New York State urban and rural measurements of continuous PM2.5 mass by FDMS, TEOM, and BAM

Field evaluations and comparisons of continuous fine particulate matter (PM2,5) mass measurement technologies at an urban and a rural site in New York state are performed. The continuous measurement technologies include the filter dynamics measurement system (FDMS) tapered element oscillating microbalance (TEOM) monitor, the stand-alone TEOM monitor (without the FDMS), and the beta attenuation monitor (BAM). These continuous measurement methods are also compared with 24-hr integrated filters collected and analyzed under the Federal Reference Method (FRM) protocol. The measurement sites are New York City (the borough of Queens) and Addison, a rural area of southwestern New York state. New York City data comparisons between the FDMS TEOM, BAM, and FRM are examined for bias and seasonality during a 2-yr period. Data comparisons for the FDMS TEOM and FRM from the Addison location are examined for the same 2-yr period. The BAM and FDMS measurements at Queens are highly correlated with each other and the FRM. The BAM and FDMS are very similar to each other in magnitude, and both are approximately 25% higher than the FRM filter measurements at this site. The FDMS at Addison measures approximately 9% more mass than the FRM. Mass reconstructions using the speciation trends network filter data are examined to provide insight as to the contribution of volatile species of PM2.5 in the FDMS mass measurement and the fraction that is likely lost in the FRM mass measurement. The reconstructed mass at Queens is systematically lower than the FDMS by approximately 10%.     

Evidence for the presence of arsenobetaine and another organoarsenical in shrimps

Hot base digestion of fish meal and shrimps in combination with sodium borohydride reduction produces only trimethylarsine (TMA). This treatment produces TMA in different amounts relative to the total arsenic content which is mainly of organic structure. These materials of marine origin yielded 94% and 69% resp. of the calculated amount of TMA. Arsenobetaine and arsenocholine were degraded under identical conditions and were found to produce only TMA (95% and 8% resp.). Furthermore, studies using thin-layer chromatography, electrophoresis and ion-exchange chromatography have confirmed the existence of one organoarsenic compound in fish meal and two organoarsenicals in shrimps. The major organoarsenic compound in fish meal was identified as arsenobetaine by masspectroscopy. In shrimps about $\text{2}\text{3}$ of the organoarsenic compounds was shown to be arsenobetaine and there is a strong indication for the presence of arsenocholine.     

New Evidence for the presence of arsenocholine in shrimps (Pandalus borealis) by use of pyrolysis gas chromatography — atomic absorption spectrometry/mass spectrometry

An analytical method for the structure elucidation of quarternary organoarsenic compounds in trace amounts in fish and crustaceans has been developed in this laboratory. The two major organoarsenicals found in shrimps have been separated by ion-exchange chromatography and their stucture has been studied by the use of pyrolysis gas chromatography. Their degradation in the pyrolyzer unit has been studied by the use of atomic absorption spectrophotometer or mass spectrometer as detectors. A comparison of the analytical data of these substances and data from synthetic reference substances show complete agreement. The structures of reference compounds have been confirmed by use of nuclear magnetic resonance spectrometry and fast atom bombardment (FAB) mass spectrometry. It is demonstrated that both of the organoarsenic compounds in shrimps have a trimethylarsonio moiety e.g. the compounds have a quarternary structure. Furthermore, the more basic organoarsenic compound has a mass spectrometric fragmentation pattern similar to synthetic arsenocholine and acetylarsenocholine. Treatment of arsenobetaine with hot base produces trimethylarsineoxide in a high yield (96%). Arsenocholine, however, remains unchanged during this treatment. Treatment with sodium benzenethiolate does not result in chemical demethylation, which shows that this method together with gas chromatography-mass spectrometry is not feasible for confirmation of its structure.     

Aerosol Measurement: The Use of Optical Light Scattering for the Determination of Particulate Size Distribution,and Particulate Mass,Including the Semi-Volatile Fraction

Abstract

The GRIMM model 1.107 monitor is designed to measure particle size distribution and particulate mass based on a light scattering measurement of individual particles in the sampled air. The design and operation of the instrument are described. Protocols used to convert the measured size number distribution to a mass concentration consistent with U.S. Environmental Protection Agency protocols for measuring particulate matter (PM) less than 10 μm (PM₁₀) and less than 2.5 μm (PM_2.5) in aerodynamic diameter are described. The performance of the resulting continuous monitor has been evaluated by comparing GRIMM monitor PM_2.5 measurements with results obtained by the Rupprecht and Patashnick Co. (R&P) filter dynamic measurement system (FDMS). Data were obtained during month-long studies in Rubidoux, CA, in July 2003 and in Fresno, CA, in December 2003. The results indicate that the GRIMM monitor does respond to total PM_2.5 mass, including the semi-volatile components, giving results comparable to the FDMS. The data also indicate that the monitor can be used to estimate water content of the fine particles. However, if the inlet to the monitor is heated, then the instrument measures only the nonvolatile material, more comparable to results obtained with a conventional heated filter tapered element oscillating microbalance (TEOM) monitor. A recent modification of the model 180, with a Nafion dryer at the inlet, measures total PM_2.5 including the nonvolatile and semi-volatile components, but excluding fine particulate water. Model 180 was in agreement with FDMS data obtained in Lindon, UT, during January through February 2007     

Isolation and identification of beta-nitrostyrene from smoked chicken

Extraction and identification of beta-nitrostyrene from smoked chicken is described. Commercially obtained smoked chicken was homogenised and extracted with chloroform-methanol (2:1). The extracts were fractioned by silicic acid column chromatography. The purified extract using thin-layer chromatography was identified by a colour reaction (this qualitative method for some nitrated compounds is developed this time), high pressure liquid chromatography and gas chromatography/mass spectrometry. The concentration of beta-nitrostyrene in the smoked chicken was 94 ppb. The average recovery of added beta-nitrostyrene was 107%. However, the toxicity of this material was not tested in the present paper.     

On-line speciation of arsenical compounds in fish and mussel extracts by HPLC-ICP-MS

The separation and determination of sub-μmol/l levels of six environmentally significant As compounds was accomplished by means of high performance liquid chromatography (HPLC) combined online with inductively coupled plasma mass spectrometry (ICP-MS). The species of interest (arsenite and arsenate, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine and arsenocholine) were quantified in fish and mussel extracts after separation on a Dionex AS7 column equipped with an on-guard AG7 column using a bicarbonate buffer as the mobile phase in a gradient mode. The species thus eluted were directly forwarded to the ICP-MS detector. The detection power of the overall system allows each As form to be determined at concentrations as low a 0.0013–0.0027 μmol 1⁻¹.     

Measurement of arsenic compounds in littoral zone algae from the Western Mediterranean Sea. Occurrence of arsenobetaine

The determination of arsenic compounds in algae collected on the Catalan coast (Western Mediterranean) is reported. Ten algae species and the seagrass Posidonia oceanica were analyzed. Total arsenic in the samples was determined by microwave digestion and inductively coupled plasma mass spectrometry (ICPMS). Arsenic speciation in water extracts of samples was analyzed by liquid chromatography with both anionic and cationic exchange with ICPMS detection (LC-ICPMS). The total arsenic content of the algae samples ranged from 2.96 to 39.0mg As kg(-1). The following compounds were detected: arsenite (As(III)), arsenate (As(V)), methylarsonate (MA), dimethylarsinate (DMA), sulfonate sugar (SO3-sug), sulfate sugar (SO4-sug), phosphate sugar (PO4-sug), arsenobetaine (AB), arsenocholine (AC), trimethylarsine oxide (TMAO) and glycerol sugar (Gly-sug). The main arsenic species found were arsenosugars. Significant percentages of arsenobetaine (0.54 mg As kg(-1), 28% of the extractable arsenic and 0.39 mg As kg(-1), 18% of the extractable arsenic) were found in Ulva rigida and Enteromorpha compressa. These results are discussed in relation to the presence of epiphytes.     

The formation of trimethylarsine oxide from arsenobetaine by biodegradation with marine microorganisms

Bottom sediments collected from coastal waters were aerobically incubated in inorganic medium containing arsenobetaine as a carbon source. An arsenic compound converted from arsenobetaine during incubation was purified from the medium by ion exchange chromatography. The purified compound was identified to be trimethylarsine oxide by TLC, HPLC, FAB-MS and NMR.     

Analysis of target and nontarget pollutants in aqueous leachates from the hazardous waste site Stringfellow, California, via ion chromatography - particle beam and inductively coupled plasma mass spectrometry

Liquid chromatography particle beam mass spectrometry (PB/MS is a powerful tool for the analysis of target pollutants but complementary methods are required for nontarget compounds. Preliminary data are presented on an anion exchange chromatography PB/MS based method for the detection of the target compound 4-chlorobenzene sulfonic acid (a contamlnant found in hazardous waste leachates) and also for nontarget pollutants in aqueous leachate samples from the Stringfellow hazardous waste site in California. Anion exchange chromatography coupled to inductively coupled plasma mass spectrometry yields qualitative and quantltative elemental analysis showing the presence or absence of key heteroatoms in organic pollutants including chlorine, other halogens, phosphorus and sulfur.     

APCA Financial Statements for FY 1979-80

The U.S. Environmental Protection Agency (EPA) has proposed a new secondary standard based on visibility in urban areas. The proposed standard will be based on light extinction, calculated from 24-hr averaged measurements. It would be desirable to base the standard on a shorter averaging time to better represent human perception of visibility. This could be accomplished by either an estimation of extinction from semicontinuous particulate matter (PM) data or direct measurement of scattering and absorption. To this end we have compared 1-hr measurements of fine plus coarse particulate scattering using a nephelometer, along with an estimate of absorption from aethalometer measurements. The study took place in Lindon, UT, during February and March 2012. The nephelometer measurements were corrected for coarse particle scattering and compared to the Filter Dynamic Measurement System (FDMS) tapered element oscillating microbalance monitor (TEOM) PM_2.5 measurements. The two measurements agreed with a mass scattering coefficient of 3.3 ± 0.3 m²/g at relative humidity below 80%. However, at higher humidity, the nephelometer gave higher scattering results due to water absorbed by ammonium nitrate and ammonium sulfate in the particles. This particle-associated water is not measured by the FDMS TEOM. The FDMS TEOM data could be corrected for this difference using appropriate IMPROVE protocols if the particle composition is known. However, a better approach may be to use a particle measurement system that allows for semicontinuous measurements but also measures particle bound water. Data are presented from a 2003 study in Rubidoux, CA, showing how this could be accomplished using a Grimm model 1100 aerosol spectrometer or comparable instrument.

Implications: Visibility is currently based on 24-hr averaged PM mass and composition. A metric that captures diurnal changes would better represent human perception. Furthermore, if the PM measurement included aerosol bound water, this would negate the need to know particulate composition and relative humidity (RH), which is currently used to estimate visibility. Methods are outlined that could accomplish both of these objectives based on use of a PM monitor that includes aerosol-bound water. It is recommended that these techniques, coupled with appropriate measurements of light scattering and absorption by aerosols, be evaluated for potential use in the visibility based secondary standard.     

Characterization of soluble and insoluble components in PM2.5 and PM10 fractions of airborne particulate matter in Kofu city,Japan

A systematic method combining water and diluted-acid extractions has been developed for the manifold evaluation of soluble and insoluble fractions in ambient aerosol. The pre-washed regenerated cellulose membrane filter was used as a collection medium of a low-volume air sampler. The collection time of 7–14 days was required to obtain the sample amounts enough for the systematic analysis. Simple and efficient extraction procedures using the filtration of water and 0.1 M hydrochloric acid were recommended in order to obtain the information about the dissolution behaviors of various elements in the aerosol. Soluble components in both the extracts were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and ion chromatography (IC). These extraction procedures were also preferred to prepare thin-layer specimens suitable to the succeeding X-ray fluorescence spectrometry (XRF) for insoluble components. Elemental compositions of the extraction residues were conveniently determined by the XRF calibrated with thin-layer standard specimens prepared with activated carbon. The determination of the 17 representative elements (Na, Mg, Al, Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Cu, Zn, Br, Pb) in these three fractions from an aerosol sample was performed rapidly within 4 h. The proposed systematic method was applied to PM_2.5 and PM₁₀ aerosol samples collected in Kofu City, Central Japan, and the enrichment behaviors of various elements and their source apportionment such as soil, anthropogenic substances and vehicle exhaust particulates could be demonstrated by the present method.     

Evaluation and comparison of continuous fine particulate matter monitors for measurement of ambient aerosols

To provide a scientific basis for the selection and use of continuous monitors for exposure and/or health effects studies, and for compliance and episode measurements at strategic locations in the State of New Jersey, we evaluated the performance of seven continuous fine particulate matter (PM2.5) monitors in the present study. Gravimetric samplers, as reference methods, were collocated with realtime instruments in both laboratory and field tests. The results of intercomparison of real-time monitors showed that the two nephelometers used in this study correlated extremely well (r2 approximately 0.97), and two tapered element oscillating monitors (TEOM 1400 and TEOM filter dynamics measurement system [FDMS]) correlated well (r2 > 0.85), whereas two beta gauges displayed a weaker correlation (r2 < 0.6). During a summertime controlled (laboratory) evaluation, the measurements made with the gravimetric method correlated well with the 24-hr integrated measurements made with the real-time monitors. The SidePak nephelometer overestimated the particle concentration by a factor of approximately 3.4 compared with the gravimetric method. During a summertime field evaluation, the TEOM FDMS monitor reported approximately 30% higher mass concentration than the Federal Reference Method (FRM); and the difference could be explained by the loss of semi-volatile materials from the FRM sampler. Results also demonstrated that 24-hr average PM2.5 mass concentrations measured by beta gauges and TEOM (50 degrees C) in winter correlated well with the integrated gravimetric method. Seasonal differences were observed in the performance of the TEOM (50 degrees C) monitor in measuring the particle mass attributed to the higher semi-volatile material loss in the winter weather. In applying the realtime particulate matter monitoring data into Air Quality Index (AQI) reporting, the Conroy method and the 8-hr end-hour average method were both found to be suitable.     

Errors in coarse particulate matter mass concentrations and spatiotemporal characteristics when using subtraction estimation methods

In studies of coarse particulate matter (PM_10-2.5), mass concentrations are often estimated through the subtraction of PM_2.5 from collocated PM₁₀ tapered element oscillating microbalance (TEOM) measurements. Though all field instruments have yet to be updated, the Filter Dynamic Measurement System (FDMS) was introduced to account for the loss of semivolatile material from heated TEOM filters. To assess errors in PM_10-2.5 estimation when using the possible combinations of PM₁₀ and PM_2.5 TEOM units with and without FDMS, data from three monitoring sites of the Colorado Coarse Rural–Urban Sources and Health (CCRUSH) study were used to simulate four possible subtraction methods for estimating PM_10-2.5 mass concentrations. Assuming all mass is accounted for using collocated TEOMs with FDMS, the three other subtraction methods were assessed for biases in absolute mass concentration, temporal variability, spatial correlation, and homogeneity. Results show collocated units without FDMS closely estimate actual PM_10-2.5 mass and spatial characteristics due to the very low semivolatile PM_10-2.5 concentrations in Colorado. Estimation using either a PM_2.5 or PM₁₀ monitor without FDMS introduced absolute biases of 2.4 µg/m³ (25%) to –2.3 µg/m³ (–24%), respectively. Such errors are directly related to the unmeasured semivolatile mass and alter measures of spatiotemporal variability and homogeneity, all of which have implications for the regulatory and epidemiology communities concerned about PM_10-2.5. Two monitoring sites operated by the state of Colorado were considered for inclusion in the CCRUSH acute health effects study, but concentrations were biased due to sampling with an FDMS-equipped PM_2.5 TEOM and PM₁₀ TEOM not corrected for semivolatile mass loss. A regression-based model was developed for removing the error in these measurements by estimating the semivolatile concentration of PM_2.5 from total PM_2.5 concentrations. By estimating nonvolatile PM_2.5 concentrations from this relationship, PM_10-2.5 was calculated as the difference between nonvolatile PM₁₀ and PM_2.5 concentrations.

Implications: Errors in the estimation of PM_10-2.5 concentrations using subtraction methods were shown to be related to the unmeasured semivolatile mass when using certain combinations of TEOM instruments. For the northeastern Colorado region, the absolute bias associated with this error significantly affects mean and 95th percentile values, which would affect assessment of compliance if PM_10-2.5 is regulated in the future. Estimating PM_10-2.5 mass concentrations using nonvolatile mass concentrations from collocated PM₁₀ and PM_2.5 TEOM monitors closely estimates the total PM_10-2.5 mass concentrations. A corrective model that removes the described error was developed and applied to data from two sites in Denver.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.     

Potential of hexadecane-utilizing soil-microorganisms for growth on hexadecanol, hexadecanal and hexadecanoic acid as sole sources of carbon and energy

Bacteria and fungi in pristine and oily desert soil samples were counted on inorganic medium aliquots containing 0.5% hexadecane, hexadecanol, hexadecanal or hexadecanoic acid, as sole sources of carbon and energy. It was found that the carbon and energy source most commonly utilized by soil bacteria was the alkane n-hexadecane, and by soil fungi hexadecanoic acid. Representative microorganisms were isolated and identified. The most predominant bacteria in all soil samples belonged to the genera Micrococcus and Pseudomonas; less dominant bacteria belonged to the group of nocardioforms. The most frequent fungal genera were Aspergillus and Penicillium, while Microsporium and Ulocladium were minor fungi. Irrespective of the substrate on which the microbial strains had initially been isolated, the majority of the isolated microorganisms could grow, albeit to a varying degree, on an inorganic medium containing any of the remaining three substrates as sole carbon and energy sources. Bacterial strains preferred the alkane as a carbon and energy source over any of its oxidation products, while fungal strains preferred to grow mainly on the fatty acids. Quantitative analysis by gas liquid chromatography revealed that the predominant bacterial and fungal isolates had a potential for the attenuation of the alkane and its immediate oxidation products in the medium. In view of the continuous release of hydrocarbon oxidation products by oil-utilizing microorganisms in oily environments, it is interesting that the indigenous microflora contribute to the uptake and utilization of all such intermediate compounds, thus, having a potential for efficient self-cleaning and bioremediation of oily soils.     

Expanding the range of halogenated 1'-methyl-1,2'-bipyrroles (MBPs) using GC/ECNI-MS and GCxGC/TOF-MS

Halogenated 1'methyl-1,2'-bipyrroles (MBPs) have been identified worldwide in marine mammals. Here we present the tentative identification of previously undetected MBP congeners in Delpinus delphis blubber using gas chromatography/electron capture negative ion mass spectrometry (GC/ECNI-MS) and comprehensive two-dimensional gas chromatography/time of flight mass spectrometry (GCxGC/TOF-MS). This is the first report of 26 congeners. The presence of numerous partially halogenated congeners suggests that they are either biosynthesized concomitantly with their perhalogenated counterparts or that their dehalogenation products can also bioaccumulate. The newly found compounds fit the geographic trend that has been previously noted. That is, samples from the Atlantic Ocean are dominated by the more brominated congeners while those from the Pacific are dominated by the more chlorinated congeners.     

Development of GC capillary column for isomer-specific separation of toxic isomer of PCDDs and PCDFs in environmental samples

Analysis of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) has been performed using gas chromatography mass spectrometry (GC-MS). Analysis of the most toxic isomers, in particular, 2,3,7,8-substituted PCDD/PCDF in the presence of other isomers requires a special isomer specific capillary column or high performance liquid chromatography (HPLC) fractionation prior to GC-MS analysis. Commercially available long (>50 m) polar columns can separate 2,3,7,8-TCDD from other tetra isomers. However, those columns are not satisfactory for the analyses of total PCDD/PCDF in the environmental samples. Gas chromatography -high resolution mass spectrometry (GC-HRMS) and GC-MS/MS techniques are not helpful in the analysis of 2,3,7,8-TCDD unless it is separated from the other tetra isomers. The analysis of 2,3,7,8-TCDD and total PCDD and PCDF in a single GC-MS run can ease the laborious techniques presently used. In this study we have developed a new stationary phase for the GC capillary column. The capillary column developed using this new stationary phase showed unsurpassed selectivity for the separation of 2,3,7,8-TCDD from other tetra isomers. There are several advantages of the newly developed GC capillary column.     

Fractionation and spectroscopic properties of fulvic acid and its extract

Novel results were obtained when a fulvic acid was isolated from Acros humic acid and fractionated by traditional preparative thin-layer chromatography. Eight colorful bands were directly viewed and analyzed showing very different fluorescence and absorption properties. The fluorescence quantum yield of the bands ranged from 2% to 9.4%, significantly higher than that of natural humic substances. An aqueous fulvic acid solution was also extracted with methylene chloride (CH(2)Cl(2)) by continuous liquid-liquid extraction. The CH(2)Cl(2) extract was further fractionated by thin-layer chromatography. Eleven highly fluorescent colorful bands and six weakly fluorescent bands were observed and examined. UV-vis absorption and fluorescence (including 3D matrix) spectra and fluorescence quantum yields revealed that each band still represented a mixture of compounds. Moreover, substantial differences in optical properties were observed among bands. A single band possessed the highest fluorescence quantum yield (6%) and highest specific fluorescence (fluorescence/mass), and accounted for 21% of the total fluorescence of the extract. The mass of individual bands varied from 1.6% to 14.1% of the total materials recovered. Components of all fractions were grouped into 11 fluorophore families according to their maxima on 3D matrix fluorescence spectra. No component is dominant in the whole fulvic acid or extracted portion in terms of optical properties. Over 40 natural products are proposed for model chromophores.     

Photodegradation of the herbicide EPTC and the safener dichlormid, alone and in combination

Photodegradation of the herbicide EPTC (S-ethyl-N, N-dipropylthiocarbamate), and the safener dichlormid (2,2-dichloro-N, N-diallylacetamide) has been examined in methanol and in water solutions. Irradiation of EPTC and dichlormid with UV light at 254 nm caused rapid degradation in both media. Remarkable and gradual changes in color of EPTC irradiated solution was observed from clear to yellow then to intense orange. EPTC half-life of elimination in water was 14.0, and 18.5 min, and in methanol 37.2 and 32.2 min, when irradiated with and without dichlormid, respectively. There was significant difference between rate of EPTC degradation in water and methanol in the presence or in the absence of dichlormid. Negligible degradation of EPTC or dichlormid at > 290 nm was observed. Photoproducts were separated and identified using GC or/and thin-layer chromatography then identified using mass spectrometry. It appeared that some products have high molecular weight that formed as a result of dimerization. This is possibly a result of the coupling of radicals that formed through EPTC degradation. The cleavage of C-S and C-N bonds accounted for the formation of these radicals. Gradual dealkylation of the acid chains of EPTC has also occurred. EPTC-sulfoxide, EPTC-sulfone, Propylamine and dipropylamine were detected as photoproducts of EPTC at 254 nm. Dichlormid pathways of degradation at 254 nm were characterized as dechlorination, dealkylation, and hydrolysis both in water and methanol. The findings showed that dichlormid did not significantly affect EPTC photodegradation either at 254 nm or at > 290 nm. The biological/toxicological properties of the photoproducts need further study, particularly the dimer compounds.     

Application of GC-MS/MS for the analysis of PCDD/Fs in sewage effluents

The application of high resolution gas chromatography in combination with tandem mass spectrometry in an ion trap was tested to substitute the expensive high resolution mass spectrometry in analysing polychlorinated dibenzo-p-dioxins and furans in sewage effluents. In tandem mass spectrometry, a set of parameters has to be optimised in order to attain the required sensitivity. To the best of our knowledge, this is the first time a method development for analysing PCDD/Fs with GC-MS/MS in an ion trap is described in this detail. Nine parameters are varied, including isolation window, collision induced dissociation (CID) amplitude, CID time, acquisition mass range, broadband amplitude, CID bandwidth, modulation range, filament current and ion trap temperature. This technique can be adapted to other analytes. By this optimisation, limits of detection of 0.01-0.05 ng/l are obtained. With its selectivity and sensitivity, tandem mass spectrometry is a powerful tool for the determination of PCDD/Fs in water samples. 55 sewage effluent samples from Germany were analysed.     

The influence of diet on intra and inter-individual variability of urinary excretion of arsenic species in Italian healthy individuals

To study the effect of eating foods with a high arsenic (As) content on the intra and inter-individual variability of urinary concentrations of the As species, daily urine samples were collected for 10 consecutive days from 12 healthy male subjects. A daily food diary was kept throughout the study period. Personal exposure to airborne As was measured once during the study. As³, As⁵, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine were determined in all urine samples by inductive coupled plasma mass spectrometry, and the sum of As³ + As⁵ + MMA + DMA (iAs) by hydride generation-atomic absorption spectrophotometry. Exposure to airborne As was below the limit of detection in all samplings. As³ was found in only 19.2% and As⁵ in only 3.3% of the urine samples, whereas high urinary concentrations of arsenobetaine were observed. With the exception of arsenobetaine, expressed as a percentage, a significant inter-individual variability was observed for all species of As, for iAs and for the MMA/DMA ratio (p < 0.001). Instead, the intra-individual variability was significant only for the MMA/DMA ratio (p < 0.001). Among foods with a high As content, only a heavy consumption of seafood was shown to influence inter-individual variability of DMA%, arsenobetaine expressed as μg g⁻¹ creatinine and iAs. In conclusion, even in populations with a high intake of organic As through foods, the finding of a significant inter-individual but no significant intra-individual variability of urinary species confirms the usefulness of urinary As speciation for biological monitoring of exposure to As.