Spatial distribution of submarine groundwater discharge and associated nutrients within a local coastal area

To understand the local-scale distribution of submarine groundwater discharge (SGD) and dissolved nutrients, a multiple-detector (222)Rn monitoring survey was undertaken along the Mt. Chokai volcanic coast in northern Japan. The surveys revealed that the highest SGD (calculated to be 6.2 × 10(4) m(3) d(-1), within an area of 2 × 10(4) m(2)) with the greatest nutrient fluxes (sum of NO(3)(-), NO(2)(-), and NH(4)(+) (DIN): 9.2 × 10(2) mol d(-1); PO(4)(3-) (DIP): 56 mol d(-1)) is present at the edge of the youngest volcanic lava flow in the area. Recharged groundwater transports nutrients through porous volcanic flows and discharges as SGD near shore. Our results demonstrate that the spatial distribution of SGD in the study area is closely regulated by the local geology and topography. Furthermore, we show that continuous (222)Rn monitoring with a multidetector system at boat speeds of 1-2 knots provides details at a scale one order of magnitude greater than has been reported previously. In addition, the results of our study suggest that SGD-borne DIP may play an important role in the important local oyster production.     

Mercury speciation and transport via submarine groundwater discharge at a southern California coastal lagoon system

We measured total mercury (Hg(T)) and monomethylmercury (MMHg) concentrations in coastal groundwater and seawater over a range of tidal conditions near Malibu Lagoon, California, and used (222)Rn-derived estimates of submarine groundwater discharge (SGD) to assess the flux of mercury species to nearshore seawater. We infer a groundwater-seawater mixing scenario based on salinity and temperature trends and suggest that increased groundwater discharge to the ocean during low tide transported mercury offshore. Unfiltered Hg(T) (U-Hg(T)) concentrations in groundwater (2.2-5.9 pM) and seawater (3.3-5.2 pM) decreased during a falling tide, with groundwater U-Hg(T) concentrations typically lower than seawater concentrations. Despite the low Hg(T) in groundwater, bioaccumulative MMHg was produced in onshore sediment as evidenced by elevated MMHg concentrations in groundwater (0.2-1 pM) relative to seawater (～0.1 pM) throughout most of the tidal cycle. During low tide, groundwater appeared to transport MMHg to the coast, resulting in a 5-fold increase in seawater MMHg (from 0.1 to 0.5 pM). Similarly, filtered Hg(T) (F-Hg(T)) concentrations in seawater increased approximately 7-fold during low tide (from 0.5 to 3.6 pM). These elevated seawater F-Hg(T) concentrations exceeded those in filtered and unfiltered groundwater during low tide, but were similar to seawater U-Hg(T) concentrations, suggesting that enhanced SGD altered mercury partitioning and/or solubilization dynamics in coastal waters. Finally, we estimate that the SGD Hg(T) and MMHg fluxes to seawater were 0.41 and 0.15 nmol m(-2) d(-1), respectively - comparable in magnitude to atmospheric and benthic fluxes in similar environments.     

Coupling automated radon and carbon dioxide measurements in coastal waters

Groundwater discharge could be a major, but as yet poorly constrained, source of carbon dioxide to lakes, wetlands, rivers, estuaries, and coastal waters. We demonstrate how coupled radon ((222)Rn, a natural groundwater tracer) and pCO(2) measurements in water can be easily performed using commercially available gas analysers. Portable, automated radon and pCO(2) gas analysers were connected in series and a closed air loop was established with gas equilibration devices (GED). We experimentally assessed the advantages and disadvantages of six GED. Response times shorter than 30 min for (222)Rn and 5 min for pCO(2) were achieved. Field trials revealed significant positive correlations between (222)Rn and pCO(2) in estuarine waterways and in a mangrove tidal creek, implying that submarine groundwater discharge was a source of CO(2) to surface water. The described system can provide high resolution, high precision concentrations of both radon and pCO(2) with nearly no additional effort compared to measuring only one of these gases. Coupling automated (222)Rn and pCO(2) measurements can provide new insights into how groundwater seepage contributes to aquatic carbon budgets.     

Evaluating behavior of oxygen,nitrate, and sulfate during recharge and quantifying reduction rates in a contaminated aquifer

This study evaluates the biogeochemical changes that occur when recharge water comes in contact with a reduced aquifer. It specifically addresses (1) which reactions occur in situ, (2) the order in which these reactions will occur if terminal electron acceptors (TEAs) are introduced simultaneously, (3) the rates of these reactions, and (4) the roles of the aqueous and solid-phase portions of the aquifer. Recharge events of waters containing various combinations of O2, NO3, and SO4 were simulated at a shallow sandy aquifer contaminated with waste fuels and chlorinated solvents using modified push-pull tests to quantify rates. In situ rate constants for aerobic respiration (14.4 day(-1)), denitrification (5.04-7.44 day(-1)), and sulfate reduction (4.32-6.48 day(-1)) were estimated. Results show that when introduced together, NO3 and SO4 can be consumed simultaneously at similar rates. To distinguish the role of aqueous phase from that of the solid phase of the aquifer, groundwater was extracted, amended with NO3 and SO4, and monitored overtime. Results indicate that neither NO3 nor SO4 was reduced during the course of the aqueous-phase study, suggesting that NO3 and SO4 can behave conservatively in highly reduced water. It is clear that sediments and their associated microbial communities are important in driving redox reactions.     

Mass balance of total mercury and monomethylmercury in coastal embayments of a volcanic island: significance of submarine groundwater discharge

To understand the contribution of submarine groundwater discharge (SGD) to the coastal mass budgets of Hg and monomethylmercury (MMHg), preliminary mass balance estimates were made for Hwasun and Bangdu Bays on Jeju Island, known to have large SGD due to the high permeability of the volcanic rocks. The mass balance results indicate that SGD is a main source of Hg in Hwasun Bay (23 ± 14 × 10(-2) mol yr(-1), 34%) and Bangdu Bay (23 ± 20 × 10(-2) mol yr(-1), 67%), although the contribution from atmospheric deposition was considerable (25% for Hwasun and 23% for Bangdu). MMHg was also discharged primarily from submarine groundwater at Hwasun (0.30 ± 0.17 × 10(-2) mol yr(-1), 55%) and Bangdu (0.65 ± 0.49 × 10(-2) mol yr(-1), 64%), which was higher than atmospheric deposition (6% for Hwasun and 2% for Bangdu) and sediment diffusion flux (5% for Hwasun and 3% for Bangdu). The overall mass balance results suggest that, although there are large spatial variations in SGD rates throughout the region, the coastal mass budgets of Hg and MMHg need to include SGD as well as atmospheric deposition and sediment diffusion as primary sources of Hg and MMHg.     

A novel method using a silicone diffusion membrane for continuous ²²²Rn measurements for the quantification of groundwater discharge to streams and rivers

222Rn is a natural radionuclide that is commonly used as tracer to quantify groundwater discharge to streams, rivers, lakes, and coastal environments. The use of sporadic point measurements provides little information about short- to medium-term processes (hours to weeks) at the groundwater-surface water interface. Here we present a novel method for high-resolution autonomous, and continuous, measurement of 222Rn in rivers and streams using a silicone diffusion membrane system coupled to a solid-state radon-in-air detector (RAD7). In this system water is pumped through a silicone diffusion tube placed inside an outer air circuit tube that is connected to the detector. 222Rn diffuses from the water into the air loop, and the 222Rn activity in the air is measured. By optimizing the membrane tube length, wall thickness, and water flow rates through the membrane, it was possible to quantify radon variations over times scales of about 3 h. The detection limit for the entire system with 20 min counting was 18 Bq m?3 at the 3σ level. Deployment of the system on a small urban stream showed that groundwater discharge is dynamic, with changes in 222Rn activity doubling on the scale of hours in response to increased stream flow.     

What is the role of fresh groundwater and recirculated seawater in conveying nutrients to the coastal ocean?

Submarine groundwater discharge (SGD) is a major process operating at the land-sea interface. Quantifying the SGD nutrient loads and the marine/terrestrial controls of this transport is of high importance, especially in oligotrophic seas such as the eastern Mediterranean. The fluxes of nutrients in groundwater discharging from the seafloor at Dor Bay (southeastern Mediterranean) were studied in detail using seepage meters. Our main finding is that the terrestrial, fresh groundwater is the main conveyor of DIN and silica to the coastal water, with loads of 500 and 560 mol/yr, respectively, per 1 m shoreline. Conversely, recirculated seawater is nutrient-poor, and its role is mainly as a dilution agent. The nutrient loads regenerated in the subterranean estuary (sub-bay sediment) are relatively small, consisting mostly of ammonium (24 mol/yr). On the other hand, the subterranean estuary at Dor Bay sequesters as much as 100 mol N/yr per 1 m shoreline, mainly via denitrification processes. These, and observations from other SGD sites, imply that the subterranean estuary at some coastal systems may function more as a sink for nitrogen than a source. This further questions the extent of nutrient contributions to the coastal water by some subterranean estuaries and warrants systematic evaluation of this process in various hydrological and marine trophic conditions.     

Influence of net groundwater discharge on the chemical composition of a coastal environment: Flanders Bay, Long Island, New York

Seasonal (October 1997 and May 1998) concentrations of dissolved (< 0.45 micron) trace metals (Ag, Al, Cd, Cu, Fe, Mn), inorganic nutrients (NO3, PO4, Si), DOC and DON were measured at seven wells during periods of low and high groundwater flow, in the aquifer around Flanders Bay in Eastern Long Island, New York. Similar measurements were made in surface waters of Flanders Bay, a shallow coastal embayment with restricted water flushing and river input. Dissolved constituents in the groundwater were classified according to their behavior under different flow conditions as follows: (1) peak during high flow (DOC, pH, Si, NO3, Al and Cu); (2) peak during low flow (salinity, DON, Ag, Cd, Mn); and (3) concentrations independent of flow conditions (PO4 and Fe). The primarily urban and agricultural land use on the North Fork of Long Island was reflected in higher concentrations of nutrients, Cu and Cd in groundwater, compared to samples from the South Fork which is mostly open parkland. Principal component analysis indicated that groundwater seepage could influence the chemical composition of Flanders Bay with respect to the major geochemical carriers (e.g. Fe and Mn). However, mass balance estimates for Cu indicated that, during low flow conditions, net groundwater Cu input was about 10% of the total input. In contrast, during high flow, net groundwater flow could account for up to 58% of all Cu inputs. Nevertheless, a large imbalance, which accounted for up to 70% of the outflux during low aquifer recharge, suggested that the Cu budget of the Bay was not adequately described by the inputs considered (river, net groundwater flow, atmospheric deposition, and tidal exchange). Important missing components of the Cu mass balance in Flanders Bay may include groundwater circulation driven by tides and waves as well as diffusive benthic fluxes.     

Geochemical cycling of arsenic in a coastal aquifer

Biogeochemically modified pore waters from subterranean estuaries, defined as the mixing zone between freshwater and saltwater in a coastal aquifer, are transported to coastal waters through submarine groundwater discharge (SGD). SGD has been shown to impact coastal and perhaps global trace metal budgets. The focus of this study was to investigate the biogeochemical processes that control arsenic cycling in subterranean estuaries. Total dissolved As, as well as a suite of other trace metals and nutrients, were measured in a series of wells and sediment cores at the head of Waquoit Bay, MA. Dissolved As ranged from below detection to 9.5 microg/kg, and was associated with plumes of dissolved Fe, Mn, and P in the groundwater. Sedimentary As, ranging from 360 to 7500 microg/kg, was highly correlated with sedimentary Fe, Mn, and P. In addition, amorphous Fe (hydr)oxides were more efficient scavengers of dissolved As than the more crystalline forms of solid-phase Fe. Given that dissolved As in the surface bay water was lower than within the subterranean estuary, our results indicate that the distribution and type of Fe and Mn (hydr)oxides in coastal aquifers exert a major influence on the biogeochemical cycling of As in subterranean estuaries and, ultimately, the fate of groundwater-derived As in marine systems influenced by SGD.     

Noble gas excess air applied to distinguish groundwater recharge conditions

The application of geochemical tracers in groundwater studies can provide valuable insights into the rates and sources of groundwater recharge, residence times, and flow dynamics that are of significant value in the management of this important natural resource. This paper demonstrates the application of noble gas excess air to distinguish groundwater bodies with different recharge histories in a layered sandstone aquifer system in the east of England. The sampled groundwaters are all supersaturated with respect to neon, indicating the presence of excess air. The lowest excess air concentrations occur where the aquifer is unconfined (deltaNe, the proportion of neon in excess of saturation, = 12-26%) and recharge occurs directly to the outcrop. Groundwater in the confined part of the aquifer can be divided into two hydrochemical types based upon the dissolved ion chemistry: Type 1 groundwaters contain more excess air (deltaNe = 115-120%) than Type 2(deltaNe = 22-62%). The difference in excess air concentrations confirms that groundwater enters the confined aquifer along two discrete pathways. Furthermore, excess neon concentrations predicted from the magnitude of annual water table fluctuation observed in the different recharge areas are in good agreement with those measured in the corresponding groundwaters. We therefore recommend that excess air may be usefully employed as a direct indicator of the volume of long-term net annual groundwater recharge.     

Regional patterns in the isotopic composition of natural and anthropogenic nitrate in groundwater, High Plains, U.S.A

Mobilization of natural nitrate (NO3-) deposits in the subsoil by irrigation water in arid and semiarid regions has the potential to produce large groundwater NO3-concentrations. The use of isotopes to distinguish between natural and anthropogenic NO3- sources in these settings could be complicated by the wide range in delta15N values of natural NO3-. An approximately 10 000 year record of paleorecharge from the regionally extensive High Plains aquifer indicates that delta15N values for NO3- derived from natural sources ranged from 1.3 to 12.3 per thousand and increased systematically from the northern to the southern High Plains. This collective range in delta15N values spans the range that might be interpreted as evidence for fertilizer and animal-waste sources of NO3-; however, the delta15N values for NO3- in modern recharge (< 50 years) under irrigated fields were, for the most part, distinctly different from those of paleorecharge when viewed in the overall regional context. An inverse relation was observed between the delta15N[NO3-] values and the NO3-/Cl- ratios in paleorecharge that is qualitatively consistent with fractionating losses of N increasing from north to south in the High Plains. N and O isotope data for NO3- are consistent with both NH3 volatilization and denitrification, having contributed to fractionating losses of N prior to recharge. The relative importance of different isotope fractionating processes may be influenced by regional climate patterns as well as by local variation in soils, vegetation, topography, and moisture conditions.     

Linking groundwater discharge to severe estuarine acidification during a flood in a modified wetland

Periodic acidification of waterways adjacent to coastal acid sulfate soils (CASS) is a significant land and water management issue in the subtropics. In this study, we use 5-months of continuous radon ((222)Rn, a natural groundwater tracer) observations to link estuarine acidification to groundwater discharge in an Australian CASS catchment (Tuckean Swamp). The radon time series began in the dry season, when radon activities were low (2-3 dpm L(-1)), and the pH of surface water was 6.4. We captured a major rain event (213 mm on 2 March 2010) that flooded the catchment. An immediate drop in pH during the flood may be attributed to surface water interactions with soil products. During the post-flood stage, increased radon activities (up to 19.3 dpm L(-1)) and floodplain groundwater discharge rates (up to 2.01 m(3) s(-1), equivalent to 19% of total runoff) coincided with low pH (3.77). Another spike in radon activities (13.2 dpm L(-1)) coincided with the lowest recorded surface water pH (3.62) after 72 mm of rain between 17 and 20 April 2010. About 80% of catchment acid exports occurred when the estuary was dominated by groundwater discharging from highly permeable CASS during the flood recession.     

Has submarine groundwater discharge been overlooked as a source of mercury to coastal waters?

We measured the mercury (Hg) in groundwater, aquifer sediments, and surface water in Waquoit Bay (Massachusetts) and found that this toxic metal (range: <3.2-262 pM) was being released within the subterranean estuary, with similarly high levels (range: 18-256 pM) found in the surface waters of the bay. None of the dissolved species (DOC, chloride, and Fe) normally observed to influence Hg partitioning correlated well with the observed Hg concentrations. It was hypothesized that this was in part due to the variable loading in time and space of Hg onto the aquifer sands in combination with the seasonality of groundwater flow through the aquifer. Aquifer sediment samples from the study site ranged from <1 to 12.5 pmol of Hg/g of sediment, suggesting log Kd values on the order of 1. We hypothesize that this was due to the low organic carbon content typical of the aquifer sediments. Last, itwas estimated that submarine groundwater discharge supplied 0.47-1.9 nmol of Hg m(-2) day(-1) to the bay, which is an order of magnitude higher than the atmospheric deposition rate for the northeastern U.S.     

Assessing the impact of animal waste lagoon seepage on the geochemistry of an underlying shallow aquifer

Evidence of seepage from animal waste holding lagoons at a dairy facility in the San Joaquin Valley of California is assessed in the context of a process geochemical model that addresses reactions associated with the formation of the lagoon water as well as reactions occurring upon the mixture of lagoon water with underlying aquifer material. Comparison of model results with observed concentrations of NH4+, K+, PO4(3-), dissolved inorganic carbon, pH, Ca2+, Mg2+, SO4(2-), Cl-, and dissolved Ar in lagoon water samples and groundwater samples suggests three key geochemical processes: (i) off-gassing of significant quantities of CO2 and CH4 during mineralization of manure in the lagoon water, (ii) ion exchange reactions that remove K+ and NH4+ from seepage water as it migrates into the underlying anaerobic aquifer material, and (iii) mineral precipitation reactions involving phosphate and carbonate minerals in the lagoon water in response to an increase in pH as well as in the underlying aquifer from elevated Ca2+ and Mg2+ levels generated by ion exchange. Substantial off-gassing from the lagoons is further indicated by dissolved argon concentrations in lagoon water samples that are below atmospheric equilibrium. As such, Ar may serve as a unique tracer for lagoon water seepage since under-saturated Ar concentrations in groundwater are unlikely to be influenced by any processes other than mechanical mixing.     

Impacts of land use change on nitrogen cycling archived in semiarid unsaturated zone nitrate profiles, southern High Plains, Texas

Nitrate (NO3) profiles in semiarid unsaturated zones archive land use change (LUC) impacts on nitrogen (N) cycling with implications for agricultural N management and groundwater quality. This study quantified LUC impacts on NO3 inventories and fluxes by measuring NO3 profiles beneath natural and rainfed (nonirrigated) agricultural ecosystems in the southern High Plains (SHP). Inventories of NO3-N under natural ecosystems in the SHP normalized by profile depth are extremely low (2-10 kg NO3-N/ha/m), in contrast to those in many semiarid regions in the southwestern U.S. Many profiles beneath cropland (9 of 19 profiles) have inventories at depth that range from 28-580 kg NO3--N/ha/m (median 135 kg/ha/m) that correspond to initial cultivation, dated using soil water Cl. These inventories represent 74% (median) of the total inventories in these profiles. This NO3 most likely originated from cultivation causing mineralization and nitrification of soil organic nitrogen (SON) in old soil water (precultivation) and is attributed to enhanced microbial activity caused by increased soil wetness beneath cropland (median matric potential -42 m) relative to that beneath natural ecosystems (median -211 m). The SON source is supported by isotopes of NO3 (delta15N: +5.3 to +11.6; delta18O: +3.6 to +12.1). Limited data in South Australia suggest similar processes beneath cropland. Mobilization of the total inventories in these profiles caused by increased drainage/ recharge related to cultivation in the SHP could increase current NO3-N levels in the underlying Ogallala aquifer by an additional 2-26 mg/L (median 17 mg/L).     

Timing of riverine export of nitrate and phosphorus from agricultural watersheds in Illinois: implications for reducing nutrient loading to the Mississippi River

Agricultural watersheds in the upper Midwest are the major source of nutrients to the Mississippi River and Gulf of Mexico, but temporal patterns in nutrient export and the role of hydrology in controlling export remain unclear. Here we reporton NO3(-)-N, dissolved reactive phosphorus (DRP), and total P export from three watersheds in Illinois during the past 8-12 years. Our program of intensive, long-term monitoring allowed us to assess how nutrient export was distributed across the range of discharge that occurred at each site and to examine mechanistic differences between NO3(-)-N and DRP export from the watersheds. Last, we used simple simulations to evaluate how nutrient load reductions might affect NO3(-)-N and P export to the Mississippi River from the Illinois watersheds. Artificial drainage through under-field tiles was the primary mechanism for NO3(-)-N export from the watersheds. Tile drainage and overland flow contributed to DRP export, whereas export of particulate P was almost exclusively from overland flow. The analyses revealed that nearly all nutrient export occurred when discharge was > or = median discharge, and extreme discharges (> or = 90th percentile) were responsible for >50% of the NO3(-)-N export and >80% of the P export. Additionally, the export occurred annually during a period beginning in mid-January and continuing through June. These patterns characterized all sites, which spanned a 4-fold range in watershed area. The simulations showed that reducing in-stream nutrient loads by as much as 50% during periods of low discharge would not affect annual nutrient export from the watersheds.     

Perchlorate in pleistocene and holocene groundwater in north-central New Mexico

Groundwater from remote parts of the Middle Rio Grande Basin in north-central New Mexico has perchlorate (ClO4-) concentrations of 0.12-1.8 micro/L. Because the water samples are mostly preanthropogenic in age (0-28000 years) and there are no industrial sources in the study area, a natural source of the ClO4- is likely. Most of the samples have Br-, Cl-, and SO4(2-) concentrations that are similar to those of modern bulk atmospheric deposition with evapotranspiration (ET) factors of about 7-40. Most of the ET values for Pleistocene recharge were nearly twice that for Holocene recharge. The N03-/Cl- and CIO-/Cl-ratios are more variable than those of Br-/Cl- or S04(2-)/Cl-. Samples thought to have recharged under the most arid conditions in the Holocene have relatively high N03-/Cl- ratios and low delta 15N values (+1 per mil (% per thousand)) similar to those of modern bulk atmospheric N deposition. The delta 18O values of the N03- (-4 to 0% per thousand) indicate that atmospheric N03- was not transmitted directly to the groundwater but may have been cycled in the soils before infiltrating. Samples with nearly atmospheric N03-/CI- ratios have relatively high Cl04- concentrations (1.0-1.8 ug/L) with a nearly constant Cl04-/CI- mole ratio of (1.4 +/- 0.1) x 10(-4), which would be consistent with an average Cl04-concentration of 0.093 0.005 ,ug/L in bulk atmospheric deposition during the late Holocene in north-central NM. Samples thought to have recharged under wetter conditions have higher delta 15N values (+3 to +8 % per thousando), lower NO3-/Cl- ratios, and lower ClO4-/Cl- ratios than the ones most likely to preserve an atmospheric signal. Processes in the soils that may have depleted atmospherically derived NO3-also may have depleted ClO4- to varying degrees prior to recharge. If these interpretations are correct, then ClO4- concentrations of atmospheric origin as high as 4 microg/L are possible in preanthropogenic groundwater in parts of the Southwest where ET approaches a factor of 40. Higher Cl04- concentrations in uncontaminated groundwater could occur in recharge beneath arid areas where ET is greater than 40, where long-term accumulations of atmospheric salts are leached suddenly from dry soils, or where other (nonatmospheric) natural sources of ClO4- exist.     

Saturated zone denitrification: potential for natural attenuation of nitrate contamination in shallow groundwater under dairy operations

We present results from field studies at two central California dairies that demonstrate the prevalence of saturated-zone denitrification in shallow groundwater with 3H/ 3He apparent ages of < 35 years. Concentrated animal feeding operations are suspected to be major contributors of nitrate to groundwater, but saturated zone denitrification could mitigate their impact to groundwater quality. Denitrification is identified and quantified using N and O stable isotope compositions of nitrate coupled with measurements of excess N2 and residual NO3(-) concentrations. Nitrate in dairy groundwater from this study has delta15N values (4.3-61 per thousand), and delta18O values (-4.5-24.5 per thousand) that plot with delta18O/delta15N slopes of 0.47-0.66, consistent with denitrification. Noble gas mass spectrometry is used to quantify recharge temperature and excess air content. Dissolved N2 is found at concentrations well above those expected for equilibrium with air or incorporation of excess air, consistent with reduction of nitrate to N2. Fractionation factors for nitrogen and oxygen isotopes in nitrate appear to be highly variable at a dairy site where denitrification is found in a laterally extensive anoxic zone 5 m below the water table, and at a second dairy site where denitrification occurs near the water table and is strongly influenced by localized lagoon seepage.     

Use of strontium isotopes to identify buried water main leakage into groundwater in a highly urbanized coastal area

Previous studies indicate that the local aquifer systems in the Mid-Levels, a highly urbanized coastal area in Hong Kong, have commonly been affected by leakage from water mains. The identification of leakage locations was done by conventional water quality parameters including major and trace elements. However, these parameters may lead to ambiguous results and fail to identify leakage locations especially where the leakage is from drinking water mains because the chemical composition of drinking water is similar to that of natural groundwater. In this study, natural groundwater, seepage in the developed spaces, leakage from water mains, and parent aquifer materials were measured for strontium isotope (87Sr/86Sr) compositions to explore the feasibility of using these ratios to better constrain the seepage sources. The results show that the 87Sr/86Sr ratios of natural groundwater and leakage from water mains are distinctly different and thus, they can provide additional information on the sources of seepage in developed spaces. A classification system based on the aqueous 87Sr/86Sr ratio is proposed for seepage source identification.     

Long-term natural attenuation of carbon and nitrogen within a groundwater plume after removal of the treated wastewater source

Disposal of treated wastewater for more than 60 years onto infiltration beds on Cape Cod, Massachusetts produced a groundwater contaminant plume greater than 6 km long in a surficial sand and gravel aquifer. In December 1995 the wastewater disposal ceased. A long-term, continuous study was conducted to characterize the post-cessation attenuation of the plume from the source to 0.6 km downgradient. Concentrations and total pools of mobile constituents, such as boron and nitrate, steadily decreased within 1-4 years along the transect. Dissolved organic carbon loads also decreased, but to a lesser extent, particularly downgradient of the infiltration beds. After 4 years, concentrations and pools of carbon and nitrogen in groundwater were relatively constant with time and distance, but substantially elevated above background. The contaminant plume core remained anoxic for the entire 10-year study period; temporal patterns of integrated oxygen deficit decreased slowly at all sites. In 2004, substantial amounts of total dissolved carbon (7 mol C m(-2)) and fixed (dissolved plus sorbed) inorganic nitrogen (0.5 mol N m(-2)) were still present in a 28-m vertical interval at the disposal site. Sorbed constituents have contributed substantially to the dissolved carbon and nitrogen pools and are responsible for the long-term persistence of the contaminant plume. Natural aquifer restoration at the discharge location will take at least several decades, even though groundwater flow rates and the potential for contaminant flushing are relatively high.