Key factors influencing metal concentrations in sediments along Western European Rivers: A long-term monitoring study (1945-2020).

Since 1945, a large amount of heterogeneous data has been acquired to survey river sediment quality, especially concerning regulatory metals such as Cd, Cr, Cu, Hg, Ni, Pb, and Zn. Large-scale syntheses are critical to assess the effectiveness of public regulations and the resiliency of the river systems. Accordingly, this data synthesis proposes a first attempt to decipher spatio-temporal trends of metal contamination along seven major continental rivers in Western Europe (France, Belgium, Germany, and the Netherlands). A large dataset (>12,000 samples) from various sediment matrices (bed and flood deposits - BFD, suspended particulate matter - SPM, dated sediment cores - DSC) was set up based on monitoring and scientific research from the 1950s to the 2010s. This work investigates the impact of analytical protocols (matrix sampling, fractionation, extraction), location and time factors (related to geology and anthropogenic activities) on metal concentration trends. Statistical analyses highlight crossed-interactions in space and time, as well as between sediment matrices (metal concentrations in SPM ≃ DSC > BFD) and extraction procedures (also related to river lithology). Major spatio-temporal trends are found along several rivers such as (i) an increase of metal concentrations downstream of the main urban industrial areas (e.g. Paris-Rouen corridor on the Seine River, Bonn-Duisburg corridor on the Rhine River), (ii) a long-term influence of former mining areas located in crystalline zones, releasing heavily contaminated sediments for decades (Upper Loire River, Middle Meuse section), (iii) a decrease of metal concentrations since the 1970s (except for Cr and Ni, rather low and stable over time). The improvement of sediment quality in the most recent years in Europe reflects a decisive role of environment policies, such as more efficient wastewater treatments, local applications of the Water Framework Directive and urban industrial changes in the river valleys.

The Impact of Climate Change on Metal Transport in a Lowland Catchment.

This study investigates the impact of future climate change on heavy metal (i.e., Cd and Zn) transport from soils to surface waters in a contaminated lowland catchment. The WALRUS hydrological model is employed in a semi-distributed manner to simulate current and future hydrological fluxes in the Dommel catchment in the Netherlands. The model is forced with climate change projections and the simulated fluxes are used as input to a metal transport model that simulates heavy metal concentrations and loads in quickflow and baseflow pathways. Metal transport is simulated under baseline climate ("2000-2010") and future climate ("2090-2099") conditions including scenarios for no climate change and climate change. The outcomes show an increase in Cd and Zn loads and the mean flux-weighted Cd and Zn concentrations in the discharged runoff, which is attributed to breakthrough of heavy metals from the soil system. Due to climate change, runoff enhances and leaching is accelerated, resulting in enhanced Cd and Zn loads. Mean flux-weighted concentrations in the discharged runoff increase during early summer and decrease during late summer and early autumn under the most extreme scenario of climate change. The results of this study provide improved understanding on the processes responsible for future changes in heavy metal contamination in lowland catchments.

The effect of short-range spatial variability on soil sampling uncertainty.

This paper aims to quantify the soil sampling uncertainty arising from the short-range spatial variability of elemental concentrations in the topsoils of agricultural, semi-natural, and contaminated environments. For the agricultural site, the relative standard sampling uncertainty ranges between 1% and 5.5%. For the semi-natural area, the sampling uncertainties are 2-4 times larger than in the agricultural area. The contaminated site exhibited significant short-range spatial variability in elemental composition, which resulted in sampling uncertainties of 20-30%.

A soil sampling reference site: the challenge in defining reference material for sampling.

In the frame of the international SOILSAMP project, funded and coordinated by the Italian Environmental Protection Agency, an agricultural area was established as a reference site suitable for performing soil sampling inter-comparison exercises. The reference site was characterized for trace element content in soil, in terms of the spatial and temporal variability of their mass fraction. Considering that the behaviour of long-lived radionuclides in soil can be expected to be similar to that of some stable trace elements and that the distribution of these trace elements in soil can simulate the distribution of radionuclides, the reference site characterised in term of trace elements, can be also used to compare the soil sampling strategies developed for radionuclide investigations.

Estimation of uncertainty arising from different soil sampling devices: the use of variogram parameters.

In the frame of the international SOILSAMP project, funded and coordinated by the National Environmental Protection Agency of Italy (APAT), uncertainties due to field soil sampling were assessed. Three different sampling devices were applied in an agricultural area using the same sampling protocol. Cr, Sc and Zn mass fractions in the collected soil samples were measured by k(0)-instrumental neutron activation analysis (k(0)-INAA). For each element-device combination the experimental variograms were calculated using geostatistical tools. The variogram parameters were used to estimate the standard uncertainty arising from sampling. The sampling component represents the dominant contribution of the measurement uncertainty with a sampling uncertainty to measurement uncertainty ratio ranging between 0.6 and 0.9. The approach based on the use of variogram parameters leads to uncertainty values of the sampling component in agreement with those estimated by replicate sampling approach.

Controls on catchment-scale patterns of phosphorus in soil, streambed sediment, and stream water.

Many models of phosphorus (P) transfer at the catchment scale rely on input from generic databases including, amongst others, soil and land use maps. Spatially detailed geochemical data sets have the potential to improve the accuracy of the input parameters of catchment-scale nutrient transfer models. Furthermore, they enable the assessment of the utility of available, generic spatial data sets for the modeling and prediction of soil nutrient status and nutrient transfer at the catchment scale. This study aims to quantify the unique and joint contribution of soil and sediment properties, land cover, and point-source emissions to the spatial variation of P concentrations in soil, streambed sediments, and stream water at the scale of a medium-sized catchment. Soil parent material and soil chemical properties were identified as major factors controlling the catchment-scale spatial variation in soil total P and Olsen P concentrations. Soil type and land cover as derived from the generic spatial database explain 33.7% of the variation in soil total P concentrations and 17.4% of the variation in Olsen P concentrations. Streambed P concentrations are principally related to the major element concentrations in streambed sediment and P delivery from the hillslopes due to sediment erosion. During base flow conditions, the total phosphorus (<0.45 microm) concentrations in stream water are mainly controlled by the concentrations of P and the major elements in the streambed sediment.

Changes in nutrient emissions, fluxes and retention in a north-eastern European lowland drainage basin.

Despite dramatic reductions in the 1990s of N and P emissions in the drainage basin, Lake Peipsi/Chudskoe (Estonia/Russia) is still suffering from algal blooms, probably caused by low N:P ratios of the lake water. To quantify the sources and changes of N and P inputs to the lake as a result of economic changes, we modelled emissions, transfer and in-stream retention using a GIS model. The model was calibrated using river monitoring data from the 1985-1989 period, and used to simulate emissions and loads for five future scenarios for 2015-2019. During the 1985-1999 period, diffuse P emissions decreased relatively more than N diffuse emissions, but this was not reflected in the loads to the lake. P loads decreased relatively less than N loads, which caused a decrease in the N:P ratio of the rivers. About 30-45% of diffuse N emissions and only 3-10% of diffuse P emissions reaches the river network. In-stream retention reduces N and P loads to the lake by about 62% and 72%, respectively. Point sources contribute negligibly to the N load to the lake, but form about one-third of the P load. A target/fast development scenario is the most likely scenario for the 2015-2019 period, resulting in higher nutrient loads than in recent years. We conclude that effective load reductions can be achieved by focussing on diffuse N and P emissions close (< 50 km2) to the lake and by upgrading P removal capacity in wastewater treatment plants of towns.

Spatial assessment of the economic feasibility of short rotation coppice on radioactively contaminated land in Belarus, Ukraine, and Russia. II. Monte Carlo analysis.

A Monte Carlo analysis of two sequential GIS-embedded submodels, which evaluate the economic feasibility of short rotation coppice (SRC) production and energy conversion in areas contaminated by Chernobyl-derived (137)Cs, was performed to allow for variability of environmental conditions that was not contained in the spatial model inputs. The results from this analysis were compared to the results from the deterministic model presented in part I of this paper. It was concluded that, although the variability in the model results due to within-gridcell variability of the model inputs was considerable, the prediction of the areas where SRC and energy conversion is potentially profitable was robust. If the additional variability in the model input that is not contained in the input maps is also taken into account, the SRC production and energy conversion appears to be potentially profitable at more locations for both the small scale and large scale production scenarios than the model predicted using the deterministic model.

Review and assessment of models for predicting the migration of radionuclides from catchments.

The present paper summarises the results of the review and assessment of models developed for predicting the migration of radionuclides from catchments to water bodies. The models were classified and evaluated according to their main methodological approaches. A retrospective analysis of the principles underpinning the model development in relation to experimental finding and results was carried out. It was demonstrated that most of the various conceptual approaches of different modellers can be integrated in a general, harmonised perspective supported by a variety of experimental evidences. Shortcomings and advantages of the models were discussed.

Assessment of spatial variation of cesium-137 in small catchments.

Surface contamination by bomb-derived and Chernobyl-derived 137Cs has been subject to changes due to physical decay and lateral transport of contaminated soil particles, which have resulted in an on-going transfer of radionuclides from terrestrial ecosystems to surface water, river bed sediments, and flood plains. Knowledge of the different sources of spatial variation of 137Cs is particularly essential for estimating 137Cs transfer to fluvial systems and for successfully applying 137Cs as an environmental tracer in soil erosion studies. This study combined a straightforward sediment redistribution model and geostatistical interpolation of point samples of 137Cs activities in soil to distinguish the effects of sediment erosion and deposition from other sources of variation in 137Cs in the small Mochovce catchment in Slovakia. These other sources of variation could then be interpreted. Besides erosion and deposition processes, the initial pattern of 137Cs deposition, floodplain sedimentation, and short-range spatial variation were identified as the major sources of spatial variation of the 137Cs inventory.