Static and dynamic source identification of trace elements in river and soil environments under anthropogenic activities in the Haraz plain, Northern Iran.

Unsustainable human activities have disrupted the natural cycle of trace elements, causing the accumulation of chemical pollutants and making it challenging to determine their sources due to interwoven natural and human-induced processes. A novel approach was introduced for identifying the sources and for quantifying the contribution of trace elements discharge from rivers to soils. We integrated fingerprinting techniques, soil and sediment geochemical data, geographically weighted regression model (GWR) and soil quality indices. The FingerPro package and the state-of-the-art tracer selection techniques including the conservative index (CI) and consensus ranking (CR) were used to quantify the relative contribution of different upland sub-watersheds in trace element discharge soil. Our analysis revealed that off-site sources (upland watersheds) and in-site sources (land use) both play an important role in transferring trace elements to the Haraz plain (northern Iran). The unmixing model's results suggest that the Haraz sub-watersheds exhibit a higher contribution to trace elements transfer in the Haraz plain, and therefore, require greater attention in terms of implementing soil and water conservation strategies. However, it is noteworthy that the Babolroud (adjacent to Haraz) exhibited a better performance of the model. A spatial correlation between certain heavy metals, such as As and Cu, and rice cultivation existed. Additionally, we found a significant spatial correlation between Pb and residential areas, particularly in the Amol region. Our result highlights the importance of using advanced spatial statistical techniques, such as GWR, to identify subtle but critical associations between environmental variables and sources of pollution. The methodology used comprehensively identifies dynamic trace element sourcing at the watershed scale, allowing for pollutant source identification and practical strategies for soil and water quality control. Tracer selection techniques (CI and CR) based on conservatives and consensus improve unmixing model accuracy and flexibility for precise fingerprinting.

Tracking the origin of trace metals in a watershed by identifying fingerprints of soils, landscape and river sediments.

The identification of the spatial distribution of soil trace-elements and the contribution of different sources to the sediment yield is necessary for a better watershed and river water quality management. Until now, less attention has been paid to comprehensive assessments of sediment sources and soil trace-elements with respect to the suspended sediment production. The present study aimed at modelling the spatial distribution of soil trace-elements, quantifying the sediment sources apportionment and relating the landforms to polluted soils. Different techniques and approaches such as the Nemerow pollution index, machine learning algorithms (Random Forest (RF), generalised boosting methods (GBM), generalised linear models (GLM) and sediment fingerprinting were applied to the Kan watershed. A total of 79 soil samples having different Nemerow index values were considered for spatial modelling. Using statistical methods (Range test, Kruskal-Wallis and discrimination function analysis), an optimal set of tracers was selected. An unmixing model was applied to calculate the relative contribution of landforms for eight rainfall events. The results of the soil trace-element mapping showed that RF had the best performance with an accuracy of 83%. The evaluation of polluted soil areas showed that the landforms 'steep hills' and 'valley' contributed the most with 51% and 27% in the riparian zone, respectively. In addition, these landforms give a high contribution to sediment production in late-winter-spring events (29%) with a GOF (goodness of fit) of 0.65. The landform 'plain' had the highest contribution (28%) in sediment yield with a GOF of 0.72 in early-winter events. This means that the valley and steep hill landforms accelerate the transport of trace-elements across the watershed. Interestingly, the contribution of landforms varies during the year. Overall, the new proposed approach enables to better trace the origin of suspended sediments and trace-elements discharge into the river environment.

Human-induced arsenic pollution modeling in surface waters - An integrated approach using machine learning algorithms and environmental factors.

In recent years, assessment of sediment contamination by heavy metals, i.e., arsenic, has attracted the interest of scientists worldwide. The present study provides a new methodology to better understand the factors influencing surface water vulnerability to arsenic pollution by two advanced machine learning algorithms including boosted regression trees (BRT) and random forest (RF). Based on the sediment quality guidelines (Effects range low) polluted and non-polluted arsenic sediment samples were defined with concentrations >8 ppm and <8 ppm, respectively. Different conditioning factors such as topographical, lithology, erosion, hydrological, and anthropogenic factors were acquired to model surface waters' vulnerability to arsenic. We trained and validated the models using 70 and 30% of both polluted and non-polluted samples, respectively, and generated surface vulnerability maps. To verify the maps to arsenic pollution, the receiver operating characteristics (ROC) curve was implemented. The results approved the acceptable performance of the RF and BRT algorithms with an area under ROC values of 85% and 75.6%, respectively. Further, the findings showed higher importance of precipitation, slope aspect, distance from residential areas, and slope length in arsenic pollution in the modeling process. Erosion, lithology, and land use maps were introduced as the least important factors. The introduced methodology can be used to define the most vulnerable areas to arsenic pollution in advance and implement proper remediation actions to reduce the damages.

Critical Considerations for Regeneration of Vascularized Composite Tissues.

Effective vascularization is vital for survival and functionality of complex tissue-engineered organs. The formation of the microvasculature, composed of endothelial cells (ECs) alone, has been mostly used to restore the vascular networks in organs. However, recent heterocellular studies demonstrate that co-culturing is a more effective approach in revascularization of engineered organs. This review presents key considerations for manufacturing of artificial vascularized composite tissues. We summarize the importance of co-cultures and the multicellular interactions with ECs, as well as design and use of bioreactors, as critical considerations for tissue vascularization. In addition, as an emerging scaffolding technique, this review also highlights the current caveats and hurdles associated with three-dimensional bioprinting and discusses recent developments in bioprinting strategies such as four-dimensional bioprinting and its future outlook for manufacturing of vascularized tissue constructs. Finally, the review concludes with addressing the critical challenges in the regulatory pathway and clinical translation of artificial composite tissue grafts. Impact statement Regeneration of composite tissues is critical as biophysical and biochemical characteristics differ between various types of tissues. Engineering a vascularized composite tissue has remained unresolved and requires additional evaluations along with optimization of methodologies and standard operating procedures. To this end, the main hurdle is creating a viable vascular endothelium that remains functional for a longer duration postimplantation, and can be manufactured using clinically appropriate source of cell lines that are scalable in vitro for the fabrication of human-scale organs. This review presents key considerations for regeneration and manufacturing of vascularized composite tissues as the field advances.

Poly(d,l-Lactic acid) Composite Foams Containing Phosphate Glass Particles Produced via Solid-State Foaming Using CO2 for Bone Tissue Engineering Applications.

This study reports on the production and characterization of highly porous (up to 91%) composite foams for potential bone tissue engineering (BTE) applications. A calcium phosphate-based glass particulate (PGP) filler of the formulation 50P2O5-40CaO-10TiO2 mol.%, was incorporated into biodegradable poly(d,l-lactic acid) (PDLLA) at 5, 10, 20, and 30 vol.%. The composites were fabricated by melt compounding (extrusion) and compression molding, and converted into porous structures through solid-state foaming (SSF) using high-pressure gaseous carbon dioxide. The morphological and mechanical properties of neat PDLLA and composites in both nonporous and porous states were examined. Scanning electron microscopy micrographs showed that the PGPs were well dispersed throughout the matrices. The highly porous composite systems exhibited improved compressive strength and Young's modulus (up to >2-fold) and well-interconnected macropores (up to ~78% open pores at 30 vol.% PGP) compared to those of the neat PDLLA foam. The pore size of the composite foams decreased with increasing PGPs content from an average of 920 µm for neat PDLLA foam to 190 µm for PDLLA-30PGP. Furthermore, the experimental data was in line with the Gibson and Ashby model, and effective microstructural changes were confirmed to occur upon 30 vol.% PGP incorporation. Interestingly, the SSF technique allowed for a high incorporation of bioactive particles (up to 30 vol.%-equivalent to ~46 wt.%) while maintaining the morphological and mechanical criteria required for BTE scaffolds. Based on the results, the SSF technique can offer more advantages and flexibility for designing composite foams with tunable characteristics compared to other methods used for the fabrication of BTE scaffolds.

How do data-mining models consider arsenic contamination in sediments and variables importance?

Arsenic (As) is one of the most important dangerous elements as more than 100 million of people are exposed to risk, globally. The permissible threshold of As for drinking water is 10 µg/L according to both the WHO's drinking water guidelines and the Iranian national standard. However, several studies have indicated that As concentrations exceed this threshold value in several regions of Iran. This research evaluates an As-susceptible region, the Tajan River watershed, using the following data-mining models: multivariate adaptive regression splines (MARS), functional data analysis (FDA), support vector machine (SVM), generalized linear model (GLM), multivariate discriminant analysis (MDA), and gradient boosting machine (GBM). This study considers 12 factors for elevated As concentrations: land use, drainage density, profile curvature, plan curvature, slope length, slope degree, topographic wetness index, erosion, village density, distance from villages, precipitation, and lithology. The susceptibility mapping was conducted using training (70%) and validation (30%). The results of As contamination in sediment showed that classifications into 4 levels of concentration are very similar for two models of GLM and FDA. The GBM calculated the areas of highest arsenic contamination risk by MARS and SVM with percentages of 30.0% and 28.7%, respectively. FDA, GLM, MARS, and MDA models calculated the areas of lowest risk to be 3.3%, 23.0%, 72.0%, 25.2%, and 26.1%, respectively. The results of ROC curve reveal that the MARS, SVM, and MDA had the highest accuracies with area under the curve ROC values of 84.6%, 78.9%, and 79.5%, respectively. Land use, lithology, erosion, and elevation were the most important predictors of contamination potential with a value of 0.6, 0.59, 0.57, and 0.56, respectively. These are the most important factors. Finally, these data-mining methods can be used as appropriate, inexpensive, and feasible options to identify As-susceptible areas and can guide managers to reduce contamination in sediment of the environment and the food chain.

Injectable drug depot engineered to release multiple ophthalmic therapeutic agents with precise time profiles for postoperative treatment following ocular surgery.

A multi-drug delivery platform is developed to address current shortcomings of post-operative ocular drug delivery. The sustained biodegradable drug release system is composed of biodegradable polymeric microparticles (MPs) incorporated into a bulk biodegradable hydrogel made from triblock copolymers with poly(ethylene glycol) (PEG) center blocks and hydrophobic biodegradable polyester blocks such as poly(lactide-co-glycolide) (PLGA), Poly(lactic acid) (PLA), or Poly(lactide-co-caprolactone) (PLCL) blocks. This system is engineered to flow as a liquid solution at room temperature for facile injection into the eye and then quickly gel as it warms to physiological body temperatures (approximately 37 °C). The hydrogel acts as an ocular depot that can release three different drug molecules at programmed rates and times to provide optimal release of each species. In this manuscript, the hydrogel is configured to release a broad-spectrum antibiotic, a potent corticosteroid, and an ocular hypotensive, three ophthalmic therapeutic agents that are essential for post-operative management after ocular surgery, each drug released at its own timescale. The delivery platform is designed to mimic current topical application of postoperative ocular formulations, releasing the antibiotic for up to a week, and the corticosteroid and the ocular hypotensive agents for at least a month. Hydrophobic blocks, such as PLCL, were utilized to prolong the release duration of the biomolecules. This system also enables customization by being able to vary the initial drug loading to linearly tune the drug dose released, while maintaining a constant drug release profile over time. This minimally invasive biodegradable multi-drug delivery system is capable of replacing a complex ocular treatment regimen with a simple injection. Such a depot system has the potential to increase patient medication compliance and reduce both the immediate and late term complications following ophthalmic surgery. STATEMENT OF SIGNIFICANCE: After ocular surgery, patients routinely receive multiple medications including antibiotics, steroids and ocular hypotensives to ensure optimal surgical outcomes. The current standard of care for postoperative treatment after ocular surgery involves using eye drops daily, which has limited effectiveness mainly due to poor patient adherence. To improve patient experience and outcomes, this article presents the first thermoresponsive hydrogel able to release multiple drug molecules for the application of post-operative treatment following ocular surgery. By varying the parameters such as hydrogel type and polymer hydrophobicity, the drug release profile, duration and dosage can finely be tuned. The approach presented in this article can readily be applied to other applications by simply changing the drug loaded in the drug delivery system.

Growth Kinetics in Layer-by-Layer Assemblies of Organic Nanoparticles and Polyelectrolytes.

The growth rates of layer-by-layer (LbL) assemblies of polyelectrolytes (PEs) with oppositely charged polystyrene (PS) nanoparticles (NPs) as a function of molecular weight (MW) of the PEs, ionic strength of the media, and NP size and charge are systematically investigated. To optimize LbL growth, the effects of suspension concentration, pH of the media, and deposition time on the growth rate of multilayers are assessed. Both linear and exponential growth behaviors are observed and, under optimal conditions, films of up to around 1 µm thick can readily be assembled after 10 or so bilayers have been deposited. For many of the cases studied, an intermediate MW of PE leads to the fastest film buildup, for both cationic poly(ethyleneimine) deposited alternately with anionic PS NPs and for anionic poly(acrylic acid) deposited alternately with cationic PS NPs. The existence of an optimal MW suggests that growth rate is determined by a balance of thermodynamic factors, including density of polymer bridges between particles, and kinetic factors, specifically the diffusivity of polymer in the film. The optimal MW, however, is very sensitive to the materials used. Moreover, depending on the MW of the PE, increasing salinity could increase or decrease the growth kinetics. Finally, the surface morphology of the films is characterized with AFM and SEM to reveal that the roughness increases less than linearly with film thickness.

Brownian dynamics simulations of coagulation of dilute uniform and anisotropic particles under shear flow spanning low to high Peclet numbers.

Brownian dynamics simulations are performed to study the binding kinetics in the dilute-sphere limit by considering interactions of two spheres under shear flow across the entire range of Peclet numbers, spanning both perikinetic (diffusion-controlled) and orthokinetic (flow-controlled) coagulation regimes. The dilute regime is attained by carrying out two-sphere simulations in periodic boxes of different sizes and aspect ratios and extrapolating toward the infinite box limit. Effects of particle type (Janus and isotropic particles), shear rate, hydrodynamic interactions, and inter-particle potential are explored. We find that rectangular boxes with appropriate aspect ratios overcome a particle "shadow effect" that cannot be overcome with cubic boxes unless huge boxes are used. With rectangular boxes, we obtain converged binding kinetics for the whole Peclet number range, while cubic boxes of increasing size allow converged results only in the absence of flow. We consider the effect of binding both in a secondary minimum controlled by a combination of electrostatic repulsion and depletion attraction, as well as in a primary minimum governed by induced-dipole attraction. Results are computed using both realistic interaction potentials and by replacing the potential with a simple cutoff gap distance at which binding is deemed to occur. Results agree with several existing reports including Smoluchowski predictions in the zero- and infinite-shear-rate limits, and high-Pe perturbation results of Feke and Schowalter [J. Fluid Mech. 133, 17-35 (1983)] at Peclet numbers (Pe) above 100. Finally, we compute binding times for anisotropic Janus particles which have both repulsive and attractive faces, for a wide range of Pe number.

Osteoblastic differentiation under controlled bioactive ion release by silica and titania doped sodium-free calcium phosphate-based glass.

Sodium-free phosphate-based glasses (PGs) doped with both SiO2 and TiO2 (50P2O5-40CaO-xSiO2-(10-x)TiO2, where x=10, 7, 5, 3, and 0mol%) were developed and characterised for controlled ion release applications in bone tissue engineering. Substituting SiO2 with TiO2 directly increased PG density and glass transition temperature, indicating a cross-linking effect of Ti on the glass network which was reflected by significantly reduced degradation rates in an aqueous environment. X-ray diffraction confirmed the presence of Ti(P2O7) in crystallised TiO2-containing PGs, and nuclear magnetic resonance showed an increase in Q(1) phosphate species with increasing TiO2 content. Substitution of SiO2 with TiO2 also reduced hydrophilicity and surface energy. In biological assays, MC3T3-E1 pre-osteoblasts effectively adhered to the surface of PG discs and the incorporation of TiO2, and hence higher stability of the PG network, significantly increased cell viability and metabolic activity indicating the biocompatibility of the PGs. Addition of SiO2 increased ionic release from the PG, which stimulated alkaline phosphatase (ALP) activity in MC3T3-E1 cells upon ion exposure. The incorporation of 3mol% TiO2 was required to stabilise the PG network against unfavourable rapid degradation in aqueous environments. However, ALP activity was greatest in PGs doped with 5-7mol% SiO2 due to up-regulation of ionic concentrations. Thus, the properties of PGs can be readily controlled by modifying the extent of Si and Ti doping in order to optimise ion release and osteoblastic differentiation for bone tissue engineering applications.

Characterization of aqueous interactions of copper-doped phosphate-based glasses by vapour sorption.

Owing to their adjustable dissolution properties, phosphate-based glasses (PGs) are promising materials for the controlled release of bioinorganics, such as copper ions. This study describes a vapour sorption method that allowed for the investigation of the kinetics and mechanisms of aqueous interactions of PGs of the formulation 50P2O5-30CaO-(20-x)Na2O-xCuO (x=0, 1, 5 and 10mol.%). Initial characterization was performed using (31)P magic angle spinning nuclear magnetic resonance and attenuated total reflectance-Fourier transform infrared spectroscopy. Increasing CuO content resulted in chemical shifts of the predominant Q(2) NMR peak and of the (POP)as and (PO(-)) Fourier transform infrared absorptions, owing to the higher strength of the POCu bond compared to PONa. Vapour sorption and desorption were gravimetrically measured in PG powders exposed to variable relative humidity (RH). Sorption was negligible below 70% RH and increased exponentially with RH from 70 to 90%, where it exhibited a negative correlation with CuO content. Vapour sorption in 0% and 1% CuO glasses resulted in phosphate chain hydration and hydrolysis, as evidenced by protonated Q(0)(1H) and Q(1)(1H) species. Dissolution rates in deionized water showed a linear correlation (R(2)>0.99) with vapour sorption. Furthermore, cation release rates could be predicted based on dissolution rates and PG composition. The release of orthophosphate and short polyphosphate species corroborates the action of hydrolysis and was correlated with pH changes. In conclusion, the agreement between vapour sorption and routine characterization techniques in water demonstrates the potential of this method for the study of PG aqueous reactions.

Inhibition of bacterial motility and spreading via release of cranberry derived materials from silicone substrates.

The motility of bacteria plays a key role in their colonization of surfaces during infection. Derivatives of cranberry fruit have been shown to interfere with bacterial motility. Herein, we report on the incorporation of cranberry derived materials (CDMs) into silicone substrates with the aim of impairing bacterial pathogen motility and spreading on the substrate surface. The release of CDMs from the silicone substrates when soaking in an aqueous medium was quantified for a period of 24h. Next, we showed that CDMs released from two silicone substrates remain bioactive as they downregulate the expression of the flagellin gene of two key uropathogens - Escherichia coli CFT073 and Proteus mirabilis HI4320. Furthermore, we demonstrate that CDM-modified silicone inhibits the swarming motility of P. mirabilis, an aggressive swarmer. The bioactive, CDM-modified substrates can find broad applications in the medical device and food industries where the impairment of bacterial colonization of surfaces is of paramount importance.

Effect of phosphate-based glass fibre surface properties on thermally produced poly(lactic acid) matrix composites.

Incorporation of soluble bioactive glass fibres into biodegradable polymers is an interesting approach for bone repair and regeneration. However, the glass composition and its surface properties significantly affect the nature of the fibre-matrix interface and composite properties. Herein, the effect of Si and Fe on the surface properties of calcium containing phosphate based glasses (PGs) in the system (50P(2)O(5)-40CaO-(10-x)SiO(2)-xFe(2)O(3), where x = 0, 5 and 10 mol.%) were investigated. Contact angle measurements revealed a higher surface energy, and surface polarity as well as increased hydrophilicity for Si doped PG which may account for the presence of surface hydroxyl groups. Two PG formulations, 50P(2)O(5)-40CaO-10Fe(2)O(3) (Fe10) and 50P(2)O(5)-40CaO-5Fe(2)O(3)-5SiO(2) (Fe5Si5), were melt drawn into fibres and randomly incorporated into poly(lactic acid) (PLA) produced by melt processing. The ageing in deionised water (DW), mechanical property changes in phosphate buffered saline (PBS) and cytocompatibility properties of these composites were investigated. In contrast to Fe10 and as a consequence of the higher surface energy and polarity of Fe5Si5, its incorporation into PLA led to increased inorganic/organic interaction indicated by a reduction in the carbonyl group of the matrix. PLA chain scission was confirmed by a greater reduction in its molecular weight in PLA-Fe5Si5 composites. In DW, the dissolution rate of PLA-Fe5Si5 was significantly higher than that of PLA-Fe10. Dissolution of the glass fibres resulted in the formation of channels within the matrix. Initial flexural strength was significantly increased through PGF incorporation. After PBS ageing, the reduction in mechanical properties was greater for PLA-Fe5Si5 compared to PLA-Fe10. MC3T3-E1 preosteoblasts seeded onto PG discs, PLA and PLA-PGF composites were evaluated for up to 7 days indicating that the materials were generally cytocompatible. In addition, cell alignment along the PGF orientation was observed showing cell preference towards PGF.

Modulation of polycaprolactone composite properties through incorporation of mixed phosphate glass formulations.

Phosphate-based glasses (PGs) and their composites are of interest as bone repair and tissue engineering scaffolds due to the totally degradable nature of the materials. This study has investigated the effect of Si and Fe on the properties of PG particulate-filled polycaprolactone (PCL) matrix composites. Two glass compositions were investigated (mol.%): 50P(2)O(5), 40CaO and 10SiO(2) or Fe(2)O(3) (Si(10) and Fe(10), respectively). All composites contained 40 vol.% particulate filler, either Si(10), Fe(10), or a blend (40Si(10)/0Fe(10), 30Si(10)/10Fe(10), 20Si(10)/20Fe(10), 10Si(10)/30Fe(10) or 0Si(10)/40Fe(10)). Ion release, weight loss and composite mechanical properties were characterised as a function of time in deionised water (DW) and phosphate-buffered saline (PBS), respectively. The potential for calcium phosphate deposition was assessed in simulated body fluid (SBF). Calcium and phosphate ion release in DW increased in tandem with the rate of composite weight loss, which increased with Si(10) content. A Si(10) content dependent rate of pH reduction was observed in DW. After 56 days the PG in the 40Si(10)/0Fe(10) composite was completely dissolved, whereas 67% of that in the 0Si(10)/40Fe(10) composite remained. The initial flexural strength of 40Si(10)/0Fe(10) composites was significantly lower when compared with the other materials. An increase in Si(10) content led to an increase in Young's modulus and a concomitant decrease in flexural strain. It was found that the PCL molecular weight (M(w)) decreased dramatically with increasing Si(10) content. FTIR analysis showed that Si incorporation into PG led to reaction with the PCL ester bonds, resulting in a reduction in PCL M(w) when processed at elevated temperatures. Changes in mechanical properties with time in PBS were glass blend dependent and a more rapid rate of reduction was observed in higher Si(10) content composites. After 28 days in SBF surface deposited brushite was formed in 20Si(10)/20Fe(10) PG containing composites. Thus, the properties of PCL-PG composites could be tailored by controlling the phosphate glass blend composition.