The spatial pattern and magnitude of mass fluxes at the stream-aquifer interface have important implications for the fate and transport of contaminants in river basins. Integral pumping tests were performed to quantify average concentrations of chlorinated benzenes in an unconfined aquifer partially penetrated by a stream. Four pumping wells were operated simultaneously for a time period of 5 days and sampled for contaminant concentrations. Streambed temperatures were mapped at multiple depths along a 60 m long stream reach to identify the spatial patterns of groundwater discharge and to quantify water fluxes at the stream-aquifer interface. The combined interpretation of the results showed average potential contaminant mass fluxes from the aquifer to the stream of 272 μg m-2 d-1 MCB and 71 μg m-2 d-1 DCB, respectively. This methodology combines a large-scale assessment of aquifer contamination with a high-resolution survey of groundwater discharge zones to estimate contaminant mass fluxes between aquifer and stream. We provide a new methodology to quantify the potential contaminant mass flux from an aquifer to a stream.

Metals released by the extraction with aqua regia, EDTA, dilute HCl and sequential extraction (SE) by the BCR protocol were studied in urban soils of Sevilla, Torino, and Glasgow. By multivariate analysis, the amounts of Cu, Pb and Zn liberated by any method were statistically associated with one another, whereas other metals were not. The mean amounts of all metals extracted by HCl and by SE were well correlated, but SE was clearly underestimated by HCl. Individual data for Cu, Pb and Zn by both methods were correlated only if each city was considered separately. Other metals gave poorer relationships. Similar conclusions were reached comparing EDTA and HCl, with much lower values for EDTA. Dilute HCl extraction cannot thus be recommended for general use as alternative to BCR SE in urban soils. Dilute HCl extraction is tested as an alternative to the BCR sequential extraction in urban soils.

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. Groundwater age dating reveals trends and trend reversal in groundwater quality.

Previously recommended rhizosphere-based method (RHIZO) applied to moist rhizosphere soils was integrated with moist bulk soils, and termed adjusted-RHIZO method (A-RHIZO). The A-RHIZO and RHIZO methods were systematically compared with EDTA, DTPA, CaCl2 and the first step of the Community Bureau of Reference (BCR1) methods for assessing metal phytoavailability under field conditions. Results suggested that moist bulk soils are equally suited or even better than rhizosphere soils to estimate metal phytoavailability. The A-RHIZO method was preferred to other methods for predicting the phytoavailability of Ni, Cu, Zn, Cd, Pb and Mn to wheat roots with correlation coefficients of 0.730 (P < 0.001), 0.854 (P < 0.001), 0.887 (P < 0.001), 0.739 (P < 0.001), 0.725 (P < 0.001) and 0.469 (P < 0.05), respectively. When including soil properties, other extraction methods were also able to predict phytoavailability reasonably well for some metals. Soil pH, organic matter and Fe-Mn oxide contents, and cation-exchange capacity mostly influenced the extraction and phytoavailability of metals. An adjusted-RHIZO method was the most promising approach for predicting metal phytoavailability to wheat under field conditions.

Surface water is frequently contaminated by the trace metals, in particular lead and zinc, produced by mining activities. The infiltration of this water is likely to pollute surface soils and ground water. The study of the transfer of trace elements, especially lead, under real conditions is difficult to carry out due to the physicochemical and hydrodynamic complexity of real soil (preferential flows, conditions of unsaturation...), of the presence of colloids and of many candidate elements. The objective of the present study was to gain a better understanding of the parameters influencing the migration processes of trace elements in simplified systems; it was based on the study of Pb transfer in laboratory columns filled with soil. The results showed that retention of lead in soil is strongly dependent on feed flow rate, particulate bed tortuosity, bed height, water-soil surface contact and volume of water. Increase in bed height, water-soil surface contact and particulate bed tortuosity leads to higher contact time thus higher lead retention by soil, whereas increase in feed flow rate and volume of water leads to lower contact time thus lower lead retention by soil.

According to recent insight, the toxicity of metals in soils is better related to the free metal ion (FMI) activity in the soil solution than to the total metal concentration in soil. However, the determination of FMI activities in soil solution is a difficult and time-consuming task. An alternative is to use empirical equations (so called transfer functions (TFs)) that relate FMI activity in solution to the reactive metal concentration in the solid phase and to soil properties (pH and organic matter content). Here we test the applicability of two sets of TF for Cd and Pb using independent data from a wide range of soil types and regions that are not represented in the datasets used to derive the TFs. From these soils, soil solution was extracted using four different methods. For all these extracts, FMI activities were calculated from total concentrations in solution using the speciation program WHAM VI. In some of the soils, Cd and Pb FMI activities were also measured using a Donnan membrane technique. Most of these FMI activities deviated from the TF predictions by less than one order of magnitude and were within the 95% confidence interval of the TFs, irrespective of the method used to extract soil solution. Predictability was higher for Pb than for Cd and differed also between the two TF sets.

In principle, conventional lysimeters are suitable for the investigation of vertical water and solute fluxes. Lateral fluxes in water-saturated fen sites are characterized by heterogeneities and abnormities due to anisotropic layering. But due to lack of adequate monitoring techniques, these fluxes have been insufficiently analyzed. The newly developed large weighable fen lysimeter (LWFL) overcomes the limitations of conventional lysimetry and enables the measurement of vertical and horizontal transport processes in undisturbed large volume soil monoliths. The LWFL has a volume of 6 m³ (4 m length, 1 m width and 1.5 m depth) and was tested by filling the lysimeter with an undisturbed fen monolith. A special extraction procedure for the horizontal sliding of the lysimeter vessel through the natural fen was developed. In front of the vessel a converted cutting tool assisted in carving the soil monolith out of the peat, both vertically and horizontally. Inlet and outlet of the LWFL was constructed to allow the adjustment of a wide range of hydraulic gradients to depict natural occurring lateral transport processes. The LWFL including the measurement techniques was tested successfully for 3 years. On the basis of these tests, we conclude that complex physical and biogeochemical research problems involving lateral flows can be tackled now with multiphase observations and measurements at high spatial and temporal resolution, transdisciplinary data evaluation and numerical modelling approaches.

Ground-level concentrations of three atmospheric mercury species were measured using manual sampling and analysis to provide data for estimates of mercury dry deposition. Three monitoring stations were operated simultaneously during winter, spring, and summer 2004, adjacent to three mercury wet-deposition monitoring stations in northern, central, and southern Indiana. The monitoring locations differed in land-use setting and annual mercury-emissions level from nearby sources. A timer-controlled air-sampling system that contained a three-part sampling train was used to isolate reactive gaseous mercury, particulate-bound mercury, and elemental mercury. The sampling trains were exchanged every 6 days, and the mercury species were quantified in a laboratory. A quality-assurance study indicated the sampling trains could be held at least 120 h without a significant change in reactive gaseous or particulate-bound mercury concentrations. The manual sampling method was able to provide valid mercury concentrations in 90 to 95% of samples. Statistical differences in mercury concentrations were observed during the project. Concentrations of reactive gaseous and elemental mercury were higher in the daytime samples than in the nighttime samples. Concentrations of reactive gaseous mercury were higher in winter than in summer and were highest at the urban monitoring location. The results of this case study indicated manual sampling and analysis could be a reliable method for measurement of atmospheric mercury species and has the capability for supplying representative concentrations in an effective manner from a long-term deposition-monitoring network.

The sampling and analysis properties of 1-stage and 2-stage filter-pack methods were studied in detail in monitoring of sulphur and nitrogen containing inorganic gases and particles (sulphur dioxide, sulphate, sum of nitric acid and nitrate and total ammonium). The limit of detection and the limit of quantitation for 24-h samples were estimated using the results of a short-term field experiment completed with available data from long-term monitoring and internal quality assurance. Furthermore, the combined expanded measurement uncertainty including sampling and analysis (Uₜₒₜ) was estimated for filter-pack methods in order to give a tool for distinguishing long-term trends in air quality from the measurement variability. Uₜₒₜ was found to be very near the analytical uncertainty when measuring higher air concentration levels, being ± 4.0% for sulphur concentrations > 1.0 μg m⁻³, ± 3.0% for sulphate concentrations > 0.5 μg m⁻³, ± 3.5% for the sum of nitrate and nitric acid concentrations > 0.3 μg m⁻³ and ± 4.5% for total ammonium concentrations > 0.8 μg m⁻³. At the lower air concentration range Uₜₒₜ increases significantly due to the field blank values. The precision of the 24-h filter-pack sample results expressed by means of modified median absolute difference (M.MAD) and coefficient of variance (CoV) gave 8.3% for sulphur dioxide and 5.4% for particulate sulphate. For the sum of gaseous nitric acid and particulate nitrate the CoV was 5.5% and for total ammonium 4.3%. In addition the suitability of the 24-h filter-pack methods in weekly sampling was proved.

The present study aimed to look at the fate of protozoan parasite Cryptosporidium parvum oocysts applied through surface drip irrigation on reclaimed water irrigation-history and non-history sandy-loam (Hamra) soil columns. A new and simple isolation method for recovery of oocysts from soil samples was developed and used along this study. The new soil isolation method of oocysts is based on the “two phase separation method” formerly used to recover Clostridium perfringens spores from sediments and soil samples with minor modifications. The range recovery achieved by this method was 64-95% (mean 61.2 ± 17.4). The objectives of the second part of this study were to investigate several physical and chemical factors governing transport and survival of C. parvum oocysts in sandy-loam soil columns by breakthrough curves. Comparison of fresh water and reclaimed water irrigation revealed that reclaimed water irrigated-history soil was more hydrophobic allowing water flow through channels with poor oocysts retention and fast flow. Examination of the organic matter effect (originating from reclaimed water irrigation) on oocysts breakthrough revealed that their soil infiltration increased. Calculations of oocysts concentration at different columns depths showed that most of the oocysts were retained in the first 5 cm of soil column. In the present study, comparing the two soil types (history and non-history of effluents irrigation) beside the surface electrostatic charge, one of the main elements found to affect oocysts infiltration and transport in soil columns was soil hydrophobicity caused by soluble organic matter originating from reclaimed water irrigation. Therefore, prior to application in soil irrigation, reclaimed water should be treated to high quality (i.e. membrane technology as the best option) to prevent enhanced transport of various pathogens through those irrigated soils.