Comparison of Measured and PTF Predictions of SWCCs for Loess Soils in China

There are significant advantages in using indirect pedo-transfer functions, (PTFs) for the estimation of unsaturated soil properties. The pedo-transfer functions can be used for the estimation of the soil–water characteristic curve (SWCC) which in turn is used for the estimation of other unsaturated soil properties. The accuracy of the indirect pedo-transfer function method for the estimation of the SWCC depends on the PTF and the equation used to best-fit the particle-size distribution (PSD) data. The objectives of this study are to: (1) evaluate the performance of the Fredlund et al. (Can Geotech J 37:817–827, 2000) equation for best-fitting the particle-size distribution, (PSD) data, and, (2) compare the predictions made by two of the commonly used PTFs; namely, Arya and Paris (Soil Sci Soc Am J 45:1023–1030, 1981) and Fredlund et al. (Can Geotech J 39:1103–1117, 2002), for estimating the SWCC from the PSD. The authors used 258 measured PSDs and SWCC datasets from the Loess Plateau, China, for this study. The dataset consisted of 187 silt–loam soils, 41 loam soils, 11 silt–clay–loam soils, 10 sand–loam soils, 6 silt–clay soils, and 3 loam–sand soils. The SWCC and PSD datasets were measured using a Pressure Plate apparatus and the pipette method, respectively. The comparison between the estimated and measured particle-size distribution curves showed that the Fredlund et al. (Can Geotech J 37:817–827, 2000) equation closely prepresented the PSD for all soils in the Loess Plateau, with a lower root mean square error (RMSE) of 0.869%. The comparison between the estimated and measured water contents at the same suction showed that the Fredlund et al. (Can Geotech J 39:1103–1117, 2002) PTF performed somewhat better than the Arya and Paris (Soil Sci Soc Am J 45:1023–1030, 1981) function. The Fredlund et al. method had RMSE value of 0.039 cm³ cm⁻³ as opposed to 0.046 cm³ cm⁻³ for the Arya and Paris (Soil Sci Soc Am J 45:1023–1030, 1981) method. The Fredlund et al. (Can Geotech J 39:1103–1117, 2002) PTF produced the closest predictions for sand–loam, loam–sand, and loam soils, with a lower RMSE for gravimetric water content ranging from 0.006 to 0.036 cm³ cm⁻³. There were consistent over-estimations observed for silt–loam, silt–clay–loam, and slit–clay soils with RMSE values for gravimetric water content ranging from 0.037 to 0.043 cm³ cm⁻³. The measured and estimated air-entry values were closest when using the Fredlund et al. (Can Geotech J 39:1103–1117, 2002) PTF. The measured and estimated maximum slopes on the SWCC were closest when using the Arya and Paris (Soil Sci Soc Am J 45:1023–1030, 1981) PTF.     

Fine-scale responses of phytoplankton to freshwater influx in a tropical monsoonal estuary following the onset of southwest monsoon

In May of 2007, a study was initiated by the National Institute of Oceanography (NIO), Goa, India, to investigate the influence of monsoonal rainfall on hydrographic conditions in the Mandovi River of India. The study was undertaken at a location ∼2 km upstream of the mouth of this estuary. During the premonsoon (PreM) in May, when circulation in the estuary was dominated by tidal activity, phytoplankton communities in the high saline (35–37 psu) waters at the study site were largely made up of the coastal neritic species Fragilaria oceanica, Ditylum brightwellii and Trichodesmium erythraeum. During the later part of the intermonsoon (InterM) phase, an abrupt decline in salinity led to a surge in phytoplankton biomass (Chlorophyll a ∼14 mg m^− 3), of a population that was dominated by Thalassiosira eccentricus. As the southwest monsoon (SWM) progressed and the estuary freshened salinity and Chlorophyll a (Chl a) concentrations decreased during the MoN, Skeletonema costatum established itself as the dominant form. Despite the low biomass (Chl a <2 mg m^− 3), the phytoplankton community of the MoN was the most diverse of the entire study. During the postmonsoon (PostM), the increase in salinity was marked by a surge in dinoflagellate populations comprising of Ceratium furca, Akashiwo sanguinea, and Pyrophacus horologium.     

Spatial and temporal patterns in sediment and water column nutrients in a eutrophic Southern California estuary

Quarterly field sampling was conducted to characterize variations in water column and sediment nutrients in a eutrophic southern California estuary with a history of frequent macroalgal blooms. Water column and sediment nutrient measures demonstrated that Upper Newport Bay (UNB) is a highly enriched estuary. High nitrate (NO₃ ⁻) loads from the river entered the estuary at all sampling times with a rainy season (winter) maximum estimated at 2,419 mol h⁻¹. This resulted in water NO₃ ⁻ concentration in the estuary near the river mouth at least one order of magnitude above all other sampling locations during every seasons; maximum mean water NO₃ ⁻ concentration was 800 μM during springer 1997. Phosphorus (P)-loading was high year round (5.7–90.4 mol h⁻¹) with no seasonal pattern. Sediment nitrogen (N)-content showed a seasonal pattern with a spring maximum declining through fall. sediment and water nutrients, as well as percent cover of three dominant macroalgae, varied between the main channel and tidal creeks. During all seasons, water column NO₃ ⁻ concentrations were higher in the main channel than in tidal creeks while tidal creeks had higher levels of sediment total Kjeldhal nitrogen (TKN) and P. During each of the four sampling periods, percent cover ofEntermorpha intestinalis andCeramium spp. was higher in tidal creeks than in the main channel, while percent cover ofUlva expansa was always higher in the main channel. Decreases in sediment N in both creek and channel habitats were concurrent with increases in macroalgal cover, possibly reflecting use of stored sediment TKN by macroalgae. Our data suggest a shift in primary nutrient sources for macroalgae in UNB from riverine input during winter and spring to recycling from sediments duirng summer and fall.     

Water quality analysis of a freshwater diversion at Caernarvon, Louisiana

Since 1991, Mississippi River water has been diverted at Caernarvon, Louisiana, into Breton Sound estuary. Breton Sound estuary encompasses 1100 km² of fresh and brackish, rapidly subsiding wetlands. Nitrite + nitrate, total Kjeldahl nitrogen, ammonium, total phosphorus, total suspended sediments, and salinity concentrations were monitored at seven locations in Breton Sound from 1988 to 1994. Statistical analysis of the data indicated decreased total Kjeldahl nitrogen with associated decrease in total nitrogen, and decreased salinity concentrations in the estuary due to the diversion. Spring and summer water quality transects indicated rapid reduction of nitrite + nitrate and total suspended sediment concentration as diverted Mississippi River water entered the estuary, suggesting near complete assimilation of these constituents by the ecosystem. Loading rates of nitrite + nitrate (5.6–13.4 g m⁻² yr⁻¹), total nitrogen (8.9–23.4 g m⁻² yr⁻¹), and total phosphorus (0.9–2.0 g m⁻² yr⁻¹) were calculated along with removal efficiencies for these constituents (nitrite + nitrate 88–97%; total nitrogen 32–57%; total phosphorus 0–46%). The low impact of the diversion on water quality in the Breton Sound estuary, along with assimilation of TSS over a very short distance, suggests that more water may be introduced into the estuary without detrimental affects. This would be necessary if freshwater diversions are to be used to distribute nitrients and sediments into the lower reaches of the estuary, in an effort to compensate for relative sea-level rise, and reverse the current trend of rapid loss of wetlands in coastal Louisiana.     

Seasonal cycling of arsenic species in a stratified,microtidal estuary (Huon River,Tasmania)

A detailed study of arsenic cycling in the Huon estuary, south-east Tasmania, was undertaken October 1996–September 1998. Arsenic species data were obtained during eight 3-monthly spatial surveys, and a time-series study at a single site in the estuary over a 7-mo period. The data have been correlated with other chemical measurements, including nutrients, salinity, and dissolved oxygen, and also with biological information about the microalgal species present. In the Huon estuary, arsenic cycling is almost entirely biologically influenced. The seasonal cycle of reduced, methylated, and hydride refractory arsenic species was similar to that found in other temperate estuaries of the Northern hemisphere, with greatest production occurring during summer months. Inorganic arsenic concentrations in the Huon River were very low [As(V+III): 0.023–0.057 μg l⁻¹], even when compared with other pristine systems. Concentrations at the seaward end of the estuary were typical of those found in unpolluted coastal seawater. The behavior of As(V+III) in the estuary was nearly conservative in all surveys except those conducted during summer (February), when significant depletion was observed at higher salinity. During these surveys, up to 60% of inorganic arsenic was apparently depleted from the water column with only a small proportion (20–25%) recycled as methylated and UV-labile arsenic species. This was particularly the case in a high salinity side-arm of the estuary, Port Cygnet. The extent of inorganic arsenic depletion correlated with cell numbers of the phytoplanktonPseudo-nitzschia. The fate of the missing inorganic arsenic is unclear, but the co-existence ofPseudo-nitzschia blooms with commercial mussel leases in Port Cygnet could provide one explanation for the loss.     

Suspended Matter,Chl-a,CDOM, Grain Sizes,and Optical Properties in the Arctic Fjord-Type Estuary,Kangerlussuaq, West Greenland During Summer

Optical constituents as suspended particulate matter (SPM), chlorophyll (Chl-a), colored dissolved organic matter (CDOM), and grain sizes were obtained on a transect in the arctic fjord-type estuary Kangerlussuaq (66°) in August 2007 along with optical properties. These comprised diffuse attenuation coefficient of downwelling PAR (K _d(PAR)), upwelling PAR (K _u(PAR)), particle beam attenuation coefficient (c _p), and irradiance reflectance R(−0, PAR). PAR is white light between 400 and 700 nm. The estuary receives melt water from the Greenland Inland Ice and stations covered a transect from the very high turbid melt water outlet to clear marine waters. Results showed a strong spatial variation with high values as for suspended matter concentrations, CDOM, diffuse attenuation coefficient K _d(PAR), particle beam attenuation coefficients (c _p), and reflectance R(−0, PAR) at the melt water outlet. Values of optical constituents and properties decreased with distance from the melt water outlet to a more or less constant level in central and outer part of the estuary. There was a strong correlation between inorganic suspended matter (SPMI) and diffuse attenuation coefficient K _d(PAR) (r ² = 0.92) and also for particle beam attenuation coefficient (c _p; r ² = 0.93). The obtained SPMI specific attenuation—K _d^*(PAR) = 0.13 m² g⁻¹ SPMI—and the SPMI specific particle beam attenuation—c _p^* = 0.72 m² g⁻¹—coefficients were about two times higher than average literature values. Irradiance reflectance R(−0, PAR) was comparatively high (0.09−0.20) and showed a high (r ² = 0.80) correlation with K _u(PAR). Scattering dominated relative to absorption—b(PAR)/a(PAR) = 12.3. Results strongly indicated that the high values in the optical properties were related to the very fine particle sizes (mean = 2–6 μm) of the suspended sediment. Data and results are discussed and compared to similar studies from both temperate and tropical estuaries.     

Sorption Model for Dissolved and Leachable Particulate Aluminium in the Great Ouse Estuary, England

The behaviour of dissolved Al in the Great Ouse estuary, in particular with respect to salinity, is complex. There is, however, evidence from field data as well as laboratory mixing experiments to suggest that flocculation and sorption mechanisms play important roles affecting the concentrations of dissolved Al during the early stages of estuarine mixing. In contrast, a near-buffering of dissolved Al occurs in the entire stretch of the estuary (salinity >0.2) with concentrations varying around 1.4 μg l⁻¹. This distribution and lack of variation with salinity is attributable to sorption processes which might dominate over other processes in these turbid estuarine waters (suspended particulate load 48–888 mg l⁻¹) impacting dissolved Al levels. Sorption models have been developed for both dissolved and leachable particulate Al concentrations in these waters. These observations provide compelling evidence of sorption processes that might be important in the geochemistry of Al in estuarine waters.     

The Contribution of Benthic Nutrient Regeneration to Primary Production in a Shallow Eutrophic Estuary,Weeks Bay,Alabama

Benthic oxygen, dinitrogen, and nutrient fluxes (NH₄⁺, NO₃⁻, and PO₄³⁻) were measured monthly during a 1-year period at two locations in Weeks Bay, a shallow (1.4 m) and eutrophic estuary in Alabama. Gross primary productivity (GPP), ecosystem respiration (R), and net ecosystem metabolism were determined from high-frequency dissolved oxygen measurements. Peak water column NO₃⁻ (55 μM) and chlorophyll a (138 μg/l) concentrations were measured during spring and fall, respectively. Sediments were a net source of NH₄⁺ (102 μmol m⁻² h⁻¹) and PO₄³⁻ (0.9 μmol m⁻² h⁻¹) but a sink for NO₃⁻ (−30 μmol m⁻² h⁻¹). Benthic N₂ fluxes indicated net N fixation (12 μmol N m⁻² h⁻¹). Sediment oxygen demand (0.55 g O₂ m⁻² day⁻¹) accounted for <10% of R (7.3 g O₂ m⁻² day⁻¹). Despite high GPP rates (4.7 g O₂ m⁻² day⁻¹), the estuary was net heterotrophic. Benthic regeneration supplied, on average, 7.5% and 4% of primary productivity N and P demands, respectively. These results contrast with the conventional view that benthic regeneration accounts for a large fraction of phytoplankton nutrient demand in shallow estuaries.     

Long-Term and Seasonal Changes in Nutrients,Phytoplankton Biomass,and Dissolved Oxygen in Deep Bay,Hong Kong

Deep Bay is a semienclosed bay that receives sewage from Shenzhen, a fast-growing city in China. NH₄ is the main N component of the sewage (>50% of total N) in the inner bay, and a twofold increase in NH₄ and PO₄ concentrations is attributed to increased sewage loading over the 21-year period (1986–2006). During this time series, the maximum annual average NH₄ and PO₄ concentrations exceeded 500 and 39 μM, respectively. The inner bay (Stns DM1 and DM2) has a long residence time and very high nutrient loads and yet much lower phytoplankton biomass (chlorophyll (Chl) <10 μg L⁻¹ except for Jan, July, and Aug) and few severe long-term hypoxic events (dissolved oxygen (DO) generally >2 mg L⁻¹) than expected. Because it is shallow (~2 m), phytoplankton growth is likely limited by light due to mixing and suspended sediments, as well as by ammonium toxicity, and biomass accumulation is reduced by grazing, which may reduce the occurrence of hypoxia. Since nutrients were not limiting in the inner bay, the significant long-term increase in Chl a (0.52–0.57 μg L⁻¹ year⁻¹) was attributed to climatic effects in which the significant increase in rainfall (11 mm year⁻¹) decreased salinity, increased stratification, and improved water stability. The outer bay (DM3 to DM5) has a high flushing rate (0.2 day⁻¹), is deeper (3 to 5 m), and has summer stratification, yet there are few large algal blooms and hypoxic events since dilution by the Pearl River discharge in summer, and the invasion of coastal water in winter is likely greater than the phytoplankton growth rate. A significant long-term increase in NO₃ (0.45–0.94 μM year⁻¹) occurred in the outer bay, but no increasing trend was observed for SiO₄ or PO₄, and these long-term trends in NO₃, PO₄, and SiO₄ in the outer bay agreed with those long-term trends in the Pearl River discharge. Dissolved inorganic nitrogen (DIN) has approximately doubled from 35–62 to 68–107 μM in the outer bay during the last two decades, and consequently DIN to PO₄ molar ratios have also increased over twofold since there was no change in PO₄. The rapid increase in salinity and DO and the decrease in nutrients and suspended solids from the inner to the outer bay suggest that the sewage effluent from the inner bay is rapidly diluted and appears to have a limited effect on the phytoplankton of the adjacent waters beyond Deep Bay. Therefore, physical processes play a key role in reducing the risk of algal blooms and hypoxic events in Deep Bay.     

Comparison of soil organic carbon content,hydraulic conductivity,and particle size fractions between a grassland and a nearby black pine plantation of 40 years in two surface depths

In highlands of semiarid Turkey, ecosystems have been significantly transformed through human actions, and today changes are taking place very rapidly, causing harmful consequences such as soil degradation. This paper examines two neighboring land use types in Indagi Mountain Pass, Cankiri, Turkey, to determine effects of the conversion of Blackpine (Pinus nigra Arn. subsp. pallasiana) plantation from grassland 40 years ago on soil organic carbon (SOC) and soil erodibility (USLE-K). For this purpose, a total of 302 disturbed and undisturbed soil samples were taken at irregular intervals from two sites and from two soil depths of 0–10 cm (D₁) and 10–20 cm (D₂). In terms of SOC, conversion did not make any statistical difference between grassland and plantation; however, there were statistically significant differences with soil depth within each land use, and SOC contents significantly decreased with the soil depth (P < 0.05) and mostly accumulated in D₁. SOC values were 2.4 and 1.8% for grassland and 2.8 and 1.6% for plantation, respectively, at D₁ and D₂. USLE-K values also statistically differed significantly with the land use, and in contrast to the statistics of SOC, there was no change in USLE-K with the soil depth. Since USLE-K was estimated using SOC, hydraulic conductivity (HC) and soil textural composition––sand (S), silt (Si), and clay (C) contents of soils––as well as SOC did not change with the land use, we ascribed the changes of USLE-K with the land uses to the differences in the HC as strongly affected by the interactions between SOC and contents of S, Si, and C. On an average, the soil of the grassland (USLE-K = 0.161 t ha h ha⁻¹ MJ⁻¹ mm⁻¹) was more erodible than those of the plantation (USLE-K = 0.126 t ha h ha⁻¹ MJ⁻¹ mm⁻¹). Additionally, topographic factors, such as aspect and slope, were statistically effective on spatial distribution of the USLE-K and SOC.     

The Kinetics of the Interaction Between Iron(III)-Ethylenediaminetetraacetate and Peroxynitrite

The kinetics of the formation of the purple-colored species between Fe^III-EDTA and peroxynitrite were studied as a function of pH (10.4–12.3) at 22°C in aqueous solutions using a stopped-flow technique. A purple-colored species was immediately formed upon mixing, which had an absorbance maximum at 520 nm. The increase in absorbance with time could be fit empirically by a power function with two parameters a and b. The power equation determined was absorbance = a*t ^b , where a increased linearly with pH and the concentration of peroxynitrite, while b almost remained constant with a value of ~0.25. The molar extinction coefficient ε_520 nm for the colored species was determined as 13 M⁻¹cm⁻¹, which is much lower than ε_520 nm = 520 M⁻¹ cm⁻¹ for the [Fe^III(EDTA)O₂]³⁻, a purple species observed in the Fe^III–EDTA–H₂O₂ system. The results of kinetics and spectral measurements of the present study are briefly discussed and compared with those of the reaction between Fe(III)-EDTA and hydrogen peroxide.     

Sulfide Inhibition of Nitrate Removal in Coastal Sediments

Microbial nitrate (NO₃⁻) removal via denitrification (DNF) at high sulfide (H₂S) concentrations was compared in sediment from a coastal freshwater pond in a developed area that receives salt-water influx during storm events, and a saline pond proximal to an undeveloped estuary. Sediments were incubated with added SO₄²⁻ (1,000 μg per gram dry weight basis (gdw)) to determine whether acid volatile sulfides (AVS) were formed. DNF in the sediments was measured with NO₃–N (300 μg gdw⁻¹) alone, and with NO₃–N and H₂S (1,000 μg S²⁻ gdw⁻¹). SO₄²⁻ addition to the freshwater sediments resulted in AVS formation (970 ± 307 μg S gdw⁻¹) similar to the wetland with no added SO₄²⁻ (986 ± 156 μg S gdw⁻¹). DNF rates measured with no added H₂S were greater in the freshwater than the wetland site (10.6 ± 0.6 vs. 6.4 ± 0.1 μg N₂O–N gdw⁻¹ h⁻¹, respectively). High H₂S concentrations retained NH₄–N in the undeveloped wetland and retained NO₃–N in the developed freshwater site, suggesting that potential salt-water influx may reduce the ability of the freshwater sediments to remove NO₃–N.     

Salinization of groundwater in arid and semi-arid zones: an example from Tajarak,western Iran

Study of the groundwater samples from Tajarak area, western Iran, was carried out in order to assess their chemical compositions and suitability for agricultural purposes. All of the groundwaters are grouped into two categories: relatively low mineralized of Ca–HCO₃ and Na–HCO₃ types and high mineralized waters of Na–SO₄ and Na–Cl types. The chemical evolution of groundwater is primarily controlled by water–rock interactions mainly weathering of aluminosilicates, dissolution of carbonate minerals and cation exchange reactions. Calculated values of pCO₂ for the groundwater samples range from 2.34 × 10⁻⁴ to 1.07 × 10⁻¹ with a mean value of 1.41 × 10⁻² (atm), which is above the pCO₂ of the earth’s atmosphere (10^−3.5). The groundwater is oversaturated with respect to calcite, aragonite and dolomite and undersaturated with respect to gypsum, anhydrite and halite. According to the EC and SAR the most dominant classes (C3-S1, C4-S1 and C4-S2) were found. With respect to adjusted SAR (adj SAR), the sodium (Na⁺) content in 90% of water samples in group A is regarded as low and can be used for irrigation in almost all soils with little danger of the development of harmful levels of exchangeable Na⁺, while in 40 and 37% of water samples in group B the intensity of problem is moderate and high, respectively. Such water, when used for irrigation will lead to cation exchange and Na⁺ is adsorbed on clay minerals while calcium (Ca²⁺) and magnesium (Mg²⁺) are released to the liquid phase. The salinity hazard is regarded as medium to high and special management for salinity control is required. Thus, the water quality for irrigation is low, providing the necessary drainage to avoid the build-up of toxic salt concentrations.     

A field study of nitrogen storage and nitrate reductase activity in the estuarine macroalgaeEnteromorpha lingulata (Chlorophyceae) andGelidium pusillum (Rhodophyceae)

The purpose of this field study was to determine the relationship between environmental conditions, particularly high nitrate (NO ₃ ⁻ ), low salinity events, and both nitrogen (N) storage (NO ₃ ⁻ , ammonium [NH ₄ ⁺ ], free amino acids [FAA], protein, and total N) and nitrate reductase (NR) activity in the macroalgaeEnteromorpha lingulata andGelidium pusillum in the lower Mobile Bay estuary (Alabama, USA). The environmental conditions at the collection site varied over the growing season with the most notable changes due to late winter and spring runoff entering the estuary (1–30 psu, 0.3–25.8 μM NO ₃ ⁻ , 0.9–12.5 μM NH ₄ ⁺ , 3–28°C, 61–2,375 μmol PAR m⁻² s⁻¹). Principal component analysis reduced the six environmental variables measured to three principal components. Stepwise, multiple regression analysis was then used to examine the relationship between the principal components and the internal NO ₃ ⁻ , NH ₄ ⁺ , and FAA pools and NR activity. The results indicate that changes in inorganic N availability and salinity rather than changes in irradiance determine patterns of N storage and NO ₃ ⁻ reduction. BothE. lingulata andG. pusillum are capable of taking up and storing NO ₃ ⁻ when it becomes available. Greater NO ₃ ⁻ availability produced larger NH ₄ ⁺ and FAA pools along with higher rates of NR activity inE. lingulata, but notG. pusillum, suggesting thatE. lingulata is able to metabolize NO ₃ ⁻ more rapidly during high NO ₃ ⁻ , low salinity events. Differences in the susceptibility ofE. lingulata andG. pusillum to NH ₄ ⁺ inhibition and salinity stress combined with their different growth strategies help to explain the seasonal trends in total N. Total N inE. lingulata ranged from 2.57% to 6.39% dw, while the slower growingG. pusillum showed no significant variation in total N content (3.8–4.1% dw). These results led to the conclusion thatE. lingulata responds more quickly thanG. pusillum to high NO ₃ ⁻ , low salinity events and that these events have a larger effect on the overall N content ofE. lingulata.     

Dissolved and particulate trace metals and their partitioning in a hypoxic estuary: The Tanshui Estuary in Northern Taiwan

The distribution and partitioning of trace metals (Co, Cu, Fe, Mn, Ni, and Zn) between dissolved and particulate phases were studied in the Tanshui Estuary. The upper reach of the estuary is hypoxic and heavily polluted due to domestic and industrial discharges. The concentration ranges of dissolved and leachable particulate trace metals in the Tanshui Estuary were: Co: 0.3–6.1 nM, 1.8–18.6 mg kg⁻¹; Cu: 5–53 nM, 22–500 mg kg⁻¹; Fe: 388–3,364 nM, 1.08–6.67%; Mn: 57–2,914 nM, 209–1,169 mg kg⁻¹; Ni: 7–310 nM, 6–108 mg kg⁻¹; and Zn: 12–176 nM, 62–1,316 mg kg⁻¹; respectively. The dissolved concentrations of the metals were 2–35 times higher than the average values of the world river water. The distributions of dissolved and particulate studied metals, except Mn, in the estuary showed scattering, which could be attributed to the discharges from many industrial wastewater disposal works located in the upper tributaries. The daily input of dissolved metals from the disposal works to the Tanshui Estuary ranged from 0.1–0.4 tons. Dissolved Mn was nearly conservative in the region with salinity higher than 10 psu, while particulate Mn decreased in the region with salinity of 10–15 psu. The concentration increased significantly seawards, corresponding with the distribution of dissolved oxygen. The distribution coefficient (K_D) for Mn in the lower estuary was nearly three orders of magnitude higher than in the upper estuary. This phenomenon may be attributed to the diffusion of Mn from the anoxic sediment in the upper estuary and gradual oxidation into particulate Mn in the middle and lower estuary as the estuarine water became more oxygenated. The distribution coefficient for Cu decreased with increasing salinity. The percentages of trace metals bound by suspended particulate matter decreased in the following order: Fe>Zn, Cu>Co>Mn>Ni.     

Distribution and enrichment of trace metals in marine sediments of Bay of Bengal,off Ennore,south-east coast of India

In order to avoid the pollution of trace metals in marine environment, it is necessary to establish the data and understand the mechanisms influencing the distribution of trace metals in marine environment. The concentration of heavy metals (Fe, Mn, Cr, Cu, Ni, Pb, Zn, Co and Cd) were studied in sediments of Ennore shelf, to understand the metal contamination due to heavily industrialized area of Ennore, south-east coast of India. Concentration of metals shows significant variability and range from 1.7 to 3.7% for Fe, 284–460 μg g⁻¹ for Mn, 148.6–243.2 μg g⁻¹ for Cr, 385–657 μg g⁻¹ for Cu, 19.8–53.4 μg g⁻¹ for Ni, 5.8–11.8 μg g⁻¹ for Co, 24.9–40 μg g⁻¹ for Pb, 71.3–201 μg g⁻¹ for Zn and 4.6–7.5 μg g⁻¹ for Cd. For various metals the contamination factor (CF) and geoaccumulation index (I _geo) has been calculated to assess the degree of pollution in sediments. The geoaccumulation index shows that Cd, Cr and Cu moderately to extremely pollute the sediments. This study shows that the major sources of metal contamination in the Ennore shelf are land-based anthropogenic ones, such as discharge of industrial wastewater, municipal sewage and run-off through the Ennore estuary. The intermetallic relationship revealed the identical behavior of metals during its transport in the marine environment.     

(Na,Ca)(Ti3+,Mg)Si2O6-clinopyroxenes at high pressure: influence of cation substitution on elastic behavior and phase transition

A compressional study of (Na,Ca)(Ti³⁺,Mg)Si₂O₆-clinopyroxenes was carried out at high pressures between 10⁻⁴ and 10.2 GPa using in situ single-crystal X-ray diffraction, Raman spectroscopy and optical absorption spectroscopy. Compressional discontinuities accompanied by structural changes, in particular, the appearance of two distinct Ti³⁺–Ti³⁺ distances within the octahedral chains at 4.37 GPa, provide evidence for the occurrence of a phase transition in NaTi³⁺Si₂O₆. Equation-of-state parameters are K ₀ = 115.9(7) GPa with K′ = −0.9(3) and K ₀ = 102.7(8) GPa with K′ = 4.08(5) for the low- and high-pressure range, respectively. The transition involves a C2/c–P [`1] \overline{1} symmetry change, which can be confirmed by the occurrence of new modes in Raman spectra. Since no significant discontinuity in the evolution of the unit-cell volume with pressure has been observed, the transition appears to be second-order in character. The influence of the coupled substitution Na⁺Ti³⁺↔Ca²⁺Mg²⁺ on the static compression behavior and the structural stability has been investigated using a sample of the intermediate composition (Na_0.54Ca_0.46)(Mg_0.46Ti_0.54)Si₂O₆. No evidence for a deviation from continuous compression behavior has been found, neither in lattice parameter nor in structural data and the fit of a third-order Birch–Murnaghan equation-of-state to the pressure–volume data yields a bulk modulus of K ₀ = 109.1(5) GPa and K′ = 5.02(13). Raman and polarized absorption spectra have been compared to NaTiSi₂O₆ and reveal major similarities. The main driving force for the phase transition in NaTi³⁺Si₂O₆ is the localization of the Ti³⁺ d-electron and the accompanying distortion, which is suppressed in the (Na,Ca)(Ti³⁺,Mg)Si₂O₆-clinopyroxene.     

Stable water isotope climate archives in springs from the Olympic Mountains,Washington

The ¹⁸O and ²H (HDO) compositions are summarized for sampled springs (n = 81) within the Elwha watershed (≈692 km²) on the northern Olympic Peninsula. Samples, collected during 2001–2009, of springs (n = 158), precipitation (n = 520), streams (n = 176), and firn (n = 3) assisted the determinations for meteoric composition of recharge waters. The local mean water line (LMWL) is defined as δ²H = 8.2δ¹⁸O − 9.3 for the watershed. Recharge history is surmised from groundwater ages ranging from 5 ± 3 years (apparent ⁸⁵Kr) to 9,490 ± 420 ¹⁴C cal years BP. About 56% of the springs were recharged over the last 1,000 years while 13% of springs were recharged over 5,000 years ago. Spring HDO values fluctuate between −11.8 to −15.6‰ δ¹⁸O and −90.9 to −119.4‰ δ²H. Deuterium excess values predominate around 4–6‰. The HDO proxy records from springs suggest a pronounced paleoclimate shift in air masses near 5,000 year BP on the Peninsula.     

A fluid inclusion and stable isotope study of 200 Ma of fluid evolution in the Galway Granite, Connemara, Ireland

Fluid inclusions in granite quartz and three generations of veins indicate that three fluids have affected the Caledonian Galway Granite. These fluids were examined by petrography, microthermometry, chlorite thermometry, fluid chemistry and stable isotope studies. The earliest fluid was a H₂O-CO₂-NaCl fluid of moderate salinity (4–10 wt% NaCl eq.) that deposited late-magmatic molybdenite mineralised quartz veins (V₁) and formed the earliest secondary inclusions in granite quartz. This fluid is more abundant in the west of the batholith, corresponding to a decrease in emplacement depth. Within veins, and to the east, this fluid was trapped homogeneously, but in granite quartz in the west it unmixed at 305–390 °C and 0.7–1.8 kbar. Homogeneous quartz δ¹⁸O across the batholith (9.5 ± 0.4‰n = 12) suggests V₁ precipitation at high temperatures (perhaps 600 °C) and pressures (1–3 kbar) from magmatic fluids. Microthermometric data for V₁ indicate lower temperatures, suggesting inclusion volumes re-equilibrated during cooling. The second fluid was a H₂O-NaCl-KCl, low-moderate salinity (0–10 wt% NaCl eq.), moderate temperature (270–340 °C), high δD (−18 ± 2‰), low δ¹⁸O (0.5–2.0‰) fluid of meteoric origin. This fluid penetrated the batholith via quartz veins (V₂) which infill faults active during post-consolidation uplift of the batholith. It forms the most common inclusion type in granite quartz throughout the batholith and is responsible for widespread retrograde alteration involving chloritization of biotite and hornblende, sericitization and saussuritization of plagioclase, and reddening of K-feldspar. The salinity was generated by fluid-rock interactions within the granite. Within granite quartz this fluid was trapped at 0.5–2.3 kbar, having become overpressured. This fluid probably infiltrated the Granite in a meteoric-convection system during cooling after intrusion, but a later age cannot be ruled out. The final fluid to enter the Granite and its host rocks was a H₂O-NaCl-CaCl₂-KCl fluid with variable salinity (8–28 wt% NaCl eq.), temperature (125–205 °C), δD (−17 to −45‰), δ¹⁸O (−3 to + 1.2‰), δ¹³C_CO2 (−19 to 0‰) and δ³⁴S_sulphate (13–23‰) that deposited veins containing quartz, fluorite, calcite, barite, galena, chalcopyrite sphalerite and pyrite (V₃). Correlations of salinity, temperature, δD and δ¹⁸O are interpreted as the result of mixing of two fluid end-members, one a high-δD (−17 to −8‰), moderate-δ¹⁸O (1.2–2.5‰), high-δ¹³C_CO2 (> −4‰), low-δ³⁴S_sulphate (13‰), high-temperature (205–230 °C), moderate-salinity (8–12 wt% NaCl eq.) fluid, the other a low-δD (−61 to −45‰), low-δ¹⁸O (−5.4 to −3‰), low-δ¹³C (<−10‰), high-δ³⁴S_sulphate (20–23‰) low-temperature (80–125 °C), high-salinity (21–28 wt% NaCl eq.) fluid. Geochronological evidence suggests V₃ veins are late Triassic; the high-δD end-member is interpreted as a contemporaneous surface fluid, probably mixed meteoric water and evaporated seawater and/or dissolved evaporites, whereas the low-δD end-member is interpreted as a basinal brine derived from the adjacent Carboniferous sequence. This study demonstrates that the Galway Granite was a locus for repeated fluid events for a variety of reasons; from expulsion of magmatic fluids during the final stages of crystallisation, through a meteoric convection system, probably driven by waning magmatic heat, to much later mineralisation, concentrated in its vicinity due to thermal, tectonic and compositional properties of granite batholiths which encourage mineralisation long after magmatic heat has abated. Received: 3 April 1996 / Accepted: 5 May 1997     

Cr and Al diffusion in chromite spinel: experimental determination and its implication for diffusion creep

Diffusion coefficients of Cr and Al in chromite spinel have been determined at pressures ranging from 3 to 7 GPa and temperatures ranging from 1,400 to 1,700°C by using the diffusion couple of natural single crystals of MgAl₂O₄ spinel and chromite. The interdiffusion coefficient of Cr–Al as a function of Cr# (=Cr/(Cr + Al)) was determined as D _Cr–Al = D ₀ exp {−(Q′ + PV*)/RT}, where D ₀ = exp{(10.3 ± 0.08) × Cr#^0.54±0.02} + (1170 ± 31.2) cm²/s, Q′ = 520 ± 81 kJ/mol at 3 GPa, and V* = 1.36 ± 0.25 cm³/mol at 1,600°C, which is applicable up to Cr# = 0.8. The estimation of the self-diffusion coefficients of Cr and Al from Cr–Al interdiffusion shows that the diffusivity of Cr is more than one order of magnitude smaller than that of Al. These results are in agreement with patterns of multipolar Cr–Al zoning observed in natural chromite spinel samples deformed by diffusion creep.