Testing of a GIS model ofEucalyptus Iargiflorens health on a semiarid,saline floodplain

Irrigated agriculture has resulted in substantial changes in water flows to the lower reaches of the River Murray. These changes have led to large-scale occurrences of dieback inEucalyptus largiflorens (black box) woodlands as well as increased inputs of salt to the river. Management options to address problems of this scale call for the use of spatial data sets via geographic information systems (GIS). A GIS exists for one floodplain of the River Murray at Chowilla, and a simple model predicted six health classes ofEucalyptus largiflorens based on groundwater salinity, flooding frequency, and groundwater depth.To determine the usefulness of the model for vegetation management, the quality of both the model and the GIS data sets were tested. Success of the testing procedure was judged by the degree of spatial matching between the model's predictions of health and that assessed from aerial photographs and by field truthing. Analyses at 80 sites showed that tree health was significantly greater where groundwater salinity was less than 40 dS/m or flooding occurred more frequently than 1 in 10 years or depth to groundwater exceeded 4 m. Testing of the GIS data sets found that vegetation was misclassified at 15% of sites. Association was shown between GIS-predicted values and field-truthed values of groundwater salinity but not groundwater depth. The GIS model of health is a useful starting point for future vegetation management and can be further improved by increasing the quality of the data coverages and further refining of the model to optimize parameters and thresholds.     

The “Short Cut” Approach for the Reality of Enhanced Groundwater Contamination

Based on the reality of (a) soil heterogeneity in the vadose zone, (b) enhanced desorption from soil and solubility in water of water insoluble contaminants in the presence of surfactants, and (c) wetting/drying cycles of groundwater recharge (a major cause of fractures formation), a coherent “short-cut” conceptual approach is advanced to account for enhanced groundwater contamination. This is an attempt to close the gap between theory, lab simulations and conventional modelling-based predictions, and observed higher concentrations and more rapid arrival times of contaminants reaching groundwater. Recent data concerning chloride ion and non-ionic surfactants concentrations in aquifers and groundwater wells, combined with previous results concerning the concentrations of tritium, chlorides, metals, organic hydrocarbons and surfactants in the unsaturated and saturated zones of Israel's aquifers, are accounted for in terms of the “short-cut” approach. The contradiction between predictions of groundwater contamination made with conventional, deterministic, homogeneous models and the actual observed behavior of contaminants in soils and aquifers is thus explaind. The “short cut” approach should not be perceived as a better type of model to guide modelling. Rather, it is a proposal for a conceptual change from the realistically invalid, but commonly accepted, conventional “buffer-protective soil/long-term groundwater contamination” to the “short cut” conceptual model to explain the enhanced groundwater contamination actually observed. Although the validity of the proposed approach is strongly supported by the data here presented for the case of Israel (serving as an illustrative case study), selected results and conclusions drawn from studies conducted worldwide suggest its general applicability and usefulness. A major conclusion evolved from the “short-cut” conceptual model is that contemporary groundwater management policies, based on the current perception of groundwater contamination processes and their modelling, may result in an irreversible detrimental effect on the environmental situation in the long run. In any case, prevention, rather than correction/remediation, is strongly recommended as the strategy of choice for rational long-term management of groundwater resources.     

Estimating Current and Future Groundwater Resources of the Maldives

The water resources of the atolls of the Republic of Maldives are under continual threat from climatic and anthropogenic stresses, including land surface pollution, increasing population, drought, and sea‐level rise (SLR). These threats are particularly acute for groundwater resources due to the small land surface area and low elevation of each island. In this study, the groundwater resources, in terms of freshwater lens thickness, total volume of fresh groundwater, and safe yield are estimated for the 52 most populous islands of the Maldives for current conditions and for the year 2030, with the latter accounting for projected SLR and associated shoreline recession. An algebraic model, designed in previous studies to estimate the lens thickness of atoll islands, is expanded in this study to also estimate volume of groundwater. Results indicate that average current lens thickness, groundwater volume, and per capita safe yield are approximately 4.6 m, 1,300 million liters, and 300 l/day, and that these values will decrease by approximately 10, 11, and 34%, respectively, by the year 2030. Based on results, it is demonstrated that groundwater, in terms of quantity, is a viable source of water for the islands of the Maldives both now and in coming decades, particularly for islands with large surface area and low population. Study results can provide water resource managers and government officials with valuable data for consideration in water security measures.     

Impact of the December 2004 tsunami on soil, groundwater and vegetation in the Nagapattinam district, India

The tsunami of 26 December 2004 struck the Nagapattinam District, Tamil Nadu, India. Sea water inundation from the tsunami caused salinization problems for soil and groundwater in coastal areas of the district, and also induced salt injuries in crops. To document the recovery of the agricultural environment from the tsunami, we conducted observations of the soil, groundwater, and vegetation. Soil electrical conductivity increased sharply after the tsunami, but returned to pre-tsunami levels the following year. Groundwater salinity returned to pre-tsunami levels by 2006. These rapid rates of recovery were due to the monsoon rainfall leaching salt from the highly permeable soils in the area. MODIS NDVI values measured before and after the tsunami showed that vegetation damaged by the tsunami recovered to its pre-tsunami state by the next rice cropping season, called samba, which starts from August to February. From these results, we conclude that the agricultural environment of the district has now fully recovered from the tsunami. Based on the results, we have also identified important management implications for soil, groundwater, and vegetation as follows: 1) due to the heavy monsoon rainfall and the high permeability of soils in this region, anthropogenic inputs like fertilizers should be applied carefully to minimize pollution, and the use of green manure is recommended; 2) areas that were contaminated by sea water extended up to 1000 m from the sea shore and over pumping of groundwater should be carefully avoided to prevent inducing sea water intrusion; and 3) data from a moderate resolution sensor of 250 m, such as MODIS, can be applied to impact assessment in widespread paddy field areas like the Nagapattinam District.     

Streamside Forest Buffer Width Needed to Protect Stream Water Quality,Habitat, and Organisms: A Literature Review

This literature review addresses how wide a streamside forest buffer needs to be to protect water quality, habitat, and biota for small streams (≤~100 km² or ~5th order watershed) with a focus on eight functions: (1) subsurface nitrate removal varied inversely with subsurface water flux and for sites with water flux >50 l/m/day (~40% avg base flow to Chesapeake Bay) median removal efficiency was 55% (26‐64%) for buffers <40 m wide and 89% (27‐99%) for buffers >40 m wide; (2) sediment trapping was ~65 and ~85% for a 10‐ and 30‐m buffer, respectively, based on streamside field or experimentally loaded sites; (3) stream channel width was significantly wider when bordered by ~25‐m buffer (relative to no forest) with no additional widening for buffers ≥25 m; (4) channel meandering and bank erosion were lower in forest but more studies are needed to determine the effect of buffer width; (5) temperature remained within 2°C of levels in a fully forested watershed with a buffer ≥20 m but full protection against thermal change requires buffers ≥30 m; (6) large woody debris (LWD) has been poorly studied but we infer a buffer width equal to the height of mature streamside trees (~30 m) can provide natural input levels; (7, 8) macroinvertebrate and fish communities, and their instream habitat, remain near a natural or semi‐natural state when buffered by ≥30 m of forest. Overall, buffers ≥30 m wide are needed to protect the physical, chemical, and biological integrity of small streams.     

Factors affecting nitrate distribution in shallow groundwater under a beef farm in South Eastern Ireland

Groundwater contamination was characterised using a methodology which combines shallow groundwater geochemistry data from 17 piezometers over a 2 yr period in a statistical framework and hydrogeological techniques. Nitrate–N (NO₃-N) contaminant mass flux was calculated across three control planes (rows of piezometers) in six isolated plots. Results showed natural attenuation occurs on site although the method does not directly differentiate between dilution and denitrification. It was further investigated whether NO₃-N concentration in shallow groundwater (<5 m below ground level) generated from an agricultural point source on a 4.2 ha site on a beef farm in SE Ireland could be predicted from saturated hydraulic conductivity (K_sat) measurements, ground elevation (m Above Ordnance Datum), elevation of groundwater sampling (screen opening interval) (m AOD) and distance from a dirty water point pollution source. Tobit regression, using a background concentration threshold of 2.6 mg NO₃-N L⁻¹ showed, when assessed individually in a step wise procedure, K_sat was significantly related to groundwater NO₃-N concentration. Distance of the point dirty water pollution source becomes significant when included with K_sat in the model. The model relationships show areas with higher K_sat values have less time for denitrification to occur, whereas lower K_sat values allow denitrification to occur. Areas with higher permeability transport greater NO₃-N fluxes to ground and surface waters. When the distribution of Cl⁻ was examined by the model, K_sat and ground elevation had the most explanatory power but K_sat was not significant pointing to dilution having an effect. Areas with low NO₃ concentration and unaffected Cl⁻ concentration points to denitrification, low NO₃ concentration and low Cl⁻ chloride concentration points to dilution and combining these findings allows areas of denitrification and dilution to be inferred. The effect of denitrification is further supported as mean groundwater NO₃-N was significantly (P < 0.05) related to groundwater N₂/Ar ratio, redox potential (Eh), dissolved O₂ and N₂ and was close to being significant with N₂O (P = 0.08). Calculating contaminant mass flux across more than one control plane is a useful tool to monitor natural attenuation. This tool allows the identification of hot spot areas where intervention other than natural attenuation may be needed to protect receptors.     

SWATMOD‐Prep: Graphical User Interface for Preparing Coupled SWAT‐MODFLOW Simulations

This article presents SWATMOD‐Prep, a graphical user interface that couples a SWAT watershed model with a MODFLOW groundwater flow model. The interface is based on a recently published SWAT‐MODFLOW code that couples the models via mapping schemes. The spatial layout of SWATMOD‐Prep guides the user through the process of importing shape files (sub‐basins, hydrologic response units [HRUs], river network) from an existing SWAT model, creating a grid, performing necessary geo‐processing operations to link the models, writing out SWAT‐MODFLOW files, and running the simulation. The option of creating a new single‐layer MODFLOW model for near‐surface alluvial aquifers is available, with the user prompted to provide groundwater surface elevation (through a digital elevation model), aquifer thickness, and necessary aquifer parameter values. The option of simulating nitrate transport in the aquifer also is available, using the reactive transport model RT3D. The interface is in the public domain. It is programmed in Python, with various software packages used for geo‐processing operations (e.g., selection, intersection of rasters) and inputting/outputting data, and is written for Windows. The use of SWATMOD‐Prep is demonstrated for the Little River Experimental Watershed, Georgia. SWATMOD‐Prep and SWAT‐MODFLOW executables are available with an accompanying user's manual at: http://swat.tamu.edu/software/swat-modflow/ . The user's manual also accompanies this article as Supporting Information.     

A GIS-BASED MODELING APPROACH FOR EVALUATING GROUNDWATER VULNERABILITY TO PESTICIDES1

ABSTRACT: The Attenuation Factor (AF), a screening model, was used to evaluate the relative degree of vulnerability of groundwater to pesticide contamination in Louisa County, Virginia. For evaluating the contamination potential of pesticides, three scenarios of pesticide leaching represented by high, moderate, and low cases of degradation and sorption in the soil were considered. Data layers were overlaid within a Geographic Information System (GIS) for spatial computation of AF for the actual and 2m groundwater depths. This spatial database was divided into five contamination potential categories namely high, medium, low, very low, and unlikely, based on the numerical values of the AF for each cell (119 ha). The results for the three most mobile pesticides are presented in this paper. The performance of the AF model was evaluated by comparing its predicted results with the field data from an experimental watershed. The AF model was able to identify most of the frequently detected pesticides in the watershed. A sensitivity analysis was also performed. The results of this study provide information about the potential groundwater threat by pesticides to the citizens ahd decision-makers in the County and can be used for formulating an appropriate land use management plan to protect the groundwater quality.     

The impact of storm events on a riverbed system and its hydraulic conductivity at a site of induced infiltration

The spatial and temporal variability of riverbed vertical hydraulic conductivity (K(v)) was investigated at a site of induced infiltration, associated with a municipal well field, to assess the impact of high-stage events on scour and subsequently the riverbed K(v). Such impacts are important when considering the potential loss of riverbank filtration capacity due to storm events. The study site, in and along the Great Miami River in southwest Ohio, overlaid a highly productive glacial-outwash aquifer. A three-layer model for this system was conceptualized: a top layer of transient sediment, a second layer comprising large sediment resistant to scour, but clogged with finer sediment (the armor/colmation layer), and a third layer that was transitional to the underlying higher-K(v) aquifer. One location was studied in detail to confirm and quantify the conceptual model. Methods included seepage meters, heat-flow modeling, grain-size analyses, laboratory permeameter tests, slug tests and the use of scour chains and pressure-load cells to directly measure the amount of sediment scour and re-deposition. Seepage meter measured riverbed K(v) ranged from 0.017 to 1.7 m/d with a geometric mean of 0.19 m/d. Heat-transport model-calibrated estimates were even lower, ranging from 0.0061 to 0.046 m/d with a mean of 0.017 m/d. The relatively low K(v) was indicative of the clogged armor layer. In contrast, slug tests in the underlying riverbed sediment yielded K(v) values an order of magnitude greater. There was a linear relationship between scour chain measured scour and event intensity with a maximum scour of only 0.098 m. Load-cell pressure sensor data over a 7-month period indicated a total sediment-height fluctuation of 0.42 m and a maximum storm-event scour of 0.28 m. Scour data indicated that the assumed armor/colmation layer almost always remained intact. Based on measured layer conductivities and thicknesses, the overall K(v) of this conceptualized system was 1.6 m/d. Sensitivity analyses indicated that even complete scour of the armor/colmation layer would likely increase the overall K(v) only by a factor of 1.5. Most scour events observed removed only the transient sediment, having very little effect on the entire system indicating low risk of losing filtration capacity during storms. The research, however, focused on the point bar, depositional side of the river. More research of the entire river profile is necessary.     

Patterns in groundwater quality: Selected observations in Iowa

Groundwater quality in Iowa varies with depth, location, ownership of well, time of sampling, and geologic features. Samples from deep wells (>30.48 m or 100 ft) are highly mineralized with sulfates and carbonates (calcium and magnesium), whereas the mineral content in samples from shallow wells (<30.48 m or 100 ft) is relatively much lower. Nitrate as a percent of dissolved solids is negligible in samples from deep wells and reaches as high as 3 to 5% in samples from shallow wells. Shallow wells, in particular non-public wells, are highly susceptible to nitrate contamination (with an average concentration of 27.8 mg/l) compared with any other category of wells studied. In shallow non-public wells, the concentration of nitrate from recent geologic deposits (31.61 mg/l) is more than twice the level found in corresponding public wells from similar deposits (13.35 mg/l). Shallow non-public wells are also subject to sharp seasonal fluctuations, with a peak nitrate concentration of 55.81 mg/l in the month of May, possibly because of spring runoff from agricultural and other surface sources. These observations are further supported by the results of nitrate analyses from a large number (over 44,000) of private wells in Iowa. Eighteen percent of these private wells were found to exceed the maximum contaminant level of 45 mg/l nitrate (NO₃ ^?). A higher proportion of the shallow wells (<30.48 m or 100 ft) exceed the maximum contaminant level of 45 mg/l (3867 out of 13,625 or 28.4%). It is proposed that the observed variability in groundwater quality be used as a first step in developing a strategy for strengthening state-wide groundwater quality monitoring programs. Strong state-wide programs would be of considerable assistance to policy makers in the resolution of major groundwater quality issues.     

Biosolids and distillery effluent amendment to Irish Miscanthus ×giganteus plantations: impacts on groundwater and soil

It is necessary to determine the risk of water pollution arising from amendment of organic by-products (OBs) to energy crops under Irish conditions. Therefore, the impact of landspreading two OBs on the quality of groundwater underlying plantations of Miscanthus X giganteus was assessed. Municipal biosolids and distillery effluent (DE) were spread annually (for 4 yr) on six 0.117-ha treatment plots at rates of 100, 50, and 0%. The 100% rate represented a maximum P load of 15 t ha(-1) as per Irish EPA regulation. Groundwater was sampled for 25 mo and tested for pH, electrical conductivity, NO(3)(-), orthophosphate (PO(4)(3-)), total soluble P, K(+), Cu, Cd, Cr, Pb, Ni, and Zn. Assessment of quality was based on comparison with Irish groundwater threshold values (GTVs). The study was limited to within-plot using a "well bottom" approach and did not investigate movement of groundwater plumes or vectors of percolation through the soil profile. Mean groundwater concentrations did not exceed GTVs during the sampling period for any species, with the exception of groundwater PO(4)(3-) in the 100% DE plot, which was almost double the GTV of 0.035 mg L(-1). There was no significant build-up of nutrients or heavy metals in groundwater (or soil) for any plot. Excessive PO(4)(3-) in the 100% DE plot groundwater is likely due to high background soil P, soil characteristics, and the occurrence of macropore/soil pore flow. These factors (particularly background soil P) should be assessed when determining suitable sites for land-spreading OBs.     

Effect of tomato packinghouse wastewater properties on phosphorus and cation leaching in a spodosol

Land application of wastewater is a common practice. However, coarse-textured soils and shallow groundwater in Florida present favorable conditions for leaching of wastewater-applied constituents. Our objective in this study was to determine phosphorus (P) and associated cations (Ca, Mg, K, Na) leaching in a Spodosol irrigated with tomato packinghouse wastewater. We packed 12 polyvinyl chloride soil columns (30 cm internal diameter × 50 cm length) with two soil horizons (Ap and A/E) and conducted 30 sequential leaching events by irrigating with wastewater at low (0.84 cm d), medium (1.68 cm d), and high (2.51 cm d) rates. The control treatment received deionized water at 1.68 cm d Leachate pH was lower (6.4-6.5) and electrical conductivity (EC) was higher in the wastewater-treated columns (0.85-1.78 dS m) than in the control treatment (pH 6.9; EC, 0.12 dS m) due to the low pH (6.2) and high EC (2.16 dS m) of applied wastewater. Mean leachate P concentrations were greatest in the control treatment (0.70 mg L), followed by the high (0.60 mg L) and low and medium wastewater-treated columns (0.28-0.33 mg L). Leachate concentrations of Na, Ca, Mg, and K were significantly ( < 0.05) greater in wastewater-treated columns than in the control. Concentrations of P, Na, and K in leachate remained lower than the concentrations in the applied wastewater, indicating their retention in the soil profile. In contrast, leachate Ca and Mg concentrations were greater than in applied wastewater during several leaching events, suggesting that additional Ca and Mg were leached from the soil. Our results suggest that tomato packinghouse wastewater can be beneficially land-applied at 1.68 cm d in Florida's Spodosols without significant P and cation leaching.     

Impact of Sea Level Rise on Groundwater Salinity in a Coastal Community of South Florida1

Guha, Hillol and Sorab Panday, 2012. Impact of Sea Level Rise on Groundwater Salinity in a Coastal Community of South Florida. Journal of the American Water Resources Association (JAWRA) 48(3): 510-529. DOI: 10.1111/j.1752-1688.2011.00630.x Abstract: Freshwater resources of coastal communities in the United States and world over are threatened by the rate of sea level rise. According to recent estimates by various governmental agencies and climate researchers, the global sea level rise is likely to be between 0.6 and 2.1 m by the year 2100. South Florida is a coastal community and much of its coastline is subject to sea level rise and potential impacts to wetlands and the water resources of the area. To understand what the impact of sea level rise would cause to the groundwater level and salinity intrusion, an integrated groundwater and surface water model was developed for North Miami-Dade and Broward Counties of South Florida. The model was calibrated against daily groundwater heads, base flows in canals, and chloride concentrations for a period of one year and six months. Three separate sensitivity analyses were conducted by increasing the sea level by 0.6, 0.9, and 1.22 m. Results of the simulations shows increase of groundwater heads in some areas from 4 to 15%; whereas the average relative chloride concentrations increased significantly by 100-600% in some wells. The increase in groundwater elevations and chloride concentrations varies from location of the wells and its proximity to the coast. The model results indicate that even a 0.6 m increase in sea level (which is the conservative estimate) is likely to impair the vital freshwater resources in many parts of South Florida.     

Predicted uranium and radon concentrations in New Hampshire (USA) groundwater—Using Multi Order Hydrologic Position as predictors

Two radioactive elements, uranium (U) and radon (Rn), which are of potential concern in New Hampshire (NH) groundwater, are investigated. Exceedance probability maps are tools to highlight locations where the concentrations of undesirable substances in the groundwater may be elevated. Two forms of statistical analysis are used to create exceedance probability maps for U and Rn in NH groundwater. The first, Boosted Regression Tree (BRT), was selected for estimating U exceedance values. It computes exceedance values directly using the Bernoulli distribution function. The second method of statistical analysis used for Rn to determine exceedance probabilities is ordinary least squares (OLS) regression. In the process of determining exceedance probabilities for U and Rn, the utility of a new dataset is investigated. That new predictor dataset is the Multi-Order Hydrologic Position (MOHP) dataset. MOHP raster datasets have been produced nationally for the conterminous United States at a 30-m resolution. The concept behind MOHP is that, for any given point on the earth's surface, there is the potential for a longer groundwater flow path as one goes deeper beneath the land surface. MOHP predictors were tested in both models. Three MOHP predictors were found useful in the BRT model and two in the OLS model. MOHP data were found useful as predictors along with other site characteristics in predicting U and Rn exceedance probabilities in New Hampshire groundwater.     

Incomplete mixing in a small, urban stream

Conservative solute tracer experiments were conducted in Indian Creek, a small urban stream located in Philadelphia, Pennsylvania, USA. Estimated flow rates were between 46 Ls(-1) and 81 Ls(-1), average stream width was 5.5m and average stream depth was 0.2m. Given these dimensions, most researchers would think it reasonable to assume that the stream is completely mixed vertically and horizontally. However, we found that the stream was not vertically completely mixed in a 1.0m deep, 30 m long pool. The limited mixing was demonstrated by the vertical stratification of a tracer cloud which was completely mixed both laterally and vertically across the stream prior to entering the pool. We suggest that the cause of limited mixing is due to a balance between groundwater inflow and transverse dispersion at the cross-section. We show that the unsupported assumption of complete mixing may result in a wide range, and thus increased uncertainty, of the values of stream flow and longitudinal dispersion coefficient estimated from these data. We conclude that the assumption of complete mixing and one-dimensional modeling must be checked against actual field conditions, even in small streams.     

Determining long-term (decadal) deep drainage rate using multiple tracers

The deep drainage rate is a critical hydrological parameter in understanding contamination mechanisms of soil and groundwater. Little research has been conducted on the temporal variations in deep drainage rate during the last century. The objective of this study was to determine the long-term deep drainage rate on a cultivated loamy soil in the Canadian Prairies. Three tracers were used: KCl applied in 1971, fallout tritium in 1963, and NO3* released during the initial cultivation of the field (1923). Two soil cores to a depth of 3.6 m were taken along a flat portion of the field, and soil Cl(-), 3H, and NO3* concentrations were measured as a function of depth. An additional four cores were taken for soil water content measurements between 2000 and 2003. Distinct peaks in the depth distribution of these three tracers were located at 1.27 m for Cl(-), 1.31 m for 3H, and 1.52 m for NO3*, 32, 40, and 80 yr after the application of Cl(-), 3H, and NO3*, respectively. The average deep drainage rates, calculated as the product of the estimated tracer velocity and volumetric soil water content below the active root zone, were 2.0 mm yr(-1) from the Cl(-) tracer, 2.2 mm yr(-1) from 3H, and 2.5 mm yr(-1) from the NO3* tracer. Therefore, there was little temporal variability in the groundwater recharge over the eight decades that the field has been cultivated. The recharge rates are less than 1% of the mean annual precipitation (333 mm).     

Improving lake riparian source area management using surface and subsurface runoff indices

Sensitivity indices, which rank factors pertinent to surface and subsurface runoff pathways, were used to identify phosphorus source areas in riparian zones of 15 northern Minnesota lakes. Watershed models were first developed using a geographic information system (GIS). Empirical models were then developed correlating water quality with land use, lake morphometry, and riparian sensitivity. Base models of forested, cultivated, pasture/open, wetland and residential land use within 100, 200, 400, and 2000 m of the study lakes were regressed on total phosphorus and chlorophyll-a. Area-weighted groundwater and surface runoff sensitivity indices were then incorporated into each model and tested for significance. Within the 200-m buffer, the total phosphorus base model was improved by including the groundwater index alone. The chlorophyll-a base model at 200 m was improved by including: (1) the groundwater index alone, and (2) both the groundwater and surface runoff sensitivity indices. Results suggest that surface and subsurface runoff analysis of potential source areas can improve decision making for lake riparian management.     

Evaluating Flow Diversion Impacts to Groundwater‐Dependent Riparian Vegetation with Flow Alteration and Groundwater Model Analysis

An approach for assessing the potential ecologic response of groundwater‐dependent riparian vegetation to flow alteration is developed, focusing on change to groundwater. Groundwater requirements for riparian vegetation are reviewed in conjunction with flow alteration statistics. Where flow alteration coincides with groundwater‐related vegetation sensitivities, scenarios are developed for groundwater simulation. Groundwater depths and recession rates in the riparian zone are simulated for baseline and altered stream hydrographs, with changes to river stage and width represented with a transient, flow‐dependent boundary condition. Potential flow diversion from the Upper Gila River in New Mexico is examined. Statistical flow alteration analysis, applying prospective diversions to a 76‐year record of daily flow, shows that flows in the winter‐spring months and within the high‐pulse to small flood range are subject to greatest potential change. Groundwater simulation scenarios are developed for these flow conditions in representative dry, near‐average, and wet years. Differences in groundwater elevations, generally less than 0.25 m during the flow alteration period, dissipate rapidly following cessation of diversion. Relating groundwater depth, recession rates and range of fluctuations to riparian vegetation needs, we find adverse ecological response is not expected from groundwater impacts for the flow alteration examined.     

Characterization of cation-pi interactions in aqueous solution using deuterium nuclear magnetic resonance spectroscopy

Chemical interactions of aromatic organic contaminants control their fate, transport, and toxicity in the environment. Recent molecular modeling studies have suggested that strong interactions can occur between the pi electrons of aromatic molecules and metal cations in aqueous solutions and/or on mineral surfaces, and that such interactions may be important in some environmental systems. However, spectroscopic evidence for these so-called cation-pi interactions has been extremely limited to date. In this paper, cation-pi interactions in aqueous salt solutions were characterized via 2H nuclear magnetic resonance (NMR) spin-lattice relaxation times (T1) and calculations of molecular correlation times (tau(c)) for a series of perdeuterated (d6-benzene) benzene-cation complexes. The T1 values for d6-benzene decreased with increasing concentrations of LiCl, NaCl, KCl, RbCl, CsCl, and AgNO3, with the largest effects observed in the AgNO3 and CsCl solutions. Upon normalizing tau(c) values by solution viscosity effects, an overall affinity trend of Ag+ > Cs+ > K+ > Rb+ > Na+ > Li+ was derived for the d6-benzene-cation complexes. The ability of Ag+ to complex d6-benzene was significantly reduced upon addition of NH3, which strongly coordinates Ag+ at high pH. Results with d6-benzene, d8-naphthalene, d2-dichloromethane, and d12-cyclohexane in 0.1 M methanolic salt solutions confirmed that spin-lattice relaxation rates are characterizing cation-pi interactions. The relatively strong cation-pi bonding observed between Ag+ and aromatic hydrocarbons probably results from covalent interactions between the aromatic pi electrons and the d orbitals of Ag+, in addition to the normal electrostatic interaction.     

Nitrate transport in shallow groundwater at the stream–riparian interface in an urbanizing catchment

Drive point peizometers were installed at the stream–riparian interface in a small urbanizing southern Ontario catchment to measure the effect of buffers (presence/ absence) and land use (urban/agricultural) on the movement of NO^? ₃-N in shallow groundwater from the riparian area to the stream. Mean NO^? ₃-N concentrations ranged from 1.0 to 1.3 mg L^?1 with maximum values of 9.4 mg L^?1. Holding land use constant, there was no significant difference (p>0.05) in NO^? ₃3-N concentration between buffered and unbuffered sites. Nitrate-N levels were not significantly different (p>0.05) as a function of land use. The lack of difference between sites as a function of buffer absence/presence and land use is probably due to the placement of some peizometers in low conductivity materials that limited groundwater flow from the riparian zone to the stream. Subsurface factors controlling the hydraulic gradient are important in defining buffer effectiveness and buffer zones should not be used indiscrim inately as a management tool in urban and agricultural landscapes to control nitrate-N loading in shallow groundwater to streams without detailed knowledge of the hydrogeo logic environment.