Dissolved and particulate organic carbon in the North Inlet estuary,South Carolina: What controls their concentrations?

Water samples have been taken daily at 1030 EST from three locations within North Inlet (South Carolina) since June of 1980 in order to evaluate the tidal, seasonal, and eventually annual variability in carbon concentrations within this system and generate hypotheses explaining the observed trends. Dissolved organic carbon (DOC) concentrations within North Inlet (South Carolina) vary inversely with salinity (r²=0.65), suggesting the main source of DOC in North Inlet is freshwater entering from the adjacent forested watershed. This assertion is supported by an observed decrease of tidal water salinity with the onset of streamflow. DOC variability is also associated with (1) groundwater advection and/or runoff and seepage from the marsh surface; (2) removal from tidal water via either physical sorption or biological uptake; (3) sampling location; and (4) origin of water mass. Particulate organic carbon (POC) concentrations vary seasonally, higher values found during the summer. POC variability is controlled by a series of physical and biological factors. Evidence suggests that in the smaller tidal creeks, POC concentrations are associated with (1) rain events scouring the marsh surface, (2) phytoplankton concentrations varying as a function of tidal stage, and (3) removal of particulate material from the marsh surface on the ebb tide. In the larger tidal creeks tidal water velocity appears to be the main factor influencing POC values.     

The Mobility of Rare Earth Elements and Redox Sensitive Elements in the Groundwater/Seawater Mixing Zone of a Shallow Coastal Aquifer

The concentrations of Rare Earth Elements (REE) and Redox Sensitive Elements (RSE) were measured in groundwaters along a transect of the forest-marsh interface of a surficial aquifer system in North Inlet, SC. The well transect extended from a forest recharge area across the marsh and tidal creek to a tidal recharge area of beach ridge. The concentrations of the RSE (Fe, Mn, and U) were consistent with reducing conditions through the transect. Fe was present at concentrations ranging from a few micromolar to greater than one hundred micromolar in most wells. U was depleted with respect to salinity predicted concentrations, indicating removal with respect to the seawater endmember. Dissolved Mn concentrations were generally low in all wells, indicating no significant solid source of Mn (as MnOx) in this system. When extrapolated to a global scale, estimates of U removal during seawater exchange with the aquifer solids equaled 10–20% of the total riverine dissolved U input flux. REE concentrations in the forest recharge area were high in shallow wells, and showed a light enriched fractionation pattern, characteristic of soil leaching by Natural Organic Matter (NOM) rich waters. A decrease in REE concentration with depth in the forest wells coupled with a trend towards Heavy REE (HREE) enriched fractionation pattern indicated removal of the REE coincident with NOM and Dissolved Organic Carbon (DOC) removal. The saline waters of the beach ridge wells show a Light REE (LREE) enriched fractionation pattern and have the highest overall concentrations of the REE, indicating a significant REE source to the seawater endmember waters. The concentration gradients along the beach ridge flow path indicate a large source in the deep wells, and net export of dissolved REE to the tidal creek system and the coastal ocean. Ultrafiltration experiments indicate a transition from a colloidal dominated reservoir for the REE in the forest wells to a colloidal and dissolved reservoir in the beach ridge wells. The ultrafiltration data coupled with a correlation with Dissolved Inorganic Carbon (DIC) release suggest that there is diagenetic mobilization of an REE rich organic carbon phase in the saline endmember wells. We suggest here that degradation of this relic terrestrial organic carbon and REE rich phase results in the export of dissolved REE equal to or exceeding river inputs in this region.     

Flow,stress and sediment resuspension in a shallow tidal channel

In October of 2004, a 3-d observational program to measure flow and sediment resuspension within a coastal intertidal salt marsh was conducted in the North Inlet/Winyah Bay National Estuarine Research Reserve located near Georgetown, South Carolina. Current and acoustic backscatter profiles were obtained from a moored acoustic Doppler current profiler (ADCP) deployed in a shallow tidal channel during the spring phase of the tidal cycle under high discharge conditions. The channel serves as a conduit between Winyah Bay, a large brackish estuary, and North Inlet, a saline intertidal coastal salt marsh with little freshwater input. Salinity measurements indicate that the water column is vertically well mixed during flood, but becomes vertically stratified during early ebb. The stratification results from brackish (15 psu) Winyah Bay water entering North Inlet via the tidal channel, suggesting an exchange mechanism that permits North Inlet to receive a fraction of the poor water quality and high discharge flow from upland rivers. Although maximum flood currents exceed maximum ebb currents by 0.2 m s⁻¹, suspended sediment concentrations are highest during the latter ebb phase and persist for a longer fraction of the ebb cycle. Even though the channel is flood-dominated, the higher concentrations occurring over a longer fraction of the ebb phase indicate net particulate transport from Winyah Bay to North Inlet during spring tide accompanied by high discharge. Our evidence suggests that the higher concentrations during ebb result from increased bed friction caused by flow asymmetries and variations in water depth in which the highest stresses occur near the end of ebb near low water despite stronger maximum currents during flood.     

Denitrification capacity in a subterranean estuary below a Rhode Island fringing salt marsh

Coastal waters are severely threatened by nitrogen (N) loading from direct groundwater discharge. The subterranean estuary, the mixing zone of fresh groundwater and sea water in a coastal aquifer, has a high potential to remove substantial N. A network of piezometers was used to characterize the denitrification capacity and groundwater flow paths in the subterranean estuary below a Rhode Island fringing salt marsh.¹⁵N-enriched nitrate was injected into the subterranean estuary (in situ push-pull method) to evaluate the denitrification capacity of the saturated zone at multiple depths (125–300 cm) below different zones (upland-marsh transition zone, high marsh, and low marsh). From the upland to low marsh, the water table became shallower, groundwater dissolved oxygen decreased, and groundwater pH, soil organic carbon, and total root biomass increased. As groundwater approached the high and low marsh, the hydraulic gradient increased and deep groundwater upwelled. In the warm season (groundwater temperature >12 °C), elevated groundwater denitrification capacity within each zone was observed. The warm season low marsh groundwater denitrification capacity was significantly higher than all other zones and depths. In the cool season (groundwater temperature <10.5 °C), elevated groundwater denitrification capacity was only found in the low marsh. Additions of dissolved organic carbon did not alter groundwater denitrification capacity suggesting that an alternative electron donor, possibly transported by tidal inundation from the root zone, may be limiting. Combining flow paths with denitrification capacity and saturated porewater residence time, we estimated that as much as 29–60 mg N could be removed from 11 of water flowing through the subterranean estuary below the low marsh, arguing for the significance of subterranean estuaries in annual watershed scale N budgets.     

Groundwater in-situ generation of aquatic humic and fulvic acids and the mineralization of sedimentary organic carbon

In this paper the groundwater in-situ generation of dissolved organic carbon (DOC) is discussed based on the origin of groundwaters, their physico-chemical and isotopic properties, chemical composition and the dissolved inorganic carbon (DIC) concentration and its ¹³C content. Three aquifer systems are investigated. Two of these have relatively well defined hydrological and geochemical conditions (Fuhrberg and Munich) and are used as reference systems. The third aquifer (Gorleben) is a complex system containing DOC concentrations up to 200 mg C/L in deep groundwaters. From this aquifer system 19 groundwaters from different hydrogeochemical conditions are analyzed. The in-situ generation of DOC is found to occur in conjunction with the microbiologically mediated mineralization of sedimentary organic carbon (SOC). Thereby, SO₄ is reduced and phosphate is released into the groundwater. Where SO₄ is depleted, the mineralization of SOC occurs via fermentation, resulting in CH₄ generation.     

The geochemistry of dissolved inorganic carbon in a surficial groundwater aquifer in North Inlet, South Carolina, and the carbon fluxes to the coastal ocean

We report measurements of pH, total dissolved inorganic carbon (DIC), total or titration alkalinity (TAlk), Ca²⁺, Mg²⁺, sulfate, and sulfide data at the seawater-freshwater interface in a shallow groundwater aquifer in North Inlet, South Carolina. These measurements and a diagenetic modeling analysis indicate that the groundwaters at North Inlet are mixtures of seawater and freshwater end-members and are seriously modified by carbon dioxide inputs from organic carbon degradation via SO₄²⁻ reduction across the entire salinity range and fermentation and CaCO₃ dissolution in the low-salinity region. DIC and TAlk are several times higher than the theoretical dilution line, whereas Ca²⁺ is slightly higher and SO₄²⁻ is somewhat lower than the dilution line. Partial pressure of CO₂ in the groundwater is extremely high (0.05 to 0.12 atm). These deviations are consistent with theoretical predictions from known diagenetic reactions. Estimated groundwater DIC fluxes to the South Atlantic Bight from either the surficial aquifer (via salt marshes) or the Upper Floridan Aquifer (direct input) are significant when compared to riverine flux in this area.     

The removal kinetics of dissolved organic matter and the optical clarity of groundwater

Concentrations of dissolved organic matter (DOM) and ultraviolet/visible light absorbance decrease systematically as groundwater moves through the unsaturated zones overlying aquifers and along flowpaths within aquifers. These changes occur over distances of tens of meters (m) implying rapid removal kinetics of the chromophoric DOM that imparts color to groundwater. A one-compartment input-output model was used to derive a differential equation describing the removal of DOM from the dissolved phase due to the combined effects of biodegradation and sorption. The general solution to the equation was parameterized using a 2-year record of dissolved organic carbon (DOC) concentration changes in groundwater at a long-term observation well. Estimated rates of DOC loss were rapid and ranged from 0.093 to 0.21 micromoles per liter per day (μM d^?1), and rate constants for DOC removal ranged from 0.0021 to 0.011 per day (d^?1). Applying these removal rate constants to an advective-dispersion model illustrates substantial depletion of DOC over flow-path distances of 200 m or less and in timeframes of 2 years or less. These results explain the low to moderate DOC concentrations (20–75 μM; 0.26–1 mg L^?1) and ultraviolet absorption coefficient values (a ₂₅₄?<?5 m^?1) observed in groundwater produced from 59 wells tapping eight different aquifer systems of the United States. The nearly uniform optical clarity of groundwater, therefore, results from similarly rapid DOM-removal kinetics exhibited by geologically and hydrologically dissimilar aquifers.     

Chemistry and transport of soluble humic substances in forested watersheds of the Adirondack Park,New York

Studies were conducted in conjunction with the Integrated Lake-Watershed Acidification Study (ILWAS) to examine the chemistry and leaching patterns of soluble humic substances in forested watersheds of the Adirondack region. During the summer growing season, mean dissolved organic carbon (DOC) concentrations in the ILWAS watersheds ranged from 21–32 mg C l^?1 in O/A horizon leachates, from 5–7 mg C l^?1 in B horizon leachates, from 2–4 mg C l^?1 in groundwater solutions, from 6–8 mg C l^?1 in first order streams, from 3–8 mg C l^?1 in lake inlets, and from 2–7 mg C l^?1 in lake outlets. During the winter, mean DOC concentrations dropped significantly in the upper soil profile. Soil solutions from mixed and coniferous stands contained as much as twice the DOC concentration of lysimeter samples from hardwood stands. Results of DOC fractionation analysis showed that hydrophobia and hydrophilic acids dominate the organic solute composition of natural waters in these watersheds. Charge balance and titration results indicated that the general acid-base characteristics of the dissolved humic mixture in these natural waters can be accounted for by a model organic acid having an average_pK_a of 3.85, an average charge density of 4–5 μeq mg^?1 C at ambient pH, and a total of 6–7 meq COOH per gram carbon.     

Nitrogen pools in Georgia coastal waters

The amount of nitrogen present as ammonia, nitrate, nitrite, dissolved organic nitrogen, and particulate nitrogen was determined for nearshore Georgia shelf waters and for tidal water inundating a 0.5 hectare dikedSpartina alterniflora salt marsh in the adjacent estuary. Concentrations of ammonia, nitrate, and nitrite were comparatively low in offshore water (<2.2 μg-at N/1), and in high tide water in the marsh (<9.9 μg-at N/1). High concentrations of ammonia, up to 73.4 μg-at N/1, were measured in low tide water draining from marsh. The largest pools of nitrogen in offshore water and in high tide water in the marsh creek were dissolved organic nitrogen (DON) (2.5 to 20.4 μg-at N/1) and particulate nitrogen (PN) (0.1 to 30.0 μg-at N/1). Concentrations in marsh creek water at low tide were higher, ranging from 4.4 to 38.0 μg-at N/1 for DON and from 13.0 to 239.0 μg-at N/1 for PN. Comparisons of the average concentrations of dissolved and particulate forms of nitrogen in the marsh tidal creek during flood and during ebb tide suggested no net movement of the inorganic nitrogen nutrients, a net influx of PN to the marsh, and a net outflux of DON from the marsh.     

Dissolved organic carbon and methane in a regional confined aquifer,southern Ontario,Canada: Carbon isotope evidence for associated subsurface sources

Information regarding the origin, composition and transport of natural dissolved organic carbon (DOC) in groundwater is necessary to understand the transport of metals and organic pollutants, as well as for the use of¹⁴C in DOC as an isotopic groundwater dating method. Previous research in several groundwater systems has suggested soil organic C is the predominant source of high molecular weight DOC to the subsurface. Through the use of stable isotopes,¹⁴C and geochemical analyses, this study shows that significant concentrations of DOC and CH₄ in a regional confined aquifer can be generated in situ from subsurface sedimentary organic sources. The DOC and CH₄ produced is a combined result of degradation of buried peats and bacterial action, resulting in high DOC concentrations and strongly methanogenic conditions in the aquifer. The DOC and CH₄ comprise, on average, nearly 50% of the total dissolved C pool in the central part of the aquifer. Methanogenic conditions complicate isotopic groundwater dating by the conventional dissolved inorganic carbon (DIC) method. Estimates of isotopic groundwater residence time using DOC¹⁴C data are proposed by the application of¹⁴C isotope and mass balance corrections.     

Nekton Use of Flooded Salt Marsh and an Assessment of Intertidal Creek Pools as Low-Tide Refuges

Patterns of nekton occurrence on the salt marsh surface at high tide and in an adjacent intertidal creek pool at low tide were used to investigate movements of nekton in an intertidal basin. Paired collections were made in North Inlet estuary, SC on 67 dates over 9 years. Comparisons of high- and low-tide total abundance indicated that what remained in the creek pool at low tide was representative of the nekton on the flooded marsh. Of the 64 taxa collected, the same 8 species ranked in the top 10 in both the high- and low-tide collections. Abundances of most resident species were positively correlated with the area of marsh flooded, but mummichog (Fundulus heteroclitus), the most abundant resident, was not. Abundances of young-of-the-year transient species were not related to the extent of tidal flooding. Some transient species used the flooded marsh but did not occupy the pool at low tide, and others found in the pool did not use the marsh. Differences in abundance, biomass, and length between the marsh and pool collections indicated differences in the tendency of species and life stages to retreat downstream of the pool to the subtidal channel. Proportionately more of the nekton that were present on the flooded marsh left the intertidal basin when large changes in temperature and salinity occurred between high and low tides. More transients left the basin following higher tides, but more residents did not. The results demonstrate a wide range of taxonomic and ontogenetic patterns among nekton using intertidal salt marsh basins and the underappreciated importance of intertidal creek pools as alternative low-tide refuges.     

Spatial and temporal dynamics of epiphytic microalgae on the cordgrassSpartina alterniflora in North Inlet Estuary, South Carolina

Epiphytic microbial biomass (as chlorophylla) was measured monthly in North Inlet Estuary, South Carolina, for 16 months on spatially distinct stem sections (bottom and middle) of dead and livingSpartina alterniflora growth forms (tall, medium, and short) exposed at low tide. The highest biomass was located on the bottom section of tall plants, presumably due to their relatively longer contact with creek water and associated phytoplankton, and their closer proximity to marsh sediments with associated benthic microalgae, both recruitment sources for epiphytes. Dead plants left standing from the previous year’s growth cycle had higher epiphytic biomass than living plants, which occurred mostly in late spring through fall. Epiphytic biomass was highest in the winter (mean of 1.77 mg chla (m² marsh)⁻¹) and lowest in the summer (mean of 0.34 mg chla (m² marsh)⁻¹). Because phytoplankton andSpartina production are lowest in the winter, the results emphasize the relative importance of epiphytes to growth of herbivores in this season.     

Sources of salinity and arsenic in groundwater in southwest Bangladesh

Background

High salinity and arsenic (As) concentrations in groundwater are widespread problems in the tidal deltaplain of southwest Bangladesh. To identify the sources of dissolved salts and As, groundwater samples from the regional shallow Holocene aquifer were collected from tubewells during the dry (May) and wet (October) seasons in 2012–2013. Thirteen drill cores were logged and 27 radiocarbon ages measured on wood fragments to characterize subsurface stratigraphy.

Results

Drill cuttings, exposures in pits and regional studies reveal a >5 m thick surface mud cap overlying a ~30 m thick upper unit of interbedded mud and fine sand layers, and a coarser lower unit up to 60 m thick dominated by clean sands, all with significant horizontal variation in bed continuity and thickness. This thick lower unit accreted at rates of ~2 cm/year through the early Holocene, with local subsidence or compaction rates of 1–3 mm/year. Most tubewells are screened at depths of 15–52 m in sediments deposited 8000–9000 YBP. Compositions of groundwater samples from tubewells show high spatial variability, suggesting limited mixing and low and spatially variable recharge rates and flow velocities. Groundwaters are Na–Cl type and predominantly sulfate-reducing, with specific conductivity (SpC) from 3 to 29 mS/cm, high dissolved organic carbon (DOC) 11–57 mg/L and As 2–258 ug/L, and low sulfur (S) 2–33 mg/L.

Conclusions

Groundwater compositions can be explained by burial of tidal channel water and subsequent reaction with dissolved organic matter, resulting in anoxia, hydrous ferric oxide (HFO) reduction, As mobilization, and sulfate (SO₄) reduction and removal in the shallow aquifer. Introduction of labile organic carbon in the wet season as rice paddy fertilizer may also cause HFO reduction and As mobilization. Variable modern recharge occurred in areas where the clay cap pinches out or is breached by tidal channels, which would explain previously measured ¹⁴C groundwater ages being less than depositional ages. Of samples collected from the shallow aquifer, Bangladesh Government guidelines are exceeded in 46 % for As and 100 % for salinity.

     

Spatial Distribution of Dissolved Radon in the Choptank River and Its Tributaries: Implications for Groundwater Discharge and Nitrate Inputs

The Choptank River, Chesapeake Bay’s largest eastern-shore tributary, is experiencing increasing nutrient loading and eutrophication. Productivity in the Choptank is predominantly nitrogen-limited, and most nitrogen inputs occur via discharge of high-nitrate groundwater into the river system’s surface waters. However, spatial patterns in the magnitude and quality of groundwater discharge are not well understood. In this study, we surveyed the activity of ²²²Rn, a natural groundwater tracer, in the Choptank’s main tidal channel, the large tidal tributary Tuckahoe Creek, smaller tidal and non-tidal tributaries around the basin, and groundwater discharging into those tributaries, measuring nitrate and salinity concurrently. ²²²Rn activities were <100 Bq m^?3 in the main tidal channel and 100–700 Bq m^?3 in the upper Choptank River and Tuckahoe Creek, while the median Rn activities of fresh tributaries and discharging groundwater were 1,000 and 7,000 Bq m^?3, respectively. Nitrate-N concentrations were <0.01 mg L^?1 throughout most of the tidal channel, 1.5–3 mg L^?1 in the upper reaches, up to 13 mg L^?1 in tributary samples, and up to 19.6 mg L^?1 in groundwater. Nitrate concentrations in tributary surface water were correlated with Rn activity in three of five sub-watersheds, indicating a groundwater nitrate source. ²²²Rn and salinity mass balances indicated that Rn-enriched groundwater discharges directly into the Choptank’s tidal waters and suggested that it consists of a mixture of fresh groundwater and brackish re-circulated estuarine water. Further sampling is necessary to constrain the Rn activity and nitrate concentration of discharging groundwater and quantify direct discharge and associated nitrogen inputs.     

Evolution of tidal creek networks in a high sedimentation environment: A 5-year experiment at Tijuana Estuary, California

In a large (8 ha) salt marsh restoration site, we tested the effects of excavating tidal creeks patterned after reference systems. Our purposes were to enhance understanding of tidal creek networks and to test the need to excavate creeks during salt marsh restoration. We compared geomorphic changes in areas with and without creek networks (n = 3; each area 1.3 ha) and monitored creek cross-sectional areas, creek lengths, vertical accretion, and marsh surface elevations for 5 yr that included multiple sedimentation events. We hypothesized that cells with creeks would develop different marsh surface and creek network characteristics (i.e., surface elevation change, sedimentation rate, creek cross-sectional area, length, and drainage density). Marsh surface vertical accretion averaged 1.3 cm yr⁻¹ with large storm inputs, providing the opportunity to assess the response of the drainage network to extreme sedimentation rates. The constructed creeks initially filled due to high accretion rates but stabilized at cross-sectional areas matching, or on a trajectory toward, equilibrium values predicted by regional regression equations. Sedimentation on the marsh surface was greatest in low elevation areas and was not directly influenced by creeks. Time required for cross-sectional area stabilization ranged from 0 to > 5 yr, depending on creek order. First-order constructed creeks lengthened rapidly (mean rate of 1.3 m yr⁻¹) in areas of low elevation and low vegetation cover. New (volunteer) creeks formed rapidly in cells without creeks in areas with low elevation, low vegetation cover, and high elevation gradient (mean rate of 6.2 m yr⁻¹). After 5 yr, volunteer creeks were, at most, one-fourth the area of constructed creeks and had not yet reached the upper marsh plain. In just 4 yr, the site’s drainage density expanded from 0.018 to reference levels of 0.022 m m⁻². Pools also formed on the marsh plain due to sediment resuspension associated with wind-driven waves. We conclude that excavated creeks jump-started the development of drainage density and creek and channel dimensions, and that the tidal prism became similar to those of the reference site in 4–5 yr.     

Macrobenthic communities from wetland impoundments and adjacent open marsh habitats in South Carolina

Forty-eight core and grab samples were taken from two impoundments and an adjacent tidal creek and salt marsh during each of six sampling periods (January, June and November 1983; and January, April and July 1984). Habitats sampled within the impoundments included the perimeter ditch and shallow vegeted areas dominated byRuppia maritima, Spartina alterniflora, andScirpus robustus. The adjacent tidal creek bottom and low marsh ofS. alterniflora were sampled for comparison with the impoundment sites. Major differences in faunal composition and density of macrobenthic invertebrates were observed between habitats in this study. Macrobenthic density was highest (475 individuals 0.05 m^?2) at the impoundment site dominated byScripus robustus, where oligochaetes were abundant. The open marsh site had a density of 254 individuals 0.05 m^?2. Among unvegetated sites, density for all sampling periods was higher in Chainey Creek than in the perimeter ditches of the impoundments. The total number of taxa was highest for the open marsh and tidal creek sites. The impoundments contained vegetated sites which were inhabited by fewer species than nonimpounded sites, while the perimeter ditch sites were comparatively depauperate. Cluster and nodal analyses identified four broad assemblages based on habitat: 1) an open marsh assemblage, 2) a creek assemblage, 3) a eurytopic assemblage, and 4) an impoundment assemblage. The separation of faunal assemblages by sampling site rather than sampling period suggests that physical differences between habitats were important factors determining distribution patterns.     

Groundwater chemistry of Al under Dutch sandy soils: Effects of land use and depth

Aluminium has received great attention in the second half of the 20th century, mainly in the context of the acid rain problem mostly in forest soils. In this research the effect of land use and depth of the groundwater on Al, pH and DOC concentration in groundwater under Dutch sandy soils has been studied. Both pH and DOC concentration play a major role in the speciation of Al in solution. Furthermore, the equilibrium with mineral phases like gibbsite, amorphous Al(OH)₃ and imogolite, has been considered. Agricultural and natural land use were expected to have different effects on the pH and DOC concentration, which in turn could influence the total Al concentration and the speciation of Al in groundwater at different depths (phreatic, shallow and deep). An extensive dataset (n = 2181) from the national and some provincial monitoring networks on soil and groundwater quality was used. Land use type and groundwater depth did influence the pH, and Al and DOC concentrations in groundwater samples. The Al concentration ranged from <0.4 μmol L⁻¹ at pH > 7 to 1941 μmol L⁻¹ at pH < 4; highest Al concentrations were found for natural-phreatic groundwater. The DOC concentration decreased and the median pH increased with depth of the groundwater. Natural-phreatic groundwater showed lower pH than the agricultural-phreatic groundwater. Highest DOC concentrations were found for the agricultural-phreatic groundwater, induced by the application of organic fertilizers. Besides inorganic complexation, the NICA-Donnan model was used to calculate Al³⁺ concentrations for complexation with DOC. Below pH 4.5 groundwater samples were mainly in disequilibrium with a mineral phase. This disequilibrium is considered to be the result of kinetic constraints or equilibrium with organic matter. Log K values were derived by linear regression and were close to theoretical values for Al(OH)₃ minerals (e.g. gibbsite or amorphous Al(OH)₃), except for natural-phreatic groundwater for which lower log K values were found. Complexation of Al with DOC is shown to be an important factor for the Al concentrations, especially at high DOC concentrations as was found for agricultural-phreatic groundwater.     

Distribution of natural uranium,thorium, lead,and polonium radionuclides in tidal phases of a Delaware salt marsh

Natural radionuclides in the uranium and thorium series were measured in solid tidal phases (suspended particles, bottom sediment, surface microlayer colloids) of a salt marsh in lower Delaware. The purpose was to identify potential processes responsible for trace element cycling (sources, redistribution and exchange) in salt water marshes and with their coastal waters. Generally, concentrations of U, Th,²¹⁰Pb, and²¹⁰Po on the tidal solid phases suggest a general mechanism by which tidal marshes appear to be trapping the nuclides into their interiors. The processes may include transport of enriched fine particles into the marsh, capture by salt marsh grass and chemical fixation by redox processes at the sediment surface. Specifically, the uranium contents of most of the samples are similar with activity ratios²³⁴U²³⁸U≧1, indicating a mixture of detrital and nondetrital (authigenic) uranium inputs such as seawater or ground water. Since the²³⁰Th daughter is generally deficient by about 50%, the authigenic enrichment process appears to favor uranium and is potentially linked to the extensive diagenetic sulfur redox cycle of salt marsh sediments. The²¹⁰Po/²¹⁰Pb activity ratio is less than one on Spartina adsorbed solids, and could suggest a general process in salt marshes which favors²¹⁰Pb enrichment by atmospheric fallout over enrichment of²¹⁰Po on time scales of weeks which correspond to complete tide marsh exchange. A²²⁸Th/²³²Th activity ratio of less than unity on the solids adsorbed onto marsh grass suggests a net process whereby diffusive loss of the intermediate daughter²²⁸Ra from the adsorbed solids to tidal waters dominates over potential²²⁸Th scavenging by suspended sediment.     

Natural organic matter in sedimentary basins and its relation to arsenic in anoxic ground water: the example of West Bengal and its worldwide implications

In order to investigate the mechanism of As release to anoxic ground water in alluvial aquifers, the authors sampled ground waters from 3 piezometer nests, 79 shallow (<45 m) wells, and 6 deep (>80 m) wells, in an area 750 m by 450 m, just north of Barasat, near Kolkata (Calcutta), in southern West Bengal. High concentrations of As (200–1180 μg L⁻¹) are accompanied by high concentrations of Fe (3–13.7 mg L⁻¹) and PO₄ (1–6.5 mg L⁻¹). Ground water that is rich in Mn (1–5.3 mg L⁻¹) contains <50 μg L⁻¹ of As. The composition of shallow ground water varies at the 100-m scale laterally and the metre-scale vertically, with vertical gradients in As concentration reaching 200 μg L⁻¹ m⁻¹. The As is supplied by reductive dissolution of FeOOH and release of the sorbed As to solution. The process is driven by natural organic matter in peaty strata both within the aquifer sands and in the overlying confining unit. In well waters, thermo-tolerant coliforms, a proxy for faecal contamination, are not present in high numbers (<10 cfu/100 ml in 85% of wells) showing that faecally-derived organic matter does not enter the aquifer, does not drive reduction of FeOOH, and so does not release As to ground water.Arsenic concentrations are high (≫50 μg L⁻¹) where reduction of FeOOH is complete and its entire load of sorbed As is released to solution, at which point the aquifer sediments become grey in colour as FeOOH vanishes. Where reduction is incomplete, the sediments are brown in colour and resorption of As to residual FeOOH keeps As concentrations below 10 μg L⁻¹ in the presence of dissolved Fe. Sorbed As released by reduction of Mn oxides does not increase As in ground water because the As resorbs to FeOOH. High concentrations of As are common in alluvial aquifers of the Bengal Basin arise because Himalayan erosion supplies immature sediments, with low surface-loadings of FeOOH on mineral grains, to a depositional environment that is rich in organic mater so that complete reduction of FeOOH is common.     

Irrigation produces elevated arsenic in the underlying groundwater of a semi-arid basin in Southwestern Idaho

The shallow aquifer beneath the Western Snake River Plain (Idaho, USA) exhibits widespread elevated arsenic concentrations (up to 120 μg L⁻¹). While semi-arid, crop irrigation has increased annual recharge to the aquifer from approximately 1 cm prior to a current rate of >50 cm year⁻¹. The highest aqueous arsenic concentrations are found in proximity to the water table (all values >50 μg L⁻¹ within 50 m) and concentrations decline with depth. Despite strong vertical redox stratification within the aquifer, spatial distribution of aqueous species indicates that redox processes are not primary drivers of arsenic mobilization. Arsenic release and transport occur under oxidizing conditions; groundwater wells containing dissolved arsenic at >50 μg L⁻¹ exhibit elevated concentrations of O₂ (average 4 mg L⁻¹) and NO₃ (average 8 mg L⁻¹) and low concentrations of dissolved Fe (<20 μg L⁻¹). Sequential extractions and spectroscopic analysis of surficial soils and sediments indicate solid phase arsenic is primarily arsenate and is present at elevated concentrations (4–45 mg kg⁻¹, average: 17 mg kg⁻¹) relative to global sedimentary abundances. The highest concentrations of easily mobilized arsenic (up to 7 mg kg⁻¹) are associated with surficial soils and sediments visibly stained with iron oxides. Batch leaching experiments on these materials using irrigation waters produce pore water arsenic concentrations approximating those observed in the shallow aquifer (up to 152 μg L⁻¹). While As:Cl aqueous phase relationships suggest minor evaporative enrichment, this appears to be a relic of the pre-irrigation environment. Collectively, these data indicate that infiltrating irrigation waters leach arsenic from surficial sediments to the underlying aquifer.