Investigation on removal of perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS) using water treatment sludge and biochar.

This work assessed the adsorption performance of three common PFAS compounds (PFOA, PFOS and PFHxS) on two water treatment sludges (WTS) and two biochars (commercial biomass biochar and semi-pilot scale biosolids biochar). Of the two WTS samples included in this study, one was sourced from poly-aluminium chloride (PAC) and the other from alum (Al2(SO4)3). The results of experiments using a single PFAS for adsorption reinforced established trends in affinity - the shorter-chained PFHxS was less adsorbed than PFOS, and the sulphates (PFOS) were more readily adsorbed than the acid (PFOA). Interestingly, PAC WTS, showed an excellent adsorption affinity for the shorter chained PFHxS (58.8%), than the alum WTS and biosolids biochar at 22.6% and 41.74%, respectively. The results also showed that the alum WTS was less effective at adsorption than the PAC WTS despite having a larger surface area. Taken together, the results suggest that the hydrophobicity of the sorbent and the chemistry of the coagulant were critical factors for understanding PFAS adsorption on WTS, while other factors, such as the concentration of aluminium and iron in the WTS could not explain the trends seen. For the biochar samples, the surface area and hydrophobicity are believed to be the main drivers in the different performances. Adsorption from the solution containing multiple PFAS was also investigated with PAC WTS and biosolids biochar, demonstrating comparable performance on overall adsorption. However, the PAC WTS performed better with the short-chain PFHxS than the biosolids biochar. While both PAC WTS and biosolids biochar are promising candidates for adsorption, the study highlights the need to explore further the mechanisms behind PFAS adsorption, which could be a highly variable source to understand better the potential for WTS to be utilized as a PFAS adsorbent.

Phosphorus adsorption and organic release from dried and thermally treated water treatment sludge.

The study investigated water treatment sludge (WTS) as a phosphorus (P) adsorbent and examined the release of organic matter during the P adsorption process. Previous studies indicated that WTS is an effective adsorbent for P but also releases organic matter, which may affect the organoleptic properties of treated water, but no study has characterised organic release and conducted an in-depth study on its behaviours. This study characterised the organic release during the P adsorption process from four different WTS samples. This study also offers results from a 60-day column experiment that indicate that WTS columns effectively removed the majority of P from the 2 mg/L feed solution. The total organic carbon (TOC) release was gradually reduced from 24.9 mg/L on day 1 to stable levels of 4.4 mg/L to 4.1 mg/L from day 22 onwards. After 60 days, when the organic matter was nearly exhausted, WTS columns were still effective in P adsorption from the solution. In addition, the thermal treatment of WTS at different temperatures was investigated to reduce TOC release and increase P adsorption. The results showed that thermal treatment not only minimized TOC release but also enhanced the P adsorption capacity of the sludge. In a 24-h batch experiment, WTS treated at 600 °C showed the highest P adsorption (1.7 mg/g) with negligible TOC release when compared to sludge treated at 500 °C WTS (1.2 mg/g), 700 °C WTS (1.5 mg/g) and dried WTS (0.75 mg/g). However, the release of inorganic compounds slightly increased after thermal treatment. Future studies could focus on determining whether the thermal processing of WTS which can enhance the WTS's adsorption to emerging pollutants like per- and poly-fluoroalkyl substances and other contaminants. The findings of this study could influence the management practices of water authorities and contribute to the water sector's sustainability objectives.

Engineering Saccharomyces cerevisiae for the de novo Production of Halogenated Tryptophan and Tryptamine Derivatives.

The indole scaffold is a recurring structure in multiple bioactive heterocycles and natural products. Substituted indoles like the amino acid tryptophan serve as a precursor for a wide range of natural products with pharmaceutical or agrochemical applications. Inspired by the versatility of these compounds, medicinal chemists have for decades exploited indole as a core structure in the drug discovery process. With the aim of tuning the properties of lead drug candidates, regioselective halogenation of the indole scaffold is a common strategy. However, chemical halogenation is generally expensive, has a poor atom economy, lacks regioselectivity, and generates hazardous waste streams. As an alternative, in this work we engineer the industrial workhorse Saccharomyces cerevisiae for the de novo production of halogenated tryptophan and tryptamine derivatives. Functional expression of bacterial tryptophan halogenases together with a partner flavin reductase and a tryptophan decarboxylase resulted in the production of halogenated tryptophan and tryptamine with chlorine or bromine. Furthermore, by combining tryptophan halogenases, production of di-halogenated molecules was also achieved. Overall, this works paves the road for the production of new-to-nature halogenated natural products in yeast.

Improvement of cis,cis-Muconic Acid Production in Saccharomyces cerevisiae through Biosensor-Aided Genome Engineering.

Muconic acid is a potential platform chemical for the production of nylon, polyurethanes, and terephthalic acid. It is also an attractive functional copolymer in plastics due to its two double bonds. At this time, no economically viable process for the production of muconic acid exists. To harness novel genetic targets for improved production of cis,cis-muconic acid (CCM) in the yeast Saccharomyces cerevisiae, we employed a CCM-biosensor coupled to GFP expression with a broad dynamic response to screen UV-mutagenesis libraries of CCM-producing yeast. Via fluorescence activated cell sorting we identified a clone Mut131 with a 49.7% higher CCM titer and 164% higher titer of biosynthetic intermediate-protocatechuic acid (PCA). Genome resequencing of the Mut131 and reverse engineering identified seven causal missense mutations of the native genes (PWP2, EST2, ATG1, DIT1, CDC15, CTS2, and MNE1) and a duplication of two CCM biosynthetic genes, encoding dehydroshikimate dehydratase and catechol 1,2-dioxygenase, which were not recognized as flux controlling before. The Mut131 strain was further rationally engineered by overexpression of the genes encoding for PCA decarboxylase and AROM protein without shikimate dehydrogenase domain (Aro1pΔE), and by restoring URA3 prototrophy. The resulting engineered strain produced 20.8 g/L CCM in controlled fed-batch fermentation, with a yield of 66.2 mg/g glucose and a productivity of 139 mg/L/h, representing the highest reported performance metrics in a yeast for de novo CCM production to date and the highest production of an aromatic compound in yeast. The study illustrates the benefit of biosensor-based selection and brings closer the prospect of biobased muconic acid.

Neurosurgical Anatomy of the Internal Carotid Artery: Magnetic Resonance Imaging Study of the Sellar Region.

BACKGROUND: Transsphenoidal surgical approaches involve dissection of the posterior wall of the sphenoid sinus in close proximity to the internal carotid arteries. To reduce the risk of vascular injury, a detailed study of embalmed cadavers' sellae was conducted and found the internal carotid artery approached within 4 mm of the midline in 10% of cases, and the closest intercarotid distance (ICD) occurred in the cavernous sinus, sphenoid sinus, and supraclinoid segments in 82%, 14%, and 4% of cases, respectively. These measurements have not previously been compared with living patients with modern imaging techniques. METHODS: This study measured the closest ICD of 233 coronal magnetic resonance imaging head scans from 183 patients (male = 88, female = 95) at the cavernous sinus, sphenoid sinus, or supraclinoid segments of the internal carotid artery. ICD at the sphenoid sinus was taken for all scans. RESULTS: The internal carotid approached within 4 mm of the midline in 1.3% of cases. The closest ICD occurred in the cavernous sinus, sphenoid sinus, and supraclinoid segments in 24.5%, 35.8%, and 39.7%, respectively. Both results were significantly different from previous cadaveric studies (chi-squared tests, P = 1.4 × 10-4 and P = 6.1 × 10-8, respectively). CONCLUSIONS: Surgically relevant measurements of the carotid arteries in the sellar are different in cadavers and living subjects. This is likely due to postmortem changes of surrounding structures. This study suggests clinically relevant anatomic studies using measurements taken from cadaveric specimens be updated with modern imaging techniques taken from living patients.

Membrane Distillation Trial on Textile Wastewater Containing Surfactants Using Hydrophobic and Hydrophilic-Coated Polytetrafluoroethylene (PTFE) Membranes.

Treating wastewater from textile plants using membrane distillation (MD) has great potential due to the high-salinity wastes and availability of waste heat. However, textile wastewaters also contain surfactants, which compromise the essential hydrophobic feature of the membrane, causing membrane wetting. To address this wetting issue, a custom-made membrane consisting of a hydrophilic layer coated on hydrophobic polytetrafluoroethylene (PTFE) was tested on textile wastewater in a pilot MD setup, and compared with a conventional hydrophobic PTFE membrane. The test was carried out with a feed temperature of 60 °C, and a permeate temperature of 45 °C. The overall salt rejection of both membranes was very high, at 99%. However, the hydrophobic membrane showed rising permeate electrical conductivity, which was attributed to wetting of the membrane. Meanwhile, the hydrophilic-coated membrane showed continually declining electrical conductivity demonstrating an intact membrane that resisted wetting from the surfactants. Despite this positive result, the coated membrane did not survive a simple sodium hydroxide clean, which would be typically applied to a membrane process. This brief study showed the viability of membrane distillation membranes on real textile wastewaters containing surfactants using hydrophilic-coated hydrophobic PTFE, but the cleaning process required for membranes needs optimization.

Membrane Distillation of Meat Industry Effluent with Hydrophilic Polyurethane Coated Polytetrafluoroethylene Membranes.

Meat rendering operations produce stick water waste which is rich in proteins, fats, and minerals. Membrane distillation (MD) may further recover water and valuable solids, but hydrophobic membranes are contaminated by the fats. Here, commercial hydrophobic polytetrafluorethylene (PTFE) membranes with a hydrophilic polyurethane surface layer (PU-PTFE) are used for the first time for direct contact MD (DCMD) on real poultry, fish, and bovine stick waters. Metal membrane microfiltration (MMF) was also used to capture fats prior to MD. Although the standard hydrophobic PTFE membranes failed rapidly, PU-PTFE membranes effectively processed all stick water samples to colourless permeate with sodium rejections >99%. Initial clean solution fluxes 5-6 L/m²/h declined to less than half during short 40% water recovery tests for all stick water samples. Fish stick water uniquely showed reduced fouling and up to 78% water recovery. Lost flux was easily restored by rinsing the membrane with clean water. MMF prior to MD removed 92% of fats, facilitating superior MD performance. Differences in fouling between stick waters were attributed to temperature polarisation from higher melt temperature fats and relative proportions to proteins. Hydrophilic coated MD membranes are applicable to stick water processing but further studies should consider membrane cleaning and longer-term stability.

Membrane potential independent transport of NH3 in the absence of ammonium permeases in Saccharomyces cerevisiae.

BACKGROUND: Microbial production of nitrogen containing compounds requires a high uptake flux and assimilation of the N-source (commonly ammonium), which is generally coupled with ATP consumption and negatively influences the product yield. In the industrial workhorse Saccharomyces cerevisiae, ammonium (NH4+) uptake is facilitated by ammonium permeases (Mep1, Mep2 and Mep3), which transport the NH4+ ion, resulting in ATP expenditure to maintain the intracellular charge balance and pH by proton export using the plasma membrane-bound H+-ATPase. RESULTS: To decrease the ATP costs for nitrogen assimilation, the Mep genes were removed, resulting in a strain unable to uptake the NH4+ ion. Subsequent analysis revealed that growth of this ∆mep strain was dependent on the extracellular NH3 concentrations. Metabolomic analysis revealed a significantly higher intracellular NHX concentration (3.3-fold) in the ∆mep strain than in the reference strain. Further proteomic analysis revealed significant up-regulation of vacuolar proteases and genes involved in various stress responses. CONCLUSIONS: Our results suggest that the uncharged species, NH3, is able to diffuse into the cell. The measured intracellular/extracellular NHX ratios under aerobic nitrogen-limiting conditions were consistent with this hypothesis when NHx compartmentalization was considered. On the other hand, proteomic analysis indicated a more pronounced N-starvation stress response in the ∆mep strain than in the reference strain, which suggests that the lower biomass yield of the ∆mep strain was related to higher turnover rates of biomass components.

Chemistry of silica scale mitigation for RO desalination with particular reference to remote operations.

Silica scaling in reverse osmosis of groundwater is a significant issue in water stressed areas due to the limitations that scaling imposes on water recovery. While calcium and magnesium scaling potential can be significantly reduced by the use of ion exchange or other softening processes, the silica scaling potential typically remains. Improving the recovery of reverse osmosis by limiting the potential for silica scale is important in ensuring maximum water recovery. This is particularly important for mining and natural gas industries that are located in remote regions. The remote nature of these sites imposes three major restrictions on the silica scale mitigation process. Firstly, the generation of poorly dewaterable sludges must be avoided. Also, the quality of any reverse osmosis (RO) permeate must be able to meet the end use requirements, particularly for boilers. Finally, silica removal should not impact upon other potentially useful or valuable components within the brine, and should not make the disposal of the unusable waste brine components more difficult. Reduction of scaling potential can be achieved in three main ways: operating RO at high pH after hardness has been removed, operating at low pH, and reducing the silica concentration either in pretreatment or by using an interstage technique. Operating at high pH has the initial requirement of hardness removal to prevent scaling and this could be an issue on some sites. Hardness removal operations that use ion exchange resins may be challenged by water chemistry and the operational costs associated with high chemical regeneration costs. Operating at low pH may be more desirable than high pH operation as this can help to reduce the risk of scale formation from calcium or magnesium salts. The drawback comes from the cost of acid, particularly for high-alkalinity waters. There are numerous silica removal techniques including chemical dosing of lime, or aluminium or iron salts, electrocoagulation, adsorption, ion exchange and seeded precipitation. Of these, adsorption onto aluminium compounds appears to give the best results and have received the most attention where restrictions on sludge production and brine disposal common to operations in remote locations are in place. Adsorption onto iron compounds appears to occur more quickly, but leads to the formation of a hard, glass-like scale that may be more difficult to remove, making this process unattractive from the point of view of sorbent regeneration.

Recovery of water and acid from leach solutions using direct contact membrane distillation.

This paper describes for the first time the use of direct contact membrane distillation (DCMD) for acid and water recovery from a real leach solution generated by a hydrometallurgical plant. The leach solutions considered contained H2SO4 or HCl. In all tests the temperature of the feed solution was kept at 60 °C. The test work showed that fluxes were within the range of 18-33 kg/m(2)/h and 15-35 kg/m(2)/h for the H2SO4 and HCl systems, respectively. In the H2SO4 leach system, the final concentration of free acid in the sample solution increased on the concentrate side of the DCMD system from 1.04 M up to 4.60 M. The sulfate separation efficiency was over 99.9% and overall water recovery exceeded 80%. In the HCl leach system, HCl vapour passed through the membrane from the feed side to the permeate. The concentration of HCl captured in the permeate was about 1.10 M leaving behind only 0.41 M in the feed from the initial concentration of 2.13 M. In all the experiments, salt rejection was >99.9%. DCMD is clearly viable for high recovery of high quality water and concentrated H2SO4 from spent sulfuric acid leach solution where solvent extraction could then be applied to recover the sulfuric acid and metals. While HCl can be recovered for reuse using only DCMD.

Convergence and remarkably consistent constraint in the evolution of carnivore skull shape.

Phenotypic similarities between distantly related marsupials and placentals are commonly presented as examples of convergence and support for the role of adaptive evolution in shaping morphological and ecological diversity. Here we compare skull shape in a wide range of carnivoran placentals (Carnivora) and nonherbivorous marsupials using a three-dimensional (3-D) geometric morphometric approach. Morphological and ecological diversity among extant carnivorans is considerably greater than is evident in the marsupial order Dasyuromorphia with which they have most commonly been compared. To examine convergence across a wider, but broadly comparable range of feeding ecologies, a dataset inclusive of nondasyuromorphian marsupials and extinct taxa representing morphotypes no longer present was assembled. We found support for the adaptive paradigm, with correlations between morphology, feeding behavior, and bite force, although skull shape better predicted feeding ecology in the phylogenetically diverse marsupial sample than in carnivorans. However, we also show that remarkably consistent but differing constraints have influenced the evolution of cranial shape in both groups. These differences between carnivorans and marsupials, which correlate with brain size and bite force, are maintained across the full gamut of morphologies and feeding categories, from small insectivores and omnivores to large meat-specialists.

Posterior ponticles and rotational stenosis of vertebral arteries. A pilot study using Doppler ultrasound velocimetry and magnetic resonance angiography.

OBJECTIVE: To determine whether the presence of posterior ponticles markedly increases by 30% or more, the incidence of major rotational stenosis of vertebral arteries. METHODS: Doppler ultrasound studies were performed in 3 private chiropractic clinics and in the radiology department of a public hospital, and magnetic resonance angiography (MRA) studies were made in the latter location. Thirty-two chiropractic patients had Doppler velocimetery, and 16 of these patients had MRA scanning. The outcome measures included changes in Doppler velocimetry signals and MRA images indicative of marked rotational stenosis of vertebral arteries. RESULTS: All vertebral arteries from the 32 patients displayed no signs indicative of marked rotational stenosis. CONCLUSION: The findings of this study show that the incidence of major rotational stenosis of vertebral arteries is not markedly increased by the presence of posterior ponticles.

Vertebral arteries and cervical rotation: modeling and magnetic resonance angiography studies.

OBJECTIVE: To determine whether lumen narrowing in vertebral arteries during atlanto-axial rotation is due to stretch or localized compression. DESIGN AND SETTING: Experiments with models were made in a private chiropractic clinic, whereas studies of cadaveric specimens were performed in an anatomy laboratory. Doppler ultrasound and magnetic resonance angiography (MRA) studies were carried out in the radiology department of a public hospital. PATIENTS: Eight patients had their vertebral arteries examined by use of a Doppler velocimeter and MRA. MAIN OUTCOME MEASURE: Stenosis of the vertebral arteries caused by stretch, localized compression, or kinking. RESULTS: All 16 vertebral arteries from the 8 patients displayed no changes in their lumen dimensions with full cervical rotation, although curves in each of the arteries did change. The model and cadaveric vertebral arteries demonstrated localized compression or kinking of the vessel wall with atlanto-axial rotation contralaterally but revealed no evidence of major contribution of stretching to stenosis. CONCLUSION: The lumen of vertebral arteries is usually unaffected by atlanto-axial rotation. In cases where there is stenosis, this is mainly due to localized compression or kinking. These findings are relevant to premanipulative screening of vertebral arteries with Doppler ultrasound scanning.

Influence of age on cervicothoracic spinal curvature: an ex vivo radiographic survey.

OBJECTIVE: To define the post-mortem cervicothoracic spinal curvature relative to age. DESIGN: Spinal curvature assessment of lateral cervicothoracic radiographs. BACKGROUND: A late consequence of age is the progressive accentuation of spinal curvatures, particularly the thoracic kyphosis. Little is known about the influence of the kyphosis on the alignment of the cervical spine. METHOD: One hundred and seventy two lateral spinal radiographs (113 males, 59 females) were analysed using two procedures: (1) sagittal curve deformation angles were derived, according to the method of Cobb, for thoracic (T1-T12), cervical (C2-C7) and cervicothoracic junctional regions (C6-T4); and (2) the cervicothoracic curvatures were digitised (C2-T12), to derive the apex of both curves and the inflexion point. RESULTS: A significantly increasing thoracic spinal curvature was determined for both genders, with the mean apex of the kyphosis close to T6. The cervical lordosis tended to flatten with increasing age, particularly in males, with the cervical apex location shifting cranially. This association was significant in older males and females. The mean location of the cervicothoracic curve inflexion point moved from T3 towards C7-T1 with increasing age. CONCLUSION: The cervicothoracic spinal curvature undergoes progressive change through the lifespan with a subsequent cranial migration of the inflexion point between the thoracic kyphosis and cervical lordosis, accompanied by a similar shift in the cervical apex. RELEVANCE: Sensitive measures of spinal curvature have utility in determining changes attributed to age, deformity or trauma on cervicothoracic spinal alignment. The value of assessing the location of curve inflexion lies in the ability to quantify changes in the relationship between different regions of the human spine without problems associated with identifying specific vertebral landmarks.