Application of cryofocusing hydride generation and atomic fluorescence detection for dissolved mercury species determination in natural water samples

The concentration levels of mercury (Hg) species in natural water samples are usually low. Consequently, accurate analysis with low detection limits is still a major problem. In this work, a method was applied for the simultaneous direct determination of dissolved mercury species in water samples by on-line hydride generation (HG), cryogenic trapping (CT), gas chromatography (GC) and detection by atomic fluorescence spectrometry (AFS). The suitability of the method for real samples with different organic matter and chloride contents was evaluated by recovery experiments in synthetic and natural spiked water samples. The HG method was compared with other current available methods for mercury analysis with respect to the different fraction of mercury analysed, i.e. 'reactive', 'reducible' or total. HG derivatization and SnCl2 reduction (with and without previous oxidation with BrCl) were applied to synthetic and natural (spiked and non-spiked) water samples. The influence of chloride and dissolved organic matter concentrations was studied. The results suggest that the HG procedure is suitable for the simultaneous determination of Hg2+ and MeHg+ in surface water samples. Inorganic mercury analysed by HG (i.e. reducible) is close to the total inorganic mercury.     

Mercury and trace elements in cloud water and precipitation collected on Mt. Mansfield,Vermont

The lack of high quality measurements of Hg and trace elements in cloud and fog water led to the design of a new collector for clean sequential sampling of cloud and fog water. Cloud water was collected during nine non-precipitating cloud events on Mt. Mansfield, VT in the northeastern USA between August 1 and October 31, 1998. Sequential samples were collected during six of these events. Mercury cloud water concentrations ranged from 7.5 to 71.8 ng l(-1), with a mean of 24.8 ng l(-1). Liquid water content explained about 60% of the variability in Hg cloud concentrations. Highest Hg cloud water concentrations were found to be associated with transport from the Mid-Atlantic and Ohio River Valley, and lowest concentrations with transport from the north of Mt. Mansfield out of Canada. Twenty-nine event precipitation samples were collected during the ten-week cloud sampling period near the base of Mt. Mansfield as part of a long-term deposition study. The Hg concentrations of cloud water were similar to, but higher on average (median of 12.5 ng l(-1)) than Hg precipitation concentrations (median of 10.5 ng l(-1)). Cloud and precipitation samples were analyzed for fifteen trace elements including Mg, Cu, Zn, As, Cd and Pb by ICP-MS. Mean concentrations were higher in cloud water than precipitation for elements with predominately anthropogenic, but not crustal origin in samples from the same source region. One possible explanation is greater in-cloud scavenging of crustal elements in precipitating than non-precipitating clouds, and greater below-cloud scavenging of crustal than anthropogenic aerosols.     

Attributes of reliable long-term landscape-scale studies: Malpractice insurance for landscape ecologists

Monitoring long-term change in forested landscapes is an intimidating challenge with considerable practical, methodological, and theoretical limitations. Current field approaches used to assess vegetation change at the plot-to-stand scales and nationwide forest monitoring programs may not be appropriate at landscape scales. We emphasize that few vegetation monitoring programs (and, thus, study design models) are designed to detect spatial and temporal trends at landscape scales. Based primarily on advice from many sources, and trial and error, we identify 14 attributes of a reliable long-term landscape monitoring program: malpractice insurance for landscape ecologists. The attributes are to: secure long-term funding and commitment; develop flexible goals; refine objectives; pay adequate attention to information management; take an experimental approach to sampling design; obtain peer-review and statistical review of research proposals and publications; avoid bias in selection of long-term plot locations; insure adequate spatial replication; insure adequate temporal replication; synthesize retrospective, experimental, and related studies; blend theoretical and empirical models with the means to validate both; obtain periodic research program evaluation; integrate and synthesize with larger and smaller scale research, inventory, and monitoring programs; and develop an extensive outreach program. Using these 14 attributes as a guide, we describe one approach to assess the potential effect of global change on the vegetation of the Front Range of the Colorado Rockies. This self-evaluation helps identify strengthes and weaknesses in our program, and may serve the same role for other landscape ecologists in other programs.     

Establishing a standard Sonoran Reference Plant and its application in monitoring industrial and urban pollution throughout the Sonoran Desert

Using analyses from honey mesquite (Prosopis glandulosa) leaves from nearly pristine locations in Arizona, an inorganic plant concentration standard is proposed for use as a Sonoran Reference Plant (SRP). Such a standard can be used as a monitoring device for different anthropogenic pollution sources throughout the Sonoran Desert. To test the application of the SRP, honey mesquite leaves were collected at different sites in southern Arizona and their chemical fingerprints compared to SRP. Sources of element origin were identified through factor analysis and correlation matrices. A terrestrial factor was found in leaves from all sites. Anthropogenic factors varied for different sites. Mesquite leaves accumulated significant amounts of elements originating from copper smelters (As, Sb) and urban pollution (La, Sm, Ce, V). These pollutants are small-sized and have been linked to human lung diseases. Mesquite is a deciduous tree; the yearly comparison of mesquite leaf element concentration spectra to the SRP standard can be used to determine seasonal improvement or deterioration of environmental quality in a particular area.     

Environmental and biological monitoring of methyl ethyl ketone (MEK)

This study was conducted to evaluate the usefulness of various biological parameters for monitoring of workers exposed to methyl ethyl ketone (MEK). Fifty male workers from a large magnetic videotape factory participated in this study. Personal air samples were collected using 3M organic vapor monitors and analysed for MEK by gas chromatography with flame ionisation detector (FID). 10 mL of urine; blood (1 mL) and exhaled air were also collected at the end of an 8-hour workshift. The headspace GC method was applied for measurement of urinary and blood MEK. MEK in expired air was analysed directly by using a GC/FID.The correlation coefficients (r) between environmental MEK and all other biological parameters measured show significant positive relationships. The r for environmental MEK and urine MEK was 0.84; for blood 0.73 and for breath 0.64. The correlation coefficients between blood and urine was 0.72; blood and breath was 0.88 and urine and breath 0.60. These findings suggest that measurements of unmetabolised MEK in blood, exhaled air and urine can be used for biological monitoring of MEK exposure. Nevertheless, laboratory methodological assessment is in favour of measuring urinary MEK as it is non-invasive and does not have to be analysed immediately after collection.     

Quantification of protein adducts of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride in human plasma

Hexahydrophthalic anhydride (HHPA) and methylhexahydrophthalic anhydride (MHHPA) are two highly allergenic compounds used in the chemical industry. A method was developed for quantification of protein adducts of HHPA and MHHPA in human plasma. The plasma was dialysed and the anhydrides were hydrolysed from the proteins at mild acidic conditions. The released hexahydrophthalic acid (HHP acid) and methylhexahydrophthalic acid (MHHP acid) were purified by reversed solid phase extraction followed by derivatisation with pentafluorobenzyl bromide. The derivatives were analysed using GC-MS in negative ion chemical ionisation mode with ammonia as moderating gas. As internal standards, deuterium labelled HHP and MHHP acids were used. The detection limits were 0.06 pmol mL(-1) plasma for HHP acid and 0.03 pmol mL(-1) plasma for MHHP acid. The between-day precisions for HHP acid were 18% at 0.3 pmol mL(-1) and 8% at 4 pmol mL(-1). For MHHP acid, the precisions were 13% at 0.3 pmol mL(-1) and 9% at 4 pmol mL(-1). There were strong correlations (r=0.94 for HHPA and 0.99 for MHHPA) between total plasma protein adduct concentrations and serum albumin adduct levels. Workers exposed to time-weighted average air levels of HHPA between < 1 and 340 microg m(-3) and between 2 and 160 microg m(-3) for MHHPA had plasma adduct levels between the detection limits of the methods and 8.40 and 19.0 pmol mL(-1), respectively.     

Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.     

Development and validation of methods for environmental monitoring of cyclophosphamide in workplaces

Methods to monitor contamination of workplaces with antineoplastic drugs have been developed and validated. Cyclophosphamide (CP) was used as a model compound as it is one of the most commonly used antineoplastic drugs. A wipe sampling method to detect contamination with CP at surfaces was developed. A personal air sampling method to sample gas and vapour on solid sorbent tubes and particles with filters was also developed. Wipe and filter samples were extracted and sorbent samples were eluted, all with ethyl acetate. The samples were analysed with liquid chromatography tandem mass spectrometry. (2)H(6)-labelled cyclophosphamide was used as an internal standard. The between-day precision was 2-5% for wipe samples, 4-6% for sorbent samples and 3-8% for filter samples. The limit of detection was 0.02 ng CP per sample for the wipe and filter methods and 0.03 ng CP per sample for the solid sorbent method. Wipe sampling on surfaces made of different materials resulted in mean recoveries between 78-106%. The desorption recovery was between 97-102% for the wipe samples, 97% for the sorbent samples and 101% for the filter samples. Samples were stable for up to 2 months at 5 degrees C and -20 degrees C and for about 2 d at room temperature. The developed methods were applied to the measurement of contamination with CP in a hospital pharmacy. Trace amounts of CP, 1.3 and 1.4 ng, were detected on surfaces in the pharmacy.     

A combination of micro-porous membrane liquid-gas extraction and solid-phase trapping for ultra trace determination of benzene in urine

A method was developed for the determination of benzene in urine. The sample was pumped through the donor channel of a membrane extraction unit with a micro-porous membrane, separating the donor channel from an identical acceptor channel purged with nitrogen. The analyte reached the acceptor channel by diffusion through the membrane and was then swept by the carrier to a solid sorbent tube, where it was trapped. The analyte was subsequently thermally desorbed and analyzed by gas chromatography (GC) with mass selective detection (MS). After optimization, the recovery was close to quantitative, or 95%. Purging the membrane unit with pure water in between the samples eliminated any memory effects. The linearity was good in the concentration range examined (20-4000 ng l(-1)), with a correlation coefficient of 0.9996. The repeatability at 50 ng l(-1) and 400 ng l(-1) was 1.4% and 1.2%, respectively. The limit of detection was 12 ng l(-1) and the limit of quantification 35 ng l(-1). This enables assessment of benzene exposures of occupationally exposed subjects, of smokers and the majority of the general population. The developed method can be easily automated.