Mathematical balance models for monitoring the state of Lake Baikal

The global cycles of man-produced pollutants entering the natural environment are reflected in changes of pollutant cycles, even in background regions.The system of mathematical balance simulation models of inorganic pollutant distribution and circulation (some heavy metals and pesticides included in the priority list for integrated background monitoring) has been developed for the Lake Baikal drainage basin. The system consists of the following units: (1) inventory and classification of regional sources of pollutants entering the atmosphere, natural waters and soils; (2) computation of the global atmospheric transfer and depositions; (3) regional spreading with atmospheric fluxes and deposition onto the underlying surfaces; (4) transport with waterflows feeding Lake Baikal; (5) transport with the lake currents and balance in the lake.The models developed have enabled improvement of existing programmes and systems of observations, in particular to substantiate the large-scale snow sampling and analysis network, and to develop the programme of integrated surveys of the state of Lake Baikal. Since 1981 these actions have been included in the operational network observations within the Lake Baikal Monitoring System.     

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.     

The influence of geometry and draught shields on the performance of passive samplers

Passive samplers provide an excellent opportunity to perform indicative measurements or establish a dense network of measuring sites. A drawback compared with conventional active measuring methods is the larger spread of results. This variation can, to a large extent, be attributed to the influence of temperature, sampler geometry and wind on sampling results. A proper design of sampler geometry and optimum choice of draught shield can reduce the influence of wind velocity on a badge type sampler to less than 10%. Wire mesh screens prove to be inadequate in damping turbulence. Filters give good results. Attention should be paid to the size and isolation value of the walls of the sampler to prevent thermal updrafts occurring within the sampler. Tube type samplers are less influenced by wind, provided that turbulence is prevented from influencing diffusion within the sampler.     

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.     

Effects of Roadway Crossings on Leaf Litter Processing and Invertebrate Assemblages in Small Streams

The effects of the Maine Turnpike (Interstate 95) on leaf litter processing were examined in five first- and second-order coastal plain streams in southern Maine, U.S.A. Invertebrate assemblages and red maple leaf softening and loss rates were compared at 53 stations arrayed upstream and downstream of the turnpike. Litter softening rate was not affected by the roadway. Litter loss rate was significantly faster at downstream stations (-0.0024 degree-day(-1)) than at upstream stations or at stations nearest the roadway, which were not different from each other (-0.0022 degree-day(-1)). Litter softening and loss rates were more strongly related to physical and chemical habitat variables than to shredder assemblage characteristics. Significant among-stream differences were observed in most community structural metrics and in biomass of important shredder taxa, but effects of the roadway were rarely consistent among streams. This is attributed in part to habitat variation, which was greater among streams than within streams. This study suggests that while the presence of the Maine Turnpike may influence stream water quality and habitat structure, the relatively subtle effects of roadway runoff and associated habitat modifications on stream ecosystem processes are masked by within- and among-stream variability in litter processing and leaf pack invertebrate assemblage structure.     

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).