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A review and evaluation of catchment transit time modeling

Agriculture has had direct and indirect effects on the rates and compositions of groundwater recharge and aquifer biogeochemistry Direct effects include dis- solution and transport of excess quantities of fertilizers and associated materials and hydrologic alterations relat- ed to irrigation and drainage Some indirect effects in- clude changes in water-rock reactions in soils and aqui- fers caused by increased concentrations of dissolved oxi- dants, protons, and major ions Agricultural activities have directly or indirectly affected the concentrations of a large number of inorganic chemicals in groundwater, for example NO 3 - , N 2 , Cl, SO 4 2- , H + , P, C, K, Mg, Ca, Sr, Ba, Ra, and As, as well as a wide variety of pesti- cides and other organic compounds For reactive con- taminants like NO 3 - , a combination of chemical, isoto- pic, and environmental-tracer analytical approaches might be required to resolve changing inputs from subse- quent alterations as causes of concentration gradients in groundwater Groundwater records derived from multi- component hydrostratigraphic data can be used to quan- tify recharge rates and residence times of water and dis- solved contaminants, document past variations in re- charging contaminant loads, and identify natural contam- inant-remediation processes These data indicate that many of the world's surficial aquifers contain transient records of changing agricultural contamination from the last half of the 20th century The transient agricultural groundwater signal has important implications for long- term trends and spatial heterogeneity in discharge

Groundwater recharge and agricultural contamination

The history and fate of groundwater nitrate (NO3−) contamination were compared in 2 small adjacent agricultural watersheds in the Atlantic coastal plain by combined use of chronologic (CCl2F2, 3H), chemical (dissolved solids, gases), and isotopic (δ15N,δ13C, δ34S) analyses of recharging groundwaters, discharging groundwaters, and surface waters. The results demonstrate the interactive effects of changing agricultural practices, groundwater residence times, and local geologic features on the transfer of NO3− through local flow systems. Recharge dates of groundwaters taken in 1990–1992 from the surficial aquifer in the Chesterville Branch and Morgan Creek watersheds near Locust Grove, Maryland, ranged from pre-1940 to the late 1980’s. When corrected for localized denitrification by use of dissolved gas concentrations, the dated waters provide a 40-year record of the recharge rate of NO3−, which increased in both watersheds by a factor of 3–6, most rapidly in the 1970's. The increase in groundwater NO3− over time was approximately proportional to the documented increase in regional N fertilizer use, and could be accounted for by oxidation and leaching of about 20–35% of the fertilizer N. Groundwaters discharging upward beneath streams in both watersheds had measured recharge dates from pre-1940 to 1975, while chemical data for second-order reaches of the streams indicated average groundwater residence times in the order of 20+ years. At the time of the study, NO3− discharge rates were less than NO3− recharge rates for at least two reasons: (1) discharge of relatively old waters with low initial NO3− concentrations, and (2) local denitrification. In the Chesterville Branch watershed, groundwaters remained oxic throughout much of the surficial aquifer and discharged relatively unaltered to the stream, which had a relatively high NO3− concentration (9–10 mg/L as N). In the Morgan Creek watershed, groundwaters were largely reduced and denitrified before discharging to the stream, which had a relatively low NO3− concentration (2–3 mg/L as N). Chemical and isotopic data indicate that quantitative denitrification occurred within buried calcareous glauconitic marine sediments that are present at relatively shallow depths beneath the Morgan Creek watershed. NO3− removal by forests, wetlands, and shallow organic-rich soils in near-stream environments was largely avoided by groundwaters that followed relatively deep flow paths before converging and discharging rapidly upward to the streams.

Combined Use of Groundwater Dating, Chemical, and Isotopic Analyses to Resolve the History and Fate of Nitrate Contamination in Two Agricultural Watersheds, Atlantic Coastal Plain, Maryland

In contrast to most other fields of noble gas geochemistry that mostly regard atmospheric noble gases as ‘contamination,’ air-derived noble gases make up the far largest and hence most important contribution to the noble gas abundance in meteoric waters, such as lakes and ground waters. Atmospheric noble gases enter the meteoric water cycle by gas partitioning during air/water exchange with the atmosphere.

In lakes and oceans noble gases are exchanged with the free atmosphere at the surface of the open water body. In ground waters gases partition between the water phase and the soil air of the quasi-saturated zone, the transition between the unsaturated and the saturated zone. Extensive measurements have shown that noble gas concentrations of open waters agree well with the noble gas solubility equilibrium according to (free) air/(free) water partitioning, whereby the aquatic concentration is directly proportional to the respective atmospheric noble gas abundance (Henry law, Aeschbach-Hertig et al. 1999b).

In applications in lakes and ground waters the gas specific Henry coefficient can simplifying be assumed to depend only on temperature and salinity of the water. Hence the equilibrium concentrations of noble gases implicitly convey information on the physical properties of the water during gas exchange at the air/water interface, i.e., air pressure, temperature and salinity of the exchanging water mass. The ubiquitous presence of atmospheric noble gases in the meteoric water cycle defines a natural baseline, which masks other noble gas components until their abundance is sufficiently large that these components can be separated against the natural atmospheric background. For most classical geochemical aspects this typical feature of natural waters may look at first sight as a disadvantage. In fact it turns out to be advantageous because in most cases the noble gas abundance in water can be understood as a binary mixture of two …

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Noble Gases in Lakes and Ground Waters

A new method is proposed to simulate groundwater age directly, by use of an advection-dispersion transport equation with a distributed zero-order source of unit (1) strength, corresponding to the rate of aging. The dependent variable in the governing equation is the mean age, a mass-weighted average age. The governing equation is derived from residence-time-distribution concepts for the case of steady flow. For the more general case of transient flow, a transient governing equation for age is derived from mass-conservation principles applied to conceptual "age mass." The age mass is the product of the water mass and its age, and age mass is assumed to be conserved during mixing. Boundary conditions include zero age mass flux across all noflow and inflow boundaries and no age mass dispersive flux across outflow boundaries. For transient-flow conditions, the initial distribution of age must be known. The solution of the governing transport equation yields the spatial distribution of the mean groundwater age and includes diffusion, dispersion, mixing, and exchange processes that typically are considered only through tracer-specific solute transport simulation. Traditional methods have relied on advective transport to predict point values of groundwater travel time and age. The proposed method retains the simplicity and tracer-independence of advection-only models, but incorporates the effects of dispersion and mixing on volume-averaged age. Example simulations of age in two idealized regional aquifer systems, one homogeneous and the other layered, demonstrate the agreement between the proposed method and traditional particle-tracking approaches and illustrate use of the proposed method to determine the effects of diffusion, dispersion, and mixing on groundwater age.

A Zuber

Papers

Mathematical models for the interpretation of environmental radioisotopes in groundwater systems