Development of perfluorocarbon (PFC) primary standards for monitoring of emissions from aluminum production

An EPA Voluntary Aluminum Industrial Partnership (VAIP) program has been formed to help US primary producers focus on reducing the emissions of two perfluorocarbons (PFCs), tetrafluoromethane (CF4) and hexafluoroethane (C2F6), during the production of aluminum. To ensure comparability of measurements over space and time, traceability to national sources was desirable. Hence, the EPA approached the NIST to develop a suite of primary standards to cover a mole fraction (concentration) range of 0.1 to 1400 micromol mol(-1) for CF4 and 0.01 to 150 micromol mol(-1) of C2F6. A total of eight gravimetric PFC gas standards were prepared with relative expanded uncertainties of < or = 0.52% (approximately 95% confidence level). These primary standards were ultimately used to assign values to a series of secondary gas standards at three mole-fraction levels with relative expanded uncertainties ranging from +/- 0.7% to 5.3% (approximately 95% confidence level). This series of secondary standards was used within the aluminum industry to calibrate instruments used to make emission measurements. Assignment of values to the secondary standards was performed by use of gas chromatography with flame-ionization detection (GC-FID) and Fourier transform infrared spectrometry (FTIR). Real time pot-line and stack samples from a local aluminum plant were also obtained and sub-samples sent to each participating facility for analysis. The data generated from each facility were sent to NIST for analysis. The maximum difference between the NIST and individual facilities' values for the same sub-sample was +/- 26%.     

QCM sensor array for monitoring terpene emissions from odoriferous plants

Abstract  An e-nose comprised of six sensing channels each coated with a molecularly imprinted polymer (MIP) selectively interacting with alpha-pinene, thymol, estragol, linalool, and camphor, respectively, was designed. When applying it for continuous online surveillance of terpenes emitted from basil and peppermint leaves as a criterion of freshness, it very appreciably reproduced the emanation patterns from these plants as shown by GC-MS. Chromatography yielded a variety of terpenes in a concentration range below 70 ppm. Trend lines obtained from the e-nose were corroborated by GC-MS and also appreciably fit the usual conduct of these plants as observable by the human nose. Graphical abstract        

Development of a closed-loop control system for production of medium-chain-length poly(3-hydroxyalkanoates) (mcl-PHAs) from bacteria

Large scale availability of bacterial polyhydroxyalkanoates (PHAs) is still limited to a few types of short-chain-length PHAs, namely poly(3-hydroxybutyrate) (PHB) and its copolymer Biopol™, consisting of 3-hydroxybutyrate and 3-hydroxyvalerate repeating units. In order to increase the number of available medium-chain-length PHA (mcl-PHA) copolymers a flexible high-cell-density fed-batch process was developed. Continuous process monitoring and substrate control were achieved by coupling on-line gaschromatography (on-line GC) to a software-based Proportional Integral (PI) substrate controller. System development time and continuous system upgrading were considerably shortened by using LABView™, a powerful graphical programming environment. The control of octanoic acid and 10-undecenoic acid at 1.5 and 0.5 gL⁻¹ respectively, enabled the production of high levels of biomass (30 gL⁻¹) and mcl-PHA (10.5 gL⁻¹) by avoiding substrate limitations or toxicities. The resulting mcl-PHA was an amorphous copolyester consisting of 37 mol% unsaturated monomers. The present system represents a valuable tool for the production of tailor-made mcl-PHAs, where the desired monomer composition is determined by the ratio of added cosubstrates.     

Automated dynamic sampling system for the on-line monitoring of biogenic emissions from living organisms

An automated system for continuous on-line monitoring of biogenic emissions is presented. The system is designed in such a way that volatiles, emitted as reaction to biotic or abiotic stress, can be unequivocally elucidated. Two identical sampling units, named target and reference bulb, are therefore incorporated into the system and consecutively analyzed in monitoring experiments. A number of precautions were considered during these experiments to avoid the application of unwanted stress onto both organisms. Firstly, the system is constructed in such a way that both bulbs are continuously flushed, i.e. before, during and after analysis, with high purity air to avoid any accumulation of emitted volatiles. Moreover, the air is pre-humidified by bubbling it through water to sustain the biological samples for longer periods in the in vitro environment. Sorptive enrichment on polydimethylsiloxane (PDMS) was used to trap the headspace volatiles. The hydrophobic nature of this material permitted easy removal of trapped moisture by direct flushing of the sampling cartridge with dry air before desorption. The system was used to monitor the emissions from in vitro mechanically wounded ivy (Hedera helix) and of in vitro grown tomato plants (Lycopersicon esculentum Mill.) upon cotton leafworm (Spodoptera littoralis) feeding. Differences in light and dark floral emissions of jasmine (Jasminum polyanthum) were also studied.     

Development of an Hg(II) fibre-optic sensor for aqueous environmental monitoring

An optical sensor for Hg(II) monitoring using a complex of zinc dithizonate immobilised on XAD 7 which is based on reflectance spectrophotometry has been developed in this study. Measurements were made using a kinetic approach whereby the reflectance signal is measured at a fixed time of 5 min. The sensor could be regenerated using a saturated solution of KCl in 1 M sulphuric acid. The sensor was found to have an optimum response at pH 3.0 with respective measurement repeatability and probe-to-probe reproducibility of 1.53% and 5.26%. A linear response was observed in the Hg(II) concentration range of 0.0-180.0 ppm with a calculated limit of detection (LOD) of 0.05 ppm. The results obtained for aqueous Hg(II) determination using this probe were found to be comparable with the well-established method of atomic absorption spectrometry.     

Development of a flow-injection analysis (FIA) enzyme sensor for fructosyl amine monitoring

An enzyme-sensor system with flow-injection analysis (FIA) has been developed for the detection of fructosyl amine compounds; the sensor utilizes fructosyl amine oxidase isolated from the marine yeast Pichia sp. N1-1 strain. With this FIA system 0.2 to 10 mmol L(-1) fructosyl valine can be determined. The sensor is approximately five times more sensitive to fructosyl valine, a model compound for glycated hemoglobin HbA1c, than to N(epsilon)-fructosyl lysine, a model compound for glycated albumin. This FIA system can also be used to detect fructosyl dipeptides. The operational stability of the sensor enabled more than 120 consecutive sample injections over a period of approximately 20 h.     

Reference measurement procedures for the quantification of platinum-group elements (PGEs) from automotive exhaust emissions

The major source of the anthropogenic platinum group element (PGE) emission is attributed to the use of catalytic converters in automobiles. This paper describes the work performed by three National Metrology Institutes (Laboratoire national de métrologie et d’essais, by the Physikalisch-technische bundesanstalt, Bundesanatalt für materialforschung und prûfung), in the framework of the Joint Research Project ‘PartEmission’ under the European Metrology Research Program. An analytical procedure based on a cationic exchange protocol and the isotope dilution or standard addition using an Inductived Coupled Plasma Mass Spectrometer, ICP-MS, for the quantification of the elements Pt, Pd and Rh from automotive exhaust emissions is described. Results obtained on a road dust certified reference (BCR 723) material showed a good agreement with the certified values, at ng/g levels, and relative expanded uncertainties within the range of 7–10%. Analysis of filters impacted with automotive exhaust particle emissions (from a diesel engine) showed the amount of collected PGE at levels of 10–1000 pg/filter. Their quantifications followed the developed analytical protocol that had been carried out with relative expanded uncertainties in the range of a few per cent up to 20% per filter. Nevertheless, a lack of homogeneity between the filters was observed, making the comparison between the project partners difficult in the sake of the validation of their analytical procedures on real samples.     

Reactions of poly(ethylene glycol) cations with iodide and perfluorocarbon anions

Multiply charged poly(ethylene glycol) ions of the form (M+nNa) ⁿ⁺ derived from electrospray ionization have been subjected to reactions with negative ions in the quadrupole ion trap. Mixtures of multiply charged positive ions ranging in average mass from about 2000 to about 14,000 Da were observed to react with perfluorocarbon anions by either proton transfer or fluoride transfer. Iodide anions reacted with the same positive ions by attachment. In no case was fragmentation of the polymer ion observed. In all cases, the multiply charged positive ion charge states could be readily reduced to +1, thereby eliminating the charge state overlap observed in the normal electrospray mass spectrum. With all three reaction mechanisms, however, the +1 product ions were comprised of mixtures of products with varying numbers of sodium ions, and in the case of iodide attachment and fluoride transfer, varying numbers of halogen anions. These reactions shift the mass distributions to higher masses and broaden the distributions. The extents to which these effects occur are functions of the magnitudes of the initial charges and the width of the initial charge state distributions. Care must be taken in deriving information about the polymer molecular weight distribution from the singly charged product ions arising from these ion/ion reactions. The cluster ions containing iodide were shown to be intermediates in sodium ion transfer. Dissociation of the adduct ions can therefore lead to a +1 product ion population that is comprised predominantly of M+Na⁺ ions. However, a strategy based on the dissociation of the iodide cluster ions is limited by difficulties in dissociating high mass-to-charge ions in the quadrupole ion trap.     

Development of a selective optical sensor for Cr(VI) monitoring in polluted waters

An optical sensor is described for the sensitive and selective determination of the Cr(VI) ion in aqueous solutions. The optode membrane is prepared by incorporating Aliquat 336 as an ionophore and a chromoionophore (4',5'-dibromofluorescein octadecyl ester) in a poly(vinyl chloride) (PVC) membrane containing ortho-nitrophenyloctyl ether (o-NPOE) as a plasticizer. The response to Cr(VI) is indicated by co-extraction of the target species and of hydrogen ions into the bulk of the membrane yielding large absorbance changes which can easily be measured in the visible spectral range. The optode membrane shows a reversible response in the concentration range of 1.1x10(-5)-1.0x10(-3) M and has been shown to be more selective towards the HCrO4(-) ion than other anions with a selectivity pattern HCrO4(-) > SCN- approximately = ClO4(-) > NO3(-) approximately = I- approximately = NO2(-) > H2PO4(-) approximately = Cl- approximately = SO4(2-). The sensing method developed has successfully been applied to the determination of Cr(VI) in spiked river water as well as in electroplating rinse waters.     

Advancement of isotope separation for the production of reference standards

Idaho National Laboratory (INL) operates a mass separator that is currently producing high purity isotopes for use as internal standards for high precision isotope dilution mass spectrometry (IDMS). In 2008, INL began the revival of the vintage 1970s era instrument. Advancements thus far include the successful upgrading and development of system components such as the vacuum system, power supplies, ion-producing components, and beam detection equipment. Progress has been made in the separation and collection of isotopic species including those of Ar, Kr, Xe, Sr, and Ba. Particular focuses on ion source improvements and developments have proven successful with demonstrated output beam currents of over 10 μA ¹³⁸Ba and 350 nA ¹³⁴Ba from a natural abundance Ba source charge (~2.4 % ¹³⁴Ba). In order to increase production and collection of relatively high quantities (mg levels) of pure isotopes, several improvements have been made in ion source designs, source material introduction, and ion detection and collection. These improvements have produced isotopes of high purity (>98 %) and in quantities in the tens of micrograms per run. The instrument and results for pure isotope production for IDMS standards will be presented.     

Preparation of mixtures of paralytic shellfish toxin (PSP) standards from mussel hepatopancreas

Summary The development and application of chemical methods for monitoring paralytic shellfish poisoning (PSP) in coastal waters requires the availability of pure PSP standards. However only a few toxins are commercially available and only very small amounts of some of the other 18 PSP toxins identified are available at some research laboratories. A project is currently in progress for the isolation and purification of significant quantities of PSP toxins from contaminated mussels under the auspices of the Community Bureau of Reference of the Commission of the European Communities (BCR Programme). The PSP toxins from hepatopancreas of 500 kg of whole mussel were extracted and purified, and the following toxin profile was determined using a method based on Oshima et al. [1] GTX1, (24%), GTX2 (<1%), GTX3 (<1%), GTX4 (2.4%), GTX5 (5.8%), GTX6 (35.4%), C1 (11.5%), C2 (1.22%), neo-STX (11.4%), dc-STX (6.2%) and STX (2.4%). These toxins can be separated into three different fractions (STX-group, GTX-group and C-group), before proceeding to the purification of the individual toxins.     

Development of nitrilase-mediated process for phenylacetic acid production from phenylacetonitrile

This study aimed at developing an efficient biotransformation process for phenylacetic acid production from phenylacetonitrile by using recombinant Escherichia coli M15 harboring a double mutant MG nitrilase (I113M/Y199G) from Burkholderia cenocepacia J2315. A yield of 2310 U/mL nitrilase was obtained by fermentation after the optimization of cultivation conditions, with a specific activity of 64 U/mg dcw. The MG nitrilase showed high substrate tolerance and completely hydrolyzed 100 mM phenylacetonitrile in 30 min under optimal conditions. To alleviate substrate inhibition, periodic or continuous batch-feeding of substrate was used during the biotransformation. Up to 164 g/L substrate was completely hydrolyzed in 9 h with continuous batch-feeding using resting cells, corresponding to 400 U/mL of nitrilase activity, and leading to production of 163.4 g/L phenylacetic acid. The hydrolysis process has potential application for phenylacetic acid production on a large scale.     

Development of an electrochemical flow injection immunoassay (FIIA) for the real-time monitoring of biospecific interactions

Not only are sensors a revolution in analysis; they themselves are also experiencing a revolution brought about by parallel developments in sensor fabrication techniques and materials, polymer chemistry, signal processing methodologies, the increased use of biomolecular processes as a means of analyte detection, and the coupling of sensors to other techniques such as flow injection analysis. Many of these developments have been incorporated into the present study, which we are undertaking in the development of our immunosensor technology. The system described here utilises screen-printed electrodes which are low-cost, disposable devices that are simple to fabricate. Incorporated into our sensor is the electroactive polymer, polyaniline, which brings about mediatorless redox coupling between the electrode and biomolecular components attached to the polymer surface. This system also utilises enzyme-labelled antibodies as the biomolecular recognition component for the analysis of the test analyte, biotin. The system has also been integrated into a flow injection system. This has led to the monitoring of real-time antibody-antigen interactions using electrochemical methods and foreshadows the development of single-step immunosensors.     

Multiple emissions and brilliant white luminescence from gold(I) O,O'-di(alkyl)dithiophosphate dimers

The Au(I) dimers Au(2)[S(2)P(OR)(2)](2) for R = Me, Et are found to exhibit a structure in which aurophilic interactions yield one-dimensional Au...Au chains with intermolecular contacts (3.09-3.16 A) similar to the Au...Au distances within the dimers (3.10-3.18 A). The dimers are luminescent in the solid state and become brilliantly emissive at low temperatures. At 77 K, Au(2)[S(2)P(OMe)(2)](2) shows multiple emission bands. The two higher energy bands at 415 and 456 nm are assigned to (1)MC and (3)MC on the basis of lifetime measurements (20 ns and 2.16 micros, respectively) and concentration-related effects, while the lower energy band at 560 nm is attributed to a LMCT excited state. In frozen glasses of different solvents, Au(2)[S(2)P(OMe)(2)](2) as well as the Et and n-Pr derivatives exhibit a bright luminescence of different colors and striking thermochromism of the emission.