Aluminum in the macrotidal Yalujiang estuary: Partitioning of Al along the estuarine gradients and flux

Water samples were collected from the Yalujiang estuary in both flood periods (August 1992 and August 1994) and dry season (May 1996) and were analyzed for aluminum (Al). Al behaves non-conservatively in the Yalujiang estuary, and a significant loss (70–80%) in dissolved concentration is observed in the upper estuary, in spite of seasonal variation in water discharge and sediment load. About 0.4×10⁶, tons of Al is annually transported from Yalujiang to the estuary, of which the particulate pool clearly dominates. The particulate Al flux through the Yalujiang contributes 35% of the total Al input from Chinese rivers to the Yellow Sea. The data sets from size fractionation and C-18 SPE separation demonstrate that a large fraction of dissolved Al is in colloidal (≈50%) and organically complex (≈60%) forms in the Yalujiang. The observed scavenging from solution to particulate pools in the estuary is most likely through the flocculation of colloidal and organic-complexed Al, which results in a considerable change in dissolved-particulate partitioning, shown by laboratory mixing experiments. Exchange between dissolved and particulate phases is examined by analysis of K_d, the distribution coefficient. The empirical relationship of K_d with chlorinity and suspended matter concentrations was investigated with field observations and model simulations. The model indicated that K_d values of Al are inversely related to the amount of total suspended matter, but K_d-chlorinity plots show different features between dry and flood seasons.     

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

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

Tracing Ni, Cu, and Zn kinetics and equilibrium partitioning between dissolved and particulate phases in South San Francisco Bay, California, using stable isotopes and high-resolution inductively coupled plasma mass spectrometry

Additions of the low occurrence stable isotopes ⁶¹Ni, ⁶⁵Cu, and ⁶⁸Zn were used as tracers to determine the exchange kinetics of metals between dissolved and particulate forms in laboratory studies of natural water and suspended sediments from South San Francisco Bay, CA. Dissolved metal isotope additions were made so that the isotope ratios (rather than total metal partitioning) were significantly altered from initial ambient conditions. Dissolved metal concentrations were determined using an organic ligand sequential extraction technique followed by analysis with high-resolution inductively coupled plasma mass spectrometry (HR-ICPMS). Exchangeable particulate concentrations were extracted using a 20% acetic acid leach followed by determination using HR-ICPMS. Equilibrium and kinetic sorption parameters were quantified according to a general model for trace metal partitioning assuming pseudo-first-order kinetics. Partition coefficients (K_D) were tracked as a function of time over the fortnight experiment. For Ni, Cu, and Zn the initial ambient K_D values were found to be 10^3.65, 10^3.88, and 10^4.52 L kg⁻¹, respectively. As a result of the dissolved metal isotope additions, the partition coefficients for all three metals dropped and then increased back to near ambient K_D values after 14 days. Curve-fitting concentration versus time profiles from both dissolved and exchangeable particulate data sets allowed determination of kinetic rate constants. The best estimates of forward and backward kinetic rate constants for Ni, Cu, and Zn respectively are k′_f = 0.03, 0.07, 0.12 d⁻¹ and k_b = 0.13, 0.12, 0.15 d⁻¹. These results predict that sorption equilibria in South Bay should be reached on the order of a month for Ni, on the order of 3 weeks for Cu, and on the order of 2 weeks for Zn. Together, the dissolved and exchangeable particulate data indicate more sluggish sorption kinetics for Ni than for Cu and Zn and suggest that different chemical forms control the speciation of these three metals in South Bay. Order of magnitude metal sorption exchange rates were estimated using these kinetic results. These calculations indicate that sorption exchange between dissolved and suspended particulate phases can cause dynamic internal cycling of these metals in South San Francisco Bay.     

Role of Suspended Particulate Matter in Regulating the Behavior of Dissolved Uranium in the Yellow River Estuary

In order to examine the mixing behavior of dissolved uranium (U) in estuaries under different suspended particulate matter (SPM) regimes, three laboratory-based experiments were conducted by mixing seawater with river water containing different concentrations of SPM. Comparing this study with other field and laboratory-based experiments, dissolved U behaved differently depending upon the concentration of SPM. When SPM concentrations are >?0.8 g/L in the Yellow River, desorption/dissolution of U from SPM becomes predominant and dissolved U is enriched relative to the theoretical mixing line. However, when SPM concentrations are <?0.8 g/L, dissolved U behaves conservatively with some extent of removal during estuarine mixing. ²³⁴U/²³⁸U activity ratios were somewhat constant showing no measurable isotopic fractionation during physical mixing and U sorption/desorption to/from particles. Addition of dissolved ²³⁸U desorbed/dissolved from SPM during the annual Yellow River water-sediment regulation scheme (Jun 30th–Jul 14th, 2014) was estimated at 6.4?×?10¹¹ dpm, about 9% of the total riverine flux of dissolved ²³⁸U during that same period. This study represents a contribution to studies of dissolved U in muddy rivers and estuaries throughout the world. Results reported here provide not only a perspective to better estimate U flux from rivers to the ocean but also new insights into better understanding its estuarine mixing behavior and controlling factors.     

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.     

Geochemistry of dissolved and particulate elements in the major rivers of China (The Huanghe,Changjiang, and Zhunjiang rivers)

The relationship between the geochemistry of dissolved and particulate materials and geographic conditions was investigated. Samples of water and suspended particulate matter were collected from five locations in three of the major rivers of China (the Huanghe, Changjiang, and Zhunjiang rivers). Because these rivers generally flow parallel to latitudes and flow through diverse geologic and climate zones, they provide excellent opportunities for comparisons of solute transport. The geochemistry of these rivers is influenced strongly by climate. The low discharge of the Huanghe River influences the character of the major ionic materials (Cl^?+SO₄ ^2? and Na⁺+K⁺) as well as the high degree of mineralization within the system. Dissolved concentrations of both major ions and trace elements are lower in the southern reaches of the rivers. The highly mobile ions, such as, Na⁺ and Ca²⁺, are depleted from the suspended particulate material in the southern regions, while the relatively immobile ions of Al, Fe, Ti, Mn, and trace metals are concentrated within the suspended mateiral. The relative mobility of some elements as measured by the Dissolved Transport Index (DTI) changes with climate. The geology of the area drained by the rivers has a major influence on the geochemistry in areas of similar climate. Lowest leaching rates in the southern climates occur in areas dominated by granite, which is resistant to weathering. The composition of both cations and anions among the three tributaries of the Zhujiang River are dependent on the rocks that dominate each eregion. Some particulate forms of the rare earth elements are present in the highest concentrations in regions dominated by granite. The DTI calculated for the major rivers in China are much smaller than those computed for other major rivers of the world. The low concentration of heavy metals in the particulate material suggests that pollution in the rivers of China is less serious than in rivers of other industrialized countries.     

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.     

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.     

Sorption of selenite in a multi-component system using the “dialysis membrane” method

⁷⁹Se is a potentially mobile long-lived fission product, which may make a dominant contribution to the long-term radiation exposure resulting from deep geological disposal of radioactive waste. Its mobility is affected by sorption on minerals. Selenium sorption processes have been studied mainly by considering interaction with a single mineral surface. In the case of multi-component systems (e.g. soils), it is difficult to predict the radioelement behaviour only from the mineral constituents. This study contributes to the understanding of multi-component controls of Se concentrations towards predicting Se behaviour in soils after migration from a disposal site. This goal was approached by measuring selenite sorption on mono and multi-phase systems physically separated by dialysis membranes. To the best of the authors’ knowledge, very few studies have used dialysis membranes to study the sorption competition of selenite between several mineral phases. Other workers have used this method to study the sorption of pesticides on montmorillonite in the presence of dissolved organic matter. Indeed, this method allows measurement of individual K_d in a system composed of several mineral phases. Dialysis membranes allowed (i) determination of the competition of two mineral phases for selenite sorption (ii) and determination of the role of humic acids (HAs) on selenite sorption in oxidising conditions. Experimental results at pH 7.0 show an average Se(IV) sorption distribution coefficient (K_d) of approximately 125 and 9410 L kg⁻¹ for bentonite and goethite, respectively. The average K_d for goethite decreases to 613 L kg⁻¹ or 3215 L kg⁻¹ in the presence of bentonite or HA, respectively. For bentonite, the average K_d decreases slightly in the presence of goethite (60 L kg⁻¹) and remains unchanged in the presence of HA. The experimental data were successfully modelled with a surface complexation model using the PHREEQC geochemical code. The drastic decrease in Se(IV) sorption on goethite in a multi-phase system is attributed to competition with dissolved silica released by bentonite. As with Si the HA compete with Se for sorption sites on goethite.     

Scavenging and particle residence times determined from 234Th/238U disequilibria in the coastal waters of Mecklenburg Bay

Activities of the naturally occurring radionuclide ²³⁴Th were determined in water samples of Mecklenburg Bay (SW Baltic Sea) using a new Th-specific diatomite adsorption technique followed by liquid scintillation spectrometry. Activities of “dissolved” (operationally defined as Th in the centrifugate) and particulate ²³⁴Th varied in the range of 1.4–6.9 and 0.9–9.3 mBq l⁻¹, respectively. A significant correlation between K_d and SPM concentration was found. From this particle-concentration effect, the “colloidal pumping” model predicts that 98% of the “dissolved” Th is associated with colloids rather than being truly dissolved. Relative to calculated activities of the parent nuclide ²³⁸U in the Bay, the ²³⁴Th data yielded mean ²³⁴Th scavenging residence times in the range of 1.2–9.7 days. Particulate ²³⁴Th activities are inversely correlated to SPM concentrations. Particle residence times ranged from a few days in winter up to 20 days in spring characterized by less intense bottom currents. The hydrodynamic regime is the master variable controlling scavenging of Th and other similarly particle-reactive elements in Mecklenburg Bay.     

Silicon isotopic composition of dissolved silicon and suspended particulate matter in the Yellow River, China, with implications for the global silicon cycle

The silicon isotopic composition of dissolved silicon and suspended particulate matter (SPM) were systematically investigated in water samples from the mainstem of the Yellow River and 4 major tributaries. The SPM content of the Yellow River varied from 1.4 to 38,560 mg/L, averaging 3568 mg/L, and the δ³⁰Si of suspended particulate matter (δ³⁰Si_SPM) varied from 0.3‰ to −0.4‰, averaging −0.02‰. The major factors affecting the SPM content and the δ³⁰Si_SPM values in the Yellow River were inferred to be the mineralogical, chemical and isotopic characteristics of the sediments from the Loess Plateau and a combination of the climate and the flow discharge of the river.The major ions in the Yellow River water were Na⁺, Ca²⁺, Mg²⁺, HCO₃⁻, SO₄²⁻ and Cl⁻. High salt concentration was observed in samples from the middle and lower reaches, likely reflecting the effects of evaporation and irrigation because the Na⁺, Mg²⁺, SO₄²⁻ and K⁺ concentrations were correlated with the Cl⁻ concentration. The dissolved Si concentration (D_Si) increased downstream, varying from 0.016 to 0.323 mM. The δ³⁰Si of dissolved Si (δ³⁰Si_Diss) varied from 0.4‰ to 2.5‰, averaging 1.28‰. The major processes controlling the D_Si and δ³⁰Si_Diss of the Yellow River are (a) the weathering of silicate rocks, (b) the formation of phytoliths in plants, (c) the evaporation of water from and the addition of meteoric water to the river system, which only affects concentrations, (d) the adsorption and desorption of aqueous monosilicic acid on iron oxide, and (e) the dissolution of phytoliths in soils.The D_Si and δ³⁰Si_Diss values of global rivers vary spatially and temporally in response to changes in climate, chemical weathering intensity and biological activity. The moderately positive δ³⁰Si_Diss values observed in the Yellow River may be attributed to the higher rates of chemical weathering and biological activities that have been observed in this catchment in comparison with those of other previously studied catchments, excluding the Yangtze River. Human activities may also potentially influence chemical weathering and biological activities and affect the D_Si and δ³⁰Si_Diss values of the major rivers of the world. Further river studies should be performed to gain a better understanding of the global Si isotope budget.     

Solid–water partitioning of elements in Czech freshwaters

Partitioning of 41 elements between solids and water was studied by filtration and dialysis in situ in Czech freshwaters. Field-based distribution (partition) coefficients, K_D, between suspended particulate matter (SPM) and filtrate (‘dissolved’ fraction) differed by 4 orders of magnitude. The highest K_D values (log K_D>2.0 l/g) were exhibited by Zr, Al, Ce, Pb, La, Ti, Fe, Sm, Th and Cr which are extremely insoluble in near-neutral water or generally poorly soluble (Zr,Ti). The K_Ds decrease with element and DOC loading due to the relative increase of the element in the low molecular fraction. Log K_D mostly increased linearly with pH within a range from 3.5 to 9. K_D^U decreased at pH >6 due to carbonate complexation. The colloidal fraction (>1 kDa <0.4 μm) in a reservoir with a pH of 6.8 was mainly preferred by Fe, Pb, Be, Nb, Y, Al, Ni, U and Zr. When the colloidal fraction is not differentiated from true solution, then incorrect information about partitioning may be obtained and the highest K_D may decrease.     

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.     

How important is it to integrate riverine suspended sediment chemical composition with depth? Clues from Amazon River depth-profiles

The vertical variability in mineralogical, chemical and isotopic compositions observed in large river suspended sediments calls for a depth-integration of this variability to accurately determine riverine geochemical fluxes. In this paper, we present a method to determine depth-integrated chemical particulate fluxes of large rivers, based on river sampling along depth-profiles, and applied to the Amazon Basin lowland tributaries. The suspended particulate matter (SPM) concentration data from depth-profiles is modeled for a number of individual grain size fractions using the Rouse model, which allows to predict the grain size distribution of suspended sediment throughout the whole river cross-section. Then, using (1) the relationship between grain size distribution and the Al/Si ratio (2) relationships between the Al/Si ratio and the chemical concentrations, the chemical composition of river sediment is predicted throughout the river cross-section, and integrated to yield the depth-integrated chemical particulate flux for a number of chemical elements (e.g. Si, Al, Fe, Na, REEs, …). For elements such as Al, Fe, REEs, Th, the depth-integrated flux is around twice as high as the one calculated from river surface sample characteristics. For Na and Si, the depth-integrated flux is three times higher than the “surface” estimate, due to the enrichment of albite and quartz at the bottom of the river. Depth-integrated ⁸⁷Sr/⁸⁶Sr composition of suspended sediment, also predictable using this method, differs by more than 10⁻³ from the surface sample composition.Finally, potential implications of depth-integrated estimates of Amazon sediment chemistry are explored. Depth-integration of particulate ⁸⁷Sr/⁸⁶Sr isotopic ratios is necessary for a reliable use of Sr isotopes as a provenance tracer. The concept of steady-state weathering of a large river basin is revisited using depth-integrated sediment composition. This analysis shows that, in the Amazon Basin river, the previously observed discrepancy between (1) weathering intensities of channel surface sediment and (2) silicate-derived dissolved fluxes is only slightly accounted for by the vertical variability of suspended sediment weathering intensities. This observation confirms that most large rivers basins are not eroding at steady-state.     

A simple empirical optical model for simulating light attenuation variability in a partially mixed estuary

Representation of the subsurface light field is a crucial component of pelagic ecosystem and water quality models. Modeling the light field in estuaries is a particularly complicated problem due to the significant influence of high concentrations of dissolved and particulate matter that are derived from both terrestrial and estuarine sources. The goal of this study was to develop a relatively simple but effective way to model light attenuation variability in a turbuid estuary (Chesapeake Bay, United States) in a coupled physical-biological model. We adopted a simple, nonspectral empirical approach. Surface water quality data (salinity was used as a proxy of chromophoric dissolved organic matter [CDOM]) and light measurements from the Chesapeake Bay Program were used to determine the absorption coefficients in a linear attenuation model using regression methods. This model predicts K_c (specific attenuation due to phytoplankton/chlorophylla [chla]), K_t (specific attenuation due to total suspended solids), and K_s (a function of specific attenuation coefficients of CDOM in relation to salinity). The Bay-wide fitted relation between the light attenuation coefficient and water quality concentrations gives generally good estimates of total light attenuation, K_d. The direct inclusion of salinity in the relationship has one disadvantage: it can yield negative values for K_d at high salinities. We developed two separate models for two different salinity regimes. This approach, in addition to solving the negative K_d problem, also accounts for some changes in specific light absorption by chla, seston (nonphytoplankton particulate matter), and CDOM that apparently occur in different salinity regimes in Chesapeake Bay. The resulting model predicts the statistical characteristics (i.e., the mean and variance) of K_d quite accurately in most regions of Chesapeake Bay. We also discuss in this paper the feasibility and caveats of using K_d converted from Secchi depth in the empirical method.     

Transport and retention of suspended particulate matter and bacteria in the Humber-Ouse Estuary, United Kingdom, and their relationship to hypoxia and anoxia

Data are presented on dissolved oxygen (DO) concentrations and their relationship to salinity, suspended particulate matter (SPM), concentrations, and the turbidity maximum in the Humber-Ouse Estuary, United Kingdom, during summer 1995. Measurements in the upper Humber during March 1995 showed DO in the range 82% to 87% of saturation. Suspended particulate matter concentrations were <5000 mg l^?1 and salinity was in the range 0.5 to 12. In contrast, a pronounced DO sag occurred in the upper reaches of the Ouse during medium and spring tide, summer conditions. The DO minimum was essentially an anoxic level and was associated with the location of the turbidity maximum, at salinities between about 0.4 and 1.5. SPM concentrations at 1 m beneath the surface reached 25,000 mg l^?1 in the turbidity maximum, between about 20 km and 40 km from the tidal limit. Suspended particulate matter concentrations were much lower at neap tides, although dense suspensions of SPM (>60,000 mg l^?1) occurred within 1 m of the bed in the turbidity maximum region. A spring-neap record showed a dramatic and tidally controlled decrease in DO at very low salinities as the tides progressed from neaps to springs. An anchor station located down-channel of the turbidity maximum showed that about 95% of the variance in DO, which varied from 28% at low-water slack to 67% at high-water slack, could be explained in terms of salinity variation. At the up-channel margins of the turbidity maximum, DO increased from zero (anoxia) near high water to 60% near low water slack, in contrast to the behavior down-channel of the turbidity maximum. About 82% of the variance in DO could be explained in terms of salinity variations alone. Only 43% of the DO variance could be explained in terms of SPM alone. Up-channel of the turbidity maximum, SPM concentrations were relatively low (<3000 mg l^?1) and DO levels varied from 48% of saturation near high water to 83% near low water slack. About 76% of the variance in DO could be explained in terms of salinity variations alone. Within the turbidity maximum region, DO varied from <2% saturation on the early flood and late ebb and maximized around 7% at high water slack. About 63% of the variance in DO could be explained in terms of salinity variation alone. This increased to 70% when suspended particulate matter was taken into account. Only 29% of the DO variance could be explained in terms of suspended particulate matter alone. Because bacteria were likely to have been the cause of the observed reduction in DO, the numbers of bacteria, both free-living and attached to particles, were measured in the turbidity maximum region. Numbers of free-living bacteria were low and most of the bacteria were attached to sediment particles. There was a linear correlation between total bacterial number and suspended particulate matter concentration, suggesting that the strong DO demand was exerted locally as a result of bacterial activity associated with increased suspended particulate matter concentrations. An order of magnitude analysis of DO consumption within the Ouse’s turbidity maximum, based on the premise that DO depletion was directly related to suspended particulate matter concentrations and that DO addition was due to reaeration, indicates that complete deoxygenation could have occurred with an oxygen depletion rate of ～0.01 mg DO h^?1/g suspended particulate matter during the residence time of waters within the turbidity maximum (～7 d). This rate was sufficiently fast that anoxic to aerobic conditions were able to develop a spring-neap periodicity within the turbidity maximum, but too slow to generate substantial intratidal fluctuations in DO. This is in accordance with the observations, which show that relatively little of the intratidal variance in DO could be explained in terms of suspended particulate matter fluctuations, whereas most of the variance could be explained in terms of salinity, which behaved as a surrogate measure for the proximity of the turbidity maximum.     

Rare Earth Element Patterns in the Karst Terrains of Guizhou Province, China: Implication for Water/Particle Interaction

The authors determine the concentrations of dissolved (<0.22 μm) rare earth elements (REE) and suspended particulate matter (SPM) of typical karst rivers in Guizhou Province, China during the high-flow period. The concentrations of acid-soluble REE extracted from SPM using diluted hydrochloric acid are also obtained to investigate water/particle interaction in the river water. The dissolved REE contents in the river water are extremely low in the rivers of the study. The dissolved REE distribution patterns normalized by the Post Archean Australia Shale (PAAS) in the karst rivers are not flat, show slight enrichment of heavy REE to light REE, and also have significant negative Ce and Eu anomalies. The acid-soluble REE appears to have similar distribution patterns as characterized by MREE enrichment and slight LREE depletion, with unremarkable Ce and Eu anomalies. The PAAS-normalized REE distribution patterns of SPM are flat with negative Eu anomalies. The contents and distribution patterns of REE in the SPM are closely related to the lithological character of the source rocks. The SPM contains almost all the REE produced in the process of surficial weathering. This demonstrates that particle-hosted REE are the most important form of REE occurrence. REE fractionation, which takes place during weathering and transport, leads to an obvious HREE enrichment in the dissolved loads relative to the SPM. Y/Ho ratio can be used to shed light on REE behaviors during water/particle interaction.     

Control of nutrient concentrations in the Seekonk-Providence River region of Narragansett Bay,Rhode Island

Six synoptic samplings of nutrient concentrations of the water column and point-source inputs (rivers, sewage treatment plants) were conducted in the Seekonk-Providence River region of Narragansett Bay. Concentrations of nutrients (NH₄ ⁺, NO₂ ^?+NO₃ ^?, PO₄ ^?3, dissolved silicon, particulate N, particulate C) were predicted using a conservative, two-layer box model in order to assess the relative influence of external inputs and internal processes on observed concentrations. Although most nutrients were clearly affected by processes internal to the system, external input and mixing explained most of the variability in and absolute magnitude of observed concentrations, especially for dissolved constituents. In the bay as a whole, two functionally distinct regions can now be identified: the Seekonk-Providence River, where dissolved nutrient concentrations are externally controlled and lower Narragansett Bay where internal processes regulate the behavior of nutrients. A preliminary nitrogen budget suggests that the Seekonk-Providence River exports some 95% of the nitrogen entering the system via point sources and bottom water from upper Narragansett Bay.     

Zn isotopes in the suspended load of the Seine River, France: Isotopic variations and source determination

We report Zn isotopic ratios (δ⁶⁶Zn) of river suspended particulate matter (SPM) and floodplain deposits (FD) from the Seine basin, France, with a precision ?0.05‰. A decrease in δ⁶⁶Zn from 0.30‰ to 0.08‰ is observed in SPM from the upstream to downstream parts of the fluvial system, associated with an increase in Zn concentration from 100 ppm to 400 ppm. The Zn/Al of SPM at the river mouth is up to five times greater than the Zn/Al of the natural background, and by normalizing to the later value we define a Zn enrichment factor. Suspended sediments from a temporal series of samples collected in Paris display a similar variation in δ⁶⁶Zn of between 0.08‰ and 0.26‰, while showing an inverse relationship between the Zn enrichment factor and δ⁶⁶Zn. The amount of Zn transported as suspended load varies from 10% to 90%, as a function of increasing discharge. The δ⁶⁶Zn of SPM and the dissolved load are correlated, suggesting that adsorption processes are probably not the dominant process by which the Zn enrichment of SPM takes place. Instead, we interpret our data as reflecting the mixture of two main populations of suspended particles with distinct δ⁶⁶Zn. The first is characteristic of natural silicate particles transported by erosion processes to the river, while the second likely represents anthropogenic particles derived from wastewater treatment plants or combined sewer overflows. Based on isotopic ratios, we calculate that 70% of Zn in SPM of the Seine River in Paris is of anthropogenic origin.     

Rare earth geochemistry in the dissolved, suspended and sedimentary loads in karstic rivers, Southwest China

The watershed in the central Guizhou Province (Guizhou Province is called simply Qian) (CQW) is a karstic area. Rare earth elements (REEs) of dissolved loads, suspended particulate material (SPM) and sediments of riverbed are first synthetically reported to investigate REE geochemistry in the three phases in karstic watershed during the high-flow season. Results show that the low dissolved REE concentrations in the CQW are attributed to these rivers draining carbonate rocks. The dissolved REE have significant negative Eu anomaly and coexistence of middle and light REE (MREE??PAAS-normalized La _N /Sm _N and Gd _N /Yb _N ; LREE??PAAS-normalized La _N /Yb _N )-enrichment, which are due to the dissolution of impure Triassic carbonates. REE concentrations in most of SPM exceed that of sediments in the CQW and the average continental crust (UCC). The SPM and the sediments show some common features: positive Eu, Ce anomalies, and MREE enrichment. The controls on the patterns seem to be from weathering profiles: the oxidation state, the REE-bearing secondary minerals (cerianite, potassium feldspar and plagioclase), which are also supported by the evidence of Y/Ho fractionations in the three phases.