Reach-scale river metabolism across contrasting sub-catchment geologies: Effect of light and hydrology.

We investigated the seasonal dynamics of in-stream metabolism at the reach scale (∼ 150 m) of headwaters across contrasting geological sub-catchments: clay, Greensand, and Chalk of the upper River Avon (UK). Benthic metabolic activity was quantified by aquatic eddy co-variance while water column activity was assessed by bottle incubations. Seasonal dynamics across reaches were specific for the three types of geologies. During the spring, all reaches were net autotrophic, with rates of up to 290 mmol C m-2 d-1 in the clay reach. During the remaining seasons, the clay and Greensand reaches were net heterotrophic, with peak oxygen consumption of 206 mmol m-2 d-1 during the autumn, while the Chalk reach was net heterotrophic only in winter. Overall, the water column alone still contributed to ∼ 25% of the annual respiration and primary production in all reaches. Net ecosystem metabolism (NEM) across seasons and reaches followed a general linear relationship with increasing stream light availability. Sub-catchment specific NEM proved to be linearly related to the local hydrological connectivity, quantified as the ratio between base flow and stream discharge, and expressed on a timescale of 9 d on average. This timescale apparently represents the average period of hydrological imprint for carbon turnover within the reaches. Combining a general light response and sub-catchment specific base flow ratio provided a robust functional relationship for predicting NEM at the reach scale. The novel approach proposed in this study can help facilitate spatial and temporal upscaling of riverine metabolism that may be applicable to a broader spectrum of catchments.

The emergence of hydrogeophysics for improved understanding of subsurface processes over multiple scales.

A review of the emergence and development of hydrogeophysicsOutline of emerging techniques in hydrogeophysicsPresentation of future opportunities in hydrogeophysics.

Fine-scale in situ measurement of riverbed nitrate production and consumption in an armored permeable riverbed.

Alteration of the global nitrogen cycle by man has increased nitrogen loading in waterways considerably, often with harmful consequences for aquatic ecosystems. Dynamic redox conditions within riverbeds support a variety of nitrogen transformations, some of which can attenuate this burden. In reality, however, assessing the importance of processes besides perhaps denitrification is difficult, due to a sparseness of data, especially in situ, where sediment structure and hydrologic pathways are intact. Here we show in situ within a permeable riverbed, through injections of (15)N-labeled substrates, that nitrate can be either consumed through denitrification or produced through nitrification, at a previously unresolved fine (centimeter) scale. Nitrification and denitrification occupy different niches in the riverbed, with denitrification occurring across a broad chemical gradient while nitrification is restricted to more oxic sediments. The narrow niche width for nitrification is in effect a break point, with the switch from activity "on" to activity "off" regulated by interactions between subsurface chemistry and hydrology. Although maxima for denitrification and nitrification occur at opposing ends of a chemical gradient, high potentials for both nitrate production and consumption can overlap when groundwater upwelling is strong.

Effect of the Type and Concentration of Salt on Production Efficiency in Smart Water Injection into Carbonate Oil Reservoir Rocks.

Smart waterflooding is one of the most practical emerging methods of enhanced oil recovery in carbonate reservoirs. In this study, the effect of salt type and its concentration in smart water on oil recovery from a carbonate reservoir rock is investigated. A series of experimental measurements, including zeta potential (ZP), interfacial tension (IFT), and contact angle (CA), were conducted to examine the effect of ions on the oil/brine/rock interaction. IFT, ZP, and CA were also used as screening methods to select effective solutions for flooding experiments. The results of the study show that synthesized brines containing sodium acetate and potassium acetate salts have a significant effect on the reduction of IFT; however, rock surface wettability due to such brines is insignificant. The presence of organic salts in the injected water can alter the properties of the fluid and rock surface, leading to improved oil recovery. The salts can reduce the interfacial tension between the oil and water phases, making it easier for the water to displace and mobilize trapped oil. This effect is particularly beneficial in reservoirs with high oil-water interfacial tension as it enhances the capillary forces and improves the sweep efficiency. Smart water with sodium acetate (MSW.NaOAc) caused a 7% increase in oil production in the tertiary injection process due to IFT and CA reduction. The secondary injection of MSW.NaOAc led to an oil production efficiency of 76%, which is 10% higher than that of the secondary injection of seawater (SW), confirming the effectiveness of acetate ions in enhancing oil recovery. Doubling the concentration of sulfate ions in modified SW (MSW.NaOAc.2S) caused a 19% increase in oil production in tertiary injections after SW flooding. The secondary injection of MSW.NaOAc.2S produced a 13% increase in the recovery factor compared to SW flooding in the secondary mode. The main driving mechanism for oil mobilization was found to be wettability alteration, which is supported by the analyses of CA and ZP. This study confirms that the salt type and concentration present in a brine solution play a vital role in the movement of trapped oil in carbonate reservoirs.

3D electrode configurations for spectral induced polarization surveys of landfills.

There is growing interest in the use of spectral induced polarization (SIP) surveys to characterize the near-surface environment. Few attempts have been made to perform field SIP surveys in a 3D configuration; when done, they are typically conducted using a series of parallel 2D electrode lines with collinear measurements. However, such measurements are limited in the resolution between the lines which is critical in the case of heterogeneous subsurface conditions, such as in landfills. To overcome this, we investigate here the enhanced resolution in SIP measurements through true 3D measurements, i.e., the resolving capabilities of different electrode configurations distributed across measuring planes. First, we investigate, through a synthetic study, the difference between results from using 2D parallel collinear electrode arrays and true 3D configurations. Second, we collected SIP data (in the frequency range between 1 and 240 Hz) using 2D and 3D configurations in two landfills to evaluate the application of our results in real field conditions. Both the synthetic and the field experiments demonstrate that measurements of parallel 2D collinear arrays result in the creation of artifacts and the loss of resolution in the 3D structure, especially of polarizable features. In contrast, the 3D configurations are able to resolve polarizable anomalies in synthetic and field measurements, resulting in a better delineation of the geometry of waste units. Our results also demonstrate that 3D configurations are better suited to recover the frequency-dependence of the electrical properties; thus, permitting an improved interpretation of waste composition and the quantification of waste volume.

Irrigation Optimization via Crop Water Use in Saline Coastal Areas-A Field Data Analysis in China's Yellow River Delta.

Freshwater resources are becoming increasingly scarce in coastal areas, limiting crop productivity in coastal farmlands. Although the characteristic of crop water use is an important factor for water conservation in coastal farmlands, it has not been studied extensively. This study aimed to depict the water use process of soil-plant systems under saline stress in coastal ecosystems and optimize water management. An intensive observation experiment was performed within China's Yellow River Delta to identify the water use processes and crop coefficients (KC) and also quantify the impacts of salt stress on crop water use. The results show that shallow groundwater did not contribute to soil water in the whole rotation; KC values for wheat-maize, wheat-sorghum, and wheat-soybean rotation systems were 45.0, 58.4, and 57% less, respectively, than the FAO values. The water use efficiency of the maize (8.70) and sorghum (9.00) in coastal farmlands was higher than that of the soybean (4.37). By identifying the critical periods of water and salt stress, this paper provides suggestions for water-saving and salinity control in coastal farmlands. Our findings can inform the sustainable development of coastal farmlands and provide new insights to cope with aspects of the global food crisis.

Hydrological properties predict the composition of microbial communities cycling methane and nitrogen in rivers.

Sediment microbial communities drive the biogeochemical cycles that make rivers globally important sources and sinks of carbon (C) and nitrogen (N). The structure of these communities is strongly determined by the local physico-chemical environment. However, we currently lack an understanding of the factors that determine microbial community structures at the catchment scale. Here, we show that the contribution of groundwater to total river flow (quantified as base flow index; BFI) predicts the structure and diversity of the different microbial functional groups that cycle N and C across nine UK rivers, spanning a geological BFI gradient from 0.23 (clay sediment) to 0.95 (chalk gravel sediment). Furthermore, the GC-content (percentage of guanine-cytosine bases in a DNA sequence) and codon-usage bias of ammonia monooxygenase DNA sequences, and the hydrophobicity and net-charge of the corresponding amino acid sequences, were all strongly correlated with BFI, likely reflecting physiological adaptations to different riverbed sediment structure along the BFI gradient. Our results offer an opportunity to overcome the "paradox of scales" that has seen microbial ecologists focus on small- rather than large-scale environmental variables, enabling us to scale-up our understanding of microbial biogeochemistry to the catchment and beyond.

Integrated hydrogeophysical modelling and data assimilation for geoelectrical leak detection.

Time-lapse electrical resistivity tomography (ERT) measurements provide indirectobservations of hydrological processes in the Earth's shallow subsurface at high spatial and temporal resolution. ERT has been used in the past decades to detect leaks and monitor the evolution of associated contaminant plumes. Specifically, inverted resistivity images allow visualization of the dynamic changes in the structure of the plume. However, existing methods do not allow the direct estimation of leak parameters (e.g. leak rate, location, etc.) and their uncertainties. We propose an ensemble-based data assimilation framework that evaluates proposed hydrological models against observed time-lapse ERT measurements without directly inverting for the resistivities. Each proposed hydrological model is run through the parallel coupled hydro-geophysical simulation code PFLOTRAN-E4D to obtain simulated ERT measurements. The ensemble of model proposals is then updated using an iterative ensemble smoother. We demonstrate the proposed framework on synthetic and field ERT data from controlled tracer injection experiments. Our results show that the approach allows joint identification of contaminant source location, initial release time, and solute loading from the cross-borehole time-lapse ERT data, alongside with an assessment of uncertainties in these estimates. We demonstrate a reduction in site-wide uncertainty by comparing the prior and posterior plume mass discharges at a selected image plane. This framework is particularly attractive to sites that have previously undergone extensive geological investigation (e.g., nuclear sites). It is well suited to complement ERT imaging and we discuss practical issues in its application to field problems.

Laboratory spectral induced polarisation signatures associated with iron and manganese oxide dissolution because of anaerobic degradation.

Degradation of organic chemicals in natural soils depends on oxidation-reduction conditions. To protect our groundwater resources we need to understand the degradation processes under anaerobic conditions. Available iron and manganese oxides are used as electron acceptors for anaerobic degradation and are reduced to the dissolved form of metallic cations in pore water. To monitor this process is a challenge, because anaerobic conditions are difficult to sample directly without introducing oxygen. A few studies have shown an impact of iron reduction on spectral induced polarisation (SIP) signature, often associated with bacterial growth. Our objective is to study the impact of iron and manganese oxide dissolution, caused by degradation of an organic compound, with spectral induced polarisation signatures. Twenty-six vertical columns (30 cm high, inner diameter 4.6 cm) were filled with a sand rich in oxides (manganese and iron) with a static water table in the middle. In half of the columns, a 2 cm high contaminated layer was installed just above the water table. As the contaminant degrades, the initial oxygen is consumed and anaerobic conditions form Every three days over a period of one month, spectral induced polarisation (twenty frequencies between 5mHz and 10 kHz) data were collected on six columns: three contaminated replicates and three control replicates. Chemical analysis was done on twenty columns assigned for destructive water sampling, ten contaminated columns and ten control. The results show an increase of the real conductivity associated with the degradation processes, independent of frequency. Compared with the pore water electrical conductivity in the saturated zone, the real conductivity measurement revealed the formation of surface conductivity before iron was released in the pore water. In parallel, we also observed an evolution of the imaginary conductivity in both saturated and unsaturated zones at frequencies below 1 Hz. Overall, the anaerobic reduction of iron and manganese oxide during the organic degradation increased both the conductive and polarisation component of the complex conductivity.

Monitoring redox sensitive conditions at the groundwater interface using electrical resistivity and self-potential.

Assessing redox conditions in soil and groundwater is challenging because redox reactions are oxygen sensitive, hence, destructive sampling methods may provide contact with air and influence the redox state. Furthermore, commonly used redox potential sensors provide only point measurements and are prone to error. This paper assesses whether combining electrical resistivity (ER) and self-potential (SP) measurements can allow the mapping of zones affected by anaerobic degradation. We use ER imaging because anaerobic degradation can release iron and manganese ions, which decreases pore water resistivity, and produces gas, which increases resistivity. Also, electrochemical differences between anaerobic and aerobic zones may create an electron flow, forming a self-potential anomaly. In this laboratory study, with four sand tanks with constant water table heights, time-lapse ER and SP mapped changes in electrical/electron flow properties due to organic contaminant (propylene glycol) degradation. Sampled pore water mapped degradation and water chemistry. When iron and manganese oxides were available, degradation reduced resistivity, because of cation release in pore water. When iron and manganese oxides were unavailable, resistivity increased, plausibly from methane production, which reduced water saturation. To bypass the reactions producing methane and release of metallic cations, a metal pipe was installed in the sand tanks between anaerobic and aerobic zones. The degradation creates an electron surplus at the anaerobic degradation site. The metal pipe allowed electron flow from the anaerobic degradation site to the oxygen-rich near surface. The electrical current sent through the metal pipe formed an SP anomaly observable on the surface of the sand tank. Time-lapse ER demonstrates potential for mapping degradation zones under anaerobic conditions. When an electrical conductor bridges the anaerobic zone with the near surface, the electron flow causes an SP anomaly on the surface. However, electrochemical differences between anaerobic and aerobic zones alone produced no SP signal. Despite their limitations, ER and SP are promising tools for monitoring redox sensitive conditions in unsaturated sandy soils but should not be used in isolation.

Mineral N stock and nitrate accumulation in the 50 to 200m profile on the Loess Plateau.

Nitrogen (N) stored in deep profiles is important in assessing regional and/or global N stocks and nitrate leaching risk to groundwater. The Chinese Loess Plateau, which is characterized by significantly thick loess deposits, potentially stores immense stocks of mineral N, posing future threats to groundwater quality. In order to determine the vertical distributions of nitrate and ammonium content in the region, as well as to characterize the potential accumulation of nitrate in the deep loess profile, we study loess samples collected at five sites (Yangling, Changwu, Fuxian, An'sai and Shenmu) through a 50 to 200m loess profile. The estimated storage of mineral N varied significantly among the five sites, ranging from 0.46 to 2.43×104kgNha-1. Ammonium exhibited fluctuations and dominated mineral N stocks within the whole profile at the sites, except for the upper 20-30m at Yangling and Changwu. Measured nitrate content in the entire profile at Fuxian, An'sai and Shenmu is low, but significant accumulations were observed to 30-50m depth at the other two sites. Analysis of δ15N and δ18O of nitrate indicates different causes for accumulated nitrate at these two sites. Mineralization and nitrification of manure and organic N respectively contribute nitrate to the 0-12 and 12-30m profile at Changwu; while nitrification of NH4+ fertilizer, NO3- fertilizer and nitrification of organic N control the nitrate distribution in the 0-3, 3-7 and 7-10m layer at Yangling, respectively. Furthermore, our analysis illustrates the low denitrification potential in the lower part of the vadose zone. The accumulated nitrate introduced by human activities is thus mainly distributed in the upper vadose zone (above 30m), indicating, currently, a low nitrate leaching risk to groundwater due to a high storage capacity of the thick vadose zone in the region.

Stoichiometric constraints on the microbial processing of carbon with soil depth along a riparian hillslope.

Soil organic matter (SOM) content is a key indicator of riparian soil functioning and in the provision of ecosystem services such as water retention, flood alleviation, pollutant attenuation and carbon (C) sequestration for climate change mitigation. Here, we studied the importance of microbial biomass and nutrient availability in regulating SOM turnover rates. C stabilisation in soil is expected to vary both vertically, down the soil profile and laterally across the riparian zone. In this study, we evaluated the influence of five factors on C mineralisation (Cmin): (i) substrate quantity, (ii) substrate quality, (iii) nutrient (C, N and P) stoichiometry, (iv) soil microbial activity with proximity to the river (2 to 75 m) and (v) as a function of soil depth (0-3 m). Substrate quality, quantity and nutrient stoichiometry were evaluated using high and low molecular weight 14C-labelled dissolved organic (DOC) along with different nutrient additions. Differences in soil microbial activity with proximity to the river and soil depth were assessed by comparing initial (immediate) Cmin rates and cumulative C mineralised at the end of the incubation period. Overall, microbial biomass C (MBC), organic matter (OM) and soil moisture content (MC) proved to be the major factors controlling rates of Cmin at depth. Differences in the immediate and medium-term response (42 days) of Cmin suggested that microbial growth increased and carbon use efficiency (CUE) decreased down the soil profile. Inorganic N and/or P availability had little or no effect on Cmin suggesting that microbial community growth and activity is predominantly C limited. Similarly, proximity to the watercourse also had relatively little effect on Cmin. This work challenges current theories suggesting that areas adjacent to watercourse process C differently from upslope areas. In contrast, our results suggest that substrate quality and microbial biomass are more important in regulating C processing rates rather than proximity to a river.

Scenario Evaluator for Electrical Resistivity Survey Pre-modeling Tool.

Geophysical tools have much to offer users in environmental, water resource, and geotechnical fields; however, techniques such as electrical resistivity imaging (ERI) are often oversold and/or overinterpreted due to a lack of understanding of the limitations of the techniques, such as the appropriate depth intervals or resolution of the methods. The relationship between ERI data and resistivity is nonlinear; therefore, these limitations depend on site conditions and survey design and are best assessed through forward and inverse modeling exercises prior to field investigations. In this approach, proposed field surveys are first numerically simulated given the expected electrical properties of the site, and the resulting hypothetical data are then analyzed using inverse models. Performing ERI forward/inverse modeling, however, requires substantial expertise and can take many hours to implement. We present a new spreadsheet-based tool, the Scenario Evaluator for Electrical Resistivity (SEER), which features a graphical user interface that allows users to manipulate a resistivity model and instantly view how that model would likely be interpreted by an ERI survey. The SEER tool is intended for use by those who wish to determine the value of including ERI to achieve project goals, and is designed to have broad utility in industry, teaching, and research.

Geoelectrical monitoring of simulated subsurface leakage to support high-hazard nuclear decommissioning at the Sellafield Site, UK.

A full-scale field experiment applying 4D (3D time-lapse) cross-borehole Electrical Resistivity Tomography (ERT) to the monitoring of simulated subsurface leakage was undertaken at a legacy nuclear waste silo at the Sellafield Site, UK. The experiment constituted the first application of geoelectrical monitoring in support of decommissioning work at a UK nuclear licensed site. Images of resistivity changes occurring since a baseline date prior to the simulated leaks revealed likely preferential pathways of silo liquor simulant flow in the vadose zone and upper groundwater system. Geophysical evidence was found to be compatible with historic contamination detected in permeable facies in sediment cores retrieved from the ERT boreholes. Results indicate that laterally discontinuous till units forming localized hydraulic barriers substantially affect flow patterns and contaminant transport in the shallow subsurface at Sellafield. We conclude that only geophysical imaging of the kind presented here has the potential to provide the detailed spatial and temporal information at the (sub-)meter scale needed to reduce the uncertainty in models of subsurface processes at nuclear sites.

Vadose zone flow model uncertainty as conditioned on geophysical data.

An approach to estimating the uncertainty in model descriptions based on a landscape space to model space mapping concept is described. The approach is illustrated by an application making use of plot scale geophysical estimates of changes in water content profiles to condition a model of recharge to the Sherwood Sandstone Aquifer in the United Kingdom. It is demonstrated that the mapping is highly uncertain and that many different parameter sets give acceptable simulations of the observations. Multiple profile measurements over time offer only limited additional constraints on the mapping. The resulting mapping weights may be used to evaluate uncertainty in the predictions of vadose zone flow dynamics for the site.

Noninvasive characterization of the Trecate (Italy) crude-oil contaminated site: links between contamination and geophysical signals.

The characterization of contaminated sites can benefit from the supplementation of direct investigations with a set of less invasive and more extensive measurements. A combination of geophysical methods and direct push techniques for contaminated land characterization has been proposed within the EU FP7 project ModelPROBE and the affiliated project SoilCAM. In this paper, we present results of the investigations conducted at the Trecate field site (NW Italy), which was affected in 1994 by crude oil contamination. The less invasive investigations include ground-penetrating radar (GPR), electrical resistivity tomography (ERT), and electromagnetic induction (EMI) surveys, together with direct push sampling and soil electrical conductivity (EC) logs. Many of the geophysical measurements were conducted in time-lapse mode in order to separate static and dynamic signals, the latter being linked to strong seasonal changes in water table elevations. The main challenge was to extract significant geophysical signals linked to contamination from the mix of geological and hydrological signals present at the site. The most significant aspects of this characterization are: (a) the geometrical link between the distribution of contamination and the site's heterogeneity, with particular regard to the presence of less permeable layers, as evidenced by the extensive surface geophysical measurements; and (b) the link between contamination and specific geophysical signals, particularly evident from cross-hole measurements. The extensive work conducted at the Trecate site shows how a combination of direct (e.g., chemical) and indirect (e.g., geophysical) investigations can lead to a comprehensive and solid understanding of a contaminated site's mechanisms.

Laboratory SIP signatures associated with oxidation of disseminated metal sulfides.

Oxidation of metal sulfide minerals is responsible for the generation of acidic waters rich in sulfate and metals. When associated with the oxidation of sulfide ore mine waste deposits the resulting pore water is called acid mine drainage (AMD); AMD is a known environmental problem that affects surface and ground waters. Characterization of oxidation processes in-situ is challenging, particularly at the field scale. Geophysical techniques, spectral induced polarization (SIP) in particular, may provide a means of such investigation. We performed laboratory experiments to assess the sensitivity of the SIP method to the oxidation mechanisms of common sulfide minerals found in mine waste deposits, i.e., pyrite and pyrrhotite, when the primary oxidant agent is dissolved oxygen. We found that SIP parameters, e.g., phase shift, the imaginary component of electrical conductivity and total chargeability, decrease as the time of exposure to oxidation and oxidation degree increase. This observation suggests that dissolution-depletion of the mineral surface reduces the capacitive properties and polarizability of the sulfide minerals. However, small increases in the phase shift and imaginary conductivity do occur during oxidation. These transient increases appear to correlate with increases of soluble oxidizing products, e.g., Fe(2+) and Fe(3+) in solution; precipitation of secondary minerals and the formation of a passivating layer to oxidation coating the mineral surface may also contribute to these increases. In contrast, the real component of electrical conductivity associated with electrolytic, electronic and interfacial conductance is sensitive to changes in the pore fluid chemistry as a result of the soluble oxidation products released (Fe(2+) and Fe(3+)), particularly for the case of pyrrhotite minerals.

A novel grass hybrid to reduce flood generation in temperate regions.

We report on the evaluation of a novel grass hybrid that provides efficient forage production and could help mitigate flooding. Perennial ryegrass (Lolium perenne) is the grass species of choice for most farmers, but lacks resilience against extremes of climate. We hybridised L. perenne onto a closely related and more stress-resistant grass species, meadow fescue Festuca pratensis. We demonstrate that the L. perenne × F. pratensis cultivar can reduce runoff during the events by 51% compared to a leading UK nationally recommended L. perenne cultivar and by 43% compared to F. pratensis over a two year field experiment. We present evidence that the reduced runoff from this Festulolium cultivar was due to intense initial root growth followed by rapid senescence, especially at depth. Hybrid grasses of this type show potential for reducing the likelihood of flooding, whilst providing food production under conditions of changing climate.