The critical point and two-phase boundary of seawater, 200–500°C

The two-phase boundary of seawater was determined by isothermal decompression of fully condensed seawater in the range of 200–500°C. The pressure at which phase separation occurred for each isotherm was determined by a comparison of the refractive index of fluid removed from the top and bottom of the reaction vessel. The critical point was determined to be in the range of 403–406°C, 285–302 bar and was located by the inflection in the two-phase boundary and by the relative volume of fluid and vapor as a function of temperature. The two-phase boundary of 3.2% NaCl solution was found to coincide exactly with that of seawater over the range tested in the present study. The boundary for both is described by a single seventh-order polynomial equation. The two-phase boundary defines the maximum temperature of seawater circulating at depth in the oceanic crust. Thus the boundary puts a limit of about 390°C for seawater circulating near the seafloor at active ocean ridges (2.5 km water depth), and about 465°C at the top of a magma chamber occurring at 2 km below the seafloor.     

The ClBrI composition of 3.23 Ga modified seawater: implications for the geological evolution of ocean halide chemistry

Fluid inclusion leachates obtained from vug and vein quartz samples from an Archean (3.23 Ga) Fe-oxide hydrothermal deposit in the west-central part of the Barberton greenstone belt, South Africa, were analyzed by ion chromatography for chloride, bromide, and iodide. The deposit, known as the ironstone pods, formed by seafloor hydrothermal activity and fluid discharge. Quartz is dominated by type I liquid-vapor, aqueous inclusions with a bimodal salinity distribution (0–0.25 M_Cl⁻ and 0.9–1.8 M_Cl⁻). Bulk analytical salinities range from 0.45 to 0.99 M_Cl⁻ represent averages of type I inclusions. Bulk fluid inclusion bromide and iodide concentrations are 1.44–3.32 mM and 0.01–0.12 mM, respectively. For comparison, modern seawater has halogen contents of 590 mM chloride, 0.9 mM bromide, and 0.5 μM total iodine. In the fluids from the ironstone pods, bromide and iodide are enriched relative to chloride, when compared with modern seawater.Approximate Br⁻Cl⁻ and I⁻Cl⁻ ratios of 3.2 Ga Barberton seawater are 2.5 × 10⁻³ and 40 × 10⁻⁶, respectively. Dispersion to higher values was caused principally by reaction with organic sediments whose trends are similar to those seen for modern vent fluids at unsedimented and sedimented ridges, relative to modern seawater. These halide ratios are greater than those of modern seawater, suggesting a change in the halide ratios of seawater over geological time. The analytical data are consistent with a model in which marine organic sedimentation has fractionated bromine and iodine out of seawater relative to chloride, thereby causing the halide ratios of seawater to decrease from high early and mid-Archean values towards their present day values.     

Gypsum and halite from the Mid-Atlantic Ridge,DSDP Site 395

Gypsum and halite crystals, together with saponite and phillipsite, were found in a vein in a basalt sill 625 m below the sea floor at DSDP Site 395A, located 190 km west of the crest of the Mid-Atlantic Ridge. The δ³⁴S value of the gypsum (+19.4‰) indicates a seawater source for the sulfate. The δ¹⁸O values of the saponite (+19.9‰) and phillipsite (+18.1‰) indicate either formation from normal seawater at about 55°C or formation from¹⁸O-depleted seawater at a lower temperature.The gypsum (which could be secondary after anhydrite) was formed by reaction between Ca²⁺ released from basalt and SO₄^2? in circulating seawater. The halite could have formed when water was consumed by hydration of basalt under conditions of extremely restricted circulation. A more probable mechanism is that the gypsum was originally precipitated as anhydrite at temperatures above 60°C. As the temperature dropped the anhydrite converted to gypsum. The conversion would consume water, which could cause halite precipitation, and would cause an increase in the volume of solids, which would plug the vein and prevent subsequent dissolution of the halite.     

Purification of seawater contaminated with undegradable aromatic ring compounds using ozonolysis followed by titanium dioxide treatment

Treatment of aromatic ring compounds, 2,4-dichlorophenoxy acetic acid (2,4-D), 2,4,5-trichloro-phenoxy acetic acid (2,4,5-T), and bisphenol A, in the artificial seawater, i.e. Allen seawater, was carried out by ozonation and titanium dioxide (TiO2) photocatalyst treatment. Each compound was degraded and varnished within 30 min by only ozonolysis at pH 9.0 and at 20 degrees C, while the TOC value of each compound decreased gradually but reached almost constant value, i.e. about 70-80% of the initial value, at even 30 min of ozonation time. Ozonolysis (30 min of ozonation time) followed by TiO2 photocatalyst treatment (50h of reaction time) was a very effective method for decreasing the TOC values of aromatic ring compounds in the artificial seawater. In consequence, TOC values of 2,4-D, 2,4,5-T, and bisphenol A could be reduced to about 28, 21, and 34% of their initial values, respectively.     

Evolving patterns of the fluids within the TAG hydrothermal field

The mixing of seawater/hydrothermal fluid within the large seafloor hydrothermal sulfide deposits plays a key role in the formation processes of the sulfide deposits. Some issues attract considerable attentions in the study of seafloor hydrothermal system in recent years, such as the relationships among different types of vent fluids, the characteristics of chemical compositions and mineral assemblages of the hydrothermal deposits and their governing factors. Combined with the measured data of hydrothermal fluid in the TAG field, the thermodynamic model of mixing processes of the heated seawater at different temperatures and the hydrothermal fluid is calculated to understand the precipitation mechanism of anhydrite and the genetic relationships between the black and white smoker fluids within the TAG mound. The results indicate that the heating of seawater and the mixing of hydrothermal fluid/seawater are largely responsible for anhydrite precipitation and the temperature of the heated seawater is not higher than 150°C and the temperature of the end-member hydrothermal fluid is not lower than 400°C. Based on the simulated results, the evolving patterns of fluids within the TAG deposit are discussed. The mixed fluid of the end-member hydrothermal fluid and the seawater heated by wall rock undergoes conductive cooling during upflowing within the deposit and forms “White Smoker” eventually. In addition, the end-member hydrothermal fluid without mixed with seawater, but undergoing conductive cooling, vents out of the deposit and forms “Black Smoker”. Supported by China Ocean Mineral Resources Research and Development Association Program (Grant No. DY115-02-1-01) and National Basic Research Program of China (Grant No. G2000078503)     

On the accuracy of the bathymetry-generated gravitational field quantities for a depth-dependent seawater density distribution

In geophysical studies investigating the lithosphere structure, the gravitational field generated by the ocean density contrast (i.e., bathymetry-generated gravitational field) represents a significant amount of the signal to be modelled and subsequently removed from the Earth’s gravity field. The ocean density contrast is typically calculated as the difference between the mean density values of the Earth’s crust and seawater. The approximation of the actual seawater density distribution by its mean value yields relative errors up to about 2% in computed quantities of the gravitational field. To reduce these errors, a more realistic model of the seawater density distribution is utilized based on the analysis of existing oceanographic data of salinity, temperature, and pressure (depth). We study the accuracy of the bathymetry-generated gravitational field quantities formulated for a depth-dependent model of the seawater density distribution. This density distribution approximates the seawater density variations due to an increasing pressure with depth, whereas smaller lateral density variations caused by salinity, temperature, and other oceanographic factors are not taken into consideration. The error analysis reveals that the approximation of the seawater density by the depth-dependent density model reduces the maximum errors to less than 0.6%. The corresponding depth-averaged errors are below 0.1%. The depth-dependent seawater density model is further facilitated in expressions for computing the bathymetry-generated gravitational field quantities by means of the spherical bathymetric (ocean bottom depth) functions. The numerical realization reveals large differences in the results obtained with and without consideration of the depth-dependent seawater density distribution. The maxima of absolute differences reach 201 m²/s² and 16.5 mGal in computed values of the potential and attraction, respectively. The application of the depth-dependent seawater density model thus significantly improves the accuracy in the forward modelling of the bathymetric gravitational field quantities.     

Impacts of Seawater Rise on Seawater Intrusion in the Nile Delta Aquifer,Egypt

Several investigations have recently considered the possible impacts of climate change and seawater level rise on seawater intrusion in coastal aquifers. All have revealed the severity of the problem and the significance of the landward movement of the dispersion zone under the condition of seawater level rise. Most of the studies did not consider the possible effects of the seawater rise on the inland movement of the shoreline and the associate changes in the boundary conditions at the seaside and the domain geometry. Such effects become more evident in flat, low land, coastal alluvial plans where large areas might be submerged with seawater under a relatively small increase in the seawater level. None of the studies combined the effect of increased groundwater pumping, due to the possible decline in precipitation and shortage in surface water resources, with the expected landward shift of the shore line. In this article, the possible effects of seawater level rise in the Mediterranean Sea on the seawater intrusion problem in the Nile Delta Aquifer are investigated using FEFLOW. The simulations are conducted in horizontal view while considering the effect of the shoreline landward shift using digital elevation models. In addition to the basic run (current conditions), six different scenarios are considered. Scenarios one, two, and three assume a 0.5 m seawater rise while the total pumping is reduced by 50%, maintained as per the current conditions and doubled, respectively. Scenarios four, five, and six assume a 1.0 m seawater rise and the total pumping is changed as in the first three scenarios. The shoreline is moved to account for the seawater rise and hence the study domain and the seaside boundary are modified accordingly. It is concluded that, large areas in the coastal zone of the Nile Delta will be submerged by seawater and the coast line will shift landward by several kilometers in the eastern and western sides of the Delta. Scenario six represents the worst case under which the volume of freshwater will be reduced to about 513 km³ (billion m³).     

Dynamic response of an offshore pile to pseudo-Stoneley waves along the interface between a poroelastic seabed and seawater

A coupled model is developed to investigate the dynamic interaction between an offshore pile, a porous seabed and seawater when subjected to the pseudo-Stoneley wave along the seabed and the seawater interface. The pile and the seabed are treated as the porous medium governed by Biot's theory, while the seawater is considered as an acoustic medium and is described by the conventional Helmholtz equation. The free field solution of the incident pseudo-Stoneley wave is obtained using Biot's theory and the potential method. Based on the boundary element method (BEM) for the porous medium and the acoustic medium, three BEM formulations are constructed for the pile, the seabed and the seawater, respectively, which are combined together using the continuity conditions between the pile, the seabed and the seawater to formulate the coupled model for the system. As shown in numerical examples, when the system is subjected to the pseudo-Stoneley wave, the maximum pore pressure of the seabed usually occurs at the region near the interfaces between the seabed and the seawater.     

Metal-depleted root zones of the Troodos ore-forming hydrothermal systems, Cyprus

The cupriferous pyrite deposits of Cyprus were precipitated from hydrothermal solutions derived by interaction of contemporaneous seawater with hot mafic rock at the ancient Troodos spreading centre. Here we identify the zones in which this interaction took place. The zones occur in the lower part of the sheeted dyke complex, and within them 30–50% of the rock is made up of epidosite, an epidote-quartz rock, replacing the dykes as sheets and pipes. The epidosites contain abundant fluid inclusions, which give trapping temperatures of 350–400°C or even higher, and contain water normally near seawater in salinity. Zones of epidosite are elongate parallel to the strike of the sheeted dykes, and are up to 1 km wide. The rocks throughout these zones are strongly depleted in Cu and Zn, and the metals removed are sufficient to supply the ore deposits. In fact several large ore deposits lie along strike from zones of epidosite. All of these features support the identification of the epidosites as the hydrothermal reaction zones.The location of the epidosite zones immediately above the gabbros of the plutonic complex supports the hypothesis that the heat to drive the ore-forming systems came from the underlying magma, as is also likely for modern black smoker springs.     

Spectral Reflectance Analysis of the Caribbean Sea

Reflectance spectral curves were analysed by a derivative method. Derivative reflectance spectra revealed concealed peaks of both reflectance and absorption curves of Caribbean seawater and elements contained within it. Reflectance curves showed a predominant blue colour (400–500 nm) characteristic of Caribbean oligotrophic waters, conspicuous peaks result from the optical properties of chlorophyll a and seawater. Reflectance curves had a similar spectral response. This paper analyses reflectance spectra of surface seawater at 31 stations in the Caribbean Sea during the summer of 2001.     

Multivariate statistical analysis to identify the major factors governing groundwater quality in the coastal area of Kimje,South Korea

The main purpose of this study is to identify the major factors affecting groundwater quality by means of multivariate statistical analysis of the physico‐chemical compositions. Cluster analysis results show that the groundwater in the study area is classified into four groups (A, B, C and D), and factor analysis indicates that groundwater composition, 81·9% of the total variance of 17 variables, is mainly affected by three factors: seawater intrusion, microbial activity and chemical fertilizers. These results might be related to the geographical characteristics of the study area. The main influence on groundwater in groups B, C and D, which are close to the Yellow Sea and contain reclaimed areas, is the seawater intrusion by the present seawater, the trapped seawater, and microbial activity. Group A, however, has been used for agriculture for a long time, and thus groundwater in this group has been largely affected by chemical fertilizers. As groundwater flows from group A to group D according to its path, the governing factor of the groundwater quality gradually changes from chemical fertilizers to microbial activity and seawater intrusion. Copyright © 2004 John Wiley & Sons, Ltd.     

Polycyclic aromatic hydrocarbons in water and sediment of the Baltic Sea

Between 1992 and 1994, the distribution of 15 polycyclic aromatic hydrocarbons (PAHs) was investigated in seawater and surface sediments of the Baltic Sea. The analysis of PAHs in seawater is very difficult due to the low concentration. High separation capability is required. A method for analysing very low concentrations of PAHs is presented. The method is based on the high-performance liquid chromatography (HPLC) with fluorescence detection. The concentrations of PAHs in seawater are discussed in relation to water depth. A seasonal variation of PAHs in seawater was observed, with lowest concentrations occurring in summer and generally higher concentrations occurring in November. According to the regional distribution, elevated concentrations of PAHs were found in coastal regions of the Baltic Sea. The regional distribution of PAHs in surface sediments of the Belt Sea and the Arkona Basin were also investigated. The relationship between the content of PAHs and the percentage of total organic carbon in sediments is discussed.     

Temporal and spatial trends of total petroleum hydrocarbons in the seawater of Bohai Bay, China from 1996 to 2005

The temporal and spatial distribution of total petroleum hydrocarbons (TPH) in the seawater of Tianjin Bohai Bay during 1996-2005 was investigated for the first time. TPH concentrations in 480 seawater samples collected from 16 stations during a 10-year span were quantified by ultra-violet fluorescence spectroscopy. Petroleum hydrocarbons were ubiquitous in the seawater, and their concentrations were highly variable, ranging from 23.7 to 508 μg L⁻¹. TPH concentrations in the seawater varied with seasons, showing a decreasing order of winter > spring > summer. Over the 10-year period, TPH at all stations steadily decreased. The highest values obtained were at stations near the port areas and Dagu outfall where shipping activities and land-based waste water discharges were the major sources of pollution. Our results provided the background information on the extent of TPH contamination in the seawater and highlighted the need to further control TPH pollution in Tianjin Bohai Bay.     

Enzymatic methods for the determination of pollution in seawater using salt resistant alkaline phosphatase from eggs of the sea urchin Strongylocentrotus intermedius

A new salt resistant alkaline phosphatase from eggs of the sea urchin Strongylocentrotus intermedius (StAP) has been shown to have a unique property to hydrolyze substrate in seawater without loss of enzymatic activity. The enzyme has pH optimum at 8.0–8.5. Model experiments showed various concentrations of copper, zinc, cadmium and lead added to seawater or a standard buffer mixture to inhibit completely the enzyme activity at the concentrations of 15–150 μg/l. StAP sensitivity to the presence in seawater of metals, pesticides, detergents and oil products appears to be considerably less. Samples of seawater taken from aquatic areas of the Troitsy Bay of the Peter the Great Bay, Japan Sea have been shown to inhibit the enzyme activity; the same was shown for the samples of fresh waters. The phosphatase inhibition assay developed proved to be highly sensitive, technically easy-to use allowing to test a great number of samples.     

A study of marine pollution caused by the release of metals into seawater following acid spills

This study examined the potential metal pollution induced by the accidental spill of different acids into seawater. The acids sink to the bottom according to their densities and subsequently react with marine sediments. The acids selected for this study were acetic, hydrochloric, nitric, sulfuric, and phosphoric acids; the metallic elements selected were Cr, Cu, Fe, Mn, Pb and Zn. The sediment was collected in Brest Harbour. The percentages of metals released from this sediment in the presence of various concentrations of acids in seawater were important; concentrations of approximately 7 mg L⁻¹ for Mn and 60 mg L⁻¹ for Zn were observed under our experimental conditions. We also examined the rate of release of these metals from the sediment into the seawater in the presence of the different acids and under different experimental conditions. We found that most of the metallic elements were released from the sediments into the seawater during the first fifteen minutes of exposure. After this time, a high degree of pollution was induced if acids leached into seawater were not rapidly diluted.     

Biomonitoring with benthic macroalgae and direct assay of heavy metals in seawater of the Oporto coast (northwest Portugal)

The concentrations of dissolved Cd, Cu, Hg and Pb in seawater and algae (Enteromorpha spp. and Porphyra spp.) were determined in parallel on three beaches located in the Oporto coast (Portugal), during 8 successive months, comprising periods of low and high biological productivity. The concentrations of dissolved metals in seawater varied markedly during the sampling period and exhibited seasonality. The concentrations of Cd were high in autumn and winter, but low in spring. The concentrations of Cu and Hg were high in autumn, low in winter and peaked in May. The concentrations of Pb were low in autumn and winter, and also peaked in May. It is likely that biological activity was, at least partially, responsible for the observed seasonal changes. The mean concentrations of dissolved metals in seawater were similar to those reported for polluted and industrialized european coastal areas. Metal concentration factors, calculated month-to-month for each alga, metal and site, varied markedly during the sampling period, indicating that concentration factors based on single or few determinations could be misleading. On the contrary, mean concentration factors (calculated by dividing the mean metal concentration in the algae by the mean metal concentration in seawater) were relatively constant at all three sites, indicating that in the Oporto coast, Enteromorpha spp. can be used to estimate the mean concentration of dissolved Cd, Cu and Hg in seawater, and Porphyra spp., the mean concentration of Cd, Cu and Pb. However, considering that future estimates of the concentrations of these metals in seawater should be based on determinations of the metal contents in Enteromorpha spp. and Porphyra spp. carried out on several occasions spanning a considerable period of time, the use of these algae as monitors of heavy metal pollution can have limited practical advantages over the direct assay of the metals in seawater.     

Inverse modeling for seawater intrusion in coastal aquifers: Insights about parameter sensitivities,variances, correlations and estimation procedures derived from the Henry problem

Inverse modeling studies employing data collected from the classic Henry seawater intrusion problem give insight into several important aspects of inverse modeling of seawater intrusion problems and effective measurement strategies for estimation of parameters for seawater intrusion. Despite the simplicity of the Henry problem, it embodies the behavior of a typical seawater intrusion situation in a single aquifer. Data collected from the numerical problem solution are employed without added noise in order to focus on the aspects of inverse modeling strategies dictated by the physics of variable-density flow and solute transport during seawater intrusion. Covariances of model parameters that can be estimated are strongly dependent on the physics. The insights gained from this type of analysis may be directly applied to field problems in the presence of data errors, using standard inverse modeling approaches to deal with uncertainty in data.     

Hydrothermal alteration of green tuff belt, Japan: Implications for the influence of seawater/volcanic rock interaction on the seawater chemistry at a back-arc basin

Abstract Chemical data on hydrothermally altered volcanic rocks from a green tuff belt in Japan indicate that the average rate of Mg removal from seawater due to seawater cycling through back-arc basins in the circum-Pacific region during the early to middle Miocene (25–15 Ma) is estimated to be 2.6±1 × 10¹³ g/year. This is similar to that through present-day mid-ocean ridges (2.4 × 10¹³ g/year). Hydrothermal fluxes of K, Ca and Si are calculated to be 4.2±1.6 × 10¹³ g/year, 4.3±1.7×10¹³ g/year and 1.0±0.4 × 10¹⁴ g/year, respectively. These calculated results indicate that the seawater/volcanic rocks interaction at subduction-related tectonic settings have to be taken into account in considering the geochemical mass balance of seawater over geologic time.     

The extent of hydrocarbon contamination in the marine environment from a research station in the Antarctic

Low level hydrocarbon contamination is measurable in the vicinity of Antarctic stations, N-alkane and polycyclic aromatic hydrocarbon (PAH) concentrations in seawater and sediment at Signy Station, South Orkney Islands indicated contamination was confined to within a few hundred metres of the station. Total n-alkane concentrations in seawater decreased from 7.6 to 2.6 μg l⁻¹ within 500 m of the station. All n-alkane values in seawater were within the limits of variation for oceanic waters proposed by cripps (1992), although the distribution pattern suggested pollution from the station. The total PAH concentration in seawater varied between 110 and 216 ng l⁻¹. These values showed no trend with distance from the station and were all slightly higher than for the open ocean. The n-alkane and PAH concentations in the surface sediment declined to low levels within 375 m of the station. This indicates that a large proportion of the hydrocarbons entering Factory Cove was deposited from the water column. Sediment n-alkane concentrations were similar at all depths of the cores when collected more than 125 m from the station. PAH levels in the sediment appeared to be due to local input, including a small spill in 1965.