Preparation and stable isotope determination of NBS-16 and NBS-17 carbon dioxide reference samples
[No abstract available]
Analytical Chemistry↗
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Back-extraction with three aqueous stripping systems for 16 elements from organometallic-halide extracts
No abstract available.
Analytical Chemistry↗
Bonded-phase extraction column isolation of organic compounds in groundwater at a hazardous waste site
A procedure for isolation of hazardous organic compounds from water for gas chromatography/mass spectrometry analysis Is presented and applied to creosote- and pentachlorophenol-contaminated groundwater resulting from wood-treatment processes. This simple procedure involved passing a 50-100-mL sample through a bonded-phase extraction column, eluting the trapped organic compounds from the column with 2-4 mL of solvent, and evaporating the sample to 100 ??L with a stream of dry nitrogen, after which the sample was ready for gas chromatography/mass spectrometry analysis. Representative compounds indicative of creosote contamination were used for recovery and precision studies from the cyclohexyl-bonded phase. Recovery of these compounds from n-octyl-, n-octadecyl-, cyclohexyl-, and phenyl-bonded phases was compared. The bonded phase that exhibited the best recovery and least bias toward acidic or basic cmpounds was the n-octadecyl phase. Detailed compound Identification Is given for compounds Isolated from creosote- and pentachlorophenol-contaminated groundwater using the cyclohexyl-bonded phase.
Analytical Chemistry↗
Recovery of dichlorobenzenes, nitrobenzene, and naphthalene during evaporative concentration
[No abstract available]
Analytical Chemistry↗
Extraction of molybdenum with a multielement liquid organic extraction system
[No abstract available]
Analytical Chemistry↗
Concentration of trace elements in water samples by reductive precipitation
No abstract available.
Analytical Chemistry↗
A bacterial method for the nitrogen isotopic analysis of nitrate in seawater and freshwater
We report a new method for measurement of the isotopic composition of nitrate (NO 3 - ) at the natural-abundance level in both seawater and freshwater. The method is based on the isotopic analysis of nitrous oxide (N 2 O) generated from nitrate by denitrifying bacteria that lack N 2 O-reductase activity. The isotopic composition of both nitrogen and oxygen from nitrate are accessible in this way. In this first of two companion manuscripts, we describe the basic protocol and results for the nitrogen isotopes. The precision of the method is better than 0.2‰ (1 SD) at concentrations of nitrate down to 1 μM, and the nitrogen isotopic differences among various standards and samples are accurately reproduced. For samples with 1 μM nitrate or more, the blank of the method is less than 10% of the signal size, and various approaches may reduce it further.
Analytical Chemistry↗
Choosing between atmospheric pressure chemical ionization and electrospray ionization interfaces for the HPLC/MS analysis of pesticides
An evaluation of over 75 pesticides by high-performance liquid chromatography/mass spectrometry (HPLC/MS) clearly shows that different classes of pesticides are more sensitive using either atmospheric pressure chemical ionization (APCI) or electrospray ionization (ESI). For example, neutral and basic pesticides (phenylureas, triazines) are more sensitive using APCI (especially positive ion). While cationic and anionic herbicides (bipyridylium ions, sulfonic acids) are more sensitive using ESI (especially negative ion). These data are expressed graphically in a figure called an ionization-continuum diagram, which shows that protonation in the gas phase (proton affinity) and polarity in solution, expressed as proton addition or subtraction (pKa), is useful in selecting APCI or ESI. Furthermore, sodium adduct formation commonly occurs using positive ion ESI but not using positive ion APCI, which reflects the different mechanisms of ionization and strengthens the usefulness of the ionization-continuum diagram. The data also show that the concept of "wrong-way around" ESI (the sensitivity of acidic pesticides in an acidic mobile phase) is a useful modification of simple pKa theory for mobile-phase selection. Finally, this finding is used to enhance the chromatographic separation of oxanilic and sulfonic acid herbicides while maintaining good sensitivity in LC/MS using ESI negative.
Analytical Chemistry↗
Analysis of trace levels of sulfonamide and tetracycline antimicrobials in groundwater and surface water using solid-phase extraction and liquid chromatography/mass spectrometry
A method has been developed for the trace analysis of two classes of antimicrobials consisting of six sulfonamides (SAs) and five tetracyclines (TCs), which commonly are used for veterinary purposes and agricultural feed additives and are suspected to leach into ground and surface water. The method used solid-phase extraction and liquid chromatography/mass spectrometry (LC/MS) with positive ion electrospray. The unique combination of a metal chelation agent (Na 2 EDTA) with a macroporous copolymer resulted in quantitative recoveries by solid-phase extraction (mean recovery, 98 ± 12%) at submicrogram-per-liter concentrations. An ammonium formate/formic acid buffer with a methanol/water gradient was used to separate the antimicrobials and to optimize the signal intensity. Mass spectral fragmentation and ionization characteristics were determined for each class of compounds for unequivocal identification. For all SAs, a characteristic m / z 156 ion representing the sulfanilyl fragment was identified. TCs exhibited neutral losses of 17 amu resulting from the loss of ammonia and 35 amu from the subsequent loss of water. Unusual matrix effects were seen only for TCs in this first survey of groundwater and surface water samples from sites around the United States, requiring that TCs be quantitated using the method of standard additions.
Analytical Chemistry↗
Accelerated solvent extraction followed by on-line solid-phase extraction coupled to ion trap LC/MS/MS for analysis of benzalkonium chlorides in sediment samples
Benzalkonium chlorides (BACs) were successfully extracted from sediment samples using a new methodology based on accelerated solvent extraction (ASE) followed by an on-line cleanup step. The BACs were detected by liquid chromatography/ion trap mass spectrometry (LC/MS) or tandem mass spectrometry (MS/MS) using an electrospray interface operated in the positive ion mode. This methodology combines the high efficiency of extraction provided by a pressurized fluid and the high sensitivity offered by the ion trap MS/MS. The effects of solvent type and ASE operational variables, such as temperature and pressure, were evaluated. After optimization, a mixture of acetonitrile/water (6:4 or 7:3) was found to be most efficient for extracting BACs from the sediment samples. Extraction recoveries ranged from 95 to 105% for C12 and C14 homologues, respectively. Total method recoveries from fortified sediment samples, using a cleanup step followed by ASE, were 85% for C12BAC and 79% for C14-BAC. The methodology developed in this work provides detection limits in the subnanogram per gram range. Concentrations of BAC homologues ranged from 22 to 206 ??g/kg in sediment samples from different river sites downstream from wastewater treatment plants. The high affinity of BACs for soil suggests that BACs preferentially concentrate in sediment rather than in water.
Analytical Chemistry↗
Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method
We report a novel method for measurement of the oxygen isotopic composition ( 18 O/ 16 O) of nitrate (NO 3 - ) from both seawater and freshwater. The denitrifier method, based on the isotope ratio analysis of nitrous oxide generated from sample nitrate by cultured denitrifying bacteria, has been described elsewhere for its use in nitrogen isotope ratio ( 15 N/ 14 N) analysis of nitrate. 1 Here, we address the additional issues associated with 18 O/ 16 O analysis of nitrate by this approach, which include (1) the oxygen isotopic difference between the nitrate sample and the N 2 O analyte due to isotopic fractionation associated with the loss of oxygen atoms from nitrate and (2) the exchange of oxygen atoms with water during the conversion of nitrate to N 2 O. Experiments with 18 O-labeled water indicate that water exchange contributes less than 10%, and frequently less than 3%, of the oxygen atoms in the N 2 O product for Pseudomonas aureofaciens. In addition, both oxygen isotope fractionation and oxygen atom exchange are consistent within a given batch of analyses. The analysis of appropriate isotopic reference materials can thus be used to correct the measured 18 O/ 16 O ratios of samples for both effects. This is the first method tested for 18 O/ 16 O analysis of nitrate in seawater. Benefits of this method, relative to published freshwater methods, include higher sensitivity (tested down to 10 nmol and 1 μM NO 3 - ), lack of interference by other solutes, and ease of sample preparation.
Analytical Chemistry↗
Linker-assisted immunoassay and liquid chromatography/mass spectrometry for the analysis of glyphosate
A novel, sensitive, linker-assisted enzyme-linked immunosorbent assay (L'ELISA) was compared to on-line solidphase extraction (SPE) with high-performance liquid chromatography/mass spectrometry (HPLC/MS) for the analysis of glyphosate in surface water and groundwater samples. The L'ELISA used succinic anhydride to derivatize glyphosate, which mimics the epitotic attachment of glyphosate to horseradish peroxidase hapten. Thus, L'ELISA recognized the derivatized glyphosate more effectively (detection limit of 0.1 μg/L) and with increased sensitivity (10-100 times) over conventional ELISA and showed the potential for other applications. The precision and accuracy of L'ELISA then was compared with on-line SPE/HPLC/MS, which detected glyphosate and its degradate derivatized with 9-fluorenylmethyl chloroformate using negative-ion electrospray (detection limit 0.1 μg/L, relative standard deviation ±15%). Derivatization efficiency and matrix effects were minimized by adding an isotope-labeled glyphosate (2- 13 C 15 N). The accuracy of L'ELISA gave a false positive rate of 18% between 0.1 and 1.0 μg/L and a false positive rate of only 1% above 1.0 μg/L. The relative standard deviation was ±20%. The correlation of L'ELISA and HPLC/MS for 66 surface water and groundwater samples was 0.97 with a slope of 1.28, with many detections of glyphosate and its degradate in surface water but not in groundwater.
Analytical Chemistry↗
Methodological refinements in the determination of 146 polychlorinated biphenyls, including non-ortho- and mono-ortho-substituted PCBs, and 26 organochlorine pesticides as demonstrated in heron eggs
A method for the determination of 146 polychlorinated biphenyls (PCBs), including four non-ortho- and eight mono-ortho-substituted congeners, and 26 chlorinated pesticides is described. The method consists of ultrasonic extraction, Florisil cleanup, HPLC fractionation over porous graphitic carbon (PGC), and final determination with GC/ECD, GC/MS, or both. Two PCB congeners (PCB 30 and PCB 161) and two polybromobiphenyls (2,4‘,5-tribromobiphenyl and 3,3‘,4,4‘-tetrabromobiphenyl) were used as surrogate standards to evaluate the analytical efficiency. Four PCB congeners, PCB 14 and PCB 159 for the first fraction, PCB 61 for the second fraction, and PCB 204 for the third fraction, were used as internal standards to monitor the GC performance. The retention behavior of PCBs and pesticides on the PGC column are discussed. The method was found to be reproducible, effective, and reliable under the operational conditions proposed and was applied successfully to the analysis of individual PCBs and chlorinated pesticides in black-crowned night heron ( Nycticorax nycticorax ) egg samples.
Maryland↗
Determination of the total oxygen isotopic composition of nitrate and the calibration of a Δ17Ο nitrate reference material
A thermal decomposition method was developed and tested for the simultaneous determination of δ 18 O and δ 17 Ο in nitrate. The thermal decomposition of AgNO 3 allows for the rapid and accurate determination of 18 O/ 16 O and 17 O/ 16 O isotopic ratios with a precision of ±1.5‰ for δ 18 O and ±0.11‰ for Δ 17 Ο (Δ 17 Ο = δ 17 Ο − 0.52 × δ 18 O). The international nitrate isotope reference material IAEA-NO3 yielded a δ 18 O value of +23.6‰ and Δ 17 Ο of −0.2‰, consistent with normal terrestrial mass-dependent isotopic ratios. In contrast, a large sample of NaNO 3 from the Atacama Desert, Chile, was found to have Δ 17 Ο = 21.56 ± 0.11‰ and δ 18 O = 54.9 ± 1.5‰, demonstrating a substantial mass-independent isotopic composition consistent with the proposed atmospheric origin of the desert nitrate. It is suggested that this sample (designated USGS-35) can be used to generate other gases (CO 2 , CO, N 2 O, O 2 ) with the same Δ 17 Ο to serve as measurement references for a variety of applications involving mass-independent isotopic compositions in environmental studies.
Analytical Chemistry↗
Comparison of δ18O measurements in nitrate by different combustion techniques
Three different KNO 3 salts with δ 18 O values ranging from about −31 to +54‰ relative to VSMOW were used to compare three off-line, sealed glass tube combustion methods (widely used for isotope studies) with a more recently developed on-line carbon combustion technique. All methods yielded roughly similar isotope ratios for KNO 3 samples with δ 18 O values in the midpoint of the δ 18 O scale near that of the nitrate reference material IAEA-NO-3 (around +21 to +25‰). This reference material has been used previously for one-point interlaboratory and intertechnique calibrations. However, the isotope ratio scale factors by all of the off-line combustion techniques are compressed such that they are between 0.3 and 0.7 times that of the on-line combustion technique. The contraction of the δ 18 O scale in the off-line preparations apparently is caused by O isotope exchange between the sample and the glass combustion tubes. These results reinforce the need for nitrate reference materials with δ 18 O values far from that of atmospheric O 2 , to improve interlaboratory comparability.
Analytical Chemistry↗
Combination of LC/TOF-MS and LC/Ion Trap MS/MS for the Identification of Diphenhydramine in Sediment Samples
Diphenhydramine (Benadryl) is a popular over-the-counter antihistaminic medication used for the treatment of allergies. After consumption, excretion, and subsequent discharge from wastewater treatment plants, it is possible that diphenhydramine will be found in environmental sediments due to its hydrophobicity (log P = 3.27). This work describes a methodology for the first unequivocal determination of diphenhydramine bound to environmental sediments. The drug is removed from the sediments by accelerated solvent extraction and then analyzed by liquid chromatography with a time-of-flight mass spectrometer and an ion trap mass spectrometer. This combination of techniques provided unequivocal identification and confirmation of diphenhydramine in two sediment samples. The accurate mass measurements of the protonated molecules were m/z 256.1703 and 256.1696 compared to the calculated mass of m/z 256.1701, resulting in errors of 0.8 and 2.3 ppm. This mass accuracy was sufficient to verify the elemental composition of diphenhydramine in each sample. Furthermore, accurate mass measurements of the primary fragment ion were obtained. This work is the first application of time-of-flight mass spectrometry for the identification of diphenhydramine and shows the accumulation of an over-the-counter medication in aquatic sediments at five different locations.
Analytical Chemistry↗
Perchlorate isotope forensics
Perchlorate has been detected recently in a variety of soils, waters, plants, and food products at levels that may be detrimental to human health. These discoveries have generated considerable interest in perchlorate source identification. In this study, comprehensive stable isotope analyses ( 37 Cl/ 35 Cl and 18 O/ 17 O/ 16 O) of perchlorate from known synthetic and natural sources reveal systematic differences in isotopic characteristics that are related to the formation mechanisms. In addition, isotopic analyses of perchlorate extracted from groundwater and surface water demonstrate the feasibility of identifying perchlorate sources in contaminated environments on the basis of this technique. Both natural and synthetic sources of perchlorate have been identified in water samples from some perchlorate occurrences in the United States by the isotopic method.
Analytical Chemistry↗