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.     

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.     

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.     

X-ray diffraction study of arsenopyrite at high pressure

The high-pressure X-ray diffraction study of a natural arsenopyrite was investigated up to 28.2 GPa using in situ angle-dispersive X-ray diffraction and a diamond anvil cell at National Synchrotron Light Source, Brookhaven National Laboratory. The 16:3:1 methanol–ethanol–water mixture was used as a pressure-transmitting medium. Pressures were measured using the ruby-fluorescence method. No phase change has been observed up to 28.2 GPa. The isothermal equation of state (EOS) was determined. The values of K ₀, and K′ ₀ refined with a third-order Birch–Murnaghan EOS are K ₀ = 123(9) GPa, and K′ ₀ = 5.2(8). Furthermore, we confirm that the linear compressibilities (β) along a, b and c directions of arsenopyrite is elastically isotropic (β _a  = 6.82 × 10⁻⁴, β _b  = 6.17 × 10⁻⁴ and β _c  = 6.57 × 10⁻⁴ GPa⁻¹).     

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.     

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.     

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.     

Hydrogeochemical processes in the groundwater environment of Heihe River Basin,northwest China

The Heihe River Basin is a typical arid inland river basin for examining stress on groundwater resources in northwest China. The basin is composed of large volumes of unconsolidated Quaternary sediments of widely differing grain size, and during the past half century, rapid socio-economic development has created an increased demand for groundwater resources. Understanding the hydrogeochemical processes of groundwater and water quality is important for sustainable development and effective management of groundwater resources in the Heihe River basin. To this end, a total of 30 representative groundwater samples were collected from different wells to monitor the water chemistry of various ions and its quality for irrigation. Chemical analysis shows that water presents a large spatial variability of chemical facies (SO₄ ²⁻–HCO₃⁻, SO₄ ²⁻–Cl⁻, and Cl⁻–SO₄ ²⁻) as groundwater flow from recharge area to discharge area. The ionic ratio indicates positive correlation between the flowing pairs of parameters: Cl⁻ and Na⁺(r = 0.95), SO₄ ²⁻ and Na⁺ (r = 0.84), HCO₃ ⁻ and Mg²⁺(r = 0.86), and SO₄ ²⁻ and Ca²⁺ (r = 0.91). Dissolution of minerals, such as halite, gypsum, dolomite, silicate, and Mirabilite (Na₂SO₄·10H₂O) in the sediments results in the Cl⁻, SO₄ ²⁻, HCO₃ ⁻, Na⁺, Ca²⁺ and Mg²⁺ content in the groundwater. Other reactions, such as evaporation, ion exchange, and deposition also influence the water composition. The suitability of the groundwater for irrigation was assessed based on the US Salinity Laboratory salinity classification and the Wilcox diagram. The results show that most of the groundwater samples are suitable for irrigation uses barring a few locations in the dessert region in the northern sub-basin.     

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.     

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.     

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.     

Nitrate pollution of groundwater in Toyserkan,western Iran

A total of 95 groundwater samples were collected from Toyserkan, western Iran to assess the chemical composition and nitrate (NO₃ ⁻) status of groundwater. The most prevalent water type is Ca–HCO₃ followed by water types Ca–Mg–HCO₃. In comparison with the World Health Organization (WHO) drinking water guideline of 50 mg l⁻¹ for NO₃ ⁻, a total of nine wells (9.5%) showed higher concentrations. In 36% of samples (34) NO₃ ⁻ concentration was low (<20 mg l⁻¹), and in 53.7% of samples (51), in the range of 20–50 mg l⁻¹. The samples were classified into four groups based on NO₃ ⁻ and chloride (Cl⁻) concentrations. Of the samples, 40% were classified as group 4 and were relatively high in Cl⁻ and NO₃ ⁻ (Cl⁻ > 47 mg l⁻¹, NO₃ ⁻ > 27 mg l⁻¹). The high correlation between NO₃ ⁻ and Cl⁻ (r = 0.86, p < 0.01) is consistent with a manure source, resulting from the practice of adding salt to animal feed. Pollution of groundwaters appeared to be affected by the application of inorganic fertilizer at greater than agronomic rates, Cl-salt inputs, and irrigation practice.     

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.     

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.     

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.     

High-pressure X-ray diffraction study of ε-FeOOH

An in situ synchrotron X-ray diffraction study was carried out on ε-FeOOH at room temperature up to a pressure of 8.6 GPa using the energy-dispersive method. The linear compressibility was determined to be β _a  = 1.69(3) × 10⁻³ GPa⁻¹, β _b  = 2.86(6) × 10⁻³ GPa⁻¹, and β _c  = 1.73(5) × 10⁻³ GPa⁻¹. The b-axis of the unit cell is more compressible than the a and c axes. The pressure–volume data were fitted to a third-order Birch–Murnaghan equation of state. The best fit was found using a room temperature isothermal bulk modulus of K ₀ = 126(3) GPa and its pressure derivative K′ = 10(1).     

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.     

Behavior of epidote at high pressure and high temperature: a powder diffraction study up to 10 GPa and 1,200 K

The thermo-elastic behavior of a natural epidote [Ca_1.925 Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH)] has been investigated up to 1,200 K (at 0.0001 GPa) and 10 GPa (at 298 K) by means of in situ synchrotron powder diffraction. No phase transition has been observed within the temperature and pressure range investigated. P–V data fitted with a third-order Birch–Murnaghan equation of state (BM-EoS) give V ₀ = 458.8(1)ų, K _T0 = 111(3) GPa, and K′ = 7.6(7). The confidence ellipse from the variance–covariance matrix of K _T0 and K′ from the least-square procedure is strongly elongated with negative slope. The evolution of the “Eulerian finite strain” vs “normalized stress” yields Fe(0) = 114(1) GPa as intercept values, and the slope of the regression line gives K′ = 7.0(4). The evolution of the lattice parameters with pressure is slightly anisotropic. The elastic parameters calculated with a linearized BM-EoS are: a ₀ = 8.8877(7) Å, K _T0(a) = 117(2) GPa, and K′(a) = 3.7(4) for the a-axis; b ₀ = 5.6271(7) Å, K _T0(b) = 126(3) GPa, and K′(b) = 12(1) for the b-axis; and c ₀ = 10.1527(7) Å, K _T0(c) = 90(1) GPa, and K’(c) = 8.1(4) for the c-axis [K _T0(a):K _T0(b):K _T0(c) = 1.30:1.40:1]. The β angle decreases with pressure, β_P(°) = β_P0 −0.0286(9)P +0.00134(9)P ² (P in GPa). The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α₀ + α₁ T ^−1/2. The refined parameters for epidote are: α₀ = 5.1(2) × 10⁻⁵ K⁻¹ and α₁ = −5.1(6) × 10⁻⁴ K^1/2 for the unit-cell volume, α₀(a) = 1.21(7) × 10⁻⁵ K⁻¹ and α₁(a) = −1.2(2) × 10⁻⁴ K^1/2 for the a-axis, α₀(b) = 1.88(7) × 10⁻⁵ K⁻¹ and α₁(b) = −1.7(2) × 10⁻⁴ K^1/2 for the b-axis, and α₀(c) = 2.14(9) × 10⁻⁵ K⁻¹ and α₁(c) = −2.0(2) × 10⁻⁴ K^1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α₀(a): α₀(b): α₀(c) = 1 : 1.55 : 1.77. The β angle increases continuously with T, with β_T(°) = β_T0 + 2.5(1) × 10⁻⁴ T + 1.3(7) × 10⁻⁸ T ². A comparison between the thermo-elastic parameters of epidote and clinozoisite is carried out.     

Groundwater quality,nitrate pollution and irrigation environmental management in the Neogene sediments of an agricultural region in central Thessaly (Greece)

The degradation of groundwater quality, which has been noted in the recent years, is closely connected to the intensification of agriculture, the unreasonable use of chemical fertilizers and the excess consumption of large volumes of irrigation water. In the hilly region of central Thessaly in Greece, which suffers the consequences of intense agricultural use, a hydrogeological study is carried out, taking groundwater samples from springs and boreholes in the Neogene aquifers. The aim of this study is the investigation of irrigation management, water quality and suitability for various uses (water supply, irrigation), the degradation degree and the spatial distribution of pollutants using GIS. The following hydrochemical types prevail in the groundwater of the study area: Ca–Mg–HCO₃, Mg–Ca–Na–HCO₃ and Na–HCO₃. In the above shallow aquifers, especially high values of NO₃ ⁻ (31.7–299.0), NH₄ ⁺ (0.12–1.11), NO₂ ⁻ (0.018–0.109), PO₄ ³⁻ (0.07–0.55), SO₄ ²⁻ (47.5–146.5) and Cl⁻ (24.8–146.5) are found, particularly near inhabited areas (values are in mg L⁻¹). The water of shallow aquifers is considered unsuitable for human use due to their high polluting load, while the water of the deeper aquifers is suitable for human consumption. Regarding water suitability for irrigation, the evaluation of SAR (0.153–7.397) and EC (481–1,680 μS cm⁻¹) resulted in classification category ‘C3S1’, indicating high salinity and low sodium water which can be used for irrigation in most soils and crops with little to medium danger of development of exchangeable sodium and salinity. The statistical data analysis, the factor analysis and the GIS application have brought out the vulnerable-problematic zones in chemical compounds of nitrogen and phosphates. The groundwater quality degradation is localized and related exclusively to human activities. Based on 2005 and 2008 estimates, the annual safe yield of the region’s aquifers were nearly 41.95 MCM. However, the existing situation is that 6.37 MCM of water is over extracted from these aquifers.