Desorption and coagulation of trace elements during estuarine mixing

Mixing experiments of seawater and the Hudson and Mississippi riverwaters with radiotracer spikes show that Co, Mn, Cs, Cd, Zn and Ba will be desorbed from river suspended particles, while significant fractions of “dissolved” Fe, Sn, Bi, Ce and Hg will be coagulated during estuarine mixing.     

Removal of dissolved boron and silicon during estuarine mixing of sea and river waters

The behaviour of dissolved boron and silicon during mixing of sea and river waters has been studied in two surveys of the estuary of the River Alde in Suffolk, England. Removal of approximately 25–30 per cent was found for both elements. This appears to be the first report of estuarine removal of dissolved boron. The extent of removal of silicon in the Alde is somewhat higher than that found in other estuaries.     

Aggregation of colloidal iron during estuarine mixing: Kinetics,mechanism, and seasonality

The colloid chemistry of iron and humic aggregation was studied in a series of laboratory experiments, which were related to seasonal aggregation extent data collected in a temperate estuary. Kinetically, the aggregation of iron occurs with a rapid initial reaction, finished within a few minutes, followed by an extensive, slow second reaction, which lasts for several hours. Organic carbon aggregation, however, occurs primarily in the first reaction. The first reaction is perikinetic while the second reaction is observed to be either perikinetic or orthokinetic, depending on the pore size of the filter used to clarify the suspension. The second reaction involves aggregation of small filtrable colloids (<0.5 μm) with larger aggregates formed in the first reaction, and follows pseudo-second order kinetics with respect to the filtrable iron concentration when finer filters (<0.5 μm) are used for clarification. Little or no temperature dependence is evident for the first reaction extent, while increasing temperature strongly enhances the second reaction. An activation energy of 9–11 kcal·mole^?1 for the second reaction is due to a combination of transport and charge repulsion terms. Field data show a correspondingly greater aggregation extent of iron with salinity in warmer months relative to colder months.     

Metals removal during estuarine mixing of Arvand River water with the Persian Gulf water

In the present study, the removal of dissolved and colloidal Cd, Co, Cu, Ni and Zn in Arvand River water during estuarine mixing with the Persian Gulf water is investigated. The flocculation process was investigated for a series of mixtures with salinities ranging from 0.48 to 30.3^. The flocculation rates were indicative of the non-conservative behavior of studied metals during estuarine mixing. Rapid flocculation in the low salinity regimes was observed. The order of the final flocculation rate of metals in the river water was as follows: Co (91.2%)> Cd (86.9%)> Zn (83%)> Cu (75.2%)> Ni (74.3%). Salinity, pH, EC and dissolved oxygen do not govern the flocculation of metals during estuarine mixing. The results of the present investigation show that estuarine processes can be considered as an effective mechanism in self purification of colloidal metals that are anthropogenically introduced into the fresh water ecosystem.     

Control of estuarine stratification and mixing by wind-induced straining of the estuarine density field

Observations from the York River Estuary, Virginia, demonstrate that the along-channel wind plays a dominant role in governing the estuarine exchange flow and the corresponding increase or decrease in vertical density stratification. Contrary to previous findings that suggest wind stress acts predominantly as a source of energy to mix away estuarine stratification, our results demonstrate that the wind can play a more important role in straining the along-channel estuarine density gradient. Down-estuary winds enhance the tidally-averaged vertical shear, which interacts with the along-channel density gradient to increase vertical stratification. Up-estuary winds tend to reduce, or even reverse the vertical shear, reducing vertical stratification. In two experiments each lasting approximately a month, the estuarine exchange flow was highly correlated with the along-channel component of the wind. The changes in stratification caused by the exchange flow appear to control the amount of vertical mixing as parameterized by the vertical eddy viscosity. The degree of stratification induced by wind straining also appears to play an important role in controlling the effectiveness of wind and tidal mixing.     

Enhanced removal of dissolved metal ions in radioactive effluents by flocculation

Decontamination of radioactive effluents of low or intermediate level of radioactivity generated from different nuclear industries is done through the chemical precipitation route. The precipitates thus formed are of very fine sizes thereby requiring flocculation for faster settlement. The presence of polyacrylamide-based polymer not only enhances settling velocity but also increases removal of dissolved non-radioactive as well as radioactive metal ions from the liquid. About 99.5% of Cu²⁺ and Fe³⁺ ions are removed due to the presence of cationic Rishabh 611. Flocculation by either cationic or anionic flocculant has shown improvement in removal of radioactive strontium while turbidity of the liquid is reduced to a very low value (0.8 NTU). Decontamination factors (DF) of the effluents from different plants are improved by 3–5 times.     

The behaviour of dissolved organic material,iron and manganese in estuarine mixing

Fractionation by ultra-filtration of the dissolved organic material (DOM) in the River Beaulieu, with typical concentrations of dissolved organic carbon (DOC) of 7–8 mg C/l, showed it to be mainly in the nominal molecular weight range of 10³–10⁵, with 16–23% of the total DOC in the fraction > 10⁵. The molecular weight distribution of DOM in the more alkaline River Test (average DOC, 2 mg C/l) was similar. In the River Beaulieu water, containing 136–314 βg Fe/l in ‘dissolved’ forms, 90% or more of this Fe was in the nominal molecular weight fraction > 10⁵. Experiments showed that DOM of nominal molecular weight <10⁵ could stabilize Fe(III) in ‘dissolved’ forms. The concentrations of ‘dissolved’ Fe in the river water probably reflect the presence of colloidal Fe stabilized by organic material and this process may influence the apparent molecular weight of the DOM. Dissolved. Mn (100–136 βg/l) in the River Beaulieu was mainly in true solution, probably as Mn(II), with some 30% in forms of molecular weight greater than ca 10⁴.During mi xing in the Beaulieu Estuary, DOC and dissolved Mn behave essentially conservatively. This contrasts with the removal of a large fraction of the dissolved Fe (Holliday and LISS, 1976, Est. Coastal Mar. Sci. 4, 349–353). Concentrations of lattice-held Fe and Mn in suspended particulate material were essentially uniform in the estuary, at 3.2 and 0.012%, respectively, whereas the non-lattice held fractions decreased markedly with increase in salinity. For Mn the decrease was linear and could be most simply accounted for by the physical mixing of riverborne and marine participates, although the possibility that some desorption occurs is not excluded. The non-linear decrease in the concentration of non-lattice held Fe in particulates reflected the more complex situation in which physical mixing is accompanied by removal of material from the ‘dissolved’ fraction.     

Metal levels in estuarine macrophytes: Differences among species

With the aim of studying the interspectific differences in the bioaccumulation of a series of elements in six species of estuarine macrophytes, we measured the concentrations of various metals (Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn), as well as C and N, in several species of macroalgae and one species of seagrass in estuaries in northwest Spain. To facilitate the interpretation of the results, we also determined the concentrations of the same metals in sediments. Contamination by particulate metal did not appear to be important. The levels of Cu in the different species were generally high in comparison with those found in similar studies; in contrast, the concentrations of Pb and Zn were relatively low. The metal concentrations showed greater variability and a distibution that was further from normal than those of C and N. In general the highest concentrations of elements were found inEnteromorpha spp. andZostera noltii, and the lowest occurred inUlva spp. There were several significant positive correlations among tissue concentrations of Cr, Cu, and Ni. There were also significant correlations between tissue concentrations of N and Zn, suggesting possible synergetic effects between them. Cluster analysis clearly revealed that the chemical composition ofZ. noltii differed from that of the macroalage. Macroalgae were not grouped according to their taxonomic position, therefore it appears that the concentrations of the elements depended more on the ecological traits of the macroalgal species rather than on any possible, physiological differences among different taxonomic groups. Of the species studied,Ascophyllum nodosum andEnteromorpha spp. appeared to be the best biomonitors of metal contamination.     

Source of sediments and metal fractionation in two Chinese estuarine marshes

The Changjiang and the Jiulong Estuaries, located in eastern and southeastern China, respectively, have different geomorphologic and tidal processes as well as anthropogenic development in their associated watersheds. Sediments in the Changjiang estuary mostly consist of SiO₂, CaO and MgO (mean percentages of 63.9, 4.34 and 2.35%), whereas sediments from the Jiulong estuary mostly consist of Al₂O₃, Fe₂O₃ and organic matter (mean percentages 19.2, 6.82 and 4.14%). The Jiulong estuarine sediments contain more than twice the concentrations of Pb, Zn, Cu, than those from the Changjiang estuary. In the Jiulong estuary, these heavy metals are associated with carbonates and organic matter, whereas in the Changjiang estuary, they are associated with residual fractions or clay. Sediments from the Changjiang estuary, mostly sediments with little organic matter, do not efficiently sequester anthropogenic-derived trace metals. In contrast, sediments from the Jiulong estuary consist of a mixture of fluvial and marine matter which can sequester heavy metals contributed by larger landscapes with industrial and municipal wastewater.     

Effect of pH and salinity on flocculation process of heavy metals during mixing of Aras River water with Caspian Sea water

The flocculation process of metals can play an effective and important role in self-purification of metals during the mixing of freshwater with seawater in estuary. Such processes are of highly ecological and biological importance. The present study deals with the effect of pH and salinity on the flocculation process of dissolved Cu, Mn, Ni, Zn and Pb on a series of mixtures with salinities ranging from 0.5 to 2.5 ‰ with various pHs values (pH 7, 7.5 and 8) during the mixing of the Aras River water with the Caspian Sea water. The flocculation trend of Pb (100 %) > Ni (62.5 %) > Zn (30.43 %) > Mn (25 %) > Cu (18.18 %) at different salinity regimes (0.5–2.5 ‰) at pH 7, indicates well that Pb, Ni, Zn and Mn have non-conservative behavior and Cu has relatively conservative behavior. At various salinity ranges (0.5–2.5 ‰) and pH 7.5, the flocculation trend of Pb (100 %) > Ni (62.5 %) > Mn (37.5 %) > Cu (24.24 %) > Zn (17.39 %) indicates that Pb, Ni, Mn and Cu have non-conservative behavior and Zn has relatively conservative behavior. Also, the flocculation trend of Pb (100 %) > Zn (78.26 %) > Ni (62.5 %) > Mn (37.5 %) > Cu (15.15 %) at different salinities (0.5–2.5 ‰) and pH 8, indicates that Pb, Zn, Ni and Mn have non-conservative behavior and Cu has relatively conservative behavior. Cluster analysis indicates Mn and Ni are mainly governed by salinity. According to the mean annual discharge of the Aras River (5,323 × 10⁶ m³/year), the annual discharge of dissolved Cu, Mn, Ni, Zn and Pb into the Caspian Sea would reduce from 175.66, 85.17, 85.17, 1,224.29 and 53.23 to 149.04, 53.23, 31.94, 266.15 and 0.00 ton/year, respectively.     

Effects of physical mixing on the attenuation of polycyclic aromatic hydrocarbons in estuarine sediments

To examine the role of physical disturbance on the long-term preservation of polycyclic aromatic hydrocarbons (PAHs) in sediments, cores were collected from two sites removed from point sources of PAHs and representing contrasting seabed mixing regimes. Although ΣPAH concentrations in sediments over the past 50 years were not significantly different between the two sites, several PAH isomer ratios were significantly different (P<0.05) between the two sites. Downcore changes in PAH isomer ratios resulted from preferential losses of the more linear PAH isomers. Thus, episodic, intense seabed mixing contributes to more efficient removal of selected PAHs. However, PAHs are still sufficiently stable relative to mixing events that historical PAH profiles can be used to reconstruct major resuspension events.     

Dissolved and particulate trace metal geochemistry during mixing of Karganrud River with Caspian Sea water

Arabian Journal of Geosciences - Estuaries are both chemically and physically dynamic ecosystems that, due to their location at the river-sea interface, act as buffer zones between the continent...     

Normalization of metal concentrations in estuarine sediments from the Gulf of Mexico

Metal concentrations were examined in sediments from 497 sites within the estuaries of the Gulf of Mexico by the United States Environmental Protection Agency's Environmental Monitoring and Assessment Program (EMAP). Data were normalized for extant concentrations of aluminum to isolate natural factors from anthropogenic ones. The normalization was based on the hypothesis that metal concentrations vary consistently with the concentration of aluminum, unless metals are of anthropogenic origin. Strong linear correlations (>75% variation explained) were observed between Al and Cr, Cu, Pb, Ni, and Zn. Moderate correlations (50–75% variation explained) were observed between Al and As or Ag. Weak but significant correlations (30–40% variation explained) were observed between Al and Hg or Cd. Based on these results, the spatial extent of contamination was examined. About 39% of sites with contamination by at least one metal occurred near population centers, industrial discharge sites, or military bases. The remainder of the observed contamination represented a dispersed pattern, including the lower Mississippi River (7%) and numerous agricultural watersheds (54%), suggesting that the contamination might be from nonpoint sources.     

Responses of estuarine phytoplankton communities to nitrogen form and mixing using microcosm bioassays

We examined the effects of different forms of nitrogen and mixed versus static conditions on the structure and function of natural Neuse River estuary phytoplankton communities incubated in 66-liter microcosms in March, May, August, and November 1999. Significant differences were found between effects of mixed versus static treatments in three of four experiments, but no differences were observed between effects of different forms of nitrogen. Mixed incubations resulted in higher contributions of diatoms to total community biomass (measured as chlorophylla) than in static tanks in May. Significantly higher rates of carbon fixation were also observed, likely due to increased suspension of diatoms in surface (illuminated) layers of the tanks. In August, we found significantly higher abundances of cyanobacteria, total community biomass, and rates of carbon fixation in static tanks than in tanks that were mixed. In November, static incubations showed significantly higher abundances of cryptophytes resulting in higher total community biomass and rates of carbon fixation in static tanks than in mixed tanks. Nitrogen additions significantly increased total community biomass relative to controls in May and August, indicating that the communities were nitrogen-limited at these times. We conclude that while nitrogen additions may result in increases in phytoplankton biomass when nitrogen is limiting, phytoplankton community structure in the Neuse River Estuary may be determined more by the hydrodynamics of the system (mixing versus stratification) than by the form of nitrogen available for growth.     

Variability of the mixing zones and estuarine turbidity maxima in the Elbe and Weser estuaries

The neighboring coastal plain estuaries of the Elbe and Weser Rivers in Northern Germany exhibit pronounced estuarine turbidity maxima (ETM). Common features and differences between the longitudinal distributions of salinity and suspended particulate matter (SPM) in both estuaries are compared as well as the mechanisms effecting them. Monthly transects of the near surface SPM indicate that the long-term variability of salinity and the ETM is mainly influenced by the freshwater runoff. The variability is reduced to certain characteristic patterns by application of Empirical Orthogonal Functions analysis. The coefficients of these patterns are then correlated to runoff and the resulting functional regressions are used for the construction of a statistical model for the distribution of salinity and SPM along the estuaries; for SPM this has not been successful.     

On the estuarine mixing of dissolved substances in relation to colloid stability and surface properties

The estuarine mixing of dissolved Fe, Cu, Ni, Si and surface-active organic matter has been investigated in the Taieri Estuary, New Zealand, simultaneously with measurements of the electrokinetic charge on colloidal particles. Dissolved Fe showed almost quantitative removal from solution characteristic of the coagulation of iron-containing colloids by seawater electrolytes. Surface active organic matter behaved conservatively, indicating that a relatively constant fraction of estuarine organic matter is surface active, but that organic species associated with iron during removal are a minor fraction. Results for Cu, Ni and Si were scattered but offered no evidence for gross removal during estuarine mixing. The negative charge on suspended colloids was not reversed by adsorption of seawater cations, but remained uniformly negative throughout the salinity range, decreasing sharply in magnitude during the first few %. salinity.     

Dilution mixing estimates of trace metal concentrations in suspended sediments

Dilution mixing equations, at first glance, appear to provide an easy and useful approach for estimating pollutant loads in sediments of unmonitored stream channels. Results from Left Hand Creek, Colorado, however, indicate that only under proper circumstances can dilution mixing models be used to estimate suspended sediment metal concentrations in unmonitored channels with any accuracy. The utility of this technique is severely limited by errors at monitored sites in measuring metal concentrations within sediments and sediment discharge. Specifically, three general constraints must be met before making dilution mixing estimates of unmonitored concentrations: (1) estimated sediment discharges in an unmonitored tributary should be at least 30 percent of that in the main channel below the confluence; (2) there must be a significant difference between the estimated or monitored metal load in the channel below the confluence and the metal loads of the upstream channels; and (3) travel times between monitoring sites must be incorporated within the calculations.     

Predation on estuarine infauna: Response patterns of component species

The effect of predation by blue crabs and fishes on all species of infaunal macrobenthos of a subtidal sandy bottom in the York River, Virginia, was investigated by manipulative field experiments. Wire mesh cages were used both to exclude all large predators from and to confine different predators to small areas of the natural bottom. After 2 months, many species showed significant differences between the various treatments. There were similar patterns of species responses in three separate years. Species tended to fit one of two categories. Those species which had tough tubes, which lived deep in the sediment, or which could quickly retract deep into the sediment were shown experimentally not to change much in abundance regardless of whether predators were excluded or included. These species were generally the numerical dominants in the natural community—e.g.Peloscolex gabriellae, Heteromastus filiformis, Spiochaetopterus oculatus, andPhoronis psammophila. Other species which lived near the surface or exposed on the surface responded to experimentally altered predation intensity with large changes in density. These species were either uncommon or only sporadically abundant in the natural community—e.g.Polydora ligni, Streblospio benedicti, Mulinia lateralis, andLyonsia hyalina. This evidence indicates that the abundant species in the natural community are abundant because they avoid predators.     

Aluminium species distribution during mixing of acid coal and slate mine drainage with neutral stream waters

We measured the spatial variation of aluminium concentrations and computed its species distribution before and during mixing of acid mine drainage containing waters with near neutral receiving waters. Acid mine drainage was collected from the Loquitz Creek, Thuringia, Germany, and Garvey Creek, Westland, New Zealand, which drain slate mine workings and coal mine workings, resp. The acidneutralizing capacity (ANC) of the receiving streams and the mixing with waters having low Al-concentrations cause a decrease of aluminium concentrations below the confluence. Depending on volumes and ANCs involved, the content of free Al and sulphate bound Al decreases after mixing in favour of organic and hydroxide bound Al. In addition, below the junction of the Loquitz Creek and the Aue Creek with its high ANC, we observe the precipitation of aluminium hydroxides and Al hydroxysulphates.

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Zusammenfassung Wir haben die räumliche Änderung der Aluminiumkonzentrationen vor und nach der Mischung von Flußwasser, versauert durch Bergwerksabwässer, mit nahezu neutralem Wasser der Vorfluter gemessen und haben dazu die Speziesverteilung berechnet. Saure Bergwerksabwässer sickern aus Halden eines Schiefertagebaus in Thüringen in die Loquitz ebenso wie aus Halden eines Kohletagebaus in den Garvey Creek, Westland, Neuseeland. Die Säuren-Neutralisierungskapazität der Vorfluter und die Mischung mit Al-armem Wasser bewirken eine Abnahme der Aluminiumkonzentrationen nach dem Zusammenfluß. In Abhängigkeit von beteiligten Abflüssen und Säuren-Neutralisierungskapazitäten nimmt der Gehalt an freiem Aluminium und sulfatgebundenem Aluminium nach der Mischung zugunsten von organisch- und hydroxy-gebundenem Aluminium ab. Ferner beobachten wir unterhalb des Zusammenflusses von Loquitz und Aue, der eine hohe Säuren-Neutralisierungskapazität eigen ist, eine Ausfällung von Aluminiumhydroxyden und Aluminiumhydroxysulfaten.

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Résumé Nous avons mesuré la variation spatiale de la teneur en Al et calculé la distribution de ses différentes formes dans deux cours d'eau différents, qui reçoivent des eaux acides venant de mines situées sur leur cours. Ces mesures ont été faites d'une part sur le cours du Loquitz (Thuringe-Allemagne) qui reçoit des aux acides venant d'une mine d'ardoise et d'autre part sur le cours du Garvey (Westland - Nouvelle Zélande) qui reçoit les eaux d'une mine de charbon. Pour chaque cours d'eau, les mesures ont été faites en amont de la source d'apport, puis en aval, c'est-à-dire après le mélange avec les eaux acides. La capacité de neutralisation des acides (ANC) des eaux des cours d'eau récepteurs et la basse teneur en Al des eaux d'apport provoquent une diminution de la teneur en Al après le mélange. Dans une mesure liée aux volumes en jeu et à l'ANC, la teneur en Al libre et en Al lié au sulfate diminue près le mélange au profit de l'Al lié soit à des substances organiques, soit à des hydroxydes. De plus, en aval du confluent du Loquitz et de l'Aue, rivière à ANC élevé, nous observons la précipitation d'hydroxydes d'Al et d'hydroxisulfates d'Al.

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Mineralogy of metal contaminated estuarine sediments,Derwent estuary,Hobart, Australia: implications for metal mobility

The mobility, bioaccessibility and transfer pathways of metals and metalloids in estuarine sediments have been the focus of much detailed research. However, to date, few studies have examined the mineralogical siting of metals and metalloids in such sediments. This is despite the fact the mineralogy of sediments is an important factor that controls which and how much of a particular metal is released to pore waters and overlying water columns. This study reports on the mineralogical siting of metals in contaminated estuarine sediments, Hobart, Australia, and aims to evaluate the mobility of metals in the contaminated substrates. Mineralogical, mineral chemical and bulk chemical analyses demonstrate that the sediments contain very high levels of several metals and metalloids. The contaminated sediments have concentrations of zinc (Zn), lead (Pb), copper (Cu) and cadmium (Cd) ranging from 0.55 to 4.23 wt%, 0.16 to 0.70 wt%, 415 to 951 mg/kg and 23 to 300 mg/kg, respectively. Franklinite and lesser sphalerite are the main repositories of Zn, whereas much of the Pb and Cu is hosted by sulfides, organic matter and undetermined iron (Fe) oxides. While the release of contaminant loads from franklinite through dissolution is likely to be insignificant, even small releases of metals from the highly contaminated sediments can still cause the deterioration of local water quality. The contaminated sediments represent long-term sources of metal pollutants, particularly Zn, to local waters. This study demonstrates that mineralogical analyses are a vital tool to recognise the potential mobility of trace metals in estuarine environments.