Continuous co-treatment of mine drainage with municipal wastewater.

Acid mine drainage (AMD) and municipal wastewater (MWW) are commonly co-occurring waste streams in mining regions. Co-treating AMD at existing wastewater facilities represents an innovative solution for simultaneous AMD reclamation and improved MWW treatment. However, unknowns related to biological processes and continuous treatment performance block full-scale use. The overarching goal of this work was to address questions related to efficacy and performance of continuous processing of AMD in a biological MWW treatment system. Synthetic AMD was co-treated with synthetic MWW in a continuously-operating bench-scale sequencing batch reactor (SBR). SBRs treated MWW with two strengths of AMD (91 and 720 mg/L as CaCO3 Acidity) to capture the variations of coal AMD chemistry and strength observed in the field. Each co-treatment phases lasted 40+ days, during which clarified effluent and settled sludge quality was routinely monitored to determine impacts of co-treatment relative to conventional MWW treatment performance. Co-treatment produced effluent that met key standards for secondary treatment including biochemical oxygen demand (BOD) < 5 mg/L, total suspended solids (TSS) < 20 mg/L, and pH ∼7.0. Addition of AMD also improved treatment performance, increasing Phosphate (PO4) removal by >60% and pathogen removal by an order of magnitude. Furthermore, AMD co-treatment did not exhibit any major impacts on the overall diversity of the wastewater microbial community. Co-treatment sludge had slightly higher settleability and a lower bound water content, but notable changes in sludge morphology was observed. This study demonstrates co-treatment allows for continuous mitigation of AMD without adversely impacting MWW treatment performance in conventional biological MWW processes.

Ten-Fold Solvent Kinetic Isotope Effect for the Nonradiative Relaxation of the Aqueous Ferrate(VI) Ion.

Hypervalent iron intermediates have been invoked in the catalytic cycles of many metalloproteins, and thus, it is crucial to understand how the coupling between such species and their environment can impact their chemical and physical properties in such contexts. In this work, we take advantage of the solvent kinetic isotope effect (SKIE) to gain insight into the nonradiative deactivation of electronic excited states of the aqueous ferrate(VI) ion. We observe an exceptionally large SKIE of 9.7 for the nanosecond-scale relaxation of the lowest energy triplet ligand field state to the ground state. Proton inventory studies demonstrate that a single solvent O-H bond is coupled to the ion during deactivation, likely due to the sparse vibrational structure of ferrate(VI). Such a mechanism is consistent with that reported for the deactivation of f-f excited states of aqueous trivalent lanthanides, which exhibit comparably large SKIE values. This phenomenon is ascribed entirely to dissipation of energy into a higher overtone of a solvent acceptor mode, as any impact on the apparent relaxation rate due to a change in solvent viscosity is negligible.

Photochemical and Photophysical Dynamics of the Aqueous Ferrate(VI) Ion.

Ferrate(VI) has the potential to play a key role in future water supplies. Its salts have been suggested as "green" alternatives to current advanced oxidation and disinfection methods in water treatment, especially when combined with ultraviolet light to stimulate generation of highly oxidizing Fe(V) and Fe(IV) species. However, the nature of these intermediates, the mechanisms by which they form, and their roles in downstream oxidation reactions remain unclear. Here, we use a combination of optical and X-ray transient absorption spectroscopies to study the formation, interconversion, and relaxation of several excited-state and metastable high-valent iron species following excitation of aqueous potassium ferrate(VI) by ultraviolet and visible light. Branching from the initially populated ligand-to-metal charge transfer state into independent photophysical and photochemical pathways occurs within tens of picoseconds, with the quantum yield for the generation of reactive Fe(V) species determined by relative rates of the competing intersystem crossing and reverse electron transfer processes. Relaxation of the metal-centered states then occurs within 4 ns, while the formation of metastable Fe(V) species occurs in several steps with time constants of 250 ps and 300 ns. Results here improve the mechanistic understanding of the formation and fate of Fe(V) and Fe(IV), which will accelerate the development of novel advanced oxidation processes for water treatment applications.

Abatement of circumneutral mine drainage by Co-treatment with secondary municipal wastewater.

Acid mine drainage is a persistent and problematic source of water pollution. Co-treatment with municipal wastewater at existing wastewater treatment plants has several advantages; however, potential impacts on plant physicochemical and biological processes have not been well explored. The primary purpose of this bench-scale study was to examine the impact of co-treatment by combining a mild acid mine drainage at various ratios with municipal wastewater, followed by sludge settling and supernatant comparative analysis using a variety of effluent water quality parameters. These measurements were combined with carbonate system and adsorption isotherm modeling to elucidate the mechanisms underlying the experimental results. Acid mine drainage addition decreased municipal wastewater effluent PO43- concentrations below 0.2 mg/L with greater than 97% removal, demonstrating co-treatment as an alternative solution for municipal wastewater nutrient removal. Biochemical oxygen demand remained similar to controls with <10% variation after co-treatment. Coagulation from metals in acid mine drainage was incomplete due to PO43- adsorption, confirmed by comparing experimental results with Langmuir isotherm behavior. Sweep flocculation was the dominating particle aggregation mechanism, and co-treatment led to improved particle clarification outcomes. Improved clarification led to up to 50% Fe removal. Final pH had little variation with all conditions having pH > 6.0. Carbonate system modeling adequately explains pH effects, and can also be applied to varying acid mine drainage matrices. The impact of acid mine drainage addition on the municipal wastewater microbial community was also investigated which provided evidence of microbial adaptation. This study demonstrates post-aeration co-treatment enables mitigation of mild acid mine drainage without adversely affecting wastewater treatment plant processes. Reported results also frame required future studies to address extant questions prior to full-scale adaptation.

A UK feasibility and validation study of the VE1 monoclonal antibody immunohistochemistry stain for BRAF-V600E mutations in metastatic melanoma.

BACKGROUND: Determining the BRAF mutation status of patients with advanced metastatic melanoma is essential in order to assess patients' eligibility for targeted BRAF inhibitor therapy. The aim of this study was to validate the utility of immunohistochemistry (IHC) to rapidly obtain the BRAF status in the UK cancer centre setting. METHODS: All samples sent for molecular testing for detection of the BRAF mutation over a 26-month period were prospectively tested using the VE1 monoclonal antibody IHC stain. RESULTS: Two-hundred and nineteen samples from 214 patients were identified. All patients were AJCC stage III/IV, except one. There was an overall 95.0% (208/219) concordance rate, with a sensitivity of 94.4% (84/89) and a specificity of 95.4% (124/130) when using genomic assays as the gold standard. Discordance resulted from the inability of the molecular technique to detect the V600E2 mutation and an inability of the IHC staining technique to detect non-V600E mutations. Molecular testing on smaller tumour deposits was also unreliable. CONCLUSIONS: IHC staining has good sensitivity and excellent specificity for BRAF V600E mutations. BRAF IHC can be incorporated into a BRAF mutation testing algorithm for UK cancer centres to as a feasible first-line assay and identify a subset of cases that require subsequent genomic testing. It has the additional major advantages of reduced cost and rapid turnaround time.

Effect of different solutes, natural organic matter, and particulate Fe(III) on ferrate(VI) decomposition in aqueous solutions.

This study investigated the impacts of buffer ions, natural organic matter (NOM), and particulate Fe(III) on ferrate(VI) decomposition and characterized Fe(VI) decomposition kinetics and exposure in various waters. Homogeneous and heterogeneous Fe(VI) decomposition can be described as a second- and first-order reaction with respect to Fe(VI), respectively. Fe(VI) decay was catalyzed by Fe(VI) decomposition products. Solutes capable of forming complexes with iron hydroxides retarded Fe(VI) decay. Fractionation of the resulting solutions from Fe(VI) self-decay and ferric chloride addition in borate- and phosphate-buffered waters showed that phosphate could sequester Fe(III). The nature of the iron precipitate from Fe(VI) decomposition was different from that of freshly precipitated ferric hydroxide from ferric chloride solutions. The stabilizing effects of different solutes on Fe(VI) are in the following order: phosphate > bicarbonate > borate. The constituents of colored and alkaline waters (NOM and bicarbonate) inhibited the catalytic effects of Fe(VI) decomposition products and stabilized Fe(VI) in natural waters. Because of the stabilizing effects of solutes, moderate doses of Fe(VI) added to natural waters at pH 7.5 resulted in exposures that have been shown to be effective for inactivation of target pathogens. Preformed ferric hydroxide was less effective than freshly dosed ferric chloride in accelerating Fe(VI) decomposition.

Characterization of particles from ferrate preoxidation.

Studies were conducted evaluating the nature of particles that result from ferrate reduction in a laboratory water matrix and in a natural surface water with a moderate amount of dissolved organic carbon. Particle characterization included size, surface charge, morphology, X-ray photoelectron spectroscopy, and transmission Fourier transform infrared spectroscopy. Characteristics of ferrate resultant particles were compared to particles formed from dosing ferric chloride, a common water treatment coagulant. In natural water, ferrate addition produced significantly more nanoparticles than ferric addition. These particles had a negative surface charge, resulting in a stable colloidal suspension. In natural and laboratory matrix waters, the ferrate resultant particles had a similar charge versus pH relationship as particles resulting from ferric addition. Particles resulting from ferrate had morphology that differed from particles resulting from ferric iron, with ferrate resultant particles appearing smoother and more granular. X-ray photoelectron spectroscopy results show ferrate resultant particles contained Fe2O3, while ferric resultant particles did not. Results also indicate potential differences in the mechanisms leading to particle formation between ferrate reduction and ferric hydrolysis.

Pilot-scale evaluation of sulfite-activated ferrate for water reuse applications.

Ferrate is a promising, "green" (i.e., iron-based) pre-oxidation technology in water treatment, but there has been limited research on its potential benefits in a water reuse (wastewater recycling) paradigm. Recent studies have shown ferrate treatment processes can be improved by activation, the addition of reductants (i.e., sulfite) to the reaction. Prior bench scale experimentation suggests sulfite-activated ferrate may be a feasible option for water reuse applications; however, extent questions need to be addressed. This study evaluated the viability of sulfite-activated ferrate in water reuse treatment through continuous-flow experiments using synthetic and field-collected secondary wastewater effluents. The effluents were processed through the piloting system which included various physicochemical processes such as ferrate pre-oxidation, coagulation, clarification, and dual-media filtration. In each trial, the system was run continuously for eight hours with data collected via grab samples and online instrumentation with real-time resolution. Results demonstrate that reuse systems using activated ferrate pre-oxidation can produce effluents with water quality meeting most regulatory requirements without major impacts on downstream physicochemical processes. When compared to traditional ferrate pre-oxidation, activation showed several improvements such as lower byproduct yields. Operationally, activated ferrate does increase the development of headloss across the dual-media filter. In general, sulfite-activated ferrate is viable in a water reuse setting, resulting in several improved water quality outcomes. Results from this work create a pathway for adaptation at scale.

Sulfite-activated ferrate for water reuse applications.

Ferrate is a promising, emerging water treatment technology. However, there has been limited research on the application of ferrate in a water reuse paradigm. Recent literature has shown that ferrate oxidation of target contaminants could be improved by "activation" with the addition of reductants or acid. This study examined the impact of sulfite-activated ferrate in laboratory water matrix and spiked municipal wastewater effluents with the goal of transforming organic contaminants of concern (e.g., 1,4-dioxane) and inactivating pathogenic organisms. Additionally, the formation of brominated disinfection byproducts by activated ferrate were examined and a proposed reaction pathway for byproduct formation is presented. In particular, the relative importance of reaction intermediates is discussed. This represents the first activated ferrate study to examine 1,4-dioxane transformation, disinfection, and brominated byproduct formation. Results presented show that the sub-stoichiometric ([Sulfite]:[Ferrate] = 0.5) activated ferrate treatment approach can oxidize recalcitrant contaminants by >50%, achieve >4-log inactivation of pathogens, and have relatively limited generation of brominated byproducts. However, stoichiometrically excessive ([Sulfite]:[Ferrate] = 4.0) activation showed decreased performance with decreased disinfection and increased risk of by-product formation. In general, our results indicate that sub-stoichiometric sulfite-activated ferrate seems a viable alternative technology for various modes of water reuse treatment.

Effect of ferrate and monochloramine disinfection on the physiological and transcriptomic response of Escherichia coli at late stationary phase.

Biological mechanisms of disinfection not only vary by disinfectant but also remain not well understood. We investigated the physiological and transcriptomic response of Escherichia coli at late stationary phase to ferrate and monochloramine in amended lake water. Although ferrate and monochloramine treatments similarly reduced culturable cell concentrations by 3-log10, 64% and 11% of treated cells were viable following monochloramine and ferrate treatment, respectively. This observed induction of viable but non-culturable (VBNC) state following monochloramine treatment but not ferrate is attributed to slower monochloramine disinfection kinetics (by 2.8 times) compared to ferrate. Transcriptomic analysis of E. coli at 15 min of exposure revealed that 3 times as many genes related to translation and transcription were downregulated by monochloramine compared to ferrate, suggesting that monochloramine treatment may be inducing VBNC through reduced protein synthesis and metabolism. Downregulation of universal stress response genes (rpoS, uspA) was attributed to growth-related physiological stressors during late stationary phase which may have contributed to the elevated expression levels of general stress responses pre-disinfection and, subsequently, their significant downregulation post-disinfection. Both disinfectants upregulated oxidative stress response genes (trxC, grxA, soxS), although levels of upregulation were time sensitive. This work shows that bacterial inactivation responses to disinfectants is mediated by complex molecular and growth-related responses.

Physicochemical implications of cyanobacteria oxidation with Fe(VI).

Increases in harmful algal blooms has negatively impacted many surface-sourced drinking water utilities. To control these blooms, many water utilities implement pre-oxidation with ozone, chlorine, or permanganate; however, pre-oxidation of algae has both positive and negative water quality outcomes. This study investigated ferrate (Fe(VI)) as an alternative oxidant by measuring its effect on cell lysing, surface characteristics, and coagulation in waters containing the cyanobacteria Microcystis aeruginosa. Bench scale studies were conducted to examine the complex combination of processes in a Fe(VI)-algae system. These processes were characterized by fluorescence index, surface charge, collision frequency modeling, particle counts and sphericity, total nitrogen, and ferrate decomposition measurements. Results showed that Fe(VI) lysed algal cells, but further oxidation of released organic matter is possible. The presence of algae did not significantly impact the rate of Fe(VI) decomposition. Fe(VI) pre-oxidation may also be capable of decreasing the formation of nitrogenated disinfection byproducts through subsequent oxidation of released nitrogen rich organic matter. Streaming current and zeta potential results indicate destabilization of the resulting algae and iron suspension was incomplete under most conditions. Particle collision frequency modeling indicates fluid shear to be an important aggregation mechanism of the resulting suspension. Overall, Fe(VI) is a viable alternative to other strong oxidants for water utilities struggling with harmful algal blooms, but the final fate of the resulting organic matter must be further studied.

The frequency of neuroendocrine cell hyperplasia in patients with pulmonary neuroendocrine tumours and non-neuroendocrine cell carcinomas.

AIMS: To evaluate the frequency of neuroendocrine cell hyperplasia (NEH) in resected neuroendocrine tumours and non-neuroendocrine cell carcinomas and to study its relationship to selected clinical parameters. METHODS AND RESULTS: Random blocks without tumour from resected typical carcinoids (TCs, n = 46), atypical carcinoids (ACs, n = 14), large cell neuroendocrine carcinomas (LCNECs, n = 18), small cell carcinomas (SCLCs, n = 22), adenocarcinomas (ADENOs, n = 26) and squamous cell carcinomas (SCCs, n = 18) were stained for CD56 and evaluated for linear proliferations, cell aggregates (>4 CD56+ cells), and tumourlets (<5 mm with basement membrane invasion). There was a statistically significant difference between the frequency of NEH in all neuroendocrine tumours (TC/AC/LCNEC/SCLC, 35/100, 35%) (P = 0.009) when compared with non-neuroendocrine carcinomas (ADENO/SCC, 6/44, 14%) and in the frequency of NEH in TC (21/46, 46%) versus all other tumours (AC/LCNEC/SCLC/SCC/ADENO, 20/98, 20%) (P = 0.001). There was increased frequency of NEH in peripheral TCs (8/13, 62%) compared with central TCs (14/33, 43%) (P = 0.33). There was no association between smoking history and NEH. Clinical and imaging data showed no evidence of an increased frequency of obliterative bronchiolitis in patients with NEH. CONCLUSIONS: NEH is significantly increased in the background lung of neuroendocrine tumours when compared with non-neuroendocrine carcinomas, supportive data for NEH having neoplastic potential.

Preliminary Assessment of Ferrate Treatment of Metals in Acid Mine Drainage.

We report a preliminary assessment of ferrate [Fe(VI)] for the treatment of acid mine drainage (AMD), focused on precipitation of metals (i.e., iron [Fe] and manganese [Mn]) and subsequent removal. Two dosing approaches were studied to simulate the two commercially viable forms of Fe(VI) production: Fe(VI) only, and Fe(VI) with sodium hydroxide (NaOH). Subsequent metal speciation was assessed via filter fractionation. When only Fe(VI) was added, the pH remained <3.6, and the precipitation of Mn and Fe was <30 and <70%, respectively, at the highest, stoichiometrically excessive Fe(VI) dose. When NaOH and Fe(VI) were added simultaneously, precipitation of Mn was much more complete, at doses near the predicted oxidation stoichiometric requirement. The optimal dosage of Fe(VI) for Mn treatment was 25 µM. The formation of Mn(VII) was noted at Fe(VI) dosages above the stoichiometric requirement, which would be problematic in full-scale AMD treatment systems. Precipitation of Fe was >99% when only NaOH was added, indicating that oxidation by Fe(VI) did not play a significant role when added. The Fe(III) and Al(III) particles were relatively large, suggesting probable success in subsequent removal through sedimentation. Resultant Mn-oxide particles were relatively small, indicating that additional particle destabilization may be required to meet Mn effluent goals. Ferrate seems viable for the treatment of AMD, especially when sourced through onsite generation due to the coexistence of NaOH in the product stream. More research on the use of Fe(VI) for AMD treatment is required to answer extant questions.

Comparison of ferrate and ozone pre-oxidation on disinfection byproduct formation from chlorination and chloramination.

This study investigated the effects of ferrate and ozone pre-oxidation on disinfection byproduct (DBP) formation from subsequent chlorination or chloramination. Two natural waters were treated at bench-scale under various scenarios (chlorine, chloramine, each with ferrate pre-oxidation, and each with pre-ozonation). The formation of brominated and iodinated DBPs in fortified natural waters was assessed. Results indicated ferrate and ozone pre-oxidation were comparable at molar equivalent doses for most DBPs. A net decrease in trihalomethanes (including iodinated forms), haloacetic acids (HAAs), dihaloacetonitrile, total organic chlorine, and total organic iodine was found with both pre-oxidants as compared to chlorination only. An increase in chloropicrin and minor changes in total organic bromine yield were caused by both pre-oxidants compared to chlorination only. However, ozone led to higher haloketone and chloropicrin formation potentials than ferrate. The relative performance of ferrate versus ozone for DBP precursor removal was affected by water quality (e.g., nature of organic matter and bromide concentration) and oxidant dose, and varied by DBP species. Ferrate and ozone pre-oxidation also decreased DBP formation from chloramination under most conditions. However, some increases in THM and dihaloacetonitrile formation potentials were observed at elevated bromide levels.

Bromide oxidation by ferrate(VI): The formation of active bromine and bromate.

Ferrate (VI) (abbreviated as Fe(VI)) has long been considered as a green oxidant that does not produce any known hazardous byproducts. However, this work shows that Fe(VI) can slowly oxidize bromide forming active bromine (HOBr/OBr(-)) and bromate, and in natural waters total organic bromine (TOBr) can also be detected. Results showed that the highest levels of active bromine and bromate were formed at lower pHs and in the absence of phosphate. Hydrogen peroxide, which forms from the reaction of Fe(VI) and water, plays an essential role in suppressing bromate formation by reducing active bromine back to bromide. Fe(VI) decomposition products (assumed to be particulate phase Fe(III)) can catalyze the decomposition of hydrogen peroxide by Fe(VI). Phosphate had a substantial inhibiting effect on the formation of active bromine, but less so on bromate formation. The presence of the raw water matrix in natural water suppressed bromate formation. For a natural water spiked with 0.1 mg/L of bromide, the bromate and TOBr concentrations after Fe(VI) oxidation were below 3.0 and 15 µg/L, respectively. No consistent trend regarding the effect of pH or buffer ions on TOBr formation was observed due to the competition between Fe(VI), hydrogen peroxide, and natural organic matter (NOM) for reaction with active bromine. Under environmentally relevant conditions, the formation of bromate and TOBr would not be a problem for Fe(VI) application as their concentration levels are quite low.

Impacts of ferrate oxidation on natural organic matter and disinfection byproduct precursors.

This study investigated the effectiveness of ferrate (Fe(VI)) oxidation in combination with ferric chloride coagulation on the removal of natural organic matter (NOM) and disinfection byproduct (DBP) precursors. Twelve natural waters were collected and four treatment scenarios were tested at bench-scale. Results showed that intermediate-ferrate treatment (i.e., coagulation and particle removal followed by ferrate oxidation) was most effective followed by pre-ferrate treatment (i.e., ferrate oxidation followed by coagulation and particle removal (conventional treatment)) or conventional treatment alone (i.e., no oxidation), and the least effective was ferrate oxidation alone (i.e., no coagulation). At typical doses, direct ferrate oxidation of raw water decreased DBP formation potentials (DBPFPs) by about 30% for trihalomethanes (THMs), 40% for trihaloacetic acids (THAAs), 10% for dihaloacetic acids (DHAAs), 30% for dihaloacetonitriles (DHANs), and 5% for haloketones (HKs). The formation potential of chloropicrin (CP) consistently increased after direct ferrate oxidation. Pre-ferrate followed by conventional treatment was similar to conventional treatment alone for NOM and DBP precursor removal. Ferrate pre-oxidation had positive effects on subsequent coagulation/particle removal for THM and THAA precursor removal and may allow the use of lower coagulant doses due to the Fe(III) introduced by ferrate decomposition. On the other hand, intermediate-ferrate resulted in substantially improved removal of NOM and DBP precursors, which can be attributed to initial removal by coagulation and particle removal, leaving precursors that are particularly susceptible to oxidation by ferrate. The Fe(III) resulting from ferrate decay during intermediate-ferrate process was primarily present as particulate iron and could be effectively removed by filtration.

Oxidation of manganese(II) with ferrate: Stoichiometry, kinetics, products and impact of organic carbon.

Manganese is a contaminant of concern for many drinking water utilities, and future regulation may be pending. An analysis of soluble manganese (Mn(II)) oxidation by ferrate (Fe(VI)) was executed at the bench-scale, in a laboratory matrix, both with and without the presence of natural organic matter (NOM) and at two different pH values, 6.2 and 7.5. In the matrix without NOM, the oxidation of Mn(II) by Fe(VI) followed a stoichiometry of 2 mol Fe(VI) to 3 mol Mn(II). The presence of NOM did not significantly affect the stoichiometry of the oxidation reaction, indicating relative selectivity of Fe(VI) for Mn(II). The size distribution of resulting particles included significant amounts of nanoparticles. Resulting manganese oxide particles were confirmed to be MnO2 via X-ray photoelectron spectroscopy. The rate of the Mn(II) oxidation reaction was fast relative to typical time scales in drinking water treatment, with an estimated second order rate constant of approximately 1 × 10(4) M(-1) s(-1) at pH 9.2 and > 9 × 10(4) M(-1) s(-1) at pH 6.2. In general, ferrate is a potential option for Mn(II) oxidation in water treatment.