Particulate barium fluxes and export production in the northwestern Mediterranean

Biogenic barium, mostly in the barite (BaSO₄) form, has been proposed as a tracer for export production in the ocean. Here we report on biogenic barium (Ba_xs) and particulate organic carbon (POC) fluxes from sediment traps deployed at the DYFAMED site in the Northwestern Mediterranean Sea. Ba_xs fluxes display average values of 37 ± 45 and 50 ± 58 μg/m²/d at 200 and 1000 m respectively, and are linearly correlated to POC fluxes (mean values of 7.9 ± 9.3 and 6.8 ± 6.8 mg C/m²/d at 200 and 1000 m). Export production estimates, calculated using published Ba_xs- or POC-based algorithms, all fall below or close to the lower limit of potential export values proposed in the literature. This work clearly demonstrates the usefulness of Ba_xs as a tracer of oceanic export production in the Northwestern Mediterranean Sea. However, development of a quantitative export production proxy requires a clear understanding of the underlying cause(s) for the observed spatial variations in the relationship between Ba_xs and POC fluxes. The present study confirms that the processes leading to barite formation differ between margin and open-ocean sites and probably account for much of the regional variability in the POC/Ba_xs ratio.     

Ocean/ice shelf interaction in the southern Weddell Sea: results of a regional numerical helium/neon simulation

Ocean/ice interaction at the base of deep-drafted Antarctic ice shelves modifies the physical properties of inflowing shelf waters to become Ice Shelf Water (ISW). In contrast to the conditions at the atmosphere/ocean interface, the increased hydrostatic pressure at the glacial base causes gases embedded in the ice to dissolve completely after being released by melting. Helium and neon, with an extremely low solubility, are saturated in glacial meltwater by more than 1000%. At the continental slope in front of the large Antarctic caverns, ISW mixes with ambient waters to form different precursors of Antarctic Bottom Water. A regional ocean circulation model, which uses an explicit formulation of the ocean/ice shelf interaction to describe for the first time the input of noble gases to the Southern Ocean, is presented. The results reveal a long-term variability of the basal mass loss solely controlled by the interaction between waters of the continental shelf and the ice shelf cavern. Modeled helium and neon supersaturations from the Filchner–Ronne Ice Shelf front show a “low-pass” filtering of the inflowing signal due to cavern processes. On circumpolar scales, the simulated helium and neon distributions allow us to quantify the ISW contribution to bottom water, which spreads with the coastal current connecting the major formation sites in Ross and Weddell Seas.

δ34S isotope values of dissolved sulfate (SO4 2−) as a tracer for battery acid (H2SO4) contamination in groundwater

The application of sulfur isotope (³⁴S) values of sulfate in groundwater provided the information necessary to evaluate the source, transport and fate of battery acid and associated contaminants at the Gulf Coast Recycling (GCR) facility. The chemical and isotopic composition of groundwater beneath the (GCR) property, a battery recycling facility in east Tampa, Florida, varies more than expected for an area of comparable size. Sulfate (SO₄^2–) values, for example, range from 1.2 to 11,500 mg/L and oxygen and hydrogen isotopes do not attenuate towards the weighted annual mean. Those samples that are high in sulfate generally have a low pH, which immediately indicates battery acid (H₂SO₄) contamination as a potential source for the sulfate. The low pH and high reactivity of the sulfuric acid groundwater cause the formation of hydrogeological microenvironments due to preferential dissolution of carbonate minerals, which in turn causes enhanced recharge and groundwater flow in certain areas; thus, the extreme scatter in the data set. Because of the difficult hydrogeology it is not straightforward to delineate the point-sources of contamination and up to five potential scenarios have to be evaluated: (1) seawater intrusion, (2) upwelling of high-sulfate groundwater, (3) local dissolution of gypsum, (4) an up-gradient contaminant source to the northeast of the GCR property and (5) battery acid contamination.     

Approximations to the ocean’s residual circulation in arbitrary tracer coordinates

The residual circulation is the flow which transports tracers. Its utility is tempered by the challenge associated with its computation: velocity must be mapped into tracer coordinates on a timescale which is short compared to eddy timescales. Several approximations have been introduced which allow the residual circulation to be evaluated using a small number of flow statistics, including the transformed Eulerian mean (TEM), the temporal residual mean (TRM), and the recently introduced statistical transformed Eulerian mean (STEM). This paper discusses the relationship between these approximations and illustrates their differences with a series of analytical and numerical examples. The STEM is found to be superior to the TEM and TRM in both its handling of the surface boundary condition and its ease of implementation.     

Recharge processes: piston flow vs preferential flow in semi-arid aquifers of India

Study of groundwater recharge processes is vital for quantification of total natural recharge to the aquifers. One of the recharge processes demonstrated earlier by tracer experiments in the unsaturated zone is that of piston flow movement of soil moisture. Based on this recharge process, environmental tritium, chloride and injected tritium studies have been carried out extensively in various geological environs of India. The purpose of this paper is to evaluate the validity of the piston flow concept in different geological environs viz. consolidated fractured and weathered granites, semi-consolidated sandstones and unconsolidated alluvial tracts, and quantify the contribution from this process as well as that from the preferential flow mechanism using different tracers. Analysis of tracer data demonstrates that the preferential flow recharge process contributes very significantly (an average of 75% of total recharge) in the case of fractured granites and is important (an average of 33% of total recharge) for semi-consolidated sandstones, whereas the preferential flow recharge component is minimal in unconsolidated alluvial tracts (piston flow model is applicable). These findings necessitate re-evaluation of the total natural recharge potential of the above mentioned geological environs in view of the significant preferential flow recharge that is evidenced and estimated. Electronic Publication     

Dripping into unsaturated rock underground excavations—literature review and geologic and hydrogeologic setting description

A literature review of dripping in underground constructions in deep, unsaturated geologic media was performed as part of a phased study. The objective is to develop and test a formulation that can be used for studying unsaturated flow through rough multi-segmented fractures, with emphasis on predicting dripping initiation time. Geologic and hydrogeologic setting for the Yucca Mountain (YM) and its exploratory studies facility, which is the site where the model will be tested, are described.     

A case study in catchment hydrochemistry: Conflicting interpretations from hydrological and chemical observations

Soil water, stream water, groundwater and rain water were sampled through a storm event in a moorland catchment. Samples were analysed for major ions and deuterium. Chloride and deuterium are used as tracers to enable separation of the stream runoff hydrograph into three components: rain, soil and groundwater. The results indicate that rain water arrives in the stream quickly during the event and contributes a significant volume to the runoff peak. The chemical signal in the rain water is, however, significantly damped, apparently due to mixing with soil water held in the catchment before the event. This is further modified before reaching the stream, apparently through mixing with a deeper groundwater component. Interpretation of tracer, chemistry and hydrological data to present an integrated picture of catchment hydrochemical response is difficult due to problems in the chemical and conceptual definition of the flow components.     

Dripping into unsaturated rock underground excavations: model testing at the Yucca Mountain exploratory studies facility

This paper presents a probabilistic formulation of unsaturated flow through rough multi-segmented fractures, with emphasis on Dripping Initiation Time (DIT), and attempts to explain the fast flow paths detected at the Yucca Mountain (YM) Exploratory Studies Facility (ESF). Three scenarios of parameters were used to test the validity of the model with these fast flow paths. The scenarios differed in the DITs and the corresponding parameter configurations were also tested for three different stratigraphic horizon depths. Each depth represented a different location where fast flow has been detected at YM. The first depth corresponds to the Bow Ridge Fault; the second represents a network of steep fractures and cooling joints with large variability in dip; and the third location, probably connected to the Diabolous Ridge Fault, has a flow path that is low dipping. Monte Carlo simulations for each configuration and depth produced probabilistic results from nine scenarios for DITs, which are quite consistent with field observations.     

A comparative modeling study of a dual tracer experiment in a large lysimeter under atmospheric conditions

In this paper, five model approaches with different physical and mathematical concepts varying in their model complexity and requirements were applied to identify the transport processes in the unsaturated zone. The applicability of these model approaches were compared and evaluated investigating two tracer breakthrough curves (bromide, deuterium) in a cropped, free-draining lysimeter experiment under natural atmospheric boundary conditions. The data set consisted of time series of water balance, depth resolved water contents, pressure heads and resident concentrations measured during 800 days. The tracer transport parameters were determined using a simple stochastic (stream tube model), three lumped parameter (constant water content model, multi-flow dispersion model, variable flow dispersion model) and a transient model approach. All of them were able to fit the tracer breakthrough curves. The identified transport parameters of each model approach were compared. Despite the differing physical and mathematical concepts the resulting parameters (mean water contents, mean water flux, dispersivities) of the five model approaches were all in the same range. The results indicate that the flow processes are also describable assuming steady state conditions. Homogeneous matrix flow is dominant and a small pore volume with enhanced flow velocities near saturation was identified with variable saturation flow and transport approach. The multi-flow dispersion model also identified preferential flow and additionally suggested a third less mobile flow component. Due to high fitting accuracy and parameter similarity all model approaches indicated reliable results.