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.     

Scenario Analysis for the San Pedro River, Analyzing Hydrological Consequences of a Future Environment

Studies of future management and policy options based on different assumptions provide a mechanism to examine possible outcomes and especially their likely benefits and consequences. The San Pedro River in Arizona and Sonora, Mexico is an area that has undergone rapid changes in land use and cover, and subsequently is facing keen environmental crises related to water resources. It is the location of a number of studies that have dealt with change analysis, watershed condition, and most recently, alternative futures analysis. The previous work has dealt primarily with resources of habitat, visual quality, and groundwater related to urban development patterns and preferences. In the present study, previously defined future scenarios, in the form of land-use/land-cover grids, were examined relative to their impact on surface-water conditions (e.g., surface runoff and sediment yield). These hydrological outputs were estimated for the baseline year of 2000 and predicted twenty years in the future as a demonstration of how new geographic information system-based hydrologic modeling tools can be used to evaluate the spatial impacts of urban growth patterns on surface-water hydrology.     

Plant Phenology in Western Canada: Trends and Links to the View From Space

One feature of climate change is the trends to earlier spring onset in many north temperate areas of the world. The timing of spring flowering and leafing of perennial plants is largely controlled by temperature accumulation; both temperature and phenological records illustrate changes in recent decades. Phenology studies date back over a century, with extensive databases existing for western Canada. Earlier spring flowering has been noted for many woody plants, with larger trends seen for species that develop at spring's start. Implications for ecosystems of trends to earlier spring arrival include changes in plant species composition, changes in timing and distribution of pests and disease, and potentially disrupted ecological interactions. While Alberta has extensive phenology databases (for species, years, and geographic coverage) for recent decades, these data cannot provide continuous ground coverage. There is great potential for phenological data to provide ground validation for satellite imagery interpretation, especially as new remote sensors are becoming available. Phenological networks are experiencing a resurgence of interest in Canada (www.plantwatch.ca) and globally, and linking these ground-based observations with the view from space will greatly enhance our capacity to track the biotic response to climate changes.     

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.     

Laboratory-polluted soils: a methodological approach to establish equilibrium conditions for different metal chemical forms in soils

An approach based on the number of extractions performed over time was applied to study the time necessary to attain equilibrium conditions between the different chemical forms present in two natural soils laboratory-loaded with heavy metals (Cu(II), Pb(II), Zn(II)). The influence of some soil parameters, such as pH value, cation exchange capacity and organic matter content, on the equilibrium time was evidenced both by the different nature of the soils and by the treatment of soils with paper mill sludge. Equilibrium conditions were determined by studying the metal partitioning in the soil on a case by case basis. The behaviour of the three metals was not the same, and the conditions of equilibrium among the different chemical forms were the result of the amount of heavy metals added as well as of the nature of the soil.     

Working backwards to move forwards: Graph-based connectivity metrics for reserve network selection

In this paper we apply graph theory in a reserve selection exercise to explore the tradeoffs between maintaining connectivity and minimizing the total area of a protected area network. Rather than focus on a single organism, we used a multi-species approach and looked at the tradeoff curves for organisms with varying dispersal abilities. We first generated the tradeoff curves using a graph-based metric to determine the importance of individual patches for maintaining connectivity. We then performed an analogous set of analyses using patch size as a surrogate measure of importance.     

Optimal and suboptimal control of anaerobic digesters

Anaerobic digester failure due to entry of inhibitors or sudden changes in the feed substrate concentration may be encompassed beneficially by applying optimal control theory. An almost proportional relationship between the dilution rate and the methane production rate leads to a simple suboptimal control law with only minor loss in performance, after the occurrence of the above mentioned events.     

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.     

Effect of Humic Acid on the Bioavailability of γ-Hexachlorocyclohexane in Marsilea Minuta (L.)

Effect of various concentrations of humic acid (0.2 to 1%) on thebioavailability of -HCH in vegetative clones of theaquatic fern Marsilea minuta was studied in a staticexperimental bioassay system on different photoperiods. Additionof humic acid showed the reduction in the bioavailability of-HCH in all the photoperiods (72 hr light to 144 hrlight) at the interval of 16 hr light (L) and 8 hr dark (D) inboth aerial and submerged portion as compared to controlindicating its protective role in toxicity.     

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.