The ionization of acids in estuarine waters

The stoichiometric, $\text{K}{}_{\mathrm{HA}}{}^1$, and apparent, K'_HA, constants for the ionization of a number of weak acids (NH₄⁺, HSO₄^?, HF, H₂O, B(OH)₃, H₂CO₃, HCO₃^?, H₃PO₄, H₂PO₄^?, HPO₄², H₃AsO₄ H₂AsO₄^? and HAsO₄^2?) in seawater at 25°C diluted with water have been fitted to equations of the form (Millero, 1979). In $\text{K}{}_{\mathrm{HA}}{}^1\text{= In K}{}_{\mathrm{HA}}\text{+ AS}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{+ BS}$ where In K_HA is the thermodynamic constant in water, S is the salinity, A and B are adjustable parameters. The validity of this equation in estuarine waters has been examined by using an ion pairing model (Millero and Schreiber, 1981). The calculated values of $\text{K}{}_{\mathrm{HA}}{}^1$ and K'_HA at S = 35%. are in good agreement with the measured values for all the systems examined. The equation used to extrapolate the measured values to pure water K_HA predicted values that agreed with those determined by using the ion pairing model. The exception was the ionization of HPO₄^2? due to the strong interactions of Ca²⁺ and Mg²⁺ with PO₄^3?. The differences in the predicted values of $\text{K}{}_{\mathrm{HA}}{}^1$ in seawater diluted with pure water and average river water were very small for all the acids except HPO₄^2? (the maximum ΔpK = 0.96 in average river water). The larger difference in the $\text{K}{}_{\mathrm{HA}}{}^1$ for HPO₄^2? in river waters is due to the strong interactions of Ca²⁺ and PO₄^3?.     

Silver in San Francisco Bay estuarine waters

Spatial gradients of silver concentrations in the surface waters of San Francisco Bay reveal substantial anthropogenic perturbations of the biogeochemical cycle of the element throughout the estuarine system. The most pronounced perturbations are in the south bay, where dissolved (<0.45 μm) silver concentrations are as high as 250 pM. This is more than one order-of-magnitude above baseline concentrations in the northern reach of the estuary (6 pM) and approximately two orders-of-magnitude above natural concentrations in adjacent coastal waters (3 pM). The excess silver is primarily attributed to wastewater discharges of industrial silver to the estuary on the order of 20 kg d^?1. The contamination is most evident in the south bay, where wastewater discharges of silver are on the order of 10 kg d^?1 and natural freshwater discharges are relatively insignificant. The limited amount of freshwater flushing in the south bay was exacerbated by persistent drought conditions during the study period. This extended the hydraulic residence time in the south bay (≥160 d), and revealed the apparent seasonal benthic fluxes of silver from anthropogenically contaminated sediments. These were conservatively estimated to average ≈16 nmol m^?2 d^?1 in the south bay, which is sufficient to replace all of the dissolved silver in the south bay within 22 d. Benthic fluxes of silver throughout the estuary were estimated to average ≈11 nmol m^?2 d^?1, with an annual input of approximately 540 kg yr^?1 of silver to the system. This dwarfs the annual fluvial input of silver during the study period (12 kg yr^?1) and is equivalent to approximately 10% of the annual anthropogenic input of silver to the estuary (3,700–7,200 kg yr^?1). It is further speculated that benthic fluxes of silver may be greater than or equal to waste water fluxes of silver during periods of intense diagenic remobilization. However, all inputs of dissolved silver to the estuary are efficiently sorbed by suspended particulates, as evidenced by the relatively constant conditional distribution coefficient for silver throughout the estuary (K_d≈10⁵).     

Sulfate enrichments in estuarine waters of North Carolina

Sulfate concentrations in the mesohaline surface waters of the Pamlico and Neuse River estuaries were enriched, relative to the conservative seawater ratio with Cl^? (0.0517 (M)), by 5 to 43% between late winter and early summer. During this period, sulfate concentrations increased to a maximum excess of 3.5 mM in the bottom waters (0.5 m deep) through intermittent periods of both very low river flow and bottom water anoxia. The calculated net sulfate production rate for this period was 18 mmol per m² per d in the bottom waters. By late summer, the excess sulfate (an average of 12 mol per m²) had been removed from the water column, presumably due to SO₄ ^?2 reduction in anoxic bottom waters and sediments. Qualitative laboratory experiments with slurries of mud exposed to excess O₂ and treated with inhibitors of cytochrome oxidase showed that it was possible to produce the excess SO₄ ^?2 under these conditions via biochemical (not chemical) oxidation of pyride that occurs within the top 5 cm of mud (ca. 100 mmol pyrite-S per g dry mud). Whether the in situ substrate for SO₄ ^?2 production was pyrite, S⁰, or S⁺², is unknown, but the predominance of aqua regia extractable pyrite-Fe and the accumulation of excess SO₄ ^?2 in slurries with insufficient other sources of oxidizable S, indicates that it may be an important substrate for biochemical production of SO₄ ^?2.     

Detoxification of chlorinated sewage effluent by dechlorination in estuarine waters

Secondary treated sewage was chlorinated to a residual level of 2–10 mg/l in a continuous flow system in the laboratory and diluted to various levels with estuarine water. A portion of the chlorinated sewage effluent was dechlorinated with sodium thiosulfate and the dechlorinated waste was diluted with estuarine water in the same proportions as the chlorinated waste.Menidia menidia, Palaemonetes pugio andCrassostrea virginica were exposed to chlorinated and dechlorinated treatments. High concentrations of chlorinated effluent caused mortalities inM. menidia andP. pugio, whereas similar concentrations of dechlorinated wastes did not cause mortalities. Mortalities in the chlorinated waste are correlated with chlorine residuals. Similarly, the chlorinated wastes depressed the shell deposition rate ofC. virginica below 50% of controls at all doses. Dechlorinated waste allowed shell deposition greater than 50% of controls. However, the occurrence of some growth inhibition inC. virginica exposed to dechlorinated waste suggests the presence of toxic material in the waste other than chlorine.     

The shot-sensor method of measuring currents in shallow estuarine waters

A current measuring device, the Shot-Sensor, was developed as a low cost alternative to measuring water flow speeds and directions using conventional, more expensive instrumentation. The device releases stainless steel shot of known size and settling speed into a flowing water mass. As the shot settles, it is dispersed by currents and ends up in settling traps. Mean current speed and direction can be calculated from the patterns of dispersal and the percentages of shot of various sizes in the traps. Determination of precision and accuracy indicate that the Shot-Sensor can measure within a few cm s^?1 of more expensive meters and may be suitable for some shallow-water applications. Speed range of the Shot-Sensor is presently limited between 3 and 40 cm s^?1, but further development could allow this range to be extended.     

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.     

Influence of land use on macrobenthic communities in nearshore estuarine habitats

Macrobenthic community indices were examined for their ability to characterize the influence of shoreline alteration and watershed land use in nearshore estuarine environments of the Chesapeake Bay, U.S.A. Twenty-three watersheds were surveyed in 2002 and 2003 for nearshore macrobenthic assemblages, environmental parameters (i.e., dissolved oxygen, pH, total suspended solids, salinity, and sediment composition), shoreline condition, and land use. Two indices of macrobenthic biological integrity, benthic index of biological integrity in the nearshore (B-IBI_N) and abundance biomass comparison (W-value), were evaluated for associations with environmental and shoreline condition, and riparian and watershed land use. Comparisons between nearshore measures of the B-IBI with offshore values (>2 m; Chesapeake Bay benthic index of biological integrity [B-IBI_CB]) were conducted to assess the ability of the index to reflect land use patterns at near and far proximities to shore. Nearshore macrobenthic communities were represented by a total of 94 species (mean number of species =9.2 ± 0.4 sample⁻¹), and were dominated by the phyla Arthropoda, Annelida, and Mollusca. Temporal variability in environmental conditions and macrobenthic abundance and biomass may be attributable to the notable increase in precipitation in 2003 that led to nutrient influxes and algal blooms. For the biotic indices applied in the nearshore, the highest scores were associated with forested watersheds (W-value, B-IBI_N). Ecological thresholds were identified with nonparametric change-point analysis, which indicated a significant reduction in B-IBI_N and W-value scores when the amount of developed shoreline exceeded 10% and developed watershed exceeded 12%, respectively.     

Survival of F-RNA coliphages and three bacterial indicators during wastewater chlorination and transport in estuarine waters

Three bacterial water quality indicators,Clostridium perfringens, enterococci, and fecal coliforms, were compared to F-RNA coliphages for their survival during chlorination at several municipal wastewater treatment plants in Rhode Island and seasonally during transport in a section of the Narragansett Bay estuary. F-RNA coliphages were used as the best available indicator for the survival of Noroviruses (formerly Norwalk-like virus), the most frequently identified agent for the most prevalent waterborne disease (an acute but benign gastroenteritis), which has yet to be propagated in tissue culture and for which there is no lower animal model. Inactivation of the enterococci and fecal coliforms during wastewater chlorination was much greater than that of the F-RNA coliphages whose inactivation was essentially the same as that of C.perfringens. Survival of the F-RNA coliphages andC. perfringens during winter transport down Narragansett Bay were comparable to each other and greater than that for the enterococci or fecal coliforms. During the summer,C. perfringens survived longer than the other three indicators, possibly because the virus-like (F-RNA coliphages) and the two vegetative bacterial indicators were more susceptible than theC. perfringens spores to the lethal effects of sunlight and elevated water temperatures during the summer. Based on these findings, F-RNA coliphages seems to be a reliable indicator of viral contamination and die-off in estuarine waters.     

Comparison of habitat use by estuarine fish assemblages in the Acadian and Virginian zoogeographic provinces

Comparison of the relative abundance of fish species from different life-history groups and their temporal patterns of estuarine habitat use from two estuaries north and south of Cape Cod indicates that the Cape acts as a zoogeographic boundary. Between April 1988 and December 1989, monthly seine and trawl samples were collected from nearshore, shallow-water marsh, and beach and deeper open-water habitats in Wells Harbor, Maine, and Waquoit Bay, Massachusetts. Forty-eight species and 80,341 individuals were collected from Waquoit Bay compared to 24 species and 22,561 individuals from Wells Harbor. Waquoit Bay had proportionally fewer resident species and more marine, nursery, and occasional species than Wells Harbor. Annual density and biomass values were greater across all habitats in Waquoit Bay, with the summer values from the marsh habitat an order of magnitude higher than comparable summer data from the Wells habitats. We suggest that marsh and beach habitats provide a nursery area for young-of-the-year fishes, while deeper, open-water habitats serve as a corridor for fishes moving to nearshore habitats or serve as a refuge during low tide.     

Occurrence and use of mineral and thermal waters in Poland

Mineral and thermal waters are defined according to Polish geological and mining law. Their occurrence in particular hydrogeological provinces of the country is characterized. Besides their use in balneotherapeutics, their role as a heat carrier and source of chemical raw materials is stressed. Topics mentioned requiring further research are: the origin of saline formation waters and the origin of CO₂ in carbonated waters.     

Concentrations,physico-chemical states and mean residence times of 210Pb and 210Po in marine and estuarine waters

The concentrations and physico-chemical states of ²¹⁰Pb have been measured in Bikini Atoll and Washington State coastal waters, and ²¹⁰Po in Washington coastal waters. Lead-210 concentrations of 113–133 dpm · m^?3 were found in surface water collections near Bikini Atoll and 29–153 dpm · m^?3 in Bikini Lagoon. The concentrations of ²¹⁰Pb in near Bikini and in Washington State waters increased with depth in the upper 150m at a rate of 0.35–0.45dpm·m^?3 · m^?1. In the North Equatorial Current waters near Bikini Atoll ²¹⁰Pb was found associated predominantly with the soluble (colloidal) fraction, but in Washington coastal waters ²¹⁰Pb and ²¹⁰Po were found associated with the paniculate (> 0.3 μm) fraction. The mean residence times of ²¹⁰Pb, calculated from the atmospheric input to marine waters from precipitation and the concentrations measured in surface water, were consistent with the physico-chemical states of ²¹⁰Pb found in samples collected in deep ocean and coastal waters. Approximate values of the mean residence times were calculated, for the upper 50 m, to be as follows: 58 days in the Strait of Juan de Fuca, 128 days at the 5-mile (8 km) station off Cape Flattery (Washington), 163 days at the 12-mile (19 km) station off Cape Flattery, and 2.6 yr near Bikini Atoll. It appears that ²¹⁰Pb and ²¹⁰Po can be used to trace particle removal rates in the upper layers of marine waters.     

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.     

The use of sediment cores to reconstruct historical trends in contamination of estuarine and coastal sediments

Most studies using sediment cores to reconstruct the contamination history of coastal and estuarine areas around the world have dealt with trace metals, and only a few have focused on organic contaminants. Almost without exception, the studies published up to 1990 have shown that sediment contamination increased in the late 1800s, accelerated in the 1940s, and reached a plateau or a maximum in the 1960–1970s. For some pollutants, such as Pb, a decrease in concentration occurred in the 1980s, following the implementation of new discharge and emission regulations. Little is known, however, about concentration trends from the mid-1980s to present and about the effect of legislation recently passed to protect the environment.     

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.     

Propagation of tides in the Mandovi-Zuari estuarine network

Located in Goa on the west coast of India and joining the Arabian Sea, the Mandovi and the Zuari are two estuaries, each about 50 km long, connected by a narrow canal. A number of small rivers join the two estuaries, forming a network of channels, whose cross-sectional area decreases rapidly in the upstream direction. They receive large freshwater influx during the southwest monsoon and little during the rest of the year. During April (dry season) and August (wet season) 1993, the water level and salinity at 15 locations in the network were monitored for 3 days to determine characteristics of tidal propagation in the network. Analysis of the data shows that the speed of propagation of both the diurnal and the semi-diurnal tide through the main channels of the network is approximately 6 m/s. Amplitudes of these tides in the channels remain unchanged over a distance of about 40 km from the mouth and then decay rapidly upstream over the next 10 km. The undamped propagation is a consequence of the balance between geometric amplification, due to decrease in the cross-sectional area in the upstream direction, and frictional dissipation. The rapid decay near the upstream end of the channels appears to result primarily from freshwater influx.     

An assessment of habitat use by larval fishes in a warm temperate estuarine creek using light traps

Habitat use by larval fishes was investigated in a tidal creek of the Swartkops estuary, South Africa, during a trial study using light traps. A total of 12 fish families represented by 28 species were recorded during October and November 2000. Fishes caught were predominantly in a postflexion stage of larval development although preflexion larvae and some early juveniles were also recorded. The distribution of larval fishes indicated that fishes were influenced by proximity to either channel or littoral regions of the creek rather than showing specific preferences for eelgrass covered areas. Estuary-dependent marine species were caught in higher numbers along the margins of the estuary. Length frequencies of both estuary-resident and estuary-dependent marine fishes showed that larger individuals were found in the littoral regions suggesting active migration of these fishes to the margins. Catches of straggler marine species were higher in the channel areas and showed no difference in size distribution between littoral and channel sites. Estuary-dependent species may be using marginal areas as a means of avoiding high flow in the channel and as a predator avoidance mechanism. Light traps were found to be a useful sampling device for localized studies on the early life stages of fishes in an estuary.     

Phosphorus uptake by microplankton in estuarine and coastal shelf waters near Sapelo Island,Georgia, U.S.A.

The residence times of orthophosphate measured in midsummer in estuarine and coastal shelf waters near Sapelo Island, Georgia, ranged from 1.6 to 105 h. Rates of orthophosphate uptake by microplankton varied from 1.4 to 62.2 μg P per 1 per h. Generally, when isotopic equilibrium was reached after the addition of³²P-orthophosphate, significant amounts of³²P-remained in solution, suggesting that the supply of phosphorus to microplankton was not limiting in these waters. In coastal shelf waters, the majority of phosphorus uptake (>60%) was associated with small microorganisms (<1μm); whereas, in estuarine waters or in a Gulf Stream intrusion usually a proportionately greater amount of phosphorus was incorporated into larger algae, or clumped or attached bacteria (>1μm). The time course of³²P-orthophosphate incorporation into a cold, 10% TCA insoluble, cellular fraction was more consistently linear than into whole cells. This criterion may be useful for comparative studies of phosphorus utilization by microplankton.     

Salmonid fishes and the estuarine environment

Salmonid fishes are typically anadromous, that is, they achieve the bulk of their growth in the sea, and migrate into rivers to reproduce. As juveniles, they may arrive in the estuary almost immediately after emergence from a gravel bed in the river, or after a few days, weeks, months, or years in fresh water, according to species and developmental opportunity. Thereafter, the length of estuarine residence depends on the estuary’s size, shape, and productivity; on water flow patterns and velocities; on salinity and temperature; and on the species and size of the salmon. It is supposed that estuaries offer salmonids three primary advantages: productive foraging, relative refuge from predators, and a physically intermediate environment for transition from fresh water to marine physiological control systems. The present paper finds the evidence for the foraging advantage strong, for the predator refuge equivocal, and for the physiological transition function applicable particularly to Pacific species migrant at the fry stage.