Smouldering to treat PFAS in sewage sludge.

Wastewater treatment plants are accumulation points for per- and polyfluoroalkyl substances (PFAS), and are threfore important facilities for PFAS treatment. This study explored using smouldering combustion to treat PFAS in sewage sludge. Base case experiments at the laboratory scale (LAB) used dried sludge mixed with sand. High moisture content (MC) LAB tests, 75% MC sludge by mass, explored impacts of MC on treatment and supplemented with granular activated carbon (GAC) to achieve sufficient temperatures for thermal destruction of PFAS. Additional LAB tests explored using calcium oxide (CaO) to support fluorine mineralization. Further tests performed at an oil-drum scale (DRUM) assessed scale on PFAS removal. Pre-treatment sludge and post-treatment ash samples from all tests were analyzed for 12 PFAS (2C-8C). Additional emissions samples were collected from all LAB tests and analyzed for 12 PFAS and hydrogen fluoride. Smouldering removed all monitored PFAS from DRUM tests, and 4-8 carbon chain length PFAS from LAB tests. For base case tests, PFOS and PFOA were completely removed from sludge; however, high contents in the emissions (79-94% of total PFAS by mass) showed volatilization without degradation. Smouldering high MC sludge at âˆ¼ 900 °C (30 g GAC/kg sand) improved PFAS degradation compared to treatment below 800 °C (<20 g GAC/kg sand). Addition of CaO before smouldering reduced PFAS content in emissions by 97-99% by mass; with minimal PFAS retained in the ash and minimal hydrofluoric acid (HF) production, as the fluorine from the PFAS was likely mineralized in the ash. Co-smouldering with CaO had dual benefits of removing PFAS while minimizing other hazardous emission by-products.

Exploring PCDD/Fs and potentially toxic elements in sewage sludge during smouldering treatment.

Potentially toxic elements (PTEs), persistent organic pollutants, and emerging contaminants make sewage sludge management challenging. There is significant interest in thermal treatment technologies that can destroy these compounds. The most common thermal treatment, incineration, poses risks due to formation and/or release of hazardous substances in process emissions such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and PTEs. Smouldering has been introduced recently as a potential treatment for managing sewage sludge. Smouldering systems present several advantages over traditional incinerators; however, there are still uncertainties regarding process by-products. This key question was investigated in three laboratory-scale tests (0.08 m radius) and five oil drum-scale tests (0.3 m radius) that were evaluated for PCDD/Fs and PTEs in the mixture before and after treatment as well as in process emissions. Volatile organic compounds (VOCs) were also measured. These experiments represent a broad spectrum of conditions to evaluate process emissions, from robust self-sustaining to extinction of smouldering. Robust smouldering had negligible PCDD/Fs in process emissions. Weak smouldering had low levels of PCDD/Fs (emissions factor: 3.3 ± 0.3 µg TEQ/Mg dried sludge destroyed), levels less than uncontrolled emissions from commercial incinerators. Overall, smouldering acted as a sink for PCDD/Fs, as only 0-3% of the PCDD/Fs originally present in the sludge were released in the emissions, and >99% of the remainder were destroyed with <1% remaining in post-treatment ash. No evidence was found to support de novo synthesis or precursor reactions forming new PCDD/Fs. In addition, 94-100% of all the PTEs analyzed were retained in the post-smouldered material. These results indicate that only minimal emissions treatment for PTEs, PCDD/Fs, and VOCs may be necessary for future sewage sludge smouldering systems. These low emissions risks combined with its unique ability to handle high moisture content waste, indicate that smouldering has significant potential as a valuable waste management technique.

Phosphorus recovery and reuse potential from smouldered sewage sludge ash.

Smouldering treatment of sewage sludge - and recapturing phosphorus - provides important steps towards a circular economy. This study reveals that bulking sludge with sand or another organic waste, e.g., woodchips, created a material that was readily converted to ash by self-sustained smouldering. Simultaneous phosphorus and regulated potentially toxic element releases from ash were evaluated using leaching methods from the USEPA Leaching Environmental Assessment Framework (LEAF). Extraction potentials were also determined to evaluate direct recovery as an alternative to land application. Compared to the parent sludge, post-treatment ash from smouldering sludge with sand contained higher quantities of inorganic phosphorus in sorbed and mineral phases, which can provide beneficial slow phosphorus release to plants and avoid early phosphorus washout during land application. Ash also released lower initial and total quantities of potentially toxic elements than virgin sludge. As an alternative to land application, approximately 42% of retained phosphorus can be recovered directly using acidic extraction, and an additional 30% from emissions. In contrast, co-smouldering sludge with woodchips was more suited for direct recovery with 78% of phosphorus potentially recoverable via emissions capture and yield increasing to 99% with acidic extraction of resulting ash. Co-smouldering also produces a single post-treatment ash and can be readily operated continuously, which aligns with current incinerator configurations at wastewater treatment plants and makes adaptation highly feasible. With phosphorus reuse opportunities for land application and direct recovery, smouldering sewage sludge creates an important opportunity for a phosphorus circular economy as part of wastewater treatment sludge management.

USEPA LEAF methods for characterizing phosphorus and potentially toxic elements in raw and thermally treated sewage sludge.

Biologically available phosphorus supports plant growth but can also cause environmental contamination. Sequential extraction methods, such as Hedley fractionation, are the most widely used to assess available phosphorus from solids. However, such methods exhibit numerous deficiencies. The USEPA Leaching Environmental Assessment Framework (LEAF) is a tiered system developed to evaluate releases of Potentially Toxic Elements (PTEs) from solids. This study compared the Hedley fractionation method to the LEAF pH-dependent, parallel batch tests (Method 1313) and dynamic leaching column test (Method 1314) to assess the bioavailability of phosphorus. The three methods were applied to wastewater treatment plant sludge before and after thermal treatment. Both methods revealed similar qualitative trends, namely that thermal treatment transformed phosphorus into less immediately available forms. However, the Hedley and LEAF methods were inconsistent in the forms and amounts of available phosphorus recovered from the solids. The Hedley method left 40% of phosphorus unextracted from sludge and 20% from ash, suggesting that it may be less appropriate for organic materials. Moreover, only 2 of the 6 Hedley phosphorus pools were within environmentally relevant pH conditions. Furthermore, the Hedley method overpredicted the readily available phosphorus. In contrast, the LEAF methods allowed for a more detailed analysis of phosphorus availability - while simultaneously assessing PTEs - across a controlled pH range. Moreover, LEAF used simpler procedures and provided more easily interpreted results. Thus, LEAF facilitates more robust and valuable assessment of organic and inorganic solids being considered for land application.

Targeting SET/I(2)PP2A oncoprotein functions as a multi-pathway strategy for cancer therapy.

The SET oncoprotein participates in cancer progression by affecting multiple cellular processes, inhibiting the tumor suppressor protein phosphatase 2A (PP2A), and inhibiting the metastasis suppressor nm23-H1. On the basis of these multiple activities, we hypothesized that targeted inhibition of SET would have multiple discrete and measurable effects on cancer cells. Here, the effects of inhibiting SET oncoprotein function on intracellular signaling and proliferation of human cancer cell lines was investigated. We observed the effects of COG112, a novel SET interacting peptide, on PP2A activity, Akt signaling, nm23-H1 activity and cellular migration/invasion in human U87 glioblastoma and MDA-MB-231 breast adenocarcinoma cancer cell lines. We found that COG112 interacted with SET protein and inhibited the association between SET and PP2A catalytic subunit (PP2A-c) and nm23-H1. The interaction between COG112 and SET caused PP2A phosphatase and nm23-H1 exonuclease activities to increase. COG112-mediated increases in PP2A activity resulted in the inhibition of Akt signaling and cellular proliferation. Additionally, COG112 inhibited SET association with Ras-related C(3) botulinum toxin substrate 1 (Rac1), leading to decreased cellular migration and invasion. COG112 treatment releases the SET-mediated inhibition of the tumor suppressor PP2A, as well as the metastasis suppressor nm23-H1. These results establish SET as a novel molecular target and that the inhibition of SET may have beneficial effects in cancer chemotherapy.

Wait times for gastroenterology consultation in Canada: the patients' perspective.

Long wait times for health care have become a significant issue in Canada. As part of the Canadian Association of Gastroenterology's Human Resource initiative, a questionnaire was developed to survey patients regarding wait times for initial gastroenterology consultation and its impact. A total of 916 patients in six cities from across Canada completed the questionnaire at the time of initial consultation. Self-reported wait times varied widely, with 26.8% of respondents reporting waiting less than two weeks, 52.4% less than one month, 77.1% less than three months, 12.5% reported waiting longer than six months and 3.6% longer than one year. One-third of patients believed their wait time was too long, with 9% rating their wait time as 'far too long'; 96.4% believed that maximal wait time should be less than three months, 78.9% believed it should be less than one month and 40.3% believed it should be less than two weeks. Of those working or attending school, 22.6% reported missing at least one day of work or school because of their symptoms in the month before their appointment, and 9.0% reported missing five or more days in the preceding month. A total of 20.2% of respondents reported being very worried about having a serious disease (ie, scored 6 or higher on 7-point Likert scale), and 17.6% and 14.8%, respectively, reported that their symptoms caused major impairment of social functioning and with the activities of daily living. These data suggest that a significant proportion of Canadians with digestive problems are not satisfied with their wait time for gastroenterology consultation. Furthermore, while awaiting consultation, many patients experience an impaired quality of life because of their gastrointestinal symptoms.

Self-sustaining smoldering combustion: a novel remediation process for non-aqueous-phase liquids in porous media.

Smoldering combustion, the slow burning process associated typically with porous solids (e.g., charcoal), is here proposed as a novel remediation approach for nonaqueous phase liquids (NAPLs) embedded in porous media. Several one-dimensional vertical smoldering experiments are conducted on quartz sand containing fresh coal tar at an initial concentration of 71 000 mg/kg (approximately 25% saturation) and employing an upward darcy air flux of 4.25 cm/s. Following a short-duration energy input to achieve ignition at the lower boundary, a self-sustaining combustion front is observed to propagate upward at 1.3 x 10(-2) cm/s. The process is self-sustaining because the energy released during NAPL smoldering is efficiently trapped and recirculated by the soil matrix, preheating the NAPL ahead of the reaction front. The smoldering process is observed to self-terminate when all of the NAPL is destroyed or when the oxygen source is removed. Pre- and post-soil analysis revealed that NAPL smoldering reduced the concentration of total extractable petroleum hydrocarbons (TPH) from 38 000 mg/kg to below detection limits (< 0.1 mg/kg) throughout the majority of the column. A comparable experiment in which conductive heating is applied in the absence of smoldering demonstrates a 6-fold reduction in the net energy in the system and residual TPH values of 2000-35 000 mg/kg. A further repeat in which the air supply is prematurely terminated demonstrated that the NAPL smoldering process can be extinguished via external control. A suite of 23 demonstration experiments shows that NAPL smoldering is successful across a range of soil types (including simple layered systems) and contaminants (including laboratory mixtures of dodecane, DCA/ grease, TCE/oil, vegetable oil, crude oil, and mineral oil) as well as field-obtained samples of materials containing coal tar, oil drill cutting waste, and oil sands.

Dithiolethione compounds inhibit Akt signaling in human breast and lung cancer cells by increasing PP2A activity.

The chemopreventative effects of dithiolethione compounds are attributed to their activation of antioxidant response elements (AREs) by reacting with the Nrf2/Keap1 protein complex. In this study, we show antiproliferative effects of the dithiolethione compound ACS-1 in human cancer cell lines (A549 and MDA-MB-231) by increasing the activity of the tumor suppressor protein phoshatase 2A (PP2A). ACS-1 inhibited epidermal growth factor (EGF)-induced cellular proliferation in a concentration- and time-dependent manner. Akt activation, as determined by serine-473 phosphorylation, was inhibited by ACS-1 in cells stimulated with either EGF or fibronectin. Furthermore, ACS-1 inhibited mammalian target of rapamycin signaling and decreased c-myc protein levels. ACS-1 did not proximally alter EGF receptor or integrin signaling, but caused a concentration-dependent increase in PP2A activity. The effect of ACS-1 on Akt activation was not observed in the presence of the PP2A inhibitor okadaic acid. ACS-1 effects on PP2A activity were independent of ARE activation and cAMP formation. In addition to ACS-1, other dithiolethione compounds showed similar effects in reducing Akt activation, suggesting that this class of compounds may have other effects beyond chemoprevention.

The impact of a gluten-free diet on adults with coeliac disease: results of a national survey.

UNLABELLED: OBJECTIVE We sought to evaluate the impact of the gluten-free diet on the 5,240 members of the Canadian Celiac Association (CCA). Data are presented on 2,681 adults (>or=16 years) with biopsy-proven celiac disease (CD). METHODS: A mail-out survey was used. Quality of life was evaluated using the 'SF12', and celiac-specific questions. RESULTS: Mean age was 56 years, mean age at diagnosis was 45 years, and 75% were female. The 'SF12' summary scores were similar to normative Canadian data, but were significantly lower for females and newly diagnosed patients. Respondents reported: following a gluten-free (GF) diet (90%), improvement on the diet (83%), and difficulties following the diet (44%), which included: determining if foods were GF (85%), finding GF foods in stores (83%), avoiding restaurants (79%), and avoiding travel (38%). Most common reactions to consumed gluten (among 73%) included pain, diarrhea, bloating, fatigue, nausea, and headache. Excellent information on CD and its treatment was provided by the CCA (64%), gastroenterologists (28%), dietitians (26%) and family doctor (12%). CONCLUSIONS: Quality of life in those with CD could be increased with early diagnosis, increased availability of gluten-free foods, improved food labelling, and better dietary instruction. Education of physicians and dietitians about CD and its treatment is essential.

Mechanisms of nitrogen oxide-mediated disruption of metalloprotein function: an examination of the copper-responsive yeast transcription factor Ace1.

Nitric oxide (NO) has been found to inhibit the copper-responsive yeast transcription factor Ace1 in an oxygen-dependent manner. However, the mechanism responsible for NO-dependent inhibition of Ace1 remains unestablished. In the present study, the chemical interaction of nitrogen oxide species with Ace1 was examined using a yeast reporter system. Exposure of yeast to various nitrogen oxides, under a variety of conditions, revealed that the oxygen-dependent inhibition of Ace1 is due to the reaction of NO with O(2). The nitrosating nitrogen oxide species N(2)O(3) is likely to be the disrupter of Ace1 activity. Considering the similarity of metal-thiolate ligation in Ace1 with other mammalian metalloproteins such as metallothionein, metal chaperones, and zinc-finger proteins, these results help to understand the biochemical interactions of NO with those mammalian metalloproteins.

DNA bending by asymmetrically tethered cations: influence of tether flexibility.

BACKGROUND: We have been studying the proposal that laterally asymmetric charge neutralization along the DNA double helix can induce collapse toward the neutralized surface. Results of previous experiments implied that such a phenomenon can occur, suggesting a role for local interphosphate repulsive forces in DNA shape and rigidity. RESULTS: We now show that, whereas six ammonium ions tethered to one DNA face on flexible propyl chains can induce detectable DNA curvature, tethering of ammonium ions on rigid propynyl tethers does not induce DNA curvature. Molecular modeling indicates differing propensities for phosphate salt bridge formation between propyl- and propynyl-tethered ammonium ions. CONCLUSIONS: Ammonium ion localization is suggested as a key factor in induced bending. Rigidification of the double helix by stacking of propyne groups cannot be excluded.

Probing structure and function with alternative nucleic acids bearing 2',5'-linked, zwitterionic, and isocytosine-isoguanine components.

The incorporation of alternative functional components into nucleic acids can provide insight into what molecular features are necessary for an informational macromolecule to be successful. It can also provide a means to improve particular physical characteristics of nucleic acids for diagnostic and therapeutic purposes, or probe mechanisms. By testing the fitness of nucleic acid-like molecules derived by structural permutations of RNA, it may also prove possible to trace a path from simple prebiotic precursors to biotic molecules. This article describes the applications of 2',5'-phosphodiester linked, zwitterionic, and base-permuted nucleic acid derivatives.

Nonenzymatic oligomerization on templates containing phosphodiester-linked acyclic glycerol nucleic acid analogues.

Nonenzymatic oligomerization reactions represent a model for studying the prebiotic replication of informational macromolecules. To explore the fitness of acyclic oligonucleotides in these reactions, we have synthesized a series of DNA hairpins appended with templates incorporating atactic glyceryl cytosine residues. Atactic glyceryl cytosine units are found to impede, but not to block, template-directed oligomerization of guanosine 5'-phosphoro-2-methylimidazole (2-MeImpG). Evidence suggests that both D and L glyceryl nucleoside configurations at a given template position contribute to product formation. The stability of DNA duplexes bearing isolated glyceryl cytosine residues has also been investigated. Duplex thermal denaturation experiments indicate that an atactic glyC. dG base-pair is intermediate in stability between a dC. dG pair and a dT. dG mismatch.

RecA protein promotes strand exchange with DNA substrates containing isoguanine and 5-methyl isocytosine.

The Escherichia coli RecA protein pairs homologous DNA molecules and promotes DNA strand exchange in vitro. We have examined DNA strand exchange between a 70 nucleotide ssDNA fragment and a 40 bp duplex, in which all G and C residues (at 18 positions distributed throughout the 40 bp exchanged region) were replaced with the nonstandard nucleosides 2'-deoxyisoguanosine (iG) and 2'-deoxy-5-methylisocytidine (MiC), respectively. We demonstrate that the nonstandard oligonucleotides are substrates for the RecA protein, permitting DNA strand exchange in vitro at a rate and efficiency comparable to exchange with normal DNA substrates. This observation provides an expanded experimental basis for discussions of potential roles for iG and MiC in a genetic code. Experiments of this type also provide another avenue for exploring RecA-facilitated DNA pairing mechanisms.

The role of oxygen and reduced oxygen species in nitric oxide-mediated cytotoxicity: studies in the yeast Saccharomyces cerevisiae model system.

The cytotoxicity of nitric oxide (NO) is well established, yet the mechanism(s) of its cytotoxicity is (are) still undefined and a matter of significant interest and speculation. Many of the previously proposed mechanisms for NO-mediated cytotoxicity involve interactions between NO and molecular oxygen (O(2)) and/or O(2)-derived species such as O(-)(2) and H(2)O(2). The yeast Saccharomyces cerevisiae represents a useful model system for evaluating the role of O(2) and O(2)-derived species in NO-mediated cytotoxicity. This study examines the contribution of O(2) and O(2)-derived species to NO-mediated cytotoxicity in the yeast S. cerevisiae. NO-mediated cytotoxicity was determined to be O(2)-dependent. However, this O(2) dependence was only minimally due to the generation of O(2)-derived species such as O(-)(2) and/or H(2)O(2).

Effects of nitric oxide on the copper-responsive transcription factor Ace1 in Saccharomyces cerevisiae: cytotoxic and cytoprotective actions of nitric oxide.

Previous studies indicate that nitric oxide (NO) can serve as a regulator/disrupter of metal-metabolizing systems in cells and, indeed, this function may represent an important physiological and/or pathophysiological role for NO. In order to address possible mechanisms of this aspect of NO biology, the effect of NO on copper metabolism and toxicity in the yeast Saccharomyces cerevisiae was examined. Exposure of S. cerevisiae to NO resulted in an alteration of the activity of the copper-responsive transcription factor Acel. Low concentrations of the NO donor DEA/NO were found to slightly enhance copper-mediated activation of Acel. Since Acel regulates the expression of genes responsible for the protection of S. cerevisiae from metal toxicity, the effect of NO on the toxicity of copper toward S. cerevisiae was also examined. Interestingly, low concentrations of NO were also found to protect S. cerevisiae against the toxicity of copper. The effect of NO at high concentrations was, however, opposite. High concentrations of DEA/NO inhibited copper-mediated Acel activity. Correspondingly, high concentrations of DEA/NO (1 mM) dramatically enhanced copper toxicity. An intermediate concentration of DEA/NO (0.5 mM) exhibited a dual effect, enhancing toxicity at lower copper concentrations (<0.5 mM) and protecting at higher (> or =0.5 mM) copper concentrations. Thus, it is proposed that the ability of NO to both protect against (at low concentrations) and enhance (at high concentration) copper toxicity in S. cerevisiae is, at least partially, a result of its effect on Acel. The results of this study have implications for the role of NO as a mediator of metal metabolism.

The interaction of nitric oxide (NO) with the yeast transcription factor Ace1: A model system for NO-protein thiol interactions with implications to metal metabolism.

Nitric oxide (NO) was found to inhibit the copper-dependent induction of the yeast CUP1 gene. This effect is attributable to an inhibition of the copper-responsive CUP1 transcriptional activator Ace1. A mechanism is proposed whereby the metal binding thiols of Ace1 are chemically modified via NO- and O(2)-dependent chemistry, thereby diminishing the ability of Ace1 to bind and respond to copper. Moreover, it is proposed that demetallated Ace1 is proteolytically degraded in the cell, resulting in a prolonged inhibition of copper-dependent CUP1 induction. These findings indicate that NO may serve as a disrupter of yeast copper metabolism. More importantly, considering the similarity of Ace1 to other mammalian metal-binding proteins, this work lends support to the hypothesis that NO may regulate/disrupt metal homeostasis under both normal physiological and pathophysiological circumstances.

A DNA pentaplex incorporating nucleobase quintets.

Supramolecular self-assembly is an integral step in the formation of many biological structures. Here we report a DNA pentaplex that derives from a metal-assisted, hydrogen bond-mediated self-assembly process. In particular, cesium ions are found to induce pentameric assembly of DNA bearing the nonstandard nucleobase iso-guanine. The pentaplex was designed by using a simple algorithm to predict nucleobase structural requirements within a quintet motif. The design principles are general and should extend to complexes beyond pentaplex. Structures exhibiting molecularities of five or more were previously accessible to peptides, but not nucleic acids.

2'-Deoxyisoguanosine adopts more than one tautomer to form base pairs with thymidine observed by high-resolution crystal structure analysis.

The questions of whether different tautomeric forms of nucleic acid bases exist to any significant extent in DNA, or what their possible roles in mutation may be, are under intense scrutiny. 2'-Deoxyisoguanosine (iG) has been suggested to have a propensity to adopt the enol form. Isoguanine (also called 2-hydroxyadenine) can be found in oxidatively damaged DNA generated from treating DNA with a Fenton-type reactive oxygen-generating system and is known to cause mutation. We have analyzed the three-dimensional structure of the DNA dodecamer d(CGC[iG]AATTTGCG) (denoted iG-DODE) by X-ray crystallography and NMR. The crystal structure of the iG-DODE complexed with the minor groove binder Hoechst 33342, refined to 1.4 A resolution, showed that the two independent iG.T base pairs in the dodecamer duplex adopt different (one in Watson-Crick and the other in wobble) conformations. The high-resolution nature of the structure also affords unprecedented clear information about the conformation and interactions of the Hoechst drug. The Hoechst 33342 binds in the narrow minor groove at the iGAATT site, with the N-methylpiperazine ring near the iG4.T21 base pair. Three hydrogen bonds are found between the NH of the Hoechst ligand and T-O2 DNA atoms. In solution, the two iG.T base pairs in iG-DODE predominantly are in the wobble form at 2 degreesC. At higher temperatures, another duplex form (likely involving the enol form of iG) is in slow exchange with the keto form and becomes significantly populated, reaching approximately 40% at 40 degreesC. Our data support the conclusion that iG pairs with T in a Watson-Crick configuration to a significant extent at physiological temperature (37 degreesC), which may explain the facile incorporation rate of T across from an iG during in vitro DNA replication.