Metal measurement in aquatic environments by passive sampling methods: Lessons learning from an in situ intercomparison exercise

Passive sampling devices (PS) are widely used for pollutant monitoring in water, but estimation of measurement uncertainties by PS has seldom been undertaken. The aim of this work was to identify key parameters governing PS measurements of metals and their dispersion. We report the results of an in situ intercomparison exercise on diffusive gradient in thin films (DGT) in surface waters. Interlaboratory uncertainties of time-weighted average (TWA) concentrations were satisfactory (from 28% to 112%) given the number of participating laboratories (10) and ultra-trace metal concentrations involved. Data dispersion of TWA concentrations was mainly explained by uncertainties generated during DGT handling and analytical procedure steps. We highlight that DGT handling is critical for metals such as Cd, Cr and Zn, implying that DGT assembly/dismantling should be performed in very clean conditions. Using a unique dataset, we demonstrated that DGT markedly lowered the LOQ in comparison to spot sampling and stressed the need for accurate data calculation.

In Situ Characterization of Optical Absorption by Carbonaceous Aerosols: Calibration and Measurement

Light absorption by aerosols has a great impact on climate change. A Photoacoustic spectrometer (PA) coupled with aerosol-based classification techniques represents an in situ method that can quantify the light absorption by aerosols in a real time, yet significant differences have been reported using this method versus filter based methods or the so-called difference method based upon light extinction and light scattering measurements. This dissertation focuses on developing calibration techniques for instruments used in measuring the light absorption cross section, including both particle diameter measurements by the differential mobility analyzer (DMA) and light absorption measurements by PA. Appropriate reference materials were explored for the calibration/validation of both measurements. The light absorption of carbonaceous aerosols was also investigated to provide fundamental understanding to the absorption mechanism. The first topic of interest in this dissertation is the development of calibration nanoparticles. In this study, bionanoparticles were confirmed to be a promising reference material for particle diameter as well as ion-mobility. Experimentally, bionanoparticles demonstrated outstanding homogeneity in mobility compared to currently used calibration particles. A numerical method was developed to calculate the true distribution and to explain the broadening of measured distribution. The high stability of bionanoparticles was also confirmed. For PA measurement, three aerosol with spherical or near spherical shapes were investigated as possible candidates for a reference standard: C60, copper and silver. Comparisons were made between experimental photoacoustic absorption data with Mie theory calculations. This resulted in the identification of C60 particles with a mobility diameter of 150 nm to 400 nm as an absorbing standard at wavelengths of 405 nm and 660 nm. Copper particles with a mobility diameter of 80 nm to 300 nm are also shown to be a promising reference candidate at wavelength of 405 nm. The second topic of this dissertation focuses on the investigation of light absorption by carbonaceous particles using PA. Optical absorption spectra of size and mass selected laboratory generated aerosols consisting of black carbon (BC), BC with non-absorbing coating (ammonium sulfate and sodium chloride) and BC with a weakly absorbing coating (brown carbon derived from humic acid) were measured across the visible to near-IR (500 nm to 840 nm). The manner in which BC mixed with each coating material was investigated. The absorption enhancement of BC was determined to be wavelength dependent. Optical absorption spectra were also taken for size and mass selected smoldering smoke produced from six types of commonly seen wood in a laboratory scale apparatus.

In situ reaction furnace for real-time XRD studies

The new furnace at the Materials Characterization by X-ray Diffraction beamline at Elettra has been designed for powder diffraction measurements at high temperature (up to 1373 K at the present state). Around the measurement region the geometry of the radiative heating element assures a negligible temperature gradient along the capillary and can accommodate either powder samples in capillary or small flat samples. A double capillary holder allows flow-through of gas in the inner sample capillary while the outer one serves as the reaction chamber. The furnace is coupled to a translating curved imaging-plate detector, allowing the collection of diffraction patterns up to 2[theta] [asymptotically equal to] 130°.

In situ synthesis and characterization of polyaniline-CaCu3Ti4O12 nanocrystal composites

High dielectric constant (ca. 2.4 x 10(6) at 1 kHz) nanocomposite of polyaniline (PANI)/CaCu3Ti4O12 (CCTO) was synthesized using a simple procedure involving in situ polymerization of aniline in dil. HCl. The PANI and the composite were subjected to X-ray diffraction, Fourier transform infrared, thermo gravimetric, scanning electron microscopy and transmission electron microscopy analyses. The presence of the nanocrystallites of CCTO embedded in the nanofibers of PANI matrix was established by TEM. Frequency dependent characteristics of the dielectric constant. dielectric loss and AC conductivity were studied for the PANI and the composites. The dielectric constant increased as the CCTO content increased in PANI but decreased with increasing frequency (100 Hz-1 MHz) of measurement. The dielectric loss was two times less than the value obtained for pure PANI around 100 Hz. The AC conductivity increased slightly up to 2 kHz as the CCTO content increased in the PANI which was attributed to the polarization of the charge carriers.

In-situ measurements of concentration and temperature during transient solidification of aqueous solution of ammonium chloride using laser interferometry

The variation in temperature and concentration plays a crucial role in predicting the final microstructure during solidification of a binary alloy. Most of the experimental techniques used to measure concentration and temperature are intrusive in nature and affect the flow field. In this paper, the main focus is laid on in-situ, non-intrusive, transient measurement of concentration and temperature during the solidification of a binary mixture of aqueous ammonium chloride solution (a metal-analog system) in a top cooled cavity using laser based Mach-Zehnder Interferometric technique. It was found from the interferogram, that the angular deviation of fringe pattern and the total number of fringes exhibit significant sensitivity to refractive index and hence are functions of the local temperature and concentration of the NH4Cl solution inside the cavity. Using the fringe characteristics, calibration curves were established for the range of temperature and concentration levels expected during the solidification process. In the actual solidification experiment, two hypoeutectic solutions (5% and 15% NH4Cl) were chosen. The calibration curves were used to determine the temperature and concentration of the solution inside the cavity during solidification of 5% and 15% NH4Cl solution at different instants of time. The measurement was carried out at a fixed point in the cavity, and the concentration variation with time was recorded as the solid-liquid interface approached the measurement point. The measurement exhibited distinct zones of concentration distribution caused by solute rejection and Rayleigh Benard convection. Further studies involving flow visualization with laser scattering confirmed the Rayleigh Benard convection. Computational modeling was also performed, which corroborated the experimental findings. (C) 2011 Elsevier Ltd. All rights reserved.

In-situ impedance spectroscopy of layer-by-layer self-assembly of polyelectrolytes

In-situ impedance spectroscopy of layer-by-layer self-assembly of weak polyelectrolytes is presented. Interdigitated capacitors with active area of 1×1 mm2 and electrode spacing of 5 μm are fabricated and used for this purpose. Measurement results indicate that the impedance decreases with increase in number of polyelectrolyte layers. About 2.5% of relative change in magnitude of impedance at 104.7 KHz is seen for four bi-layers of Poly(Allylamine Hydrochloride) (PAH)/Poly(Acrylic acid) (PAA). An electrical equivalent for polyelectrolyte binding is obtained.

In situ approach for testing the enantiopurity of chiral amines and amino alcohols by H-1 NMR

An in situ approach involving a simple mix and shake method for testing the enantiopurity of primary, secondary and tertiary chiral amines and their derivatives, chiral amino alcohols, by H-1-NMR spectroscopy is developed. The protocol involves the in situ formation of chiral ammonium borate salt from a mixture of C-2 symmetric chiral BINOL, trialkoxyborane and chiral amines. The proposed concept was demonstrated convincingly on a large number of chiral and pro-chiral amines and amino alcohols, and also aids the precise measurement of enantiomeric excess. The protocol can be completed in a couple of minutes directly in the NMR sample tube, without the need for any physical separation.

Report of the 2004 Workshop on In Situ Iron Enrichment Experiments in the Eastern and Western Subarctic Pacific

Foreword 1. BACKGROUND AND OBJECTIVES (pdf, 0.1 Mb) 2. 2004 WORKSHOP SUMMARY (pdf, < 0.1 Mb) 2.1. What have we learned from the enrichment experiments? 2.2 What are the outstanding questions? 2.3 Recommendations for SEEDS-II 3. EXTENDED ABSTRACTS OF THE 2004 WORKSHOP 3.1 Synthesis of the Iron Enrichment Experiments: SEEDS and SERIES (pdf, 0.5 Mb) Iron fertilization experiment in the western subarctic Pacific (SEEDS) by Atsushi Tsuda The response of N and Si to iron enrichment in the Northeast Pacific Ocean: Results from SERIES by David Timothy, C.S. Wong, Yukihiro Nojiri, Frank A. Whitney, W. Keith Johnson and Janet Barwell-Clarke 3.2 Biological and Physiological Responses (pdf, 0.2 Mb) Zooplankton responses during SEEDS by Hiroaki Saito Phytoplankton community response to iron and temperature gradient in the NW and NE subarctic Pacific Ocean by Isao Kudo, Yoshifumi Noiri, Jun Nishioka, Hiroshi Kiyosawa and Atsushi Tsuda SERIES: Copepod grazing on diatoms by Frank A. Whitney, Moira Galbraith, Janet Barwell-Clarke and Akash Sastri The Southern Ocean Iron Enrichment Experiment: The nitrogen uptake response by William P. Cochlan and Raphael M. Kudela 3.3 Biogeochemical Responses (pdf, 0.5 Mb) What have we learned regarding iron biogeochemistry from iron enrichment experiments? by Jun Nishioka, Shigenobu Takeda and W. Keith Johnson Iron dynamics and temporal changes of iron speciation in SERIES by W. Keith Johnson, C.S. Wong, Nes Sutherland and Jun Nishioka Dissolved organic matter dynamics during SEEDS and SERIES experiments by Takeshi Yoshimura and Hiroshi Ogawa Formation of transparent exopolymer particles during the in-situ iron enrichment experiment in the western subarctic Pacific (SEEDS) by Shigenobu Takeda, Neelam Ramaiah, Ken Furuya and Takeshi Yoshimura Atmospheric measurement by Mitsuo Uematsu 3.4 Prediction from Models (pdf, 0.3 Mb) Modelling iron limitation in the North Pacific by Kenneth L. Denman and M. Angelica Peña A proposed model of the SERIES iron fertilization patch by Debby Ianson, Christoph Voelker and Kenneth L. Denman 4. LIST OF PARTICIPANTS FOR THE 2004 WORKSHOP (pdf, < 0.1 Mb) APPENDIX 1 Report of the 2000 Planning Workshop on Designing the Iron Fertilization Experiment in the Subarctic Pacific (pdf, 1 Mb) APPENDIX 2 Terms of Reference for the Advisory Panel on Iron fertilization experiment in the subarctic Pacific Ocean (pdf, < 0.1 Mb) APPENDIX 3 Historical List of Advisory Panel Members on Iron fertilization experiment in the subarctic Pacific Ocean (pdf, < 0.1 Mb) APPENDIX 4 IFEP-AP Annual Reports (pdf, 0.1 Mb) APPENDIX 5 PICES Press Articles (pdf, 0.6 Mb) (194 page document)

Recent Developments in In Situ Nutrient Sensors: applications and future directions, Savannah, Georgia, December 11-13, 2006: workshop proceedings

The Alliance for Coastal Technologies (ACT) convened a Workshop on "Recent Developments in In Situ Nutrient Sensors: Applications and Future Directions" from 11-13 December, 2006. The workshop was held at the Georgia Coastal Center in Savannah, Georgia, with local coordination provided by the ACT partner at the Skidaway Institute of Oceanography (University System of Georgia). Since its formation in 2000, ACT partners have been conducting workshops on various sensor technologies and supporting infrastructure for sensor systems. This was the first workshop to revisit a topic area addressed previously by ACT. An earlier workshop on the "State of Technology in the Development and Application of Nutrient Sensors" was held in Savannah, Georgia from 10-12 March, 2003. Participants in the first workshop included representatives from management, industry, and research sectors. Among the topics addressed at the first workshop were characteristics of "ideal" in situ nutrient sensors, particularly with regard to applications in coastal marine waters. In contrast, the present workshop focused on the existing commercial solutions. The in situ nutrient sensor technologies that appear likely to remain the dominant commercial options for the next decade are reagent-based in situ auto-analyzers (or fluidics systems) and an optical approach (spectrophotometric measurement of nitrate). The number of available commercial systems has expanded since 2003, and community support for expanded application and further development of these technologies appears warranted. Application in coastal observing systems, including freshwater as well as estuarine and marine environments, was a focus of the present workshop. This included discussion of possible refinements for sustained deployments as part of integrated instrument packages and means to better promote broader use of nutrient sensors in observing system and management applications. The present workshop also made a number of specific recommendations concerning plans for a demonstration of in situ nutrient sensor technologies that ACT will be conducting in coordination with sensor manufacturers.[PDF contains 40 pages]

Study on the thermal stability of InN by in-situ laser reflectance system

The thermal stability of InN in the growth environment in metalorganic chemical vapor deposition was systematically investigated in situ by laser reflectance system and ex situ by morphology characterization, X-ray diffraction and X-ray photoelectron spectroscopy. It was found that InN can withstand isothermal annealing at temperature as high as 600 degrees C in NH3 ambient. While in N-2 atmosphere, it will decompose quickly to form In-droplets at least at the temperature around 500 degrees C, and the activation energy of InN decomposition was estimated to be 2.1 +/- 0.1 eV. Thermal stability of InN when annealing in NH3 ambient during temperature altering would be very sensitive to ramping rate and NH3 flow rate, and InN would sustain annealing process at small ramping rate and sufficient supply of reactive nitrogen radicals. Whereas In-droplets formation was found to be the most frequently encountered phenomenon concerning InN decomposition, annealing window for conditions free of In-droplets was worked out and possible reasons related are discussed. In addition, InN will decompose in a uniform way in the annealing window, and the decomposition rate was found to be in the range of 50 and 100 nm/h. Hall measurement shows that annealing treatment in such window will improve the electrical properties of InN. (c) 2005 Elsevier B.V. All rights reserved.

In-Situ Boron and Aluminum Doping and Their Memory Effects in 4H-SiC Homoepitaxial Layers Grown by Hot-Wall LPCVD

The in-situ p-type doping of 4H-SiC grown on off-oriented (0001) 4H-SiC substrates was performed with trimethylaluminum (TMA) and/or diborane (B2H6) as the dopants. The incorporations of Al and B atoms and their memory effects and the electrical properties of p-type 4H-SiC epilayers were characterized by secondary ion mass spectroscopy (SIMS) and Hall effect measurements, respectively. Both Al- and B-doped 4H-SiC epilayers were p-type conduction. It was shown that the profiles of the incorporated boron and aluminum concentration were in agreement with the designed TMA and B2H6 flow rate diagrams. The maximum hole concentration for the Al doped 4H-SiC was 3.52x10(20) cm(-3) with Hall mobility of about 1 cm(2)/Vs and resistivity of 1.6 similar to 2.2x10(-2) Omega cm. The heavily boron-doped 4H-SiC samples were also obtained with B2H6 gas flow rate of 5 sccm, yielding values of 0.328 Omega cm for resistivity, 5.3x10(18) cm(-3) for hole carrier concentration, and 7 cm(2)/VS for hole mobility. The doping efficiency of Al in SiC is larger than that of B. The memory effects of Al and B were investigated in undoped 4H-SiC by using SIMS measurement after a few run of doped 4H-SiC growth. It was clearly shown that the memory effect of Al is stronger than that of B. It is suggested that p-type 4H-SiC growth should be carried out in a separate reactor, especially for Al doping, in order to avoid the join contamination on the subsequent n-type growth. 4H-SiC PiN diodes were fabricated by using heavily B doped epilayers. Preliminary results of PiN diodes with blocking voltage of 300 V and forward voltage drop of 3.0 V were obtained.

In situ analysis of electropolymerization of aniline by combined electrochemistry and surface plasmon resonance

The combination of electrochemistry with surface plasmon resonance (SPR) has been used to characterize the growth of polyaniline (PAn) on a gold electrode surface during potential cycling. Potential-modulated SPR characteristics of the PAn film were also revealed. The potential switch between the oxidized and reduced states of PAn can lead to a large change of SPR response due to the variation in the imaginary part of the dielectric constant of PAn film resulting from the transition of the film in conductivity. The redox transition of the PAn film during potential cycling is very profitable to the SPR measurements. Two modes of SPR measurement, SPR angular scan (R-theta) and the time evolution of the reflectivity change at a fixed angle (R-t), were displayed to study the growth process of the PAn film. The angle shift of the resonance minimum recorded at each cathodic limit of cyclic potential scanning allows for the unambiguous measurement of the film growth. During cyclic potential scanning, the R-t curve was repeatedly modulated with the direction of the potential ramp as a result of the redox switch of the PAn film, and the amplitude of potential-modulated reflectivity change was well correlated with the cyclic number. The time differential of the R-t curve permits continuous monitoring of the film growth process. These results illustrate that the combined technique is suitable for studying the electropolymerization process of a conducting polymer.

Rapid automated in-situ monitoring of total dissolved iron and total dissolved manganese in underground water by reverse-flow injection with chemiluminescence detection during the process of water treatment

Measurement of iron and manganese is very important in evaluating the quality of natural waters. We have constructed an automated Fe(II), total dissolved iron(TDI), Mn(II), and total dissolved manganese(TDM) analysis system for the quality control of underground drinking water by reverse flow injection analysis and chemiluminescence detection(rFIA-CL), The method is based on the measurement of the metal-catalyzed light emission from luminol oxidation by potassium periodate. The typical signal is a narrow peak, in which the height is proportional to light emitted and hence to the concentration of metal ions. The detection limits were 3 x 10(-6) mu g ml(-1) for Fe(II) and the linear range extents up to 1.0 x 10(-4) and 5 x 10(-6) mu g ml(-1) for Mn(II) cover a linear range to 1.0 x 10(-4) mu g ml(-1). This method was used for automated in-situ monitoring of total dissolved iron and total dissolved in underground water during water treatment. (C) 1997 Elsevier Science B.V.

Development of an in-situ, non-destructive ultrasonic monitoring technique for solder pastes

This paper concerns the use of a non-destructive ultrasonic technique for characterising the rheological properties of solder paste and specifically, the use of through-mode microsecond ultrasonic pulses for evaluation of viscoelastic properties of paste materials at the molecular level. Ultrasonic techniques are a widely used and a reliable form of non-destructive testing of materials. This is because techniques such as ultrasounds while used for testing or monitoring material properties, has offered immense benefits in applications where access to the sample is restricted or when handling the sample for testing could interfere with the monitoring or analysis process. Very often, this would mean that the measurements taken are not a true representation of the behaviour of the material (due to externally incorporated changes into the material's physical state during the removal or testing process). Ultrasonic based techniques are being increasingly used for quality control and production monitoring functions which requires evaluation of the changes in material properties over wide range of industrial applications such as cement paste quality, plastic/polymer extrusion process, dough, and even sugar content in beverage drinks. In addition, ultrasound techniques are of great interest for their capacity to take rapid measurements in systems which are optically opaque. The viscometer and rheometer are two of the most widely used rheological instruments used in industry for monitoring the quality of solder pastes, during the production and packaging stage. One of the potential limitations of viscometer and rheometer based measurements is that the collection and preparation of the solder paste samples can irreversibly alter the structure and flow behaviour of the sample. Hence the measurement may not represent the actual quality of the whole production batch. Secondly, rheological measurements and the interpretation of rheological data is a very technical and time consuming process, which requires professionally trained R&D personnel. It is for these reasons that materials suppliers (who formulate and produce solder pastes) and solder paste consumers (especially, contract electronics manufacturers) are keen to see the development of simple, easy to use and accurate techniques for the theological characterisation of solder pastes. The results from the work show that the technique can be used by R&D personnel involved in paste formulation and manufacture to monitor the batch-to-batch quality and consistency.