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Aluminium has received great attention in the second half of the 20th century, mainly in the context of the acid rain problem mostly in forest soils. In this research the effect of land use and depth of the groundwater on Al, pH and DOC concentration in groundwater under Dutch sandy soils has been studied. Both pH and DOC concentration play a major role in the speciation of Al in solution. Furthermore, the equilibrium with mineral phases like gibbsite, amorphous Al(OH)3 and imogolite, has been considered. Agricultural and natural land use were expected to have different effects on the pH and DOC concentration, which in turn could influence the total Al concentration and the speciation of Al in groundwater at different depths (phreatic, shallow and deep). An extensive dataset (n = 2181) from the national and some provincial monitoring networks on soil and groundwater quality was used. Land use type and groundwater depth did influence the pH, and Al and DOC concentrations in groundwater samples. The Al concentration ranged from 7 to 1941 μmol L-1 at pH < 4; highest Al concentrations were found for natural-phreatic groundwater. The DOC concentration decreased and the median pH increased with depth of the groundwater. Natural-phreatic groundwater showed lower pH than the agricultural-phreatic groundwater. Highest DOC concentrations were found for the agricultural-phreatic groundwater, induced by the application of organic fertilizers. Besides inorganic complexation, the NICA-Donnan model was used to calculate Al3+ concentrations for complexation with DOC. Below pH 4.5 groundwater samples were mainly in disequilibrium with a mineral phase. This disequilibrium is considered to be the result of kinetic constraints or equilibrium with organic matter. Log K values were derived by linear regression and were close to theoretical values for Al(OH)3 minerals (e.g. gibbsite or amorphous Al(OH)3), except for natural-phreatic groundwater for which lower log K values were found. Complexation of Al with DOC is shown to be an important factor for the Al concentrations, especially at high DOC concentrations as was found for agricultural-phreatic groundwater. © 2007 Elsevier Ltd. All rights reserved.

Recent EU legislation is directed to reverse the upward trends in the concentrations of agricultural pollutants in groundwater. However, uncertainty of the groundwater travel time towards the screens of the groundwater quality monitoring networks complicates the demonstration of trend reversal. We investigated whether trend reversal can be demonstrated by relating concentrations of pollutants in groundwater to the time of recharge, instead of the time of sampling. To do so, we used the travel time to monitoring screens in sandy agricultural areas in the Netherlands, determined by 3H/3He groundwater dating. We observed that concentrations of conservative pollutants increased in groundwater recharged before 1985 and decreased after 1990. Thereby, we demonstrated trend reversal of groundwater quality. From this research we concluded that 3H/3He dating can be used to facilitate (re)interpretation of existing groundwater quality data. The presented approach is widely applicable in areas with unconsolidated granular aquifers and large agricultural pressures on groundwater resources. © 2007 Elsevier Ltd. All rights reserved.

Changes in agricultural practices are expected to affect groundwater quality by changing the loads of nutrients and salts in recharging groundwater, but regional monitoring networks installed to register the changes often fail to detect them and interpretation of trend analysis results is difficult. This study aims to improve the detection and understanding of groundwater quality changes with time, combining time series information, concentration-depth profiles, age dating and concentration-depth prognoses based on the historical inputs of solutes. For trend detection, a combination of trend analysis on time series at specific depths and time-averaged concentration-depth profiles was used. To reveal trends that have become obscured by chemical reactions, additional conditionally conservative indicators were introduced that are insensitive to those reactions under specific conditions. Detected trends were matched with prognoses of conservative and reactive transport to aid the understanding of trends. Data of the regional networks in 2 area-types with intensive livestock farming in the Dutch province of Noord-Brabant were used to illustrate the approach. The downward movement of the agricultural pollution front was demonstrated for the 2 area-types. However, many targeted contaminants have become retarded or delayed and quality changes were hard to detect for many reactive solutes, including nitrate. Pollution fronts of these targeted chemical components are still limited to the first 15 m of the subsoil. At deeper level, about 20-25 m, the effects of agricultural pollution and acidification were indicated by chemical indicators that have not been considered by others: oxidation capacity, the sum of cations and chloride. Increasing trends of the conditionally conservative indicators 'oxidation capacity' and 'sum of cations' were found at a depth of 18-25 m below surface. Increasing trends for potassium were found at shallower depth (7-13 m), which is explained by retardation of potassium due to cation-exchange with calcium and magnesium. The modelled cation-exchange explained the shape of the concentration-depth profile and the increasing trends at shallow depth in the aquifer. © 2004 Elsevier B.V. All rights reserved.