Accuracy and traceability in environmental monitoring--pitfalls in methylmercury determinations as a case study

The concepts of accuracy and traceability as applied to environmental analysis are still prone to misunderstandings. While accuracy refers to the closeness of analytical values to "true values" (trueness) and among various repetitions (precision), the term traceability implies a link of data obtained to established references through an unbroken chain of comparisons all with stated uncertainties. These misunderstandings, possibly occurring among the analytical community, may have consequences on environmental data interpretation. Recent discussions in the field of environmental speciation analysis illustrated that accuracy and traceability issues are still not firmly established within the environmental chemistry community. This paper discusses this issue, taking methylmercury as a case study.     

Analysis of two-way layout of count data with negative binomial variation

A number of methods has been proposed for dealing with single-factor or factorial experiments when the requirements for performing the normal theory analysis of variance procedure are not satisfied. This paper suggests the use of the likelihood ratio statistic for testing the main effects and the interaction between the factors in two-way layout of count data following negative binomial distributions with a common dispersion parameter. The likelihood ratio statistic for testing the equality of the dispersion parameters of several groups of count data is also derived. The methods is illustrated by an example concerning the study of spatial and temporal variation of bacterial counts.     

Spatial analysis and mapping the annual mean concentrations of acidity and major ions in precipitation over the United Kingdom in 1986

The composition of precipitation is being monitored in collectors sited throughout the United Kingdom. In the first year, 1986, hydrogen ion, nitrate, ammonium and non-marine sulphate were measured in samples from 47 sites and annual mean concentrations determined. Spatial analysis based on Regionalized Variable Theory revealed autocorrelation in all four ions and reasonable bounded models were fitted to the sample variogram of all four. These were then used to estimate values of a fine mesh grid by simple kriging, and the estimates were then contoured. The estimation errors were similarly mapped, and both sets of maps are presented. The maps show that concentrations of these ions are greatest in eastern parts of the country, as expected from consideration of European emissions and weather patterns. For the first time estimation errors were also mapped and show how the network could be improved.     

Robust graphical methods for diagnosing trend in irregularly spaced water quality time series

Graphical methods can play an important role in the reliable assessment of trends in typically ill behaved river quality data series both as diagnostic tools and as visual corroborative evidence when assumptions required for formal statistical tests are not met. Robust, graphically-oriented trend diagnosis procedures are presented for data series characterized by nonnormal populations, uneven time spacing, nonmonotonic trend and other factors which can create serious problems for standard parametric time series methods. Cleveland's robust locally weighted regression (RLWR) developed for investigating nonlinearity in x-y scatterplots is adapted as a robust/resistant smoothing filter for the analysis of irregular time series comprising quantitative observations. Low powered RLWR trend lines reveal temporally local phenomena, e.g. abrupt jumps (often associated with point source impacts) and periodicities, while higher powered RLWR yields smooth lines characterizing medium and longer term trends. Simple variants of Tukey smoothing concepts are developed for series with censored observations. Applications to Ontario river quality series reveal that graphical evidence is frequently sufficient to obviate the need for formal trend testing. The methods are generally applicable to most time series.     

Information needs for marine pollution studies

Information needed for the resolution of environmental problems is a commodity with an economic value. The minimum necessary information implies minimal costs. The formulation of the information is considered for the case of biocides that can disrupt marine ecosystems.     

The characteristics of size distribution of suspended particulates in the air for sulphates and selected metals in different areas and seasons

The characteristics of the distribution of particles by size were investigated for sulphates and selected metals (Pb, Fe, Mn, and Cu) in the air in two urban and an industrial area during the winter and summer periods using an Andersen cascade impactor.In the case of metals, but not sulphates, the character of the area affected the value of mass median diameter. Lowest values were obtained in a sparsely populated urban area, whereas in a densely populated urban area and in the industrial area the values were higher.In the industrial area a high correlation coefficient was found between sulphate and manganese, and between sulphate and lead, as well as a high value of the equivalent Mn²⁺/SO _inf4 ^sup2- ratio for the total sample. It may therefore be assumed that in the industrial area manganese produces a catalytic effect on SO₂ conversion to sulphate. Among the investigated metals lead stands out as a dominant cation which binds to the sulphate ion in the industrial and densely populated areas.     

Relevance of radiation compensation litigation to compensation for toxic exposures

Several recent court decisions add to the growing body of law concerning the responsibility of Government in radiation matters and the quantum of proof needed to show causation between radiation exposures and certain types of cancer and leukemia. The courts have also been addressing a wide range of compensation claims for exposures to toxic chemicals with demonstration of causation being a particularly difficult task. Meanwhile, the Congress has been attempting to legislate a far reaching administrative and judicial framework for compensating toxic victims, including an easing of burden-of-proof requirements for demonstrating causation and a broadening of the basis for admissibility of scientific evidence. Drawing parallels between radiation and toxic exposure problems can be both instructive and misleading. Some of the technical issues are quite similar, including the importance of person-specific exposure estimates and of epidemiological studies. However, the uncertainties associated with toxic exposures are usually far greater, and the scientific data base for relating exposures and effects is much more uncertain.     

Determination of the working level of radon/thoron mixtures by personal α-dosimeters and environmental α-monitors using gross α-counting

Analytical procedures are presented which permit the determination of the Working Levels of the radon and thoron progenies with personal α-dosimeters and α-particle environmental monitors, operating on time integrating principles, from gross α-counts. Experiments have been carried out in an underground uranium mine and in a radon/thoron environmental chamber, specially designed for calibration purposes, to verify theoretical data. In general, and notwithstanding a number of complicating factors, fair to good agreement has been found between theoretical and experimental data. Experimental values have been found to be lower than theoretical values, an observation which is partly ascribed to plate-out of decay products in the instrument's sampling heads.