The efficacy of protoporphyrin as a predictive biomarker for lead exposure in canvasback ducks: Effect of sample storage time

We used 363 blood samples collected from wild canvasback dueks (Aythya valisineria) at Catahoula Lake, Louisiana, U.S.A. to evaluate the effect of sample storage time on the efficacy of erythrocytic protoporphyrin as an indicator of lead exposure. The protoporphyrin concentration of each sample was determined by hematofluorometry within 5 min of blood collection and after refrigeration at 4 °C for 24 and 48 h. All samples were analyzed for lead by atomic absorption spectrophotometry. Based on a blood lead concentration of 0.2 ppm wet weight as positive evidence for lead exposure, the protoporphyrin technique resulted in overall error rates of 29%, 20%, and 19% and false negative error rates of 47%, 29% and 25% when hematofluorometric determinations were made on blood at 5 min, 24 h, and 48 h, respectively. False positive error rates were less than 10% for all three measurement times. The accuracy of the 24-h erythrocytic protoporphyrin classification of blood samples as positive or negative for lead exposure was significantly greater than the 5-min classification, but no improvement in accuracy was gained when samples were tested at 48 h. The false negative errors were probably due, at least in part, to the lag time between lead exposure and the increase of blood protoporphyrin concentrations. False negatives resulted in an underestimation of the true number of canvasbacks exposed to lead, indicating that hematofluorometry provides a conservative estimate of lead exposure.The U.S. Government's right to retain a non-exclusive, royalty-free licence in and to any copyright is acknowledgedDeceased     

Cadmium and zinc source assessment in the Sepetiba Bay and basin region

Industrial and weathering inputs of Cd and Zn to the Sepetiba Bay and basin were assessed, based on production parameters obtained from local environment and industry authorities, and literature data. The results are compared with similar evaluations from other coastal regions and field data obtained in measuring Zn and Cd transport by rivers, direct run-off and atmospheric deposition in the region. Cadmium and zinc inputs to the bay increased by three orders of magnitude relative to pre-industrial fluxes and presently reach up to 1.6 and 180 tonnes per year for Cd and Zn, respectively, which represents a large input-to-area ratio, and explains the high concentration of these metals previously reported in the estuarine biota and sediments of Sepetiba Bay. Industrial activities, mainly metallurgical and chemical, comprise 94% and 84% of the total Cd and Zn inputs to the Bay. This figure identifies the point sources as being responsible for the environmental contamination and for regional poisoning risks.     

Microbiological characteristics in a zero-valent iron reactive barrier

Zero-valent iron (Fe⁰)-based permeable reactive barriertreatment has been generating great interest for passivegroundwater remediation, yet few studies have paid particularattention to the microbial activity and characteristics withinand in the vicinity of the Fe⁰-barrier matrix. The presentstudy was undertaken to evaluate the microbial population andcommunity composition in the reducing zone of influence byFe⁰ corrosion in the barrier at the Oak Ridge Y-12 Plantsite. Both phospholipid fatty acids and DNA analyses were usedto determine the total microbial population and microbialfunctional groups, including sulfate-reducing bacteria,denitrifying bacteria, and methanogens, in groundwater andsoil/iron core samples. A diverse microbial community wasidentified in the strongly reducing Fe⁰ environment despitea relatively high pH condition within the Fe⁰ barrier (up topH 10). In comparison with those found in the backgroundsoil/groundwater samples, the enhanced microbial populationranged from 1 to 3 orders of magnitude and appeared to increase from upgradient of the barrier to downgradient soil. Inaddition, microbial community composition appeared to change overtime, and the bacterial types of microorganismsincreased consistently as the barrier aged. DNA analysisindicated the presence of sulfate-reducing and denitrifyingbacteria in the barrier and its surrounding soil. However, theactivity of methanogens was found to be relatively low,presumably as a result of the competition by sulfate/metal-reducing bacteria and denitrifying bacteria because of the unlimited availability of sulfate and nitrate in the site groundwater. Results of this study provide evidenceof a diverse microbial population within and in the vicinity ofthe iron barrier, although the important roles of microbial activity, either beneficially or detrimentally, on the longevityand enduring efficiency of the Fe⁰ barriers are yet to be evaluated.     

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.     

The analysis of monitoring data with the aid of time-series analysis

Methods derived from time-series analysis are proposed for processing monitoring data. The necessity for the use of these methods is demonstrated. In a case study time-series analysis was applied to assess the impact of the closure of the Grevelingen estuary (S. W. Netherlands) in 1971 on a local wintering population of Oystercatchers (Haematopus ostralegus) in the adjacent Oosterschelde estuary.Communication No. 328 of the Delta Institute for Hydrobiological Research.     

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.     

A historical study of mineral elements in forest plants from South Norway

Herbarium plants were used as a material to study possible long-term changes in mineral elements of forest plants. Plants from South Norway collected in the period 1870 to 1930 were compared to plants collected in 1982. Relative to mineral contents in plants from 1870 to 1930, the 1982 material showed elevated levels of Zn, Cd, Rb, K, Mn and Ti and decreased levels of Sr, B, Ca and Mo in some of the plant species analysed. Most of these differences may be explained by changes in the environmental conditions, due to differences in chemical composition of precipitation, accelerated soil acidification and subsequent increasing mineral weathering. Consequently analysis of herbarium plants seems to provide valuable information about preindustrial levels of mineral elements and seems to detect changes in mineral elements brought about by recent anthropogenic activity.     

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.