Using process-based models to filter out natural variability in observed concentrations of nitrogen and phosphorus in river water

Advances in process-based modelling of loads of nitrogen and phosphorus carried by rivers have created new possibilities to interpret time series of water quality data. We examined how model runs with constant anthropogenic forcing can be used to estimate and filter out weather-driven variation in observational data and, thereby, draw attention to other features of such data. An assessment of measured and modelled nutrient concentrations at the outlets of 45 Swedish rivers provided promising results for total nitrogen. In particular, joint analyses of observational data and outputs from the catchment model S-HYPE strengthened the evidence that downward trends in nitrogen were due to mitigation measures in agriculture. Evaluation of modelled and observed total phosphorus concentrations revealed considerable bias in the collection or chemical analysis of water samples and also identified weaknesses in the model outputs. Together, our results highlight the need for more efficient two-way communication between environmental modelling and monitoring.     

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.     

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.     

Trends in Nitrogen Transport in Swedish Rivers

Concern about nitrogen loads in marine environments has drawn attention to the existence and possible causes of long-term trends in nitrogen transport in rivers. The present study was based on data from the Swedish environmental monitoring programme for surface water quality; the continuity of these data is internationally unique. A recently developed semiparametric method was employed to study the development of relationships between runoff and river transport of nitrogen since 1971; the observed relationships were then used to produce time series of flow-normalised transports for 66 sites in 39 river basins. Subsequent statistical analyses of flow-normalised data revealed only few significant downward trends (p 0.05) during the time period 1971–1994, and the most pronounced of these downward trends were caused by reduced point emissions of nitrogen. The number of significant upward trends was substantially larger (15 for total-N and 18 for NO₃-N). Closer examination of obtained results revealed the following: (i) the most pronounced upward trends were present downstream of lakes, and (ii) observed increases in nitrogen transport coincided in time and space with reduced point emissions of phosphorus or organic matter. This indicated that changes in the retention of nitrogen in lakes were responsible for the upward nitrogen trends. The hypothesis that nitrogen saturation of forest soils has caused a general increase in the riverine export of nitrogen from forested catchments in Sweden was not confirmed. Neither did the results indicate that improved agricultural practices have reduced the export of nitrogen from agricultural catchments.     

Estimation of the Human Impact on Nutrient Loads Carried by the Elbe River

The reunification of Germany led to dramatically reduced emissions of nitrogen (N) and phosphorus (P) to the environment. The aim of the present study was to examine how these exceptional decreases influenced the amounts of nutrients carried by the Elbe River to the North Sea. In particular, we attempted to extract anthropogenic signals from time series of riverine loads of nitrogen and phosphorus by developing a normalization technique that enabled removal of natural fluctuations caused by several weather-dependent variables. This analysis revealed several notable downward trends. The normalized loads of total-N and NO3-N exhibited an almost linear trend, even though the nitrogen surplus in agriculture dropped dramatically in 1990 and then slowly increased. Furthermore, the decrease in total-P loads was found to be considerably smaller close to the mouth of the river than further upstream. Studying the predictive ability of different normalization models showed the following: (i) nutrient loads were influenced primarily by water discharge; (ii) models taking into account water temperature, load of suspended particulate matter, and salinity were superior for some combinations of sampling sites and nutrient species; semiparametric normalization models were almost invariably better than ordinary regression models.     

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 riverine loads of nitrogen and phosphorus to the Baltic Sea, 1970–1993

This article presents the results of the first critical examination of time series of riverine nutrient-load data for the entire Baltic Sea drainage area. Water quality data collected by or for the different national environmental agencies were compiled and analysed statistically to identify and remove inconsistent or obviously incorrect observations. Moreover, sampling tours were undertaken to acquire additional information about the present nutrient concentrations in the largest rivers in the study area. Gaps in the time series of approved data were then filled in by employing statistical interpolation and extrapolation methods. Thereafter, the concentration and runoff data were combined to obtain estimates of monthly nutrient loads for the time period 1970–93. The results of the calculations showed that although there had been substantial changes in land use, atmospheric deposition and wastewater treatment in many parts of the study area, the total riverine loads of nitrogen (N) and phosphorus (P) to the Baltic Sea have been fairly constant since 1980, and most likely also since 1970. Moreover, the interannual variation was clearly correlated to the runoff. The mean annual loads for the time period 1980–93 were found to be about 825 000 tonnes N and 41 000 tonnes P, respectively. This implies that (i) several other investigators have strongly underestimated the riverine loads of nutrients, especially the nitrogen, and that (ii) the riverine loads by far exceed the input to the Baltic Sea from other sources, {i.e.} atmospheric deposition, direct emissions from cities and industries along the Baltic Sea coast and nitrogen fixation by marine algae.     

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.     

Leaching of nitrogen in Swedish agriculture — a historical perspective

There is a need to examine long-term changes in nitrogen leaching from arable soils. The purpose of this study was to analyse variations in specific leaching rates (kg ha⁻¹ per year) and gross load (Mg per year) of N from arable land to watercourses in Sweden from a historical perspective. The start of the study was set to 1865 because information on crop distribution, yield and livestock has been compiled yearly since then. The SOIL/SOILN model was used to calculate nitrogen leaching. Calculations were done for cereals, grass and bare fallow for three different soil types in nine agricultural regions covering a range of climatic conditions. Results indicate that both specific leaching rates and gross load of nitrogen in the middle of 19th century were approximately the same as they are today for the whole of south and central Sweden. Three main explanations for this were (1) large areas of bare fallow typical for the farming practice at the time; (2) enhanced mineralisation from newly cultivated land; and (3) low yield . From 1865, i.e. the start of the calculations, N leaching rates decreased and were at their lowest around 1930. During the same period, gross load was also at its lowest despite the fact that the acreage of arable land was at its most extensive. After 1930, average leaching increased by 60% and gross load by 30%, both reaching a peak in the mid-1970s to be followed by a declining trend. The greatest increase in leaching was in regions where the increase in animal density was largest and these regions were also those where the natural conditions for leaching such as mild winters and coarse-textured soils were found. Extensive draining projects occurred during the period of investigation, in particular an intensive exploitation of lakes and wetlands. This caused a substantial drop in nitrogen retention and the probable increase in net load to the sea might thus have been more affected by this decrease in retention than the actual increase in gross load.