Determination of carbonyls using liquid chromatography-mass spectrometry with atmospheric pressure chemical ionization

A liquid chromatographic method for the determination of aldehydes and ketones based on mass spectrometric detection is described. Recently developed modular derivatizing agents are employed for analysis. These hydrazine reagents, e.g. 4-dimethylamino-6-(4-methoxy-1-naphthyl)-1,3,5-triazine-2-hydrazine (DMNTH), react with the carbonyl compounds with the formation of the respective hydrazones, which are separated by HPLC-MS with atmospheric pressure chemical ionization in the positive mode. Electrospray ionization may also be used for analysis. Particular focus is directed on various calibration approaches, including external calibration with standard solutions and internal calibration with a hydrazone standard of cyclobutanone, an aldehyde not likely to occur in real samples. A second approach for internal calibration is based on the 13C2-labelled acetaldehyde hydrazone standard. Different calibration approaches may then be used for the analysis of real samples. Limits of detection range from 2 x 10(-8) to 5 x 10(-8) mol L-1 for a series of hydrazones, including hydrazones of saturated aldehydes with alkyl chain lengths from 1 to 7 carbon atoms, and hydrazones of selected unsaturated and aromatic aldehydes as well as ketone hydrazones.     

Arsenic compounds in the haemolymph of the Dungeness crab, Cancer magister, as determined by using HPLC on-line with inductively coupled plasma mass spectrometry

Arsenobetaine, two arsenosugars, dimethylarsinate and several unidentified arsenic species were detected in extracts of the haemolymph of the Dungeness crab, Cancer magister, by using HPLC-ICP-MS. This is the first report of the presence of arsenosugars in the haemolymph/blood of marine animals. Total, extractable and residual arsenic concentrations were determined by ICP-MS. The concentration of total arsenic was in the range of 1.4-3.8 [micro sign]g ml(-1). Nearly all (98%) the arsenic was found to be extractable, and accounted for primarily by arsenobetaine, two arsenosugars and dimethylarsinate. The results demonstrate that arsenic compounds present in the diet of crabs are not fully metabolized in the gut. They are, at least partly, taken up into the haemolymph. The concurrence of arsenobetaine and arsenosugars suggests that the use of repeated haemolymph sampling in crustaceans could facilitate investigations into the kinetics of the biotransformation pathways of arsenic compounds. Finally, the present study clearly demonstrates the unique capabilities of HPLC-ICP-MS for the detection and identification of minor arsenic components amongst the predominant arsenobetaine.     

Statistical distributions of trace metal concentrations in the northwestern Mediterranean atmospheric aerosol

The concentrations of 11 crustal and anthropogenic trace metals (Li, Al, V, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb) were measured from 2006 to 2008 in the atmospheric aerosol at a northwestern Mediterranean coast (station of Cap Ferrat, situated on the southeastern coast of France). Statistical models (lognormal, Weibull, and gamma) that best represented the trace metal distribution for this environment are described. The lognormal model was selected for the distributions of (in decreasing strength of the fit) Al, Co, Li, Zn, Mn, Cu, Pb, and Cd, i.e., metals that are introduced into the atmospheric aerosol by pulses inducing temporal variability in their concentrations. The gamma model was associated with Fe, i.e., metals that exhibit less inter-annual variability than the former trace metals. The third mode (Weibull) represented the distribution of the concentrations of V and Ni. The statistical approach presented in this study contributed to better define and constrain the distribution of the 11 trace metals of the atmospheric aerosol from the northwestern Mediterranean coast. In a close future, knowledge of these statistical distributions will allow using convolution models to separate their natural and anthropogenic contributions, therefore increasing our ability to study anthropogenic emissions of trace metals and their impact on the environment.     

Determination of six anti-infectives in wastewater using tandem solid-phase extraction and liquid chromatography-tandem mass spectrometry

A rugged and specific method based on tandem solid-phase extraction and liquid chromatography-tandem mass spectrometry for the determination of anti-infectives in raw sewage and wastewater plant effluents was developed. Analyte recoveries from spiked effluents ranged from 68 to 104%. Two specific selected reaction monitoring transitions and their peak area ratios were used to avoid false positives and confirm the presence of the targeted substances. Detection limits allowed low nanogram per litre detection (0.3-22 ng L(-1)). The method was successfully applied to real samples from the Montréal wastewater treatment plant. All the studied anti-infectives were found in the wastewater samples in concentrations ranging from 39 to 276 ng L(-1). Mean flows of anti-infectives were estimated from effluent concentrations and it was found that large amounts (>118 g day(-1) up to 830 g day(-1)) are discharged in the receiving waters of the St Lawrence River.     

Estimation of the contributions of long range transported aerosol in East Asia to carbonaceous aerosol and PM concentrations in Seoul, Korea using highly time resolved measurements: a PSCF model approach

The contributions of long range transported aerosol in East Asia to carbonaceous aerosol and particulate matter (PM) concentrations in Seoul, Korea were estimated with potential source contribution function (PSCF) calculations. Carbonaceous aerosol (organic carbon (OC) and elemental carbon (EC)), PM(2.5), and PM(10) concentrations were measured from April 2007 to March 2008 in Seoul, Korea. The PSCF and concentration weighted trajectory (CWT) receptor models were used to identify the spatial source distributions of OC, EC, PM(2.5), and coarse particles. Heavily industrialized areas in Northeast China such as Harbin and Changchun and East China including the Pearl River Delta region, the Yangtze River Delta region, and the Beijing-Tianjin region were identified as high OC, EC and PM(2.5) source areas. The conditional PSCF analysis was introduced so as to distinguish the influence of aerosol transported from heavily polluted source areas on a receptor site from that transported from relatively clean areas. The source contributions estimated using the conditional PSCF analysis account for not only the aerosol concentrations of long range transported aerosols but also the number of transport days effective on the measurement site. Based on the proposed algorithm, the condition of airmass pathways was classified into two types: one condition where airmass passed over the source region (PS) and another condition where airmass did not pass over the source region (NPS). For most of the seasons during the measurement period, 249.5-366.2% higher OC, EC, PM(2.5), and coarse particle concentrations were observed at the measurement site under PS conditions than under NPS conditions. Seasonal variations in the concentrations of OC, EC, PM(2.5), and coarse particles under PS, NPS, and background aerosol conditions were quantified. The contributions of long range transported aerosols on the OC, EC, PM(2.5), and coarse particle concentrations during several Asian dust events were also estimated. We also investigated the performance of the PSCF results obtained from combining highly time resolved measurement data and backward trajectory calculations via comparison with those from data in low resolutions. Reduced tailing effects and the larger coverage over the area of interest were observed in the PSCF results obtained from using the highly time resolved data and trajectories.     

Microscopic and chemical studies of metal particulates in tree bark and attic dust: evidence for historical atmospheric smelter emissions, Humberside, UK

Tree barks and attic dusts were examined as historical archives of smelter emissions, with the aim of elucidating the pathways of pollution associated with a plume of Sn and Pb contamination in top soils, found close to the former Capper Pass smelter, Humberside, UK. Samples were collected from three villages within the area of the contamination plume. Scanning electron microscopy (SEM) and bulk chemical analyses were used to assess particle type, number and deposition patterns. SEM analysis of dusts and bark revealed that Sn and Pb particles were present in samples from all three villages along with copper, zinc and iron particles. These were almost entirely <10 microm in diameter and occurred mostly as oxides, frequently forming clusters of sub-micron crystals. Samples further from the smelter contained considerably fewer particles. We present images of smelter derived Sn particles. Chemical assays of the barks and attic dusts demonstrated that concentrations of Sn, Pb, Cu, As, Sb and Cd diminished with increasing distance from the source. Strong positive correlations were found between Sn and Pb, As, Sb and Cd in the attic dusts. Enrichment factors (EF) were calculated for these trace elements based on topsoil element concentrations obtained from the soil survey of the study area. Decreases in these trace element concentrations and EF values with distance away from the smelter are consistent with trends found in the soil survey for Sn and Pb and are typical of deposition patterns around smelter stacks. The study demonstrates that tree bark and attic dusts can be effective archives of metal particulates deposited from large static emission sources.     

Monitoring of the natural environment by chemical speciation of elements in aerosol and sediment samples

The development of a monitoring network for chemical speciation of elements of aerosol and sediment samples collected at Lake Balaton has been carried out. Sequential leaching procedures for the determination of the distribution of elements in aerosols (3 steps) and sediments (4 steps) were used. These methods were recently successfully applied to describe environmentally mobile and stable fractions of toxic metals. In aerosol matrices the partition of elements was accomplished by particle size and chemical bonding. In sediments the distribution was performed by chemical bonding. The processes are called fractionation of elements. Particular attention was paid to distinguishing between environmentally mobile and environmentally immobile fractions because these represent the two extreme modes by which the metals are bound to solid matrices. The monitoring objectives were to assess pollution effects on man and his environment and to identify any possible cause and effect relationship between pollutant concentrations and health effects. The results of dry and wet deposition rates showed that most of the toxic metals were dissolved in an aqueous phase and the wet deposition played an important role. It has been found that, while the concentration of Cd and Pb in aerosols is low (0.7 and 29 ng m(-3), respectively), environmentally mobile fractions are considerable. Based upon the data it can be concluded that the effect of the anthropogenic sources on the quality of the lake is minor. This has been the first attempt to correlate speciation results between aerosols and sediments.     

A study on the behaviour of pesticides and their transformation products in the Scheldt estuary using liquid chromatography-electrospray tandem mass spectrometry

Off-line solid-phase extraction (SPE) combined with liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS-MS) was used to study the estuarine behaviour of the polar pesticides, atrazine, chloridazon, diuron and metolachlor, and their transformation products (TPs), hydroxyatrazine (HA), desisopropylatrazine (DIA), desethylatrazine (DEA), 3,4-dichlorophenylmethylurea (DPMU) and monuron. The compounds were identified by comparing their LC retention times and product-ion spectra with those of standard solutions. In all but one case the detection limits of the method were sufficient to determine the compounds of interest over the entire salinity range in the estuary. The concentrations of the dissolved pesticides ranged from 70 ng l-1 for chloridazon to 1350 ng l-1 for diuron. The levels of TPs were 3-8% of the levels of their parent pesticide. The mixing plots of polar pesticides and their TPs indicated that TPs, which are present in fresh river water, are conservatively transported to the sea and that no additional amounts of TPs are formed during their transport through the estuary. The one exception was HA, of which approximately 10% of the amount transported to the North Sea is formed in the lower part of the estuary by photochemical oxidation of atrazine. The latter was concluded from the ratios of each analyte over the sum total of the parent pesticide and all TPs along the salinity gradient, which proved to be a useful tool for identifying such estuarine transformations.     

Determination of bismuth in environmental samples by slurry sampling graphite furnace atomic absorption spectrometry using combined chemical modifiers

Persistence behavior of insecticides chlorpyriphos, profenofos, triazophos, cypermethrin, and deltamethrin following the use of three combination formulations Action 505 (chlorpyriphos?+?cypermethrin), Roket 44EC (profenofos?+?cypermethrin), and Anaconda Plus (triazophos?+?deltamethrin) was studied in cabbage following the spray application at the recommended and double doses. Bio-efficacy of these formulations was also evaluated against mustard aphids (Lipaphis erysimi Kaltenbach) and diamondback moth (Plutella xylostella L.). The residues of different insecticides persisted for 5–8 days at low dose and 8–12 days at high dose. The residues dissipated with time and 87–100 % dissipation was recorded on the 8th day. The half-life values varied from 0.4 to 1.6 days. Based on the acceptable daily intake (ADI) values, a safe waiting period of 1 day has been suggested for the formulations Action 505 and Roket 44EC and 3 days for Anaconda Plus at the recommended dose of application. Action (1.6 L/ha) treatment was found to be the best as it significantly reduced the diamondback moth (DBM) (~60 %) and aphid population (~70 %) besides giving the highest yield (170 % increase over control).     

Seasonal variation, source, and regional representativeness of the background aerosol from two remote sites in western China

Using observations from two remote sites during July 2004 to March 2005, we show that at Akdala (AKD, 47° 06′ N, 87° 58′ E, 562 m asl) in northern Xinjiang Province, there were high wintertime loadings of organic carbon (OC), elemental carbon (EC), and water-soluble (WS) ${\rm SO}_{4}^{2-}$ , ${\rm NO}_{3}^{2-}$ , and ${\rm NH}_{4}^{+}$ , which is similar to the general pattern in most areas of China and East Asia. However, at Zhuzhang (ZUZ, 28° 00′ N, 99° 43′ E, 3,583 m asl) in northwestern Yunnan Province, the aerosol concentrations and compositions showed little seasonal variation except for a decreasing trend of OC from August to autumn–winter. Additionally, the OC variations dominated the seasonal variation of PM₁₀ (particles ≤10 μm diameter) level. Chemical characteristics combined with transport information suggested sea salt origin of ionic Na^?+?, Mg^2?+?, and Cl^??? at ZUZ. At AKD, ionic Ca^2?+?, Mg^2?+?, Na^?+?, and Cl^??? primarily originated from salinized soil. Furthermore, the WS Ca^2?+? contributions (5.4–6%) to the PM₁₀ mass during autumn, winter, and early spring reflected a constant dust component. The results of this study indicated that both sites were regionally representative. However, the representative regions and scales of these background sites may vary seasonally as the regional atmospheric transport patterns change. Seasonal variations in the background aerosol levels from these two areas need to be considered when evaluating the regional climate effects of the aerosols.     

Study of chemical composition and morphology of airborne particles in Chandigarh, India using EDXRF and SEM techniques

The elemental composition and morphology of aerosols, collected from March 95 to February 96 and March 96 to August 96 respectively in the city of Chandigarh, India is determined using Energy Dispersive X-ray fluorescence and scanning electron microscopic techniques. The elemental concentration levels are found to be higher by a factor of 2-7 in the spring season as compared to the rainy season. The concentration of spherical and non-spherical (i.e. elongated) aerosols is more in the spring season and is reduced drastically in the rainy season due to the prominent wash out effect of rains. More accurate particle classification and source identification is obtained when based on combination of chemical composition and particle morphology. Possible sources identified from this analysis are soil dust, Industrial activity, Agricultural and Garbage burning, Maritime aerosols and Automobile exhaust.     

Five-year monitoring study of chemical characteristics of Wet atmospheric precipitation in the southern region of Jordan

Wet atmospheric samples were collected from different locations in the southern region of Jordan during a 5-year period (October 2006 to May 2011). All samples were analyzed for pH, EC, major ions (Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2?), and trace metals (Fe²⁺, Al³⁺,Cu²⁺, Pb²⁺, and Zn²⁺). The highest ion concentrations were observed during the beginning of the rainfall events because large amounts of dust accumulated in the atmosphere during dry periods and were scavenged by rain. The rainwater in the study area is characterized by low salinity and neutral pH. The major ions found in rainwater followed the order of HCO₃?>?Cl^??>?SO₄ ^2? and Ca²⁺?>?Na⁺ > Mg²⁺ > NH₄ ⁺ > K⁺. Trace metals were identified to be of anthropogenic origin resulting from cement and phosphate mining activities located within the investigated area and from heating activities during the cold period of the year (January to April). The wet precipitation chemistry was analyzed using factor component analysis for possible sources of the measured species. Factor analysis (principal component analysis) was used to assess the relationships between the concentrations of the studied ions and their sources. Factor 1 represents the contribution of ions from local anthropogenic activities, factor 2 represents the contribution of ions from natural sources, and factor 3 suggests biomass burning and anthropogenic source. Overall, the results revealed that rainwater chemistry is strongly influenced by local anthropogenic sources rather than natural and marine sources, which is in a good agreement with the results obtained by other studies conducted in similar sites around the world.     

Determination of 14 amines in air samples using midget impingers sampling followed by analysis with ion chromatography in tandem with mass spectrometry

An Ion Chromatography-Mass Spectrometry (IC-MS) method was developed for the simultaneous quantification of 14 volatile amines in air. The method includes collection of compounds into two midget impingers in a row filled with 15 ml of ultrapure water. The analytical performances with mass spectrometry detection were compared to those obtained with classical conductivity detection. The use of mass spectrometry detection (in SIM mode) overcomes most of the coelutions encountered with conductivity detection. Although the linearity domain of calibrations is reduced for the MS detection as compared with the CD detection, the detection limits in MS detection are highly lowered allowing the quantification of amines at the levels of μg m(-3) in air with a good accuracy for most compounds (RSD of less than 10%). This method was successfully applied to the analysis of amines released from polyurethane foams. Seven amines were identified and some in high concentrations, like dimethylaminoethanol, NIAX and TEDA.     

Simultaneous analysis of endosulfan, chlorpyrifos, and their metabolites in natural soil and water samples using gas chromatography-tandem mass spectrometry

Analysis of endosulfan, chlorpyrifos, and their nonpolar metabolites in extracts from environmental aqueous and soil samples was performed using a gas chromatography-tandem mass spectrometry (GC–MS/MS) technique. Full-scan GC–MS analysis showed poor sensitivity for some of the metabolites (endodiol and endosulfan ether). A multisegment MS/MS method was developed and MS/MS parameter isolation time, excitation time, excitation voltage, and maximum excitation energy were optimized for chosen precursor ions to enhance selectivity and sensitivity of the analysis. The use of MS/MS with optimized parameters quantified analytes with significantly higher accuracy, and detection limits were lowered to ~1/6th compared with the full-scan method. Co-eluting compounds, chlorpyrifos and chlorpyrifos oxon, were also analyzed successfully in the MS/MS mode by choosing exclusive precursor ions. Analysis of soil and water phase samples from contaminated soil slurry bioreactors showed that the MS/MS method could provide more reliable estimates of these pesticide and metabolites (especially those present in low concentrations) by annulling interferences from soil organic matter.     

Determination of toxic inorganic elements pollution in ground waters of Kahuta Industrial Triangle Islamabad, Pakistan using inductively coupled plasma mass spectrometry

The present study deals with the ground water quality assessment in Kahuta Industrial Triangle Islamabad, Pakistan. The objective of the study was to assess ground water quality against the drinking water standards for various toxic inorganic elements. Representative groundwater samples were collected and analyzed in the Water Quality Laboratory of Pakistan Council of Research in Water Resources (PCRWR) at Islamabad, Pakistan. The samples were run on ICP-MS (Inductively coupled plasma mass spectrometry), which has the capability to separate and quantify 70 elements at a time. One of the finding of study is that ICP-MS is a very good tool to analyze broad range of toxic inorganic elements to the level of parts per billion (ppb). World Health Organization drinking water standards shows that these toxic inorganic elements such as heavy metals even at this concentration level (ppb) are injurious to human health. This analysis indicated pollution of various toxic elements including Selenium. Vertical leachate through industrial waste septic tanks is identified as major cause of groundwater pollution in the Industrial Triangle. Monitoring of the septic tanks and groundwater quality in study area is suggested along with remedial measures.     

Screening and quantification of emerging contaminants in Periyar River,Kerala (India) by using high-resolution mass spectrometry (LC-Q-ToF-MS)

The presence of emerging contaminants (ECs) in different aquatic systems may contribute to hazardous effects on aquatic organisms and subsequently on human health. In the present work, liquid chromatography coupled to a quadrupole time of flight mass spectrometer (LC-Q-ToF-MS) was used to identify and quantify a series of ECs in Periyar River in Aluva region, Kerala, India. The water samples were pre concentrated using solid-phase extraction (SPE) prior to analysis. The compounds were probed in both positive and negative ionization mode using electro spray ionization (ESI). Method validations were performed for linearity, limit of detection (LOD), limit of quantification (LOQ), accuracy, and precision (intraday and inter day). The ECs were quantified using standard calibration curve. The identified nine ECs include pharmaceuticals, personal care products, steroids, surfactants, and phthalate. A relatively high concentration was observed in the case of 2-dodecyl benzene sulfonic acid (1012 ng/l) and low concentration was observed for lignocaine (4.3 ng/l; since this is below LOQ, the value is only approximate). In addition, we have identified another 28 organic compounds using the technique of non-target analysis out of which seven compounds fall in the category of surfactants. Being the first report on ECs in Periyar River, the data is very important as this river is one of the biggest and important rivers of Kerala having several purification units for drinking water in the province.     

An alternative method for the determination of estrogens in surface water and wastewater treatment plant effluent using pre-column trimethylsilyl derivatization and gas chromatography/mass spectrometry

A procedure using pre-column trimethylsilyl derivatization and gas chromatography/ mass spectrometry (GC/MS) was developed and applied in determining trace estrogens in complex matrix. Main conditions were optimized, including pH value, salinity of water sample, elution reagents, clean procedure, derivative solvent and temperature. The optimized method was used to determine steroid estrogens in surface water and effluents of wastewater treatment plant (WWTP). Low detection limits of 0.01, 0.03, 0.03, 0.07, 0.09 and 0.13 ng/l for DES, E1, E2, EE2, E3 and E(V), respectively were obtained under optimism condition. No apparent interferences appeared in chromatography in comparison with ultrapure water blank. Mean recovery ranged from 72.6% to 111.0% with relative standard deviation of 1.1-4.6% for spiked surface water, and from 66.6% to 121.1% with relative standard deviation of 1.5-4.7% for spiked effluent of WWTP. The results suggested that the optimized method provides a robust solution for the determination of trace steroid estrogens in complex matrix.     

10th Anniversary review: applications of analytical techniques in laboratory studies of the chemical and climatic impacts of mineral dust aerosol in the Earth's atmosphere

It is clear that mineral dust particles can impact a number of global processes including the Earth's climate through direct and indirect climate forcing, the chemical composition of the atmosphere through heterogeneous reactions, and the biogeochemistry of the oceans through dust deposition. Thus, mineral dust aerosol links land, air, and oceans in unique ways unlike any other type of atmospheric aerosol. Quantitative knowledge of how mineral dust aerosol impacts the Earth's climate, the chemical balance of the atmosphere, and the biogeochemistry of the oceans will provide a better understanding of these links and connections and the overall impact on the Earth system. Advances in the applications of analytical laboratory techniques have been critical for providing valuable information regarding these global processes. In this mini review article, we discuss examples of current and emerging techniques used in laboratory studies of mineral dust chemistry and climate and potential future directions.