Patchy distributions: Optimising sample size

A method for estimating sample size which does not require an a priori definition of desired precision, or the assumption that the population is normally distributed with constant variance, has recently been proposed. This paper discusses this method and presents five modifications which make the method easier to use and reduce the probability of estimating a larger sample size than is actually required. The method is extended and used to estimate the mean abundance of patchily distributed benthic organisms. The technique can be used to guide the design of any environmental sampling programme, be it physical, chemical or biological, where comparisons between times and/or locations are required. Trade-offs between numbers of replicates and numbers of levels/sites are discussed.     

Monitoring of the three organophosphate esters TBP,TCEP and TBEP in river water and ground water (Oder,Germany)

The behaviour of the three organophosphate esters tributyl phosphate (TBP), tris(2-chloroethyl)phosphate (TCEP) and tris(2-butoxyethyl)phosphate (TBEP) during infiltration of river water to ground water has been investigated. The monitoring site is the Oder River and the adjacent Oderbruch aquifer. From March 2000 to July 2001, 76 ground water samples from monitoring wells located close to the Oder River and nine river water samples were collected. Additionally, influent and effluent samples from local waste water treatment plants, one sample of rain water and samples of roof runoff were collected. All samples were analysed by solid-phase-extraction followed by gas chromatography/mass spectrometry. TBP, TCEP and TBEP were detected at mean values of 622 ng l(-1), 352 ng l(-1), and 2955 ng l(-1), respectively in municipal waste water effluents. This points to a major input of these compounds into the Oder River by municipal waste water discharge. The concentrations of TBP and TBEP decreased downstream the Oder River possibly due to aerobic degradation. TBP, TCEP and TBEP were detected in ground water influenced predominantly by bank-filtered water. This demonstrates a transport of organic compounds by river water infiltration to ground water. TBP, TCEP and TBEP were also detected in rain water precipitation, roof runoff and ground water predominantly influenced by rain water infiltration. This hints to an input of these compounds to ground water by dry and wet deposition after atmospheric transport. Organophosphate esters were also detected in parts of the aquifer at 21 m depth. This demonstrates low anaerobic degradation rates of TBP, TCEP and TBEP.     

Distribution of polychlorinated biphenyls (PCBs) and organochlorine pesticides in soils from the East Antarctic coast

Concentrations of hexachlorobenzene (HCB), alpha-, beta- and gamma-hexachlorocyclohexane (HCH) isomers, 6 o,p'-and p,p'-isomers of DDT and 28 PCB congeners have been measured in eleven soil samples and one lichen collected on the Eastern coast of Antarctica from 5 Russian stations. For samples with low concentrations of PCBs (range 0.20-0.41 ng g(-1) dry weight) and pesticides (0.86-4.69 ng g(-1) and 0.11-1.22 ng g(-1) dry weight for HCHs and DDTs, respectively), atmospheric long-range transport from Africa, South America or Australia was suggested as the sole source of contamination. The profile of PCB congeners was dominated by the more volatile tri-, tetra- and penta-PCBs congeners, thus supporting long-range transport hypothesis. Four samples contained moderate levels of PCBs (range 1.98-6.94 ng g(-1) dry weight) and variable concentrations of pesticides (gamma-HCH, p,p'-DDT and o,p'-DDT being the main contaminants). For samples with high concentrations of PCBs (range 90.26-157.45 ng g(-1)) and high concentrations of pesticides, the presence of high molecular weight PCB congeners such as: 153, 180, 187, 170 etc, strongly suggest a local source (biotic) of PCBs rather than atmospheric transport. It is likely that on a local scale, biotic focussing of pollutants, due to bird activities (nesting and excrement) can cause high contamination levels and become more significant than contaminant input via abiotic pathways.     

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.     

Partitioning of mercury onto suspended sediments in estuaries

Radiochemical partitioning experiments using 203Hg have been undertaken with mixtures of river, seawater and sediment samples taken from three geochemically contrasting UK estuaries: the Plym, Beaulieu and Mersey. Species of dissolved Hg were determined using reversed-phase C18 chelating columns and particulate species were determined by sequential leaching with 1 M NH4OAc and 1 M HCl. Mercury had a high particle reactivity with partition coefficients, KDs, ranging from 10(4) to 5 x 10(5) ml g(-1), depending on salinity, the chemical composition of the end-member waters, and on the physico-chemical characteristics of the sediment. Dissolved organic matter present in the waters (humic substances and/or anthropogenic compounds) was found to be the main factor governing the forms of dissolved Hg and their reactivity. From the spiked 203Hg, up to 95% of the dissolved metal was retained on the C18 columns for the Mersey waters, whereas this fraction was < 60% in the Plym and Beaulieu waters. Quasi-irreversible adsorption of Hg onto particles from each estuary was observed over a time-scale of a few hours and < 20% of total particulate Hg was released by the sequential leach. In this paper, physico-chemical processes are proposed to explain the estuarine behaviour of Hg and the results are discussed in terms of Hg availability in estuarine systems.     

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).     

Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials

The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission proposed a three-step sequential extraction procedure for sediment analysis, following extensive expert consultations and two interlaboratory studies. This scheme was recently used to certify the extractable trace element contents of a sediment reference material (CRM 601). Although this procedure offers a means to ensure the comparability of data in this field, some difficulties concerning the interlaboratory reproducibility still remain, and a new project is currently being conducted to determine the causes of poor reproducibility in the extraction scheme. The final objective of the project is the certification of new sediment and soil reference materials for their extractable contents of Cd, Cr, Cu, Ni, Pb and Zn. This paper presents the results of a small-scale interlaboratory study, which aimed to test a revised version of the extraction schemes by comparing the original and the modified protocols using the CRM 601 sample. This work offers an improvement to the BCR sequential extraction procedure through intercomparison exercises. This improved procedure will allow the obtaining of CRMs to validate analytical data in the analysis of soils and sediments, and it will also facilitate comparability of data in the European Union.     

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.