Use of an Artificial Sweetener to Identify Sources of Groundwater Nitrate Contamination

The artificial sweetener acesulfame (ACE) is a potentially useful tracer of waste water contamination in groundwater. In this study, ACE concentrations were measured in waste water and impacted groundwater at 12 septic system sites in Ontario, Canada. All samples of septic tank effluent (n = 37) had ACE >6 µg/L, all samples of groundwater from the proximal plume zones (n = 93) had ACE >1 µg/L and, almost all samples from the distal plume zones had ACE >2 µg/L. Mean mass ratios of total inorganic nitrogen/ACE at the 12 sites ranged from 680 to 3500 for the tank and proximal plume samples. At five sites, decreasing ratio values in the distal zones indicated nitrogen attenuation. These ratios were applied to three aquifers in Canada that are nitrate‐stressed and an urban stream where septic systems are present nearby to estimate the amount of waste water nitrate contamination. At the three aquifer locations that are agricultural, low ACE values (<0.02‐0.15 µg/L) indicated that waste water contributed <15% of the nitrate in most samples. In groundwater discharging to the urban stream, much higher ACE values (0.2‐11 µg/L) indicated that waste water was the likely source of >50% of the nitrate in most samples. This study confirms that ACE is a powerful tracer and demonstrates its use as a diagnostic tool for establishing whether waste water is a significant contributor to groundwater contamination or not.     

Modelling the spatial distribution of plaice (Pleuronectes platessa), sole (Solea solea) and thornback ray (Raja clavata) in UK waters for marine management and planning

Species distribution maps are needed for ecosystem-based marine management including the development of marine spatial plans. If such maps are based on predictive models then modelling procedures should aim to maximise validation success, and any uncertainty in the predictions needs to be made explicit. We developed a predictive modelling approach to produce robust maps of the distributions of selected marine species at a regional scale. We used 14 years of survey data to map the distributions of plaice, sole and thornback ray in three hydrographic regions comprising parts of the Irish Sea, Celtic Sea and the English Channel with the help of the hybrid technique regression kriging, which combines regression models with geostatistical tools. For each species–region combination we constructed logistic Generalized Linear Models (GLMs) based on presence–absence data using the environmental variables: depth, bottom temperature, bed shear stress and sediment type, as predictors. We selected GLMs using the mean squared error of prediction (MSEP) estimated by cross-validation then conducted a geostatistical analysis of the residuals to incorporate spatial structure in the predictions. In general, we found that species occurrence was positively related to shallow areas, a bed shear stress of between 0 and 1.5 N/m², and the presence of sandy sediment. Predicted species occurrence probabilities were in good agreement with survey observations. This modelling framework selects environmental models based on predictive ability and considers the effect of spatial autocorrelation on predictions, together with the simultaneous presentation of observations, associated uncertainties, and predictions. The potential benefit of these distribution maps to marine management and planning is discussed.     

Potentially mobile pools of phosphorus and silicon in sediment from the Bay of Brest: Interactions and implications for phosphorus dynamics

Competitive interactions between silicate and phosphate at ligand exchange sites in the sediment surface layer may increase the release of phosphorus (P) from the sediment into the water column. In this study, the role of silicon (Si) in the release of P from the sediment surface layer was studied in a marine estuarine environment, the Bay of Brest, with the aid of a sequential sediment fractionation procedure developed for P, and the addition of inorganic or diatom-bound Si to surface sediment samples in vitro. The potentially mobile pools of P in the surface sediment (loosely bound P + Fe/Al-bound-P) amounted to 5.0 μmol g⁻¹ dry sed., 42% of the total extractable and 33% of the total amount of P in the sediment, while the similarly extracted pools of Si were bigger (ca. 20 μmol g⁻¹ dry sed., 50% of the total extractable Si). Additions of inorganic Si increased the concentration of dissolved P in the sediment interstitial water in a bottle experiment, and the addition of both inorganic Si and cultivated diatoms to intact sediment cores increased the outward flux of dissolved P. Model calculations based on the regression equation from the bottle experiment and Si and P water column data showed that the sedimentation of spring diatoms could cause Si pulses to the sediment which would produce a P flux to the water column of ca. 44 μmol m⁻² d⁻¹. Field data from the bay show that in spring, decreases in P and Si and an increase in chl a due to diatom production are often followed by a small separate P peak which may be caused by Si-induced P fluxes from the sediment surface.     

Flux between soil and atmosphere, vertical concentration profiles in soil, and turnover of nitric oxide: 1. Measurements on a model soil core

A stainless steel soil corer which was filled with homogenized soil was used to measure the flux (J) of NO between soil and atmosphere and the vertical profile of the NO mixing ratios (m) in the soil atmosphere, both as function of the NO mixing ratio (mm _a ) in the atmosphere of the headspace. The NO emission flux decreased linearly with increasing NO mixing ratio and turned into a deposition flux after passage of the compensation point (m _c) at about 400 ppbv NO. Almost the same compensation point was obtained when the turnover of NO was measured in flask-incubated soil samples as function of the NO mixing ratio. The flux (J) of NO at the soil-atmosphere interface was calculated from the production rate (P) of NO and the NO uptake rate constant (k) that were measured in these flask-incubated soil samples using the diffusion model of Galbally and Johansson (1989). The calculated fluxes agreed within <15% with those actually measured. The vertical profiles of NO were fitted to an exponential function and analyzed by Fick's first law of diffusion. The shape of the profiles indicated a net production of NO in the upper 10 cm soil layer when the atmospheric NO mixing ratio was below the compensation point and in a net consumption of NO when the atmospheric NO mixing ratio was above the compensation point. In soil layers below 10 cm depth, the turnover of NO resulted in compensation of production and consumption rates. Measurement of the actual diffusion coefficient using SF₆ showed that gas transport in the soil core was not only due to molecular diffusion but in addition due to a bidirectional gas flow. The experimentally determined diffusion coefficient was smaller than that computed from soil porosities, but resulted together with the additional transport term in NO fluxes that were close (< ±15%) to those measured. This is the first comprehensive study of NO concentration profiles and turnover rates in soil providing a theoretical basis for modelling NO fluxes at the soil-atmosphere interface.     

The Stable Carbon Isotope Ratio of Biogenic Emissions of Isoprene and the Potential Use of Stable Isotope Ratio Measurements to Study Photochemical Processing of Isoprene in the Atmosphere

A technique was developed that allows the determination of the stable carbon isotope ratio of isoprene in air. The method was used for a limited number of ambient measurements as well as laboratory studies of isoprene emitted from Velvet Bean (Mucana pruriens L. var. utilis), including the light and temperature dependence. The mean stable carbon isotope ratio ( ¹³C) of isoprene emitted from Velvet Bean (Mucana pruriens L. var. utilis) for all our measurements is –27.7 ± 2.0 (standard deviation for 23 data points). Our results indicate a small dependence of the stable carbon isotope ratios on leaf temperature and photosynthetic photon flux density (PPFD). The light dependence is 0.0026 ± 0.0012/( mol of photons m^–2 s^–1) for the studied range from 400 to 1700 mol of photons m^–2 s^–1. The temperature dependence is 0.16 ± 0.09/K. On average, the emitted isoprene is 2.6 ± 0.9 lighter than the leaf carbon. An uncertainty analysis of the possibility to use stable carbon isotope ratio measurements of isoprene for estimates of its mean photochemical age suggests that meaningful results can be obtained. This is supported by the results of a small number of measurements of the stable carbon isotope composition of ambient isoprene at different locations. The results range from approximately –29 to –16. They are consistent with vegetation emissions of isoprene that is slightly depleted in ¹³C relative to the plant material and enrichment of ¹³C in the atmosphere due to isotope fractionation associated with the reaction with OH-radicals. The stable carbon isotope ratio of ambient isoprene at locations directly influenced by isoprene emissions is very close to the values we found in our emission studies, whereas at sites located remote from isoprene emitting vegetation we find substantial enrichment of ¹³C. This suggests that stable carbon isotope ratio measurements will be a valuable, quantitative method to determine the extent of photochemical processing of isoprene in ambient air.     

Sensitivity analysis of hydraulic conductivity and Manning's n parameters lead to new method to scale effective hydraulic conductivity across model resolutions

Hydrological modelling is an important tool for research, policy, and management, but uncertainty remains about parameters transferability from field observations made at small scale to models at the catchment scale and larger. This uncertainty compels the need to develop parameter relationships that are translatable across scale. In this study, we compare the changes to modelled processes as resolution is coarsened from 100‐m to 1‐km in a topographically complex, 255‐km² Colorado River headwater catchment. We conducted a sensitivity analysis for hydraulic conductivity (K) and Manning's n parameters across four orders of magnitude. Results showed that K acts as a moderator between surface and subsurface contributions to streamflow, whereas n moderates the duration of high intensity, infiltration‐excess flow. The parametric sensitivity analysis informed development of a new method to scale effective hydraulic conductivity across modelling resolutions in order to compensate for the loss of topographic gradients as resolution is coarsened. A similar mathematical relationship between n and lateral resolution changes was not found, possibly because n is also sensitive to time discretization. This research provides an approach to translate hydraulic conductivity parameters from a calibrated coarse model to higher resolutions where the number of simulations are limited by computational demand.     

Fracture penetration in planetary ice shells

The proposed past eruption of liquid water on Europa and ongoing eruption of water vapor and ice on Enceladus have led to discussion about the feasibility of cracking a planetary ice shell. We use a boundary element method to model crack penetration in an ice shell subjected to tension and hydrostatic compression. We consider the presence of a region at the base of the ice shell in which the far-field extensional stresses vanish due to viscoelastic relaxation, impeding the penetration of fractures towards a subsurface ocean. The maximum extent of fracture penetration can be limited by hydrostatic pressure or by the presence of the unstressed basal layer, depending on its thickness. Our results indicate that Europa's ice shell is likely to be cracked under 1-3 MPa tension only if it is ?2.5 km thick. Enceladus' ice shell may be completely cracked if it is capable of supporting ∼1-3 MPa tension and is less than 25 km thick.     

Patuxent landscape model: 1. Hydrological model development

We developed a spatially explicit, process-based model of the 2352 km² Patuxent river watershed in Maryland, and its subwatersheds to integrate data and knowledge over several spatial, temporal and complexity scales, and to serve as an aid to regional management. The model was developed using the Library of Hydro-Ecological Modules (LHEM, http://giee.uvm.edu/LHEM), which was designed to create flexible landscape model structures that can be easily modified and extended to suit the requirements of a variety of goals and case studies. The LHEM includes modules that simulate various aspects of ecosystem dynamics. In this paper we consider modules that represent the physical conditions in the environment (climatic factors, geoporphology), and hydrologic processes, both locally and spatially. Where possible the modules are formulated as Stella(R) models, spatial transport processes are presented as C++ code.