The application of HPLC-F and GC-MS to the analysis of selected hydroxy polycyclic hydrocarbons in two certified fish bile reference materials

Four selected hydroxy polycyclic aromatic hydrocarbons (OH-PAHs), 2-hydroxy-naphthalene (2-OH-NPH), 1-hydroxy-phenanthrene (1-OH-PHE), 1-hydroxy-pyrene (1-OH-PYR) and 3-hydroxy-benzo[a]pyrene (3-OH-BaP) have been analysed in two certified fish bile reference materials (CRMs) for exposure monitoring of PAHs in the aquatic environment. The two materials, BCR 720 and BCR 721, consist of bile from fish exposed to contaminated sediment and dispersed crude oil, respectively. Both bile samples have been analysed by two different analytical techniques, gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography-fluorescence detection (HPLC-F), and the separation performance, detection limits, recoveries and reproducibility for the four target compounds were evaluated. HPLC-F requires a simple sample preparation and the separation capacity is adequate for quantification of 1-OH-PYR and 3-OH-BaP. Detection limits are excellent for 1-OH-PYR (6 pg injected) and 3-OH-BaP (3 pg injected) and generally improved with increasing molecular size. Recoveries ranged from 48 to 99% for the four selected compounds, depending on compound and concentration. Sample preparation prior to GC-MS analysis was more demanding, as reflected by the obtained recoveries for 2-OH-NPH, 1-OH-PHE and 1-OH-PYR (35 to 61%). The sensitivity improved with decreasing molecular size, 2-OH-NPH (1.2 pg injected), 1-OH-PHE (2.4 pg injected) and 1-OH-PYR (6 pg injected). Because of the superior separation power of GC and the extra selectivity of MS detection, GC-MS was the method of choice for the determination of 2-OH-NPH and 1-OH-PHE in both CRMs. In fish bile samples these two compounds are more likely to suffer from chromatographic overlap, and HPLC-F was not sufficiently selective. Determination of 1-OH-PYR was performed with success by both methods, but HPLC-F would be preferred because of the simpler and less time-consuming sample preparation. Detectable concentrations of 3-OH-BaP were present in BCR 720 and could only be determined by HPLC-F. The present work aims to present HPLC-F and GC-MS as complementary methods for the quantitative analysis of OH-PAHs in fish bile.     

Aerosol chemical characteristics of an island site in the Bay of Bengal (Bhola-Bangladesh)

Aerosol constituents (elemental carbon, organic carbon, soluble ions including organic acids, and selected trace metals) were investigated from samples of a field campaign taking place at Bhola Island in the Bay of Bengal (Bangladesh). The campaign took place in the pre-monsoon season (May 2001) using low volume samplers. Carbonaceous material comprised the majority of the analysed components. The average concentrations of EC and OC were 2.8 and 4.6 microg m(-3), respectively. Oxalic acid was the most abundant dicarboxylic acid (average 268 ng m(-3)) followed by malonic and malic acid. The contribution of carboxylic acids-carbon to organic carbon was 2.0%. Average concentrations observed for sulfate and nitrate were 3.7 microg m(-3) and 1.5 microg m(-3). Two different types of aerosol were identified at the rural background site on Bhola Island during southerly synoptic flow by means of trajectory analysis: air masses were transported from the Bay of Bengal to the sampling site in all cases. However, during "Period 1" they experienced longer residence times over the Indian Ocean, while the "Period 2" trajectories came along the Indian coast or passed over the Indian continent. During Period 1 the concentration levels of soluble ions were a factor of 4-6 lower than during Period 2. The concentrations of EC, OC and K differed less than a factor of 1.5 between the two periods. The Period 1 aerosol showed similarities to the haze layers observed during winter-monsoon conditions south of India during the INDOEX experiment. Based on EC/TC and K/EC ratios we find that around 80% of the carbonaceous aerosol from Period 1 in Bhola is from fossil fuel and only around 50% from Period 2. Absolute concentrations of carbonaceous species, soluble ions and trace metals indicate that the background site on Bhola Island is affected by emissions from urbanized regions of Southeast Asia.     

Occurrence of dissolved PAHs in the Jinsha River (Panzhihua)--upper reaches of the Yangtze River,Southwest China

16 priority polycyclic aromatic hydrocarbons (PAHs) were determined in water samples from the Jinsha River (Panzhihua part), Southwest China. Total dissolved PAH concentrations varied from 21.89 microg l(-1) to 382.8 microg l(-1). It was found that the concentration of PAHs decreased along the flow direction due to the higher density distribution of coal chemical industry in the upstream of our study rivers. The pollution levels in our study area are significantly higher than previously reported values in other waters both in China and other countries. The predominance of benzo[k]fluoranthene and indeno[1,2,3-cd]pyrene was clearly observed in all water samples. On average these two compounds accounted for 98.3% of the total dissolved PAH concentration in water. The results showed the positive correlations among total dissolved PAHs, benzo[k]fluoranthene and indeno[1,2,3-cd]pyrene, which suggested that these two predominant PAHs have similar source and environmental behaviors in our study area. When compared with the survey results of organic micropollutants two decades ago, it was found that hydrocarbon pollution both predominated and even increased with the development of coal chemical industry in this area during the past 20 years. The results therefore provide important information on the current contamination status of a key industrial city in China, and points to the need for urgent action to investigate the relationship between the PAH composition and concentration in water from the Jinsha River and the wastewater discharge from coal chemical industry, and to identify the source, transport pathway and fate of PAHs in the area. It should then be necessary to adopt appropriate and instant measures to control the pollution around this area.     

Application of PCR and probe hybridization techniques in detection of airborne fungal spores in environmental samples

Specific PCR amplification and probe hybridization techniques were applied to examine the compositions of airborne fungi in samples from three different environments. The results from microscopic and CFU counting were compared to those of the molecular-based detections. The detection sensitivity for PCR amplifications was 9 to 73 spores and 1.3 to 19.3 CFUs per PCR reaction. The hybridization detection limit was 2 to 4 spores and 0.2 to 1.2 CFU. The hybridization method was more sensitive than PCR amplification and showed less variation among samples. Using specific PCR primers and probes we identified the presence of several fungal groups and species in the air samples. Specific detections through probe hybridization to PCR products amplified with universal or group-specific fungal primers have promising applications in the examination of air samples for environmental monitoring.     

Organotin compounds in the marine environment of the Bay of Piran,northern Adriatic Sea

In the year 2000, organotin pollution was investigated in the Bay of Piran, Slovenia, at the northern extremity of the Adriatic Sea. Gas chromatography-mass spectrometry with single ion monitoring GC/MS-SIM was applied for speciation analysis of pentylated organotin compounds in water and mussels. Sampling of marine waters was performed in summer and autumn at 8 locations. Mussels Mytilus galloprovincialis were collected only in summer at 3 locations. The highest concentrations of tributyltin (TBT) in marine water ranged from 500 to 630 ng L(-1) (as Sn) in summer and from 180 to 230 ng L(-1) (as Sn) in autumn. TBT concentration in mussels varied from 500 to 3500 ng g(-1) dry weight (d.w.) (as Sn). The study indicated remarkable butyltin pollution of the Slovenian coastline. Accuracy of the analytical procedure was verified by BCR CRM 477.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

Soil properties and crop productivity as influenced by flyash incorporation in soil

Field experiments were carried out during 1996–97at Gulawathi, Muthiani and Salarpur Villages, IARI Farm, NewDelhi and NCPP Campus, Dadri to evaluate changes in soilcharacteristics and growth of wheat (Triticum aestivum L.),mustard (Brassica juncea L.), lentil (Lence esculentaMoench.), rice (Oryza sativa L.) and maize (Zea mays L.) byvarying amounts of flyash addition (up to 50t ha^-1) in soils atsowing/transplanting time of crops. Flyash addition in areasadjoining NCPP Thermal Power Plant, Dadri, Ghaziabad, U.P.ranged from 5–12 t ha^-1 yr^-1 in 1995–96. Shoot and root growthand yield of test crops at different locations after flyashincorporation resulted in beneficial effects of flyashaddition in most cases. The silt dominant texture of flyashimproved loamy sand to sandy loam textures of the surfacesoils at the farmers' fields. The increased growth in yield ofcrops with flyash incorporation was possibly due tomodifications in soil moisture retention and transmissioncharacteristics, bulk density, physico-chemical characterssuch as pH and EC and organic carbon content. The response offlyash addition in the soil on soil health and cropproductivity needs to be evaluated on long-term sustainableaspects.     

Using environmental stressor information to predict the ecological status of Maryland non-tidal streams as measured by biological indicators

In Maryland, U.S., an interim framework has recentlybeen developed for using biologically based thresholds, or `biocriteria', to assess the health of nontidal streams statewide at watershed scales. The evaluation of impairment is based on indices of biological integrity from the Maryland Biological Stream Survey (MBSS). We applied logistic regression to quantify how the biotic integrity of streams at a local scale is affected by cumulative effects resulting from catchment land uses, point sources, and nearby transmission line rights-of-way. Indicators for land use were developed from the remote sensing National Land Cover Data and applied at different scales. We determined that the risk of local impairment in nontidal streams rapidly increases with increased urban land use in the catchment area. The average likelihood of failing biocriteria doubled with every 10% points increment in urban land, thus an increase in urban land use from 0 to 20% quadruples the risk of impairment. For the basins evaluated in this study, catchments with more than 40–50% urban land use had greater than 80% probability of failing biocriteria, on average. Inclusion of rights-of-way and point sources in the model did not significantly improve the fit for this data set, most likely because of their low numbers. The overall results indicate that our predictive modeling approach can help pinpoint stream ecosystems experiencing or vulnerable to degradation.     

Determining Ecoregions for Environmental and GMO Monitoring Networks

A representative environmental monitoring network at the regional scale cannot use raster-based or random sampling designs, but requires a stratified sampling procedure integrating different information layers, and it has to occur in ecologically differing homogeneous regions (ecoregions). These we have determined using a set of spatial strata with ecological variables which we analysed with classification and regression trees (CART). We present a framework for environmental monitoring, that covers different scales, and we transfer the framework to a potential GMO (genetically modified organisms) monitoring network. We use ecoregion and other environmental strata together with existing environmental monitoring networks to determine GMO monitoring sites more precisely.     

Measurements of Ozone Concentrations in Zagreb

Ozone concentrations were measured in Zagreb at four sites from May 1999 to April 2001 in order to categorize the air quality with respect to ozone. In the summer of 2000, the ozone measurements were also extended to four sites in the suburbs of Zagreb. Methods of active and passive sampling with nitrite ion as a reagent were used. In the northern part of the town ozone was analyzed by an automatic device. Automatic device measurements in the years 1999 and 2000 showed that hourly averages of ozone concentrations did not exceed the Croatian recommended value of the 98th percentile (180 g m^–3). Over the two-year period, 24-h averages occasionally exceed 110 g m^–3 in city center and in the northern part of the town. Regardless of these isolated examples, ozone was well within acceptable concentrations. Ozone concentrations measured in summer 2000 were higher in the suburbs of Zagreb than in the city. The 98th percentile values higher than 110 g m^–3 were recorded at three sites.