Denis R. LeBlanc

Large-scale natural gradient tracer test in sand and gravel, Cape Cod, Massachusetts: 1. Experimental design and observed tracer movement

A large-scale natural gradient tracer experiment was conducted on Cape Cod, Massachusetts, to examine the transport and dispersion of solutes in a sand and gravel aquifer. The nonreactive tracer, bromide, and the reactive tracers, lithium and molybdate, were injected as a pulse in July 1985 and monitored in three dimensions as they moved as far as 280 m down-gradient through an array of multilevel samplers. The bromide cloud moved horizontally at a rate of 0.42 m per day. It also moved downward about 4 m because of density-induced sinking early in the test and accretion of areal recharge from precipitation. After 200 m of transport, the bromide cloud had spread more than 80 m in the direction of flow, but was only 14 m wide and 4-6 m thick. The lithium and molybdate clouds followed the same path as the bromide cloud, but their rates of movement were retarded about 50% relative to bromide movement because of sorption onto the sediments.

Long-term fate of organic micropollutants in sewage-contaminated groundwater

Disposal of secondary sewage effluent by rapid infiltration has produced a plume of contaminated groundwater over 3500 m long near Falmouth, MA. Approximately 50 volatile organic compounds were detected and identified in the plume, at concentrations ranging from 10 ng/L to 500 {mu}g/L, by closed-loop stripping and purge-and-trap in conjunction with gas chromatography-mass spectrometry. The dominant contaminants were di-, tri- and tetrachloroethene, o- and p-dichlorobenzene, C{sub 1} to C{sub 6} alkylbenzenes, 2,6-di-tert-butylbenzoquinone, and several isomers of p-nonylphenol. The chloroethenes and chlorobenzenes had the same general distribution as chloride and boron and appear to be transported with little retardation. Less soluble compounds, such as nonylphenol and di-tert-butylbenzoquinone, appear to be retarded during subsurface transport by sorption processes. Although biodegradation of labile organic compounds occurs near the infiltration beds, many trace compounds, including chlorinated benzenes, alkylbenzenes, and aliphatic hydrocarbons, have persisted for more than 30 years in the aquifer.

Importance of closely spaced vertical sampling in delineating chemical and microbiological gradients in groundwater studies

Abstract Vertical gradients of selected chemical constituents, bacterial populations, bacterial activity and electron acceptors were investigated for an unconfined aquifer contaminated with nitrate and organic compounds on Cape Cod, Massachusetts, U.S.A. Fifteen-port multilevel sampling devices (MLSs) were installed within the contaminant plume at the source of the contamination, and at 250 and 2100 m downgradient from the source. Depth profiles of specific conductance and dissolved oxygen at the downgradient sites exhibited vertical gradients that were both steep and inversely related. Narrow zones (2–4 m thick) of high N 2 O and NH 4 + concentrations were also detected within the contaminant plume. A 27-fold change in bacterial abundance; a 35-fold change in frequency of dividing cells (FDC), an indicator of bacterial growth; a 23-fold change in 3 H-glucose uptake, a measure of heterotrophic activity; and substantial changes in overall cell morphology were evident within a 9-m vertical interval at 250 m downgradient. The existence of these gradients argues for the need for closely spaced vertical sampling in groundwater studies because small differences in the vertical placement of a well screen can lead to incorrect conclusions about the chemical and microbiological processes within an aquifer.

Movement and fate of detergents in groundwater: a field study

Abstract The major cations, anions, and detergents in a plume of contaminated groundwater at Otis Air Base on Cape Cod (Mass., U.S.A.) have moved approximately 3.5 km down gradient from the disposal beds. We hypothesize that the detergents form two distinct plumes, which consist of alkyl benzene sulfonates (ABS) detergents and linear alkyl sulfonates (LAS) and sodium dodecyl sulfate (NaLS) detergents. The ABS detergents were deposited from approximately 1940 through 1965, when ABS detergents were banned. From 1965 to the present, LAS and NaLS detergents were in the sewage. The ABS detergents appear to be transported in the aquifer at the same rate as the specific conductance (major cations and anions) and boron, which are currently used as conservative tracers of the plume of contaminated groundwater. There appears to be little or no biological degradation of the ABS detergents in the aquifer, based on their concentration in the plume. On the other hand, the LAS and NaLS detergents have degraded rapidly and have been detected only 0.6 km down gradient. The roleof the detergents in the transport of other organic compounds in the plume is nuclear. There is a separation of the ABS detergent plume and the volatile organic compound plume; however, the time of entry of the detergents and the volatile organic compounds is unknown. Therefore, it is not possible to conclude on the interaction of these two classes of compounds.

Infiltration and solute transport experiments in unsaturated sand and gravel, Cape Cod, Massachusetts: Experimental design and overview of results

A series of infiltration and tracer experiments was conducted in unsaturated sand and gravel deposits on Cape Cod, Massachusetts. A network of 112 porous cup lysimeters and 168 time domain reflectometry (TDR) probes was deployed at depths from 0.25 to 2.0 m below ground surface along the centerline of a 2-m by 10-m test plot. The test plot was irrigated at rates ranging from 7.9 to 37.0 cm h−1 through a sprinkler system. Transient and steady state water content distributions were monitored with the TDR probes and spatial properties of water content distributions were determined from the TDR data. The spatial variance of the water content tended to increase as the average water content increased. In addition, estimated horizontal correlation length scales for water content were significantly smaller than those estimated by previous investigators for saturated hydraulic conductivity. Under steady state flow conditions at each irrigation rate, a sodium chloride solution was released as a tracer at ground surface and tracked with both the lysimeter and TDR networks. Transect-averaged breakthrough curves at each monitoring depth were constructed both from solute concentrations measured in the water samples and flux concentrations inferred from the TDR measurements. Transport properties, including apparent solute velocities, dispersion coefficients, and total mass balances, were determined independently from both sets of breakthrough curves. The dispersion coefficients tended to increase with depth, reaching a constant value with the lysimeter data and appearing to increase continually with the TDR data. The variations with depth of the solute transport parameters, along with observations of water and solute mass balance and spatial distributions of water content, provide evidence of significant three-dimensional flow during the irrigation experiments. The TDR methods are shown to efficiently provide dense spatial and temporal data sets for both flow and solute transport in unsaturated sediments with minimal sediment and flow field disturbance. Combined implementation of lysimeters and TDR probes can enhance data interpretation particularly when three-dimensional flow conditions are anticipated.

Simulation of variable-density flow and transport of reactive and nonreactive solutes during a tracer test at Cape Cod, Massachusetts

A multispecies numerical code was developed to simulate flow and mass transport with kinetic adsorption in variable-density flow systems. The two-dimensional code simulated the transport of bromide (Br−), a nonreactive tracer, and lithium (Li+), a reactive tracer, in a large-scale tracer test performed in a sand-and-gravel aquifer at Cape Cod, Massachusetts. A two-fraction kinetic adsorption model was implemented to simulate the interaction of Li+ with the aquifer solids. Initial estimates for some of the transport parameters were obtained from a nonlinear least squares curve-fitting procedure, where the breakthrough curves from column experiments were matched with one-dimensional theoretical models. The numerical code successfully simulated the basic characteristics of the two plumes in the tracer test. At early times the centers of mass of Br− and Li+ sank because the two plumes were closely coupled to the density-driven velocity field. At later times the rate of downward movement in the Br− plume due to gravity slowed significantly because of dilution by dispersion. The downward movement of the Li+ plume was negligible because the two plumes moved in locally different velocity regimes, where Li+ transport was retarded relative to Br−. The maximum extent of downward transport of the Li+ plume was less than that of the Br− plume. This study also found that at early times the downward movement of a plume created by a three-dimensional source could be much more extensive than the case with a two-dimensional source having the same cross-sectional area. The observed shape of the Br− plume at Cape Cod was simulated by adding two layers with different hydraulic conductivities at shallow depth across the region. The large dispersion and asymmetrical shape of the Li+ plume were simulated by including kinetic adsorption-desorption reactions.

Effects on Groundwater Microbial Communities of an Engineered 30-Day In Situ Exposure to the Antibiotic Sulfamethoxazole

Effects upon microbial communities from environmental exposure to concentrations of antibiotics in the μg L(-1) range remain poorly understood. Microbial communities from an oligotrophic aquifer (estimated doubling rates of only once per week) that were previously acclimated (AC) or unacclimated (UAC) to historical sulfamethoxazole (SMX) contamination, and a laboratory-grown Pseudomonas stutzeri strain, were exposed to 240-520 μg L(-1) SMX for 30 days in situ using filter chambers allowing exposure to ambient groundwater, but not to ambient microorganisms. SMX-exposed UAC bacterial communities displayed the greatest mortality and impairment (viable stain assays), the greatest change in sensitivity to SMX (dose-response assays), and the greatest change in community composition (Terminal Restriction Fragment Length Polymorphism; T-RFLP). The sul1 gene, encoding resistance to SMX at clinically relevant levels, and an element of Class I integrons, was not detected in any community. Changes in microbial community structure and SMX resistance over a short experimental period in previously nonexposed, slow-growing aquifer communities suggest concentrations of antibiotics 2-3 orders of magnitude less than those used in clinical applications may influence ecological function through changes in community composition, and could promote antibiotic resistance through selection of naturally resistant bacteria.

Hydrologic controls on nitrogen cycling processes and functional gene abundance in sediments of a groundwater flow-through lake

The fate and transport of inorganic nitrogen (N) is a critically important issue for human and aquatic ecosystem health because discharging N-contaminated groundwater can foul drinking water and cause algal blooms. Factors controlling N-processing were examined in sediments at three sites with contrasting hydrologic regimes at a lake on Cape Cod, MA. These factors included water chemistry, seepage rates and direction of groundwater flow, and the abundance and potential rates of activity of N-cycling microbial communities. Genes coding for denitrification, anaerobic ammonium oxidation (anammox), and nitrification were identified at all sites regardless of flow direction or groundwater dissolved oxygen concentrations. Flow direction was, however, a controlling factor in the potential for N-attenuation via denitrification in the sediments. Potential rates of denitrification varied from 6 to 4500 pmol N/g/h from the inflow to the outflow side of the lake, owing to fundamental differences in the supply of labile organic matter. The results of laboratory incubations suggested that when anoxia and limiting labile organic matter prevailed, the potential existed for concomitant anammox and denitrification. Where oxic lake water was downwelling, potential rates of nitrification at shallow depths were substantial (1640 pmol N/g/h). Rates of anammox, denitrification, and nitrification may be linked to rates of organic N-mineralization, serving to increase N-mobility and transport downgradient.

Geochemical and Hydrologic Factors Controlling Subsurface Transport of Poly- and Perfluoroalkyl Substances, Cape Cod, Massachusetts

Growing evidence that certain poly- and perfluoroalkyl substances (PFASs) are associated with negative human health effects prompted the U.S. Environmental Protection Agency to issue lifetime drinking water health advisories for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in 2016. Given that groundwater is a major source of drinking water, the main objective of this work was to investigate geochemical and hydrological processes governing the subsurface transport of PFASs at a former fire training area (FTA) on Cape Cod, Massachusetts, where PFAS-containing aqueous film-forming foams were used historically. A total of 148 groundwater samples and 4 sediment cores were collected along a 1200-m-long downgradient transect originating near the FTA and analyzed for PFAS content. The results indicate that unsaturated zones at the FTA and at hydraulically downgradient former domestic wastewater effluent infiltration beds both act as continuous PFAS sources to the groundwater despite 18 and 20 years of inactivity, respectively. Historically different PFAS sources are evident from contrasting PFAS composition near the water table below the FTA and wastewater-infiltration beds. Results from total oxidizable precursor assays conducted using groundwater samples collected throughout the plume suggest that some perfluoroalkyl acid precursors at this site are transporting with perfluoroalkyl acids.

The influence of topology on hydraulic conductivity in a sand-and-gravel aquifer

A field experiment consisting of geophysical logging and tracer testing was conducted in a single well that penetrated a sand-and-gravel aquifer at the U.S. Geological Survey Toxic Substances Hydrology research site on Cape Cod, Massachusetts. Geophysical logs and flowmeter/pumping measurements were obtained to estimate vertical profiles of porosity phi, hydraulic conductivity K, temperature, and bulk electrical conductivity under background, freshwater conditions. Saline-tracer fluid was then injected into the well for 2 h and its radial migration into the surrounding deposits was monitored by recording an electromagnetic-induction log every 10 min. The field data are analyzed and interpreted primarily through the use of Archies (1942) law to investigate the role of topological factors such as pore geometry and connectivity, and grain size and packing configuration in regulating fluid flow through these coarse-grained materials. The logs reveal no significant correlation between K and phi, and imply that groundwater models that link these two properties may not be useful at this site. Rather, it is the distribution and connectivity of the fluid phase as defined by formation factor F, cementation index m, and tortuosity alpha that primarily control the hydraulic conductivity. Results show that F correlates well with K, thereby indicating that induction logs provide qualitative information on the distribution of hydraulic conductivity. A comparison of alpha, which incorporates porosity data, with K produces only a slightly better correlation and further emphasizes the weak influence of the bulk value of varphi on K.