Dissolved aluminium in the Tamar Estuary,southwest England

Distributions of dissolved Al in the Tamar Estuary have been recorded through spring-neap tidal cycles in winter and summer. Dissolved Al is a highly reactive constituent in this estuary, undergoing net removal in the very low salinity region and net input to the mid-estuary. The extent of both the depletion and the augmentation varied systematically with tidal energy input, indicating that tidal sediment disturbance was the principal controlling agency.These field data, supported by the results of laboratory simulations, show that the removal is regulated by sorption onto resuspended sediment particles, which dominates kinetically over authigenic aluminosilicate formation. Removal of dissolved Al by flocculation of riverborne colloids is not significant. The mid-estuarine input is consistent with dissolution of authigenic aluminosilicate following net remobilization of estuarine sediment. The internal cycling of Al in the estuary, generated by these processes, alters both the time-course and the soluble-particulate balance of the riverine discharge of Al to the adjacent coastal water.     

Dissolved organic carbon in pore waters from a hypersaline environment

Pore waters were collected from a sea-marginal, hypersaline pond in the Sinai and analyzed for dissolved organic carbon (DOC). The pore water DOC values ranged from 121 to 818 mg 1⁻¹ with maxima between 15 and 54 cm deep. These values are some of the highest observed from recent sediments and probably reflect production via abiotic as well as biotic sources.     

Modeling of cadmium speciation and dynamics in the Seine estuary (France)

A complexation model (MOCO) was used to describe cadmium (Cd) speciation during estuarine transit in the Seine estuary. This model was developed from field data. Laboratory experiments based on the use of¹⁰⁹Cd enabled checking of certain model simplifications and hypotheses and evaluation of parameters which could not be measured directly. MOCO was coupled with a 3D multivariable hydrosedimentary model (SAM3D) to simulate Cd dynamics in the estuary. These results were compared with measurements (dissolved and particulate Cd) obtained during cruises representative of various hydrodynamic conditions. The purpose of this article is to present the modeling approach used, and its expected applications and limits.     

Distribution and speciation of metals,phosphorus, sulfate and organic material in brackish estuary water affected by acid sulfate soils

Dissolved (<1 kDa) and colloidal (1 kDa-0.45 μm) size fractions of sulfate, organic carbon (OC), phosphate and 17 metals/metalloids were investigated in the acidic Vörå River and its estuary in Western Finland. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these waters. The sampling was carried out during high-water flow in autumn and in spring when the abundantly occurring acid sulfate (AS) soils in the catchment area are extensively flushed. Based on the high concentrations of sulfate, acidity and several metals, it is clear that the Vörå River and its estuary is strongly affected by AS soils. The high dissolved form of metals limits also the existence of fish and other organisms in this estuary, and certainly also in other similar shallow brackish estuaries elsewhere in the Gulf of Bothnia. However, generally already <20% saline sea water reduces the concentration for OC and several elements (Al, Cu, Cr, Fe, Pb, PO₄ and U) by half and c. 20–30% saline sea water is needed to halve concentrations of Cd, Co, Mn, Ni and Zn. Consequently, these elements as well as organic matters were rapidly precipitated in the estuary, even after mixing with fairly small amounts of the alkaline brackish sea water. Aluminium, Cu, Fe and U most likely precipitate together with organic matter closest to the river mouth. Manganese is relatively persistent in solution and, thus, precipitates further down the estuary as Mn oxides, which concomitantly capture Ba, Cd, Co, Cu, Ni and Zn. In the inner estuary, the high contents of Al is as important than Fe in removing PO₄ and, thus, also reducing the risk of algae blooms in near coastal areas influenced by AS soils in the Gulf of Bothnia. Moreover, the dispersion of metals far out in the estuary is dependent on hydrological conditions, i.e. with high flows the plume of metal-rich water will spread further out in the estuary. Furthermore, the extensive drainage of the catchment and subsequent artificial enlargement of the river channel during recent decades has not only enabled oxidation of sulfidic sediments, but strongly increased flow peaks that reach further out in the estuary.     

Dissolved organic matter (DOM) export to a temperate estuary: seasonal variations and implications of land use

Inputs of dissolved carbon, nitrogen, and phosphorus were assessed for an estuary and its catchment (Horsens, Denmark). Seasonal patterns in the concentrations of DOM in the freshwater supply to the estuary differed depending on the soil and drainage characteristics of the area. In streams draining more natural areas the, patterns observed were largely driven by seasonal temperature fluctuations. The material exported from agricultural areas was more variable and largely controlled by precipitation events. Positive exponential relationships were found between the nitrogen and phosphorus loading, and the percentage of catchment area used for agriculture. Colored DOM (CDOM) loading measurements were found to be a good predictor of dissolved organic carbon (DOC) loading across the different subcatchments, offering a rapid and inexpensive alternative of operationally monitoring DOC export. For all the dissolved nutrient inputs to the estuary, dissolved inorganic nitrogen (DIN) and dissolved organic phosphorus dominated the loadings. Although 81% of the nitrogen annually supplied to the estuary was DIN, 83% of the nitrogen exported from the estuary was dissolved organic nitrogen (DON). Results show that increasing the area of the catchment covered by forest and natural pastures would have a positive effect on the trophic status of the estuary, leading to a considerable decrease in the phosphorus loading and a shift in the nitrogen loading from DIN to DON. Such a change in land use would also increase the export of DOC and CDOM to the estuary having the potential to increase oxygen consumption and reduce the photic depth.     

Dissolved organic carbon and volatile fatty acids in marine sediment pore waters

The results of a study of the contribution of microbial metabolic products to total dissolved organic carbon (DOC) levels in coastal sediments are presented. The data indicate that acidic volatile compounds make up a substantial fraction of pore water DOC's in both oxic and anoxic pore waters of coastal marine sediments. Formic, acetic and butyric acids are the principal volatile species identified at levels exceeding 10 μM. Acid concentrations are up to five times higher in anoxic pore waters than in oxic waters. Volatile organic acids show promise as indicators of diagenetic processes in marine sediments and of the ecological succession of microorganisms, in particular.     

Transformation of phosphorus in the Elbe estuary

The distribution of dissolved and particle-bound phosphorus (P) was investigated in the Elbe estuary during March 1995. The forms of particulate P were studied with a sequential extraction technique. Organic P dominated particle-bound P in the outer reaches of the estuary (52%), decreased to a minimum of 21% in the turbidity zone, and increased to 33% further upstream. Fe-bound P was the second most important P species in the outer reaches (27%) and dominated in the turbidity zone (up to 57%) and upstream of the turbidity zone (up to 48%). The P:Fe ratio increased with decreasing salinity, from 0.11 in the outer reaches to about 0.22 at zero salinity. Dissolved inorganic P release from reverine suspended matter was about two to three times larger than release, from marine suspended matter and was dominated by release of Fe-bound P. Dissolved inorganic P release from marine and from riverine organic matter were of equal importance. Because marine suspended matter dominates in the estuary, this suggests riverine organic matter is remineralized much faster than marine organic matter. This is in line with the refractory nature of marine organic matter (no phytoplankton bloom) and the easily degradable character of the riverine suspended matter (phytoplankton bloom) in the Elbe estuary during March 1995.     

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.     

Dissolved silicate dynamics of the Rhode River watershed and estuary

We continuously measured dissolved silicate concentrations and fluxes discharged from various Rhode River subwatersheds for a period of 14 yr from 1984 to 1998 and for 15 mo in 1971–1972. We also measured dissolved silicate concentrations along a transect from the head of the tide in Rhode River estuary to Chesapeake Bay. The average concentration of dissolved silicate discharged from the Rhode River watershed was 10.8 mg Si l^?1. There were consistent and significant differences in silicate concentrations discharged over time and space among subwatersheds. Mean annual silicate flux from the watershed was 26.6 kg Si ha^?1 and 93% of this occurred during the winter and spring seasons. There were large interannual variations in silicate flux, due primarily to differences in precipitation and water discharge, rather than silicate concentration. Land use had little or no effect on silicate flux from various subwatersheds. Silicate concentrations discharged from a subset of subwatersheds in 1995–1996 were 25% to 35% lower than in a period with similar precipitation in 1971–1972. Mean annual concentrations of silicate discharged from nine subwatersheds have been declining about 1.5% yr^?1 or by 0.21–0.26 mg Si l^?1 yr^?1 over the last 25 yr. Despite high average silicate fluxes from the watershed, at times the Rhode River estuary developed low dissolved silicate concentrations, which could have been limiting to the growth of diatoms. Examples were in the spring after a winter with low watershed discharge (as low as 0.019 mg Si l^?1 in 1995) and after protracted drought (as low as 0.041 mg Si l^?1 in 1993).     

Retention of phosphorus and nitrogen in the Ems estuary

From February 1992 until June 1993, the distribution of dissolved and particulate phosphorus and nitrogen was investigated in the Ems estuary at approximately monthly intervals. Nutrient import was quantified from the river load. Nutrient export to sea was quantified from river discharge and from the salinity-nutrient gradient in the outer estuary. In addition, sediment cores were taken from four sites along the main axis of the estuary in October 1992. On the basis of these data a nitrogen and phosphorus budget was made. On an annual basis, 45 × 10⁶ mol P and 2,360 × 10⁶ mol N are imported into the Ems estuary. Freshwater runoff is the main source of input, accounting for about 92% of the nitrogen input and 71% of the phosphorus input. Import of particulate phosphorus from the sea is important in the phosphorus budget (27%). Seventy-five percent of the nitrogen input is transported to the North Sea. Denitrification is the major loss factor (19% of the nitrogen input), and burial explains 6%. Of the phosphorus input, 60% is transported to the North Sea and 40% accumulates in the sediment. Nitrogen import during summer explains about one third of the annual primary production, indicating that nitrogen turn over is about three times. Phosphorus import during summer explains less than 16% of the annual primary production. We suggest that trapping of particulate P and adsorption onto Fe(oxy)hydroxides during the entire year and the release of Fe-bound P during summer after reduction of Fe(oxy)hydroxides is instrumental in sustaining high primary production, which could not be sustained if it depended only on P imported during the growing season.     

Nutrient uptake in a highly turbid estuary (the Humber, United Kingdom) and adjacent coastal waters

Surveys were conducted in April and June 1995 to quantify the uptake of dissolved nutrients in a highly turbid estuary (the Humber, United Kingdom) and to determine the factors controlling nutrient uptake rates. A combination of isotope labelling methods were used in conjunction with on-deck incubation techniques to estimate the uptake of dissolved nutrients (PO₄ ^3?, NH₄ ⁺, NO₃ ^?, and urea) in surface samples collected from coastal waters. Similarly, isotope labelling and laboratory incubgation techniques were employed to estimate dissolved nitrogen uptake (NH₄ ⁺, NO₃ ^?, and urea) in surface samples collected from the estuary mouth. Nutrient uptake rates were at the low end of ranges for coastal and estuarine environments reported in the literature. Concentrations of chlorophyll and the availability of photosynthetically active radiation were identified as potentially important factors controlling the uptake rates of nutrients. Uptake rates of dissolved nitrogen in the Humber mouth appeared to be related to the location of smapling sites. Depletion rates of dissolved nutrients in situ were estimated on the basis of integrated water column nutrient uptake rates and indicated assimilation of up to 16% of nutrients in the entire water column. Estimated depletion rates did not indicate preferential loss of any of the nutrient species investigated.     

Hypoxia of bottom waters of the Razdolnaya River estuary

The hypoxia of the bottom waters in the Razdolnaya River estuary was observed for the first time in September 2014 during the survey. It is formed as in the seaward part: oxygen is absorbed as a result of destruction of excessive phytoplankton biomass that settles to the bottom and is synthesized on the upper horizon. The high value of primary production in the riverine part of the estuary was caused by the pycnocline formed. Thus, phytoplankton “blooms” above and undergoes destruction beneath the pycnocline. Oxygen is distributed symmetrically in both parts of the estuary with respect to a bar: similar oxygen concentrations, which are maximum on the surface and minimum at the bottom, 300 and <60 μm/L, respectively, are recorded. The anomalies of hydrochemical parameters that have been formed during this process are sharply different in the two parts of the estuary, which most vividly manifests itself in the N/P value and the partial pressure of carbon dioxide pCO₂. The causes of this unique situation are discussed.

     

Dissolved aluminium in interstitial waters of recent marine sediments

Measurements of the concentration and vertical distribution of dissolved aluminium and silica, and of pH. in interstitial waters of recent marine sediments from the North Sea and the Mediterranean Sea were performed to evaluate the behaviour of aluminium during early diagenesis. The results suggest that thermodynamic equilibria alone do not control the concentrations of dissolved species in the system Al-Si-O₂-H₂O during early diagenesis. Rather, these concentrations are governed by dynamic factors involving mineral dissolution-precipitation reactions and diffusion.     

Fractionation of phosphorus in the sediments of a tropical estuary

Fractionation of phosphorus in the sediments of the Cochin estuary situated along the southwest coast of India was studied by applying sequential chemical extraction. The different forms of phosphorus were estimated seasonally (premonsoon, monsoon, and postmonsoon) under eight different schemes. The major forms of phosphorus analyzed were exchangeable P, anion exchangeable P, carbonate-bound P, labile and resistant organic P, Fe and Al P, calcium-bound P, and hydrolyzable surplus P. Quantitatively, the above fractions in isolation or in combination vary in content due to chemoestuarine variability and seasonal fluctuations. Changes in speciation have been noted in association with salinity variations in the waterway, especially following enhanced river runoff during the monsoon. The chemical forms of the sediment-bound phosphorus in the northern parts of this estuary have been shown to be modified by nonpoint sources. Sediment P fractionation defines the role of chemical speciation of phosphates (as nutrients) and is indicative of the processes controlling the pathways of P into the coastal waters. The changes in the exchangeable P, together with marked regional variations in calcium-bound P, exemplify the complex estuarine variability of phosphorus. Enhanced amounts of exchangeable P mark its appearence in high saline waters, signifying the presence of biologically available nutrient phosphorus. The calcium-bound P and hydrolyzable surplus P show significant relation with sediment organic carbon and Fe whereas other forms do not exhibit any marked covariation. The Ca and Na NTA extraction scheme is very specific in its selectivity.     

Environmental set-up and tidal propagation in a tropical estuary with dual connection to the sea (SW Coast of India)

The Kochi Backwater (KB) is the second largest wetland system in India. It is connected to the sea at Fort Kochi and Munambam (Pallipuram) (30 km north of Kochi). As the tide is forced through two openings, its propagation in the backwater system is very complicated, particularly in the northern arm of the estuary. Using synchronous water level (WL) and current measurements in the KB from a network of stations during 2007–2008, it was convenient to demarcate the northern KB into two distinct regions according to the tidal forcing from the north (Pallipuram) and south (Vallarpadam). This demarcation is useful for computing the propagation speeds of the dominant tidal constituents in the northern branch of the KB with dual opening for opposing tides. WL variations indicated that M₂ tide (Principal lunar semidiurnal constituent) dominated in the sea level variance, followed by the K₁ constituent (Luni-solar declinational diurnal constituent). The M₂ tidal influence was the strongest near the mouth and decayed in the upstream direction. The propagation speed of the M₂ tide in the southern estuary was ~3.14 m/s. The ratio of the total annual runoff to the estuarine volume is ~42 that indicates the estuary will be flushed 42 times in a year. KB can be classified as a monsoonal estuary where the river discharge exhibits large seasonal variation.     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^?1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^?1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

Contribution of organic complexation to Ni,Co and Cu speciation in surface waters: Implications for hydrogeochemicalsurveys

Organic materials dissolved in surface waters have long been implicated in metal binding and transport. In particular, fulvic and humic acids are considered to have a significant impact on speciation, total metal levels in solution and on the persistence of those metals. This work emphasizes the role played by dissolved organic matter (DOM) on the complexation of nickel, copper and cobalt and on its application to interpretation of surface water hydrogeochemical survey data. Waters from a number of well-known mining districts in Canada have been studied; in particular from Cobalt (Ontario), Sackville (New Brunswick) and Thetford Mines (Quebec). The diafiltration binding technique was used and shows that nickel, copper and cobalt are complexed significantly by DOM in natural waters. The tendency towards complexation was found to be Cu > Ni > Co. The binding functions determined were observed to be highly sensitive to pH and ligand:metal ratios; a gradation of binding site strength is evident.Data from some hydrogeochemical surveys conducted in the Kenora, Algoma and Ottawa districts of Ontario have been reinterpreted in the light of available data on the complexation behaviour of nickel, copper and cobalt. Occurrence of large water-borne anomalies unsupported by lake sediment loadings is most likely for cobalt and nickel and least likely for copper according to both field observations and experimental data. These studies provide good evidence for the formation of strong solution stable metal-organic species; the principal differences in persistence and migration behaviour are probably due to rates of coagulation and adsorption-precipitation processes which preferentially remove copper from solution. It is fair to conclude that these metals can be of use in mineral exploxation surveys using surface waters provided caution is exercised in interpretation of anomalies, especially in the absence of supporting sediment anomalies. Dissolved organic matter concentrations should always be determined when nickel, copper and cobalt are to be employed.     

Dissolved inorganic carbon (DIC) and hydrologic mixing in a subtropical riverine estuary,southwest Florida,USA

Physical and chemical parameters were measured in a subtropical estuary with a blind river source in southwest Florida, United States, to assess seasonal discharge of overland flow and groundwater in hydrologic mixing. Water temperature, pH, salinity, alkalinity, dissolved inorganic carbon (DIC), δ¹⁸O, and δ¹³C_DIC varied significantly due to seasonal rainfall and climate. Axial distribution of the physical and chemical parameters constrained by tidal conditions during sampling showed that river water at low tide was a mixture of freshwater from overland flow and saline ground-water in the wet season and mostly saline groundwater in the dry season. Relationships between salinity and temperature, δ¹⁸O, and DIC for both the dry and wet seasons showed that DIC was most sensitive to seawater mixing in the estuary as DIC changed in concentration between values measured in river water at the tidal front to the most seaward station. A salinity-δ¹³C_DIC model was able to describe seawater mixing in the estuary for the wet season but not for the dry season because river water salinity was higher than that of seawater and the salinity gradient between seawater and river water was small. A DIC-δ¹³C_DIC mixing model was able to describe mixing of carbon from sheet flow and river water at low tide, and river water and seawater at high tide for both wet and dry seasons. The DIC-δ¹³C_DIC model was able to predict the seawater end member DIC for the wet season. The model was not able to predict the seawater end member DIC for the dry season data due to secondary physical and biogeochemical processes that altered estuarine DIC prior to mixing with seawater. The results of this study suggest that DIC and δ¹³C_DIC can provide additional insights into mixing of river water and seawater in estuaries during periods where small salinity gradients between river water and seawater and higher river water salinities preclude the use of salinity-carbon models.     

The chemical control of soluble phosphorus in the Amazon estuary

The factors which control concentrations of soluble inorganic phosphorus in the Amazon estuary are described and the efflux of phosphorus through the estuary is estimated using estuarine data collected on three field excursions (two in December, 1982 and one in May, 1983), and various laboratory mixing experiments. There is evidence to suggest that suspended sediments release significant quantities of inorganic phosphate to the estuarine waters. Bottom sediments collected from the estuary released soluble inorganic phosphorus at rates of approximately 0.2 μM day⁻¹, when suspended in mixtures of seawater and deionized water. Release rates depended on salinity but were independent of sediment concentrations. Inputs of phosphate persisted for approximately 3 days in suspensions with sediment concentrations of 0.5 g l⁻¹, but the duration of release increased to greater than 8 days at concentrations greater than 10 gl⁻¹. A one-dimensional dispersion model was developed incorporating input rates derived from the laboratory mixing experiments. The model predicts phosphate concentrations which are consistent with field observations, and it provides quantitative estimates for total fluxes of soluble inorganic phosphorus to the high salinity fringes of the estuary (~25 ppt) of approximately 15 × 10⁶molesday⁻¹ and 27 × 10⁶molesday⁻¹ during December, 1982 and May, 1983 respectively. The data indicate a significant phosphate loss from estuarine waters at salinities from 0–4 ppt, possibly associated with iron and humate removal. More than 50% of the predicted flux could be contributed by phosphate released from suspended sediments within the turbid part of the estuary.     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^–1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^–1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).