Combining spectroscopic techniques and chemometrics for the interpretation of lichen biomonitoring of air pollution.

A screening evaluation of lichen thalli, based on spectroscopic techniques coupled with chemometrics, is proposed as fast, simple and "green" method for the biomonitoring of air pollution. For two consecutive years, lichen thalli of Pseudevernia furfuracea were exposed for three months in selected sites of Liguria (NW-Italy) according to different levels and types of air pollution. At the end of the exposure period, transplanted thalli were analyzed by a set of monitoring techniques, including Front-Face Fluorescence Spectroscopy (FFFS), Near Infrared Spectroscopy (NIRS) and Plant Efficiency Analyser (PEA). Data were compared with values of air pollutants recorded during the exposure period by the Regional Agency for Environmental Protection, in order to relate lichen physiological indicators with the effects of atmospheric concentrations. A chemometric evaluation of the analytical signals, including principal component analysis (PCA) and quadratic discriminant analysis (QDA), was performed; the mean prediction rate of the discriminant models calculated on the FFFS emission spectra ranged from 70 to 75% on the external test sets. Front-face fluorescence spectroscopy proved to be a promising technique for the determination of level and type of pollutants in lichen thalli.

Extensive study on physicochemical properties of polychlorinated biphenyls in a commercial ion trap mass spectrometer, relevance in analytical and environmental chemistry.

Polychlorinated biphenyls (PCBs) exist as 209 congeners, consisting of biphenyl molecules, where the number and substitution positions of halogen atoms are known to affect industrial uses, environmental transport mechanisms, distribution, fate, and toxicity. The complexity of the problem requires accurate physicochemical studies of an increasing number of congeners in order to understand the environmental and biological processes at play. This work presents a systematic study on the thermodynamic and kinetic properties of PCBs by quadrupole ion trap mass spectrometry. A clear relationship between structure and behavior of PCBs in mass spectrometry experiments has been observed. Overall data demonstrate that di-ortho congeners show lower thermodynamic stability and higher fragmentation rate than non/mono-ortho. Congeners follow different fragmentation mechanisms according to the number of chlorine atoms in ortho position of the biphenyl system. Experimental kinetic curves of mono/non-ortho and di-ortho congeners show a strong similarity with classical first-order kinetics curves; in particular, di-ortho congeners follow a first-order consecutive reaction, while mono/non-ortho follow a first-order parallel reaction. For each studied congener, the kinetic constant of reaction (fragmentation) has been determined. Data support environmental levels and biochemical transformations described in literature. The general picture of the PCB behavior inside a quadrupole ion trap provides the basis for the development of reliable and cost-effective analytical methods to the determination of ultra-low level trace of PCB congeners.

Dynamics of inorganic components in lake waters from Terra Nova Bay, Antarctica.

Water and Suspended Particulate Material (SPM) samples analysed in this work were collected in the austral summer 2011/12 from six shallow Antarctic lakes (Carezza, Edmonson Point 14 and 15a, Gondwana, Inexpressible Island 10b and Tarn Flat 20) of Terra Nova Bay (Northern Victoria Land, Antarctica). The total concentrations of a large suite of inorganic analytes were determined, in order to gain insight into the natural processes regulating species distribution, define natural background values and detect possible present or future local and/or global anthropogenic contamination. Lake water composition was found to be influenced by marine spray, lake geographical position and meltwater input. Seasonal variability was also evaluated for each analyte, and explained considering the natural transport processes involving each species. Multivariate chemometric techniques were used in order to identify groups of samples with similar characteristics and find out similarities and correlations among variables. The variability observed within the water samples is closely connected to the marine aerosol input; hence, it is primarily a consequence of geographical and meteorological factors, such as distance from the ocean and period of year. Higher element concentrations have been found in SPM than in water, suggesting that weathering plays an important role on the chemistry of these lakes or that adsorption processes take place. SPM samples were also examined with a Scanning Electron Microscope (SEM), and many diatoms belonging to different species were detected. No clear evidence of a relevant metal contamination was found in the investigated area.

A comprehensive approach to actual polychlorinated biphenyls environmental contamination.

Worldwide polychlorinated biphenyls (PCBs) pollution is due to complex mixtures with high number of congeners, making the determination of total PCBs in the environment an open challenge. Because the bulk of PCBs production was made of Aroclor mixtures, this analysis is usually faced by the empirical mixture identification via visual inspection of the chromatogram. However, the identification reliability is questionable, as patterns in real samples are strongly affected by the frequent occurrence of more than one mixture. Our approach is based on the determination of a limited number of congeners chosen to enable objective criteria for Aroclor identification, summing up the advantages of congener-specific analysis with the ones of total PCBs determination. A quantitative relationship is established between congeners and any single mixture, or mixtures combination, leading to the identification of the actual contamination composition. The approach, due to its generality, allows the use of different sets of congeners and any technical mixture, including the non-Aroclor ones. The results confirm that PCB environmental pollution in northern Italy is based on Aroclor. Our methodology represents an important tool to understand the source and fate of the PCBs contamination.

An updated Italian normative dataset for the Stroop color word test (SCWT).

The Stroop color and word test (SCWT) is widely used to evaluate attention, information processing speed, selective attention, and cognitive flexibility. Normative values for the Italian population are available only for selected age groups, or for the short version of the test. The aim of this study was to provide updated normal values for the full version, balancing groups across gender, age decades, and education. Two kinds of indexes were derived from the performance of 192 normal subjects, divided by decade (from 20 to 90) and level of education (4 levels: 3-5; 6-8; 9-13; >13 years). They were (i) the correct answers achieved for each table in the first 30 s (word items, WI; color items, CI; color word items, CWI) and (ii) the total time required for reading the three tables (word time, WT; color time, CT; color word time, CWT). For each index, the regression model was evaluated using age, education, and gender as independent variables. The normative data were then computed following the equivalent scores method. In the regression model, age and education significantly influenced the performance in each of the 6 indexes, whereas gender had no significant effect. This study confirms the effect of age and education on the main indexes of the Stroop test and provides updated normative data for an Italian healthy population, well balanced across age, education, and gender. It will be useful to Italian researchers studying attentional functions in health and disease.

A normative study of the Italian printed word version of the free and cued selective reminding test.

According to the new research criteria for the diagnosis of Alzheimer's disease, episodic memory impairment, not significantly improved by cueing, is the core neuropsychological marker, even at a pre-dementia stage. The FCSRT assesses verbal learning and memory using semantic cues and is widely used in Europe. Standardization values for the Italian population are available for the colored picture version, but not for the 16-item printed word version. In this study, we present age- and education-adjusted normative data for FCSRT-16 obtained using linear regression techniques and generalized linear model, and critical values for classifying sub-test performance into equivalent scores. Six scores were derived from the performance of 194 normal subjects (MMSE score, range 27-30, mean 29.5 ± 0.5) divided per decade (from 20 to 90), per gender and per level of education (4 levels: 3-5, 6-8, 9-13, >13 years): immediate free recall (IFR), immediate total recall (ITR), recognition phase (RP), delayed free recall (DFR), delayed total recall (DTR), Index of Sensitivity of Cueing (ISC), number of intrusions. This study confirms the effect of age and education, but not of gender on immediate and delayed free and cued recall. The Italian version of the FCSRT-16 can be useful for both clinical and research purposes.

Efficient inscription of Bragg gratings in As2S3 fibers using near bandgap light.

Efficient inscription of Fiber Bragg gratings (FBGs) in single-mode, thin cladding As(2)S(3) fibers is demonstrated by using near bandgap light at 532 nm. The FBGs with the reflectivity of over 80% can be induced in only 80-90 s, substantially faster than in previous reports. The dynamics of the grating growth are investigated in the photosensitivity process, showing a fast blue shift of the Bragg wavelength and then a somewhat slower red shift. The aging of the grating after fabrication is also reported, indicating a 37% decay of the grating strength.

Reconfigurable photonic crystal waveguides created by selective liquid infiltration.

We experimentally demonstrate reconfigurable photonic crystal waveguides created directly by infiltrating high refractive index (n≈2.01) liquids into selected air holes of a two-dimensional hexagonal periodic lattice in silicon. The resulting effective index contrast is large enough that a single row of infiltrated holes enables light propagation at near-infrared wavelengths. We include a detailed comparison between modeling and experimental results of single line defect waveguides and show how our infiltration procedure is reversible and repeatable. We achieve infiltration accuracy down to the single air hole level and demonstrate control on the volume of liquid infused into the holes by simply changing the infiltration velocity. This method is promising for achieving a wide range of targeted optical functionalities on a "blank" photonic crystal membrane that can be reconfigured on demand.

Major and trace element partitioning between dissolved and particulate phases in Antarctic surface snow.

In order to provide a new insight into the Antarctic snow chemistry, partitioning of major and trace elements between dissolved and particulate (i.e. insoluble particles, >0.45 µm) phases have been investigated in a number of coastal and inland snow samples, along with their total and acid-dissolvable (0.5% nitric acid) concentrations. Alkaline and alkaline-earth elements (Na, K, Ca, Mg, Sr) were mainly present in the dissolved phase, while Fe and Al were predominantly associated with the particulate matter, without any significant difference between inland and coastal samples. On the other hand, partitioning of trace elements depended on the sampling site position, showing a general decrease of the particulate fraction by moving from the coast to the plateau. Cd, Cu, Pb and Zn were for the most part in the dissolved phase, while Cr was mainly associated with the particulate fraction. Co, Mn and V were equally distributed between dissolved and particulate phases in the samples collected from the plateau and preferentially associated with the particulate in the coastal samples. The correlation between the elements and the inter-sample variability of their concentration significantly decreased for the plateau samples compared to the coastal ones, according to a change in the relative contribution of the metal sources and in good agreement with the estimated marine and crustal enrichment factors. In addition, samples from the plateau were characterised by higher enrichment factors of anthropogenic elements (Cd, Cr, Cu, Pb and Zn), compared to the coastal area. Finally, it was observed that the acid-dissolvable metal concentrations were generally lower than the total concentration values, showing that the acid treatment can dissolve only a given fraction of the metal associated with the particulate (<20% for iron and aluminium).

Liquid crystal dynamics in a photonic crystal cavity created by selective microfluidic infiltration.

A microfluidic double heterostructure cavity is created in a silicon planar photonic crystal waveguide by selective infiltration of a liquid crystal. The spectral evolution of the cavity resonances probed by evanescent coupling reveals that the liquid crystal evaporates, even at room temperature, despite its relatively low vapor pressure of 5 × 10(-3) Pa. We explore the infiltration and evaporation dynamics of the liquid crystal within the cavity using a Fabry-Perot model that accounts for the joint effects of liquid volume reduction and cavity length variation due to liquid evaporation. While discussing how the pattern of the infiltrated liquid can be optimized to restrict evaporation, we find that the experimental behavior is consistent with basic microfluidic relations considering the small volumes of liquids and large surface areas present in our structure.

Characterization of picosecond pulse nonlinear propagation in chalcogenide As(2)S(3) fiber.

We characterize the nonlinear propagation of picosecond pulses in chalcogenide As(2)S(3) single-mode fiber using a pump-probe technique. The cross-phase modulation (XPM)-induced sideband broadening and stimulated Raman scattering (SRS)-induced sideband amplification are measured in order to map out the Raman gain spectrum of this glass across the C-band. We extract the Raman response function from the Raman gain spectrum and determine the power and polarization dependence of the SRS. In contrast to previous work using As(2)Se(3) fiber, we find that the As(2)S(3) fiber does not suffer from large two-photon absorption (TPA) in the wavelength range of the telecommunications band. We achieved a 20 dB peak Raman gain at a Stokes shift of 350 cm(-1) in a 205 mm length of As(2)S(3) single-mode fiber. The Raman gain coefficient is estimated to be 4.3x10(-12) m/W and the threshold pump peak power is estimated to be 16.2 W for the 205 mm As(2)S(3) fiber. We also demonstrate that we can infer the dispersion of the As(2)S(3) fiber and justify the Raman response function by comparing simulation and experimental results.

Combining passive samplers and biomonitors to evaluate endocrine disrupting compounds in a wastewater treatment plant by LC/MS/MS and bioassay analyses.

Two types of integrative sampling approaches (passive samplers and biomonitors) were tested for their sampling characteristics of selected endocrine disrupting compounds (EDCs). Chemical analyses (LC/MS/MS) were used to determine the amounts of five EDCs (nonylphenol, bisphenol A, estrone, 17beta-estradiol and 17alpha-ethinylestradiol) in polar organic chemical integrative samplers (POCIS) and freshwater mussels (Unio pictorum); both had been deployed in the influent and effluent of a municipal wastewater treatment plant (WWTP) in Genoa, Italy. Estrogenicity of the POCIS samples was assessed using the yeast estrogen screen (YES). Estradiol equivalent values derived from the bioassay showed a positive correlation with estradiol equivalents calculated from chemical analyses data. As expected, the amount of estrogens and EEQ values in the effluent were lower than those in the influent. Passive sampling proved to be the preferred method for assessing the presence of these compounds since employing mussels had several disadvantages both in sampling efficiency and sample analyses.

High bit rate all-optical signal processing in a fiber photonic wire.

We report the first demonstration of high bit rate signal processing by a fiber-based photonic wire. We achieve 160 Gb/s demultiplexing via four wave mixing in a 1.9 microm diameter photonic wire tapered from As(2)S(3) chalcogenide glass single mode fibre, with very low pump power requirements ( < 20 mW average power, 0.45 W peak power), enabled by a very high nonlinearity (gamma approximately 7850 W(-1) km (-1) ) and greatly reduced dispersion.

Helminths of wild boar in the isolated population close to the northern border of its habitat area.

One hundred wild boars (Sus scrofa) from a geographically isolated population on the island Saaremaa of western Estonia were examined for visceral helminths. Seven helminth species, Metastrongylus pudendotectus, M. salmi, M. elongatus, Ascaris suum, Trichuris suis, Dicrocoelium dendriticum and Taenia hydatigena larva, were found. The predominant helminths discovered were lung nematodes (prevalence 82%, mean intensity 96.2 per animal). A significant negative correlation was observed between the weight of wild boars and the number of lungworms and helminth species. The number of helminth species found in the wild boar population on the island was lower compared to that of the adjacent mainland.

Preoperative chemoradiation and flap reconstruction provide high local control and low wound complication rates for patients undergoing limb salvage surgery for upper extremity tumors.

BACKGROUND AND OBJECTIVES: Neoadjuvant protocols in the management of upper extremity sarcoma have improved local control rates but have been associated with high complication rates. We present a refinement of the Eilber protocol using judicious preoperative chemoradiation, limb salvage surgery, and flap coverage to achieve high local control rates with acceptable wound healing complications. METHODS: Patients presenting with upper extremity neoplasms from 1986 to 2002 were treated with a modified Eilber protocol, consisting of 3 days of adriamycin (30 mg/day) and sequential radiotherapy (300 cGy/day for 10 days). Limb salvage surgery with flap coverage where needed was performed 4-8 weeks later. Patients were followed prospectively for recurrence. RESULTS: Fifty-three consecutive patients with upper extremity tumors were treated and followed for a mean of 6.1 years. This cohort included 44 sarcomas and nine non-metastasizing, locally aggressive tumors. There were two local recurrences (3.8%). Limb salvage was achieved in all patients. Flaps were required in 43.4% of patients. Major complications occurred in 11%, were all flap related (partial flap loss, venous congestion), and went on to heal promptly with treatment. CONCLUSION: This modified Eilber protocol achieved 96% local control for upper extremity tumors with a wound complication rate of 11%. The liberal use of flaps of resulted in healed, stable wounds in all patients.

Enhanced Kerr nonlinearity in sub-wavelength diameter As(2)Se(3) chalcogenide fiber tapers.

We experimentally demonstrate enhanced Kerr nonlinear effects in highly nonlinear As(2)Se(3) chalcogenide fiber tapered down to sub-wavelength waist diameter of 1.2 mum. Based on self phase modulation measurements, we infer an enhanced nonlinearity of 68 W(-1)m(-1). This is 62,000 times larger than in standard silica singlemode fiber, owing to the 500 times larger n(2) and almost 125 times smaller effective mode area. We also consider the potential to exploit the modified dispersion in these tapers for ultra-low threshold supercontinuum generation.

Tuning properties of long period gratings in photonic bandgap fibers.

We investigate the thermal tuning properties of long period gratings (LPGs) in a fluid-filled photonic bandgap fiber (PBGF). The combination of strong, resonant waveguide dispersion, characteristic of all PBGF modes, and the large thermo-optic coefficients of fluids yields highly tunable grating resonances. We measure grating resonances in three transmission bands with large tuning coefficients of up to -1.58 nm/degrees C, which match numerical results. We derive an analytic model for the PBGF LPG tuning coefficient to show how it depends on both the shift of the transmission bands and the dispersion of the coupled modes.

Long period grating resonances in photonic bandgap fiber.

We demonstrate the formation of stress-induced long period gratings (LPGs) in fluid-filled photonic bandgap fiber (PBGF). Based on our experimental results, simulations, and theoretical understanding of LPGs, we identify coupling to a guided LP(11)-like mode of the core and lossy LP1x-like modes of cladding microstructure for a single grating period. The periodic modal properties of PBGFs allow for coupling to the same mode at multiple wavelengths without a dispersion turning point. Simulations identify inherent differences in the modal structure of even and odd bands.

Widely tunable, acousto-optic resonances in Chalcogenide As2Se3 fiber.

We report for the first time acousto-optical transmission resonances in a non-silica fiber. The resonances, generated in highly nonlinear, single-mode Chalcogenide (As2Se3) fiber, are up to -9 dB deep and tunable over 235 nm around 1450 nm by varying the frequency of an acoustic wave propagating in the fiber, creating a variable period long period grating. The material properties of Chalcogenide modify the acoustic wave propagation leading to a different frequency range of operation when compared to Silica fiber. A tunable resonant structure in this medium opens up possibilities for all-optical processing and mid-IR applications.

Manipulation of spontaneous emission in a tapered photonic crystal fibre.

We characterize the spontaneous emission of dye that is introduced into the central core of a tapered photonic crystal fiber. Since the photonic crystal period in the fibre cladding varies along the taper, the transmission and spontaneous emission spectra over a wide range of relative frequencies can be observed. The spontaneous emission spectra of the fibre transverse to the fiber axis show suppression due to partial band-gaps of the structure, and also enhancement of spontaneous emission near the band edges. We associate these with van Hove features, as well as finite cluster size effects.