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.     

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.     

Dose-time-response functions for toxic chemicals

In many situations, the effect of a toxic chemical on a biological system depends on both the intensity and the duration of exposure. The dependence on the time dimension can be the expression of a range of processes including the physical accumulation of toxic chemicals or their metabolites and the functional accumulation of damage. Measures and functions that have been used to describe this dependence are reviewed.Some of these functions are compared through a case study of the neurotoxicity of methylmercury. Use is made of data that indicates a dependency between the blood concentration at which monkeys were exposed and the length of time before damage was detected. Several exposure functions are fitted to these data and their appropriateness is compared. Using the most appropriate function, an exposure-response relationship is developed using probit analysis. An alternative data analysis procedure is also investigated. The apparent threshold after a 100 day exposure is estimated to be greater by a factor of 3–5 compared to the threshold for chronic exposure. Applying this factor to man, the blood concentration threshold for chronic exposure is estimated to be 40–170 ppb, a finding consistent with recent reports of neurological damage in humans exposed below the generally accepted threshold.     

Problems of correlation of global and local monitoring of air pollution

1. The Air Polluttion Monitoring System has got a significant development of late, which is in direct relation with a considerable extention and improvement of the observation network in cities and industrial areas, with creation of a new network for assessing regional and global background of the atmosphere pollution, as well as with the wide involvement of meteorologists to monitoring organization.
2. While developing a new global monitoring system, it is necessary to take into account its relationship with the local monitoring within the region of air pollution sources, i.e. at the \lsimpact\rs level. The need in such an account is dictated first of all by the physics of pollutant spreading that states: changes in air pollution over large territories must be in a certain agreement with greater changes in the vicinity of emission sources. Methods applied in the global and local monitoring have also a number of common peculiarities. White organizing regional network for observations of the background pollution of the atmosphere twin stations (one of the pair of stations located outside the city boundaries in a small community, and the other, in the nearest city with the population of 200–400 thousand inhabitants) were established in the U.S.S.R. and in a number of socialist countries in Europe.
3. Implementation of the twin-station principles in the U.S.S.R. has contributed to data interpretation and representativity assessment as well as to correction of the station location. Observation results from the Soviet background stations and those abroad have been compared by now according to a number of indices.
4. The correlation of monitoring systems of various scales tells positively both on mutual improvement and completion of observational methods. The methods of obtaining integral characteristics of air pollution were used for the global monitoring, in particular spectral actinometric observations and chemical analysis of the precipitation composition. Now they find still wider employment. Thus methods of spectral actinometric measurements and data processing were used to estimate the degree of aerosol pollution of a number of industrial centres. The theory of solar radiation spreading and aerosol contents determination in urban atmosphere has also been developed. It is a generalization of an earlier developed theory, used to estimate global atmosphere pollution basing on actinometric data. The organization of precipitation collection and analysis on a network of stations around Leningrad and in Donbass area enables us to compare the admixture content in precipitations falling in industrial and agricultural areas.
5. A considerable increase of possibilities to measure microconcentrations of sulphur dioxide, nitrogen oxides and of a number of other pollutants is connected with the use of solid solvents for sampling. Their use will allow to avoid establishment of special laboratories at background stations and only send samples by post for their analysis in centralized laboratories.

They will also allow to considerably increase precision and accuracy of measurements. The international comparisons of methods of air pollution measurements on the background level allow to judge about the effiency of these methods.     

Indoor concentrations of carbon monoxide in selected urban microenvironments

CO concentrations were measured in five kindergartens, one children's hospital and two homes for aged, practically without indoor sources, all situated in the city centre, for ten random days in winter and ten in summer. The indoor CO concentrations were the result of the distance from and the traffic density in the nearest street, of general pollution level, seasonal differences, day-to-day variations and daily cycle of air pollution, the vicinity of traffic having a dominant influence. Therefore location of institutions for sensitive population groups in old city centres within a block of houses seems to be a suitable solution as far as exposure to CO is concerned.Revised version of a paper presented as poster at the VIth World Congress on Air Quality, Paris 1983.     

Determination of biomass burning emission factors: Methods and results

Biomass burning, in a broad sense, encompasses different burning practices, including open and confined burnings, and different types of vegetation. Emission factors of gaseous or particulate trace compounds are directly dependent both on the fuel type and the combustion process. Emission factors are generally calculated by stoichiometric considerations using the carbon mass balance method, applied either to combustion chamber experiments or to field experiments based on ground-level measurements or aircraft sampling in smoke plumes. There have been a number of experimental studies in the last 10 years to investigate wildfires in tropical, temperate, or boreal regions. This article presents an overview of measurement methods and experimental data on emission factors of reactive or radiatively active trace compounds, including trace gases and particles. It focuses on fires in tropical regions, that is, forest and savanna fires, agricultural burns, charcoal production, use of fuelwood, and charcoal combustion.     

Factor analysis of trace-element data from tree-bark samples in The Netherlands

Monte Carlo-assisted factor analysis has been applied to a data set of 20 trace-element concentrations in tree-bark samples obtained from 123 locations in The Netherlands, with the aim to investigate the suitability of bark as a biomonitor for air pollution. A Monte Carlo approach was used to give more insight to the uncertainties and significance levels of the factor analysis results. Notwith-standing a rather strong influence of soil material on the concentration levels, factor analysis enabled the identification of five significant pollution source types, all of which corresponded with source types found in an earlier biomonitoring study in The Netherlands using epiphytic lichens. A more detailed comparison with the lichen results showed a remarkable difference in lead concentrations between bark and lichen. It was concluded that bark can be successfully employed as a biomonitor for air pollution. The power of factor analysis to adequately determine the soil contribution may render extensive sample washing procedures superfluous.     

Evaluation of the Industrial Source Complex short-term model in a large-scale multiple source region for different stability classes

The original Industrial Source Complex Model (ISCST, 90346) and its latest version, the ISCST2 (92090), are evaluated for the 1- and 24-hour averaging periods, using six statistical parameters. The confidence limits on two parameters were obtained using the bootstrap, jacknife, seductive, and robust resampling techniques. Evaluation is conducted in a multiple point source environment and in all the different stability categories, using a year of meteorological data, emission inventory of the Lucas County, in Toledo, Ohio, and monitoring data from two nearby stations for the year 1987. This was representative of a real time situation in which the ISCST is generally applied for regulatory work. The sensitivity analysis shows that the ISC is a poor performing model in the 1-h and 24-h averaging period, neutral and stable categories, and modifications to it are necessary in order to improve its performance. Its performance changes depending on the chosen paired values. A better relative performance is observed in the unstable category relative to the neutral and stable categories. Improved model performance may be achieved by applying modifications to the physics on which the model is based.     

Field scale variability of cadmium and zinc in soil and barley

CaCl₂-extractable soil Cd and Zn contents have been suggested as a measure of bioavailability. To investigate the ability of this measure to reflect spatial patterns of Cd and Zn concentrations in barley (Hordeum vulgare L.) in an arable field, plant and soil samples were taken from a 0.5 ha area sandy soil contaminated with Cd and Zn. Cd and Zn contents in barley and yield were spatially variable. Yield was low, which may have been caused by Zn toxicity or atrazine turnover. For Cd, CaCl₂-extractable soil contents explained only 17% of the variation in Cd contents in grain, and for Zn no significant correlation was observed. Nevertheless, surface plots of CaCl₂-extractable soil contents and contents of barley grain illustrated their corresponding spatial patterns. Despite the poor linear correlation between CaCl₂-extractable soil-Cd and grain-Cd, a stochastic model for long term behaviour of Cd in field soils predicted observed variability in Cd contents of barley grain well from spatial variability of soil pH and organic matter content. The probabilistic model predicted behaviour of Cd in terms of probability, and was more appropriate than the deterministic approach.