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.

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.

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.

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.

Buffer capacity analysis of open atmospheric gas-liquid systems containing main acidic and basic atmospheric pollutants was carried out. Usually the buffer capacity is considered as a function of pH as an independent variable. In this work the buffer capacity is analysed including the dependence of pH on the composition of a system. Such an approach allows finding an important, from the viewpoint of atmospheric water acidification, relationship between the gas phase composition and the buffer capacity. It was found that buffer capacity of the open gas-liquid systems may be very high and it may cause the liquid phase pH to remain at low levels. The buffer capacity of the analysed systems is most strongly affected by the simultaneous presence of ammonia and strong acids in the gas phase. The higher concentrations of strong acid gases the lower NH₃ concentration is sufficient to achieve high buffer capacity. In the presence of strong acid gases, calcium ions affect both the buffer capacity and the liquid phase pH only at low NH₃ concentrations. High buffer capacity of open gas-liquid systems may be one of the reasons why the reduction in emissions of acidic gas pollutants has little effect on decrease in atmospheric water acidity.

Fluvial bed sediments are widely used for characterizing anthropogenic contaminant signals in urban watersheds. This study presents the first preliminary examination of sequentially extracted Pb from grain size fractionated bed sediments using the optimized (standardized) BCR procedure. Baseline sediment samples and samples from the vicinity of three storm-sewer outlets in Nuuanu Stream, Honolulu, Hawaii, were examined. The weighted average Pb liberated from four sequentially extracted phases was 144 ± 26 mg/kg (±SD). These Pb concentrations are high compared to 3 mg/kg leached by a 0.5 M HCl solution, and 13 mg/kg from a 4-acid total digestion of baseline sediments. Over a 1.8 km section of stream channel, land use variations and traffic density differences had little impact on the magnitude of Pb in specific phases for each of the six grain size fractions examined. Regardless of grain size or spatial location, Pb in the reducible phase exceeded that in oxidizable, residual and acid extractable phases. Weighted reducible Pb concentrations for three sewer outlet sites ranged from 69 to 92 mg/kg, and this phase typically accounted for 70-80% of all labile Pb. The <63 μm grain size class did not exhibit the highest Pb concentration, instead this was found in either the 125-250 μm or 500-1,000 μm fractions. Examining bed sediment phase associations of Pb over a smaller length dimension (i.e., 40 m) centered around one sewer outlet, indicated higher concentrations at the outlet (180 mg/kg) compared to upstream (132 mg/kg) or downstream (150 mg/kg). The differences were primarily associated with higher Pb concentrations in the reducible and oxidizable phases of the coarse sand fractions (500-2,000 μm) at the outlet. Overall, all data point to a significant anthropogenic signal for Pb in bed sediments in the urbanized section of Nuuanu Stream.

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.

A simple and very sensitive method determining microgram quantities of indium in soil has been developed. The spectrophotometric method (ε = 1.74 x 10⁵ l mol⁻¹ cm⁻¹) based on the mixed complex In (III) with Chrome Azurol S and benzyldodecyldimethylammonium bromide was used for the analysis. A preliminary separation is made by extracting indium into butyl acetate from 5 M HBr solution. The selectivity of indium extraction and determination in the presence of macro- and micro components of soil was studied. Prior reduction of Fe (III) to Fe (II) with ascorbic acid prevents its co-extraction with indium. Indium was determined in synthetic mixtures corresponding to soil compositions and real samples of soil from different agricultural and industrial regions of Poland. The content of indium was found from the calibration graph (in the range, 0.12-0.48 μg/ml; r = 0.9991) obtained after extraction. The precision was satisfactory: % RSD (n = 6) ranged from 2.7 to 8.2. The average indium standard recovery ranged from 95 to 101%. Analysis using an ICP-OES method gave comparable results.

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.