Submarine groundwater discharge to coastal waters can be a significant source of both contaminants and biologically limiting nutrients. Nitrogen cycling across steep gradients in salinity, oxygen and dissolved inorganic nitrogen in sandy 'subterranean estuaries' controls both the amount and form of nitrogen discharged to the coastal ocean. We determined the effect of these gradients on betaproteobacterial ammonia-oxidizing bacteria (beta-AOB) and ammonia-oxidizing archaea (AOA) in a subterranean estuary using the functional gene encoding ammonia monooxygenase subunit A (amoA). The abundance of beta-AOB was dramatically lower in the freshwater stations compared with saline stations, while AOA abundance remained nearly constant across the study site. This differing response to salinity altered the ratio of beta-AOB to AOA such that bacterial amoA was 30 times more abundant than crenarchaeal amoA at the oxic marine station, but nearly 10 times less abundant at the low-oxygen fresh and brackish stations. As the location of the brackish mixing zone within the aquifer shifted from landward in winter to oceanward in summer, the location of the transition from a beta-AOB-dominated to an AOA-dominated community also shifted, demonstrating the intimate link between microbial communities and coastal hydrology. Analysis of ammonia-oxidizing enrichment cultures at a range of salinities revealed that AOA persisted solely in the freshwater enrichments where they actively express amoA. Diversity (as measured by total richness) of crenarchaeal amoA was high at all stations and time points, in sharp contrast to betaproteobacterial amoA for which only two sequence types were found. These results offer new insights into the ecology of AOA and beta-AOB by elucidating conditions that may favour the numerical dominance of beta-AOB over AOA in coastal sediments.

Side-by-side experiments were conducted in a sulfate-reducing aquifer at a former fuel station to evaluate the effect of ethanol on biodegradation of other gasoline constituents. On one side, for approximately 9 months we injected groundwater amended with 1-3 mg/L benzene, toluene, and o-xylene (BToX). On the other side, we injected the same, adding approximately 500 mg/L ethanol. Initially the BToX plumes on both sides ("lanes") extended approximately the same distance. Thereafter, the plumes in the "No Ethanol Lane" retracted significantly, which we hypothesize to be due to an initial acclimation period followed by improvement in efficiency of biodegradation under sulfate-reducing conditions. In the "With Ethanol Lane", the BToX plumes also retracted, but more slowly and not as far. The preferential biodegradation of ethanol depleted dissolved sulfate, leading to methanogenic/acetogenic conditions. We hypothesize that BToX in the ethanol-impacted lane were biodegraded in part within the methanogenic/acetogenic zone and, in part, within sulfate-reducing zones developing along the plume fringes due to mixing with sulfate-containing groundwater surrounding the plumes due to dispersion and/or shifts in flow direction. Overall, this research confirms that ethanol may reduce rates of biodegradation of aromatic fuel components in the subsurface, in both transient and near steady-state conditions.

a b s t r a c tSubmarine groundwater discharge (SGD) to the coastal environment along the eastern Yucatan Peninsula, Quintana Roo, Mexico was investigated using a combination of tracer mass balances and analytical solutions. Two distinct submarine groundwater sources including water from the unconfined surficial aquifer discharging at the beach face and water from a deeper aquifer discharging nearshore through submarine springs (ojos) were identified. The groundwater of nearshore ojos was saline and significantly enriched in short-lived radium isotopes ( 223 Ra, 224 Ra) relative to the unconfined aquifer beach face groundwater. We estimated SGD from ojos using 223 Ra and used a salinity mass balance to estimate the freshwater discharge at the beach face. Analytical calculations were also used to estimate wave set-up and tidally driven saline seepage into the surf zone and were compared to the salinity-based freshwater discharge estimates. ). Discharge at the beach face was in the range of 3.3-8.5 m 3 d À 1 m À 1 for freshwater and 2.7 m 3 d À 1 m À 1 for saline water based on the salinity mass balance and wave-and tidally-driven discharge, respectively. Although discharge from the ojos was larger in volume than discharge from the unconfined aquifer at the beach face, dissolved inorganic nitrogen (DIN) was significantly higher in beach groundwater; thus, discharge of this unconfined beach aquifer groundwater contributed significantly to total DIN loading to the coast. DIN fluxes were up to 9.9 mol d À 1 m À 1 from ojos and 2.1 mol d À 1 m À 1 from beach discharge and varied regionally along the 500 km coastline sampled. These results demonstrate the importance of considering the beach zone as a significant nutrient source to coastal waters for future management strategies regarding nutrient loading to reef environments and coastal development. This study also identifies the importance of understanding the connectivity of submarine spring discharge to the nearshore coastal environment and the impact of inland anthropogenic activities may have on coastal health.

The influence of fortnightly spring-neap tidal variability on submarine discharge of fresh and saline groundwater was examined at Stinson Beach, California. Stinson Beach is a residential community that utilizes on-site systems for wastewater disposal. Fresh, shallow groundwater at the site contains high concentrations of nutrients (dissolved inorganic nitrogen [DIN], soluble reactive phosphate [SRP], and silicate) and human fecal bacteria. A groundwater-derived freshening and nutrification of the surf zone during neap tides was observed, followed by a 4-d increase in chlorophyll a concentrations. Analytical models and a freshwater budget in the surf zone were used to estimate the saline and fresh discharge of submarine groundwater. We estimate fresh groundwater discharge between 1.2 and 4.7 L min 21 m 21 shoreline during neap tides compared with 0.1 and 0.5 L min 21 m 21 during spring tides. This compares with 15.9 and 22.0 L min 21 m 21 saline groundwater discharge (forced by waves and tides) during neap and spring tides, respectively. Despite the smaller total (fresh + saline) flux of groundwater during neap compared with spring tides, the larger fresh discharge component during neap tides raises surf zone silicate, DIN, and SRP by 14%, 35%, and 27%, respectively, relative to spring tides. This observed fortnightly pulsing of fresh groundwater-derived nutrients was consistent with seaward hydraulic gradients across the fresh part of the beach aquifer, which varied due to aquifer overheight near the beach face. Darcy-Dupuit estimates of seaward fresh groundwater flow in this area agreed well with the fresh discharge results of the mass balance.

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Fluxes of total mercury (Hg(T)) and monomethylmercury (MMHg) associated with submarine groundwater discharge (SGD) at two sites onthe central California coast were estimated by combining measurements of Hg(T) and MMHg in groundwater with the use of short-lived, naturally occurring radium isotopes as tracers of groundwater inputs. Concentrations of Hg(T) were relatively low, ranging from 1.2 to 28.3 pM in filtered groundwater, 0.8 to 11.6 pM in filtered surface waters, and 2.5 to 12.9 pM in unfiltered surface waters. Concentrations of MMHg ranged from < 0.04 to 3.1 pM in filtered groundwater, < 0.04 to 0.53 pM in filtered surface waters, and 0.07 to 1.2 pM in unfiltered surface waters. Multiple linear regression analysis identified significant (p < 0.05) positive correlations between dissolved groundwater concentrations of Hg(T) and those of NH4+ and SiO2, and between dissolved groundwater concentrations of MMHg and those of Hg(T) and NH4+. However, such relationships did not account for the majority of the variability in concentration data for either mercury species in groundwater. Fluxes of Hg(T) via SGD were estimated to be 250 +/- 160 nmol day m(-1) of shoreline at Stinson Beach and 3.0 +/- 2.0 nmol m(-2) day(-1) at Elkhorn Slough. These Hg(T) fluxes are substantially greater than net atmospheric inputs of Hg(T) reported for waters in nearby San Francisco Bay. Calculated fluxes of MMHg to coastal waters via SGD were 10 +/- 12 nmol day(-1) m(-1) of shoreline at Stinson Beach and 0.24 +/- 0.21 nmol m(-2) day at Elkhorn Slough. These MMHg fluxes are similar to benthic fluxes of MMHg out of surface sediments commonly reported for estuarine and coastal environments. Consequently, this work demonstrates that SGD is an important source of both Hg(T) and MMHg to coastal waters along the central California coast.

In a field experiment at Vandenberg Air Force Base (VAFB) designed to mimic the impact of a small-volume release of E10 (10% ethanol and 90% conventional gasoline), two plumes were created by injecting extracted groundwater spiked with benzene, toluene, and o-xylene, abbreviated BToX (No-Ethanol Lane) and BToX plus ethanol (With-Ethanol Lane) for 283 days. We developed a reactive transport model to understand processes controlling the fate of ethanol and BToX. The model was calibrated to the extensive field dataset and accounted for concentrations of sulfate, iron, acetate, and methane along with iron-reducing bacteria, sulfate-reducing bacteria, fermentative bacteria, and methanogenic archaea. The benzene plume was about 4.5 times longer in the With-Ethanol Lane than in the No-Ethanol Lane. Matching this different behavior in the two lanes required inhibiting benzene degradation in the presence of ethanol. Inclusion of iron reduction with negligible growth of iron-reducers was required to reproduce the observed constant degradation rate of benzene. Modeling suggested that vertical dispersion and diffusion of sulfate from an adjacent aquitard were important sources of sulfate in the aquifer. Matching of methane data required incorporating initial fermentation of ethanol to acetate, methane loss by outgassing, and methane oxidation coupled to sulfate and iron reduction. Simulation of microbial growth using dual Monod kinetics, and including inhibition by more favorable electron acceptors, generally resulted in reasonable yields for microbial growth of 0.01-0.05.

Two 14-day experiments conducted in the dry summer (July 2006) and wet winter (March 2007) seasons, respectively, examined tidal, wave-driven, and seasonal variability of submarine groundwater discharge (SGD) at Stinson Beach, CA, using natural radium tracers. Tide stage, tide range, breaker height, and season each explained a significant degree of radium variability in the surf zone. A mass balance of excess radium in the surf zone was used to estimate SGD for each season, confirming larger discharge rates during the wet season. Our results indicate median groundwater discharge rates of 6 to 8 L min