Tutorial review of error evaluation in experimental water research at the example of membrane filtration.

Experimental water research lacks clear methodology to estimate experimental error. Especially when natural waters are involved, the characterization tools bear method-specific artifacts while the varying environmental conditions prevent regular repeats. This tutorial review identifies common mistakes, and proposes a practical procedure to determine experimental errors at the example of membrane filtration. Statistical analysis is often applied to an insufficient number of repeated measurements, while not all error sources and contributions are considered. This results in an underestimation of the experimental error. Variations in relevant experimental parameters need to be investigated systematically, and the related errors are quantified as a half of the variation between the max and min values when standard deviation is not applicable. Error of calculated parameters (e.g. flux, pollutant removal and mass loss) is estimated by applying error propagation, where weighing contributions of the experimental parameters are considered. Appropriate judgment and five-time repetition of a selected experiment under identical conditions are proposed to validate the propagated experimental error. For validation, the five repeated data points should lie within the estimated error range of the error bar. The proposed error evaluation procedure is adaptable in experimental water research and intended for researchers to identify the contributing factors of an experimental error and carry out appropriate error quantification and validation. The most important aim is to raise awareness of the necessity to question error methodology and reproducibility of experimental data, to produce and publish high quality research.

Direct Laser Writing of Chitosan-Borax Composites: Toward Sustainable Electrochemical Sensors.

In this study, the laser-induced graphitization process of sustainable chitosan-based formulations was investigated. In particular, optimal lasing conditions were investigated alongside the effect of borax concentration in the chitosan matrix. In all cases, it was found that the obtained formulations were graphitizable with a CO2 laser. This process gave rise to the formation of high surface area, porous, and electrically conductive laser-induced graphene (LIG) structures. It was found that borax, as a cross-linker of chitosan, enabled the graphitization process when its content was ≥30 wt % in the chitosan matrix, allowing the formation of an LIG phase with a significant content of graphite-like structures. The graphitization process was investigated by thermogravimetric analysis (TGA), Raman, X-ray photoemission (XPS), and Fourier transform infrared (FTIR) spectroscopies. LIG electrodes obtained from CS/40B formulations displayed a sheet resistance as low as 110 Ω/sq. Electrochemical characterization was performed after a 10 min electrode activation by cycling in 1 M KCl. A heterogeneous electron transfer rate, k0, of 4 × 10-3 cm s-1 was determined, indicating rapid electron transfer rates at the electrode surface. These results show promise for the introduction of a new class of sustainable composites for LIG electrochemical sensing platforms.

Energy Barriers for Steroid Hormone Transport in Nanofiltration.

Nanofiltration (NF) membranes can retain micropollutants (MPs) to a large extent, even though adsorption into the membrane and gradual permeation result in breakthrough and incomplete removal. The permeation of MPs is investigated by examining the energy barriers (determined using the Arrhenius concept) for adsorption, intrapore diffusion, and permeation encountered by four different steroid hormones in tight and loose NF membranes. Results show that the energy barriers for steroid hormone transport in tight membrane are entropically dominated and underestimated because of the high steric exclusion at the pore entrance. In contrast, the loose NF membrane enables steroid hormones partitioning at the pore entrance, with a permeation energy barrier (from feed toward the permeate side) ranging between 96 and 116 kJ/mol. The contribution of adsorption and intrapore diffusion to the energy barrier for steroid hormone permeation reveals a significant role of intrapore diffusive transport on the obtained permeation energy barrier. Overall, the breakthrough phenomenon observed during the NF of MPs is facilitated by the low energy barrier for adsorption. Experimental evidence of such principles is relevant for understanding mechanisms and ultimately improving the selectivity of NF.

Cell Theranostics on Mesoporous Silicon Substrates.

The adhesion, proliferation, and migration of cells over nanomaterials is regulated by a cascade of biochemical signals that originate at the interface of a cell with a substrate and propagate through the cytoplasm to the nucleus. The topography of the substrate plays a major role in this process. Cell adhesion molecules (CAMs) have a characteristic size of some nanometers and a range of action of some tens of nanometers. Controlling details of a surface at the nanoscale-the same dimensional over which CAMs operate-offers ways to govern the behavior of cells and create organoids or tissues with heretofore unattainable precision. Here, using electrochemical procedures, we generated mesoporous silicon surfaces with different values of pore size (PS≈11 nm and PS≈21 nm), roughness (Ra≈7 nm and Ra≈13 nm), and fractal dimension (Df≈2.48 and Df≈2.15). Using electroless deposition, we deposited over these substrates thin layers of gold nanoparticles. Resulting devices feature (i) nanoscale details for the stimulation and control of cell assembly, (ii) arrays of pores for drug loading/release, (iii) layers of nanostructured gold for the enhancement of the electromagnetic signal in Raman spectroscopy (SERS). We then used these devices as cell culturing substrates. Upon loading with the anti-tumor drug PtCl (O,O'-acac)(DMSO) we examined the rate of adhesion and growth of breast cancer MCF-7 cells under the coincidental effects of surface geometry and drug release. Using confocal imaging and SERS spectroscopy we determined the relative importance of nano-topography and delivery of therapeutics on cell growth-and how an unbalance between these competing agents can accelerate the development of tumor cells.

Estradiol Uptake in a Combined Magnetic Ion Exchange - Ultrafiltration (MIEX-UF) Process During Water Treatment.

BACKGROUND: Estrogens and their synthetic analogues are widely used as pharmaceuticals. Upon oral administration these drugs are eventually excreted via urine. The persistence of these pharmaceuticals and inefficient removal by water treatment lead to accumulation in surface water and effluents with negative effects for aquatic life and human health. METHODS: In this study, the uptake of estradiol by a combined magnetic ion exchange resin - ultrafiltration process (MIEX-UF) was investigated. This is a relatively common process used in drinking water treatment for the removal of natural organic matter. However, uptake of micropollutants, such as steroidal pharmaceuticals, may occur as a side effect of water treatment due to the high affinity for polymeric materials. To elucidate the mechanism governing estradiol partitioning between water, resin and membrane, the influence of different parameters, such as pH, humic acid concentration and membrane molecular-weight-cut-off (MWCO) was studied. RESULTS: Humic acid concentration and pH affected estradiol uptake most. At pH 11 the most significant increase of estradiol uptake was observed for MIEX-UF process (30 ng/g corresponding to 80%) compared with individual UF (17 ng/g corresponding to 12%). The presence of humic acid slightly reduced estradiol uptake at pH 11 (about 55%) due to competition for the ion exchange binding sites. CONCLUSION: Results demonstrated that the uptake of estradiol, which is amongst the most potent EDCs detected in surface water, in the MIEX-UF process can reach significant quantities (30 ng/g of resin) leading to uncontrolled accumulation of this micropollutant during drinking water treatment. This study gives a novel contribution in the understanding the mechanism of the unanticipated accumulation of pharmaceuticals, such as estradiol, in the drinking water treatment process.