Seasonal variations of phosphorus species in sediment from the middle Adriatic Sea

Phosphorus (P) species concentrations in 0–2 cm surface sediment layer were investigated monthly from November 2001 to December 2002 at the bay, channel and open sea stations in the middle Adriatic. Modified SEDEX method was used for inorganic phosphorus species determination [P in biogenic (P-FD), authigenic (P-AUT), detrital apatite (P-DET) and P adsorbed on to iron oxides and hydroxides (P–Fe)], and organic phosphorus (P-ORG). P-FD, P-AUT and P-DET concentration ranges (1.5–5.4, 0–2.7 and 0.4–3.4 μmol g⁻¹, respectively) were similar at all stations, and showed no obvious common trend of seasonal changes. P–Fe ranged from 1.9 to 11.9 μmol g⁻¹ with the highest values at bay station and higher seasonal oscillations than other inorganic P forms. P-ORG ranged from 0.3 to 18.7 μmol g⁻¹ with higher concentrations at stations of fine-sized sediments and showed increased concentrations in warm part of the year at all stations. Correlation between concentrations of P–Fe in the surface sediment layer and orthophosphate sediment-water interface concentration gradients at bay and channel stations indicated to P–Fe importance in the orthophosphate benthic flux. For the bay station, linkage between sediment P-ORG and chlorophyll a concentrations, primary production and microzooplankton abundance was established, indicating a 1 month delay of sediment response to production fluctuations in the water column.     

Chemical and physical properties affecting strontium distribution coefficients of surficial-sediment samples at the Idaho National Engineering and Environmental Laboratory, Idaho

 The U.S. Geological Survey and Idaho State University, in cooperation with the U.S. Department of Energy, conducted a study to determine strontium distribution coefficients (K_ds) of surficial sediments at the Idaho National Engineering and Environmental Laboratory (INEEL). Batch experiments using synthesized aqueous solutions were used to determine K_ds, which describe the distribution of a solute between the solution and solid phase, of 20 surficial-sediment samples from the INEEL. The K_ds for the 20 surficial-sediment samples ranged from 36 to 275 ml/g. Many properties of both the synthesized aqueous solutions and sediments used in the experiments also were determined. Solution properties determined were initial and equilibrium concentrations of calcium, magnesium, and strontium, pH and specific conductance, and initial concentrations of potassium and sodium. Sediment properties determined were grain-size distribution, bulk mineralogy, whole-rock major-oxide and strontium and barium concentrations, and Brunauer-Emmett-Teller (BET) surface area. Solution and sediment properties were correlated with strontium K_ds of the 20 surficial sediments using Pearson correlation coefficients. Solution properties with the strongest correlations with strontium K_ds were equilibrium pH and equilibrium calcium concentration correlation coefficients, 0.6598 and –0.6518, respectively. Sediment properties with the strongest correlations with strontium K_ds were manganese oxide (MnO), BET surface area, and the >4.75-mm-grain-size fraction correlation coefficients, 0.7054, 0.7022, and –0.6660, respectively. Effects of solution properties on strontium K_ds were interpreted as being due to competition among similarly charged and sized cations in solution for strontium-sorption sites; effects of sediment properties on strontium K_ds were interpreted as being surface-area related. Multivariate analyses of these solution and sediment properties resulted in r² values of 0.8071 when all five properties were used and 0.8043 when three properties, equilibrium pH, MnO, and BET surface area, were used. Received: 30 November 1998 · Accepted: 16 February 1999     

Phosphorus distribution in the sediments of a shallow eutrophic lake,Lake Chaohu,China

In this study, the sediment profiles of total phosphorus (TP), inorganic phosphorus (P_i), organic phosphorus (P_o), C/P and N/P were used to investigate time-dependent P distribution changes in Lake Chaohu. The characteristics of P_i and P_o fractions in the surface sediments were studied and the difference between east and west lake region was also discussed. The P_i and P_o contents displayed a clear gradient from east to west in sediments of Lake Chaohu, and the P_o/P ratios were lower in sediments with industrial and urban pollution sources input in west lake region. The study indicated that different sediments area had diverse concentrations and distributions of P_o fractions due to their different drainage basin and pollution sources. The profile distribution of the C/P and N/P ratios decreased with increasing depths and stayed relatively constant ratios at the depths of 15–30 cm. The C/P and N/P ratios were always below Redfield ratios in sediment profile, indicating P enrichment but likely due to the preferential loss of carbon in respect to phosphorus. The rank order of P_i-fractions extracted was HCl-P_i > NaOH-P_i > NaHCO₃-P_i in surface sediments. The relative distribution of NaHCO₃-P_i and HCl-P_i was in agreement with the trophic conditions of the regions studied. Among the sequentially extracted P_o forms, the rank order of P_o fractions was residual P_o > HCl-P_o > fulvic acid-P > humic acid-P > NaHCO₃-P_o, with mean relative proportion of 5.4:3.4:2.2:1.1:1.0.     

Phosphorus adsorption characteristics at the sediment–water interface and relationship with sediment properties in FUSHI reservoir, China

This study was designed to survey the reservoir sediment properties, assess the phosphorus (P) sorption isotherm, and analyze the relationship between sediment properties and sorption parameters. Physicochemical analysis indicated that sediment from the FUSHI reservoir in Zhejiang Province, China, has similar physical and chemical properties and has been contaminated by P. Sorption isotherm experiments showed that the sorption process could be described by Langmuir and Freundlich models. The parameters of Q _max (Phosphorus sorption maximum) and K (Freundlich adsorption isotherm constant) ranged from 618.98 to 825.70?mg?kg^?1 and 114.18 to 170.74?l?kg^?1, respectively. EPC₀ (zero P equilibrium concentration) ranged from 0.14 to 0.24?mg?l^?1, more than the total P concentration in the water of the reservoir. Thus, the reservoir sediment releases P into the water and acts as a ??P resource??. The clay, Fe_o, Al_t, and Fe_t?+?Al_t content were the main active components in P sorption. Q _max had a highly significant positive relationship with some properties and could be estimated by a combination of these.     

Pyrite oxidation during sample storage determines phosphorus fractionation in carbonate-poor anoxic sediments

We investigated the phosphorus (P) and iron (Fe) fractionation in four cores with anoxic sediments, deposited during the mid-Cretaceous oceanic anoxic event 2 (∼94 Ma) and the Paleocene-Eocene thermal maximum (∼55 Ma), that were exposed to oxygen after core recovery. Surprisingly, P associated with iron oxyhydroxides (Fe-bound P) was a major P phase in these laminated sediments deposited under euxinic conditions. A significant fraction of total Fe was present as (poorly) crystalline ferric Fe. This fraction increased with increasing storage time of the investigated cores. In carbonate-poor samples, Fe-bound P accounted for up to 99% of total P and its abundance correlated with pyrite contents. In samples with higher CaCO₃ contents (>5 wt% in the investigated samples), P was mostly present in authigenic Ca-P minerals, irrespective of pyrite contents. We conclude that the P fractionation in anoxic, carbonate-poor, sediments is strongly affected by pyrite oxidation that occurs when these sediments are exposed to oxygen. Pyrite oxidation produces sulfuric acid and iron oxyhydroxides. The abundance of poorly crystalline Fe oxyhydroxides provides further evidence that these were indeed formed through recent (post-recovery) oxidation rather than in situ tens of millions of years ago. The acid dissolves apatite and the released phosphate is subsequently bound in the freshly formed iron oxyhydroxides. Pyrite oxidation thus leads to a conversion of authigenic Ca-P to Fe-bound P. In more calcareous samples, CaCO₃ can act as an effective buffer against acidic dissolution of Ca-P minerals. The results indicate that shielding of sediments from atmospheric oxygen is vital to preserve the in situ P fractionation and to enable a valid reconstruction of marine phosphorus cycling based on sediment records.     

Evaluation of elemental enrichments in surface sediments off southwestern Taiwan

Surface slices of 20 sediment cores, off southwestern Taiwan, and bed sediment of River Kaoping were measured for major and trace elements (Al, As, Ca, Cd, Cl, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Si, Ti, V, and Zn) to evaluate the geochemical processes responsible for their distribution, including elemental contamination. Major element/Al ratio and mean grain size indicate quartz-dominated, coarse grained sediments that likely derived from sedimentary rocks of Taiwan and upper crust of Yangtze Craton. Bi-plot of SiO₂ versus Fe₂O₃^T suggests the possible iron enrichment in sediments of slag dumping sites. Highest concentrations of Cr, Mn, P, S, and Zn found in sediments of dumping sites support this. Correlation analysis shows dual associations, detrital and organic carbon, for Cr, P, S, and V with the latter association typical for sediments in dumping sites. Normalization of trace elements to Al indicates high enrichment factors (>2) for As, Cd, Pb, and Zn, revealing contamination. Factor analysis extracted four geochemical associations with the principal factor accounted for 25.1% of the total variance and identifies the combined effects of dumped iron and steel slag-induced C–S–Fe relationship owing to authigenic precipitation of Fe–Mn oxyhydroxides and/or metal sulfides, and organic matter complexation of Fe, Mn, Ca, Cr, P, and V. Factors 2, 3, and 4 reveal detrital association (Ti, Al, Ni, Pb, Cu, and V), effect of sea salt (Cl, Mg, Na, and K) and anthropogenic component (As and Zn)-carbonate link, respectively, in the investigated sediments.     

Abundance and Chemical Speciation of Phosphorus in Sediments of the Mackenzie River Delta, the Chukchi Sea and the Bering Sea: Importance of Detrital Apatite

Utilizing a sequential extraction technique this study provides the first quantitative analysis on the abundance of sedimentary phosphorus and its partitioning between chemically distinguishable phases in sediments of the Bering Sea, the Chukchi Sea and the Mackenzie River Delta in the western Arctic Ocean. Total sedimentary phosphorus (TSP) was fractionated into five operationally defined phases: (1) adsorbed inorganic and exchangeable organic phosphorus, (2) Fe-bound inorganic phosphorus, (3) authigenic carbonate fluorapatite, biogenic apatite and calcium carbonate-bound inorganic and organic phosphorus, (4) detrital apatite, and (5) refractory organic phosphorus. TSP concentrations in surface sediments increased from the Chukchi Sea (18 μmol g⁻¹ of dried sediments) to the Bering Sea (22 μmol g⁻¹) and to the Mackenzie River Delta (29 μmol g⁻¹). Among the five pools, detrital apatite phosphorus of igneous or metamorphic origin represents the largest fraction (~43%) of TSP. The second largest pool is the authigenic carbonate fluorapatite, biogenic apatite as well as CaCO₃ associated phosphorus (~24% of TSP), followed by the Fe-bound inorganic phosphorus, representing ~20% of TSP. The refractory organic P accounts for ~10% of TSP and the readily exchangeable adsorbed P accounts for only 3.5% of TSP. Inorganic phosphorus dominates all of phosphorus pools, accounting for an average of 87% of the TSP. Relatively high sedimentary organic carbon and total nitrogen contents and low δ¹³C values in the Mackenzie River Delta together with the dominance of detrital apatite in the TSP demonstrate the importance of riverine inputs in governing the abundance and speciation of sedimentary phosphorus in the Arctic coastal sediments.     

Rate of strontium sorption and the effects of variable aqueous concentrations of sodium and potassium on strontium distribution coefficients of a surficial sediment at the Idaho National Engineering Laboratory, Idaho

 The rate of strontium sorption and the effects of variable aqueous concentrations of sodium and potassium on strontium sorption were measured as part of an investigation to determine strontium chemical transport properties of a surficial sediment at the Idaho National Engineering Laboratory (INEL), Idaho. Batch experimental techniques were used to determine the rate of strontium sorption and strontium distribution coefficients (K_ds) between aqueous and solid phases. Rate experiments indicate that strontium in solution reached an apparent equilibrium with the sediment in 26 h. K_ds were derived using the linear isotherm model at initial sodium concentrations from 100 to 5,000 mg/l and initial potassium concentrations from 2 to 150 mg/l. K_ds ranged from 56±2 to 62±3 ml/g at initial aqueous concentrations of sodium and potassium equal to or less than 300 and 150 mg/l, respectively. K_ds ranged from 4.7±0.2 to 19±1 ml/g with initial aqueous concentrations of sodium between 1,000 and 5,000 mg/l. These data indicate that sodium concentrations greater than 300 mg/l in wastewater increase the availability of strontium for transport beneath waste disposal ponds at the INEL by decreasing strontium sorption on the surficial sediment. Wastewater concentrations of sodium and potassium less than 300 and 150 mg/l, respectively, have little effect on the availability of strontium for transport. Received: 6 February 1997 · Accepted: 31 March 1997     

Transport and sediment–water partitioning of trace metals in acid mine drainage: an example from the abandoned Kwangyang Au–Ag mine area, South Korea

Transport and sediment–water partitioning of trace metals (Cr, Co, Fe, Pb, Cu, Ni, Zn, Cd) in acid mine drainage were studied in two creeks in the Kwangyang Au–Ag mine area, southern part of Korea. Chemical analysis of stream waters and the weak acid (0.1 N HCl) extraction, strong acid (HF–HNO₃–HClO₄) extraction, and sequential extraction of stream sediments were performed. Heavy metal pollution of sediments was higher in Chonam-ri creek than in Sagok-ri creek, because there is a larger source of base metal sulfides in the ores and waste dump upstream of Chonam-ri creek. The sediment–water distribution coefficients (K _d) for metals in both creeks were dependent on the water pH and decreased in the order Pb ≈ Al > Cu > Mn > Zn > Co > Ni ≈ Cd. K _d values for Al, Cu and Zn were very sensitive to changes in pH. The results of sequential extraction indicated that among non-residual fractions, Fe–Mn oxides are most important for retaining trace metals in the sediments. Therefore, the precipitation of Fe(–Mn) oxides due to pH increase in downstream sites plays an important role in regulating the concentrations of dissolved trace metals in both creeks. For Al, Co, Cu, Mn, Pb and Zn, the metal concentrations determined by 0.1 N HCl extraction (Korean Standard Method for Soil Pollution) were almost identical to the cumulative concentrations determined for the first three weakly-bound fractions (exchangeable + bound to carbonates + bound to Fe–Mn oxides) in the sequential extraction procedure. This suggests that 0.1 N HCl extraction can be effectively used to assess the environmentally available and/or bioavailable forms of trace metals in natural stream sediments.     

Effect of organic matter on DOM sorption on lake sediments

The effect of organic matter on the sorption of dissolved organic matter (DOM) on lake sediments is critical to understanding the fate and transport of contaminants at the sediment–water interface in lake ecosystems. Results indicate that DOM sorption on sediment is largely due to ligand exchange between the DOM and hydroxyl groups, and the amount of DOC sorbed is a linear function of added DOC. With increasing organic matter content the sediment has lower binding strength, higher releasing ability for DOM, and the higher amount of DOM sorbed by sediment naturally. There was no clear difference before and after the sediment was treated with H₂O₂, but the constant b implied that after the sediments were treated DOC release was promoted. Organic matter in the sediment tends to impede the sorption of DOC and results in a remarkable decrease in DOC sorption rates.     

Phosphate sorption desorption characteristics of some ferruginous soils of tropical region in Eastern India

Phosphate sorption and desorption experiments were conducted with four ferruginous soils (alfisols) of Eastern India, in view of the low native phosphate concentrations in tropical Indian soils. From the P-isotherm curve, standard P requirement (SPR) of the soils was determined. Phosphate sorption data were fitted to both Langmuir and Freundlich equations and mean sorption maximum values obtained for the different soil series were in the decreasing order as Matimahal > Anandapur > Mrigindih > Kashipur. The fraction of added P sorbed followed the same trend as SPR, P sorption maximum (P_max), phosphate affinity constant (K), maximum phosphate buffering capacity (MPBC), Freundlich constant K′ and phosphate desorption values. Phosphate sorption maximum was significantly correlated with MPBC, Freundlich 1/n, SPR, clay and different forms of Fe and Al. The value of K (bonding energy) was significantly correlated with MPBC, Freundlich K′ and pyrophosphate extractable Fe and Al. The MPBC was significantly correlated with Freundlich K′, Freundlich constant 1/n, clay, oxalate and dithionite extractable, amorphous and crystalline form of Fe and Al. Freundlich K′ was significantly correlated with Freundlich 1/n, pH_water, clay, dithionite extractable and crystalline form of Fe and Al. The results suggested that the soils having higher amount of extractable and reactive Fe and Al shared higher P sorbtion capacity and such soils may need higher levels of P application     

Phosphorus speciation in the sediment and mass balance for the central region of the Great Barrier Reef continental shelf (Australia)

Solid phase P speciation has been determined in sediments from a transect across the central section of the continental shelf and slope of the Great Barrier Reef (GBR) lagoon. This region is characterized by a gradient of riverine aluminosilicate clay and silt nearshore, seawards of which biogenic carbonate sediment predominates. Phosphorus speciation results show large variations along this transect. Organic P and authigenic (apatite) P are the major chemical forms of phosphorus in the central GBR continental shelf sediments. Post-depositional reorganization of P was also observed, converting organic P and iron bound P (Fe-P) to authigenic (apatite) P. Phosphorus burial rate was estimated from measurements of total P concentration and excess ²¹⁰Pb sediment mass accumulation rates. Burial efficiency varies significantly over the shelf. Inshore areas showed significant P remobilization from sediments to the water column (up to ∼50%). The mid and the outer shelf showed little evidence for remobilization (except for coral reef platform sediments), with more of the sediment P being in the less reactive authigenic apatite phases. An appreciable fraction of this non-labile authigenic apatite phase was identified as fish bone. P sources and sinks over the central part of the GBR shelf were quantified using a mass balance approach. This showed that Coral Sea shelf edge upwelling events are essential to satisfy the large P nutrient demand of the whole GBR lagoon. P inputs due to upwelling events were greater than those contributed by local rivers over an average year.     

Benthic metabolism and nutrient cycling along an estuarine salinity gradient

Benthic metabolism and nutrient exchange across the sediment-water interface were examined over an annual cycle at four sites along a freshwater to marine transect in the Parker River-Plum Island Sound estuary in northeastern Massachusetts, U.S. Sediment organic carbon content was highest at the freshwater site (10.3%) and decreased along the salinity gradient to 0.2% in the sandy sediments at the marine end of the estuary. C:N ratios were highest in the mid estuary (23:1) and lowest near the sea (11:1). Chlorophyll a in the surface sediments was high along the entire length of the estuary (39–57 mg chlorophyll a m⁻²) but especially so in the sandy marine sediments (172 mg chlorophyll a m⁻²). Chlorophyll a to phaeophytin ratios suggested most chlorophyll is detrital, except at the sandy marine site. Porewater sulfide values varied seasonally and between sites, reflecting both changes in sulfate availability as overlying water salinity changed and sediment metabolism. Patterns of sediment redox potential followed those of sulfide. Porewater profiles of inorganic N and P reflected strong seasonal patterns in remineralization, accumulation, and release. Highest porewater NH₄ ⁺ values were found in upper and mid estuarine sediments, occasionally exceeding 1 mM N. Porewater nitrate was frequently absent, except in the sandy marine sediments where concentrations of 8 μM were often observed. Annual average respiration was lowest at the marine site (13 mmol O₂ m⁻² d⁻¹ and 21 mmol TCO₂ m⁻² d⁻¹) and highest in the mid estuary (130 mmol O₂ m⁻² d⁻¹ and 170 mmol TCO₂ m⁻² d⁻¹) where clam densities were also high. N₂O and CH₄ fluxes were low at all stations throughout the year: Over the course, of a year, sediments varied from being sources to sinks of dissolved organic C and N, with the overall spatial pattern related closely to sediment organic content. There was little correlation between PO₄ ³⁻ flux and metabolism, which we attribute to geochemical processes. At the two sites having the lowest salinities, PO₄ ³⁻ flux was directed into the sediments. On average, between 22% and 32% of total system metabolism was attributable to the benthos. The mid estuary site was an exception, as benthic metabolism accounted for 95% of the total, which is attributable to high densities of filter-feeding clams. Benthic remineralization supplied from less than 1% to over 190% of the N requirements and 0% to 21% of the P requirements of primary producers in this system. Estimates of denitrification calculated from stoichiometry of C and N fluxes ranged from 0% for the upper and mid estuary site to 35% for the freshwater site to 100% of sediment organic N remineralization at the marine site. We hypothesize that low values in the upper and mid estuary are attributable to enhanced NH₄ ⁺ fluxes during summer due to desorption of exchangeable ammonium from rising porewater salinity. NH₄ ⁺ desorption during summer may be a mechanism that maintains high rates of pelagic primary production at a time of low inorganic N inputs from the watershed.     

Geochemical and thermodynamic aspects of sorption of strontium on kaolinite dominated clay samples at Kalpakkam

The mobility of strontium in subsurface is largely influenced by sorption on to clay minerals. In the present study, kaolinite clay samples collected from the Kalpakkam nuclear plant site were employed to understand the sorption characteristics of strontium by batch method. The effect of several parameters such as time, strontium ion concentration, pH, temperature and ionic strength was investigated. The kinetic studies suggested pseudo-second-order mechanism. The experimental sorption data was fitted to Langmuir adsorption model for obtaining the sorption capacity of the sorbent. The maximum sorption capacity was 5.77 mg/g at 298 K and was found to increase with an increase in temperature. It was observed that the distribution coefficient (K _d) of strontium on clay increased as the pH of the solution increased. The distribution coefficient was found to decrease with an increase in concentration of Na⁺ and Ca²⁺ ions. This variation of K _d suggests that cation exchange is the predominant sorption process. It was also observed that sorption process is endothermic. The thermodynamic parameters such as ∆G ⁰, ∆H ⁰ and ∆S ⁰ were calculated. The negative values obtained for ∆G ⁰ indicated that the sorption of strontium on clay was spontaneous at all studied concentrations. ∆G ⁰ becomes more negative with an increase in temperature, suggests that the sorption process is more favorable at higher temperatures.     

Competitive adsorption of trace elements in calcareous soils as affected by sewage sludge,poultry manure,and municipal waste compost

The competitive adsorption of trace elements is a key issue in assessing the mobility of trace elements in calcareous soils and can be affected by disposal of sewage sludge, municipal waste, and poultry manure. The effect of municipal sewage sludge, poultry manure, and municipal waste compost on the sorption of cadmium (Cd), copper (Cu), zinc (Zn), and nickel (Ni) in surface samples of three calcareous soils was studied. As the applied concentrations increased, Cu and Cd adsorption increased, while Zn and Ni adsorption decreased in all treatments. Based on the distribution coefficient (K _d) values and proportion of increase or decrease in metal adsorption, the selectivity sequence in control and amended soils found was Cu ≫ Cd ≫ Ni > Zn and Cu ≫ Cd ≫ Zn > Ni, respectively. In general, among control and amended soils, control soils showed the highest K _d for Cd, Cu, and Ni, while sludge, poultry manure, and composted waste-amended soils had lowest K _d for Cd, Cu, and Ni, respectively. In the case of Zn, composted waste-amended and control soils had highest and lowest K _d, respectively. The present experimental results indicated that the addition of organic amendments to these calcareous soils reduced the sorption of Cd, Cu, and Ni. Thus, the effects of preferential adsorption and organic matter should be considered in assessing the risk associated with applying sewage sludge, poultry manure, and composted material to calcareous soils.     

In situ adsorption of mercury,methylmercury and other elements by iron oxyhydroxides and organic matter in lake sediments

Samples of authigenic material, sediment overlying water and oxic surface sediment (0–0.5-cm depth) from a perennially oxygenated lacustrine basin were analysed to investigate which solid phases are important for binding a suite of trace elements (Ag, As, Ca, Cd, Cu, Hg, In, methylmercury (MeHg), Mg, Mo, Pb, Sb and Zn). The authigenic material, which was collected with inert Teflon sheets deployed for several years across the sediment–water interface, contained mainly poorly crystallized Fe oxyhydroxides and natural organic matter, presumably humic substances derived from the watershed. Manganese oxyhydroxides were not present in the collected authigenic material due to the slightly acidic condition (pH = 5.6) of the lake that prevents the formation and recycling of these compounds. Conditional equilibrium constants for the adsorption of cationic (K_Fe–M) and anionic (K_Fe–A) trace elements onto the authigenic Fe oxyhydroxides were estimated from their concentrations in the authigenic material and in bottom water samples. These field-derived values of K_Fe–M and K_Fe–A were compared with those predicted by the surface complexation model, using laboratory-derived intrinsic adsorption constants and the water composition at the study site. Equilibrium constants (K_POM–M) were also calculated for the adsorption of the cationic trace elements onto the humic substances contained in the diagenetic material. The field-derived values of K_POM–M were compared to those predicted by the speciation code WHAM 6 for the complexation of the trace elements by dissolved humic substances in the lake. Combining the results of the present study with those on the distributions of trace elements in the porewater and solid-phase sediments reported in previous studies at the same site, it was determined whether the trace elements bind preferentially to Fe oxyhydroxides or natural organic matter in oxic sediments. The main inferences are that the anionic trace elements As, Mo and Sb, as well as the cationic metal Pb are preferentially bound to the authigenic Fe oxyhydroxides whereas the other trace elements, and especially Hg and MeHg, are preferentially bound to the humic substances.     

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.     

Prediction of the thermodynamic properties of metal–arsenate and metal–arsenite aqueous complexes to high temperatures and pressures and some geological consequences

The standard thermodynamic properties at 25°C, 1 bar (ΔG _f^o, ΔH _f^o, S ^o, C _P^o, V ^o, ω) and the coefficients of the revised Helgeson–Kirkham–Flowers equations of state were evaluated for several aqueous complexes formed by dissolved metals and either arsenate or arsenite ions. The guidelines of Shock and Helgeson (Geochim Cosmochim Acta 52:2009–2036, 1988) and Sverjensky et al. (Geochim Cosmochim Acta 61:1359–1412, 1997) were followed and corroborated with alternative approaches, whenever possible. The SUPCRT92 computer code was used to generate the log K of the destruction reactions of these metal–arsenate and metal–arsenite aqueous complexes at pressures and temperatures required by the EQ3/6 software package, version 7.2b. Apart from the AlAsO₄^o and FeAsO₄^o complexes, our log K at 25°C, 1 bar are in fair agreement with those of Whiting (MS Thesis, Colorado School of Mines, Golden, CO, 1992). Moreover, the equilibrium constants evaluated in this study are in good to fair agreement with those determined experimentally for the Ca–dihydroarsenate and Ca–hydroarsenate complexes at 40°C (Mironov et al., Russ J Inorg Chem 40:1690, 1995) and for Fe(III)–hydroarsenate complex at 25°C (Raposo et al., J Sol Chem 35:79–94, 2006), whereas the disagreement with the log K measured for the Ca–arsenate complex at 40°C (Mironov et al., Russ J Inorg Chem 40:1690, 1995) might be due to uncertainties in this measured value. The implications of aqueous complexing between dissolved metals and arsenate/arsenite ions were investigated for seawater, high-temperature geothermal liquids and acid mine drainage and aqueous solutions deriving from mixing of acid mine waters and surface waters. Electronic Supplementary Material The online version of this article () contains supplementary material, which is available to authorized users.     

Competitive adsorption,release and speciation of heavy metals in the Yellow River sediments,China

The competitive adsorption and the release of selected heavy metals and their speciation distribution before and after adsorption in the Yellow River sediments are discussed. The adsorption of metals onto sediments increases with increasing pH value and decreases with increasing ionic strength. The competitive coefficient K _c and the distribution coefficient K _d are obtained to analyze the competitive abilities of selected heavy metals, which are ranked as Pb > Cu >> Zn > Cd. The competition among selected heavy metals becomes more impetuous with increasing ion concentration in water. Speciation analysis was done by an improved analytical procedure involving five steps of sequential extraction. Cu, Pb and Zn were mainly transformed into the carbonate-bound form (50.8–87.7%) in adsorption. Most of (60.7–77.3%) Cd was transformed into the exchangeable form, and the percentage of carbonate-bound Cd was 19.7–30.4%. The release reaction was so quick that the release capacity of selected heavy metals from sediments to aqueous solution reached half of the maximum value only in 30 s. As opposed to adsorption, the release capacities of selected heavy metals were ranked as Cd > Zn >> Cu > Pb. In this study, Cd produces the most severe environmental hazards, because its concentration in the release solution is 85.8 times more than the human health criteria of US EPA.     

Phosphorus Sorption Dynamics of Hawaii’s Coastal Wetlands

While phosphorus (P) sorption has been studied in Hawaii’s terrestrial soils, P sorption dynamics have yet to be investigated in coastal wetlands. In other coastal zones, wetlands have been shown to sorb P and act as P sinks at the land–sea interface. Thus, the objectives of this study were to examine variance in the P sorption index (PSI) within wetlands along hydrologic gradients and among wetlands of different types and to identify soil properties that best explain variability in the PSI. Forty wetlands on five islands were sampled and P sorption and related properties were measured. Phosphorus sorption index values ranged from −16.4–1,732.5. Hydrologic zone (within sites) and surface water salinity (among sites) accounted for significant proportions of the variance in the PSI. While texture, pH, and carbon content were found to be important predictors of PSI, the highest correlations were found for oxalate-extractable iron.