Iron Nitride Nanoparticles for Enhanced Reductive Dechlorination of Trichloroethylene.

Nitriding has been used for decades to improve the corrosion resistance of iron and steel materials. Moreover, iron nitrides (FexN) have been shown to give an outstanding catalytic performance in a wide range of applications. We demonstrate that nitriding also substantially enhances the reactivity of zerovalent iron nanoparticles (nZVI) used for groundwater remediation, alongside reducing particle corrosion. Two different types of FexN nanoparticles were synthesized by passing gaseous NH3/N2 mixtures over pristine nZVI at elevated temperatures. The resulting particles were composed mostly of face-centered cubic (γ'-Fe4N) and hexagonal close-packed (ε-Fe2-3N) arrangements. Nitriding was found to increase the particles' water contact angle and surface availability of iron in reduced forms. The two types of FexN nanoparticles showed a 20- and 5-fold increase in the trichloroethylene (TCE) dechlorination rate, compared to pristine nZVI, and about a 3-fold reduction in the hydrogen evolution rate. This was related to a low energy barrier of 27.0 kJ mol-1 for the first dechlorination step of TCE on the γ'-Fe4N(001) surface, as revealed by density functional theory calculations with an implicit solvation model. TCE dechlorination experiments with aged particles showed that the γ'-Fe4N nanoparticles retained high reactivity even after three months of aging. This combined theoretical-experimental study shows that FexN nanoparticles represent a new and potentially important tool for TCE dechlorination.

Groundwater Chemistry Has a Greater Influence on the Mobility of Nanoparticles Used for Remediation than the Chemical Heterogeneity of Aquifer Media.

The application of nanoscale zerovalent iron (nano-ZVI) particles for groundwater remediation has spurred research into the influence of the collector heterogeneity on the nano-ZVI mobility. The chemical heterogeneity of surfaces within aquifer media affects their surface charge distribution and their affinity for nano-ZVI. The groundwater chemistry affects the properties of both aquifer surfaces and the nano-ZVI particles. Commercial poly(acrylic acid)-coated nano-ZVI (PAA-nano-ZVI) particles were tested in column experiments using two solution chemistries and silica collectors with different degrees of chemical heterogeneity, achieved by ferrihydrite coating. A porous media filtration model was used to determine the attachment efficiency of PAA-nano-ZVI particles, and the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was used to describe the interactions between PAA-nano-ZVI particles and the aquifer "collectors". The mobility of PAA-nano-ZVI particles suspended in ultrapure water depended on the extent of ferrihydrite coating on the collector surfaces. The mobility of PAA-nano-ZVI particles under environmentally relevant conditions was independent of the collector chemical heterogeneity. The size of PAA-nano-ZVI aggregates doubled, inducing gravitational sedimentation and possibly straining as mechanisms of particle deposition. There was no repulsive energy barrier between particles and collectors, and the DLVO theory was unable to explain the observed particle attachment. Our results suggest that the groundwater chemistry has a greater influence on the mobility of PAA-nano-ZVI particles than the collector chemical heterogeneity. A better understanding of polymer adsorption to nanoparticles and its conformation under natural groundwater conditions is needed to further elucidate nanoparticle-collector interactions.

Impact of Sodium Humate Coating on Collector Surfaces on Deposition of Polymer-Coated Nanoiron Particles.

The affinity between nanoscale zerovalent iron (nano-ZVI) and mineral surfaces hinders its mobility, and hence its delivery into contaminated aquifers. We have tested the hypothesis that the attachment of poly(acrylic acid)-coated nano-ZVI (PAA-nano-ZVI) to mineral surfaces could be limited by coating such surfaces with sodium (Na) humate prior to PAA-nano-ZVI injection. Na humate was expected to form a coating over favorable sites for PAA-nano-ZVI attachment and hence reduce the affinity of PAA-nano-ZVI for the collector surfaces through electrosteric repulsion between the two interpenetrating charged polymers. Column experiments demonstrated that a low concentration (10 mg/L) Na humate solution in synthetic water significantly improved the mobility of PAA-nano-ZVI within a standard sand medium. This effect was, however, reduced in more heterogeneous natural collector media from contaminated sites, as not an adequate amount of the collector sites favorable for PAA-nano-ZVI attachment within these media appear to have been screened by the Na humate. Na humate did not interact with the surfaces of acid-washed glass beads or standard Ottawa sand, which presented less surface heterogeneity. Important factors influencing the effectiveness of Na humate application in improving PAA-nano-ZVI mobility include the solution chemistry, the Na humate concentration, and the collector properties.

Application of envelope trend to analyze early EEG changes in the frontal regions during intracarotid amobarbital procedure in children.

BACKGROUND: Intracarotid amobarbital procedure (IAP) is acknowledged as the gold standard test for language lateralization. EEG is performed routinely during IAP to monitor the anesthetization of a brain hemisphere. Here, we studied the correlation between the early EEG changes using envelope trend and the clinical outcome of IAP. METHOD: Fifty consecutive patients underwent IAP at Texas Children's Hospital (2004-2009). Intracarotid amobarbital procedure was considered "complete" or "incomplete" based on the outcome if the procedure was completed or aborted due to behavior changes. Envelope trend was used to calculate the median EEG amplitude changes within the first 60s of IAP. Statistical analysis was performed to determine the role of EEG changes and clinical features on the procedure outcome. RESULTS: Only 30 IAP-EEG files were available for review. Amobarbital was administered at the dose of 60-150mg (mean: 110±20). The intracarotid amobarbital procedure was recorded as complete in 23 patients and incomplete in 7 patients. EEG changes occurred within the first few seconds following amobarbital injection. Following amobarbital injection, focal slowing was present in the ipsilateral frontal region or both ipsilateral and contralateral frontal regions. Elapsed time to the first EEG change or duration and change in median EEG amplitude in the ipsilateral frontal regions were indifferent between the complete and incomplete groups (p>0.05). However, the median amplitude changes between the ipsilateral and contralateral frontal regions within each group were found significant only in the complete group (p<0.05), suggesting ipsilateral without contralateral frontal slowing. Other than age at the time of IAP (p=0.03), none of the other clinical features correlated with the clinical outcome of IAP (p>0.05). CONCLUSION: Early EEG changes during IAP using envelope trend may predict successful completion of the IAP test. Younger children are at risk of behavioral changes during IAP.

Iron nitride nanoparticles for rapid dechlorination of mixed chlorinated ethene contamination.

Sulfidation and, more recently, nitriding have been recognized as promising modifications to enhance the selectivity of nanoscale zero-valent iron (nZVI) particles for trichloroethene (TCE). Herein, we investigated the performance of iron nitride (FexN) nanoparticles in the removal of a broader range of chlorinated ethenes (CEs), including tetrachloroethene (PCE), cis-1,2-dichloroethene (cis-DCE), and their mixture with TCE, and compared it to the performance of sulfidated nZVI (S-nZVI) prepared from the same precursor nZVI. Two distinct types of iron nitride (FexN) nanoparticles, containing γ'-Fe4N and ε-Fe2-3N phases, exhibited substantially higher PCE and cis-DCE dechlorination rates compared to S-nZVI. A similar effect was observed with a CE mixture, which was completely dechlorinated by both types of FexN nanoparticles within 10 days, whereas S-nZVI was able to remove only about half of the amount, most of which being TCE. Density functional theory calculations further revealed that the cleavage of the first C-Cl bond was the rate-limiting step for all CEs dechlorinated on the γ'-Fe4N(001) surface, with the reaction barriers of PCE and cis-DCE being 29.9, and 40.8 kJ mol-1, respectively. FexN nanoparticles proved to be highly effective in the remediation of PCE, cis-DCE, and mixed CE contamination.

Emerging contaminants in sediment core from the Iron Gate I Reservoir on the Danube River.

The Iron Gate I Reservoir is the largest impoundment on the Danube River. It retains >50% of the incoming total suspended solids load and the associated organic contaminants. In the sediment core of the Iron Gate I Reservoir we report the presence and fate of four classes of emerging contaminants (pharmaceuticals, pesticides, steroids and perfluorinated compounds), predominantly not covered by the EU monitoring programs, but considered as future candidates. Based on contaminant's partitioning behavior in the water/sediment system and the suspected ecotoxicological potential asserted from the literature data, the risk of recorded concentrations for sediment-dwelling organisms was discussed. The high anticipated risk was associated with antibiotics sulfamethoxazole and erythromycin, and pesticides linuron and carbendazim (banned in the EU, but still approved for use in the investigated area) and malathion. This indicated the need for better control of release of these compounds into the river, and implied their inclusion in future regular monitoring. Higher concentrations of pharmaceuticals and most pesticides and sterols were recorded in the fragment of allochthonous coarser sediment, assumed to have entered the reservoir during a high discharge event. Only one perfluorinated compound was recorded in the upper part of the sediment core. The vertical concentration profiles of pesticides propazine and malathion indicated their uniform source, most likely atmospheric transport and deposition of particles deriving from agricultural land.

Chemosymbiotic bivalves contribute to the nitrogen budget of seagrass ecosystems.

In many seagrass sediments, lucinid bivalves and their sulfur-oxidizing symbionts are thought to underpin key ecosystem functions, but little is known about their role in nutrient cycles, particularly nitrogen. We used natural stable isotopes, elemental analyses, and stable isotope probing to study the ecological stoichiometry of a lucinid symbiosis in spring and fall. Chemoautotrophy appeared to dominate in fall, when chemoautotrophic carbon fixation rates were up to one order of magnitude higher as compared with the spring, suggesting a flexible nutritional mutualism. In fall, an isotope pool dilution experiment revealed carbon limitation of the symbiosis and ammonium excretion rates up to tenfold higher compared with fluxes reported for nonsymbiotic marine bivalves. These results provide evidence that lucinid bivalves can contribute substantial amounts of ammonium to the ecosystem. Given the preference of seagrasses for this nitrogen source, lucinid bivalves' contribution may boost productivity of these important blue carbon ecosystems.

Effect of ageing on the properties and polycyclic aromatic hydrocarbon composition of biochar.

The influence of ageing on biochar properties has been investigated by comparing three fresh biochars with biochars artificially aged by either H2O2 thermal oxidation or horseradish peroxidase enzymatic oxidation. In addition, a field-aged counterpart for one of the biochars was recovered from an agricultural field site, four years after application. Biochar properties, including surface areas and pore volumes (derived by N2 and CO2 physisorption) and elemental compositions, showed only minor changes following both artificial and field ageing, indicating high biochar stability. Concentrations of the 16 US EPA PAHs were measured in all of the biochars and a contaminant trap was used to investigate the effect of ageing on their bioaccessibility. The concentrations of total and bioaccessible PAHs ranged from 4.4 to 22.6 mg kg-1 and 0.0 to 9.7 mg kg-1, respectively. Concentrations of the 16 US EPA PAHs decreased following field ageing, but the proportion of low molecular weight PAHs increased. The observed changes in PAH composition with field ageing can be explained by uptake from the surrounding soil and intra-biochar transfer processes. To better understand changes in PAH composition with ageing, an additional broad range of alkylated PAHs was also analyzed in selected samples. Our results show that the tested artificial ageing protocols are unable to approximate the changes in PAH composition resulting from field ageing. Nevertheless, total and bioaccessible PAH concentrations decreased for both artificially and field-aged biochars, indicating that biochars release PAHs when they are freshly produced and that the risk of PAH release decreases with ageing.

Agar agar-stabilized milled zerovalent iron particles for in situ groundwater remediation.

Submicron-scale milled zerovalent iron (milled ZVI) particles produced by grinding macroscopic raw materials could provide a cost-effective alternative to nanoscale zerovalent iron (nZVI) particles for in situ degradation of chlorinated aliphatic hydrocarbons in groundwater. However, the aggregation and settling of bare milled ZVI particles from suspension presents a significant obstacle to their in situ application for groundwater remediation. In our investigations we reduced the rapid aggregation and settling rate of bare milled ZVI particles from suspension by stabilization with a "green" agar agar polymer. The transport potential of stabilized milled ZVI particle suspensions in a diverse array of natural heterogeneous porous media was evaluated in a series of well-controlled laboratory column experiments. The impact of agar agar on trichloroethene (TCE) removal by milled ZVI particles was assessed in laboratory-scale batch reactors. The use of agar agar significantly enhanced the transport of milled ZVI particles in all of the investigated porous media. Reactivity tests showed that the agar agar-stabilized milled ZVI particles were reactive towards TCE, but that their reactivity was an order of magnitude less than that of bare, non-stabilized milled ZVI particles. Our results suggest that milled ZVI particles could be used as an alternative to nZVI particles as their potential for emplacement into contaminated zone, their reactivity, and expected longevity are beneficial for in situ groundwater remediation.

Measuring the reactivity of commercially available zero-valent iron nanoparticles used for environmental remediation with iopromide.

The high specific surface area and high reactivity of nanoscale zero-valent iron (nZVI) particles have led to much research on their application to environmental remediation. The reactivity of nZVI is affected by both the water chemistry and the properties of the particular type of nZVI particle used. We have investigated the reactivity of three types of commercially available Nanofer particles (from Nanoiron, s.r.o., Czech Republic) that are currently either used in, or proposed for use in full scale environmental remediation projects. The performance of one of these, the air-stable and thus easy-to-handle Nanofer Star particle, has not previously been reported. Experiments were carried out first in batch shaking reactors in order to derive maximum reactivity rates and provide a rapid estimate of the Nanofer particle's reactivity. The experiments were performed under near-natural environmental conditions with respect to the pH value of water and solute concentrations, and results were compared with those obtained using synthetic water. Thereafter, the polyelectrolyte-coated Nanofer 25S particles (having the highest potential for transport within porous media) were chosen for the experiments in column reactors, in order to elucidate nanoparticle reactivity under a more field-site realistic setting. Iopromide was rapidly dehalogenated by the investigated nZVI particles, following pseudo-first-order reaction kinetics that was independent of the experimental conditions. The specific surface area normalized reaction rate constant (kSA) value in the batch reactors ranged between 0.12 and 0.53Lm(-2)h(-1); it was highest for the uncoated Nanofer 25 particles, followed by the polyacrylic acid-coated Nanofer 25S and air-stable Nanofer Star particles. In the batch reactors all particles were less reactive in natural water than in synthetic water. The kSA values derived from the column reactor experiments were about 1000 times lower than those from the batch reactors, ranging between 2.6×10(-4) and 5.7×10(-4)Lm(-2)h(-1). Our results revealed that the easy-to-handle and air-stable Nanofer Star particles are the least reactive of all the Nanofer products tested. The reaction kinetics predicted by column experiments were more realistic than those predicted by batch experiments and these should therefore be used when designing a full-scale field application of nanomaterials for environmental remediation.

Mobility enhancement of nanoscale zero-valent iron in carbonate porous media through co-injection of polyelectrolytes.

The mobility of nanoscale zero-valent iron (nZVI), which is used for in situ groundwater remediation, is affected by chemical and physical heterogeneities within aquifers. Carbonate minerals in porous aquifers and the presence of divalent cations reduce nZVI mobility. This study assesses the potential for enhancing the mobility of polyacrylic acid coated nZVI (PAA-nZVI) in such aquifers through the co-injection of polyelectrolytes (natural organic matter, humic acid, carboxymethyl cellulose, and lignin sulfonate). When applied at the same concentration, all of the polyelectrolytes produced similar enhancement of PAA-nZVI mobility in carbonate porous media. This increase in mobility was a result of increased repulsion between PAA-nZVI and the carbonate matrix. Lignin sulfonate, an environmentally friendly and inexpensive agent, was identified as the most suitable polyelectrolyte for field applications. The greatest increase in PAA-nZVI mobility was achieved with co-injection of lignin sulfonate at concentrations ≥50 mg L(-1); at these concentrations the maximum PAA-nZVI travel distance in carbonate porous media was twice of that in the absence of lignin sulfonate.

Carbonate minerals in porous media decrease mobility of polyacrylic acid modified zero-valent iron nanoparticles used for groundwater remediation.

The limited transport of nanoscale zero-valent iron (nZVI) in porous media is a major obstacle to its widespread application for in situ groundwater remediation. Previous studies on nZVI transport have mainly been carried out in quartz porous media. The effect of carbonate minerals, which often predominate in aquifers, has not been evaluated to date. This study assessed the influence of the carbonate minerals in porous media on the transport of polyacrylic acid modified nZVI (PAA-nZVI). Increasing the proportion of carbonate sand in the porous media resulted in less transport of PAA-nZVI. Predicted travel distances were reduced to a few centimeters in pure carbonate sand compared to approximately 1.6 m in quartz sand. Transport modeling showed that the attachment efficiency and deposition rate coefficient increased linearly with increasing proportion of carbonate sand.

Generalized periodic epileptiform discharges in critically ill children: clinical features, and outcome.

PURPOSE: Generalized periodic epileptiform discharges (GPDs) are a specific periodic EEG pattern, reported as having a poor clinical outcome. The incidence and clinical implications of this EEG pattern in children are not known. In this study, we examined the clinical features of children with GPDs. METHODS: EEG-video monitoring reports of children with critical illness in the intensive care unit were retrospectively reviewed to detect GPDs. The clinical history, hospital course and seizure characteristics were reviewed and outcome was based on the clinical findings at hospital discharge. RESULTS: Twenty one children (age 2-18 years) were identified with GPDs. The most common underlying etiology was encephalitis (N=11). At the time of EEG, a continuous intravenous infusion (cIV) of an anticonvulsant drug was used to treat refractory status epilepticus (RSE). Non-convulsive seizures (NCS) were identified in 15, and clinical seizures in 13 children after GPDs were detected. GPDs occurred after a dose reduction in the cIV in 43%. Neuroimaging done in 16 children showed an acute change in 13/16 (81%) and chronic changes in 2/16 (13%). Five children (23%) died. Seven (33%) children had a favorable outcome, whereas the remaining children had a moderate to severe disability at the time of hospital discharge. CONCLUSION: GPDs are seen during the course of RSE in critically ill children and are associated with seizure recurrence. A lower mortality rate occurs in children with GPDs compared to adult counterparts, likely related to different etiologies. Although the significance of GPDs must be determined within the context of the clinical situation, GPDs suggest a still active epileptic process.

Seizure detection using digital trend analysis: Factors affecting utility.

BACKGROUND: EEG monitoring is important for the early detection of seizures during the course of critical illness. However, the logistics of real time EEG interpretation is challenging for the neurophysiology and critical care medicine teams. This study evaluated factors affecting the utility of digital trend analysis (DTA) for rapid seizure identification in children. METHODS: digital EEG files of seizures in critically ill children were retrieved for DTA. The envelop trend (ET) and compressed spectral array (CSA) were applied to the raw EEG data and presented to an experienced and inexperienced user for interpretation who were blinded to conventional EEG findings. The EEG findings with and without presence of seizures and features of seizures were analyzed. RESULTS: we found that a number of factors affected accurate seizure detection including factors related to interpreter's experiences, display size and type of DTA methods used for analysis in addition to baseline EEG findings. ET was more dependent on user experience, furthermore, display size and multimodal DTA application (CSA and ET combined) increased the sensitivity of seizure detection for the experienced user compared to inexperience users. The artifacts were reported as seizures regardless of experience without presence of conventional EEG recording. The maximum spike amplitude, seizure duration, and seizure frequency were other important determinants for accuracy. Electrographic seizures with shorter duration were better detected by ET, and the maximum spike amplitude was important for both the ET and CSA. Repetitive seizures are readily detected by both digital trending methods. Artifacts may be reported as seizures regardless of experience if conventional EEG recording is not available for the interpretation. CONCLUSION: DTA applied to the raw EEG data does produce a graphic display that facilitates identification of seizures. The actual characteristics of the electrographic seizure may predict which DTA method is better and the overall accuracy of seizure detection may increase when multimodal trending is used simultaneously. Application of DTA alone with display of conventional EEG is beneficial for rapid interpretation of EEG findings regardless of experience.

Occurrence and behaviour of selected hydrophobic alkylphenolic compounds in the Danube River.

Six hydrophobic alkylphenolic compounds were investigated for the first time simultaneously in four different matrices in the Danube River. Maximum sediment concentrations were 2.83, 2.10, 0.28, and 0.035 mg kg(-1) for nonylphenol, nonylphenol monoethoxylate, nonylphenol diethoxylate and octylphenol. Maximum levels in suspended particulate matter (SPM) were 0.18, 0.12, 0.10, and 0.003 mg kg(-1). No correlation between concentrations in SPM and sediments was found. Octylphenol monoethoxylate and octylphenol diethoxylate were recorded only in sediment at one location. In mussels and water only nonylphenol and octylphenol were found. Nonylphenol concentrations in mussels (up to 0.34 mg kg(-1)) correlate with concentrations found in SPM and indicate a slight bioaccumulation. Concentrations in water were close to the limit of quantification. We assume in situ formation of nonylphenol monoethoxylate and nonylphenol in sediments at some locations. In some cases nonylphenol in sediments exceeded the provisional EU environmental quality standards.