Using CDOM spectral shape information to improve the estimation of DOC concentration in inland waters: A case study of Andean Patagonian Lakes.

For the last two decades different scientific disciplines have focused on lacustrine dissolved organic matter (DOM) given its importance in the biogeochemistry of carbon and in ecosystem functioning. New satellites supply the appropriate resolutions to evaluate chromophoric dissolved organic matter (CDOM) in inland waters, opening the possibility to estimate DOM at appropriate spatiotemporal scales. This requires, however, a robust relationship between CDOM and dissolved organic carbon (DOC). In this work, we evaluated the use of CDOM as a proxy of DOC in 7 Andean Patagonian lakes. Considering the entire data set, CDOM absorption coefficients (a355 and a440) were linearly related with DOC. Shallow lakes, however, drove this relationship showing a moderate relationship, whereas, deep lakes with lower colour presented a weaker relationship. Therefore, we assessed the use of CDOM spectral shape information to improve DOC estimates regardless of observed DOM differences due to climatic seasonality and lakes' morphometry. The use of well-known CDOM spectral shape metrics (i.e., S275-295 and a250:a365 ratio) significantly improved DOC estimation. Particularly, using a Gaussian decomposition approach we found that much of the variation in the spectral shape, associated with the variability of CDOM:DOC ratio, was explained by differences in two dynamic regions centred at 270 and 320 nm. A strong nonlinear relationship was found between the a270:a320 ratio and the DOC-specific absorption coefficients a*355 and a*440. This was translated into a further improvement in DOC estimation yielding the higher R2 and lower mean absolute differences (MAPD < 16%), either considering the entire data set or shallow and deep lakes separately. Our results highlight that incorporating the CDOM spectral shape information improves the characterization of the DOC pool of inland waters, which is particularly relevant for remote and/or inaccessible sites and has significant implications for the environmental management, biogeochemical studies and future remote sensing applications.

Fluorescence components of natural dissolved organic matter (DOM) from aquatic systems of an Andean Patagonian catchment: Applying different data restriction criteria for PARAFAC modelling.

Fluorescence spectroscopy is a widely applied technique to characterize the composition of the fluorescent fraction of dissolved organic matter (DOM), allowing to infer sources and diagenetic state of soil, marine and freshwater DOM samples. The analysis of fluorescent DOM (FDOM) is often carried out by multi-way models such as parallel factor analysis (PARAFAC), which allows decomposing excitation-emission matrices (EEMs) obtained from DOM samples into their underlying chemical components. Some aspects of the performance/accuracy of the EEM-PARAFAC technique regarding the use of selective vs. non-selective EEM data are still in discussion. In this investigation, we evaluated the outcome of two different approaches (non-selective and selective) applied to study the composition of DOM from four headwater streams (Case 1) and from two neighboring shallow lakes (Case 2), all belonging to the same Andean watershed within Nahuel Huapi National Park in North Patagonia (Argentina). In both cases, the outcome of the PARAFAC performed to non-selective data (EEM datasets from all the streams and the two lakes) vs. selective datasets (EEMs from each stream and each lake treated separately) is compared on the basis of modelled fluorescent components. Regardless of the restriction criteria applied for the analyses, the results obtained indicated similar component loadings in the four streams and in the two lakes. The similarity of the outcomes likely relates to the low internal variation of the EEMs, since these are located in the same catchment, influenced by similar soils and vegetation which are the main DOM sources. Therefore, we conclude that the use of a small selective EEM dataset may not condition the validation of the FDOM components and their temporal dynamics.

Biologically enabled sub-diffractive focusing.

Evolution shows that photonic structures are a constituent part of many animals and flora. These elements produce structural color and are useful in predator-prey interactions between animals and in the exploitation of light for photosynthetic organisms. In particular, diatoms have evolved patterned hydrated silica external valves able to confine light with extraordinary efficiency. Their evolution was probably guided by the necessity to survive in harsh conditions of sunlight deprivation. Here, we exploit such diatom valves, in conjunction with structured illumination, to realize a biological super-resolving lens to achieve sub-diffractive focusing in the far field. More precisely, we consider a single diatom valve of Arachnoidiscus genus which shows symmetries and fine features. By characterizing and using the transmission properties of this valve using the optical eigenmode technique, we are able to confine light to a tiny spot with unprecedented precision in terms of resolution limit ratio, corresponding in this case to 0.21λ/NA.

Treatment and recycling of asbestos-cement containing waste.

The remediation of industrial buildings covered with asbestos-cement roofs is one of the most important issues in asbestos risk management. The relevant Italian Directives call for the above waste to be treated prior to disposal on landfill. Processes able to eliminate the hazard of these wastes are very attractive because the treated products can be recycled as mineral components in building materials. In this work, asbestos-cement waste is milled by means of a high energy ring mill for up to 4h. The very fine powders obtained at all milling times are characterized to check the mineralogical and morphological transformation of the asbestos phases. Specifically, after 120 min of milling, the disappearance of the chrysotile OH stretching modes at 3690 cm(-1), of the main crystalline chrysotile peaks and of the fibrous phase are detected by means of infrared spectroscopy and X-ray diffraction and scanning electron microscopy analyses, respectively. The hydraulic behavior of the milled powders in presence of lime is also tested at different times. The results of thermal analyses show that the endothermic effects associated to the neo-formed binding phases significantly increase with curing time. Furthermore, the technological efficacy of the recycling process is evaluated by preparing and testing hydraulic lime and milled powder-based mortars. The complete test set gives good results in terms of the hydration kinetics and mechanical properties of the building materials studied. In fact, values of reacted lime around 40% and values of compressive strength in the range of 2.17 and 2.29 MPa, are measured.

Multi-wavelength study of light transmitted through a single marine centric diatom.

The characterization of partially coherent light transmission by micrometer sized valves of marine diatoms is an interesting optical challenge and, from the biological point of view, is of outmost relevance in order to understand evolution mechanisms of such organisms. In the present work, we have studied the transmission of light coming from a monochromator through single valves of Coscinodiscus wailesii diatoms. Incoming light is confined by the regular pore pattern of the diatom surface into a spot of few microns, its dimensions depending on wavelength. The effect is ascribed to the superposition of wavefronts diffracted by the pores' edges. Numerical simulations help to demonstrate how this effect is not present in the ultraviolet region of the light spectrum, showing one of the possible evolutionary advantages represented by the regular pores patterns of the valves.

Bioactive modification of silicon surface using self-assembled hydrophobins from Pleurotus ostreatus.

A crystalline silicon surface can be made biocompatible and chemically stable by a self-assembled biofilm of proteins, the hydrophobins (HFBs) purified from the fungus Pleurotus ostreatus. The protein-modified silicon surface shows an improvement in wettability and is suitable for immobilization of other proteins. Two different proteins were successfully immobilized on the HFBs-coated chips: the bovine serum albumin and an enzyme, a laccase, which retains its catalytic activity even when bound on the chip. Variable-angle spectroscopic ellipsometry (VASE), water contact angle (WCA), and fluorescence measurements demonstrated that the proposed approach in silicon surface bioactivation is a feasible strategy for the fabrication of a new class of hybrid devices.

Marine diatoms as optical biosensors.

We have chemically modified the frustules of the marine diatom Coscinodiscus concinnus Wm. Smith to properly bind a highly selective bioprobe such as an antibody. By measuring the changes in the photoluminescence emission of diatoms frustules, we have monitored the molecular recognition event between the antibody and its ligand: the dissociation constant estimated is of the same order of that measured by standard Biacore. The nanostructured silica frustules, a low-cost and natural available material, have shown high sensitivity, equal to 1.2+/-0.2 nm microM(-1), and a detection limit of 100 nM, and thus are quite ideal candidates for lab-on-particle applications.

Langmuir-Blodgett film of hydrophobin protein from Pleurotus ostreatus at the air-water interface.

We present results concerning the formation of Langmuir-Blodgett (LB) films of a class I hydrophobin from Pleurotus ostreatus at the air-water interface, and their structure as Langmuir-Blodgett (LB) films when deposited on silicon substrates. LB films of the hydrophobin were investigated by atomic force microscopy (AFM). We observed that the compressed film at the air-water interface exhibits a molecular depletion even at low surface pressure. In order to estimate the surface molecular concentration, we fit the experimental isotherm with Volmer's equation describing the equation of state for molecular monolayers. We found that about (1)/ 10 of the molecules contribute to the surface film formation. When transferred on silicon substrates, compact and uniform monomolecular layers about 2.5 nm thick, comparable to a typical molecular size, were observed. The monolayers coexist with protein aggregates, under the typical rodlet form with a uniform thickness of about 5.0 nm. The observed rodlets appear to be a hydrophilic bilayer and can then be responsible for the surface molecular depletion.

Interfacing the nanostructured biosilica microshells of the marine diatom Coscinodiscus wailesii with biological matter.

Biosilicified nanostructured microshells from the marine diatom Coscinodiscus wailesii have been properly functionalised to bind a molecular probe which specifically recognises a target analyte. The chemical modification process has been characterised by Fourier transformed infrared spectroscopy. Fluorescence measurements demonstrate that the antibodies we used, even if linked to the amorphous silica surface of C. wailesii microshells, still efficiently recognise their antigens. These low cost and largely available natural materials can be thus used as transducers elements for optical biosensors or as targeting microcapsules for drug delivery.

Myocardial contractility of the isovolumetrically beating isolated rat heart

Several indexes of myocardial contractility have been proposed to assess ventricular function in the isovolumetrically beating isolated heart. However, the conclusions reached on the basis of these indexes may be influenced by ventricular geometry rather than contractility itself. The objective of the present study was to assess the performance of widely used contractility indexes in the isovolumetrically beating isolated heart in two experimental models of hypertrophy, the spontaneously hypertensive rat (SHR) and infrarenal aortocava fistula. Compared to normotensive controls (N = 8), SHRs with concentric hypertrophy (N = 10) presented increased maximum rate of ventricular pressure rise (3875 ± 526 vs 2555 ± 359 mmHg/s, P < 0.05) and peak of isovolumetric pressure (187 ± 11 vs 152 ± 11 mmHg, P < 0.05), and decreased developed stress (123 ± 20 vs 152 ± 26 g/cm², P < 0.05) and slope of stress-strain relationship (4.9 ± 0.42 vs 6.6 ± 0.77 g/cm²/ percent). Compared with controls (N = 11), rats with volume overload-induced eccentric hypertrophy (N = 16) presented increased developed stress (157 ± 38 vs 124 ± 22 g/cm², P < 0.05) and slope of stress-strain relationship (9 ± 2 vs 7 ± 1 g/cm²/ percent, P < 0.05), and decreased maximum rate of ventricular pressure rise(2746 ± 382 vs 3319 ± 352 mmHg, P < 0.05) and peak of isovolumetric pressure (115 ± 14 vs 165 ± 13 mmHg/s, P < 0.05). The results suggested that indexes of myocardial contractility used in experimental studies may present opposite results in the same heart and may be influenced by ventricular geometry. We concluded that several indexes should be taken into account for proper evaluation of contractile state, in the isovolumetrically beating isolated heart.

Myocardial contractility of the isovolumetrically beating isolated rat heart.

Several indexes of myocardial contractility have been proposed to assess ventricular function in the isovolumetrically beating isolated heart. However, the conclusions reached on the basis of these indexes may be influenced by ventricular geometry rather than contractility itself. The objective of the present study was to assess the performance of widely used contractility indexes in the isovolumetrically beating isolated heart in two experimental models of hypertrophy, the spontaneously hypertensive rat (SHR) and infrarenal aortocava fistula. Compared to normotensive controls (N = 8), SHRs with concentric hypertrophy (N = 10) presented increased maximum rate of ventricular pressure rise (3875 +/- 526 vs 2555 +/- 359 mmHg/s, P < 0.05) and peak of isovolumetric pressure (187 +/- 11 vs 152 +/- 11 mmHg, P < 0.05), and decreased developed stress (123 +/- 20 vs 152 +/- 26 g/cm(2), P < 0.05) and slope of stress-strain relationship (4.9 +/- 0.42 vs 6.6 +/- 0.77 g/cm(2)/%). Compared with controls (N = 11), rats with volume overload-induced eccentric hypertrophy (N = 16) presented increased developed stress (157 +/- 38 vs 124 +/- 22 g/cm(2), P < 0.05) and slope of stress-strain relationship (9 +/- 2 vs 7 +/- 1 g/cm(2)/%, P < 0.05), and decreased maximum rate of ventricular pressure rise(2746 +/- 382 vs 3319 +/- 352 mmHg, P < 0.05) and peak of isovolumetric pressure (115 +/- 14 vs 165 +/- 13 mmHg/s, P < 0.05). The results suggested that indexes of myocardial contractility used in experimental studies may present opposite results in the same heart and may be influenced by ventricular geometry. We concluded that several indexes should be taken into account for proper evaluation of contractile state, in the isovolumetrically beating isolated heart.

Spectroscopic ellipsometry study of liquid crystal and polymeric thin films in visible and near infrared.

In this work, we propose spectroscopic ellipsometry as a suitable method for measuring optical properties in soft materials, polymers and liquid crystals, specially selected for use in photonics applications. We show the results of our measurements on some multilayered samples, in the range from visible to the near-IR region, of interest for telecom applications. We point out potentialities and limits of the technique and compare the obtained results with another experimental method, the m-lines spectroscopy, and/or with existing data in the literature. The results about the optical parameters for the analysed materials (the nematic liquid crystal 5CB, one commercial and one lab made optical polymer, and an Indium Tin Oxide film) are useful and interesting by themselves. In fact, as a paradigmatic example, we briefly discuss how an incomplete knowledge of this kind of data can lead to a wrong design of a Bragg grating device. However, more than in the provided data, we put the interest of the present analysis in the warnings about spectroscopic ellipsometry utilization and eventually the necessity of getting complementary information.

Solid state dehalogenation of PCBs in contaminated soil using NaBH4.

In this work we present the results of an experimental study on the abatement of polychlorinated biphenyl (PCBs) in contaminated soil using a high energy milling technique, that promotes a reaction only by impact between milling bodies. A sample of soil from a controlled landfill was treated with powdered NaBH(4) using two different hydride/soil ratios (5 and 2.5% w/w). The efficiency of the dehalogenation/hydrogenation reaction was studied as a function of the milling time (3.5 up to 30 h). After each run, the total PCBs content and the production of inorganic chloride were measured. The complete abatement was obtained with a starting PCBs concentration of about 2600 mg/kg. The residual PCBs concentration resulted to be <0.2 mg/kg. The final products of the treatment were biphenyl and NaCl. Other toxic or hazardous organic by-products were not generated. Boron was found as boric acid.

Preparation of activated carbons from heavy-oil fly ashes.

The use of heavy oil fly ash with high ash content (45 wt.%) as a precursor for the preparation of activated carbons has been investigated. The raw fly ash and the fly ash with lower ash content, obtained by a HCl/HF washing treatment, have been pyrolyzed at 900 degrees C and then activated with CO(2) in the temperature range of 800-900 degrees C for different times. The activated carbons have been characterised as regards the surface area and the pore volume. The evolution of the porosity has been related to the burn-off degree.

Accurate quantitative measurements of asbestos in XRPD analysis.

X-ray Powder Diffraction (XRPD) quantitative analysis of fibrous substances like asbestos, is strongly influenced by systematic errors due to preferred orientation, as a consequence of their morphology. In the present work we have compared the accuracy of quantitative measurements performed by using the Internal Standard (IS) method and the Reference Intensity Ratio (RIR) method in the analysis of the same diffractographs. Both these analytical methods are based on the same principle but the data analysis procedures are different. We have particularly studied how, in the RIR case, the evaluation of several diffraction lines of both phases, standard and unknown, increases the accuracy of a quantitative determination, balancing the different effect due to systematic errors on the measurements of distinct peaks.

Defective expression of IL-2 receptors on peripheral blood lymphocytes from patients with cluster headache.

In a previous study we demonstrated that cluster headache (CH) patients present an increased Natural Cytotoxic response after incubation of their peripheral blood lymphocytes (PBL) with Interleukin-2 (IL-2). This phenomenon led to an investigation of the phenotypic expression of PBL before and after IL-2 incubation, and of the IL-2 lymphocyte receptor. IL-2 receptor is expressed on T-lymphocytes activated with an high-affinity binding site. The analysis of the function of human IL-2 receptor was facilitated by the production of a specific monoclonal antibody (MAb). This MAb identifies the IL-2 receptors by blocking the binding of radiolabelled IL-2 to T-cells. In addition, we studied the expression of Leu-4, specific for T-cells; of Leu-11b, specific for FC receptor on NK cells; and the Transferrin Receptor, specific for lymphoblasts and monocytes. Twenty-three episodic CH patients were selected for this study. Ten sex and age-matched healthy volunteers were used as the control group. We evaluated the PBL phenotypic expression of cells subsets before incubation with IL-2 (1,000 I.U./ml) and after 72 hours. The following Becton Dickinson MAbs have been used: anti-Leu-4 (CD3), anti-IL-2 receptors (CD25), anti-Transferrin receptor (TFR) and anti-Leu-11b (CD16). Indirect fluorescence with a Becton Dickinson FACS-420 flow cytometer was used to analyze the cells.(ABSTRACT TRUNCATED AT 250 WORDS)