Respirable Metals, Bacteria, and Fungi during a Saharan-Sahelian Dust Event in Houston, Texas.

Although airborne bacteria and fungi can impact human, animal, plant, and ecosystem health, very few studies have investigated the possible impact of their long-range transport in the context of more commonly measured aerosol species, especially those present in an urban environment. We report first-of-kind simultaneous measurements of the elemental and microbial composition of North American respirable airborne particulate matter concurrent with a Saharan-Sahelian dust episode. Comprehensive taxonomic and phylogenetic profiles of microbial communities obtained by 16S/18S/ITS rDNA sequencing identified hundreds of bacteria and fungi, including several cataloged in the World Health Organization's lists of global priority human pathogens along with numerous other animal and plant pathogens and (poly)extremophiles. While elemental analysis sensitively tracked long-range transported Saharan dust and its mixing with locally emitted aerosols, microbial diversity, phylogeny, composition, and abundance did not well correlate with the apportioned African dust mass. Bacterial/fungal diversity, phylogenetic signal, and community turnover were strongly correlated to apportioned sources (especially vehicular emissions and construction activities) and elemental composition (especially calcium). Bacterial communities were substantially more dissimilar from each other across sampling days than were fungal communities. Generalized dissimilarity modeling revealed that daily compositional turnover in both communities was linked to calcium concentrations and aerosols from local vehicles and Saharan dust. Because African dust is known to impact large areas in northern South America, the Caribbean Basin, and the southern United States, the microbiological impacts of such long-range transport should be assessed in these regions.

Quantifying international and interstate contributions to primary ambient PM2.5 and PM10 in a complex metropolitan atmosphere.

We quantify the contributions of long-range and regionally transported aerosols to ambient primary PM2.5 and PM10 in a representative United States industrialized/urban atmosphere via detailed elemental analysis and chemical mass balance (CMB) modeling after identifying their presence using a variety of publicly available satellite data/information, software products, and synoptic-scale aerosol models. A year-long study in Houston, Texas identified North African dust as the principal long-range global source of primary particulate matter (PM). CMB estimated transatlantic dust from the Sahara-Sahel region to be dominant in the summer months contributing an average of 3.5 µg m-3 to PM2.5 and 7.9 µg m-3 to PM10 during May-August, i.e., the active Saharan dust season. Biomass burning was the chief source of regionally transported PM impacting air quality on different occasions throughout the year depending on the fire location. Four major biomass combustion events affecting air quality in Texas were calculated to contribute an average of 1.3 µg m-3 to PM2.5 and 1.4 µg m-3 to PM10 in corresponding samples whose origins were tracked to Canada, southeastern states of USA, and Central America using fire maps, HYSPLIT back trajectories, and the Navy Aerosol Analysis and Prediction System global aerosol model. Elemental concentrations and signature ratios revealed significant mixing of potassium, rare earth metals, and vanadium from proximal and distal crustal (natural) sources with anthropogenically emitted PM. This demonstrates the need to isolate the non-mineral components of these metals to employ them as tracers for primary PM emitted by biomass burning, petroleum refineries, and oil combustion. Transboundary contributions to primary PM2.5 were 1.5 µg m-3 and 3.1 µg m-3 to PM10 adding 16% to annual average mass concentration of both size fractions demonstrating that local sources were primarily responsible for ambient air quality with non-trivial contributions from international and interstate sources. Rigorously identifying and quantifying aerosol sources assists in improving air quality management policies designed to protect public health and comply with ever-decreasing federal PM standards that allow state agencies to exclude contributions that are not reasonably controllable or preventable from regulatory decisions and actions.

Coupling Sr-Nd-Hf Isotope Ratios and Elemental Analysis to Accurately Quantify North African Dust Contributions to PM2.5 in a Complex Urban Atmosphere by Reducing Mineral Dust Collinearity.

Tracking Saharan-Sahelian dust across the globe is essential to elucidate its effects on Earth's climate, radiation budget, hydrologic cycle, nutrient cycling, and also human health when it seasonally enters populated/industrialized regions of Africa, Europe, and North America. However, the elemental composition of mineral dust arising locally from construction activities and aeolian soil resuspension overlaps with African dust. Therefore, we derived a novel "isotope-resolved chemical mass balance" (IRCMB) method by employing radiogenic strontium, neodymium, and hafnium isotopes to accurately differentiate and quantitatively apportion collinear proximal and synoptic-scale crustal and anthropogenic mineral dust sources. IRCMB was applied to two air masses that transported African dust to Barbados and Texas to track particulate matter (PM) spikes at both locations. During Saharan-Sahelian intrusions, the radiogenic content of urban PM2.5 increased with respect to 87Sr/86Sr and 176Hf/177Hf but decreased in terms of 143Nd/144Nd, demonstrating the ability of these isotopes to sensitively track African dust intrusions even in complex metropolitan atmospheres. The principal aerosol strontium, neodymium, and hafnium end members were concrete dust and soil, soil and motor vehicles, and motor vehicles and North African dust, respectively. IRCMB separated and quantified local soil and distal crustal dust even when PM2.5 concentrations were low, opening a promising source apportionment avenue for urbanized/industrialized atmospheres.

Virus Removal and Inactivation Mechanisms during Iron Electrocoagulation: Capsid and Genome Damages and Electro-Fenton Reactions.

Virus destabilization and inactivation are critical considerations in providing safe drinking water. We demonstrate that iron electrocoagulation simultaneously removed (via sweep flocculation) and inactivated a non-enveloped virus surrogate (MS2 bacteriophage) under slightly acidic conditions, resulting in highly effective virus control (e.g., 5-logs at 20 mg Fe/L and pH 6.4 in 30 min). Electrocoagulation simultaneously generated H2O2 and Fe(II) that can potentially trigger electro-Fenton reactions to produce reactive oxygen species such as •OH and high valent oxoiron(IV) that are capable of inactivating viruses. To date, viral attenuation during water treatment has been largely probed by evaluating infective virions (as plaque forming units) or genomic damage (via the quantitative polymerase chain reaction). In addition to these existing means of assessing virus attenuation, a novel technique of correlating transmission electron micrographs of electrocoagulated MS2 with their computationally altered three-dimensional electron density maps was developed to provide direct visual evidence of capsid morphological damages during electrocoagulation. The majority of coliphages lost at least 10-60% of the capsid protein missing a minimum of one of the 5-fold and two of 3- and 2-fold regions upon electrocoagulation, revealing substantial localized capsid deformation. Attenuated total reflectance-Fourier transform infrared spectroscopy revealed potential oxidation of viral coat proteins and modification of their secondary structures that were attributed to reactive oxygen species. Iron electrocoagulation simultaneously disinfects and coagulates non-enveloped viruses (unlike conventional coagulation), adding to the robustness of multiple barriers necessary for public health protection and appears to be a promising technology for small-scale distributed water treatment.

Removal and Inactivation of an Enveloped Virus Surrogate by Iron Conventional Coagulation and Electrocoagulation.

It is imperative to understand the behavior of enveloped viruses during water treatment to better protect public health, especially in the light of evidence of detection of coronaviruses in wastewater. We report bench-scale experiments evaluating the extent and mechanisms of removal and/or inactivation of a coronavirus surrogate (ϕ6 bacteriophage) in water by conventional FeCl3 coagulation and Fe(0) electrocoagulation. Both coagulation methods achieved ∼5-log removal/inactivation of ϕ6 in 20 min. Enhanced removal was attributed to the high hydrophobicity of ϕ6 imparted by its characteristic phospholipid envelope. ϕ6 adhesion to freshly precipitated iron (hydr)oxide also led to envelope damage causing inactivation in both coagulation techniques. Fourier transform infrared spectroscopy revealed oxidative damages to ϕ6 lipids only for electrocoagulation consistent with electro-Fenton reactions. Monitoring ϕ6 dsRNA by a novel reverse transcription quantitative polymerase chain reaction (RT-qPCR) method quantified significantly lower viral removal/inactivation in water compared with the plaque assay demonstrating that relying solely on RT-qPCR assays may overstate human health risks arising from viruses. Transmission electron microscopy and computationally generated electron density maps of ϕ6 showed severe morphological damages to virus' envelope and loss of capsid volume accompanying coagulation. Both conventional and electro- coagulation appear to be highly effective in controlling enveloped viruses during surface water treatment.

Antitumor activity of a hydrogel loaded with lipophilic bismuth nanoparticles on cervical, prostate, and colon human cancer cells.

The objective of this study was to analyze the antitumor activity of a hydrogel loaded with lipophilic bismuth nanoparticles on human cervical, prostate, and colon cancer cell lines. The effect of lipophilic bismuth nanoparticles on the viability of cancer cell lines (HeLa, DU145, and HCT-116) and non-cancer lung fibroblasts (HLF; LL 47[MaDo]) was determined with the MTT cell viability assay and compared with known antineoplastic drugs. The biocompatibility at an organismal level was verified in a murine model by histological examination. A lipophilic bismuth nanoparticle hydrogel at 50 µM time-dependently inhibited the growth of the three cancer cell lines, in a time-dependent way. A 1-hour exposure to 250 µM lipophilic bismuth nanoparticle hydrogel, inhibited the growth of the three cancer cell lines. The in-vitro efficacy of lipophilic bismuth nanoparticle was similar to the one of docetaxel and cisplatin, but without inhibiting the growth of non-cancer control cells. Histology confirmed the biocompatibility of lipophilic bismuth nanoparticles as there were no signs of cytotoxicity or tissue damage in any of the evaluated organs (kidney, liver, brain, cerebellum, heart, and jejunum). In conclusion, a lipophilic bismuth nanoparticle hydrogel is an innovative, low-cost alternative for the topical treatment of cervicouterine, prostate, and colon human cancers.

Indoor/Outdoor Relationships and Anthropogenic Elemental Signatures in Airborne PM2.5 at a High School: Impacts of Petroleum Refining Emissions on Lanthanoid Enrichment.

Outdoor emissions of primary fine particles and their contributions to indoor air quality deterioration were examined by collecting PM2.5 inside and outside a mechanically ventilated high school in the ultraindustrialized ship channel region of Houston, TX over a 2-month period. By characterizing 47 elements including lanthanoids (rare earth elements), using inductively coupled plasma-mass spectrometry, we captured indoor signatures of outdoor episodic emissions arising from nonroutine operations of petroleum refinery fluidized-bed catalytic cracking units. Average indoor-to-outdoor (I/O) abundance ratios for the majority of elements were close to unity providing evidence that indoor metal-bearing PM2.5 had predominantly outdoor origins. Only Co had an I/O abundance ratio >1 but its indoor sources could not be explicitly identified. La and 17 other elements (Na, K, V, Ni, Co, Cu, Zn, Ga, As, Se, Mo, Cd, Sn, Sb, Ba, W, and Pb), including air toxics were enriched relative to the local soil both in indoor and outdoor PM2.5 demonstrating their noncrustal origins. Several lines of evidence including receptor modeling, lanthanoid ratios, and La-Ce-Sm ternary diagrams pointed to petroleum refineries as being largely responsible for enhanced La and total lanthanoid concentrations in the majority of paired indoor and outdoor PM2.5.

Free Diffusivity of Icosahedral and Tailed Bacteriophages: Experiments, Modeling, and Implications for Virus Behavior in Media Filtration and Flocculation.

The aqueous bulk diffusivities of several near-spherical (icosahedral) and nonspherical (tailed) bacterial viruses were experimentally determined by measuring their flux across large pore membranes and using dynamic light scattering, with excellent agreement between values measured using the two techniques. For the icosahedral viruses, good agreement was also found between measured diffusivity values and values predicted with the Stokes-Einstein equation. However, when the tailed viruses were approximated as spheres, poor agreement was found between measured values and Stokes-Einstein predictions. The shape of the tailed organisms was incorporated into two modeling approaches used to predict diffusivity. Model predictions were found to be in good agreement with measured values, demonstrating the importance of the tail in the diffusive transport of these viruses. Our calculations also show that inaccurate estimates of virus diffusion can lead to significant errors when predicting diffusive contributions to flocculation and to single collector efficiency in media filtration.

Cytotoxic Effect of Lipophilic Bismuth Dimercaptopropanol Nanoparticles on Epithelial Cells.

Bismuth nanoparticles have many interesting properties to be applied in biomedical and medicinal sectors, however their safety in humans have not been comprehensively investigated. The objective of this research was to determine the cytotoxic effect of bismuth dimercaptopropanol nanoparticles (BisBAL NPs) on epithelial cells. The nanoparticles are composed of 18.7 nm crystallites on average and have a rhombohedral structure, agglomerating into chains-like or clusters of small nanoparticles. Based on MTT viability assay and fluorescence microscopy, cytotoxicity was not observed on monkey kidney cells after growing with 5 µM of BisBAL NPs for 24 h. Employing same techniques, identical results were obtained with human epithelial cells (HeLa), showing a not strain-dependent phenomenon. The absence of toxic effects on epithelial cells growing with BisBAL NPs was corroborated with long-time experiments (24-72 hrs.), showing no difference in comparison with growing control (cells without nanoparticles). Further, genotoxicity assays, comet assay and fluorescent microscopy and electrophoresis in bromide-stained agarose gel revealed no damage to genomic DNA of MA104 cells after 24 h. of exposition to BisBAL NPs. Finally, the effect of bismuth nanoparticles on protein synthesis was studied in cells growing with BisBAL NPs for 24 h. SDS-PAGE assays showed no difference between treated and untreated cells, suggesting that BisBAL NPs did not interfere with protein synthesis. Hence BisBAL NPs do not appear to exert cytotoxic effects suggesting their biological compatibility with epithelial cells.

Mechanisms of physically irreversible fouling during surface water microfiltration and mitigation by aluminum electroflotation pretreatment.

A modified poly(vinylidene fluoride) membrane was used to directly microfilter untreated Lake Houston water, which was then regenerated by surface washing and hydraulic backwashing, a process that was cycled five times. The source water was also electrochemically precoagulated using aluminum and microfiltered, and the membrane was physically regenerated for five cycles. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) were used to characterize foulants on membrane surfaces and rigorously deduce their contributions to physically irreversible fouling after cycles 1 and 5. Hydrophobic molecules primarily appeared to initiate fouling during microfiltration of untreated raw water because O-H/N-H bands were attenuated while C-H bands remained relatively unchanged in FTIR-spectra of membrane surfaces after only one cycle. However, O-H/N-H and symmetric and asymmetric C(═ O)O(-) stretching bands significantly intensified with continued filtration/regeneration of untreated water, showing the importance of hydrophilic molecules and the role of complexation, respectively, to longer term irreversible fouling. Distinct C-H bands were detected in floated flocs after electrolysis, suggesting the sorption and subsequent removal of a substantial portion of the hydrophobic moieties present in Lake Houston water during pretreatment. Consequently, hydrophilic compounds appeared to contribute more to irreversible fouling in pretreated waters throughout the course of filtration as evidenced by significantly more intense O-H bands (compared with C-H bands) on the membrane surface after cycles 1 and 5. Therefore, electroflotation pretreatment reduced accumulation of hydrophobic foulants but simultaneously increased complexation of hydrophilic foulant molecules along with any carried-over aluminum hydroxide precipitates evidenced by increasing Al and O concentrations via XPS and intense C(═ O)O(-) stretching bands in IR spectra.

Relative insignificance of virus inactivation during aluminum electrocoagulation of saline waters.

Combined removal and inactivation of the MS2 bacteriophage from model saline (0-100 mM NaCl) waters by electrochemical treatment using a sacrificial aluminum anode was evaluated. Both chemical and electrodissolution contributed to coagulant dosing since measured aluminum concentrations were statistically higher than purely electrochemical predictions using Faraday's law. Electrocoagulation generated only small amounts of free chlorine in situ but effectively destabilized viruses and incorporated them into Al(OH)3(s) flocs during electrolysis. Low chlorine concentrations combined with virus shielding and aggregation within flocs resulted in very slow disinfection rates necessitating extended flocculation/contact times to achieve significant log-inactivation. Therefore, the dominant virus control mechanism during aluminum electrocoagulation of saline waters is "physical" removal by uptake onto flocs rather than "chemical" inactivation by chlorine. Attenuated total reflectance-Fourier transform infrared spectroscopy provided evidence for oxidative transformations of capsid proteins including formation of oxyacids, aldehydes, and ketones. Electrocoagulation significantly altered protein secondary structures decreasing peak areas associated with turns, bends, α-helices, ß-structures, and random coils for inactivated viruses compared with the MS2 stock. Quantitative reverse transcription polymerase chain reaction (qRT-PCR) measurements showed rapid initial RNA damage following a similar trend as plaque assay measurements of infectious viruses. However, ssRNA cleavage measured by qRT-PCR underestimated inactivation over longer durations. Although aluminum electrocoagulation of saline waters disorders virus capsids and damages RNA, inactivation occurs at a sufficiently low rate so as to only play a secondary role to floc-encapsulation during residence times typical of electrochemical treatment.

Elemental characterization of PM2.5 and PM10 emitted from light duty vehicles in the Washburn Tunnel of Houston, Texas: release of rhodium, palladium, and platinum.

We report the elemental composition, including Rh, Pd, and Pt, of total (i.e., tailpipe and nontailpipe) PM2.5 and PM10 emissions from predominantly gasoline-driven light-duty vehicles (LDVs) traversing the Washburn Tunnel in Houston, Texas during November and December, 2012. Using a novel sample preparation and dynamic reaction cell-quadrupole-inductively coupled plasma-mass spectrometry technique, we quantify the emission of numerous representative, transition, and lanthanoid elements. Two sets of time integrated PM samples were collected over 3-4week duration both inside the tunnel as well as from the tunnel ventilation air supply to derive accurate LDV source profiles incorporating three platinum group elements (PGEs) for the first time. Average Rh, Pd, and Pt concentrations from the tunnel ventilation air supply were 1.5, 11.1, and 4.5pgm(-3) in PM2.5 and 3.8, 23.1, and 15.1pgm(-3) in PM10, respectively. Rh, Pd, and Pt levels were elevated inside the Washburn Tunnel reaching 12.5, 91.1, and 30.1pgm(-3) in PM2.5 and 36.3, 214, and 61.1pgm(-3) in PM10, respectively. Significantly higher enrichment factors of Cu, Zr, Rh, Pd, Sb, and Pt (referenced to Ti in the upper continental crust) inside the tunnel compared with the ventilation air supply suggested that they are unique elemental tracers of PM derived from gasoline-driven LDVs. This highlights the importance of advancing methods to quantify the trace level PGE emissions as a technique to more accurately estimate LDVs' contributions to airborne PM. Using the emission profile based on PGEs and ambient quantification, mass balancing revealed that approximately half the fine PM mass in the tunnel could be attributed to tailpipe emissions, approximately one-quarter to road dust, with smaller contributions from brake (7%) and tire (3%) wear. On the other hand, PM10 mostly originated from resuspended road dust (∼50%), with progressively lower contributions from tailpipe emissions (14%), brake wear (9%), and tire wear (2%).

Antimicrobial and antitumor activities of an alginate-based membrane loaded with bismuth nanoparticles and cetylpyridinium chloride.

OBJECTIVE: To evaluate the antitumor and antimicrobial properties of an alginate-based membrane (ABM) loaded with bismuth lipophilic nanoparticles (BisBAL NPs) and cetylpyridinium chloride (CPC) on clinically isolated bacteria and a pancreatic cancer cell line. MATERIAL AND METHODS: The BisBAL NP-CPC ABM was characterized using optical and scanning electron microscopy (SEM). The antimicrobial potential was measured using the disk-diffusion assay, and antibiofilm activity was determined through the live/dead assay and fluorescence microscopy. The antitumor activity was analyzed on the pancreatic cell line (Panc 03.27) using the MTT assay and live/dead assay with fluorescence microscopy. RESULTS: After a 24-h exposure (37°C, aerobic conditions), 5 µM BisBAL NP reduced the growth of K. pneumoniae by 77.9%, while 2.5 µM BisBAL NP inhibited the growth of Salmonella, E. faecalis and E. faecium by 82.9%, 82.6%, and 78%, respectively (p < 0.0001). The BisBAL NPs-CPC ABM (at a ratio of 10:1; 500 and 50 µM, respectively) inhibited the growth of all isolated bacteria, producing inhibition halos of 9.5, 11.2, 7, and 10.3 mm for K. pneumoniae, Salmonella, E. faecalis, and E. faecium, respectively, in contrast to the 6.5, 9.5, 8.5, and 9.8 mm obtained with 100 µM ceftriaxone (p < 0.0001). The BisBAL NPs-CPC ABM also reduced bacterial biofilms, with 81.4%, 74.5%, 97.1%, and 79.5% inhibition for K. pneumoniae, E. faecium, E. faecalis, and Salmonella, respectively. Furthermore, the BisBAL NPs-CPC ABM decreased Panc 03.27 cell growth by 76%, compared to 18% for drug-free ABM. GEM-ABM reduced tumoral growth by 73%. The live/dead assay confirmed that BisBAL NPs-CPC-ABM and GEM-ABM were cytotoxic for the turmoral Panc 03.27 cells. CONCLUSION: An alginate-based membrane loaded with BisBAL NP and CPC exhibits dual antimicrobial and antitumoral efficacy. Therefore, it could be applied in cancer treatment and to diminish the occurrence of surgical site infections.

Sweep flocculation and adsorption of viruses on aluminum flocs during electrochemical treatment prior to surface water microfiltration.

Bench-scale experiments were performed to evaluate virus control by an integrated electrochemical-microfiltration (MF) process from turbid (15 NTU) surface water containing moderate amounts of dissolved organic carbon (DOC, 5 mg C/L) and calcium hardness (50 mg/L as CaCO3). Higher reductions in MS2 bacteriophage concentrations were obtained by aluminum electrocoagulation and electroflotation compared with conventional aluminum sulfate coagulation. This was attributed to electrophoretic migration of viruses, which increased their concentrations in the microenvironment of the sacrificial anode where coagulant precursors are dissolved leading to better destabilization during electrolysis. In all cases, viruses were not inactivated implying measured reductions were solely due to their removal. Sweep flocculation was the primary virus destabilization mechanism. Direct evidence for virus enmeshment in flocs was provided by two independent methods: quantitative elution using beef extract at elevated pH and quantitating fluorescence from labeled viruses. Atomic force microscopy studies revealed a monotonically increasing adhesion force between viruses immobilized on AFM tips and floc surfaces with electrocoagulant dosage, which suggests secondary contributions to virus uptake on flocs from adsorption. Virus sorption mechanisms include charge neutralization and hydrophobic interactions with natural organic matter removed during coagulation. This also provided the basis for interpreting additional removal of viruses by the thick cake formed on the surface of the microfilter following electrocoagulation. Enhancements in virus removal as progressively more aluminum was electrolyzed therefore embodies contributions from (i) better encapsulation onto greater amounts of fresh Al(OH)3 precipitates, (ii) increased adsorption capacity associated with higher available coagulant surface area, (iii) greater virus-floc binding affinity due to effective charge neutralization and hydrophobic interactions, and/or (iv) additional removal by a dynamic membrane if a thick cake layer of flocs is deposited.

Quantifying the contribution of long-range Saharan dust transport on particulate matter concentrations in Houston, Texas, using detailed elemental analysis.

The trans-Atlantic transport of North African dust by summertime trade winds occasionally increases ambient particulate matter (PM) concentrations in Texas above air quality standards. Exemptions from such exceedences can be sought for episodic events that are beyond regulatory control by providing qualitative supportive information such as satellite images and back-trajectories. Herein we demonstrate that chemical mass balancing can successfully isolate, differentiate, and quantify the relative contributions from local and global mineral dust sources through detailed measurements of a wide suite of elements in ambient PM. We identified a major dust storm originating in Northwest Africa in mid-July 2008 which eventually impacted air quality in Houston during July 25, 26, and 27, 2008. Daily PM2.5 and PM10 samples were collected at two sites in Houston over a 2-week period encompassing the Saharan dust episode to quantify the transported mineral dust concentrations during this peak event. Average PM concentrations more than doubled during the Saharan intrusion compared with non-Saharan. Relative concentrations of several elements often associated with anthropogenic sources were significantly diluted by crustal minerals coincident with the large-scale Saharan dust intrusion. During non-Saharan days, local mineral dust sources including cement manufacturing and soil and road dust contributed in total 26% to PM2.5 mass and 50% to PM10 mass; during the three-day Saharan episode the total dust contribution increased to 64% for PM2.5 and 85% for PM10. Importantly, this approach was also able to determine that local emissions of crustal minerals dominated the period immediately following the Saharan dust episode: simple quantification of bulk crustal materials may have misappropriated this elevated PM to trans-Atlantic transport of Saharan dust.

A transient biological fouling model for constant flux microfiltration.

Microfiltration is a widely used engineering technology for fresh water production and water treatment. The major concern in many applications is the formation of a biological fouling layer leading to increased hydraulic resistance and flux decline during membrane operations. The growth of bacteria constituting such a biological layer implicates the formation of a multispecies biofilm and the consequent increase of operational costs for reactor management and cleaning procedures. To predict the biofouling evolution, a mono-dimensional continuous free boundary model describing biofilm dynamics and EPS production in different operational phases of microfiltration systems has been well studied. The biofouling growth is governed by a system of hyperbolic PDEs. Substrate dynamics are modeled through parabolic equations accounting for diffusive and advective fluxes generated during the filtration process. The free boundary evolution depends on both microbial growth and detachment processes. What is not addressed is the interplay between biofilm dynamics, filtration, and water recovery. In this study, filtration and biofilm growth modeling principles have been coupled for the definition of an original mathematical model able to reproduce biofouling evolution in membrane systems. The model has been solved numerically to simulate biologically relevant conditions, and to investigate the hydraulic behavior of the membrane. It has been calibrated and validated using lab-scale data. Numerical results accurately predicted the pressure drop occurring in the microfiltration system. A calibrated model can give information for optimization protocols as well as fouling prevention strategies.

Cumulative antitumor effect of bismuth lipophilic nanoparticles and cetylpyridinium chloride in inhibiting the growth of lung cancer.

OBJECTIVE: To determine the combined antitumor effect of bismuth lipophilic nanoparticles (BisBAL NP) and cetylpyridinium chloride (CPC) on human lung tumor cells. MATERIAL AND METHODS: The human lung tumor cells A549 were exposed to 1-100 µM BisBAL NP or CPC, either separately or in a 1:1 combination. Cell viability was measured with the PrestoBlue assay, the LIVE/DEAD assay, and fluorescence microscopy. The integrity and morphology of cellular microtubules were analyzed by immunofluorescence. RESULTS: A 24-h exposure to 1 µM solutions reduced A549 growth with 21.5% for BisBAL NP, 70.5% for CPC, and 92.4% for the combination (p < 0.0001), while a 50 µM BisBAL NP/CPC mixture inhibited cell growth with 99% (p < 0.0001). BisBAL NP-curcumin conjugates were internalized within 30 min of exposure and could be traced within the nucleus of tumor cells within 2 h. BisBAL NP, but not CPC, interfered with microtubule organization, thus interrupting cell replication, similar to the action mechanism of docetaxel. CONCLUSION: The growth inhibition of A549 human tumor cells by BisBAL NP and CPC was cumulative as of 1 µM. The BisBAL NP/CPC combination may constitute an innovative and cost-effective alternative for treating human lung cancer.

Bacteriophage inactivation by UV-A illuminated fullerenes: role of nanoparticle-virus association and biological targets.

Inactivation rates of the MS2 bacteriophage and (1)O(2) generation rates by four different photosensitized aqueous fullerene suspensions were in the same order: aqu-nC(60) < C(60)(OH)(6) ≈ C(60)(OH)(24) < C(60)(NH(2))(6). Alterations to capsid protein secondary structures and protein oxidation were inferred by detecting changes in infrared vibrational frequencies and carbonyl groups respectively. MS2 inactivation appears to be the result of loss of capsid structural integrity (localized deformation) and the reduced ability to eject genomic RNA into its bacterial host. Evidence is also presented for possible capsid rupture in MS2 exposed to UV-A illuminated C(60)(NH(2))(6) through TEM imagery and detection of RNA infrared fingerprints in ATR-FTIR spectra. Fullerene-virus mixtures were also directly visualized in the aqueous phase using a novel enhanced darkfield transmission optical microscope fitted with a hyperspectral imaging (HSI) spectrometer. Perturbations in intermolecular extended chains, HSI, and electrostatic interactions suggest that inactivation is a function of the relative proximity between nanoparticles and viruses and (1)O(2) generation rate. MS2 log survival ratios were linearly related to CT (product of (1)O(2) concentration C and exposure time T) demonstrating the applicability of classical Chick-Watson kinetics for all fullerenes employed in this study. Results suggest that antiviral properties of fullerenes can be increased by adjusting the type of surface functionalization and extent of cage derivatization thereby increasing the (1)O(2) generation rate and facilitating closer association with biological targets.

Sr-Nd-Hf isotopic analysis of reference materials and natural and anthropogenic particulate matter sources: Implications for accurately tracing North African dust in complex urban atmospheres.

We present novel chemical separation protocols for isotopic analysis of low mass aliquots (0.3 mg and 25 mg) of several reference materials and real-world samples of relevance to urban airborne particulate matter (PM) investigations. A high-yielding gravity flow column chromatography scheme was developed for facile and quantitative separation of Sr, Nd, and Hf prior to multi collector - inductively coupled plasma - mass spectrometry (MC-ICP-MS). Because we are interested in isolating and accurately quantitating individual anthropogenic and natural aerosol sources in complex industrial/metropolitan atmospheric environments, laboratory protocols were optimized using National Institute of Standards and Technology Standard Reference Material (SRM) 1648a (urban atmospheric PM), SRM 1633b (coal fly ash), and European Commission standards BCR-723 (vehicular road dust), and BCR-2 (basalt rock standard). Sr, Nd, and Hf procedural blanks from column chromatography were low (averaging only 37 pg, 17 pg, 11 pg, respectively) and recoveries were high (averaging 95%, 82%, and 92%, respectively). A volume-adjustment protocol was established using isotope reference solutions SRM 987 (SrCO3), JNdi (Nd2O3), and in-house Hf standards to dilute the dried samples prior to MC-ICP-MS based on projected uncertainties for low sample masses. 87Sr/86Sr, 143Nd/144Nd, and 176Hf/177Hf isotopic ratios in SRM 1648a, BCR-723, and SRM 1633b are reported for the first time that can serve as provisional reference values. The novel method was used to characterize isotopic ratios and elemental abundances in two anthropogenic urban aerosol sources, namely motor vehicles and petroleum refining using airborne fine PM collected in a vehicular tunnel and fluidized-bed catalytic cracking catalysts, respectively. Two other important mineral-rich urban PM sources, namely soil (i.e., resuspended crustal material) and concrete/cement dust (i.e., construction activity) were also characterized. These are the first isotopic measurements in these environmental compartments and were compared with literature data for long-range transported North African dust, which is a prominent summertime PM source in urban regions in southeastern United States. We demonstrate the capability of coupled Sr-Nd-Hf isotopes to uniquely trace different mineral dust sources with overlapping elemental composition (Sahara-Sahel region, local soil, and concrete/cement) and accurately isolate various urban PM sources demonstrating the superiority of isotopic markers over elemental tracers.

Hypersaline produced water clarification by dissolved air flotation and sedimentation with ultrashort residence times.

Treatment and reuse of some produced waters is made difficult due to their hypersalinity, high concentrations of myriad other dissolved and suspended components, specialized technology requirements (modularity, portability, and short residence times), and lack of existing information on their processing. In this work, produced water containing ∼100,000 mg/L total dissolved solids from the Permian Basin was coagulated with aluminum chlorohydrate (ACH) and flocculated with an anionic high molecular weight organic polymer prior to dissolved air flotation (DAF) and sedimentation to reduce turbidity to < 4 NTU and iron < 0.8 mg/L (>95% removal in both cases) with a total coagulation-flocculation-sedimentation/flotation residence time of only 5 min. Two advantages of DAF over sedimentation were noted: (i) DAF required only half the dosage of the pre-hydrolyzed ACH coagulant to remove ∼90% of turbidity and iron even without the organic polymeric flocculant and (ii) DAF even operated successfully without ACH coagulation (i.e., using only the organic polymeric flocculant) evidencing its lower chemical dosing needs. Further, DAF attained all water quality and operational goals at a recycle ratio of only 12% demonstrating that it outperformed sedimentation to generate clean brine at relatively reduced excess energies necessary for air saturation. Higher DAF recycle ratios reduced turbidity and iron removal possibly due to floc breakage. Colloids were effectively destabilized by double layer compression (due to high water salinity), charge neutralization (via adsorption of Al13 polycations), and enmeshment (precipitation of amorphous aluminum). They were flocculated via interparticle bridging (by the anionic organic polymeric flocculant) to create large, compact flocs facilitating ultrashort flotation/sedimentation times. Direct evidence for these individual coagulation and flocculation mechanisms were obtained using electrophoretic mobility measurements, thermogravimetric analysis, X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, optical microscopy, computational image and video analysis, and scanning electron microscopy - energy dispersive X-ray spectroscopy.