Meteorological normalisation and non-parametric smoothing for quality assessment and trend analysis of tropospheric ozone data.

Despite extensive efforts to ensure that sampling and installation and maintenance of instruments are as efficient as possible when monitoring air pollution data, there is still an indisputable need for statistical post processing (quality assessment). We examined data on tropospheric ozone and found that meteorological normalisation can reveal (i) errors that have not been eliminated by established procedures for quality assurance and control of collected data, as well as (ii) inaccuracies that may have a detrimental effect on the results of statistical tests for temporal trends. Moreover, we observed that the quality assessment of collected data could be further strengthened by combining meteorological normalisation with non-parametric smoothing techniques for seasonal adjustment and detection of sudden shifts in level. Closer examination of apparent trends in tropospheric ozone records from EMEP (European Monitoring and Evaluation Programme) sites in Finland showed that, even if potential raw data errors were taken into account, there was strong evidence of upward trends during winter and early spring.

Changes in nutrient levels in some Eastern European rivers in response to large-scale changes in agriculture.

Since the late 1980s, the use of commercial fertilisers in most Eastern European countries has decreased at an unprecedented rate. We examined the impact of this dramatic reduction in agricultural inputs on concentrations of nutrients in four rivers in Eastern Europe: the Emajogi and Ohnejogi (Estonia), the Daugava (Latvia), and the Tisza (Hungary). Time series of nitrate (NO3-N) and phosphate (PO4-P) concentrations and data on runoff were selected to represent catchments with substantial areas of agricultural land and available time series of sufficient length and frequency. The study period was 1987-1998. We detected downward trends in nitrate-N and phosphate-P in only two of the four rivers. Our results imply that the response to the extensive decrease in agricultural intensity since the late 1980s has been slow and limited in many rivers. Corresponding results in the literature are inconclusive and comprise several examples of both decreasing and non-decreasing nutrient concentrations. Our findings, along with similar data from other studies, indicate that large cuts in nutrient inputs do not necessarily induce an immediate response, particularly in medium-sized and large catchment areas. Moreover, the difference we noted between nitrogen and phosphorus suggests that factors other than reduced fertiliser application influenced the inertia of the water quality response.

The SOIL-N/WEKU model system--a GIS-supported tool for the assessment and management of diffuse nitrogen leaching at the scale of river basins.

The SOIL-N/WEKU model system was developed to estimate groundwater-borne nitrogen inputs into river systems. The core of this model system is composed of a soil nitrogen leaching model (SOIL-N) and a groundwater residence time/denitrification model (WEKU). The application of the model system was carried out in the framework of the EU-project RANR (Regional analysis of subsurface nitrogen retention and its impact on the nitrogen export from land to sea) for a macroscale study river basin in Germany (the Uecker basin, ca. 2,400 km2) and a mesoscale study catchment area in Denmark (the Gjern basin, ca. 200 km2). For both catchment areas, the modelled average nitrogen loads leached into the groundwater were about 40 kg N/ha a, while the remaining groundwater-borne nitrogen intake to rivers was quantified to an average of about 2 kg/ha a. The comparison with observed groundwater-borne riverine nitrogen loads showed a very good agreement, proving the key role nitrogen retention in groundwater plays in the two catchment areas.

Model system for the management of nitrogen leaching at the scale of river basins and regions.

In the framework of the EU-project RANR (Regional analysis of subsurface nitrogen retention and its impact on the nitrogen export from land to sea) a model system was developed to estimate groundwaterborne nitrogen inputs into river systems. The core of this model system is composed of a soil nitrogen leaching model (SOIL-N) and a groundwater residence time/denitrification model (WEKU). The application of the model system was carried out for the study catchment areas of the Uecker basin (ca. 2400 km2, Germany) and the Gjern basin (ca. 200 km2, Denmark). For both catchment areas, the modelled average nitrogen loads leached into the groundwater were about 40 kg N/ha a, while the remaining groundwaterborne nitrogen intake to rivers was quantified to an average of about 2 kg/ha a. The comparision with observed groundwaterborne riverine nitrogen loads showed a very good agreement, proofing the key role nitrogen retention in groundwater plays in the two catchment areas. With regard to the generalisation and transfer of the SOIL-N/WEKU model concept we assume that the model can be applicated in catchment areas in the European Pleistocene Lowland, which ranges from the Netherlands in the west to the Baltic States and the Ukraine in the east.

Determination of group parameters for organically bound chlorine, bromine and iodine in precipitation

The presence of organically bound halogens in precipitation was studied by first adsorbing organics on activated carbon and then analysing the chloride, bromide and iodide formed during combustion of the carbon. A standard instrument for the group parameter AOX (adsorbable organic halogens) was used for the combustion. The halides formed were trapped in an alkaline solution and analysed by capillary zone electrophoresis. The method described enabled determination of sub-ppb concentrations of the group parameters AOCl, AOBr and AOI (adsorbable organic chlorine, bromine and iodine, respectively). Analysis of rain and snow collected at different sites in Europe showed that organochlorines were responsible for the major part of the AOX content in all samples collected. Organically bound bromine was found in sub-ppb concentrations in all of the samples, whereas organic iodine was detected in only two of the samples.

Fractionation of halogenated organic matter present in rain and snow

Organic matter in samples of rain and snow from Sweden, Poland, Germany and the Republic of Ireland was fractionated by employing a series of filtration, purging, evaporation and extraction steps. Determinations of the group parameter AOX (adsorbable organic halogens) in aqueous phases and EOX (extractable organic halogens) in organic phases showed that halogenated organic matter present in bulk precipitation is composed of several different groups of compounds. The largest amounts of organically bound halogens were found in fractions of relatively polar and non-volatile to semivolatile compounds. In particular, a significant part of the AOX could be attributed to alkaline-labile organic bases. Gas chromatographic analysis of different organic extracts in the chlorine channel of an atomic emission detector (AED) resulted in chromatograms with few distinct peaks, and analysis in the bromine channel did not produce any distinct peaks. Chlorinated acetic acids were the most abundant halogenated organic acids, and chlorinated alkyl phosphates were normally responsible for the largest peaks in the chlorine chromatogram of neutral, hexane-extractable compounds. When analysing volatiles, 1,4-dichlorobenzene and a thus far unidentified chloroorganic compound often caused the largest response in the chlorine channel of the AED system.

Monitoring nutrient transport in large rivers.

The problem of estimating nutrient transport in large rivers and the uncertainty of such load estimates was studied both empirically and theoretically. In the empirical part of the study, time series of data from the Rhine, Meuse, Vistula and Oder Rivers were examined. The results of this data analysis justify the use of linear interpolation to estimate concentrations prevailing between sampling occasions. A special study of the spatial variation of concentrations within different cross-sections of the Vistula river showed that such variation can contribute substantially to the uncertainty of load estimates. In general, however, sampling at one point in the cross-section did not result in biased load estimates. In the theoretical part of the study, simple ARMA (autoregressive-moving average) models were used to derive generally applicable formulas for the expected mean square error of load estimates based on serially dependent concentration data. These formulas were then used to estimate the uncertainty of calculated nutrient loads in the Rhine and the Vistula, respectively.

Estimation of nonpoint source loadings with data obtained from limited sampling programs.

The feasibility of estimating nonpoint source loadings with data obtained from limited sampling programs was analyzed in conjunction with a study of sediment and nutrient loadings in a Swedish river basin. The study showed that different loading estimation methods can yield significantly different results, even if sampling during events (e.g. peak flows) occurs. This was particularly true for the temporal distribution of the estimated loadings. The estimated spatial distribution of loadings in the monitored subbasins was more independent of the applied estimation technique. Theoretical calculations showed that sampling strategies with evenly spaced sampling intervals may systematically over- or underestimate the true loading.The study basin was characterized by a pronounced snowmelt period and partly erosion-controlled nutrient loadings. Guidelines for the estimation of nonpoint loadings in such basins are summarized in a matrix. Factors influencing the choice of estimation method include the characteristics of the collected data, the relative influence of point sources, and the desired detail of loading estimates. Possible correlations between flow and concentration, and the presence of extreme events (and whether or not the events were sampled), also determine the appropriateness of the different methods.

Impact of bleached kraft mill effluents on drinking water quality.

Bleaching effluents from kraft pulp mills contain large quantities of chlorinated organic compounds, some of which are mutagenic. Mutagenic chloro-organic compounds are also formed as by-products in chlorination of drinking water. The work reported here was a combined field and laboratory study aimed at comparing the evidence of health risks from pulp mill contaminants in drinking water, with corresponding evidence from normal, chlorine disinfection by-products. The study was performed in a Swedish river basin with a large, public water works located downstream from a bleached kraft mill. Chemical analyses (gas chromatography and determination of adsorbable organic halogen) and bioassays for mutagenic activity (bacterial and mammalian cell bioassays) were performed on samples of river water, drinking water and laboratory produced drinking water. The study showed that the bleached kraft effluents caused a considerable, long-range transport of chloro-organic substances in the receiving waters, and a substantial increase in the total amount of organic chlorine in drinking water produced downstream from the mill. As regards Ames mutagenic compounds, however, chlorination of naturally occurring humic substances during the chlorine disinfection step in drinking water production, proved to be a far more important source. The contribution of volatile chloro-organic compounds from the kraft mill was also much smaller than the contribution from normal disinfection by-products. The chromosome aberration tests gave no clear evidence of a positive response for any of the samples tested.

A comparison of methods for concentrating mutagens in drinking water--recovery aspects and their implications for the chemical character of major unidentified mutagens.

A comparison of techniques for concentrating mutagenic compounds in drinking water has shown that XAD-2 adsorption and dichloromethane extraction have acceptable and almost identical enrichment properties, while purging at an elevated temperature is inappropriate in this context. Quantitatively, the most important drinking water mutagens could only be adsorbed (extracted) after acidification of the water, and even then recovery was far from complete. Recovery experiments with known mutagens from pulp mill effluents have shown that none of the major chlorination-stage mutagens identified thus far can explain the mutagenic activity of extracts from neutral or acidified chlorinated drinking water.