Bi-national assessment of the Great Lakes: SOLEC partnerships

Many administrative jurisdictions have authority over parts of the Great Lakes, sometimes with competing purposes as well as governance at differing scales of time and space. As demand increases for high quality information that is relevant to environmental managers, environmental and natural resource agencies with limited budgets must look to interdisciplinary, collaborative approaches for the collection, analysis and reporting of data. The State of the Lakes Ecosystem Conferences (SOLEC) were begun in 1994 in response to reporting requirements of the Great Lakes Water Quality Agreement between Canada and the U.S. The biennial conferences provide independent, science-based reporting on the state of health of the Great Lakes ecosystem components. A suite of indicators necessary and sufficient to assess Great Lakes ecosystem status was introduced in 1998, and assessments based on a subset of the indicators were presented in 2000. Because SOLEC is a multi-agency, multi-jurisdictional reporting venue, the SOLEC indicators require acceptance by a broad spectrum of stakeholders in the Great Lakes basin. The SOLEC indicators list is expected to provide the basis for government agencies and other organizations to collaborate more effectively and to allocate resources to data collection, evaluation and reporting on the state of the Great Lakes basin ecosystem.     

Seasonal variations in physico-chemical characteristics of River Yamuna in Haryana and its ecological best-designated use

Various physico-chemical characteristics of the River Yamuna flowing in Haryana through Delhi were studied in the summer (April 1998) and winter (Jan.-Feb. 1999). Ecological parameters like dissolved oxygen (DO), pH, nitrate (NO3-), sulfate (SO4(2-)), and phosphate (PO4(3-)), were analyzed and compared with standard permissible limits to assess the best-designated use of the river water for various purposes. The river in Delhi upstream was of better quality whereas the Delhi downstream stretch was polluted as indicated by very low DO and high total dissolved solids (TDS), electric conductivity (EC), total hardness, Na+, K+, Cl-, F- and SO4(2-). The differences in various parameters were statistically significant (p < 0.01) when compared for the Delhi upstream and downstream stretches of the river, particularly in summer. DO and TDS were found to be two important parameters, which showed strong correlation with several other parameters and hence can serve as good indices of river water quality. The river tended to recover from the pollution stress after flowing through a distance of about 80 km downstream of Delhi.     

Diffusive sampling of methyl isocyanate using 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ) as derivatizing agent

A diffusive sampling method for the determination of methyl isocyanate (MIC) in air is introduced. MIC is collected using a glass fiber filter impregnated with 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ). The urea derivative formed is desorbed from the filter with acetonitrile and analyzed by means of high-performance liquid chromatography (HPLC) using fluorescence detection (FLD) with lambdaex = 471 nm and lambdaex = 540 nm. Additionally, a method was developed using tandem mass spectrometric (MS-MS) detection, which was performed as selected reaction monitoring (SRM) on the transition [MIC-NBDPZ + H]+ (m/z 307) to [NBDPZ + H]+ (m/z 250). The diffusive sampler was tested with MIC concentrations between 1 and 35 microg m(-3). The sampling periods varied from 15 min to 8 h, and the relative humidity (RH) was set from 20% up to 80%. The sampling rate for all 15 min experiments was determined to be 15.0 mL min(-1) (using HPLC-FLD) with a relative standard deviation of 9.9% for 56 experiments. At 80% RH, only 15 min sampling gave acceptable results. Further experiments revealed that humidity did not affect the MIC derivative but the reagent on the filter prior to and during sampling. The sampling rate for all experiments (including long term sampling) performed at 20% RH was found to be 15.0 mL min(-1) with a relative standard deviation of 6.3% (N = 42). The limit of quantification was 3 microg m(-3) (LC-MS-MS: 1.3 microg m(-3)) for 15 min sampling periods and 0.2 microg m(-3) (LC-MS-MS: 0.15 microg m(-3)) for 8 h sampling runs applying fluorescence detection.     

Impact of automobile emissions on the levels of platinum and lead in Accra,Ghana

Examination of car fleet records in Accra demonstrates an increasing proportion of catalytic converter-equipped cars in the relatively old car fleet (average age 13 years) due to their import from developed countries. However, only leaded petrol is sold in Ghana. Lead anti-knocking additives, which are known to affect catalyst activity and promote thermal sintering and mechanical abrasion, may increase Pt emissions. This possible synergism prompted the concomitant determination of Pb and Pt levels in road dust and roadside soils in Ghana. Both metals followed traffic density with higher concentrations in urban areas compared to remote sites. In urban areas, the range for Pb (365 +/- 93 microg g(-1) for dust and 291 +/- 76 microg g(-1) for soil) reflects precatalyst levels in Europe and the US, while the range for Pt (39 +/- 24 ng g(-1) for dust and 15 +/- 5.3 ng g(-1) for soil) is typical for the same countries. The elevated Pt concentrations were unexpected due to recent introduction of catalysts to Ghana compared to the prolonged use of catalysts in Europe and the US.     

Adenine nucleotides in snail muscles as one of biomarkers of fluoride toxicity

The aim of this work was to determine the extent of bioaccumulation of fluorides in tissues of Helix aspersa maxima. The toxicity of fluorides administered orally on the energy balance of the snail's foot was investigated based on measurements of concentrations of adenine nucleotides and their metabolism degradation products. Quantitation of fluoride levels was done in soft tissues (foot, hepatopancreas) and shells of mature snails. Qualitative and quantitative analysis of purine compounds was performed in slices of foot from mature snails. Fluoride concentrations in pulverized shells were measured using an ion-selective electrode. Gas chromatography was used to determine fluoride concentrations in soft tissues (hepatopancreas and foot). Purines were measured in foot muscle slices with high-performance liquid chromatography (HPLC). Fluoride levels in soft tissues of the snail cannot serve as an indicator for biomonitoring purposes as no significant accumulation was observed during exposure to maximum allowable concentrations of fluoride in drinking water. Contrary to this, levels of fluoride in the shell rose significantly with this concentration of fluoride in drinking water. The effect of fluorides on energy metabolism of foot muscle was evidenced by elevated AMP levels, increased adenine nucleotide pool and reduced conversion of ADP to ATP. Exposure to rising F(-) concentrations was accompanied by decreasing values of the adenylate energy charge AEC. Determination of AMP or AEC in foot muscle of exposed snails seems to be a useful indicator of fluoride effects on metabolic activity.     

Arsenic speciation in human hair: a new perspective for epidemiological assessment in chronic arsenicism

The analysis for arsenic in hair is commonly used in epidemiological studies to assess exposure to this toxic element. However, poor correlation between total arsenic concentration in hair and water sources have been found in previous studies. Exclusive determination of endogenous arsenic in the hair, excluding external contamination has become an analytical challenge. Arsenic speciation in hair appears as a new possibility for analytical assessing in As-exposure studies. This study applied a relative simple method for arsenic speciation in human hair based on water extraction and HPLC-HG-ICP-MS. The concentration of arsenic species in human hair was assessed in chronically As(V)-exposed populations from two villages (Esqui?a and Illapata) of the Atacama Desert, Chile. The arsenic concentrations in drinking water are 0.075 and 1.25 mg L(-1), respectively, where As(V) represented between 92 and 99.5% of the total arsenic of the consumed waters. On average, the total arsenic concentrations in hair from individuals of Esqui?a and Illapata were 0.7 and 6.1 microg g(-1), respectively. Four arsenic species, As(III), DMA(V), MMA(V) and As(V), were detected and quantified in the hair extracts. Assuming the found species in extracts represent the species in hair, more than 98% of the total arsenic in hair corresponded to inorganic As. On average, As(III) concentrations in hair were 0.25 and 3.75 microg g(-1) in Esqui?a and Illapata, respectively; while, the As(V) average concentrations were 0.15 and 0.45 microg g(-1) in Esqui?a and Illapata, respectively. Methylated species represent less than 2% of the extracted As (DMA(V)+ MMA(V)) in both populations. As(III) in hair shows the best correlation with chronic exposure to As(V) in comparison to other species and total arsenic. In fact, concentrations of As(total), As(III) and As(V) in hair samples are correlated with the age of the exposed individuals from Illapata (R= 0.65, 0.69, 0.57, respectively) and with the time of residence in this village (R= 0.54, 0.71 and 0.58, respectively).     

Speciation of iron in river water using a specific catalytic determination and size fractionation

A comprehensive speciation scheme was proposed for the speciation of iron in river water (0.45 microm filtrate). The speciation was based on the catalytic determination of reactive iron as Fe3+ and Fe(III)Li/(3 -in)+, where i = 1 or 2 for a unidentate and i = 1 for a bidentate ligand, Ln-. The scheme incudes size fractionation and acid decomposition of the sample and determination of the coexisting species. The proposed scheme was applied to natural and artificial samples and acidified preparations of these. Resulting fractionation patterns of reactive and unreactive iron and of coexisting humic acid were useful for the characterization of iron species in the natural samples. The reactive iron in the molecular weight (Mr) > or = 10(4) fraction was associated with humic iron aggregates and estimated as iron complexed with them. The unreactive iron in this fraction dissociated in 0.1 M HCI and was estimated as iron in the aggregates of iron(III) hydroxide (s) and humic iron. From the fractionation results of the artificial sample, the reactive and unreactive iron in the Mr < 10(3) fraction may be formed by complexing simple anions like F- and C2O4(2-) at their naturally-occurring concentration levels. The fractionation results also suggested that humic acid and Si contributed to the formation of reactive and unreactive iron in the Mr > or = 10(4) fraction.     

用广义λ—分布拟合空气污染数据

广义λ-分布是一个四参数可变通的概率模型,包括多种单变量分布,这一模型可用于表示空气污染浓度的频率分布。本文采用土耳其安卡拉每日的烟和SO_2监测数据,来证明广义λ-分布具有良好的拟合性质。这里还讨论了与分位数估计和拟合优度有关的一些结果,并与经典对数正态分布进行了比较。     

Suggested protocol for collecting, handling and preparing peat cores and peat samples for physical, chemical, mineralogical and isotopic analyses

For detailed reconstructions of atmospheric metal deposition using peat cores from bogs, a comprehensive protocol for working with peat cores is proposed. The first step is to locate and determine suitable sampling sites in accordance with the principal goal of the study, the period of time of interest and the precision required. Using the state of the art procedures and field equipment, peat cores are collected in such a way as to provide high quality records for paleoenvironmental study. Pertinent field observations gathered during the fieldwork are recorded in a field report. Cores are kept frozen at -18 degree C until they can be prepared in the laboratory. Frozen peat cores are precisely cut into 1 cm slices using a stainless steel band saw with stainless steel blades. The outside edges of each slice are removed using a titanium knife to avoid any possible contamination which might have occurred during the sampling and handling stage. Each slice is split, with one-half kept frozen for future studies (archived), and the other half further subdivided for physical, chemical, and mineralogical analyses. Physical parameters such as ash and water contents, the bulk density and the degree of decomposition of the peat are determined using established methods. A subsample is dried overnight at 105 degree C in a drying oven and milled in a centrifugal mill with titanium sieve. Prior to any expensive and time consuming chemical procedures and analyses, the resulting powdered samples, after manual homogenisation, are measured for more than twenty-two major and trace elements using non-destructive X-Ray fluorescence (XRF) methods. This approach provides lots of valuable geochemical data which documents the natural geochemical processes which occur in the peat profiles and their possible effect on the trace metal profiles. The development, evaluation and use of peat cores from bogs as archives of high-resolution records of atmospheric deposition of mineral dust and trace elements have led to the development of many analytical procedures which now permit the measurement of a wide range of elements in peat samples such as lead and lead isotope ratios, mercury, arsenic, antimony, silver, molybdenum, thorium, uranium, rare earth elements. Radiometric methods (the carbon bomb pulse of (14)C, (210)Pb and conventional (14)C dating) are combined to allow reliable age-depth models to be reconstructed for each peat profile.     

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.