Radiocarbon dating of modern groundwater: the role of the unsaturated zone

Biological and physical processes occurring in soils may lead to significant isotopic changes between the isotopic compositions of atmospheric CO2 and of soil CO2. Also, during water and gas transport from the soil surface to the water table, isotopic changes likely occur due to numerous physical processes such as gas production and diffusion, water advection, and gas-water-rock interactions. In most cases, these changes are not included in the correction models developed for groundwater dating, whereas they can significantly impact the calculation of the 14C age. We explore the role of these processes using: i) experimental data from two aquifer sites (Fontainebleau sands and Astian sands, France), ii) a distributed model to simulate the 14C activities of soil CO2, and iii) numerical simulations in order to highlight the role of the physical processes.¦The 13C content in soil CO2 showed seasonal variations and highlighted the competition between CO2 production and CO2 diffusion. Their respective contributions played a significant role in defining the isotopic composition of CO2 at the water table. On both study sites, variations of the 14C activity in soil CO2 reflect the competition between the fluxes of root derived-CO2 and organic matter derived-CO2. Since the nuclear weapon tests in the fifties and sixties, soil CO2 became significantly depleted in 14C compared to modern atmospheric CO2. Models that take into account this 14C depletion in soil CO2 for dating modern groundwater would lead to apparent younger 14C ages than models that only consider the 14C activity in atmospheric CO2. Moreover, since 2000-2005, the inverse effect is observed as soil CO2 is enriched in 14C compared to atmospheric CO2.¦Therefore, we conclude that the isotopic composition of CO2 at the water table have to be taken into account for the dating of modern groundwater. This requires a systematic sampling of soil CO2 and the measurement of its 13C and 14C contents. We used this information in a numerical simulation to calculate the evolution of isotopic composition of CO2 from the soil surface to the water table. This simulation integrated physical processes in the unsaturated zone (e.g. CO2 production and diffusion, water advection, etc.) and gas-water-rock interactions.

Groundwater dating and past climate reconstruction

In the past decade aquifers have increasingly become palaeoclimatic archives in their own right alongside ice cores, sediments and other proxy records. The main tool for this task has been the noble gas palaeo-thermometer in combination with quantitative groundwater dating using radionuclides. Noblegas radionuclides play a unique role as tracers in environmental studies due to their chemical inertness and low concentration making them ideal tracers. The same properties on the other hand make them difficult to measure on natural concentration levels. Therefore for decades low level counting (LLC) was the only method for detecting radioisotopes of argon and krypton at an atmospheric level. In recent times and with the increase of interest and potential applications the analytical efforts with novel detection methods have been intensified. In the talk noble gas groundwater dating techniques over times scales from decades to millions of years are discussed in relation to noble gas palaeo records at different locations in Europe and elsewhere.

Imaging and quantifying salt-tracer transport in a riparian groundwater system by means of 3D ERT monitoring

Determining groundwater flow paths of infiltrated river water is necessary for studying biochemical processes in the riparian zone, but their characterization is complicated by strong temporal and spatial heterogeneity. We investigated to what extent repeat 3D surface electrical resistance tomography (ERT) can be used to monitor transport of a salt-tracer plume under close to natural gradient conditions. The aim is to estimate groundwater flow velocities and pathways at a site located within a riparian groundwater system adjacent to the perialpine Thur River in northeastern Switzerland. Our ERT time-lapse images provide constraints on the plume's shape, flow direction, and velocity. These images allow the movement of the plume to be followed for 35 m. Although the hydraulic gradient is only 1.43 parts per thousand, the ERT time-lapse images demonstrate that the plume's center of mass and its front propagate with velocities of 2x10(-4) m/s and 5x10(-4) m/s, respectively. These velocities are compatible with groundwater resistivity monitoring data in two observation wells 5 m from the injection well. Five additional sensors in the 5-30 m distance range did not detect the plume. Comparison of the ERT time-lapse images with a groundwater transport model and time-lapse inversions of synthetic ERT data indicate that the movement of the plume can be described for the first 6 h after injection by a uniform transport model. Subsurface heterogeneity causes a change of the plume's direction and velocity at later times. Our results demonstrate the effectiveness of using time-lapse 3D surface ERT to monitor flow pathways in a challenging perialpine environment over larger scales than is practically possible with crosshole 3D ERT.

Effect of groundwater composition on arsenic detection by bacterial biosensors.

A luminescent bacterial biosensor was used to quantify bioavailable arsenic in artificial groundwater. Its light production above the background emission was proportional to the arsenite concentration in the toxicologically relevant range of 0 to 0.5 mu M. Effects of the inorganic solutes phosphate, Fe(II) and silicate on the biosensor signal were studied. Phosphate at a concentration of 0.25 g L-1 phosphate slightly stimulated the light emission, but much less than toxicologically relevant concentrations of the much stronger inducer arsenite. No effect of phosphate was oberved in the presence of arsenite. Freshly prepared sodium silicate solution at a concentration of 10 g L-1 Si reduced the arsenite-induced light production by roughly 37%, which can be explained by transient polymerization leading to sequestration of some arsenic. After three days of incubation, silicate did not have this effect anymore, probably because depolymerization occurred. In the presence of 0.4 g L-1 Fe(II), the arsenite-induced light emission was reduced by up to 90%, probably due to iron oxidation followed by arsenite adsorption on the less soluble Fe(III) possibly along with some oxidation to the stronger adsorbing As(V). Addition of 100 mu M EDTA was capable of releasing all arsenic from the precipitate and to transform it into the biologically measurable, dissolved state. The biosensor also proved valuable for monitoring the effectiveness of an arsenic removal procedure based on water filtration through a mixture of sand and iron granules.

Field testing of arsenic in groundwater samples of Bangladesh using a test kit based on lyophilized bioreporter bacteria.

A test kit based on living, lyophilized bacterial bioreporters emitting bioluminescence as a response to arsenite and arsenate was applied during a field campaign in six villages across Bangladesh. Bioreporter field measurements of arsenic in groundwater from tube wells were in satisfying agreement with the results of spectroscopic analyses of the same samples conducted in the lab. The practicability of the bioreporter test in terms of logistics and material requirements, suitability for high sample throughput, and waste disposal was much better than that of two commercial chemical test kits that were included as references. The campaigns furthermore demonstrated large local heterogeneity of arsenic in groundwater, underscoring the use of well switching as an effective remedy to avoid high arsenic exposure.

Groundwater Monitoring in Iowa, 2004

Water fact sheet for Iowa Department of Natural Resources and the Geological Bureau.

Reorganization of a deeply incised drainage: role of deformation, sedimentation and groundwater flow

Deeply incised drainage networks are thought to be robust and not easily modified, and are commonly used as passive markers of horizontal strain. Yet, reorganizations (rearrangements) appear in the geologic record. We provide field evidence of the reorganization of a Miocene drainage network in response to strike-slip and vertical displacements in Guatemala. The drainage was deeply incised into a 50-km-wide orogen located along the North America-Caribbean plate boundary. It rearranged twice, first during the Late Miocene in response to transpressional uplift along the Polochic fault, and again in the Quaternary in response to transtensional uplift along secondary faults. The pattern of reorganization resembles that produced by the tectonic defeat of rivers that cross growing tectonic structures. Compilation of remote sensing data, field mapping, sediment provenance study, grain-size analysis and Ar(40)/Ar(39) dating from paleovalleys and their fill reveals that the classic mechanisms of river diversion, such as river avulsion over bedrock, or capture driven by surface runoff, are not sufficient to produce the observed diversions. The sites of diversion coincide spatially with limestone belts and reactivated fault zones, suggesting that solution-triggered or deformation-triggered permeability have helped breaching of interfluves. The diversions are also related temporally and spatially to the accumulation of sediment fills in the valleys, upstream of the rising structures. We infer that the breaching of the interfluves was achieved by headward erosion along tributaries fed by groundwater flow tracking from the valleys soon to be captured. Fault zones and limestone belts provided the pathways, and the aquifers occupying the valley fills provided the head pressure that enhanced groundwater circulation. The defeat of rivers crossing the rising structures results essentially from the tectonically enhanced activation of groundwater flow between catchments.

Groundwater Quality: Dakota Aquifer, 2008

This monthly report from the Iowa Department of Natural Resources is about the water quality management of Iowa's rivers, streams and lakes.

Groundwater Availability Modeling: Lower Dakota Aquifer, 2008

This monthly report from the Iowa Department of Natural Resources is about the water quality management of Iowa's rivers, streams and lakes.

Open to closed system transition traced through the TDIC isotopic signature at the aquifer recharge stage, implications for groundwater 14C dating

14C dating models are limited when considering recent groundwater for which the carbon isotopic signature of the total dissolved inorganic carbon (TDIC) is mainly acquired in the unsaturated zone. Reducing the uncertainties of dating thus implies a better identification of the processes controlling the carbon isotopic composition of the TDIC during groundwater recharge. Geochemical interactions between gas, water and carbonates in the unsaturated zone were investigated for two aquifers (the carbonate-free Fontainebleau sands and carbonate-bearing Astian sands, France) in order to identify the respective roles of CO2 and carbonates on the carbon isotopic signatures of the TDIC; this analysis is usually approached using open or closed system terms. Under fully open system conditions, the seasonality of the 13C values in the soil CO2 can lead to important uncertainties regarding the so-called "initial 14C activity" used in 14C correction models. In a carbonate-bearing unsaturated zone such as in the Astian aquifer, we show that an approach based on fully open or closed system conditions is not appropriate. Although the chemical saturation between water and calcite occurs rapidly within the first metre of the unsaturated zone, the carbon isotopic contents (δ13C) of the CO2 and the TDIC evolve downward, impacted by the dissolution-precipitation of the carbonates. In this study, we propose a numerical approach to describe this evolution. The δ13C and the A 14C (radiocarbon activity) of the TDIC at the base of the carbonate-hearing unsaturated zone depends on (i) the δ13C and the A 14C of the TDIC in the soil determined by the soil CO2, (ii) the water's residence time in the unsaturated zone and (iii) the carbonate precipitation-dissolution fluxes. In this type of situation, the carbonate δ13C-A 14C evolutions indicate the presence of secondary calcite and permit the calculation of its accretion flux, equal to ~ 4.5 ± 0.5 x 10-9 mol grock-1 yr-1. More generally, for other sites under temperate climate and with similar properties to the Astian sands site, this approach allows for a reliable determination of the carbon isotopic composition at the base of the unsaturated zone as the indispensable "input function" data of the carbon cycle into the aquifer.

Groundwater Availability Modeling of the Lower Dakota Aquifer in Northwest Iowa, October 2008

The 2007 Iowa General Assembly, recognizing the increased demand for water to support the growth of industries and municipalities, approved funding for the first year of a multi-year evaluation and modeling of Iowa’s major aquifers by the Iowa Department of Natural Resources. The task of conducting this evaluation and modeling was assigned to the Iowa Geological and Water Survey (IGWS). The first aquifer to be studied was the Lower Dakota aquifer in a sixteen county area of northwest Iowa.

Bacterial bioassay for rapid and accurate analysis of arsenic in highly variable groundwater samples.

In this study, we report the first ever large-scale environmental validation of a microbial reporter-based test to measure arsenic concentrations in natural water resources. A bioluminescence-producing arsenic-inducible bacterium based on Escherichia coli was used as the reporter organism. Specific protocols were developed with the goal to avoid the negative influence of iron in groundwater on arsenic availability to the bioreporter cells. A total of 194 groundwater samples were collected in the Red River and Mekong River Delta regions of Vietnam and were analyzed both by atomic absorption spectroscopy (AAS) and by the arsenic bioreporter protocol. The bacterial cells performed well at and above arsenic concentrations in groundwater of 7 microg/L, with an almost linearly proportional increase of the bioluminescence signal between 10 and 100 microg As/L (r2 = 0.997). Comparisons between AAS and arsenic bioreporter determinations gave an overall average of 8.0% false negative and 2.4% false positive identifications for the bioreporter prediction at the WHO recommended acceptable arsenic concentration of 10 microg/L, which is far betterthan the performance of chemical field test kits. Because of the ease of the measurement protocol and the low application cost, the microbiological arsenic test has a great potential in large screening campaigns in Asia and in other areas suffering from arsenic pollution in groundwater resources.