Analysis of herbicide Krovar I by liquid chromatography with atmospheric pressure chemical ionization mass spectrometry

A simple, very efficient method is presented for routine analysis of herbicide Krovar I (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid-liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 microg L(-1) and for diuron 0.03 microg L(-1). Method detection limit for soil samples is 0.01 microg g(-1) dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.     

Characterization of three major toxaphene congeners in arctic ringed seal by electron ionization and electron capture negative ion mass spectrometry

Three environmentally significant chlorinated bomane (CHB) congeners were extracted from Arviat ringed seal blubber and identified by using gas chromatography/mass spectrometry (HRGC/HRECNIMS (CH₄), low resolution EIMS, and linked field scanning). They are referred to as TS2 (Parlar#39, B8-531) [2-exo,3-endo,5-exo,6,6,8b,9c,10c (or 10a)-octachlorobonane], TS3 (Parlar#40, B8-1414) [2-endo,3-exo,5-endo,6-exo,8c,9b,10a,10c (or 10b)-octachlorobornane] and TS4 (Parlar#42, Toxicant A, B8-806/809) [2-exo,3-endo,6,6,8b,8c,9c,10c (or 10a)-octachlorobonane/2-exo,3-endo,6,6,8b,9b,9c,10a (or 10b)-octachlorobonane]. This is the first time Toxicant A, known to be the most toxic CHB congener in technical toxaphene, has been found in any significant concentration in a marine mammal.     

Secondary ozonides of substituted cyclohexenes: a new class of pollutants characterized by collision-induced dissociation mass spectrometry using negative chemical ionization

Recent studies indicate that secondary ozonides of cyclic alkenes are formed in atmospheric reactions and may be relatively stable. The secondary ozonides (SOZs) of cyclohexene (1), 1-methylcyclohexene (2), 4-isopropyl-1-methylcyclohexene (3) and 4-isopropenyl-1-methylcyclohexene (limonene) (4) have been characterized by rapid gas chromatography electron ionization (EI), negative and positive chemical ionization (CI: ammonia, isobutane and methane) and collision-induced dissociation (CID) mass spectrometry. Both EI and positive CI spectra were found unsuitable for reproducible analysis. However, negative CI showed stable (M−H)⁻ ions with minor fragmentation. CID of the (M−H)⁻ ions resulted in simple and reproducible fragmentation patterns for all four SOZs with loss of m/z 18, 44 and 60, tentatively assigned as H₂O, CO₂ and C₂H₄O₂ or CO₃, respectively. Thus, negative CI-MS–MS in combination with rapid gas chromatography is the preferred method for identification of secondary ozonides of cyclohexenes.     

On-line analysis of secondary ozonides from cyclohexene and d-limonene ozonolysis using atmospheric sampling townsend discharge ionization mass spectrometry

An on-line technique has been developed for analysis of gas-phase oxidation products formed in a reaction flow tube using different reaction times, concentrations and humidities. Products of ozonolysis, including thermally labile secondary ozonides (SOZ), were directly introduced into an atmospheric sampling townsend discharge ionization (ASTDI) source coupled to a triple quadrupole mass spectrometer (MS). Instant changes in the product composition were monitored in the total-ion chromatogram, or by fragment ions in the collision activated dissociation mass spectra by use of MS/MS scan techniques. Assignment of the individual ions was accomplished by inspection of the products’ mass spectra obtained by pre-concentration of the gas phase on a dedicated short column followed by chromatographic analysis. The observed reaction products correspond to those identified with other techniques. Of relevance for future mechanistic modelling, is the point that conditions of excess d-limonene favoured the formation of the d-limonene SOZ (major product), which was observed to be quite stable in dry and humid air, without oxidants. The d-limonene/ozone ratio was observed to be crucial for the stability of the SOZ, because it is prone to ozonolysis, and no SOZ could be detected in completely reacted 1:1 mixtures.     

Direct quantification of organic acids in aerosols by desorption electrospray ionization mass spectrometry

Desorption electrospray ionization mass spectrometry (DESI-MS) is a novel analytical technique for direct surface analysis under ambient conditions. In this work, we report the first application of DESI-MS to the analysis of organic acids in atmospheric aerosols. We took oxalic and oleic acids as two typical representatives of the particulate organic acids. Experimental parameters for DESI-MS were optimized to enhance the signal intensity. Calibrations for both acids showed great linearity over a concentration range of 5 orders of magnitude with correlation coefficients R²>0.99. The relative standard deviation (RSD) was less than 10% for oxalic acid and within 15% for oleic acid measurement. The detection limits for oxalic acid and oleic acid are about 1 pg mm^?2 with 5–10 s sampling time. Mass concentrations of organic acids in both laboratory-generated biomass burning and ambient aerosols were measured by DESI-MS and the results agree well with the ion chromatography (IC) and GC–MS values. This work demonstrates that DESI-MS is a promising method for rapid quantitative analysis of organic acids in atmospheric aerosols.     

The determination of toxaphene in environmental samples by negative ion electron capture high resolution mass spectrometry

A method is described for the analysis of toxaphene in environmental samples by high resolution gas chromatography high resolution mass spectrometry in selected ion electron capture negative ion mode. Toxaphene is detected by monitoring [M-Cl]- fragments ions of chlorobornanes (Cl6-Cl10) and chlorobornenes (Cl6-Cl7) using formal ion ratio criteria. The method shows high sensitivity and excellent specificity for the detection of chlorobornanes with negligible interference from of a wide range of common environmental organochlorines including chlordanes, PCBs and PCB-oxygen adducts. The analytical scheme is applicable to sediment and biological tissue samples and typically provide sample detection limits of less than 0.2 ng/g technical toxaphene for a 10 g sample.     

Vapor-phase concentrations of PAHs and their derivatives determined in a large city: Correlations with their atmospheric aerosol concentrations

Thirteen PAHs, five nitro-PAHs and two hydroxy-PAHs were determined in 55 vapor-phase samples collected in a suburban area of a large city (Madrid, Spain), from January 2008 to February 2009. The data obtained revealed correlations between the concentrations of these compounds and a series of meteorological factors (e.g., temperature, atmospheric pressure) and physical–chemical factors (e.g., nitrogen and sulfur oxides). As a consequence, seasonal trends were observed in the atmospheric pollutants. A “mean sample” for the 14-month period would contain a total PAH concentration of 13 835 ± 1625 pg m⁻³ and 122 ± 17 pg m⁻³ of nitro-PAHs. When the data were stratified by season, it emerged that a representative sample of the coldest months would contain 18 900 ± 2140 pg m⁻³ of PAHs and 150 ± 97 pg m⁻³ of nitro-PAHs, while in an average sample collected in the warmest months, these values drop to 9293 ± 1178 pg m⁻³ for the PAHs and to 97 ± 13 pg m⁻³ for the nitro-PAHs. Total vapor phase concentrations of PAHs were one order of magnitude higher than concentrations detected in atmospheric aerosol samples collected on the same dates. Total nitro-PAH concentrations were comparable to their aerosol concentrations whereas vapor phase OH-PAHs were below their limits of the detection, indicating these were trapped in airborne particles.     

Airborne concentrations of toxaphene congeners at Point Petre (Ontario) using gas-chromatography-electron capture negative ion mass spectrometry (GC-ECNIMS).

A reliable analytical method has been developed using GC-ECNIMS for the determination of individual toxaphene congeners in ambient air. To allow a reasonable comparison with previous data for toxaphene reported by Muir and co-workers using GC-ECD, this method has adopted their approach of focussing upon the identification and quantification of specific peaks or clusters ("T" species) typically observed in environmental samples, with the sum of these "T" species then being reported as "total toxaphene". Technical toxaphene has been used as the analytical standard, but independent response factors have been assigned to the target peaks and clusters. Because of the appreciable variability in ECNIMS response shown by individual toxaphene congeners, this is considered to be a reasonable and potentially more accurate procedure than the application of a "single response factor" used by many other workers. The methodology has been used for the determination of toxaphene in air samples collected over the annual cycle in 1992 and then from October 1995 to September 1997 at Point Petre, Ontario. Of the forty-four calibrated components, only 10 were detected in all of the air samples collected over the latter 2-year period. Airborne concentrations of toxaphene (defined as the sum of the calibrated components) range from 0.9 pg/m3 to 10.1 pg/m3. A clear seasonality has been observed, with a summer-to-winter concentration ratio of about 6.     

High-molecular weight sulfur-containing aromatics refractory to weathering as determined by Fourier transform ion cyclotron resonance mass spectrometry

Biomarkers and low-molecular weight polyaromatic compounds have been extensively studied for their fate in the environment. They are used for oil spill source identification and monitoring of weathering and degradation processes. However, in some cases, the absence or presence of very low concentration of such components restricts the access of information to spill source. Here we followed the resistance of high-molecular weight sulfur-containing aromatics to the simulated weathering condition of North Sea crude oil by ultra high-resolution Fourier transform ion cyclotron resonance mass spectrometry. The sulfur aromatics in North Sea crude having double bond equivalents (DBE) from 6 to 14 with a mass range 188-674 Da were less influenced even after 6 months artificial weathering. Moreover, the ratio of dibenzothiophenes (DBE 9)/naphthenodibenzothiophenes (DBE 10) was 1.30 and 1.36 in crude oil and 6 months weathered sample, respectively reflecting its weathering stability. It also showed some differences within other oils. Hence, this ratio can be used as a marker of the studied crude and accordingly may be applied for spilled oil source identification in such instances where the light components have already been lost due to environmental influences.     

Estimating the contribution of point sources to atmospheric metals using single-particle mass spectrometry

Single-particle mass spectra were collected using an Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) during December of 2003 and February of 2004 at an industrially impacted location in East St. Louis, IL. Hourly integrated peak areas for twenty ions were evaluated for their suitability in representing metals/metalloids, particularly those reported in the US EPA Toxic Release Inventory (TRI). Of the initial twenty ions examined, six (Al, As, Cu, Hg, Ti, and V) were found to be unsuitable due to strong isobaric interferences with commonly observed organic fragments, and one (Be) was found to have no significant signal. The usability of three ions (Co, Cr, and Mn) was limited due to suspected isobaric interferences based on temporal comparisons with commonly observed organic fragments. The identity of the remaining ions (Sb, Ba, Cd, Ca, Fe, Ni, Pb, K, Se, and Zn) was substantiated by comparing their signals with the integrated hourly signals of one or more isotope ions. When compared with one-in-six day integrated elemental data as determined by X-ray fluorescence spectroscopy (XRF), the daily integrated ATOFMS signal for several metal ions revealed a semi-quantitative relationship between ATOFMS peak area and XRF concentrations, although in some cases comparison of these measurements were poor at low elemental concentrations/ion signals due to isobaric interferences. A method of estimating the impact of local point sources was developed using hourly integrated ATOFMS peak areas, and this method attributed as much as 85% of the concentration of individual metals observed at the study site to local point sources. Hourly surface wind data were used in conjunction with TRI facility emissions data to reveal likely point sources impacting metal concentrations at the study site and to illustrate the utility of using single-particle mass spectral data to characterize atmospheric metals and identify point sources.     

Synthesis and relative response factors for the 22 tetrachlorodibenzo-p-dioxins (TCDDs) by electron-impact ionization mass spectrometry

We report the response factors of all of the tetrachlorodibenzo-p-dioxins (TCDDs) relative to 2, 3, 7, 3-TCDD by electron-impact ionization mass spectrometry. We used CP SIL 88 capillary column interfaced a ZAB-2F high-resolution mass spectrometer operating at 10,000 resolving power     

Characterization of biomass pyrolysis vapors with molecular beam, single photon ionization time-of-flight mass spectrometry

A single photon ionization, molecular beam sampling, reflectron time-of-flight mass spectrometer (SPI/MBTOFMS) has been developed and used to study pyrolysis products from a selection of biomass materials. Spectra are characterized by high resolution and decreased fragmentation compared to electron-impact ionization mass spectra from related molecular beam mass spectrometer systems equipped with quadrupole mass analyzers.     

Determination of toxic cyclic heptapeptides by liquid chromatography with detection using ultra-violet, protein phosphatase assay and tandem mass spectrometry

Microcystins, toxic cyclic heptapeptides and nodularin-R, a toxic cyclic pentapeptide, were determined using liquid chromatography (LC) with detection using photo-diode array ultra-violet (PDA-UV) and protein phosphatase (PP) assay. Positive fractions were analysed for toxins using collision-induced dissociation (CID) and tandem MS/MS experiments which were carried out simultaneously using electrospray ion-trap instrumentation. Reversed-phase liquid chromatography (LC) using an acetonitrile/water gradient was used for the LC-MS(2) determination of six microcystins standards and nodularin. The molecular related ion species, [M+H](+)([M+2H](2+) in the case of MC-RR), were used as the precursor ions for MS(2) experiments. Optimum calibration and reproducibility data were obtained for MC-LR using LC-MS(2); 0.1-5.0 microg/ml, r2 = 0.992 (n = 3); % RSD < or =7.3 at 0.25 microg MC-LR/ml (n = 3). The detection limit (S/N = 3) was better than 0.1 ng. Water samples for microcystin analysis were first screened using protein phosphatase (PP) assays and positives were concentrated using C-18 solid-phase extraction. The developed method was applied to examine a lake in Ireland contaminated by Microcystis sp. and MC-LR and MC-LA were identified.     

Investigating the chemical nature of humic-like substances (HULIS) in North American atmospheric aerosols by liquid chromatography tandem mass spectrometry

The high-molecular weight water-soluble organic compounds present in atmospheric aerosols underwent functional-group characterization using liquid chromatography tandem mass spectrometry (LC-MS/MS), with a focus on understanding the chemical structure and origins of humic-like substances (HULIS) in the atmosphere. Aerosol samples were obtained from several locations in North America at times when primary sources contributing to organic aerosol were well-characterized: Riverside, CA, Fresno, CA, urban and peripheral Mexico City, Atlanta, GA, and Bondville, IL. Chemical analysis targeted identification and quantification of functional groups, such as aliphatic, aromatic, and bulk carboxylic acids, organosulfates, and carbohydrate-like substances that comprise species with molecular weights (MW) 200–600 amu. Measured high-MW functional groups were compared to modeled primary sources with the purpose of identifying associations between aerosol sources, high-MW aerosol species, and HULIS. Mobile source emissions were linked to high-molecular weight carboxylic acids, especially aromatic acids, biomass burning was associated with carboxylic acids and carbohydrate-like substances, and secondary organic aerosol (SOA) correlated well with the total amount of HULIS measured, whereas organosulfates showed no correlation with aerosol sources and exhibited unique spatial trends. These results suggested the importance of motor vehicles, biomass burning, and SOA as important sources of precursors to HULIS. Structural characteristics of atmospheric HULIS were compared to terrestrial humic and fulvic acids and revealed striking similarities in chemical structure, with the exception of organosulfates which were unique to atmospheric HULIS.     

Congener group patterns of chloroparaffins in marine sediments obtained by chloride attachment chemical ionization and electron capture negative ionization

Congener group patterns of technical short chain and medium chain chloroparaffins (SCCP and MCCP) were determined by electron capture negative ionization (ECNI) and chloride attachment chemical ionization (CACI) mass spectrometry (MS). In contrast to CACI-MS, congener patterns obtained by ECNI showed always a shift to the next higher chlorinated congener and carbon chain length group. Consequently, the calculated molecular masses and chlorine contents were higher for ECNI (factor 1.10+/-0.03 and 1.09+/-0.03, respectively). ECNI/CACI ratios in sediment samples from the North and Baltic Sea were also slightly higher. However, a more pronounced shift of the congener pattern for a given carbon chain length to congeners with 2-3 more chlorine atoms was observed. SCCP and MCCP concentrations obtained by ECNI-MS were in the range of 8-63ngg(-1) (North Sea) and 22-149ngg(-1) dry weight (Baltic Sea). MCCP levels were highest in all samples (MCCP/SCCP factor 1.1-3.2).     

Quantification of low levels of organochlorine pesticides using small volumes (<or=100 microl) of plasma of wild birds through gas chromatography negative chemical ionization mass spectrometry

A solid phase extraction and gas chromatography with negative chemical ionization mass spectrometry in scan mode (GC-NCI-MS) method was developed to identify and quantify for the first time low levels of organochlorine pesticides (OCs) in plasma samples of less than 100 microl from wild birds. The method detection limits ranged from 0.012 to 0.102 pg/microl and the method reporting limit from 0.036 to 0.307 pg/microl for alpha, gamma, beta and delta-hexachlorocyclohexane (HCH), heptachlor, aldrin, heptachlor epoxide, endosulfan I, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p,p'-DDE), dieldrin, endrin, endosulfan-II, endrin-aldehyde and endosulfan-sulfate. Pesticide levels in small serum samples from individual Falco sparverius, Sturnella neglecta, Mimus polyglottos and Columbina passerina were quantified. Concentrations ranged from not detected (n/d) to 204.9 pg/microl for some OC pesticides. All levels in the food web in and around cultivated areas showed the presence of pesticides notwithstanding the small areas for agriculture existing in the desert of Baja California peninsula.     

A simplified approach to the indirect evaluation of the chemical composition of atmospheric aerosols from PM mass concentrations

The present work shows a straightforward procedure to indirectly estimate the chemical composition at a given site only from the determination of the PM concentrations, and the classification of the days according to the main meteorological scenarios. A previous study based on the mean chemical composition associated to the main meteorological scenarios is required.This experiment has been carried out with data from two monitoring sites in the North-Western Mediterranean, one regional and one suburban background. At both sites, one-year datasets on chemical PM₁₀ composition were obtained. Based on these datasets, the mean PM₁₀ compositions according to the most relevant meteorological situations were calculated for both locations. After that, the reconstruction of the chemical composition for all the days with available PM₁₀ concentrations was completed. Subsequently, the estimated PM₁₀ composition was compared with that determined experimentally. The comparison between the rebuilt and the experimental results was very satisfactory in the case of the regional background site, and relatively replaced in the other case. Furthermore, the validation of the method at the regional background site has been conducted from the reconstruction of a 4-year data base, and subsequent comparison with the experimental chemical composition.Our results show that it is possible to attain a good approach to the chemical composition at regional background sites, where local emission sources are negligible. Conversely, when the local sources rise in importance, i.e., at a suburban background site, the approach is suitable only for those components with a more regional origin and/or those from long range transport of air masses.     

PCB mass transfer coefficients determined by application of a water surface sampler

A water surface sampler (WSS) was employed in combination with greased surface deposition plates (GSDPs) to measure the particulate dry deposition and gas exchange of polychlorinated biphenyls (PCBs) in Chicago, IL. Vapor phase PCB fluxes were calculated by subtracting the particulate fluxes obtained from GSDPs from total (particulate+gas) fluxes obtained from the WSS. Vapor phase PCB fluxes were divided by ambient air concentrations measured with a high volume sampler to calculate overall gas phase PCB mass transfer coefficients (K(G)). The calculated average PCB MTC was 0.54+/-0.47 cm s(-1). This experimentally determined average gas phase overall mass transfer coefficient, K(G), agreed well with the ones reported from studies using similar techniques and agreed well with modeled values obtained using MTC correlations developed for the WSS.