Modeling on adsorption–desorption of trace metals to suspended particle matter in the Changjiang Estuary

The uptake and release of trace metals (Cu, Ni, Zn, Cd, and Co) in estuaries are studied using river and sea end-member waters and suspended particulate matter (SPM) collected from the Changjiang Estuary, China. The kinetics of adsorption and desorption were studied in terms of environmental factors (pH, SPM loading, and salinity) and metal concentrations. The uptake of the metals studied onto SPM occurred mostly within 10 h and reached an asymptotic value within 40 h in the Changjiang Estuary. As low pH river water flows into the high pH seawater and the water become more alkaline as it approaches to the seaside of estuary, metals adsorb more on SPM in higher pH water, thus, particulate phase transport of metal become increasingly important in the seaward side of the estuary. The percentage of adsorption recovery and the distribution coefficients for trace metals remained to be relatively invariable and a significant reduction only occurred in very high concentrations of metals (>0.1 mg L⁻¹). The general effect of salinity on metal behavior was to decrease the degree of adsorption of Cu, Zn, Cd, Co, and Ni onto SPM but to increase their adsorption equilibrium pH. The adsorption–desorption kinetics of trace metals were further investigated using Kurbatov adsorption model. The model appears to be most useful for the metals showing the conservative behavior during mixing of river and seawater in the estuary. Our work demonstrates that dissolved concentration of trace metals in estuary can be modeled based on the metal concentration in SPM, pH and salinity using a Kurbatov adsorption model assuming the natural SPM as a simple surfaced molecule.     

Trace metal adsorption onto urban stream suspended particulate matter (Auckland region,New Zealand)

Trace metal adsorption to suspended particulate matter (SPM) influences bioavailability and toxicity of trace metals in natural waters. For highly contaminated urban catchments in the greater Auckland (New Zealand) area, trace metal adsorption to SPM was assessed and compared to similar data from non-urban catchments in the Auckland region, to determine whether there was any difference in the ability of the SPM to adsorb Cu, Pb and Zn. The degree of trace metal adsorption onto the SPM was assessed by way of adsorption edge experiments. It was found that the ability of the Auckland urban SPM to adsorb trace metals decreased in the order Pb > Cu > Zn. Little difference in adsorption was observed between the non-urban Waikato and Kaipara River SPM and urban SPM, or between urban SPM from different flow regimes and seasons, despite some compositional differences in the SPM. This suggests that on the basis of a single surface-binding site, metal adsorption onto SPM could be readily predicted across a range of urban and non-urban catchments in the Auckland region. Adsorption edges were modelled with a diffuse layer, surface complexation model to assess the role of Fe-oxide in adsorption. The MINTEQA2 model was used, assuming Fe-oxide (as HFO) was the only adsorbing surface. There was generally good agreement between observed and modelled adsorption for Pb, indicating the importance of Fe-oxide surfaces for Pb adsorption. However, the model did not predict Zn or Cu adsorption as well. The TOC content of the SPM, and presence of dissolved ligands and organic matter in the water column, appeared to play an important role in Cu adsorption to the SPM. For Zn, the presence of adsorbing surfaces other than HFO appeared to influence adsorption.     

Antimony in the environment: a review focused on natural waters: I. Occurrence

Antimony is ubiquitously present in the environment as a result of natural processes and human activities. It exists mainly as Sb(III) and Sb(V) in environmental, biological and geochemical samples. Antimony and its compounds are considered to be priority pollutants interest by the USEPA and the EU. In this first review paper on antimony occurrence in natural waters, 420 papers on freshwaters, marine waters, estuaries, soils, and sediments have been reviewed. All data are quoted from the original sources. Typical concentrations of total dissolved antimony are usually less than 1.0 μg/l in non-polluted waters. When redox speciation determinations are performed, most studies report the dominance of Sb(V) under oxic conditions. However, the presence of significant proportions of Sb(III) is sometimes detected. This is in contrast with thermodynamic equilibrium predictions and discrepancies are often attributed to biological activity or kinetic effects but proofs are lacking. Similarly, the existence of Sb(V), although not thermodynamically predicted, is often reported under anoxic conditions. Low concentrations of methylated antimony species are mentioned in a few studies. Antimony is not considered to be a highly reactive element in oceans, with concentrations of the order of 200 ng/l. In estuarine waters, both conservative and non-conservative behaviours are reported depending on the estuaries' characteristics. Elevated concentrations of antimony in soils and sediments are either related to anthropogenic sources or associated with high arsenic concentrations in sulfidic ores. Antimony appears to be highly unreactive in soils. Low accumulation factors are reported in algae. Airborne supply of antimony to aquatic and terrestrial systems seems to be important in systems far from direct pollution sources. However, the limited available data do not allow firm conclusions to be drawn on the reactivity and cycling of the element in natural systems and a list of research priorities is given.     

Quantifying arsenate partitioning in aquatic systems: Narrowing the laboratory-real world gap with kinetic sediment extractions and the Diffuse Layer Model

Many studies have proposed that silicic acid and phosphate (P^V) can displace arsenic sorbed to iron oxides leading to elevated As concentrations in aquatic systems. While surface complexation models are adept at quantifying sorption to synthetic oxides in laboratory systems their application to complex natural systems remains challenging. In this study we provide a systematic approach to developing a robust use of models for understanding As^V distribution in natural systems in which hydrated iron oxides are the main adsorptive phase. The Waikato River provides a useful laboratory for this work because it contains high H₄SiO₄, As^V and P^V loadings due to geothermal and agricultural inputs. A 15 min oxalate extraction and a 48 h ethylenediaminetetraacetic acid (EDTA) extraction of river sediment contained the same ratios of As:Fe, P:Fe and Si:Fe. Both of these extracts target the poorly ordered iron oxide phases (typically ferrihydrite) and by following the release of elements over time in the EDTA extraction it was possible to demonstrate that the extracted As, P, and Si were associated with the ferrihydrite. This demonstrates for the first time that a single oxalate extraction can quantify ferrihydrite sorbed H₄SiO₄, As and P^V and provides a basis to quantify the role of these ligands in inhibiting As^V sorption to sediments. The measured concentrations of ferrihydrite sorbed As^V, P^V and H₄SiO₄ for the Waikato River suspended sediment allow for the informed selection of appropriate model parameters for applying the Diffuse Layer Model to the system. In this way it was possible to quantify the effect of the individual components in the river water on As^V sorption. This study provides an explanation for the observation that the proportion of sorbed As in the Waikato River is generally significantly lower than that observed in rivers closer to the world average concentrations. More generally the study provides a method to quantify the role of individual water chemistry components on As^V distribution in natural systems.     

Seasonal distributions of suspended particulate material and dissolved nutrients in a coastal plain estuary

The temporal and spatial distributions of salinity, dissolved oxygen, suspended particulate material (SPM), and dissolved nutrients were determined during 1983 in the Choptank River, an estuarine tributary of Chesapeake Bay. During winter and spring freshets, the middle estuary was strongly stratified with changes in salinity of up to 5‰ occurring over 1 m depth intervals. Periodically, the lower estuary was stratified due to the intrusion of higher salinity water from the main channel of Chesapeake Bay. During summer this intrusion caused minimum oxygen and maximum NH₄ ⁺ concentrations at the mouth of the Choptank River estuary. Highest concentrations of SPM, particulate carbon (PC), particulate nitrogen (PN), total nitrogen (TN), total phosphorous (TP) and dissolved inorganic nitrogen (DIN) occurred in the upper estuary during the early spring freshet. In contrast, minimum soluble reactive phosphate (SRP) concentrations were highest in the upper estuary in summer when freshwater discharge was low. In spring, PC:PN ratios were >13, indicating a strong influence by allochthonous plant detritus on PC and PN concentrations. However, high concentrations of PC and PN in fall coincided with maximum chlorophyll a concentrations and PC:PN ratios were <8, indicating in situ productivity controlled PC and PN levels. During late spring and summer, DIN concentrations decreased from >100 to <10 μg-at l^?1, resulting mainly from the nonconservative behavior of NO₃ ^?, which dominated the DIN pool. Atomic ratios of both the inorganic and total forms of N and P exceeded 100 in spring, but by summer, ratios decreased to <5 and <15, respectively. The seasonal and spatial changes in both absolute concentrations and ratios of N and P reflect the strong influence of allochthonous inputs on nutrient distributions in spring, followed by the effects of internal processes in summer and fall.     

Iron isotope fractionation during biogeochemical cycle: Information from suspended particulate matter (SPM) in Aha Lake and its tributaries,Guizhou, China

Iron isotope compositions of suspended particulate matters (SPM) collected from the Aha Lake, an artificial lake in the karst area of Yun-Gui Plateau, and its tributaries in summer and winter were investigated for our understanding of the behavior of Fe isotopes during iron biogeochemical cycling in lake. δ⁵⁶Fe values of SPM display statistically negative shift relative to IRMM-014. Samples from the lake display a range from ?1.36‰ to ?0.10‰ in summer and from ?0.30‰ to ?0.07‰ in winter, while river samples vary from ?0.88‰ to 0.07‰ in summer and from ?0.35‰ to ?0.03‰ in winter. The average iron isotope composition of aerosol samples is + 0.10‰, which is very similar to that of igneous rocks (0.09‰). The SPM in most rivers and water column showed seasonal variation in δ⁵⁶Fe value: the δ⁵⁶Fe values of SPM in summer were lower than in winter. The seasonal variation in δ⁵⁶Fe value of the riverine SPM should be ascribed to the change in source of particulate Fe and geochemical process in the watershed: More particulate Fe was leached from soil and produced by weathering of pyrite widely distributed in coal-containing strata. It is suggested that both allochthonous inputs and the redox iron cycling control the variations of δ⁵⁶Fe values for SPM in lake.During summer stratification, an Fe cycle named “ferrous wheel” is established near the redox boundary where the upwardly diffusing Fe(II) is oxidized and the reactive Fe oxides formed will continuously sink back into the reduction zone to complete the cycle. The δ⁵⁶Fe values for SPM reach the minima, ?0.88‰ for DB station and ?1.36‰ for LJK station, just near the redox boundary as a result of the Fe cycling, where a rough 45% to 76% of Fe in these particles was produced by the repetitive cycle. Due to random transportation and diffusion, δ⁵⁶Fe values of the particles near the redox zone distributed into approximately a Gaussian shape. The good negative correlation existed between δ⁵⁶Fe values and Fe/Al ratios for DB station, suggesting that they together can be used as good indicators of the redox-driven Fe transformations.     

Assessing the concentration,speciation, and toxicity of dissolved metals during mixing of acid-mine drainage and ambient river water downstream of the Elizabeth Copper Mine,Vermont, USA

The authors determine the composition of a river that is impacted by acid-mine drainage, evaluate dominant physical and geochemical processes controlling the composition, and assess dissolved metal speciation and toxicity using a combination of laboratory, field and modeling studies. Values of pH increase from 3.3 to 7.6 and the sum of dissolved base metal (Cd + Co + Cu + Ni + Pb + Zn) concentrations decreases from 6270 to 100 μg/L in the dynamic mixing and reaction zone that is downstream of the river’s confluence with acid-mine drainage. Mixing diagrams and PHREEQC calculations indicate that mixing and dilution affect the concentrations of all dissolved elements in the reach, and are the dominant processes controlling dissolved Ca, K, Li, Mn and SO₄ concentrations. Additionally, dissolved Al and Fe concentrations decrease due to mineral precipitation (gibbsite, schwertmannite and ferrihydrite), whereas dissolved concentrations of Cd, Co, Cu, Ni, Pb and Zn decrease due to adsorption onto newly formed Fe precipitates.     

The coagulation,solubility and adsorption properties of Fe,Mn, Cu,Ni, Cd,Co and humic acids in a river water

River water (Water of Luce, Scotland) is used in laboratory experiments designed to investigate physical and chemical properties of Fe. Mn, Cu, Ni, Co, Cd and humic acids in riverine and estuarine systems. Using NaCl, MgCl₂ and CaCl₂ as coagulating agents, coagulation of dissolved (0.4 μm filtered) Fe, Cu, Ni, Cd and humic acids increases in a similar matter with increasing salt molarily: Ca²⁺ is the most dominant coagulating agent. Removal by coagulation with Ca²⁺ at seawater concentrations ranges from large (Fe-80%. HA-60%, Cu-40%) to small (Ni, Cd-15%) to essentially nothing (Cd, Mn-3%). Destabilization of colloids is the indicated mechanism. Solubility-pH measurements show that between a pH of 3 and 9, Fe, Cu, Ni, Mn, Co and Cd are being held in the dissolved phase by naturally occurring organic substances. Between pH of 2.2 and 1.2 a large proportion of dissolved Fe, Cu. Ni and Cd (72, 35,44 and 36% respectively) is precipitated along with the humic acids; in contrast, Mn and Co show little precipitation (3%). Adsorption-pH experiments, using unfiltered river water spiked with Cu, indicate that adsorption of Cu onto suspended particles is inhibited to a large extent by the formation of dissolved Cu-organic complexes.The experimental results demonstrate that solubilities and adsorption properties of certain trace metals in freshwaters can be opposite to those observed with artificial solutions or predicted with chemical models. Interaction with organic substances is a critical factor.     

Arsenic mobility in fluvial environment of the Ganga Plain,northern India

In the northern part of the Indian sub-continent, the Gomati River (a tributary of the Ganga River) was selected to study the dynamics of Arsenic (As) mobilization in fluvial environment of the Ganga Plain. It is a 900-km-long, groundwater-fed, low-gradient, alluvial river characterized by monsoon-controlled peaked discharge. Thirty-six water samples were collected from the river and its tributaries at low discharge during winter and summer seasons and were analysed by ICP-MS. Dissolved As and Fe concentrations were found in the range of 1.29–9.62 and 47.84–431.92 μg/L, respectively. Arsenic concentration in the Gomati River water has been detected higher than in its tributaries water and characteristically increases in downstream, attributed to the downstream increasing of Fe₂O₃ content, sedimentary organic carbon and silt-clay content in the river sediments. Significant correlation of determination (r ² = 0.68) was also observed between As and Fe concentrations in the river water. Arsenic concentrations in the river water are likely to follow the seasonal temperature variation and reach the level of World Health Organization’s permissible limit (10 μg/L) for drinking water in summer season. The Gomati River longitudinally develops reducing conditions after the monsoon season that mobilize As into the river water. First, dissolved As enters into pore-water of the river bed sediments by the reductive dissolution of Fe-oxides/hydroxides due to microbial degradation of sedimentary organic matter. Thereafter, it moves upward as well as down slope into the river water column. Anthropogenically induced biogeochemical processes and tropical climatic condition have been considered the responsible factors that favour the release of As in the fluvial environment of the Ganga Plain. The present study can be considered as an environmental alarm for future as groundwater resources of the Ganga–Brahmaputra Delta are seriously affecting the human–environment relationship at present.     

Wash-out processes of evaporitic sulfate salts in the Tinto river: Hydrogeochemical evolution and environmental impact

This work deals with the wash-out processes of evaporitic salts in the Tinto river in October 2005, with the arrival of the first rainfall after the summer. In order to monitor water levels and electrical conductivity, a datalogger was set up in the river, while sampling was performed by a portable autosampler. Thirty-two samples were selected for analysis for a wide range of elements by ICP-AES. Three different flood events, with a maximum discharge of 8.1 m³/s, were monitored. River waters suffered from a dilution effect at the beginning of the first event, recording a concentration decrease of most elements, just before the wash-out of soluble salts precipitated during the summer took place. Wash-out processes provoked a sharp increase in most element concentrations coinciding with an intense decrease in Na and Sr. After the first event, there was strong enrichment of As, and to a lesser extent in Fe, Cr and Pb, due probably to the redissolution/transformation of Fe oxyhydroxysulfates. During the third event, evaporitic sulfate salts were depleted from riverbanks ending wash-out processes, and a decrease in most element concentrations was observed. Barium exhibited different behaviour to the rest of elements owing to the solubility control exerted by barite. Lead also showed a different pattern throughout the study period, its concentration decreasing due probably to its great affinity for coprecipitate on jarosite-group minerals, and increasing when schwertmannite precipitation is thermodynamically favoured. In October 2005, the Tinto river carried around 8100 t SO₄, 1300 t Fe, 400 t Al, 100 t Zn and Cu, etc., highlighting the importance of wash-out processes of soluble salts in the Ría de Huelva ecosystem and metal fluxes into the Atlantic Ocean.     

Behavior of arsenic and antimony in the surface freshwater reaches of a highly turbid estuary, the Gironde Estuary, France

This study reports on the behavior of two redox-sensitive elements, As and Sb, along the turbidity gradient in the freshwater reaches of the turbid Gironde Estuary. During a 17-month survey, surface water and suspended particulate matter (SPM) were sampled monthly at six sites representing both fluvial branches of the Gironde Estuary. Additionally, two longitudinal high resolution profiles were sampled along the fluvial estuary of the Garonne Branch during two contrasted seasons, i.e. with and without the presence of the maximum turbidity zone (MTZ). Seasonal variability and spatial distribution of dissolved (<0.2 μm; <0.02 μm) and particulate As, Sb and Fe were measured and combined with SPM data to understand metalloid behavior in the estuarine freshwater turbidity gradient.At the two main fluvial entries of the Gironde Estuary, dissolved As and Sb concentrations showed strong (by a factor of 2–4) seasonal variations, that were only partly controlled by discharge-related dilution. Seasonal addition of dissolved As and Sb was attributed to the degradation of particulate As and Sb carrier phases in bottom sediment and/or in the adjacent aquifers, rather than release from SPM. In the surface freshwater reaches of the Gironde Estuary, Sb behaved conservatively under all hydrological conditions. In contrast, As was strongly reactive in the presence of the MTZ, with opposite behaviors in the two fluvial branches of the estuary: in the Garonne Branch As was removed from the dissolved phase, whereas in the Dordogne Branch As was added. Redistribution of As between the dissolved and the particulate phases along the turbidity gradient in estuarine freshwater only affected the <0.02 μm fraction, as the 0.02–0.2 μm fraction remained constant (300 ng L⁻¹ in September 2005). Accordingly, As removal seemed to be decoupled from concomitant “colloidal” (0.02–0.2 μm) Fe flocculation in the turbidity gradient. The contrasting behavior of dissolved As in the fluvial estuaries of the Garonne and Dordogne Branches was attributed to sorption processes during equilibration of river-borne dissolved As with estuarine SPM forming the MTZ. This equilibrium, described by a distinct distribution coefficient K_d(As)  11,000 L kg⁻¹ in the MTZ, resulted in either As release (desorption; Dordogne Branch) or removal (adsorption; Garonne Branch) in the respective fluvial estuaries. A mixing experiment under controlled laboratory conditions tended to support that equilibration between the dissolved phase and MTZ particles may induce both As release and removal in the estuarine freshwater reaches, with As distribution evolving towards a distinct K_d value for increasing SPM concentrations. The long-term survey allowed estimating annual (2004) dissolved fluxes of As and, for the first time Sb, at the main fluvial entries of the Gironde Estuary at 30.7 t a⁻¹ and 3.2 t a⁻¹ (Garonne River) and at 8.0 t a⁻¹ and 2.3 t a⁻¹ (Dordogne River), respectively.     

Diel oxygen dynamics and anoxic events in an eutrophic estuary of Waquoit Bay,Massachusetts

As a result of nutrient loading from septic systems, a thick canopy of macroalgae covers the bottom of Waquoit Bay, an embayment on Cape Cod, Massachusetts. Using automated conductivity-temperature-oxygen recorders and manual profiles, we measured diel water column O₂ changes during summer in the Childs River, the estuary of the bay with the highest housing density. At dawn in midsummer, bottom waters in the Childs River are chronically hypoxic due to high rates of benthic respiration. On sunny days benthic photosynthesis drives bottom water O₂ to 10–15 mg l^?1 by afternoon. The extent of the daily O₂ excursion is directly proportional to daily irradiance. Large diel O₂ excursions in bottom water are due to limited mixing of surface and bottom water. Density stratification exceeded two sigma-t units 85% of the time during midsummer in the Childs River. Because of stratification, hypoxia and even anoxia occur in this estuary. The first of several anoxic events was observed in Waquoit Bay in 1988, and we have attempted to evaluate factors that trigger anoxia. High rates of benthic respiration result in anoxia when replenishment of O₂ during the day is limited by insufficient light. Our analysis of meteorological records during two recent anoxic events shows that anoxia develops overnight in midsummer during periods of peak summertime temperatures after several days of cloudy, moderately calm weather. Similarly critical conditions existed most summers since 1975, yet anoxic events in the bay have not been reported historically. If climatic warming occurs, anoxic events in the bay may occur more frequently even if algal stocks remain unchanged. Eutrophication of Waquoit Bay is similar to many other embayments in populated coastal areas, and anoxic events may indicate a chronic growing problem in these important ecosystems. However, in shallow, stratified embayments, anoxia may be transient and easily missed without frequent monitoring.     

Oxyanion Concentrations in Eastern Sierra Nevada Rivers – 3. Boron, Molybdenum, Vanadium, and Tungsten

Water samples were collected from 10 locations along the Truckee River system, 14 locations along the Walker River system, and 12 locations along the Carson River, and analyzed for B, Mo, V, W, Na, Cl, and pH. Boron concentrations ranged from approximately 2 mol/kg in the upper reaches of the Truckee River to almost 1,200 mol/kg in Pyramid Lake. Molybdenum, V, and W had concentrations in the nanomolal range; Mo varied from a low of about 12 nmol/kg to a high of 3,200 nmol/kg (Walker Lake); V ranged from 9 nmol/kg to approximately 470 nmol/kg; and W varied from a low value around 0.8 nmol/kg (West Walker River) to 1,030 nmol/kg. The high concentrations of these oxyanion-forming trace elements in the rivers reflects (1) the relative stability of these oxyanions (e.g., MoO₄ ^2-, HVO₄ ^2-, WO₄ ^2-, B(OH)₃, and/or B(OH)₄ ^-) in the alkaline, well oxygenated river and lake waters, (2) contributions of hydrothermal waters (especially for B), and (3) weathering of rocks/regolith with high concentrations of these elements. In the case of Mo, V, and W, each exhibited relatively conservative behavior in the upper, oxygenated reaches of all three rivers. During the study period the region experienced a prolonged drought such that the lower reaches of each river were typified by no flow or stagnant waters and probably low oxygen and/or anoxic conditions (although not measured). Reductive processes occurring in the low flow to stagnant reaches of each river could have led to removal of Mo, V, and W from solution as coprecipitates with Fe monosulfides, or via sorption to Fe oxides/oxyhydroxides and/or organic matter. Boron, however, exhibited essentially no or minor removal from these rivers, and instead was added to each river via B-rich hydrothermal waters (e.g., Steamboat Creek from Steamboat Hot Springs), or by B-rich groundwaters via base-flow during the extensive drought.     

Magnitudes, spatial scales and processes of environmental antimony mobility from orogenic gold–antimony mineral deposits, Australasia

Antimony (Sb) is strongly concentrated into hydrothermal mineral deposits, commonly with gold, in metasedimentary sequences around the Pacific Rim. These deposits represent potential point sources for Sb in the downstream environment, particularly when mines are developed. This study documents the magnitude and scale of Sb mobility near some mineral deposits in Australia and New Zealand. Two examples of New Zealand historic mining areas demonstrate that natural groundwater dissolution of Sb from mineral deposits dominates the Sb load in drainage waters, with Sb concentrations between 3 and 24 μg/L in major streams. Mine-related discharges can exceed 200 μg/L Sb, but volumes are small. Sb flux in principal stream waters is ca 1–14 mg/s, compared to mine tunnel fluxes of ca 0.001 mg/s. Dissolved Sb is strongly attenuated near some mine tunnels by adsorption on to iron oxyhydroxide precipitates. Similar Sb mobilisation and attenuation processes are occurring downstream of the historic/active Hillgrove antimony–gold mine of New South Wales, Australia, but historic discharges of Sb-bearing debris has resulted in elevated Sb levels in stream sediments (ca 10–100⁺ mg/kg) and riparian plants (up to 100 mg/kg) for ca 300 km downstream. Dissolution of Sb from these sediments ensures that river waters have elevated Sb (ca 10–1,000 μg/L) over that distance. Total Sb flux reaching the Pacific Ocean from the Hillgrove area is ca 8 tonnes/year, of which 7 tonnes/year is particulate and 1 tonne/year is dissolved.     

Hydrology,hydrogeology and hydrochemistry of wetlands: a case study in Izmir Bird Paradise,Turkey

Izmir Bird Paradise is one of the most valuable wetlands in Turkey, but this area is now being threatened by the drying out of marshes and water pollution. This wetland consists of two ecosystems: fresh- and saltwater. The recharge of marshes is from rainfall, the Gediz River and groundwater from Can Suyu Pond. The water type of the river is Ca-Mg-Na-HCO₃-SO₄, whereas the groundwater is a Na-Cl water type. The reasons for the drying are long-term drought (evapotranspiration at 894 mm is >> rainfall at 546 mm), and excessive pumping of groundwater and seawater intrusion into Menemen Plain. Therefore, an additional freshwater resource is necessary. This water can be supplied from the limestone levels of Neogene sedimentary rocks in and around Izmir Bird Paradise that have a Ca-HCO₃ water type. Water pollution levels were also analysed. In the freshwater ecosystem Cd, Cr, Fe, Mn, Ni, Pb, Sb and Zn values, in the open channel in Izmir Bird Paradise Sb, Fe, Ni and Cd values, and in the river Fe, Pb and Sb values exceed the TSE 266 and EPA 2000 standards probably due to agricultural and industrial sources.     

Seasonal and spatial water quality changes in the outflow plume of the Atchafalaya River,Louisiana, USA

The objective of this study was to examine the interaction between the Atchafalaya River and the Atchafalaya Delta estuarine complex. Measurements of suspended sediments, inorganic nutrients (NO₃ ^?, NH₄ ⁺, PO₄ ^3?), chlorophylla (chla), and-salinity were taken monthly from December 1996 to January 1998. These data were compiled by season, and the Atchafalaya River plume data were also analyzed using the Generalized Additive Model technique. There were significant decreases in NO₃ ^? concentrations during summer, fall, and winter as river water passed through the estuary, that were attributable to chemical and biological processes rather than dilution with ambient water. In some regions there were higher chla concentrations during summer and fall compared to winter and spring, when river discharge and the introduction of inorganic nutrients were highest, suggesting biological processes were active during this study. The presence of NH₄ ⁺, as a percentage of available dissolved inorganic nitrogen, increased with distance from the Atchafalaya River, indicative of remineralization processes and NO₃ ^? reduction. Mean PO₄ ^3? concentrations were often higher in the estuarine regions compared to the Atchafalaya River. During summer total suspended solid (TSS) concentrations increased with distance from the river mouth, suggesting a turbidity maximum. Highest chla concentrations were found in the bayous and shallow water bodies of the Terrebonne marshes, as were the lowest TSS concentrations. The low chla concentrations found in other areas of this study, despite high inorganic nutrient concentrations, suggest light limitation as the major control of phytoplankton growth. Salinity reached near seawater concentrations at the outer edge of the Atchafalaya River plume, but much lower salinities (<10 psu) were observed at all other regions. The Atchafalaya Delta estuarine complex buffers the impact of the Atchafalaya River on the Louisiana coastal shelf zone, with a 41% of 47% decrease in Atchafalaya River NO₃ ^? concentrations before reaching Gulf waters.     

Relationships Between Geochemical Parameters (pH, DOC, SPM, EDTA Concentrations) and Trace Metal (Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn) Concentrations in River Waters of Texas (USA)

Water samples from eight major Texas rivers were collected at different times during 1997–1998 to determine the dissolved and particulate trace metal concentrations, expected to show differences in climate patterns, river discharge and other hydrochemical conditions, and human activities along the different rivers. Specifically, two eastern Texas rivers (Sabine, Neches) lie in a region with high vegetation, flat topography, and high rainfall rates, while four Central Texas rivers (Trinity, Brazos, Colorado, and San Antonio) flow through large population centers. Relatively high dissolved organic carbon (DOC) concentrations in the eastern Texas rivers and lower pH led to higher Fe and Mn concentrations in river waters. The rivers that flow through large population centers showed elevated trace metal (e.g., Cd, Pb, Zn) concentrations partly due to anthropogenically produced organic ligands such as ethylenediaminetetraacetic acid (EDTA) present in these rivers. Trace metal levels were reduced below dams/reservoirs along several Texas rivers. Statistical analysis revealed four major factors (suspended particulate matter [SPM], EDTA, pH, and DOC) that can explain most of the observed variability of trace metal concentrations in these rivers. SPM concentrations directly controlled particulate metal contents. Variation in pH correlated with changes of dissolved Co, Fe, Mn, and Ni, and particulate Mn concentrations, while DOC concentrations were significantly related to dissolved Fe concentrations. Most importantly, it was found that, more than pH, EDTA concentrations exerted a major control on dissolved concentrations of Cd and Zn, and, to a lesser extent, Cu, Ni, and Pb.     

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.     

Mercury in the Lot–Garonne River system (France): Sources,fluxes and anthropogenic component

Dissolved and particulate Hg fluxes in the Lot–Garonne–Gironde fluvial-estuarine system were obtained from observation of daily discharge and suspended particulate matter (SPM) concentrations. In addition to the measurements of the total dissolved (<0.45 μm) and particulate Hg (>0.45 μm), called HgT_D and HgT_P respectively, the dissolved inorganic Hg species (HgR_D) were determined monthly. Geochemical background values for HgT_P in sediments and SPM were similar to crustal values and to typical concentrations in SPM of non-contaminated river systems, respectively. The Riou Mort watershed already known as the origin of important historical polymetallic (e.g., Cd, Zn) pollution was identified as an important Hg point source. In the downstream Lot River, Hg concentrations were clearly higher than those in other moderately contaminated systems. The mean relative contribution of HgR_D to HgT_D in the Lot River and in the Garonne River was close to 25% and 50%, respectively, and showed no correlation with water discharge or SPM concentration. Depending on the origin and nature of SPM, HgT_P concentrations were correlated or not with particulate organic C (POC). Maximum HgT_P concentrations were measured in samples containing low POC concentrations and were attributed to sediment resuspension. In contrast, high POC concentrations (6–17%) during algal blooms were associated with low/moderate HgT_P concentrations (<0.5 mg kg⁻¹) at different sites, suggesting that Hg concentrations in fluvial phytoplankton may be limited by bioavailability of dissolved Hg and/or physiologically controlled Hg accumulation. Mercury was mostly (up to 98%) transported in the particulate phase with estimated annual Hg fluxes at the outlet of the Lot River system ranging from 35 to 530 kg a⁻¹ for the past decade. The minimum anthropogenic component (58–84% of total Hg fluxes) could not be explained by present Riou Mort point source contributions, suggesting important Hg release from contaminated sediment as a major source and from downstream point sources (e.g., coal-fired power plants and/or metal processing industries). HgT_P concentrations and fluxes were strongly related to hydrologic variations and were clearly increased by riverbed dredging during lock construction. Therefore, the estimated Hg stocks in the Lot River sediment (5–13 tons) represent an important potential Hg source for the downstream fluvial-estuarine system.     

Present environment of Dam Lake Sambe,southwestern Japan: a geochemical study of bottom sediments

Geochemical analyses of lakebed and core sediments from Lake Sambe on the outskirts of Oda City in Shimane prefecture in southwestern Japan were carried out in order to assess the water quality and the concentration and distribution patterns of sixteen elements. The lake water showed a stratified condition with respect to dissolved O₂, and As, Fe, and Mn concentrations in the bottom layers which increased in the summer. The chemical composition of the sediments, as measured by X-ray fluorescence, included major and trace elements (P, Ca, Sc, Ti, V, Cr, Fe, Ni, Cu, Zn, As, Sr, Zr, Pb, and Th), and total sulfur (TS). Elevated values of As, Zn, V, Fe, P, and TS were present in several layers of the upper cores (from 0 to 5 cm) and other surface sediments. Increases in the abundances of these metals in lake sediments are probably related to the reducing condition of the sediments, fine-grained organic rich sediments, and post-depositional diagenetic remobilization. Moreover, correlations between the concentrations of trace metals and iron in the sediments suggest their adsorption onto Fe (oxy)hydroxides, whereas correlations with sulfur indicate that they were precipitated as Fe-sulfides. The average abundances of As, Pb, Zn, and Cu exceeded the lowest effect level and Interim Sediment Quality Guideline values that the New York State Department of Environmental Conservation and the Canadian Council of Ministers of the Environment determined to have moderate impact on aquatic organisms. In addition, concentrations of As and Zn exceeded the Coastal Ocean Sediment Database threshold value, indicating potentially toxic levels. Therefore, the presence of trace metals in the lake sediments may result in adverse effects on biota health.