Solid-phase Sample Research Articles

Molecular environment of Ni after its use for removal of CMP nanoparticle

X-ray absorption spectroscopy (XAS) is employed to investigate the molecular environment around nickel that, in the form of nickel sulfate solution, has been added to precipitate nanoparticles in chemical mechanical polishing (CMP) waste water. After phase separation, for the liquid-phase sample, both the white line intensity in the normalized Ni K-edge X-ray absorption near edge structure (XANES) spectrum and the amplitude of the extended X-ray absorption fine structure (EXAFS) spectrum are enhanced due to the presence of solvation of water molecules, as compared to the solid-phase sample. Meanwhile, with the presence of water molecules, the coordination number increases; yet the Debye–Waller factor slightly decreases. The lack of chemical reduction of Ni 2+ in the CMP solution is suggested as the main reason why the charge neutralization precipitation method through the use of Ni 2+ is less effective than the system using Cu 2+ to precipitate nanoparticles as previously reported.

Photostability of gas- and solid-phase biomolecules under astrophysical analog soft X-rays field

AbstractWe present experimental studies on the interaction of soft X-rays on gas-phase and solid-phase amino acids and nucleobases in an attempt to verify if these molecules (supposed to be formed in molecular clouds/protostellar clouds) can survive long enough to be observed or even to be found in meteorites. Measurements have been undertaken employing 150 eV photons under high vacuum conditions at the Brazilian Synchrotron Light Laboratory (LNLS). The produced ions from the gas-phase experiments (glycine, adenine and uracil) have been mass/charge analyzed by time-of-flight spectrometer. The analysis of solid phase samples (glycine, DL-proline, DL-valine, adenine and uracil) were performed by a Fourier transform infrared spectrometer coupled to the experimental chamber. Photodissociation cross sections and halflives were determined and extrapolated to astrophysical environments. The nucleobases photostability was up to two orders of magnitude higher than for the amino acids.

A model for uranium, rhenium, and molybdenum diagenesis in marine sediments based on results from coastal locations

The purpose of this research is to characterize the mobilization and immobilization processes that control the authigenic accumulation of uranium (U), rhenium (Re), and molybdenum (Mo) in marine sediments. We analyzed these redox-sensitive metals (RSM) in benthic chamber, pore water, and solid phase samples at a site in Buzzards Bay, Massachusetts (USA) that has high bottom water oxygen concentrations (230–300 μmol/L) and high organic matter oxidation rates (390 μmol C/cm 2/y). The oxygen penetration depth varies from 2 to 9 mm below the sediment-water interface, but pore water sulfide is below detection (<2 μM). The RSM pore water profiles are modeled with a steady-state diagenetic model that includes irrigation, which extends 10–20 cm below the sediment-water interface. To present a consistent description of trace metal diagenesis in marine sediments, RSM results from sediments in Buzzards Bay are compared with previous research from sulfidic sediments (Morford et al., GCA 71). Release of RSM to pore waters during the remineralization of solid phases occurs near the sediment-water interface at depths above the zone of authigenic RSM formation. This release occurs consistently for Mo at both sites, but only in the winter for Re in Buzzards Bay and intermittently for U. At the Buzzards Bay site, Re removal to the solid phase extends to the bottom of the profile, while the zone of removal is restricted to ∼2–9 cm for U and Mo. Authigenic Re formation is independent of the anoxic remineralization rate, which is consistent with an abiotic removal mechanism. The rate of authigenic U formation and its modeled removal rate constant increase with increasing anoxic remineralization rates and is consistent with U reduction being microbially mediated. Authigenic Mo formation is related to the formation of sulfidic microenvironments. The depth and extent of Mo removal from pore water is closely associated with the balance between iron and sulfate reduction and the consumption of pore water sulfide via iron sulfide formation. Pore water RSM reach constant asymptotic concentrations in sulfidic sediments, but only pore water Re is constant at depth in Buzzards Bay. The increases in pore water U at the Buzzards Bay site are consistent with addition via irrigation and subsequent upward diffusion to the removal zone. Deep pore water Mo concentrations exceed its bottom water concentration due to irrigation-induced oxidation and remobilization from the solid phase. In sulfidic sediments, there is no evidence for higher pore water U or Mo concentrations at depth due to the absence of irrigation and/or the presence of more stable authigenic RSM phases. There are good correlations between benthic fluxes and authigenic accumulation rates for U and Mo in sulfidic sediments. However, results from Buzzards Bay suggest irrigation ultimately results in the partial loss of U and Mo from the solid phase, with accumulation rates that are 20–30% of the modeled flux. Irrigation can augment (Re, possibly U) or compromise (U, Mo) authigenic accumulation in sediments and is important when determining burial rates in continental margin sediments.

Characteristics and emission factors of PCDD/Fs in various industrial wastes in South Korea

Since South Korea ratified Stockholm Convention in January 2007, there is an obligation to survey the national emission of PCDD/Fs through environmental routes other than the air for taking actions to reduce and/or eliminate the release of PCDD/Fs. In this study, PCDD/F-containing wastes from various industrial emission sources in Korea ( n = 388) except from incinerators were investigated to elucidate the emission characteristics and their emission factors of PCDD/Fs in each industry. The concentrations of PCDD/Fs in waste samples ranged ND–96 200 ng I-TEQ kg −1 (or 66 600 ng WHO-TEQ kg −1) for solid phase samples and ND–11 100 pg I-TEQ L −1 (or 6800 ng WHO-TEQ L) for liquid samples, respectively. Elevated levels of PCDD/F concentrations and emission factors were found in the wastes from productions of Cu, Al, Zn, Iron/steel, Pb, EDC/VCM/PVC and from waste landfill sites. The wastes from productions of cement (kilns) and acetylene (carbide method) showed elevated levels of PCDD/F emission factors only. The dominant congeners were OCDD, OCDF, 1,2,3,4,6,7,8-HpCDF and 1,2,3,4,5,7,8-HpCDD. The PCDF ratios in samples from thermal processes and solid phase samples were 69% and 70%, respectively. The ratio of OCDD congener (about 23.5%) was higher than that of other congeners in both solid and liquid phase wastes. These results can be used as a useful reference for the establishment of the PCDD/F inventory and their management plans.

Effect of Host Medium on the Fluorescence Emission Intensity of Rhodamine B in Liquid and Solid Phase

In this work, we study the effect of concentration, host medium, PH and phase states on the fluorescence emission from the laser dye Rhodamine B pumped by UV laser as exited source. The polymethylmethacrylate PMMA is used as a host medium in case of solid phase samples while, ethanol and Tetrahydrofuran (THF) are used in case of a liquid one. Laser Induced Fluorescence (LIF) technique was used to study the fluorescence properties of both cases of liquid and thin film solid-state samples. In addition, the Dual Thermal Lens (DTL) technique was used to study the quantum yield of these samples. The concentrations of Rhodamine B in ethanol as solvent between 2 x 10(-2) M and 5 x 10(-6) M were studied. The maximum fluorescence emission is observed at concentration of Rhodamine B C = 3 x 10(-4) M. Comparison studies were investigated for different host medium such as ethanol, THF, PMMA in liquid phase state and PMMA in solid phase state. The measurements revealed that, the behavior of both phases state was analogous. Rhodamine B/PMMA thin film sample by ratio of 4:1 and thickness 0.12 mm was found to have the best photostability sample with a quantum yield about approximately 0.82.

Spatial and Temporal Distributions of Geobacter lovleyi and Dehalococcoides spp. during Bioenhanced PCE-NAPL Dissolution

The spatial and temporal distributions of multiple reductively dechlorinating bacteria were simultaneously assessed in a one-dimensional sand column containing a tetrachloroethene (PCE) nonaqueous phase liquid (NAPL) source and associated plume zones. The column was uniformly inoculated with a PCE-to-ethene dechlorinating microbial consortium that contained Dehalococcoides spp., Dehalobacter spp., and Geobacter lovleyi strain SZ. Geobacter and Dehalococcoides populations grew and colonized the column material, including the mixed-NAPL (0.25 mol/mol PCE in hexadecane) source zone. In contrast, Dehalobacter cells did not colonize the porous column material, and planktonic Dehalobacter cell titers remained below the detection limit of ca. 2.6 x 10(2) cells/mL throughout the experiment. Significant PCE dechlorination was observed and resulted in bioenhanced NAPL dissolution up to 21-fold (maximum) and 5.2-fold (cumulative) relative to abiotic dissolution. cis-1,2-Dichloroethene (cis-DCE) wasthe primary dechlorination product although vinyl chloride (VC) was also formed throughout the experiment. Ethene production occurred after significant depletion of PCE from the NAPL and when cis-DCE concentrations dropped below 6 microM. Data obtained after increasing the column residence time from 1.1 to 2.8 days and introducing a VC pulse to the column indicated that both the residence time and cis-DCE inhibition limited significant VC and ethene production. Although both Geobacter and Dehalococcoides cells were present and active in the mixed-NAPL source zone and plume region, Geobacter cell numbers were typically more than 1 order of magnitude higher than Dehalococcoides cell numbers, which is consistent with the production of predominantly cis-DCE. Analysis of both liquid- and solid-phase samples indicated that Geobacter cells grew and remained attached to the porous medium within the source zone but were largely planktonic in the plume region. In contrast Dehalococcoides cell were attached throughoutthecolumn,and Dehalococcoides cell titers increased by 1 to 2 orders of magnitude over the length of the column, correlating to increases in VC concentrations. The results from this study highlight that bioenhanced dissolution is governed by a complex interplay between resident dechlorinators, contaminant concentrations, and other aquifer-specific characteristics (e.g., hydrology).

The usefulness of total concentrations and pore water concentrations of pesticides in soil as metrics for the assessment of ecotoxicological effects ‐ Scientific Opinion of the Panel on Plant Protection Products and their Residues (PPR)

The usefulness of total concentrations and pore water concentrations of pesticides in soil as metrics for the assessment of ecotoxicological effects ‐ Scientific Opinion of the Panel on Plant Protection Products and their Residues (PPR)

Extraction method of PCDD/DFs in solid phase samples containing moisture and activated carbons

Extraction method of PCDD/DFs in solid phase samples containing moisture and activated carbons

Synthetic temporal aperture coherent molecular phase spectroscopy

Coherent Raman vibrations in solid, liquid and gas phase samples, excited by impulsive stimulated Raman scattering, are probed via optical spectral interferometry. High vibrational spectral resolution is possible with a synthetic temporal aperture technique and we investigate the effects of this approach numerically. Measured spectra are determined either by direct Fourier transform or by linear prediction. This new Raman spectroscopy technique is shown to be well-suited to strongly damped as well as polarized and depolarized vibrational modes.

Mitigation of the Impact of Terrestrial Contamination on Organic Measurements from the Mars Science Laboratory

The objective of the 2009 Mars Science Laboratory (MSL), which is planned to follow the Mars Exploration Rovers and the Phoenix lander to the surface of Mars, is to explore and assess quantitatively a site on Mars as a potential habitat for present or past life. Specific goals include an assessment of the past or present biological potential of the target environment and a characterization of its geology and geochemistry. Included in the 10 investigations of the MSL rover is the Sample Analysis at Mars (SAM) instrument suite, which is designed to obtain trace organic measurements, measure water and other volatiles, and measure several light isotopes with experiment sequences designed for both atmospheric and solid-phase samples. SAM integrates a gas chromatograph, a mass spectrometer, and a tunable laser spectrometer supported by sample manipulation tools both within and external to the suite. The sub-part-per-billion sensitivity of the suite for trace species, particularly organic molecules, along with a mobile platform that will contain many kilograms of organic materials, presents a considerable challenge due to the potential for terrestrial contamination to mask the signal of martian organics. We describe the effort presently underway to understand and mitigate, wherever possible within the resource constraints of the mission, terrestrial contamination in MSL and SAM measurements.

Absorption spectra in the vacuum ultraviolet region of small molecules in condensed phases

With radiation from a synchrotron we measured the spectra of several small molecular species, in the solid phase at 10 K, either pure – O 2, NO, CO 2, N 2O, H 2O and NH 3 – or, for NH 3, also dispersed in Ar at molar ratio 1/250, from the onset of absorption in the ultraviolet region until the limits of transmission by crystalline LiF or solid Ar. In a quantitative treatment of spectral data, we fitted the total absorption profile divided by wavenumber to Gaussian curves of minimal number, and made tentative assignments of electronic transitions and vibrational structure by comparison with spectra of gaseous species. These results illuminate the nature of electronic spectra of samples in solid phases in the vacuum ultraviolet region.

Geochemistry of natural wetlands in former uranium milling sites (eastern Germany) and implications for uranium retention

Discharge from former uranium mining and milling areas is a source of elevated uranium contents in wetlands worldwide. In this work, the efficiency of organic-rich wetland environments for entrapment and accumulation of uranium was assessed using hydrogeochemical field studies of natural small-sized wetlands in Thuringia and Saxony, Germany. The objective was to estimate if artificial wetlands can be used in a similar way: as a sustainable ‘passive’ treatment methodology. Worldwide, a dozen such systems have been implemented for uranium-bearing mine waters as experiments, primarily aiming at uranium reduction and precipitation. Pore water and solid phase samples were collected from the upper decimetres of substrate profiles in minerotrophic ‘volunteer’ wetlands and natural fen-type wetlands that facilitate uranium accumulation. Elemental analyses, correlation techniques and sequential chemical extraction were applied to evaluate retention mechanisms (e.g., reduction, mineral sorption). No process was dominant but the bulk of uranium is retained in moderately labile forms, predominantly as operationally defined organically bound or acid soluble (‘specifically adsorbed’) phases. Macrophyte intracellular uranium accumulation (‘phytoaccumulation’) is not responsible for the high uranium concentrations in the wetland substrates. Although there is no evidence for stable U(IV) mineralisation via ‘reductive precipitation’, high accumulation efficiency of the wetlands results from processes involving species regarded as more labile. According to the findings, the previous concept for treatment wetland that was commonly designed for uranium reduction needs modification.

Comparison of MALDI to ESI on a Triple Quadrupole Platform for Pharmacokinetic Analyses

This present work describes the systematic experimental comparison of electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) for pharmacokinetic (PK) analysis of two drug candidates from rat plasma using single reaction monitoring (SRM) on a triple quadrupole mass spectrometer. The electrospray assay is an established method using a fast liquid chromatography (LC) separation of the sample extracts prior to mass spectrometry analysis. The novel MALDI assays measured the concentration levels of the drug candidates directly from the spotted sample extracts. Importantly, for both LC-ESI and MALDI the same solid-phase sample extraction protocol, internal standards, triple quadrupole mass analyzer platform, and SRM conditions were used, thus effectively standardizing all experimental parameters of the two assays. Initially, analytical figures of merit such as linearity, limit of quantitation, precision, and accuracy were determined from the calibration curves, indicating very similar performance for both LC-ESI and MALDI. Moreover, the LC-ESI rat plasma concentration time profiles of the drug candidates after orally dosing the animals were accurately reproduced by the MALDI assay, giving virtually identical PK results. The direct MALDI assay, however, was able to generate the data at least 50 x faster than the LC-ESI assay. It is shown in this study that analyzing the entire PK curve for one animal took less than 2 min using MALDI (with five replicate analyses per sample), whereas the corresponding LC-ESI assay required 80 min, however, allowing only two replicate measurements in that time frame.

Spatial variation of redox and trace metal geochemistry in a minerotrophic fen

Pore water and solid phase samples were collected from the upper 50 cm of a peat profile at four sites within a 10 m2 area in Kleinstuck Marsh, a minerotropic fen located in Kalamazoo, MI. Although the chosen sites are in close proximity to each other, they differ with respect to vegetation species and density. Pore water analyses for a suite of redox sensitive species (pH, alkalinity, dissolved Mn(II), Fe(II), Fe(III), sulfide, sulfate), together with Fe and Mn distributions inferred from operationally-defined sequential extractions, demonstrate that Fe(III) and Mn(IV) reduction occurs in the shallow peat at three of the four sites. At the fourth site, the only site containing the invasive purple loosestrife (Lythrum salicaria), accumulation of dissolved sulfide in the pore waters and increased levels of oxidizable phases in the shallow peat point to increased net sulfate reduction relative to the other three sites. Speciation calculations indicate that pore water concentrations of phosphate, especially below ∼10 cm depth, are largely controlled by the solubility of phases such as strengite or hydroxylapatite, and that at all but the loosestrife site, dissolved Ca and Mg are likely determined by carbonate solubility. Fe and Mn distribution among operationally defined solid phase fractions are consistent with reductive dissolution of FMO in the uppermost peat, leading to precipitation of Fe sulfides and Mn carbonates deeper in the peat profile. Zn, Co, Cr and Ni distributions are consistent with release from FMO to form sulfides or organic associations deeper in the peat. Pb and Cu may also be released by reductive dissolution of FMO, or more likely, shift from primary association with organic matter to increased association with sulfides under more sulfidic conditions. This study highlights the existence of extreme lateral variations in peat pore water and solid phase geochemical profiles, even over quite small areas.

Silicon microstructure arrays for DNA extraction by solid phase sample contacting at high flow rates

Rapid and large sample volume processing capabilities are required for many clinical and environmental point of care genetic diagnostics scenarios. In this paper we describe the development of a silicon monolithic device for high flow rate DNA extraction. The silicon presents silica surfaces and with chaotropic salt solutions can be used for solid phase extraction. The microfluidic device was designed with the aid of simulation methods and consists of a chamber containing a densely packed alternating array of teardrop-shaped microstructures. The microstructures repeatedly separate and recombine flows, and produce a near homogeneous flow distribution to favour DNA contact with the large silica surface areas. Extremely high flow rate operation (e.g. 10 mL min−1) can be achieved without device failure. Low DNA loading and elution flow rates were used to determine a binding capacity of 57 ± 5 ng cm−2. At high flow rates the DNA extraction capability is retained and is independent of the sample DNA concentration. High flow rate operation is preferred for the rapid extraction of rare DNA species from large sample volumes, and makes the device ideal for inclusion within a fully integrated genetic diagnostics system.

Bead-Based DNA Diagnostic Assay for Chlamydia Using Nanoparticle-Mediated Surface-Enhanced Resonance Raman Scattering Detection within a Lab-on-a-Chip Format

There is a continued interest in the development of new on-chip protocols for the determination of the causes of infectious disease. In this paper, we demonstrate the use of surface-enhanced resonance Raman scattering (SERRS) for detecting the clinically relevant nucleic acid sequences of Chlamydia trachomatis in a bead-based lab-on-a-chip format, incorporating a solid-phase sample clean-up on-chip. The assay uses streptavidinated polymer microspheres to capture a biotinylated PCR product of the oligonucleotide sequence, which was subsequently hybridized against a complementary rhodamine-labeled, Raman active probe. Central to the assay is an in-channel integrated microfilter, which was used to retain the microspheres, enabling the bound target to be separated from the rest of the sample as part of a solid-phase clean-up (thereby removing any contributions from the background). After washing, the bound Rhodamine labeled detection probe was released thermally from the microspheres by heating and was subsequently mixed on-chip with a stream of silver nanoparticles. The signal was detected downstream using a Raman spectrometer to collect the SERRS response. The assay offers several advantages over traditional laboratory methods, including: the speed of the assay on-chip, the potential for sample clean-up; and the low volume of sample required.

Improving the sensitivity of the determination of ceftiofur by capillary electrophoresis in environmental water samples: In-line solid phase extraction and sample stacking techniques

This paper describes two different approaches for increasing the sensitivity for the analysis of ceftiofur by capillary electrophoresis (CE). Two different techniques based on the introduction of an enlarged volume of sample, namely large volume sample stacking (LVSS) and in-line solid phase extraction (SPE) were studied and compared. LVSS allowed the on-column electrophoretic preconcentration of ceftiofur without modification of the separation capillary. In-line SPE-CE was developed by using a home-made microcartridge that was filled with a reversed-phase sorbent (C 18). The microcartridge was coupled in-line near the inlet of the separation capillary. LVSS and in-line SPE-CE allowed automated operation and improved sensitivity for the analysis of ceftiofur with respect to conventional CE. When environmental water samples were analyzed, an additional pretreatment step based on off-line SPE was necessary in both cases to further decrease the detection limits. In terms of sensitivity for the determination of ceftiofur in river water samples, the combination of off-line SPE with in-line SPE-CE was found the most sensitive with a detection limit of 10 ng L −1, whereas the method based on the use of off-line SPE with LVSS presented a detection limit of 100 ng L −1.

Estrógenos em água: otimização da extração em fase sólida utilizando ferramentas quimiométricas

Muitos métodos analíticos estão sendo desenvolvidos visando à determinação de contaminantes orgânicos, especialmente alteradores endócrinos. Tais métodos baseiam-se geralmente na extração em fase sólida (SPE) seguida por determinação cromatográfica (CG ou HPLC). No presente trabalho utilizou-se ferramentas quimiométricas no processo de SPE para avaliar os principais fatores que influenciam tal processo e as interações entre os mesmos. Foram analisadas matrizes de água subterrânea fortificada com hormônios (17 b estradiol, estrona e 17 b etinilestradiol) e a determinação analítica foi feita por HPLC/Fluorescência. Um planejamento fatorial completo foi utilizado. Os fatores escolhidos incluíram: condicionamento da fase sólida, concentração dos analitos, volume da amostra e solvente de eluição. As melhores condições obtidas foram: 500 mL da amostra, condicionamento da fase sólida (C18) com acetona (4mL), metanol (6 mL) e água pH 3(10 mL), e eluição dos analitos com 4 mL de acetona.

Distribution of PAHs and PCBs to dissolved organic matter: High distribution coefficients with consequences for environmental fate modeling

Dissolved organic carbon/water distribution coefficients (K(DOC)) were measured for a selection of PCBs with octanol/water partition coefficients (K(OW)) ranging from 10(5.6) to 10(7.5). A solid phase dosing and sampling technique was applied to determine K(DOC) to Aldrich humic acid. This technique is in particular suitable for determining the distribution of very hydrophobic chemicals to complex matrices like humic acids. The K(DOC) values were calculated from the experimental data using a linear model. Determined K(DOC)'s were evaluated in relation to octanol/water partition coefficients of the test compounds, and compared to literature data. Measured K(DOC) values were somewhat higher than literature data, which can probably be attributed to the overestimation of freely dissolved aqueous concentration as a result of incomplete phase separation in other studies, and to the unique character of Aldrich humic acid as a "sorbent" or co-solute or to the fact that Aldrich humic acid is not a typical DOC, and other (adsorption) processes can occur. This study reports DOC distribution coefficients that belong to the highest ones ever measured. In addition, the DOC distribution was discussed in relation to current risk assessment modeling.

Enzyme-Linked Immunosorbent Assay (ELISA) and Sol−Gel-Based Immunoaffinity Purification (IAP) of the Pyrethroid Bioallethrin in Food and Environmental Samples

Enzyme-linked immunosorbent assay (ELISA) and sol-gel-based immunoaffinity purification (IAP) methods for the pyrethroid bioallethrin were developed and applied for monitoring bioallethrin in spiked food, soil, and dust samples. Attempts to determine bioallethrin content in fruit and vegetable extracts revealed high variability between sample preparations and marked interferences with the assay. Sol-gel IAP followed by solid-phase sample concentration was effective in removing the interfering components and resulted in high recovery of bioallethrin from spiked crude acetonic extracts of fruits and vegetables, even in the presence of high extract concentrations (28%). Solid-phase treatment alone failed to remove the interfering components from the spiked sample. Gas chromatography-mass spectrometry analysis of the IAP samples revealed bioallethrin as a doublet unsolved peak because of the cis and trans isomer present in the standard with confirmation of its mass. Unlike fruit and vegetable extracts, soil and dust samples did not interfere with the ELISA, and the bioallethrin content in those samples could be determined with high precision without the need of any further purification.