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.     

Impact of distillery effluent application to land on soil microflora

A pot culture experiment was conducted to evaluate the effect of different treatments of distillery wastewater, i.e. raw, treated, diluted and raw distillery wastewater mixed with domestic waste stabilization pond effluent (1:1) on populations of bacteria, fungi, actinomycetes and nitrogen fixing bacteria. The results indicated that raw wastewater decreased the population of bacteria, fungi and actinomycetes. The growth rates of Rhizobium and Azotobacter were also reduced after raw wastewater application. The toxic effect of raw wastewater was minimized when it was mixed with stabilization pond effluent (1:1), this was demonstrated by an increase in the populations of all the microorganisms studied. When a groundnut plant was irrigated with raw distillery wastewater, no fruits were produced and there was also less nodulation. This study indicates that raw distillery wastewater is very toxic to the soil microorganisms which are important in the soil ecosystem.     

A study on the behaviour of pesticides and their transformation products in the Scheldt estuary using liquid chromatography-electrospray tandem mass spectrometry

Off-line solid-phase extraction (SPE) combined with liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS-MS) was used to study the estuarine behaviour of the polar pesticides, atrazine, chloridazon, diuron and metolachlor, and their transformation products (TPs), hydroxyatrazine (HA), desisopropylatrazine (DIA), desethylatrazine (DEA), 3,4-dichlorophenylmethylurea (DPMU) and monuron. The compounds were identified by comparing their LC retention times and product-ion spectra with those of standard solutions. In all but one case the detection limits of the method were sufficient to determine the compounds of interest over the entire salinity range in the estuary. The concentrations of the dissolved pesticides ranged from 70 ng l-1 for chloridazon to 1350 ng l-1 for diuron. The levels of TPs were 3-8% of the levels of their parent pesticide. The mixing plots of polar pesticides and their TPs indicated that TPs, which are present in fresh river water, are conservatively transported to the sea and that no additional amounts of TPs are formed during their transport through the estuary. The one exception was HA, of which approximately 10% of the amount transported to the North Sea is formed in the lower part of the estuary by photochemical oxidation of atrazine. The latter was concluded from the ratios of each analyte over the sum total of the parent pesticide and all TPs along the salinity gradient, which proved to be a useful tool for identifying such estuarine transformations.     

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.     

Spectrophotometric determination of ferbam (iron(III) dimethyldithiocarbamate) in commercial sample and wheat grains using 4,7-diphenyl-1,10-phenanthroline after extraction into mesityl oxide

A procedure has been developed for the determination of iron(III) dimethyldithiocarbamate by converting it into iron(II)-bathophenanthroline complex, which is then extracted into mesityl oxide in the presence of potassium perchlorate. The absorbance is then measured at 534 nm against a reagent blank. Beer's law is obeyed over the concentration range 0.5-20 microg ml(-1) in the final solution. The method is sensitive, highly selective and can be used for the determination of ferbam in a commercial sample, and in mixtures with various dithiocarbamates (ziram, zineb, maneb, etc.) and in wheat grains.     

Drainage Effects on Stream Nitrate-N and Hydrology in South-Central Minnesota (USA)

Excessive nitrate-N in south-central Minnesota ditches and streams is related to land-use change, and may be contributing to the development of the zone of hypoxia in the Gulf of Mexico. Intensive land-use (agricultural management) has progressively increased as subsurface drainage has improved crop productivity over the past 25 years. We have examined water at varying scales for delta18O and, nitrate-N concentrations. Additionally, analysis of annual peak flows, and channel geomorphic features provided a measure of hydrologic change. Laboratory and field results indicate that agricultural drainage has influenced riverine source waters, concentrations of nitrate-N, channel dimensions and hydrology in the Blue Earth River (BER) Basin. At the mouth of the BER shallow ground water comprises the largest source water component. The highest nitrate-N concentrations in the BER and tributaries typically occurred in May and June and ranged from 7-34 mg L(-1). Peak flows for the 1.01-2-yr recurrence intervals increased by 20-to-206% over the past 25 years. Geomorphic data suggest that small channels (ditches) were entrenched by design, whereas, natural that are disconnected from an accessible riparian corridor. Frequent access to a functioning riparian zone is important for denitrification.     

Paleolimnological assessment of Grove and Plow Shop Ponds, Ayer, Massachusetts, USA--a superfund site

Three sediment cores from each of severely polluted Grove and Plow Shop Ponds, Ayer, Massachusetts, USA, were dated using (210)Pb, characterized for plant macrofossil assemblages, and analyzed for H(2)O, loss-on-ignition, stable Pb isotopes, and concentrations of As, Ca, Cd, Cr, Cu, Fe, Hg, methyl-Hg, Ni, Pb, and Zn. A core from nearby kettle Spectacle Pond, Littleton, Massachusetts, was similarly characterized (except for plant macrofossil assemblages) to assess the regional air pollution signal in sediment for comparison with the six cores. Accumulation rates for metals (mass per area per year), the anthropogenic component (mass per area per year), and total accumulation of the anthropogenic component (mass per area) indicate that As, Cd, Cr, Cu, Hg, methyl-Hg, Ni, Pb, and Zn have accumulated in sediment as a consequence of point source pollution from within the drainage basins of Grove and Plow Shop Ponds. Three distinct sources of pollution are inferred. As is entering Plow Shop Pond via groundwater in the southwest. Cd, Ni, Pb, and Zn are entering the system predominantly at the eastern end of, or upstream from, Grove Pond. Pb also comes from the northwest corner of Grove Pond, the principal source of Cr, Cu, and Hg. These results are consistent with chemistry of modern surface sediments. The history of pollution extends back more than 100 years. Intra- and inter-core variability of concentrations and accumulation rates indicate that much of the pollution was likely in particulate form with little physical redistribution. Recently, concentrations and accumulation rates have generally decreased substantially for those elements present in excessive concentrations in the past. This is a consequence of accumulation of recent, less polluted sediment. In Spectacle Pond, the nearby reference lake, accumulation rates for As, Cd, Hg, and Pb, adjusted for background values and changes in sedimentation rate, increased above background starting in the late 19th century, peaked about 1980, and declined substantially to 2000. These decreases suggest that the anthropogenic (pollution) component of atmospheric deposition of these elements declined after 1980 by at least 50%(As), 80%(Cd), 80%(Hg), and 80%(Pb).     

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.     

Natural mercury enrichment in a minerogenic fen--evaluation of sources and processes

Mercury (Hg) records in natural archives such as peat bogs are often used to evaluate anthropogenic or climatic influences on atmospheric Hg deposition. In this context, there is an ongoing discussion about natural sources or processes of Hg enrichment in natural archives. In the present study we estimated Hg fluxes from rock weathering, direct atmospheric deposition and from indirect atmospheric deposition in the catchment of a pristine minerogenic fen (GC2) located in the Magellanic Moorlands, southernmost Chile. The Hg record in the bog covers 11 174 cal. (14)C years and shows Hg concentrations of up to 570 [micro sign]g kg(-1) with an average of 268 [micro sign]g kg(-1). Hg was found to be enriched in the peat by a factor of 81 if compared to the mean Hg concentrations in the rocks of the catchment (3.2 [micro sign]g kg(-1)). Hg and also Pb, Fe, and As were found to be enriched predominately in goethite layers indicating high retention of these elements in the bog by iron oxyhydrates. It could also be demonstrated that the high peat decomposition rates in minerogenic bogs can increase the Hg concentrations in the minerogenic peat by a factor of approximately 2 at the same atmospheric Hg deposition rate if compared to ombrotrophic sites. This study has shown that Hg in minerogenic peat can be naturally enriched especially through the retention by autochthonous formed goethite and can be a solely internal process which does not require increased external Hg fluxes.     

High frequency monitoring of the coastal marine environment using the MAREL buoy

The MAREL Iroise data buoy provides physico-chemical measurements acquired in surface marine water in continuous and autonomous mode. The water is pumped 1.5 m from below the surface through a sampling pipe and flows through the measuring cell located in the floating structure. Technological innovations implemented inside the measuring cell atop the buoy allow a continuous cleaning of the sensor, while injection of chloride ions into the circuit prevents biological fouling. Specific sensors for temperature, salinity, oxygen and fluorescence investigated in this paper have been evaluated to guarantee measurement precision over a 3 month period. A bi-directional link under Internet TCP-IP protocols is used for data, alarms and remote-control transmissions with the land-based data centre. Herein, we present a 29 month record for 4 parameters measured using a MAREL buoy moored in a coastal environment (Iroise Sea, Brest, France). The accuracy of the data provided by the buoy is assessed by comparison with measurements of sea water weekly sampled at the same site as part of SOMLIT (Service d'Observation du Milieu LIToral), the French network for monitoring of the coastal environment. Some particular events (impact of intensive fresh water discharges, dynamics of a fast phytoplankton bloom) are also presented, demonstrating the worth of monitoring a highly variable environment with a high frequency continuous reliable system.