Simultaneous Speciation Research Articles

Simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate in welding fume alkaline extracts by HPLC–ICP-MS

A novel analytical procedure was developed for the simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate by anion-exchange high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC–ICP-MS). Linear gradient elution from 100% water to 100% 0.7M NaCl was applied for chromatographic separation of metal species. In standard aqueous solution at neutral pH molybdate, tungstate and vanadate exist in several aqueous species, while chromate is present as a single CrO42- species. Consequently, only chromate can be separated from this solution in a sharp chromatographic peak. For obtaining sharp chromatographic peaks for molybdate, tungstate and vanadate, the pH of aqueous standard solutions was raised to 12. At highly alkaline conditions single CrO42-, MoO42- and WO42- are present and were eluted in sharp chromatographic peaks, while VO43- species, which predominates at pH 12 was eluted in slightly broaden peak. In a mixture of aqueous standard solutions (pH 12) chromate, molybdate, tungstate and vanadate were eluted at retention times from 380 to 420s, 320 to 370s, 300 to 350s and 240 to 360s, respectively. Eluted species were simultaneously detected on-line by ICP-MS recording m/z 52, 95, 182 and 51. The developed procedure was successfully applied to the analysis of leachable concentrations of chromate, molybdate, tungstate and vanadate in alkaline extracts (2% NaOH+3% Na2CO3) of manual metal arc (MMA) welding fumes loaded on filters. Good repeatability and reproducibility of measurement (RSD±3.0%) for the investigated species were obtained in both aqueous standard solutions (pH 12) and in alkaline extracts of welding fumes. Low limits of detection (LODs) were found for chromate (0.02ngCrmL−1), molybdate (0.1ngMomL−1), tungstate (0.1ngWmL−1) and vanadate (0.2ngVmL−1). The accuracy of analytical procedure for the determination of chromate was checked by analysis of CRM 545, Cr(VI) in welding dust loaded on a filter. Good agreement between determined and reported certified values was obtained. For molybdate, tungstate and vanadate the assessment of accuracy was performed by spiking welding fume filters. Good recoveries for all investigated species (98–101%) confirmed the accuracy of the analytical procedure.

Simultaneous speciation of inorganic arsenic, selenium and tellurium in environmental water samples by dispersive liquid liquid microextraction combined with electrothermal vaporization inductively coupled plasma mass spectrometry

A new method based on dispersive liquid liquid microextraction (DLLME) combined with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) was developed for the simultaneous speciation of inorganic arsenic (As), selenium (Se) and tellurium (Te) with sodium diethyldithiocarbamate (DDTC) as both chelating reagent and chemical modifier. As(III), Se(IV) and Te(IV) were transformed into DDTC-chelates at pH 7 and extracted into the fine droplets formed by injecting the binary solution of bromobenzene (extraction solvent) and methanol (dispersive solvent) into the sample solution. After phase separation by centrifugation, As(III), Se(IV) and Te(IV) preconcentrated in the organic phase were determined by ETV-ICP-MS. Total inorganic As, Se and Te were obtained by reducing As(V), Se(VI) and Te(VI) to As(III), Se(IV) and Te(IV) with l-cysteine, which were then subjected to the same DLLME-ETV-ICP-MS process. The concentration of As(V), Se(VI), Te(VI) were calculated by subtracting the concentration of As(III), Se(IV) and Te(IV) from the total inorganic As, Se and Te, respectively. The main factors affecting the microextraction efficiency and the vaporization behavior of target species were investigated in detail. Under the optimal conditions, the limits of detection were 2.5, 8.6 and 0.56ngL−1 for As(III), Se(IV) and Te(IV), respectively, with the relative standard deviations (n=7) of 8.5–9.7%. The developed method was applied to the speciation of inorganic As, Se and Te in Certified Reference Materials of GSBZ50004-88, GBW(E)080395 and GBW(E)080548 environmental waters, and the determined values are in good agreement with the certified values. The method was also successfully applied to the simultaneous speciation of inorganic As, Se and Te in different environmental water samples with the recoveries in the range of 86.3–107% for the spiked samples.

Simultaneous speciation and determination of arsenic, chromium and cadmium in water samples by high performance liquid chromatography with inductively coupled plasma mass spectrometry

The simultaneous separation and determination of As(iii), As(v), monomethylarsenic acid (MMA), dimethylarsenic acid (DMA), Cr(iii), Cr(vi) and Cd(ii) in water samples have been carried out by anion exchange liquid chromatography with inductively coupled plasma mass spectrometry.

Universal enantioselective discrimination by Raman spectroscopy.

Distinguishing between the enantiomers of chiral substances and their quantification is an analytical challenge, in particular in the pharmaceutical and biochemical sectors. A Raman spectroscopic method for discrimination of enantiomers is proposed. Advantage is taken of the polarization properties when Raman scattering occurs in an optically active medium. It is shown that a conventional polarization-resolved Raman setup leads to identical spectra of the two enantiomers. However, inserting a half-wave retarder to rotate the signal polarization by a fixed angle enables the efficient and universal enantiomeric discrimination. Hence, the applicability of any polarization-resolved Raman experiment can be improved substantially without significant modification of the setup or the use of chiral labeling or the addition of a substrate for selective plasmonic enhancement. In principle, the proposed technique allows simultaneous speciation, enantiomeric discrimination, as well as structural and quantitative analysis.

Speciation Determination of Selenium in Seafood by High-Performance Ion-Exchange Chromatography-Hydride Generation-Atomic Fluorescence Spectrometry

A high-performance ion-exchange chromatography coupled with hydride generation-atomic fluorescence spectrometry (HPIEC-HG-AFS) method was developed for simultaneous speciation of selenium in seafood. Three selenium species including of selenocystine (Se-Cys), selenome-thionine (Se-Met), and selenite Se(IV) were separated on an anion-exchange column (PRP-X100) with eluent of 30 mM NH4H2PO4 and methanol (39:1, v/v) in 10 min at the flow rate of 1.0 mL min−1. Variables affecting the HG-AFS detection of selenium species were optimized. The optimum conditions found were the following: reducing agent, 2.0 % of KBH4, and 5.0 % of HCl; lamp current, 90 mA; photomultiplier tube voltage, 280 V; flow rate of carrier gas, 300 mL min−1; and shielding gas, 800 mL min−1. Under the optimized conditions, the good linearity of calibration curves (R 2 > 0.999) between signal of fluorescence and concentration of selenium species was obtained in the range of detection limits (DLs), 80 μg L−1, and the DLs of Se-Cys, Se-Met, Se(IV) were 1.66, 0.990, 1.10 μg L−1, respectively. The repeatability of the method, expressed as relative standard deviation, was less than 5.0 % (n = 10), and the average recoveries for spiked test were from 87.3 to 103 % for three analytes in real seafood samples. The developed HPIEC-HG-AFS method was successfully applied for the speciation of selenium in seafood samples.

Simultaneous speciation analysis of inorganic arsenic, chromium and selenium in environmental waters by 3-(2-aminoethylamino) propyltrimethoxysilane modified multi-wall carbon nanotubes packed microcolumn solid phase extraction and ICP-MS

Speciation analysis of inorganic arsenic, chromium and selenium in environmental waters is of great significance for the monitoring of environmental pollution. In this work, 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTS) functionalized multi-wall carbon nanotubes (MWCNTs) were synthesized and employed as the adsorbent for simultaneous speciation analysis of inorganic arsenic, chromium and selenium in environmental waters by microcolumn solid-phase extraction (SPE)-inductively coupled plasma mass spectrometry (ICP-MS). It was found that As(V), Cr(VI) and Se(VI) could be selectively adsorbed on the microcolumn packed with AAPTS-MWCNTs adsorbent at pH around 2.2, while As(III), Cr(III) and Se(IV) could not be retained at this pH and passed through the microcolumn directly. Total inorganic arsenic, chromium and selenium was determined after the oxidation of As(III), Cr(III) and Se(IV) to As(V), Cr(VI) and Se(VI) with 10.0μmolL−1 KMnO4. The assay of As(III), Cr(III) and Se(IV) was based on subtracting As(V), Cr(VI) and Se(VI) from the total As, Cr and Se, respectively. Under the optimized conditions, the detection limits of 15, 38 and 16ngL−1 with the relative standard deviations (RSDs) of 7.4, 2.4 and 6.2% (c=1µgL−1, n=7) were obtained for As(V), Cr(VI) and Se(VI), respectively. The developed method was validated by analyzing four Certified Reference Materials, rainwater, Yangtze River and East Lake waters.

Simultaneous speciation of selenoproteins and selenometabolites in plasma and serum by dual size exclusion-affinity chromatography with online isotope dilution inductively coupled plasma mass spectrometry

A method for the simultaneous speciation of selenoproteins and selenometabolites in mouse plasma has been developed based on in series two-dimensional size exclusion and affinity high-performance liquid chromatography (2D/SE-AF-HPLC), using two columns of each type, and hyphenation to inductively coupled plasma-(quadrupole) mass spectrometry (ICP-QMS). The method allows the quantitative determination of selenoprotein P (SeP), extracellular glutathione peroxidase (eGPx), selenoalbumin (SeAlb), and selenometabolites in mouse plasma using species-unspecific isotope dilution (SUID). The 2D chromatographic separation is proposed to remove typical spectral interferences in plasma from chloride and bromide on (77)Se ((40)Ar(37)Cl) and (82)Se ((81)Br(1)H). In addition, the approach increases chromatographic resolution allowing the separation of eGPx from Se metabolites of low molecular mass. The method is robust, reliable, and fast with a typical chromatographic runtime less than 20 min. Precision in terms of relative standard deviation (n = 5) is in the order of 4 %, and detection limits are in the range of 0.2 to 1.0 ng Se g(-1). Method accuracy for determination of total protein bound to Se was assessed by analyzing human serum reference material (BCR-637) certified for total Se content, and latterly applied to mouse plasma (Mus musculus). In summary, a reliable speciation method for the analysis of eGPx, selenometabolites, SeP, and SeAlb in plasma/serum samples is proposed for the first time and is applicable to the evaluation of Se status in human in clinical studies and other mammals for environmental or toxicological assessment.

Development of anion-exchange high-performance liquid chromatography-inductively coupled plasma mass spectrometry methods for the speciation analysis of inorganic selenium and iodine in groundwater

An HPLC-ICP-MS method for simultaneous speciation of selenium and iodine has been developed. Species in groundwater samples from a potential Chinese HLW repository site were determined at ultra-trace level.

Simultaneous speciation analysis of As, Sb and Se redox couples by SF-ICP-MS coupled to HPLC

A new method for the simultaneous speciation analysis of inorganic arsenic (iii, v), antimony (iii, v) and selenium (iv, vi) using anion exchange column.

Application of metallomic and metabolomic approaches in exposure experiments on laboratory mice for environmental metal toxicity assessment

Metals have a central role in biological systems, regulating numerous cellular processes, and in other cases having toxic or deleterious effects on the metabolism. Hence, the study of metal-induced changes in cellular metabolic pathways is crucial to understanding the biological response associated with environmental issues. In this context, the finding of biomarkers has great interest, representing -omics techniques, such as metallomics and metabolomics, powerful tools for this purpose. The present work evaluates the exposure of mice Mus musculus to toxic metals (As, Cd and Hg), considering the changes induced in both the metallome and metabolome as a consequence of the high genetic homology between Mus musculus/Mus spretus mice, which allows the use of the database from M. musculus to identify the proteins and metabolites expressed by M. spretus. For this purpose a metallomic approach based on size exclusion chromatography (SEC) in combination with other complementary orthogonal separation techniques and heteroelement monitoring by ICP-ORS-qMS was performed, followed by identification of metallobiomolecules by organic mass spectrometry. In addition, simultaneous speciation of selenoproteins and selenometabolites in mouse plasma was accomplished by tandem (double) SEC-(dual) affinity chromatography (AF)-HPLC and online isotope dilution analysis (IDA)-ICP-ORS-qMS. Finally, the simultaneous changes in metabolic expression in mice caused by metal exposure (metabolome) were considered, using direct infusion mass spectrometry (DI-ESI-QqQ-TOF-MS) of extracts from mice plasma. Subsequently altered metabolites were identified using MS/MS experiments. The results obtained under controlled conditions were extrapolated to homologous free-living mice captured in Doñana National Park (DNP) and surroundings (southwest Spain) affected by As, Cd and Hg pollution. In summary, such studies are needed to understand the effect of heavy metal exposure and cope with heavy metal toxicity.

Development of a new column switching method for simultaneous speciation of selenometabolites and selenoproteins in human serum

A method for the simultaneous speciation of selenoproteins and selenometabolites in human serum has been developed on the basis of in series three dimensional chromatography: size exclusion, affinity and anion exchange high performance liquid chromatography (3D/SE-AF-AEC-HPLC), using different columns of each type and hyphenation to inductively coupled plasma-(quadrupole) mass spectrometry (ICP-qMS). The method allows the quantitative simultaneous analysis of selenoprotein P (SeP), extracellular glutathione peroxidase (eGPx), selenoalbumin (SeAlb), selenite and selenate in human serum using species-unspecific isotope dilution (SUID). The 3D chromatographic separation is proposed to remove typical spectral interferences in this matrix from chloride and bromide on 77Se (40Ar37Cl), 80Se (79Br1H) and 82Se (81Br1H). In addition, a previous method based on 2D/SE-AF-HPLC is proposed as a simple alternative when low molecular mass selenium species are absent in the samples. The method is robust, reliable and fast with typical chromatographic runtime less than 35min. Detection limits are in the range of 0.2–1.3ng of Seg−1. Method accuracy for determination of total protein-bound to Se was assessed by analyzing an human serum reference material (BCR-637) certified for total Se content and method reliability checked in samples of human serum providing results in good agreement with the total selenium concentration. In addition, the application of the method to commercial human serum and plasma reference materials for quality control analysis, certified for total Se, has provided, for the first time, indicative levels of selenium containing proteins in these samples.

Preconcentration and speciation of vanadium by three phases liquid–liquid microextraction prior to electrothermal atomic absorption spectrometry

We developed a new method three phase liquid–liquid microextraction (TPLLME) for simultaneous speciation of vanadium. This efforts were launched to know the species and aqueous transport chemistry of the binary V-(1-(2-Pyridylazo)-2-naphthol) complex across the interface of the three phases. Various analytical parameters were optimized. The limit of detection (LOD) was 0.034μgL−1 and 0.028μgL−1 for V(V) and V(IV) with preconcentration factor of 100. Relative standard deviation (RSD) was found 4.32% for V(V) and 4.22% for V(IV). The proposed method was applied to species of vanadium successfully in sea water and tap water samples. The method was also applied to certified reference material and food samples for total vanadium determination.

Silica gel modified with polyaniline as a stationary phase in the ion chromatography of nitrate(III) and nitrate(V) ions

Summary The new obtained sorbent based on silica gel modified with polyaniline was used as a stationary phase in the ion chromatography of anions. NO3- and NO2- ions were analyzed by UV spectrophotometric detection (200 nm). It can be stated that the optimal mobile phase was a 0.05 M hydrochloric acid and the optimal flow speed was 0.3 mL min−1. The separation of both anions in the presented condition was satisfactory. The resolution factor (peak resolution) was 3.3. It suggests the possibility of the column application for simultaneous speciation analysis of nitrate ions.

Vicariant speciation due to 1.55 Ma isolation of theRyukyu islands,Japan, based on geological andGenBank data

AbstractTheRyukyu island arc, originally a continental margin arc, separated from theChinese continent by the rifting of theOkinawa trough, a process which began at 1.55 million years ago (Ma) and continues to the present. In addition, theRyukyu arc was simultaneously divided into the northernAmami–Okinawa and southernYaeyama islands by theKerama rift valley, and consequently formed two isolated island units. TheKuroshio warm current began to flow into theOkinawa trough from theYonaguniStrait, and flow out through theTsushima andTokara straits also at 1.55 Ma, and these seaways effectively acted as barriers between theRyukyu islands andTaiwan,China andJapan. Through this geological process, vicariant speciation generatedRyukyu endemic animal species. We support this hypothesis by drawing linearized maximum likelihood (ML) phylogenetic trees of the species in four endemic insect groups (peacock butterfly,Chinese windmill butterfly, golden‐ringed dragonfly, window firefly) usingGenBank sequence data. We determined the precise branching ages for these phylogenetic trees, and show simultaneous speciation at 1.55 Ma forAmami–Okinawa andYaeyama units. TheTaiwan andTsushima straits, barriers betweenTaiwan andChina, andJapan andKorea, respectively, did not form sufficient barriers to migration during glacial low stands, and species were intermingled. A marine embayment may have posed as a migration barrier between northern and southernChina in theQuaternary or a little earlier. From our study we also estimate the precise molecular evolution rate and justify the molecular clock.

Simultaneous speciation and preconcentration of ultra trace concentrations of mercury and selenium species in environmental and biological samples by hollow fiber liquid phase microextraction prior to high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry

Nowadays, hollow fiber membrane extraction techniques are widely used due to the high enrichment factors obtained with many different types of analytes and samples. In this paper, we propose a new analytical method that allows the simultaneous extraction of methylmercury, inorganic mercury and Se4+ and determination by high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC–ICP-MS). The detection limits obtained are very low (110–230ng/L) with relative standard deviations below 15% for all the analytes and averaged recoveries in fortified samples in the range of 71–99%. The precision of the analytical method is very good which overcomes one of the most important shortcomings of membrane extraction techniques. Several variables were studied to get optimal extraction conditions for the analytes. This method has been validated with real world samples such as water (tap, river and estuarine) and human blood plasma.

Simultaneous Speciation of Iron(II) and Iron(III) by Ion Chromatography with Chemiluminescence Detection

This study reports on a method for the speciation of iron in aqueous samples by the simultaneous analysis of divalent and trivalent iron ions with ion chromatography equipped with chemiluminescence detection (IC-CLD). Ferrous and ferric ions are first chelated by pyridine-2,6-dicarboxylic acid (PDCA) to form complexed anions, and separated by a mixed-bed ion-exchange column. The separated complexed ions are then detected with a CLD system containing luminol and hydrogen peroxide in a basic solution. This luminescence system has a linear dynamic range of ca. 3 orders of magnitude, with method detection limits as low as 7 µg L(-1) for Fe(II) and 3 µg L(-1) for Fe(III), measured in the simultaneous detection mode. This system resists interferences from common cations such as Cd, Ca, Cr, Cu, Mg, Ni, Pb, and Zn. Evaluation by analyzing real samples shows that this method is rapid, accurate, sensitive, and selective.

Synthesis of mixed coating with multi-functional groups for in-tube hollow fiber solid phase microextraction–high performance liquid chromatography–inductively coupled plasma mass spectrometry speciation of arsenic in human urine

A novel method based on in-tube hollow fiber-solid phase microextraction (in-tube HF-SPME) on-line coupled with ion pair reversed phase high performance liquid chromatography (IP-RP-HPLC)–inductively coupled plasma mass spectrometry (ICP-MS) was developed for arsenic speciation. Partially sulfonated poly(styrene) (PSP) and mixed-sol of 3-mercapto propyltrimethoxysilane (MPTS) and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AAPTS) were prepared and immobilized in the pores and the inner surface of polypropylene hollow fiber (HF). The prepared MPTS–AAPTS/PSP immobilized HF was characterized by FT-IR spectroscopy and scanning electron microscope (SEM). With arsenite (As(III)), arsenate (As(V)), monomethylarsonic acid (MMA), dimethylarsenic acid (DMA), arsenobetaine (AsB) and arsenocholine (AsC) as model arsenic species, a series of factors that influence the extraction of target arsenic species by in-tube HF-SPME, including pH value, sample volume and flow rate, elution conditions and interference of co-existing ions were investigated in details, and the conditions for subsequent HPLC–ICP-MS determination were also optimized. Under the optimal conditions, the sampling frequency was 6.5h−1, the detection limits for six target arsenic species were in the range of 0.017–0.053μgL−1 with the relative standard deviations (cAs(V),MMA=0.1μgL−1, cAs(III),DMA,AsB,AsC=0.5μgL−1, n=5) ranging in 3.1–8.7%, and the enrichment factors were varied from 4 to 19-fold. To validate the accuracy of this method, certified reference materials DORM-2 (dogfish) and CRM No. 18 (human urine) were analyzed, and the determined values were in good agreement with the certified values. The proposed method was also successfully applied for arsenic speciation in human urine samples, and the recoveries for the spiked samples were in the range of 92.6–107%. The self-designed in-tube HF-SPME–HPLC–ICP-MS system shows high efficiency and good stability, and the proposed method is sensitive and suitable for simultaneous speciation of organic and inorganic arsenic species (including anions and cations) in biological samples.

Phase transfer membrane supported liquid–liquid–liquid microextraction combined with large volume sample injection capillary electrophoresis–ultraviolet detection for the speciation of inorganic and organic mercury

In this paper, a novel sample pretreatment technique termed phase transfer based liquid-liquid-liquid microextraction (PT-LLLME) was proposed for the simultaneous extraction of inorganic and organic mercury species. In PT-LLLME, an intermediate solvent (acetonitrile) was added into the donor phase to improve the contacting between target mercury species and complexing reagent. Meanwhile, a membrane supported (MS)-LLLME unit was designed to realize the PT-LLLME procedure. By using nylon membrane as supporting carrier, larger than 50 μL of acceptor solution could be hung up. Following PT/MS-LLLME, the acceptor solutions were directly analyzed by large volume sample stacking capillary electrophoresis/ultraviolet detection (LVSS-CE/UV). Accordingly, a new method of PT/MS-LLLME combined with LVSS-CE/UV was developed for the simultaneous speciation of inorganic and organic mercury species. Parameters affecting the extraction efficiency of PT/MS-LLLME were investigated in details. Under the optimized conditions, enrichment factors (EFs) ranging from 160- to 478-fold were obtained for the extraction of target mercury species by PT/MS-LLLME. By combining PT/MS-LLLME with LVSS-CE/UV, EFs were magnified up to 12,138-fold and the limits of detection (at a signal-to-noise ratio of 3) were at sub ppb level. The established approach of PT/MS-LLLME-LVSS-CE/UV was successfully applied to simultaneous determination of inorganic and organic mercury species in biological samples and environmental water samples.

Inorganics in Organics: Quantification of Organic Phosphorus and Sulfur and Trace Element Speciation in Natural Organic Matter Using HPLC-ICPMS

A method is presented for the chemical characterization of natural organic matter (NOM). We combined reversed-phase chromatographic separation of NOM with high resolution inductively coupled plasma mass spectrometry. A desolvation technique was used to remove organic solvent derived from the preceding chromatographic separation. We applied our method to solid-phase extracted marine dissolved organic matter samples from South Atlantic and Antarctic surface waters. The method provided a direct and quantitative determination of dissolved organic phosphorus and sulfur in fractions of differing polarity and also allowed simultaneous speciation studies of trace elements. Dissolved organic carbon/phosphorus and carbon/sulfur ratios for the different chromatographic fractions of our two samples ranged between 341-3025 for C/P and 11-1225 for C/S. Differences in elemental distribution between the fractions were attributed to different biochemical environments of the samples. Sulfur was exclusively found in one hydrophilic fraction, while uranium showed a strong affinity to the hydrophobic fractions. Our method was designed to be easily adapted to other separation techniques. The elemental information will deliver valuable information for ultrahigh resolution molecular analyses.

Simultaneous speciation of arsenic, selenium, and chromium: species stability, sample preservation, and analysis of ash and soil leachates

An analytical method using high-performance liquid chromatography separation with inductively coupled plasma mass spectrometry (ICP-MS) detection previously developed for the determination of Cr(III) and Cr(VI) has been adapted to allow the determination of As(III), As(V), Se(IV), Se(VI), Cr(III), and Cr(VI) under the same chromatographic conditions. Using this method, all six inorganic species can be determined in less than 3 min. A dynamic reaction cell (DRC)-ICP-MS system was used to detect the species eluted from the chromatographic column in order to reduce interferences. A variety of reaction cell gases and conditions may be utilized with the DRC-ICP-MS, and final selection of conditions is determined by data quality objectives. Results indicated all starting standards, reagents, and sample vials should be thoroughly tested for contamination. Tests on species stability indicated that refrigeration at 10 °C was preferential to freezing for most species, particularly when all species were present, and that sample solutions and extracts should be analyzed as soon as possible to eliminate species instability and interconversion effects. A variety of environmental and geological samples, including waters and deionized water [leachates] and simulated biological leachates from soils and wildfire ashes have been analyzed using this method. Analytical spikes performed on each sample were used to evaluate data quality. Speciation analyses were conducted on deionized water leachates and simulated lung fluid leachates of ash and soils impacted by wildfires. These results show that, for leachates containing high levels of total Cr, the majority of the chromium was present in the hexavalent Cr(VI) form. In general, total and hexavalent chromium levels for samples taken from burned residential areas were higher than those obtained from non-residential forested areas. Arsenic, when found, was generally in the more oxidized As(V) form. Selenium (IV) and (VI) were present, but typically at low levels.