Groundwater and pore water inputs to the coastal zone

Both terrestrial and marine forces drive underground fluid flows in the coastal zone. Hydraulic gradients on land result in groundwater seepage near shore and may contribute to flows further out on the shelf from confined aquifers. Marine processes such as tidal pumping and current-induced pressure gradients may induce interfacial fluid flow anywhere on the shelf where permeable sediments are present. The terrestrial and oceanic forces overlap spatially so measured fluid advection through coastal sediments may be a result of composite forcing. We thus define “submarine groundwater discharge” (SGD) as any and all flow of water on continental margins from the seabed to the coastal ocean, regardless of fluid composition or driving force. SGD is typically characterized by low specific flow rates that make detection and quantification difficult. However, because such flows occur over very large areas, the total flux is significant. Discharging fluids, whether derived from land or composed of re-circulated seawater, will react with sediment components. These reactions may increase substantially the concentrations of nutrients, carbon, and metals in the fluids. These fluids are thus a source of biogeochemically important constituents to the coastal ocean. Terrestrially-derived fluids represent a pathway for new material fluxes to the coastal zone. This may result in diffuse pollution in areas where contaminated groundwaters occur. This paper presents an historical context of SGD studies, defines the process in a form that is consistent with our current understanding of the driving forces as well as our assessment techniques, and reviews the estimated global fluxes and biogeochemical implications. We conclude that to fully characterize marine geochemical budgets, one must give due consideration to SGD. New methodologies, technologies, and modeling approaches are required to discriminate among the various forces that drive SGD and to evaluate these fluxes more precisely.     

Nitrogen inputs to a marine embayment: the importance of groundwater

We examined the importance of nitrogen inputs from groundwater and runoff in a small coastal marine cove on Cape Cod, MA, USA. We evaluated groundwater inputs by three different methods: a water budget, assuming discharge equals recharge; direct measurements of discharge using bell jars; and a budget of water and salt at the mouth of the Cove over several tidal cycles. The lowest estimates were obtained by using a water budget and the highest estimates were obtained using a budget of water and salt at the Cove mouth. Overall there was more than a five fold difference in the freshwater inputs calculated by using these methods. Nitrogen in groundwater appears to be largely derived from on site septic systems. Average nitrate concentrations were highest in the region where building density was greatest. Nitrate in groundwater appeared to behave conservatively in sandy sediments where groundwater flow rates were high (> 11/m²/h), indicating that denitrification was not substantially reducing external nitrogen loading to the Cove. Nitrogen inputs from groundwater were approximately 300 mmol-N/m³/y of Cove water. Road runoff contributed an additional 60 mmol/m³/y. Total nitrogen inputs from groundwater and road runoff to this cove were similar in magnitude to river dominated estuaries in urbanized areas in the United States.     

Nitrogen inputs to a marine embayment: the importance of groundwater

We examined the importance of nitrogen inputs from groundwater and runoff in a small coastal marine cove on Cape Cod, MA, USA. We evaluated groundwater inputs by three different methods: a water budget, assuming discharge equals recharge; direct measurements of discharge using bell jars; and a budget of water and salt at the mouth of the Cove over several tidal cycles. The lowest estimates were obtained by using a water budget and the highest estimates were obtained using a budget of water and salt at the Cove mouth. Overall there was more than a five fold difference in the freshwater inputs calculated by using these methods. Nitrogen in groundwater appears to be largely derived from on site septic systems. Average nitrate concentrations were highest in the region where building density was greatest. Nitrate in groundwater appeared to behave conservatively in sandy sediments where groundwater flow rates were high (> 11/m²/h), indicating that denitrification was not substantially reducing external nitrogen loading to the Cove. Nitrogen inputs from groundwater were approximately 300 mmol-N/m³/y of Cove water. Road runoff contributed an additional 60 mmol/m³/y. Total nitrogen inputs from groundwater and road runoff to this cove were similar in magnitude to river dominated estuaries in urbanized areas in the United States.     

Groundwater seepage stimulates the growth of aquatic macrophytes

1. The impact of groundwater seepage on the growth of submerged macrophytes was investigated in experiments on the isoetid Littorella uniflora and the elodeid Myriophyllum alterniflorum both in the laboratory and in the field. Isoetids rely mostly on sediment‐derived CO₂ and nutrients via root uptake, whereas elodeids acquire their inorganic carbon and nutrients from the water column. We thus hypothesised that L. uniflora would respond positively to seeping ground water as it should improve both CO₂ and nutrient supply. 2. Laboratory experiments were conducted by percolating vegetated cores containing natural sediment or technical sand with artificial ground water of high CO₂ concentrations and with either high or low levels of nutrients. Field experiments were conducted in the oligotrophic Lake Hampen, Denmark, with custom‐built seepage‐growth chambers that permitted a near‐natural flow‐through of seeping ground water. Chambers with a solid bottom, and thus no flow‐through of seeping ground water, served as controls in both laboratory and field experiments. In the field, seepage chambers were installed at a site with relatively high seepage fluxes (ground water from forest catchment), at a site with much lower seepage fluxes but with higher nutrient concentrations (ground water from agricultural catchment) and at a reference site with no net discharge or recharge of ground water. 3. Positive growth responses were observed in the field at transects with high groundwater discharge compared to the control chambers with no seepage. No growth response was observed at the reference transect with low or alternating direction of groundwater seepage. The growth rates of L. uniflora in the field were significantly higher in seepage treatments compared to control treatments, and final plant mass was up to 70% higher than that for plants where seepage was excluded. In areas with high groundwater discharge, a strong positive correlation was found between groundwater seepage fluxes, growth rates, and final plant mass for L. uniflora, while there was no such relationship at the reference transect. The growth of M. alterniflorum was also significantly affected by groundwater seepage, but to a lesser degree than L. uniflora. Laboratory experiments generally showed the same trend for both L. uniflora and M. alterniflorum, and the positive influence of seeping ground water was apparently related to increased inorganic carbon supply and, to a lesser degree, improved nutrient availability. 4. Groundwater discharge results in enhanced growth of isoetids and to some extent elodeids inhabiting a groundwater‐fed softwater lake. We propose that the shallow dense vegetation present where most of the discharge takes place acts as a biological filter that retains nutrients that otherwise would end up in the water column and could result in increased algal growth.     

Submarine groundwater discharge in Osaka Bay, Japan

Submarine groundwater discharge (SGD) rates in Osaka Bay were continuously measured and analyzed to evaluate seawater–groundwater interactions. Fast Fourier transfer and power spectrum density methods were applied to analyze the dominant periods of the SGD variations. Diurnal and semidiurnal periods of SGD variation were found, and they were caused by tidal effects. According to the separation of SGD into fresh and recirculated water components using automated seepage meter measurements and terrestrial groundwater flow analyses, the fresh groundwater component in SGD was evaluated to be in the range 4%–29% at Tannowa, Osaka. Therefore, SGD rates depend mainly on the volume of recirculated seawater. Correlation analyses between SGD and sea level show that SGD is delayed by 4h after sea level changes.     

Seepage rate variability in Florida Bay driven by Atlantic tidal height

Atlantic tidal fluctuations drive pressure head variations in shallow offshore wells drilled into the limestone subsurface on both the Florida Bay and Atlantic sides of Key Largo, Florida, USA. We tested the hypothesis that these pressure head variations influence groundwater flow and that flux rate variability is associated with tidal variability. We used an automated Rn monitor to make continuous measurements of ²²²Rn, a natural tracer of groundwater discharge, in Florida Bay waters. We also deployed three types of seepage meters, including an automated heat pulse meter to collect a continuous record of seepage from the sediments. Drum type seepage meters inserted into soft sediments and fiberglass meters cemented to the rocky bay floor were utilized with pre-filled 4-l bag collectors, and monitored on an hourly basis. Maximum Rn inventories in Florida Bay waters were associated with high tide on the Atlantic side of the island. Modeling of the Rn variation indicated variable groundwater discharge rates with maximum flux occurring at high Atlantic tide. Seepage meter results in Florida Bay were consistent with ²²²Rn modeling. Florida Bay seepage meter rates showed positive correlation with Atlantic tide, meter 1, r?=?0.63, n?=?12, p?<?0.025 and meter 2, r?=?0.67, n?=?12, p?<?0.025. A seepage meter offshore of the Atlantic side of Key Largo exhibited rates that were inversely correlated with Atlantic tide (r?=?0.87, n?=?9, p?<?0.005) showing negative rates when the tide was high, and positive rates when the tide was low. Overall, our results are consistent with the hypothesis of Reich et al. (2002), that pressure head variations driven by Atlantic tide influence groundwater seepage rate variability in Florida Bay off Key Largo. Effectively, as proposed by Reich et al. (2002), Key Largo functions as a semi-permeable dam separating Florida Bay and the Atlantic Ocean.     

Trypanosoma cruzi: Immunological predictors of benznidazole efficacy during experimental infection

C3H/HeN male mice were infected with a lethal population of Trypanosoma cruzi and treated with benznidazole (Bz). Parasitemia, body weight and survival rate were registered during the therapy with significant improvement for T. cruzi-infected Bz-treated animals. Besides, flow cytometry resulted a useful method to discriminate between cured animals from those not cured by monitoring IgG₁ bound to live trypomastigotes levels. At the end of Bz therapy, the LT splenocyte compartment was studied for activation/memory cell surface markers ( and ). Cytofluorometric analysis showed that T. cruzi-infected untreated mice increased their activated LT numbers and this effect was completely abolished only in cured mice at the end of Bz administration. The same behavior was observed for the memory LT subpopulation correlating to an effector memory () displayed by T. cruzi infection. Bz treatment was able to modulate the immunological response by reducing the deleterious effect of the acute phase in all T. cruzi-infected mice.     

Biogeochemical Processes of Methane Cycle in the Soils,Bogs, and Lakes of Western Siberia

The biogeochemical processes of methane production and oxidation were studied in the upper horizons of tundra and taiga soils and raised bogs and lake bottom sediments near the Tarko-Sale gas field in western Siberia. Both in dry and water-logged soils, the total methane concentration (in soil particles and gaseous phase) was an order of magnitude higher than in the soil gaseous phase alone (22 and 1.1 nl/cm³, respectively). In bogs and lake bottom sediments methane concentration was as high as 11 l/cm³. Acetate was the major precursor of the newly formed methane. The rate of aceticlastic methanogenesis reached 55 ng C/(cm³day), whereas that of autotrophic methanogenesis was an order of magnitude lower. The most active methane production and oxidation were observed in bogs and lake sediments, where the ¹³C values of CO₂were inversely related to the intensity of bacterial methane oxidation. Methane diffusing from bogs and lake bottom sediments showed ¹³C values ranging from –78 to –47, whereas the ¹³C value of carbon dioxide ranged from –18 to –1. In these ecosystems, methane emission comprised from 3 to 206 mg CH₄/(m²day). Conversely, the dry and water-logged soils of the tundra and taiga took up atmospheric methane at a rate varying from 0.3 to 5.3 mg CH₄/(m²day). Methane consumption in soils was of biological nature. This was confirmed by the radioisotopic method and chamber experiments, in which weighting of methane carbon was observed (the ¹³C value changed from –51 to –41).     

Kinetic studies of the reduction of hexaaquacobalt(III) perchlorate by a cobaloxime, [Co(dmgBF2)2(H2O)2]

The reaction of with Co(dmgBF₂)₂(H₂O)₂ in 1.0 M HClO₄/LiClO₄ was found to be first-order in both reactants and the [H⁺] dependence of the second-order rate constant is given by k_2obs = b/[H⁺], b at 25 °C is 9.23 ± 0.14 × 10² s⁻¹. The [H⁺] dependence at lower temperatures shows some saturation effect that allowed an estimate of the hydrolysis constant for as K_a = 9.5 × 10⁻³ M at 10 and 15 °C. Marcus theory and the known self-exchange rate constant for Co(OH₂)₅OH^2+/+ were used to estimate an electron self-exchange rate constant of k₂₂ = 1.7 × 10⁻⁴ M⁻¹ s⁻¹ for .     

Methane emissions from an Amazon floodplain lake: Enhanced release during episodic mixing and during falling water

Soil respiration rates vary significantly among major plant biomes, suggesting that vegetation type influences the rate of soil respiration. However, correlations among climatic factors, vegetation distributions, and soil respiration rates make cause-effect arguments difficult. Vegetation may affect soil respiration by influencing soil microclimate and structure, the quantity of detritus supplied to the soil, the quality of that detritus, and the overall rate of root respiration. At the global scale, soil respiration rates correlate positively with litterfall rates in forests, as previously reported, and with aboveground net primary productivity in grasslands, providing evidence of the importance of detritus supply. To determine the direction and magnitude of the effect of vegetation type on soil respiration, we collated data from published studies where soil respiration rates were measured simultaneously in two or more plant communities. We found no predictable differences in soil respiration between cropped and vegetation-free soils, between forested and cropped soils, or between grassland and cropped soils, possibly due to the diversity of crops and cropping systems included. Factors such as temperature, moisture availability, and substrate properties that simultaneously influence the production and consumption of organic matter are more important in controlling the overall rate of soil respiration than is vegetation type in most cases. However, coniferous forests had 10% lower rates of soil respiration than did adjacent broad-leaved forests growing on the same soil type, and grasslands had, on average, 20% higher soil respiration rates than did comparable forest stands, demonstrating that vegetation type does in some cases significantly affect rates of soil respiration.     

Evaluations of groundwater discharge rates from subsurface temperature in Cockburn Sound, Western Australia

Groundwater discharge rates were estimated from borehole groundwater temperature and pore water temperature under the seabed to be 0.92–3.6?cm/day in Cockburn Sound, Western Australia. Automated and manual seepage meters measured larger groundwater discharge rates of 13.7–16.3?cm/day. This difference may be because the observed seepage rates measured by seepage meters include not only terrestrial fresh groundwater discharge but also recirculated salt water. On the other hand, the discharge rates estimated from subsurface temperature may consist of only terrestrial fresh groundwater discharge.     

Losses of inorganic carbon and nitrous oxide from a temperate freshwater wetland in relation to nitrate loading

We studied the export of inorganic carbon and nitrous oxide (N₂O) from a Danish freshwater wetland. The wetland is situated in an agricultural catchment area and is recharged by groundwater enriched with nitrate (NO₃ ^–) (1000 M). NO₃ ^– in recharging groundwater was reduced (57.5 mol NO₃ ^– m^–2 yr^–) within a narrow zone of the wetland. Congruently, the annual efflux of carbon dioxide (CO₂) from the sediment was 19.1 mol C m^–2 when estimated from monthly in situ measurements. In comparison the CO₂ efflux was 4.8 mol C m^–2 yr^–1 further out in the wetland, where no NO₃ ^– reduction occurred. Annual exports of inorganic carbon in groundwater and surface water was 78.4 mol C m^–2 and 6.1 mol C m^–2 at the two sites, respectively. N₂O efflux from the sedimenst was detectable on five out of twelve sampling dates and was significantly (P < 0.0001) higher in the NO₃ ^– reduction zone (0.35–9.40 mol m^–2 h^–1, range of monthly means) than in the zone without NO₃ ^– reduction (0.21–0.41 mol m^–2 h^–1). No loss of dissolved N₂O could be measured. Total annual export of N₂O was not estimated. The reduction of oxygen (O₂) in groundwater was minor throughout the wetland and did not exceed 0.2 mol 0₂ m^–2yr^–1. Sulfate (SO₄ ^––) was reduced in groundwater (2.1 mol SO₄ ^–– m^–2 yr^–1) in the zone without NO₃ ^– reduction. Although the NO₃ ^– in our wetland can be reduced along several pathways our results strongly suggest that NO₃ ^– loading of freshwater wetlands disturb the carbon balance of such areas, resulting in an accelerated loss of inorganic carbon in gaseous and dissolved forms.     

The Measurement of Groundwater Discharge into a Lake by a Direct Method

An apparatus is described which allows groundwater discharge through lake beds to be measured directly. On transects at right angles to-the shore-line of Lake Taupo, New Zealand, discharges Mere found to decrease rapidly with distance from the shore. The potential use of this technique in the construction of nutrient budgets for lakes is outlined.     

Brown Tide blooms in Long Island's coastal waters linked to interannual variability in groundwater flow

There has been a widespread increase in the reporting of harmful and ‘nuisance’ algal blooms in the coastal ocean over the past few decades. On the global scale this is suspected to be a consequence of coastal eutrophication, however, on a case-by-case basis there is usually insufficient evidence to discriminate between the effects of human and natural causal factors. Intense blooms of the ‘Brown Tide’ unicellular algae (Aureococcus anophagefferens) have occurred sporadically since 1985 in coastal waters of Eastern Long Island and have devastated the local commercial scallop fishery. Analysis of an 11-year time-series dataset from this region indicates that bloom intensity is correlated with higher salinities and inversely correlated with the discharge of groundwater. Laboratory and field studies suggest that whereas salinity is unlikely to represent a direct physiological control on Brown Tide blooms, the addition of inorganic nitrogen tends to inhibit Brown Tide blooms. Budget calculations indicate that the inorganic nitrogen supply from groundwater is 1–2 orders of magnitude higher than any other external source of nitrogen for this ecosystem. Biweekly time series data collected in 1995 demonstrate that Brown Tide blooms utilize dissolved organic nitrogen (DON) for growth, as evidenced by a large decrease in DON parallel with an increase in cell abundance. On an interannual basis, bloom intensity was also positively correlated with mean DON concentrations. We hypothesize that bloom initiation is regulated by the relative supply of inorganic and organic nitrogen, determined to a large extent by temporal variability in groundwater flow. The 1980s and 1990s were characterized by exceptionally high and interannually variable groundwater discharge, associated with a large-scale climate shift over the North Atlantic. This, coupled with the time-lagged discharge of groundwater with high nitrate concentrations resulting from increased fertilizer use and population increase during the 1960s and 1970s, may have been a key factor in the initiation of Brown Tide blooms in 1985.     

Dinitrogen fixation in the world's oceans

The surface water of themarine environment has traditionally beenviewed as a nitrogen (N) limited habitat, andthis has guided the development of conceptualbiogeochemical models focusing largely on thereservoir of nitrate as the critical source ofN to sustain primary productivity. However,selected groups of Bacteria, includingcyanobacteria, and Archaea canutilize dinitrogen (N₂) as an alternativeN source. In the marine environment, thesemicroorganisms can have profound effects on netcommunity production processes and can impactthe coupling of C-N-P cycles as well as the netoceanic sequestration of atmospheric carbondioxide. As one component of an integrated Nitrogen Transport and Transformations project, we have begun to re-assess ourunderstanding of (1) the biotic sources andrates of N₂ fixation in the world'soceans, (2) the major controls on rates ofoceanic N₂ fixation, (3) the significanceof this N₂ fixation for the global carboncycle and (4) the role of human activities inthe alteration of oceanic N₂ fixation. Preliminary results indicate that rates ofN₂ fixation, especially in subtropical andtropical open ocean habitats, have a major rolein the global marine N budget. Iron (Fe)bioavailability appears to be an importantcontrol and is, therefore, critical inextrapolation to global rates of N₂fixation. Anthropogenic perturbations mayalter N₂ fixation in coastal environmentsthrough habitat destruction and eutrophication,and open ocean N₂ fixation may be enhancedby warming and increased stratification of theupper water column. Global anthropogenic andclimatic changes may also affect N₂fixation rates, for example by altering dustinputs (i.e. Fe) or by expansion ofsubtropical boundaries. Some recent estimatesof global ocean N₂ fixation are in therange of 100–200 Tg N (1–2 × 10¹⁴ g N)yr^–1, but have large uncertainties. Theseestimates are nearly an order of magnitudegreater than historical, pre-1980 estimates,but approach modern estimates of oceanicdenitrification.     

Effect of magnesium chloride (2:1 electrolyte) on the aqueous solution behavior of some saccharides over the temperature range of 288.15-318.15 K: a volumetric approach

Infinite-dilution standard partial molar volumes, , for various mono-, di-, and trisaccharides, and their derivatives (methyl glycosides) at molalities ranging from 0.04 to 0.12 mol kg⁻¹ in aqueous solutions of magnesium chloride of 0.5, 1.0, 2.0, and 3.0 mol kg⁻¹, have been evaluated over a range of temperatures from 288.15 to 318.15 K by density measurements employing a vibrating-tube densimeter. These data have been utilized to determine the corresponding standard partial molar volumes of transfer, , of saccharides and methyl glycosides from water to aqueous magnesium chloride solutions. The values have been found to be positive, and their magnitudes increase with an increasing concentration of magnesium chloride in all cases. Partial molar expansion coefficients, and second derivatives thereof, have been estimated. The magnitude of values increases with an increase in temperature, indicating that hydration effects in solutions are strongly sensitive to temperature. Pair and higher order volumetric interaction coefficients (V_AB, V_ABB) have also been obtained from values by using the McMillan-Mayer theory. The various parameters have been discussed in terms of the solute (saccharide or methyl glycoside)-co-solute (magnesium chloride) interactions and are thus used to understand the mixing effects due to these interactions. These results have been compared with those earlier reported in the presence of electrolytes. An attempt is made to interpret the volumetric properties data in terms of the stereochemistry of the solutes.     

Denitrification in a seashore sandy deposit influenced by groundwater discharge

The chemical compositions of ground water and organic matter in sediments were investigated at a sandy shore of Tokyo Bay, Japan to determine the fate of ground water NO₃ ^–. On the basis of Cl^– distribution in ground water, the beach was classified into freshwater (FR)-, transition (TR)-, and seawater (SW)-zones from the land toward the shoreline. The NO₃ ^– and N₂O did not behave conservatively with respect to Cl^– during subsurface mixing of freshwater and seawater, suggesting NO₃ ^– consumption and N₂O production in the TR-zone. Absence of beach vegetation indicated that NO₃ ^– assimilation by higher plants was not as important as NO₃ ^– sink. Low NH₄ ⁺ concentrations in ground water revealed little reduction of NO₃ ^– to NH₄ ⁺. These facts implied that microbial denitrification and assimilation were the likely sinks for ground water NO₃ ^–. The potential activity and number of denitrifiers in water-saturated sediment were highest in the low-chlorinity part of the TR-zone. The location of the highest potential denitrification activity (DN-zone) overlapped with that of the highest NO₃ ^– concentration. The C/N ratio and carbon isotope ratio (¹³C) of organic matter in sediment (< 100 -m) varied from 12.0 to 22.5 and from –22.5 to –25.5, respectively. The ¹³C value was inversely related to the C/N ratio (r ² = 0.968, n = 11), which was explained by the mixing of organic matters of terrestrial and marine origins. In the DN-zone, the fine sediments were rich in organic matters with high C/N ratios and low ¹³C values, implying that dissolved organic matters of terrestrial origin might have been immobilized under slightly saline conditions. A concurrent supply of NO₃ ^– and organic matter to the TR-zone by ground water discharge probably generates favorable conditions for denitrifiers. Ground water NO₃ ^– discharged to the beach is thus partially denitrified and fixed as microbial biomass before it enters the sea. Further studies are necessary to determine the relative contribution of these processes for NO₃ ^– removal.