction. We hypothesize hydrogen species (H∗) which spill from the ZVI surface to the carbon surface and initiate reductive transformations there. The role of carbonaceous adsorbents is different for different degradation pathways: in contrast to hydrodechlorination (reduction), adsorption protects DDT from dehydrochlorination (hydrolysis).

In-situ treatment of herbicide-contaminated groundwater-Feasibility study for the cases atrazine and bromacil using two novel nanoremediation-type materials.

Two injectable reactive and sorption-active particle types were evaluated for their applicability in permeable reaction zones for in-situ removal of herbicides ("nanoremediation"). As model substances, atrazine and bromacil were used, two herbicides frequently occurring in groundwater. In order to provide recommendations for best use, particle performance was assessed regarding herbicide degradation and detoxification. For chemical reduction, Carbo-Iron® was studied, a composite material consisting of zerovalent iron and colloidal activated carbon. Carbo-Iron reduced bromacil with increased activity compared to nanoscale zerovalent iron (nZVI). The sole reaction product, 3-sec-butyl-6-methyluracil, showed 500-fold increase in half-maximal-effect concentration (EC50) towards the chlorophyte Scendesmus vacuolatus compared to the parent compound. The detoxification based on dehalogenation confirmed the dependency of the specific mode-of-action on the carbon-halide bond. For atrazine, neither nZVI nor Carbo-Iron showed significant degradation under the conditions applied. As novel subsurface treatment option, Trap-Ox® zeolite FeBEA35 was studied for generation of in-situ permeable oxidation barriers. Both adsorbed atrazine and bromacil underwent fast unselective oxidation. The transformation products of the Fenton-like reaction were identified, and oxidation pathways derived. For atrazine, a 300-fold increase in EC50 for S. vacuolatus was found over the duration of the reaction, and a loss of phytotoxicity to non-detectable levels for bromacil.

Environmental risk or benefit? Comprehensive risk assessment of groundwater treated with nano Fe0-based Carbo-Iron®.

Groundwater is essential for the provision of drinking water in many areas around the world. The performance of the groundwater-bearing aquifer relies on the ecosystem services provided by groundwater-related organisms. Therefore, if remediation of contaminated groundwater is necessary, the remediation method has to be carefully selected to avoid risk-risk trade-offs that might impact these ecosystems. In the present study, the environmental risk of the in situ remediation agent Carbo-Iron was performed. Carbo-Iron® is a composite of zero valent nano-iron and active carbon. Existing ecotoxicity data were complemented by studies with Daphnia magna (Crustacea), Scenedesmus vacuolatus (Algae), Chironomus riparius (Insecta) and nitrifying soil microorganisms. The predicted no effect concentration of 0.1 mg/L was derived from acute and chronic ecotoxicity studies. It was compared to measured and modelled environmental concentrations of Carbo-Iron applied in a groundwater contaminated with chlorohydrocarbons in a field study and risk ratios were derived. A comprehensive assessment approach was developed further based on existing strategies and used to identify changes of the environmental risk due to the remediation of the contaminated site with Carbo-Iron. With the data used in the present study, the total environmental risk decreased by approximately 50% in the heavily contaminated zones after the application of Carbo-Iron. Thus, based on the results of the present study, the benefit of remediation with Carbo-Iron seems to outweigh its negative effects on the environment.

Sulfidation of ZVI/AC composite leads to highly corrosion-resistant nanoremediation particles with extended life-time.

Nanoscale zero-valent iron (nZVI) is a powerful reductant for many water pollutants. The lifetime of nZVI in aqueous environments is one of its limitations. Sulfidation of the nZVI surface by reduced sulfur species is known to significantly modify the particle properties. In the present study we examined various post-synthesis sulfidation methods applied on Carbo-Iron, a composite material where iron nanostructures are embedded in colloidal activated carbon (AC) particles. In such cases, where ZVI is surrounded by carbon, sulfidation largely inhibits the anaerobic corrosion of ZVI in water whereas its dechlorination activity was slightly increased. Even at a very low molar S/Fe ratio of 0.004 a strong decrease of the corrosion rate by a factor of 65 was achieved, while concurrently dechlorination of tetrachloroethene (PCE) was accelerated by a factor of three compared to the untreated particles. As a consequence, over 98% of the reduction equivalents of the sulfidated ZVI were utilized for the reduction of the target contaminant (33 mg L-1 PCE) under simulated groundwater conditions. In a long-term experiment over 160 days the extended life-time and the preservation of the reduction capacity of the embedded ZVI were confirmed. Reasons for the modified reaction behavior of Carbo-Iron after sulfidation compared to previously studied nZVI are discussed. We hypothesize that the structure of the carbon-embedded iron is decisive for the observed reaction behavior. In addition to reaction rates, the product pattern is vastly different compared to that of sulfidated nZVI. The triple combination of ZVI, AC and sulfur makes the composite particle very suitable for practical in-situ applications.

Acceleration of microiron-based dechlorination in water by contact with fibrous activated carbon.

Zero-valent iron (ZVI) is widely applied for reduction of chlorohydrocarbons in water. Since the dechlorination occurs at the iron surface, marked differences in rate constants are commonly found for nanoscale and microscale ZVI. It has already been shown for trichloroethene (TCE) adsorbed to activated carbon (AC) that the dechlorination reaction is shifted to the carbon surface simply by contacting the AC with highly reactive nanoscale ZVI particles. Transfer of reactive species to the adsorbed pollutant was discussed. The present study shows that even low price and very low reactive microscale ZVI can also be utilized for an effective dechlorination process. Compared to the reaction rate at the iron surface itself, an enormous acceleration of the dechlorination rate for chlorinated ethenes was observed, reaching activity levels such as known for nanoscale ZVI. When fibrous AC is brought into direct contact with microscale ZVI the iron-surface-normalised dechlorination rate constants increased by up to four orders of magnitude. This implies that the dechlorination reaction is fully transferred to the AC surface. At the same time, the anaerobic corrosion of the same material was not substantially affected. Thus, the utilization of iron's reduction equivalents towards dechlorination (dechlorination efficiency) can be considerably enhanced. A screening with various AC types showed that the extent of rate acceleration depends strongly on the surface chemistry of the AC. By means of temperature-programmed desorption, it could be shown that concentration and type of oxygen surface groups determine the redox-mediation properties. Quinone/hydroquinone groups were identified as being the main drivers for electron-transfer processes, but to some extent other redox-active groups such as chromene and pyrone can also act as redox mediators. AC overall plays the role of a catalyst rather than a reactant. The present study derives recommendations for practical application of the findings in water-treatment approaches.

Linkage Disequilibrium and Evaluation of Genome-Wide Association Mapping Models in Tetraploid Potato.

Genome-wide association studies (GWAS) have become a powerful tool for analyzing complex traits in crop plants. The current study evaluates the efficacy of various GWAS models and methods for elucidating population structure in potato. The presence of significant population structure can lead to detection of spurious marker-trait associations, as well as mask true ones. While appropriate statistical models are needed to detect true marker-trait associations, in most published potato GWAS, a 'one model fits all traits' approach has been adopted. We have examined various GWAS models on a large association panel comprising diverse tetraploid potato cultivars and breeding lines, genotyped with single nucleotide polymorphism (SNP) markers. Phenotypic data were generated for 20 quantitative traits assessed in different environments. Best Linear Unbiased Estimates (BLUEs) for these traits were obtained for use in assessing GWAS models. Goodness of fit of GWAS models, derived using different combinations of kinship and population structure for all traits, was evaluated using Quantile-Quantile (Q-Q) plots and genomic control inflation factors (λGC). Kinship was found to play a major role in correcting population confounding effects and results advocate a 'trait-specific' fit of different GWAS models. A survey of genome-wide linkage disequilibrium (LD), one of the critical factors affecting GWAS, is also presented and our findings are compared to other recent studies in potato. The genetic material used here, and the outputs of this study represent a novel resource for genetic analysis in potato.

Combined chemical and microbiological degradation of tetrachloroethene during the application of Carbo-Iron at a contaminated field site.

After the injection of Carbo-Iron® into an aquifer contaminated with tetrachloroethene (PCE), combined chemical and microbiological contaminant degradation processes were found in a long-term study of the field site in Lower Saxony (Germany). The applied composite material Carbo-Iron, which consists of colloidal activated carbon and embedded nanoscale zero-valent iron (ZVI) structures, functioned as intended: accumulating the pollutants and promoting their reductive dechlorination. Furthermore, the particles decreased the redox potential of the groundwater due to their reaction with oxygen and to the ZVI-corrosion-induced formation of molecular hydrogen up to 190 days after the injection, the latter promoting sulphate-reducing conditions. The emergence of cis-dichloroethene (cis-DCE), which was only found in trace quantities before the injection of Carbo-Iron, together with the presence of organisms related to Sulfospirillum multivorans, Desulfitobacterium spp. and Dehalococcoides mccartyi, indicate that Carbo-Iron is also able to support microbial degradation of PCE. However, cis-DCE did not accumulate in the present case study, although it is often observed at sites with active microbial dechlorination. The results of compound-specific isotope analysis in combination with pyrosequencing data suggested the oxidative degradation of cis-DCE by an organism related to Polaromonas sp. strain JS666. Consequently, the formation of the carcinogenic degradation intermediate vinyl chloride was circumvented. Overall, the moderate and slow change of environmental conditions mediated by Carbo-Iron not only supported organohalide-respiring bacteria, but also created the basis for a subsequent microbial oxidation step.

Biological effects of four iron-containing nanoremediation materials on the green alga Chlamydomonas sp.

As nanoremediation strategies for in-situ groundwater treatment extend beyond nanoiron-based applications to adsorption and oxidation, ecotoxicological evaluations of newly developed materials are required. The biological effects of four new materials with different iron (Fe) speciations ([i] FerMEG12 - pristine flake-like milled Fe(0) nanoparticles (nZVI), [ii] Carbo-Iron® - Fe(0)-nanoclusters containing activated carbon (AC) composite, [iii] Trap-Ox® Fe-BEA35 (Fe-zeolite) - Fe-doped zeolite, and [iv] Nano-Goethite - 'pure' FeOOH) were studied using the unicellular green alga Chlamydomonas sp. as a model test system. Algal growth rate, chlorophyll fluorescence, efficiency of photosystem II, membrane integrity and reactive oxygen species (ROS) generation were assessed following exposure to 10, 50 and 500 mg L-1 of the particles for 2 h and 24 h. The particles had a concentration-, material- and time-dependent effect on Chlamydomonas sp., with increased algal growth rate after 24 h. Conversely, significant intracellular ROS levels were detected after 2 h, with much lower levels after 24 h. All Fe-nanomaterials displayed similar Z-average sizes and zeta-potentials at 2 h and 24 h. Effects on Chlamydomonas sp. decreased in the order FerMEG12 > Carbo-Iron® > Fe-zeolite > Nano-Goethite. Ecotoxicological studies were challenged due to some particle properties, i.e. dark colour, effect of constituents and a tendency to agglomerate, especially at high concentrations. All particles exhibited potential to induce significant toxicity at high concentrations (500 mg L-1), though such concentrations would rapidly decrease to mg or µg L-1 in aquatic environments, levels harmless to Chlamydomonas sp. The presented findings contribute to the practical usage of particle-based nanoremediation in environmental restoration.

Enhanced protection of PDMS-embedded palladium catalysts by co-embedding of sulphide-scavengers.

For Pd-containing hydrodechlorination catalysts, coating with poly(dimethyl siloxane) (PDMS) was proposed earlier as promising protection scheme against poisoning. The PDMS coating can effectively repel non-permeating poisons (such as SO32-) retaining the hydrodechlorination Pd activity. In the present study, the previously achieved protection efficiency was enhanced by incorporation of sulphide scavengers into the polymer. The embedded scavengers were able to bind permeating non-ionic poisons (such as H2S) during their passage through PDMS prior to Pd contact which ensured an extended catalyst lifetime. Three scavenger types forming non-permeable sulphur species from H2S - alkaline, oxidative or iron-based compounds - were either incorporated into single-layer coats around individual Pd/Al2O3 particles or into a second layer above Pd-containing PDMS films (Pd-PDMS). Hydrodechlorination and hydrogenation were chosen as model reactions, carried out in batch and continuous-flow reactors. Batch tests with all scavenger-containing catalysts showed extended Pd protection compared to scavenger-free catalysts. Solid alkaline compounds (Ca(OH)2, NaOH, CaO) and MnO2 showed the highest instantaneous scavenger efficiencies (retained Pd activity=30-60%), while iron-based catalysts, such as nano zero-valent iron (nZVI) or ferrocene (FeCp2), proved less efficient (1-10%). When stepwise poisoning was applied, the protection efficiency of iron-based and oxidizing compounds was higher in the long term than that of alkaline solids. Long-term experiments in mixed-flow reactors were performed with selected scavengers, revealing the following trend of protection efficiency: CaO2>Ca(OH)2>FeCp2. Under field-simulating conditions using a fixed-bed reactor, the combination of sulphide pre-oxidation in the water phase by H2O2 and local scavenger-enhanced Pd protection was successful. The oxidizing agent H2O2 does not disturb the Pd-catalysed reduction, while the PDMS-incorporated scavenger considerably extends the catalyst life in the presence of H2S. This work demonstrates that the scavenger-based protection strategy is an effective means to increase the resistance of PDMS-embedded Pd against permeating poisons.

Accelerated Catalytic Fenton Reaction with Traces of Iron: An Fe-Pd-Multicatalysis Approach.

An accelerated catalytic Fenton (ACF) reaction was developed based upon a multicatalysis approach, facilitating efficient contaminant oxidation at trace levels of dissolved iron. Beside the Fe(II)/H2O2 catalyst/oxidant pair for production of OH-radicals, the ACF system contains Pd/H2 as catalyst/reductant pair for fast reduction of Fe(III) back to Fe(II) which accelerates the Fenton cycle and leads to faster contaminant degradation. By this means, the concentration of the dissolved iron catalyst can be reduced to trace levels (1 mg L(-1)) below common discharge limits, thus eliminating the need for iron sludge removal, which is one of the major drawbacks of conventional Fenton processes. ACF provides fast degradation of the model contaminant methyl tert-butyl ether (MTBE, C0 = 0.17 mM) with a half-life of 11 min with 1 mg L(-1) dissolved iron, 500 mg L(-1) H2O2, 5 mg L(-1) Pd (as suspended Pd/Al2O3 catalyst) and 0.1 MPa H2, pH 3. The effects of pH, H2 partial pressure and H2O2 concentration on MTBE degradation rates were studied. Results on kinetic deuterium isotope effect and quenching studies are in conformity with OH-radicals as main oxidant. The heterogeneous Pd/Al2O3 catalyst was reused within six cycles without significant loss in activity.

Fluorescence labelling as tool for zeolite particle tracking in nanoremediation approaches.

Colloidal Fe-zeolites such as Fe-BEA-35 are currently under study as new adsorbent and catalyst materials for in-situ chemical oxidation with H2O2. As for nanoremediation in general, the availability of suitable particle detection methods is a requirement for successful process development and particle tracing. Detection and distinguishing between natural colloids and introduced particles with a similar composition are a challenge. By means of fluorescence labelling, a highly specific detection option for Fe-BEA-35 was developed. 'Ship-in-a-bottle' synthesis of fluorescein within the zeolite pores, which was applied for the first time for a BEA type zeolite, provides a product with stable and non-extractable fluorescence. When the fluorescent labelled zeolite is added at a concentration of 1wt.% referring to the total zeolite mass, a very low detection limit of 1mg/L of total zeolite is obtained. Compared to commonly applied turbidity measurements, detection via fluorescence labelling is much more specific and sensitive. Fluorescence is only marginally affected by carboxymethyl cellulose, which is frequently applied as stabilizer in application suspensions but will be depleted upon contact with H2O2. Transport properties of fluorescent labelled and non-labelled Fe-zeolite particles are in agreement as determined in a column study with quartz sand and synthetic groundwater (classified as very hard).

Carbo-Iron as improvement of the nanoiron technology: From laboratory design to the field test.

In a first pilot-scale field test the use of Carbo-Iron® was successfully demonstrated. Carbo-Iron was developed with the goal to overcome significant shortcomings of nanoscale zero-valent iron (NZVI) for in-situ groundwater remediation. The composite material of colloidal activated carbon and embedded nanoiron structures has been tested for the remediation of a tetrachloroethene (PCE) contaminated field site in Lower Saxony, Germany. The results of the two-step field test confirmed the properties intended by its design and the particle performance achieved in the laboratory experiments. The material showed transport lengths of several metres in the field and fast PCE decomposition with no vinyl chloride formation. Extended longevity of the PCE decrease in the treated area and evidence for microbiological participation were found. Carbo-Iron is now under study in the framework of the EU-project NanoREM where its performance is being further optimized at various scales from laboratory via large-scale tank to field testing. Targeted property adjustment was successful for Carbo-Iron performance in both directions: plume treatment and source attack.