Changes in dissolved organic matter characteristics in Chincoteague Bay during a bloom of the pelagophyte<Emphasis Type="Italic">Aureococcus anophagefferens</Emphasis>

Aureococcus anophagefferens, the pelagophyte responsible for brown tide blooms, occurs in coastal bays along the northeast coast of the United States. This species was identified in Chincoteague Bay, Maryland, in 1997 and has bloomed there since at least 1998. Time series of dissolved organic matter (DOM) concentrations and characteristics are presented for two sites in Chincoteague Bay: one that experienced a brown tide bloom in 2002 and one that did not. Characteristics of the bulk DOM pool were obtained using dissolved organic carbon (DOC) and ultraviolet-visible (UV-Vis) measurements (spectral slope and specific UV absorbance). High molecular weight DOM (HMW-DOM) was characterized in terms of DOC concentration, carbon: nitrogen (C:N) ratio, isotopic signature, and molecular-level characteristics as determined by direct temperature resolved mass spectrometry (DT-MS). Compositional changes in the DOM pool are associated with brown tide blooms, although a direct relationship between DOM characteristics and bloom development could not be confirmed. DOC measurements suggest that during the brown tide bloom, HMW-DOM was released into the surface water. UV-Vis analysis on the bulk DOM and molecular-level characterization of the HMW-DOM using DT-MS show that this material was optically active and more aromatic in nature. Based upon C:N ratio and HMW-DOC measurements, it appears that this HMW-DOM was more nitrogen enriched. Whether this material was released as exudates or was due to lysis ofA. anophagefferens could not be determined.     

Identifying environmental and geochemical variables governing metal concentrations in a stream draining headwaters in NW Spain

Headwater stream, draining from a rural catchment in NW Spain, was sampled during baseflow and storm-event conditions to investigate the temporal variability in dissolved and particulate Al, Fe, Mn, Cu and Zn concentrations and the role of discharge (Q), pH, dissolved organic carbon (DOC) and suspended sediment (SS) in the transport of dissolved and particulate metals. Under baseflow and storm-event conditions, concentrations of the five metals were highly variable. The results of this study reveal that all metal concentrations are correlated with SS. DOC and SS appeared to influence both the metal concentrations and the partitioning of metals between dissolved and particulate. The SS was a good predictor of particulate metal levels. Distribution coefficients (K_D) were similar between metals (4.72–6.55) and did not change significantly as a function of discharge regime. Stepwise multiple linear regression analysis reveals that the most important variable to explain storm-event K_D for Al and Fe is DOC. The positive relationships found between metals, in each fraction, indicate that these elements mainly come from the same source. Metal concentrations in the stream were relatively low.     

Spatial and temporal dynamics of dissolved trace metals, organic carbon, mineral nutrients, and phytoplankton in a coastal lagoon: Great South Bay, New York

Although marine lagoons are ubiquitous features along coastal margins, studies investigating the dynamics of metal, organic matter, and nutrient concentrations in such systems are rare. Here we present a comprehensive examination of the temporal and spatial gradients in dissolved trace metals (Ag, Cd, Cu, Mn, Pb), organic and inorganic nutrients (POC, PON, DOC, N0₃ ⁻, NH₄ ⁺, H₄SiO₄, PO₄ ⁻³, and urea), and algal biomass in a lagoon estuary, Great South Bay (GSB), New York, USA. While this estuary has experienced a series of environmental problems during recent decades (urbanization, loss of fisheries, harmful algal blooms), root causes are largely unknown, in part because levels of bioactive substances, such as trace metals, have never been measured. Sampling was undertaken within multiple estuarine, riverine, and groundwater sites during spring, summer, and fall. Trace metal tracers (e.g., Ag, Mn) and statistical analyses were used to differentiate the influences of natural and anthropogenic processes on the chemical composition of the lagoon. Our analyses revealed three clusters of biogeochemical constituents that behaved similarly in GSB: constituents under strong biological control such as POC, PON, DOC and chlorophyll,a; elements indicative of benthic remobilization processes such as Mn, Cd, and Cu; and constituents strongly influence by anthropogenic processes such as Ag, Pb, PO₄ ⁻³, NO₃ ⁻, and NH₄ ⁺. Although GSB is surrounded by a densely populated watershed (c. 1 million people), it does not appear to be significantly contaminated by trace metals compared to other urban estuaries. Levels of DOC (up to 760 μM) in GSB were well correlated with phytoplankton biomass and exceeded at least 98% of values reported in similar mid Atlantic estuaries at the same salinities. These high levels of DOC are likely to be an important source of carbon export to the coastal ocean and likely promote mixotrophic harmful algal blooms in this system.     

Dissolved Trace Metal–Organic Complexes in the Lot–Garonne River System Determined Using the C18 Sep-Pak System

An 11-month observation of dissolved and particulate organic matter, chlorophyll a(Chl a), C18 Sep-Pak extractable hydrophobic dissolved organic matter (hDOM) fraction and associated dissolved trace metals (Cd, Cu, V, Co, Ni, Mo, U) was performed in the Lot–Garonne River system. This system includes the Riou Mort, the Lot River and the downstream reaches of the Garonne River and represents the fluvial transport path of trace metals between the major point source of polymetallic pollution, located in the Riou Mort watershed and the Gironde estuary. Spatial and temporal variations of dissolved and particulate organic carbon and Chl areflect the presence of different types of organic matter and their relation with the hDOM fraction. Maximum Chl a/POC ratios (up to 0.03), indicate intense phytoplankton production from March to May. In the Lot River (Temple), DOC and POC concentrations were clearly higher and mean Chl a concentration (2.8 mg g⁻¹) was about three times higher than those of the other sites. High Chl a/POC ratios suggest high phytoplankton activity with maxima in spring and late summer. In the Riou Mort River, very high POC concentrations of up to 40 (mean: 20) occurred, whereas Chl a concentrations were relatively low indicating low phytoplankton activity. High, strongly variable DOC and POC concentrations suggest important natural (Carboniferous soils, forests) or anthropogenic (e.g., former coal mines, waste areas, agriculture, sewage) carbon sources within the small Riou Mort watershed. Despite high DOC concentrations in the Riou Mort River, hDOM metal fractions were generally lower than those at the other sites. The general order of decreasing binding strength between metals and the organic hydrophobic phase (Cu, U > Co, Ni > V, Mo > Cd) at all four sites was in good agreement with the Irving–William series of transition element affinity towards organic ligands. Accordingly, the role of the hydrophobic phase in dissolved Cd transport appeared to be negligible, whereas the hDOM–Cu fraction strongly contributed to dissolved Cu transport.     

Temporal Trends of Dissolved Trace Metals in Jamaica Bay,NY: Importance of Wastewater Input and Submarine Groundwater Discharge in an Urban Estuary

Jamaica Bay, NY, is a highly urbanized estuary within the boroughs of New York City conspicuously lacking published information on dissolved trace metal concentrations. The current study examines the distribution and cycling of trace metals in that embayment with data gathered during cruises in November 2004, April 2005, and June 2006. Most of the metal distributions (Fe, Zn, Co, Ag, Cu, Pb, Ni) in the water column are explained by the input of substantial volumes of treated wastewater effluent. However, several lines of evidence suggest that submarine groundwater discharge (SGD) is also an important source of dissolved Fe, Zn, Co, Ni, and isotopically distinct stable Pb ratios (²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb) in the Bay. Conversely, the recirculated seawater component of SGD is an apparent sink for dissolved Mo. This study provides the first measurements of dissolved trace metals in the Jamaica Bay water column and subterranean estuary and provides evidence for trace metal input due to SGD.     

Early diagenesis of trace metals (Cd, Cu, Co, Ni, U, Mo, and V) in the freshwater reaches of a macrotidal estuary

Vertical profiles from the water column, including the maximum turbidity zone (MTZ) to the consolidated sediment were sampled in September 2000 in the freshwater reaches of the Gironde Estuary during a complete neap tide-spring tide cycle. The vertical distributions of dissolved major redox parameters and metals (Mn, Fe, Cd, Cu, V, Co, Ni, Mo, and U) were determined. Reactive particulate metal fractions were also determined from selective leaching. The studied system is characterized by density layers functioning at different time-scales, consisting of two mobile layers, i.e., the liquid (LM) and the soft mud (SM), overlying consolidated sediments (CS). This results in a three-zone diagenetic regime where (1) O₂ dynamics are fast enough to show depletion in the rapidly mixed LM sequence (tidal time-scale), (2) denitrification occurs on the weekly time-scale mixing SM sequence, and (3) the Mn, Fe, and sulfate cycling occurs in the CS layer (annual time-scale). The studied trace metals show differential behavior during early diagenesis: (1) Cd, Cu, and V are released into pore water preferentially from organic matter in the SM, (2) Co, Ni, and U are released in the CS from Mn and Fe oxides during reductive dissolution, and (3) Mo from both processes. Transient conditions (i.e., oscillations of redox fronts and reoxidation processes), due to the dynamics of the mobile layers, strongly influence the trace metal distributions as inducing resolubilization (Cd, Cu, and Mo). In the CS, authigenic metal phases accumulate, either by direct precipitation with sulfides (Cu, Cd) or co-precipitation with Fe-sulfides (Mo). Microbially mediated reduction of Fe oxides is proposed to control U removal from pore water by reduction of U(VI) to U(IV) at depth. However, a significant fraction of the trace metals is trapped in the sediment in exchangeable forms, and therefore is susceptible to be mobilized due to resuspension of estuarine sediment during strong river flood periods and/or dredging activities.     

Particulate trace metal and major element distributions over consecutive tidal cycles in Port Jackson Estuary,Australia

Particulate trace metal (Cu, Cr, Ni, Pb and Zn) and major element (Fe, Mn and Al) concentrations have been determined following intensive sampling over two consecutive spring tidal cycles in the 'turbidity maximum zone' (TMZ) of the Port Jackson estuary, Australia. Salinity, temperature, pH, dissolved oxygen, suspended particulate matter (SPM) and chlorophyll a were also determined. A three-factor analysis of variance was used to test temporal variability in concentrations of particulate trace metals and major elements as a result of tidal oscillation. Estuarine master variables, such as temperature and pH, varied within a narrow range; nevertheless, the tidal signal was clear for surface and bottom waters. In surface water, no variance was detected in SPM concentrations between consecutive tidal cycles or between tidal stages (i.e. flood, ebb and slack water). In bottom water, however, SPM concentrations were significantly higher (PА.05) at flood tide than at slack high water and ebb tide. Concentrations of particulate trace metals and major elements in surface water do not display significant variability between tidal cycles or stages. Nevertheless, differences within each tidal stage were significant (PА.05) for all elements. In bottom water, only particulate Fe and Al exhibited significant differences (PА.05) between tidal cycles, whereas particulate Ni was the only trace element that presented significant differences (PА.05) between tidal stages, following the distribution of SPM, with highest concentrations at flood tide. Among the metals studied, significant variation was found at all three temporal scales examined (i.e. from hours to consecutive tidal cycles), although the patterns of variation were different for each metal. The semi-diurnal fluctuation of SPM and particulate trace metal concentrations during spring tides is interpreted as a resuspension-deposition cycle caused by cyclical oscillations of bottom currents. The results are discussed in the context of the implications of tidal cycle influence on the geochemistry and cycling of particulate trace metals in the Port Jackson estuary.     

Importance of geochemical transformations in determining submarine groundwater discharge-derived trace metal and nutrient fluxes

Seasonal (Spring and Summer 2002) concentrations of dissolved (<0.22 μm) trace metals (Ag, Al, Co, Cu, Mn, Ni, Pb), inorganic nutrients (NO₃, PO₄, Si), and DOC were determined in groundwater samples from 5 wells aligned along a 30 m shore-normal transect in West Neck Bay, Long Island, NY. Results show that significant, systematic changes in groundwater trace metal and nutrient composition occur along the flowpath from land to sea. While conservative mixing between West Neck Bay water and the groundwaters explains the behavior of Si and DOC, non-conservative inputs for Co and Ni were observed (concentration increases of 10- and 2-fold, respectively) and removal of PO₄ and NO₃ (decreases to about half) along the transport pathway. Groundwater-associated chemical fluxes from the aquifer to the embayment calculated for constituents not exhibiting conservative behavior can vary by orders of magnitude depending on sampling location and season (e.g. Co, 3.4 × 10²– 8.2 × 10³ μmol d⁻¹). Using measured values from different wells as being representative of the true groundwater endmember chemical composition also results in calculation of very different fluxes (e.g., Cu, 6.3 × 10³ μmol d⁻¹ (inland, freshwater well) vs. 2.1 × 10⁵ μmol d⁻¹(seaward well, S = 17 ppt)). This study suggests that seasonal variability and chemical changes occurring within the subterranean estuary must be taken into account when determining the groundwater flux of dissolved trace metals and nutrients to the coastal ocean.     

Marsh-water column interactions in two Louisiana estuaries. II. Nutrient dynamics

The exchange of dissolved nutrients between marshes and the inundating water column was measured using throughflow marsh flumes built, in two microtidal Louisiana estuaries: the Barataria Basin estuary and Fourleague Bay. The flumes were sampled between September 1986 and April 1988, coincident with an extended period of low sea level on the Louisiana coast. The Barataria Basin estuary is in the later, deteriorating stage of the deltaic cycle, characterized by low freshwater inputs and subsiding marshes. Both brackish and saline marshes supplied dissolved organic nitrogen (DON), inorganic nitrogen (ammonium + nitrate + nitrite = DIN), dissolved organic carbon (DOC), and total nitrogen (as total Kjeldahl nitrogen = TKN) to the water column. The export of DIN is probably related to the N accumulated in earlier stages of deltaic development and released as these marshes deteriorate. Coastal brackish marshes of Fourleague, Bay, part of an accreting marsh system in an early, developmental stage of the deltaic cycle, exported TKN to the open water estuary in all samplings. This marsh apparently acted as a short-term buffer of DIN by taking up NH₄ ⁺ in spring, when baywide concentrations were high, and supplying DIN to the estuary in summer and fall, when concentrations, in the bay were lower. Differences in phosphorus (P), DOC, and DON fluxes between these two estuaries were also observed. The Fourleague Bay site exported soluble reactive phosphorus (SRP) and total phosphorus (TP) and imported DOC. This P export may be related to remobilization of sediment-bound riverine P by the reducing, soils of the marshes. Fluxes of SRP at the Barataria Basin sites were variable and low while DOC was imported. Most imports of dissolved nutrients were correlated with higher upstream [source] concentrations, and flux rates were fairly consistent throughout the tide. Dissolved nutrient exports, did not correlate with upstream concentrations, though, and in many cases the flux was dominated by early, flood tide nutrient release. This pulsed behavior may be caused by rapid diffusion from the sediments early in the tidal cycle, when the sediment-water concentration gradient is largest. Interestuary differences were also seen in particulate organic matter fluxes, as the Fourleague Bay marsh exported POC and PON during all samplings while Barataria Basin imported these nutrients. In general, the magnitude and direction of nutrient exchanges in Louisiana marshes, seem to reflect the deltaic successional stage of the estuary.     

Distribution of colloidal trace metals in the San Francisco Bay estuary

The size distribution of trace metals (Al, Ag, Cd, Cu, Fe, Mn, Ni, Sr, and Zn) was examined in surface waters of the San Francisco Bay estuary. Water samples were collected in January 1994 across the whole salinity gradient and fractionated into total dissolved (<0.2 μm colloidal (10 KDa–0.2 μm) and < 10 kDa molecular weight phases. In the low salinity region of the estuary, concentrations of colloidal A1, Ag, and Fe accounted for ≥84% of the total dissolved fraction, and colloidal Cu and Mn accounted for 16–20% of the total. At high salinities, while colloidal Fe was still relatively high (40% of the dissolved), very little colloidal Al, Mn, and Cu (<10%) and no colloidal Ag was detectable. Colloidal Zn accounted for <3% of the total dissolved along the estuary, and colloidal Ni was only detectable (<2%) at the river endmember. All of the total dissolved Cd and Sr throughout the estuary consisted of relatively low molecular weight (<10 kDa) species. The relative affinity of metals for humic substances and their reactivity with particle surfaces appear to determine the amounts of metal associated with colloids. The mixing behavior of metals along the estuary appears to be determined by the relative contribution of the colloidal phase to the total dissolved pool. Metals with a small or undetectable colloidal fraction showed a nonconservative excess (Cd, Cu, Ni, and Mn) or conservative mixing (Sr) in the total dissolved fraction, relative to ideal dilution of river water and seawater along the estuary.

The salt-induced coagulation of colloidal A1, Fe, and Cu is indicated by their highly nonconservative removal along the salinity gradient. However, colloidal metals with low affinity for humic substances (Mn and Zn) showed conservative mixing behavior, indicating that some riverine colloids are not effectively aggregated during their transport to the sea. While colloidal metal concentrations correlated with dissolved organic carbon, they also covaried with colloidal Al, suggesting that colloids are a mixture of organic and inorganic components. Furthermore, the similarity between the colloidal metal:A1 ratios with the crustal ratios indicated that colloids could be the product of weathering processes or particle resuspension. Distribution coefficients for colloidal particles (K_c) and for large, filter-retained particles (K_d) were of the same magnitude, suggesting similar binding strength for the two types of particles. Also, the dependence of the distribution coefficients on the amount of suspended particulate matter (the so-called particle concentration effect) was still evident for the colloids-corrected distribution coefficient (K_p+c) and for metals (e.g., Ni) without affinity for colloidal particles.     

The behaviour of dissolved organic material,iron and manganese in estuarine mixing

Fractionation by ultra-filtration of the dissolved organic material (DOM) in the River Beaulieu, with typical concentrations of dissolved organic carbon (DOC) of 7–8 mg C/l, showed it to be mainly in the nominal molecular weight range of 10³–10⁵, with 16–23% of the total DOC in the fraction > 10⁵. The molecular weight distribution of DOM in the more alkaline River Test (average DOC, 2 mg C/l) was similar. In the River Beaulieu water, containing 136–314 βg Fe/l in ‘dissolved’ forms, 90% or more of this Fe was in the nominal molecular weight fraction > 10⁵. Experiments showed that DOM of nominal molecular weight <10⁵ could stabilize Fe(III) in ‘dissolved’ forms. The concentrations of ‘dissolved’ Fe in the river water probably reflect the presence of colloidal Fe stabilized by organic material and this process may influence the apparent molecular weight of the DOM. Dissolved. Mn (100–136 βg/l) in the River Beaulieu was mainly in true solution, probably as Mn(II), with some 30% in forms of molecular weight greater than ca 10⁴.During mi xing in the Beaulieu Estuary, DOC and dissolved Mn behave essentially conservatively. This contrasts with the removal of a large fraction of the dissolved Fe (Holliday and LISS, 1976, Est. Coastal Mar. Sci. 4, 349–353). Concentrations of lattice-held Fe and Mn in suspended particulate material were essentially uniform in the estuary, at 3.2 and 0.012%, respectively, whereas the non-lattice held fractions decreased markedly with increase in salinity. For Mn the decrease was linear and could be most simply accounted for by the physical mixing of riverborne and marine participates, although the possibility that some desorption occurs is not excluded. The non-linear decrease in the concentration of non-lattice held Fe in particulates reflected the more complex situation in which physical mixing is accompanied by removal of material from the ‘dissolved’ fraction.     

Mobilisation of arsenic and other trace elements in fluviolacustrine aquifers of the Huhhot Basin,Inner Mongolia

Observed As concentrations in groundwater from boreholes and wells in the Huhhot Basin of Inner Mongolia, northern China, range between <1 μg l⁻¹ and 1480 μg l⁻¹. The aquifers are composed of Quaternary (largely Holocene) lacustrine and fluvial sediments. High concentrations are found in groundwater from both shallow and deep boreholes as well as from some dug wells (well depths ranging between <10 m and 400 m). Populations from the affected areas experience a number of As-related health problems, the most notable of which are skin lesions (keratosis, melanosis, skin cancer) but with internal cancers (lung and bladder cancer) also having been reported. In both the shallow and deep aquifers, groundwaters evolve down the flow gradient from oxidising conditions along the basin margins to reducing conditions in the low-lying central part of the basin. High As concentrations occur in anaerobic groundwaters from this low-lying area and are associated with moderately high dissolved Fe as well as high Mn, NH₄, dissolved organic C (DOC), HCO₃ and P concentrations. Many of the deep groundwaters have particularly enriched DOC concentrations (up to 30 mg l⁻¹) and are often brown as a result of the high concentrations of organic acid. In the reducing groundwaters, inorganic As(III) constitutes typically more than 60% of the total dissolved As. The highest As concentrations tend to be found in groundwater with low SO₄ concentrations and indicate that As mobilisation occurs under strongly reducing conditions, where SO₄ reduction has been an active process. High concentrations of Fe, Mn, NH₄, HCO₃ and P are a common feature of reducing high-As groundwater provinces (e.g. Bangladesh, West Bengal). High concentrations of organic acid (humic, fulvic acid) are not a universal feature of such aquifers, but have been found in groundwaters from Taiwan and Hungary for example. The observed range of total As concentrations in sediments is 3–29 mg kg⁻¹ (n=12) and the concentrations correlate positively with total Fe. Up to 30% of the As is oxalate-extractable and taken to be associated largely with Fe oxides. The release of As into solution under the reducing conditions is believed to be by desorption coupled with reductive dissolution of the Fe oxide minerals. The association of dissolved As with constituents such as HCO₃, DOC and P may be a coincidence related to the prevalent reducing conditions and slow groundwater flow, but they may also be directly involved because of their competition with As for binding sites on the Fe oxides. The Huhhot groundwaters also have some high concentrations of dissolved U (up to 53 μg l⁻¹) and F⁻ (up to 6.8 mg l⁻¹). In contrast to As, U occurs predominantly under the more oxidising conditions along the basin margins. Fluoride occurs dominantly in the shallow groundwaters which have Na and HCO₃ as the dominant ions. The combination of slow flow of groundwater and the young age of the aquifer sediments are also considered potentially important causes of the high dissolved As concentrations observed as the sediments are likely to contain newly-formed and reactive minerals and have not been well flushed since burial.     

Geochemical Control of Heavy Metal Concentrations and Distribution Within Bahia Blanca Estuary (Argentina)

Chromium and lead concentrations and distribution have been fully studied within Bahía Blanca estuary inner area, which is strongly influenced by urban and industrial stress. Not only metals dissolved in estuarine water but also those included in sediments and suspended particulate matters (SPM) were measured. In all cases, internationally standardized protocols were applied to metal measurements, including analytical quality check test through analysis of certified reference materials. Total metal contents from surface sediments and SPM were compared with those from a historical database of the area, as well as with values representing the natural geochemical baseline within the system. Results showed that heavy metal pollution is mainly localized in the areas close to both industrial effluents discharge system and urban sewage outfall discharge. Data from sequential extractions indicate that metals from anthropogenic sources (i.e., Pb) are potentially more mobile than those inherited from geological parent material (i.e., Cr). The influences of other potential sources of metals (i.e., streams, runoff) were also considered. SPM was clearly identified as the main carrier of the studied heavy metals within the system, and its significance to metals input into sediments and/or biota was verified. Finally, the normalization of measured metal concentrations against background reference elements (i.e., Al or Fe) has allowed to identify that most of the measured Cr was lithogenic, while a significant percentage of Pb was from anthropogenic origin within Bahía Blanca estuary.     

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.     

Fractionation of dissolved organic matter affected by polyvalent metal cations

The purpose of the study was to evaluate the influence of polyvalent cations known to form complexes with natural organic substances on the operational fractionation of dissolved organic matter (DOM) using XAD-8 adsorber resin. Dissolved organic matter solutions from a forest floor were treated with increasing concentrations of polyvalent metal cations (Ca²⁺, Al³⁺, Fe³⁺) at different pH levels. Then the concentrations of total dissolved organic carbon (DOC) and the distribution between hydrophilic and hydrophobic DOC were determined. The concentrations of total DOC decreased slightly when the C/metal ratio was less than 10, especially for Al and Fe. Hydrophilic DOC increased and hydrophobic DOC decreased with increasing concentrations of metal cations. Effects increased in the order Ca<Al<Fe and were more pronounced at low DOC concentrations and high pH values. The reason for the reduction of the DOC concentrations seemed to be the formation of insoluble metal–DOM complexes, while soluble metal–DOM complexes may induce an alteration of the distribution between hydrophilic and hydrophobic DOC. Thus, the polyvalent cations and their concentration need to be considered when DOM fraction distributions, determined with XAD-8 resin, of different waters are compared, especially at low DOC contents and high pH.     

Al(III) and Fe(III) binding by humic substances in freshwaters, and implications for trace metal speciation

Published experimental data for Al(III) and Fe(III) binding by fulvic and humic acids can be explained approximately by the Humic Ion-Binding Model VI. The model is based on conventional equilibrium reactions involving protons, metal aquo ions and their first hydrolysis products, and binding sites ranging from abundant ones of low affinity, to rare ones of high affinity, common to all metals. The model can also account for laboratory competition data involving Al(III), Fe(III) and trace elements, supporting the assumption of common binding sites. Field speciation data (116 examples) for Al in acid-to-neutral waters can be accounted for, assuming that 60-70 % (depending upon competition by iron, and the chosen fulvic acid : humic acid ratio) of the dissolved organic carbon (DOC) is due to humic substances, the rest being considered inert with respect to ion binding. After adjustment of the model parameter characterizing binding affinity within acceptable limits, and with the assumption of equilibrium with a relatively soluble form of Fe(OH)₃, the model can simulate the results of studies of two freshwater samples, in which concentrations of organically complexed Fe were estimated by kinetic analysis.The model was used to examine the pH dependence of Al and Fe binding by dissolved organic matter (DOM) in freshwaters, by simulating the titration with Ca(OH)₂ of an initially acid solution, in equilibrium with solid-phase Al(OH)₃ and Fe(OH)₃. For the conditions considered, Al, which is present at higher free concentrations than Fe(III), competes significantly for the binding of Fe(III), whereas Fe(III) has little effect on Al binding. The principal form of Al simulated to be bound at low pH is Al³⁺, AlOH²⁺ being dominant at pH >6; the principal bound form of Fe(III) is FeOH²⁺ at all pH values in the range 4-9. Simulations suggest that, in freshwaters, both Al and Fe(III) compete significantly with trace metals (Cu, Zn) for binding by natural organic matter over a wide pH range (4-9). The competition effects are especially strong for a high-affinity trace metal such as Cu, present at low total concentrations (∼1 nM). As a result of these competition effects, high-affinity sites in humic matter may be less important for trace metal binding in the field than they are in laboratory systems involving humic matter that has been treated to remove associated metals.     

Delivery of Trace Metals (Al,Fe, Mn,V, Co,Ni, Cu,Cd, Ag,Pb) from the Trinity River Watershed Towards the Ocean

The Trinity River (Texas, USA) contains in its watershed 23 different reservoir lakes, the largest one being Lake Livingston situated in the lower Trinity River watershed and two potentially polluting metroplexes, Dallas and Houston. In order to determine fluxes of nutrients and trace metals to Galveston Bay, a survey that included 24 discreet samples collected over a year and at various stages of discharge was carried out during 2000–2001. Geochemical (i.e., sorption by Fe oxyhydroxides), biological (i.e., seasonal uptake by sinking algae in Lake Livingston), and hydrological (i.e., dilution effects by increasing flow rates) controls were found to be mainly responsible for variations in dissolved trace metal concentrations rather than pollution sources. The Trinity River loads of suspended sediments and pollutant trace metals entering Galveston Bay at Anahuac were <20% of those reaching Lake Livingston, and only a few percent of the total upstream trace metal load is entering the Gulf of Mexico. Thus, during the transit through the 23 man-made lakes and an estuary, >96% of the pollutant trace metal load is lost to sediments.     

Retention of strontium,cesium, lead and uranium by bacterial iron oxides from a subterranean environment

Bacteriogenic Fe oxides (BIOS) and groundwater samples were collected 195 m underground at the Stråssa Mine in central Sweden. Ferrous iron oxidizing bacteria, including stalked Gallionella ferruginea and filamenous Leptothrix sp., were prominent in the BIOS samples. The BIOS samples were found to contain only poorly ordered (amorphous) hydrous ferric oxide, as determined by X-ray diffraction. Inductively coupled plasma mass spectroscopy revealed hydroxylamine-reducible Fe and Mn oxide contents that ranged from 55 to 85% on a dry weight basis. Concentrations of Sr, Cs, Pb and U in filtered groundwater ranged from 0.002 to 1.8 μM. Solid phase concentrations of these heavy metals in the BIOS spanned the 0.04–2.23 mmol/kg range. Distribution coefficients (K_d values), calculated as the ratio between BIOS and dissolved heavy metal concentrations, revealed solid phase enrichments that, depending on the heavy metal and Fe oxide content of the sample, extended from 10^3.0 to 10^4.7. At the same time, however, a strong inverse linear relationship was found between log K_d values and the corresponding mass fraction of reducible oxide in the samples, implying that metal uptake was strongly influenced by the relative proportion of bacterial organic matter in the composite solids. Based on the metal accumulation properties of the BIOS, an important role can be inferred for intermixed Fe oxides and bacterial organic matter in the transport and fate of dissolved metals in groundwater systems.     

Heavy metal anomalies in the Tinto and Odiel River and estuary system,Spain

The Tinto and Odiel rivers drain 100 km from the Rio Tinto sulphide mining district, and join at a 20-km long estuary entering the Atlantic Ocean. A reconnaissance study of heavy metal anomalies in channel sand and overbank mud of the river and estuary by semi-quantitative emission dc-arc spectrographic analysis shows the following upstream to downstream ranges in ppm (μg g^?1): As 3,000 to <200, Cd 30 to <0.1, Cu 1,500 to 10, Pb 2,000 to <10, Sb 3000 to <150, and Zn 3,000 to <200. Organic-rich (1.3–2.6% total organic carbon, TOC), sandysilty overbank clay has been analyzed to represent suspended load materials. The high content of heavy metals in the overbank clay throughout the river and estuary systems indicates the importance of suspended sediment transport for dispersing heavy metals from natural erosion and anthropogenic mining activities of the sulfide deposit. The organic-poor (0.21–0.37% TOC) river bed sand has been analyzed to represent bedload transport of naturally-occurring sulfide minerals. The sand has high concentrations of metals upstream but these decrease an order of magnitude in the lower estuary. Although heavy metal contamination of estuary mouth beach sand has been diluted to background levels estuary mud exhibits increased contamination apparently related to finer grain size, higher organic carbon content, precipitation of river-borne dissolved solids, and input of anthropogenic heavy metals from industrial sources. The contaminated estuary mud disperses to the inner shelf mud belt and offshore suspended sediment, which exhibit metal anomalies from natural erosion and mining of upstream Rio Tinto sulphide lode sources (Pb, Cu, Zn) and industrial activities within the estuary (Fe, Cr, Ti). Because heavy metal contamination of Tinto-Odiel river sediment reaches or exceeds the highest levels encountered in other river sediments of Spain and Europe, a detailed analysis of metals in water and suspended sediment throughout the system, and epidemiological analysis of heavy metal effects in humans is appropriate.     

Heavy metal distribution in surface sediments of the Tirumalairajan river estuary and the surrounding coastal area, east coast of India

Surface sediments collected at the Tirumalairajan river estuary and their surrounding coastal areas were analyzed for the bulk metal concentration. The sediments were collected from post- and premonsoon seasons. Dominances of heavy metals are in the following order: Fe > Mn > Zn > Pb > Cu in both seasons from estuary and coastal area. The results reveal that Fe, Mn, Cu, Pb, and Zn demonstrated an increased pattern from the estuary when compared to the coastal area. The heavy metal pattern of the sediments of the Tirumalairajan river estuary and its surrounding coastal area offered strong evidence that the coastal area was a major source of heavy metals to the estuarine region. For various metals, the contamination factor and geoaccumulation index (I _geo) have been calculated to assess the degree of pollution in sediments. The contamination factor and geoaccumulation index show that Zn, Pb, and Cu unpolluted to moderately pollute the sediments in estuarine part. This study shows the major sources of metal contamination in catchment and anthropogenic ones, such as agriculture runoff, discharge of industrial wastewater, and municipal sewage through the estuary and adjoining coastal area.