Sample Uptake Research Articles

Non-spectral interferences due to the presence of sulfuric acid in inductively coupled plasma mass spectrometry

Results of a systematic study concerning non-spectral interferences from sulfuric acid containing matrices on a large number of elements in inductively coupled plasma–mass spectrometry (ICP-MS) are presented in this work. The signals obtained with sulfuric acid solutions of different concentrations (up to 5% w w−1) have been compared with the corresponding signals for a 1% w w−1− nitric acid solution at different experimental conditions (i.e., sample uptake rates, nebulizer gas flows and r.f. powers). The signals observed for 128Te+, 78Se+ and 75As+ were significantly higher when using sulfuric acid matrices (up to 2.2-fold for 128Te+ and 78Se+ and 1.8-fold for 75As+ in the presence of 5 w w-1 sulfuric acid) for the whole range of experimental conditions tested. This is in agreement with previously reported observations. The signal for 31P+ is also higher (1.1-fold) in the presence of sulfuric acid. The signal enhancements for 128Te+, 78Se+, 75As+ and 31P+ are explained in relation to an increase in the analyte ion population as a result of charge transfer reactions involving S+ species in the plasma. Theoretical data suggest that Os, Sb, Pt, Ir, Zn and Hg could also be involved in sulfur-based charge transfer reactions, but no experimental evidence has been found. The presence of sulfuric acid gives rise to lower ion signals (about 10–20% lower) for the other nuclides tested, thus indicating the negative matrix effect caused by changes in the amount of analyte loading of the plasma.The elemental composition of a certified low-density polyethylene sample (ERM-EC681K) was determined by ICP-MS after two different sample digestion procedures, one of them including sulfuric acid. Element concentrations were in agreement with the certified values, irrespective of the acids used for the digestion. These results demonstrate that the use of matrix-matched standards allows the accurate determination of the tested elements in a sulfuric acid matrix.

Current challenges in air sampling of semivolatile organic contaminants: sampling artifacts and their influence on data comparability.

With current science and policy needs, more attention is being given to expanding and improving air sampling of semivolatile organic contaminants (SVOCs). However, a wide range of techniques and configurations are currently used (active and passive samplers, different deployment times, different sorbents, etc.) and as the SVOC community looks to assess air measurements on a global scale, questions of comparability arise. We review current air sampling techniques, with a focus on sampling artifacts that can lead to uncertainties or biases in reported concentrations, in particular breakthrough, degradation, meteorological influences, and assumptions regarding passive sampling. From this assessment, we estimate the bias introduced for SVOC concentrations from all factors. Due to the effects of breakthrough, degradation, particle fractions and sampler uptake periods, some current passive and active sampler configurations may underestimate certain SVOCs by 30-95%. We then recommend future study design, appropriateness of sampler types for different study goals, and finally, how the SVOC community should move forward in both research and monitoring to best achieve comparability and consistency in air measurements.

Measurement of cyclic volatile methylsiloxanes in the aquatic environment using low-density polyethylene passive sampling devices using an in-field calibration study – Challenges and guidance

Cyclic volatile methylsiloxanes (cVMS) are used in personal care products and are hydrophobic, volatile and persistent. Their environmental water concentrations are low and are difficult to detect using conventional sampling methods. This study shows the potential of passive sampling for cVMS. We used low-density polyethylene (LDPE) samplers and in-field calibration methods for octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5). 13C-D4 and 13C-D5, methyltris(trimethylsiloxy)silane (MT), tetrakis(trimethylsiloxy)silane (TK), and five deuterated polycyclic aromatic hydrocarbons (PAHs) were used as performance reference compounds (PRCs). Samplers were calibrated (7-d) using effluent at a treatment plant, with uptake of cVMS and losses of the PRCs measured at 12 time-points. Concentrations of D4 (53ngL−1) and D5 (1838ngL−1) were stable in the effluent. Uptake of D4 and loss of 13C-D4 were isotropic and equilibrium was approached by 7-d. Two estimates of sampler uptake rate (Rs) were 2.1Ld−1 and 2.5Ld−1. The estimated log LDPE/water partition coefficient was 4.4. The uptake of D5 was slower (Rs=0.32Ld−1) and equilibrium was not reached. Offloading of 13C-D5, MT and TK were slow, and isotropic behaviour was not demonstrated for D5. Offloading of PAHs followed the predicted pattern for LDPE. Uptake of cVMS appeared to be under membrane control, due to low diffusion coefficients in LDPE. Samplers can monitor time-weighted average concentrations of D4 for less than a week, and D5 for longer periods. LDPE samplers allow cVMS to be determined at lower concentrations than by spot sampling methods.

Assessment of Envi-Carb™ as a passive sampler binding phase for acid herbicides without pH adjustment

The graphitised carbon solid phase extraction (SPE) sorbent Envi-Carb has been used to fabricate glass fibre filter- Envi-Carb “sandwich” disks for use as a passive sampler for acid herbicides. Passive sampler uptake of a suite of herbicides, including the phenoxyacetic acid herbicides 4-chloro-o-tolyloxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 3,6-dichloro-2-methoxybenzoic acid (Dicamba), was achieved without pH adjustment, demonstrating for the first time a suitable binding phase for passive sampling of acid herbicides at neutral pH. Passive sampling experiments with Duck River (Tasmania, Australia) water spiked at 0.5μgL−1 herbicide concentration over a 7d deployment period showed that sampling rates in Duck River water decreased for seven out of eight herbicides, and in the cases of 3,6-dichloro-2-pyridinecarboxylic acid (Clopyralid) and Dicamba no accumulation of the herbicides occurred in the Envi-Carb over the deployment period. Sampling rates for 4-amino-3,5,6-trichloro-2-pyridinecarboxylic acid (Picloram), 2,4-D and MCPA decreased to approximately 30% of the sampling rates in ultrapure water, whilst sampling rates for 2-(4,6-dimethylpyrimidin-2-ylcarbamoylsulfamoyl) benzoic acid, methyl ester (Sulfometuron-methyl) and 3,5,6-Trichloro-2-pyridinyloxyacetic acid (Triclopyr) were approximately 60% of the ultrapure water sampling rate. For methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-D-alaninate (Metalaxyl-M) there was little variation in sampling rate between passive sampling experiments in ultrapure water and Duck River water. SPE experiments undertaken with Envi-Carb disks using ultrapure water and filtered and unfiltered Duck River water showed that not only is adsorption onto particulate matter in Duck River water responsible for a reduction in herbicide sampling rate, but interactions of herbicides with dissolved or colloidal matter (matter able to pass through a 0.2μm membrane filter) also reduces the herbicide sampling rate.

Advantages and effects of nitrogen doping into the central channel of plasma in axially viewed-inductively coupled plasma optical emission spectrometry

The effects and benefits of N2 addition to the central channel of the ICP through the nebulizer gas used in ICP OES with axial view configuration were investigated in the present study. The N2 flow rate, nebulizer gas flow rate, RF power and sample uptake rate were evaluated and compared for two sample introduction systems (pneumatic nebulization/aerosol desolvation and conventional pneumatic nebulization). It was observed that N2 did not affect solution nebulization and aerosol transport but affects the ICP characteristics. The higher thermal conductivity of N2 (in comparison with Ar) changes energy distribution in the ICP, observed by monitoring the signals of Ar emission lines and sodium emission. The ratio Mg(II)-280.270nm/Mg(I)-285.213nm was utilized as a diagnostic tool for plasma robustness. The addition of N2 (20mLmin−1) increased plasma robustness significantly and mitigated effects caused by Na, K and Ca. For 40 spectral lines evaluated, it was observed that the emission signals of ionic spectral lines were in general more affected by N2 than those of atomic spectral lines. Detection limits, precision, sensitivity and linearity of calibration curves obtained using N2-Ar-ICP were almost similar to those obtained using Ar-ICP. The analysis of 5 different reference materials revealed that accuracy was not degraded by adding N2 to the Ar-ICP.

A systematic study on the influence of carbon on the behavior of hard-to-ionize elements in inductively coupled plasma–mass spectrometry

A systematic study on the influence of carbon on the signal of a large number of hard-to-ionize elements (i.e. B, Be, P, S, Zn, As, Se, Pd, Cd, Sb, I, Te, Os, Ir, Pt, Au, and Hg) in inductively coupled plasma–mass spectrometry has been carried out. To this end, carbon matrix effects have been evaluated considering different plasma parameters (i.e. nebulizer gas flow rate, r.f. power and sample uptake rate), sample introduction systems, concentration and type of carbon matrix (i.e. glycerol, citric acid, potassium citrate and ammonium carbonate) and type of mass spectrometer (i.e. quadrupole filter vs. double-focusing sector field mass spectrometer). Experimental results show that P, As, Se, Sb, Te, I, Au and Hg sensitivities are always higher for carbon-containing solutions than those obtained without carbon. The other hard-to-ionize elements (Be, B, S, Zn, Pd, Cd, Os, Ir and Pt) show no matrix effect, signal enhancement or signal suppression depending on the experimental conditions selected. The matrix effects caused by the presence of carbon are explained by changes in the plasma characteristics and the corresponding changes in ion distribution in the plasma (as reflected in the signal behavior plot, i.e. the signal intensity as a function of the nebulizer gas flow rate). However, the matrix effects for P, As, Se, Sb, Te, I, Au and Hg are also related to an increase in analyte ion population caused as a result of charge transfer reactions involving carbon-containing charged species in the plasma. The predominant specie is C+, but other species such as CO+, CO2+, C2+ and ArC+ could also play a role. Theoretical data suggest that B, Be, S, Pd, Cd, Os, Ir and Pt could also be involved in carbon based charge transfer reactions, but no experimental evidence substantiating this view has been found.

Polyoxymethylene passive samplers to monitor changes in bioavailability and flux of PCBs after activated carbon amendment to sediment in the field

Field and laboratory exposures of polyoxymethylene passive samplers to sediments and the water column were applied to monitor changes in bioavailability and flux of polychlorinated biphenyls (PCBs) following a pilot-scale amendment of activated carbon in Grasse River. Following amendment, reductions in passive sampler uptake tracked reductions in bioaccumulation in a freshwater invertebrate, which supports a biological basis for utilizing passive samplers for in situ site investigations following a remediation. Freely dissolved concentrations of PCBs were reduced in sediment pore waters compared to untreated sediments indicating reduced bioavailability of PCBs after activated carbon amendment. Freely dissolved PCB concentrations in sediment pore water in treated sites were also lower than overlying water concentrations indicating a reversal of the sediment from being a source to a sink of PCBs from the water column. These observations indicate that activated carbon amendment to sediment limits contaminant exposure to both the benthic and pelagic food webs through reductions in bioavailability and flux of PCBs into the water column.

Total introduction of microsamples in inductively coupled plasma mass spectrometry by high-temperature evaporation chamber with a sheathing gas stream

A systematic study on the high-temperature Torch Integrated Sample Introduction System (TISIS) for use in Inductively Coupled Plasma Mass Spectrometry (ICP-MS) has been performed. The investigation included the optimization of the relevant parameters (chamber temperature, sheathing gas flow rate, nebulizer gas flow rate, sample uptake rate), the evaluation of its performance characteristics (sensitivity, limits of detection, stability, memory effects, use with the dynamic reaction cell) and representative applications to environmental, biological and clinical samples. Under the optimal conditions (T=150°C; nebulizer gas flow rate of 0.7Lmin−1 along with sheathing gas flow rate of 0.35Lmin−1 and a sample uptake rate of 20μLmin−1), the sensitivity was from 2 to 8 times higher than that measured using a conventional micronebulizer/mini-spray chamber system, due to the enhanced analyte mass transport toward the plasma and the solvent introduction in the vapour form. In addition, for several elements, TISIS provided lower limits of detection than the conventional system, even when the latter worked at 5-fold higher sample uptake rate. Short-term and long-term precision was better than 5%. Spectroscopic interferences arising from common matrices were efficiently removed by the dynamic reaction cell technique. The application of TISIS/ICP-MS to representative certified reference samples (spinach leaves, marine plankton, bone tissue, human blood) proved the suitability of this system for the accurate analysis of limited-size samples.

On-line microwave-based preconcentration device for inductively coupled plasma atomic emission spectrometry: Application to the elemental analysis of spirit samples

A microwave-based thermal nebulizer (MWTN) has been employed for the first time as on-line preconcentration device in inductively coupled plasma atomic emission spectrometry (ICP-AES). By the appropriate selection of the experimental conditions, the MWTN could be either operated as a conventional thermal nebulizer or as on-line analyte preconcentration and nebulization device. Thus, when operating at microwave power values above 100W and highly concentrated alcohol solutions, the amount of energy per solvent mass liquid unit (EMR) is high enough to completely evaporate the solvent inside the system and, as a consequence, the analyte is deposited (and then preconcentrated) on the inner walls of the MWTN capillary. When reducing the EMR to the appropriate value (e.g., by reducing the microwave power at a constant sample uptake rate) the retained analyte is swept along by the liquid-gas stream and an analyte-enriched aerosol is generated and next introduced into the plasma cell. Emission signals obtained with the MWTN operating in preconcentration-nebulization mode improved when increasing preconcentration time and sample uptake rate as well as when decreasing the nozzle inner diameter. When running with pure ethanol solution at its optimum experimental conditions, the MWTN in preconcentration-nebulization mode afforded limits of detection up to one order of magnitude lowers than those obtained operating the MWTN exclusively as a nebulizer.To validate the method, the multi-element analysis (i.e. Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Pb and Zn) of different commercial spirit samples in ICP-AES has been performed. Analyte recoveries for all the elements studied ranged between 93% and 107% and the dynamic linear range covered up to 4 orders of magnitude (i.e. from 0.1 to 1000μgL−1). In these analysis, both MWTN operating modes afforded similar results. Nevertheless, the preconcentration-nebulization mode permits to determine a higher number of analytes due to its higher detection capabilities.

Method development for the determination of alkali metals in samples from pyrochemical reprocessing using ICP-OES and comparison with sector field ICP-MS

An analytical procedure for the reliable determination of the alkaline elements Na, K, and Li in radioactive samples was developed and validated. To this end, a high efficiency, desolvating nebulizer (Apex E) was coupled to a commercial high resolution ICP-OES instrument operated at 1000W. Because of their radioactive nature, all investigated samples were handled in appropriate glove boxes operated in under-pressure, following strict safety and security procedures. After optimization of the ICP-OES operational parameters, detection limits (LODs) of 0.15μg/L, 0.8μg/L, and 1.3μg/L were obtained for Li (λ=670.784nm), Na (λ=589.592nm), and K (λ=766.490nm). Compared to conventional sample uptake rates of 1–2mL/min, the 350μL/min used in this study helped to lower the radiation dose to the ICP-OES operator and produced much less radioactive waste while at the same time improving LODs. Calibration curves were linear up to 4mg/L with a correlation coefficient of better than 0.999. Because of its robust and reproducible performance, no internal standard was required to correct for potential drifts in sensitivity of the ICP-OES. Three certified water reference materials (BCR®-617, LGC6177, SRM® 1643a) were employed to assess the accuracy of the developed ICP-OES procedure, the results of which underpin its reliability. In addition, Na and K concentrations calculated from emission intensities measured at two wavelengths confirmed that each dataset is consistent in itself. A comparison of sector field ICP-MS results of 23 samples originating from pyrochemical reprocessing with the data obtained applying the newly developed ICP-OES procedure revealed that the latter provides a reliable, straightforward and more robust analytical approach to determine Na, K, and Li in radioactive specimens.

Testing the use of passive sampling systems for understanding air mercury concentrations and dry deposition across Florida, USA

This paper describes the use of passive sampling systems and surrogate surfaces for monitoring atmospheric mercury (Hg) concentrations and dry deposition, respectively, in Florida,USA. Although this area has been reported to have low air concentrations, wet deposition values, reported by the Mercury Deposition Network, are some of the highest in the United States, and little is known about the magnitude of dry deposition to the region. To address this uncertainty, dry deposition of gaseous oxidized mercury (GOM) was estimated based on data collected using surrogate surfaces and through the application of a dry deposition model that utilized Tekran® Mercury Analyzer data for three sites (Davie near Fort Lauderdale, Tampa and Pensacola) over a year (July 2009-July 2010). Passive sampler systems for monitoring GOM and total gaseous mercury (TGM) concentrations were also deployed. In general, higher surrogate surface deposition, and GOM and TGM passive sampler uptake were observed at the DVE location. Across all sites, empirically derived dry deposition was higher than that determined using modeled values. Tekran® Instrument derived GOM concentrations, as well as modeled deposition rates, followed the same seasonal and spatial patterns as that measured by the samplers, however there were some spatial and temporal trends captured by the samplers that were not seen in the Tekran® derived data. Results indicate that these samplers may be applied to identify spatial and temporal trends in air Hg concentrations and potential deposition at sites with low and fairly constant GOM concentrations as reported by the Tekran® system (2–8pgm-3). When viewed collectively, trends in sampler and Tekran® derived data also suggest the potential for different forms of GOM in air. Using empirical and modeled values, dry deposition in Florida during the year of this study could account for 1.5 to 14% of total annual Hg deposition (wet+dry).

A Method for Rapid Determination of Re and Os Isotope Compositions Using ID‐MC‐ICP‐MS Combined with the Sparging Method

A simple, rapid method for the determination of Re and Os concentrations and isotope compositions using isotope dilution multi‐collector inductively coupled plasma‐mass spectrometry (ID‐MC‐ICP‐MS) combined with Carius tube digestion and sparging introduction of Os was developed. For Os measurement, four channeltron ion counters to detect different Os isotopes were used simultaneously, which led to a drastic reduction in the measurement time. Rhenium isotopes were measured by means of eight Faraday cups with solution nebulisation and an ultrasonic membrane desolvator. The representative 188Os count rate of an Os standard solution containing 50 pg of total Os was approximately 110000–120000 cps at the onset of measurement; the Re intensity of our in‐house 10 pg g−1 standard solution reached 1820 V/μg g−1 with a sample uptake rate of 95–99 μl min−1. These values indicate that the sensitivity of the method was sufficient even for samples with low Re and Os concentrations, such as chert. As the temporal variations of the amplification efficiency of the ion counters differed from one another, we adopted a sample‐calibrator bracketing method to correct the measured Re and Os isotope ratios. The Re and Os concentrations via the isotope dilution method and the 187Os/188Os ratios of two sedimentary rock reference materials (JMS‐2 and JCh‐1) on the basis of the isotope ratios determined by the MC‐ICP‐MS and by negative thermal ionisation mass spectrometry (N‐TIMS) were comparable within their ranges. Based on Os isotope measurement of the IAG reference material [Durham Romil Os (DROsS)], the average difference from the recommended value and precision of Os isotope measurements by the sparging method in combination with multi‐ion‐counters were 0.72% and 0.76% [1RSD (%), n = 29], respectively. The precisions in the 187Os/188Os ratios [1RSD (%)] of JMS‐2, JCh‐1 and DROsS were 0.35–0.71, 1.56–3.31 and 0.99–1.28%, respectively, which depended on their Os ion intensities. No systematic difference was observed between the Re and Os geochemical compositions of JCh‐1 and JMS‐2 obtained by means of digestion with inverse aqua regia and CrO3‐H2SO4 solutions, suggesting that either acid solution can be used for the sparging method of sedimentary rock samples. As CrO3‐H2SO4 solution is believed to liberate predominantly the hydrogenous Re and Os fraction from organic‐rich sediment, the sparging method combined with CrO3‐H2SO4 digestion and multi‐ion‐counters in the mass spectrometry is expected to be a powerful tool for reconstructing the secular change in marine Os isotope compositions with high sample throughput.

Long-term monitoring and modeling of the mass transfer of polychlorinated biphenyls in sediment following pilot-scale in-situ amendment with activated carbon

The results of five years of post-treatment monitoring following in-situ activated carbon (AC) placement for stabilization of polychlorinated biphenyls (PCBs) at an inter-tidal mudflat adjacent to Hunters Point Shipyard, San Francisco Bay, CA, USA are reported in this paper. After five years, AC levels of the sediment cores were comparable to those at earlier sampling times. Passive sampler uptake validated the benefit of the AC amendment with a strong local sorbent dose–response relationship. The PCB uptakes in passive samplers decreased up to 73% with a 3.7 dry wt.% AC dose after five years, confirming the temporal enhancement of the amendment benefit from a 19% reduction with a 4.4% dose observed within one month. The long-term effectiveness of AC, the local AC dose response, the impact of fouling by NOM, the spatial heterogeneity of AC incorporation, and the effects of advective sediment pore-water movement are discussed with the aid of a PCB mass transfer model. Modeling and experimental results indicated that the homogeneous incorporation of AC in the sediment will significantly accelerate the benefit of the treatment.

Design and evaluation of a new fully microwave-assisted liquid sample introduction device for inductively coupled plasma atomic emission spectrometry

A new fully microwave-assisted liquid sample introduction system (MASIS) is presented and evaluated in Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). The device employs a single TM010 microwave cavity for the simultaneous aerosol generation and desolvation. The different experimental requirements of both physical processes demand a careful system design and a judicious selection of the experimental conditions. The behavior of the MASIS depends on the: (i) microwave power; (ii) nebulizer nozzle inner diameter; (iii) sample uptake rate; and, (iv) matrix nature (i.e. acids, salts) and concentration. Thus, optimum operating conditions are obtained when increasing the microwave power, the matrix concentration and the sample uptake rate as well as when decreasing the nebulizer nozzle inner diameter. The analytical figures of merit afforded by the MASIS in ICP-AES are compared to those obtained with: (1) a pneumatic concentric nebulizer coupled to a cyclonic spray chamber (CS); (2) a microwave thermal nebulizer (MWTN) coupled to a cyclonic spray chamber; and (3) a pneumatic nebulizer coupled to a microwave desolvation system (MWDS). MASIS provides limits of detection up to 50 times lower than those obtained with the CS and up to 8 times lower than those with the MWTN and MWDS. No significant difference in the signal precision between the different devices tested is observed (i.e. 2–5%). Regarding the wash-out times, both MASIS and MWDS show the highest values of this parameter (i.e. 70 s) due to their higher inner volume. Wash-out time values for both MWTN and CS are lower than 30 s.

A passive sampler for ambient gaseous oxidized mercury concentrations

This paper reports on the development of a passive sampler for estimating gaseous oxidized mercury concentrations. Atmospheric gaseous oxidized mercury concentrations calculated from passive sampler data were correlated with those obtained using an automated analyzer ( r 2 = 0.71, p < 0.01, n = 110 for one-week deployments; r 2 = 0.89, p < 0.01, n = 22 for two-week deployments). Sampler uptake was not significantly affected by changes in temperature, humidity, or ozone concentration, but it was slightly dependent on wind speed. As such, an equation for correcting data due to this factor was developed based on wind tunnel and field data. The detection limit for a two-week sampler deployment was ∼5 pg m −3. Field data collected in Nevada and the southeastern United States showed these samplers are useful for investigating spatial and temporal variability in gaseous oxidized mercury concentrations.

Comparing Polychaete and Polyethylene Uptake to Assess Sediment Resuspension Effects on PCB Bioavailability

Polyethylene sampler uptake was compared to polychaete uptake to assess bioavailability of polychlorinated biphenyls (PCBs) from resuspended sediments. New Bedford Harbor (MA, U.S.) sediment contaminated with PCBs, was resuspended under four different water column oxidation conditions: resuspension alone, resuspension under aeration, resuspension under helium, and no resuspension (control). Residuals were tested for differences in PCB availability to the marine polychaete Nereis virens and to polyethylene (PE) passive samplers. Few significant differences between the four resuspension treatments were observed: under aeration, three of 23 PCBs analyzed showed significant increases in polychaete accumulation, while resuspension alone showed increased concentrations in PE samplers for nine of 23 PCBs. Otherwise, no differences were observed and overall we concluded that resuspension had no effect on residual PCB availability. The relationship between disequilibrium-corrected PE and lipid-normalized polychaete PCB concentrations was nearly 1:1 with a strong linear correlation (r2 = 0.877), demonstrating PCBs are taken up similarly into PE and lipid. On average, PE samplers suggested dissolved PCB concentrations 3.6 times greater than those calculated with lipid-water partitioning, though on a congener-specific basis this was only observed for lower chlorinated PCBs; for higher chlorinated PCBs, PE-water partitioning suggested lower dissolved concentrations than those based on lipid. Organic carbon (OC)-water and OC and black carbon combined (OC+BC)-water partitioning suggested average dissolved concentrations 29 and 10 times greater, respectively, than those estimated with lipid-water partitioning. This demonstrates that PE-measured porewater concentrations can provide a more reliable estimate of bioavailability than sediment geochemistry.

Altitudinal Transect of Atmospheric and Aqueous Fluorinated Organic Compounds in Western Canada

Neutral perfluorinated alkyl substances (PFASs), which are thought to be volatile precursors of environmentally ubiquitous perfluorocarboxylates (PFCAs) and perfluorooctanesulfonate (PFOS), were quantified in XAD-2 resin based passive air samplers deployed along an altitudinal transect from 800 to 2740 m above sea level (asl) in Western Canada (based at N51degrees 20' W117degrees 00') over the spring and summer seasons of 2004. The amounts of fluorotelomer alcohols (FTOHs) and perfluorinated sulfonamido alcohols (FOSEs) sequestered in the samplers increased with altitude, being lowest at an elevation of 1300 m asl and highest at either the 2340 or the 2740 m asl sites. A variety of potential reasons for these gradients are discussed, including changes in sampler uptake kinetics and phase capacity caused by changes in atmospheric pressure,temperature, and wind speed. Vapor phase concentrations were estimated to range from 3.7 to 19 pg m(-3) for perfluorinated sulfonamides (FOSAs) and from below detection limits (25 pg m(-3)) to 88 pg m(-3) for FOSEs. Over a similar altitudinal range (800-2350 m asl), 9 L lake water samples were collected in stainless steel cans, extracted with solid phase extraction columns, and analyzed for PFCAs and PFOS. Aqueous concentrations in lake water, ranging from 0.07 to 1.0 ng L(-1) for single PFCAs and from 0.04 to 0.1 ng L(-1) for PFOS, were more constant with altitude and were not correlated with the amount of the precursor compounds in the atmosphere. The relative abundance of FTOHs in air and PFCAs in water supports atmospheric FTOH degradation as the source of PFCAs in the mountain lakes.

Design and evaluation of an improved microwave-based thermal nebulizer for liquid sample introduction in inductively coupled plasma atomic emission spectrometry

A re-designed microwave-based thermal nebulizer (MWTN) that overcomes all the drawbacks shown by previous prototypes (i.e. lack of robustness, poor heating efficiency) is presented. The new device employs an optimized TM010 cavity and nozzle design. MWTN performance was evaluated in inductively coupled plasma atomic emission spectrometry (ICP-AES) and compared to that provided by a concentric pneumatic nebulizer. Current MWTN design improves sample heating efficiency and system robustness. As a consequence, a 10 times lower matrix concentration than previous designs can be employed. The minimum inorganic (i.e. acids and salts) and organic (i.e. alcohols) concentrations required to nebulize are 0.25 and 40% w/w, respectively. The influence of microwave power (180–290 W), matrix nature (acids, salts and organics), sample uptake rate (0.9–1.8 mL min–1) and nebulizer critical dimensions, such as nozzle and PTFE capillary internal diameter (150–300 and 300–800 µm) and PTFE capillary length (50–150 cm) on the behaviour of the MWTN was studied. Optimum operating conditions for this nebulizer are obtained employing high microwave powers, matrix concentration and sample uptake rate, as well as nozzle and PTFE capillary with a narrow internal diameter. Although the MWTN behavior depends on the samples physical properties, aerosol drop size distributions and analyte transport rate for inorganic solutions above 2% w/w are independent of matrix composition. Current MWTN shows higher sensitivity and lower limits of detection (up to 12 times for acid solutions) than a conventional pneumatic nebulizer. The performance of the new prototype has been evaluated analyzing a certified bovine liver (CRM 185 R) and a spirit sample. Experimental results indicate that MWTN can be employed successfully for routine sample analysis.

Design and evaluation of a continuous flow, integrated nebulizer-hydride generator for flame atomic absorption spectrometry

An evaluation of the performance of a continuous flow hydride generator-nebulizer for flame atomic absorption spectrometry was carried out. Optimization of nebulizer gas flow rate, sample acid concentration, sample and tetrahydroborate uptake rates and reductant concentration, on the As and Se absorbance signals was carried out. A hydrogen-argon flame was used. An improvement of the analytical sensitivity relative to the conventional bead nebulizer used in flame AA was obtained (2 (As) and 4.8 (Se) µg L-1). Detection limits (3σb) of 1 (As) and 1.3 (Se) µg L-1 were obtained. Accuracy of the method was checked by analyzing an oyster tissue reference material.

Carbon-related matrix effects in inductively coupled plasma atomic emission spectrometry

In Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES), it has been observed that the emission intensity of some atomic lines is enhanced or depressed by the presence of carbon in the matrix. The goal of this work was to investigate the origin and magnitude of the carbon-related matrix effects in ICP-AES. To this end, the influence of the carbon concentration and source (i.e. glycerol, citric acid and potassium hydrogen phthalate), the experimental conditions and sample introduction system on the aerosol characteristics and transport, plasma excitation conditions and the emission intensity of several atomic and ionic lines of a total of 15 elements has been studied. Results indicate that carbon related matrix effects do not depend on the carbon source and they become more severe when the amount of carbon loaded into the plasma increases, i.e., when using: (i) carbon concentrations higher than 5 g L − 1 ; (ii) high sample uptake rates; and (iii) efficient sample introduction systems. Thus, when introducing carbon into the plasma, the emission intensity of atomic lines with excitation energies below 6 eV is depressed (up to 15%) whereas the emission intensity of atomic lines of higher excitation energies (i.e. As and Se) are enhanced (up to 30%). The emission intensity of the ionic lines is not affected by the presence of carbon. The origin of the carbon-related interferences on the emission intensity of atomic lines is related to changes in the line excitation mechanism since the carbon containing solutions show the same aerosol characteristics and transport efficiencies as the corresponding aqueous solutions. Based on the previous findings, a calibration approach for the accurate determination of Se in a Se-enriched yeast certified material (SELM-1) has been proposed.