Microbial processes in the San Francisco Bay estuarine turbidity maximum

We examined microbial processes and the distribution of particulate materials in the estuarine turbidity maximum (ETM, salinity 2–10 PSS) of northern San Francisco Bay on three cruises during the late spring of 1994 (low flow: April 19, April 28, May 17) and two cruises during the early summer of 1995 (high flow; June 13, July 18). Under low flow conditions, chlorophyll concentrations decreased by a factor of 2–4, bacterial abundance decreased by 20%, and L-leucine incorporation rate decreased by a factor of about 2 over a salinity range of 0–2 PSS, then remained relatively constant at higher salinities. Over this same salinity range under high flow conditions, chlorophyll concentration was c. twofold lower, bacterial abundance was c. threefold higher, and L-leucine incorporation rate was in the same range as during low flow. Under high flow conditions, chlorophyll concentration increased by 20%., bacterial abundance decreased by a factor of 2, and L-leucine incorporation rate decreased by half (June 13) or remained unchanged (July 19) with increasing salinity. Under low flow conditions the concentration of suspended particulate material (SPM), particulate organic carbon (POC), and particulate organic nitrogen (PON) increased 3–10 fold with salinity, to a maximum at intermediate salinities (c. 6 PSS). As a result, the contribution of phytoplankton to POC decreased from a maximum of 32% in fresh water to c. 6% in the ETM. The contribution of bacterial biomass similarly decreased from 5% in fresh water to 0.8% in the ETM. The C:N ratio of particulate material increased from <10 in fresh water to >12 in the ETM. High variability in abundance estimates confounded analysis of patterns in bacterial biomass partitioning between particle-associated and free-living fractions along the salinity gradient. However, the partitioning of L-leucine incorporation shifted dramatically from being predominantly by free-living cells in fresh water to being predominantly by particleassociated populations in the ETM. The metabolic fate of thymidine taken up differed, between particle-associated and free-living bacteria, suggesting some metabolic divergence of these assemblages.     

Silver in San Francisco Bay estuarine waters

Spatial gradients of silver concentrations in the surface waters of San Francisco Bay reveal substantial anthropogenic perturbations of the biogeochemical cycle of the element throughout the estuarine system. The most pronounced perturbations are in the south bay, where dissolved (<0.45 μm) silver concentrations are as high as 250 pM. This is more than one order-of-magnitude above baseline concentrations in the northern reach of the estuary (6 pM) and approximately two orders-of-magnitude above natural concentrations in adjacent coastal waters (3 pM). The excess silver is primarily attributed to wastewater discharges of industrial silver to the estuary on the order of 20 kg d^?1. The contamination is most evident in the south bay, where wastewater discharges of silver are on the order of 10 kg d^?1 and natural freshwater discharges are relatively insignificant. The limited amount of freshwater flushing in the south bay was exacerbated by persistent drought conditions during the study period. This extended the hydraulic residence time in the south bay (≥160 d), and revealed the apparent seasonal benthic fluxes of silver from anthropogenically contaminated sediments. These were conservatively estimated to average ≈16 nmol m^?2 d^?1 in the south bay, which is sufficient to replace all of the dissolved silver in the south bay within 22 d. Benthic fluxes of silver throughout the estuary were estimated to average ≈11 nmol m^?2 d^?1, with an annual input of approximately 540 kg yr^?1 of silver to the system. This dwarfs the annual fluvial input of silver during the study period (12 kg yr^?1) and is equivalent to approximately 10% of the annual anthropogenic input of silver to the estuary (3,700–7,200 kg yr^?1). It is further speculated that benthic fluxes of silver may be greater than or equal to waste water fluxes of silver during periods of intense diagenic remobilization. However, all inputs of dissolved silver to the estuary are efficiently sorbed by suspended particulates, as evidenced by the relatively constant conditional distribution coefficient for silver throughout the estuary (K_d≈10⁵).     

Composition of estuarine colloidal material: major and trace elements

Colloidal-sized material from the Patuxent River estuary, Maryland, was analyzed for more than 30 elements by instrumental neutron activation analysis. Sample data from stations ranging in salinity from 0.04 g/kg to 12 g/kg indicate that the winter colloidal material is dominated upstream by poorly crystallized clay minerals and iron oxide, but above a salinity of 10 g/kg, it consists primarily of carbonaceous material. Winter colloidal material decreases non-conservatively seaward from 29 to 0.6 mg/l. The summer colloidal material, however, is carbon-rich throughout the estuary and the amount of colloidal material in the upper water column does not change appreciably with increasing salinity. Many trace elements (Cs, Hf, Rb, Se, Th, V and the REE) covary with Al and probably are associated with the clay component. Other elements (As, Ba, Sb, Se, U and Zn) are considerably enriched relative to Al and may covary with the organic component. The results suggest that the freshwater winter colloidal system is a product of continental weathering processes, whereas the summer colloidal material is derived primarily from estuarine biological processes.     

Microbial mercury cycling in sediments of the San Francisco Bay-Delta

Microbial mercury (Hg) methylation and methylmercury (MeHg) degradation processes were examined using radiolabled model Hg compounds in San Francisco Bay-Delta surface sediments during three seasonal periods: late winter, spring, and fall. Strong seasonal and spatial differences were evident for both processes. MeHg production rates were positively correlated with microbial sulfate reduction rates during late winter only. MeHg production potential was also greatest during this period and decreased during spring and fall. This temporal trend was related both to an increase in gross MeHg degradation, driven by increasing temperature, and to a build-up in pore water sulfide and solid phase reduced sulfur driven by increased sulfate reduction during the warmer seasons. MeHg production decreased sharply with depth at two of three sites, both of which exhibited a corresponding increase in reduced sulfur compounds with depth. One site that was comparatively oxidized and alkaline exhibited little propensity for net MeHg production. These results support the hypothesis that net MeHg production is greatest when and where gross MeHg degradation rates are low and dissolved and solid phase reduced sulfur concentrations are low.     

Desorption and coagulation of trace elements during estuarine mixing

Mixing experiments of seawater and the Hudson and Mississippi riverwaters with radiotracer spikes show that Co, Mn, Cs, Cd, Zn and Ba will be desorbed from river suspended particles, while significant fractions of “dissolved” Fe, Sn, Bi, Ce and Hg will be coagulated during estuarine mixing.     

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.     

Regional geochemistry of trace elements in Chesapeake Bay sediments

The concentrations of Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in 177 surface sediment samples from throughout Chesapeake Bay are reported. Analyses were made of both unfractionated samples and the <63 μm fractions. Analytical uncertainty, always less than ±10%, controlled reproducibility in analyses of the <63 μm fractions, but sampling variance controlled reproducibility in the unfractionated samples, especially when coarse-grained sediments were being analyzed. Sediments in the northernmost part of the bay are enriched relative to average continental crust in all elements except Cr. This reflects the composition of dissolved and suspended material being delivered to that region by the Susquehanna River. The enriched sediments appear not to be transported south of Baltimore in significant quantily. Zinc, cadmium, and lead are enriched relative to average crust throughout the bay and in most other estuaries in the eastern United States.     

Systematic use of trace elements in igneous processes

Trace element concentration data can be used in a systematic way for the study of igneous processes by means of constructing models of such processes which satisfactorily account for the observations. We propose to treat the problem as an inverse problem. The concept of trace element paths (TEP) is introduced as a representation of the solution to the direct problem. The inverse problem consists of estimating, by a resolution of the equations, the various parameters of a model so as to provide a best fit to observed TEP. A detailed account of the theory is given in the case of equilibrium fractional crystallization. The estimated parameters are then those figuring in the Rayleigh distillation law, namely, 1) the initial concentrations of trace elements in the parental magma, 2) the bulk partition coefficients of the elements, and 3) the degree of crystallization corresponding to each sample of the magmatic suite analyzed.A slightly generalized maximum likelihood method is used to solve the linearized equation by a stable, iterative algorithm. Information theory is then shown to yield an account of the distribution and flow of information during the process of solving the inverse problem. The concept of Data Importances is generalized, and its use in optimizing the study justified. The technique is successfully applied to a synthetic data set, and then illustrated on a data set from Terceira (Azores). The results are used to refine the conclusions reached in part I, and permit a more detailed discussion of the model.Now at Dept. Geological and Planetary Sciences, California Institute of Technology, Pasadena, Calif., USA     

Systematic use of trace elements in igneous processes

This paper develops an application of the inverse method proposed by Allégre et al. (1977) and Minster et al. (1977). Using a set of trace element data in a suite of primary lavas, it is possible to statistically test whether the data can be described by batch partial melting. Once this is achieved, one can inverse the problem and calculate the parameters which govern the process, that is: the degrees of melting corresponding to each lava, the initial source concentrations and partition coefficients for each element. This is a non-linear, strongly underdetermined problem, but when the set of trace elements is restricted to REE, taking advantage of the fact that their properties are smoothly related, the problem can be overconstrained by assuming a set of poorly constrained model parameters. Information contained in the data and in the external constraints can then be estimated and used to build a strategy of data acquisition. From a table of mineral-liquid partition coefficients, the mineralogies of the source and of the material entering the liquid can be calculated. The method has been tested on synthetic data sets representing natural cases, and proved to converge towards the real solution even when a very poor definition of the external constraints is introduced.The calculations have been applied to REE data on Grenada basanitoids (Shimizu and Arculus, 1976). It is confirmed that these lavas can be derived by 4 to 17% batch partial melting of a garnet lherzolite source (7% gt, 23% cpx) that is relatively enriched in light REE. This result is discussed in relation with Nd and Sr isotopic composition data.     

Constraints from strontium and neodymium isotopic ratios and trace elements on the sources of the sediments in Lake Huguang Maar

The sediments in Lake Huguang Maar in coastal South China were previously thought to originate mainly from wind-blown dust transported from North China, such that the lake sediments recorded the varying strength of the Asian winter monsoon. An alternative explanation was that the local pyroclastic rocks supplied the lake sediments, but the actual contributions from the different sources remained unclear. Geochemical analyses including ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd and trace elements support the local pyroclastic rock as the dominant source: < 22% of the total Sr in the lake sediments and  17% of the Nd arises from the distant source. Nb/Ta and Zr/Hf for the lake sediments are identical to those for the local rock but differ from the ratios for the wind-blown dust, and chondrite-normalized rare earth element patterns for the lake sediments are similar to those for the local rock and soil, but differ from those for the distant source. The sediments in Lake Huguang Maar are probably input into the lake through runoff and thus controlled by the hydrology of the lake. Wind-blown dust transported by the Asian winter monsoon from arid North China is only a minor contribution to the sediments.     

Relationship between some trace elements and magmatic processes

Relationships between magmatic differentiation, volcanological evolution and occurrence of some trace elements have been pointed out by a petrographic and volcanological study of the Quaternary magmatic products of the Northern Latium alkali-potassic volcanoes (Sabatini, Vico, Vulsini).Several hundred analyses of U, Th, Be, Zr, Rb, Sr have been carried out. The above elements are contained in exceptional quantity in the examined alkaline rocks. The distribution pattern of these elements helps for a better understanding of some types of differentiation and, above all, allows to identify the processes related to the uplift and outflow of magmas which are undetectable with the usual petrochemical methods.In particular, the trace elements considered allow us to distinguish a deepseated magma evolution from superficial differentiations related to the volcanic conditions. Moreover, a loss of alkalies from the upper levels of the magmatic chambers has been ascertained which determines peculiar deformations in the normal petrogenetic trends.-- (: Sabatini, Vico, Vulsini). , . .

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Zusammenfassung Das petrographische und vulkanologische Studium der quartären Vulkanite der Mediterranen Sippe des nördlichen Latiums (die Vulkane Sabatini, Vico und Vulsini) haben uns die Gelegenheit gegeben, die Verhältnisse zwischen Magmenentwicklung, vulkanologischer Evolution und Verteilung einiger Spurenelemente zu bestätigen.Zu diesem Zweck sind Hunderte von Analysen von U, Th, Be, Zr, Sr, Rb — Elemente welche in ungemein großen Mengen in den untersuchten alkalischen Gesteinen enthalten sind — vorgenommen worden. Das Studium der Verteilung dieser Elemente hat ein gründliches Verstehen einiger Differentiationstypen erlaubt, und vor allem den Ablauf des Prozesses des Magmen-Aufstiegs und Abflusses gezeigt, welcher nicht mittels der normalen petrochemischen Untersuchungen ersichtlich ist.Besonders die in Betracht gezogenen Spurenelemente erlauben die Unterscheidung der magmatischen Evolution in den tiefen Lagen von den oberflächlicheren Differentiationen, welche an das vulkanische Geschehen gebunden sind.In dieser Hinsicht ist ein wichtiges Schlußergebnis die Bestätigung des Alkaliverlustes seitens der oberflächlichen Sektoren der Magmaherde, ein Verlust welcher eigenartige Deformationen von den normalen petrogenetischen Linien gezeigt hat.

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Résumé L'étude pétrographique et volcanologique des manifestations magmatiques quaternaires de la province alcalin-potassique du Latium septentrional (Volcans Sabatini, Vico et Vulsini) nous a permis de vérifier les rapports entre la différenciation magmatique, l'évolution volcanologique et la distribution de quelques éléments en traces.Dans ce but on a exécuté plusieurs centaines d'analyses de U, Th, Be, Zn, Rb, Sr, éléments qui sont présents en quantité exceptionellement élevé dans les roches alcalines examinées.L'étude de la distribution de ces éléments a permis une compréhension plus approfondie de certains types de differenciation et surtout, elle a indiqué l'existence de processus liés à la remontée et effusion des magmas, qui ne sont pas relevables par les examens pétrochimiques normaux.En particulier les éléments en traces considérés permettent de distinguer l'évolution magmatique de milieu profond des différenciations superficielles liées aux situations volcaniques.A ce propos une conclusion importante a été la constatation de la perte d'alcali par les portions plus superficielles des réservoirs magmatiques; une perte qui a déterminé des déformations particulières qui les éloignent des lignes pétrogénétiques normales.

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Authors are indepded to Dr. S.Smcana and to Dr. G.Falchi for the analyses performance.     

The role of trace elements in controlling H incorporation in San Carlos olivine

We conducted a series of hydroxylation experiments using mm-sized cuboids cut from six different crystals of San Carlos olivine with a range of trace-element concentrations. The cuboids were pre-annealed and then hydroxylated under identical conditions, ensuring that variation in the amounts of H incorporated depended only on the compositional variables. The pre-anneal was at 1400 °C, atmospheric pressure and an oxygen fugacity equivalent to Δlog FMQ?+?1, with the subsequent hydroxylation at 800 °C and 1.5 GPa, for 3 days. Hydrogen was incorporated into all six crystals by the four main substitution mechanisms [Si], [Mg], [Ti] and [triv], with homogeneous H contents in the cores of the crystals, indicating H diffusion rates faster than 10^??11 m²/s. Total H as H₂O in the homogeneous cores calculated by summing all the infrared absorbance bands ranges from 13 to 27 wt. ppm. The total H₂O in the six pre-annealed crystals is poorly correlated with any measured compositional variable. However, when the H₂O associated with individual infrared bands is compared, clear trends emerge. The intensity of absorption bands at 3572 and 3525 cm^??1 are strongly correlated with Ti concentrations, whose range in the six crystals exceeds an order of magnitude. Bands between 3400 and 3300 cm^??1, correlate negatively with Na⁺, but are positively correlated with the difference between molar Cr³⁺ and Na⁺. This highlights a previously unrecognised role for Na in suppressing H incorporation in natural olivines. The results confirm the important role that the trace constituents of olivine play in H incorporation. Two of these trace elements, Na and Ti, tend to be similarly enriched or depleted by partial melting or metasomatism of the mantle, but have opposite effects on H incorporation, with Ti enhancing it but Na suppressing it. Models estimating the effect of H in olivine on mantle rheology must, therefore, consider carefully the availability of these trace elements.     

Influences of organic matter and calcification rate on trace elements in aragonitic estuarine bivalve shells

A suite of elements (B, Na, Mg, S, K, Ca, V, Mn, Cr, Sr, and Ba) was measured in aragonitic shells of the estuarine bivalve Corbula amurensis, the Asian clam, using the Sensitive High-Resolution Ion MicroProbe with Reverse Geometry (SHRIMP RG). Our initial intent was to explore potential geochemical proxy relationships between shell chemistry and salinity (freshwater inflow) in northern San Francisco Bay (SFB). In the course of this study we observed variations in shell trace element to calcium ([M]/Ca) ratios that could only be attributed to internal biological processes. This paper discusses the nature and sources of internal trace element variability in C. amurensis shells related to the shell organic fraction and shell calcification rates. The average organic content of whole C. amurensis shells is 19%. After treating whole powdered shells with an oxidative cleaning procedure to remove organic matter, shells contained on average 33% less total Mg and 78% less total Mn. Within our analytical uncertainty, Sr and Ba contents were unchanged by the removal of organic matter. These results show that aragonitic C. amurensis shells have a large component of non-lattice-bound Mg and Mn that probably contribute to the dissimilarity of [M]/Ca profiles among five same-sized shells. Non-lattice-bound trace elements could complicate the development and application of geochemical proxy relationships in bivalve shells. Because B, Ba and Sr occur exclusively in shell aragonite, they are good candidates for external proxy relationships. [M]/Ca ratios were significantly different in prismatic and nacreous aragonite and in two valves of the same shell that had different crystal growth rates. Some part of these differences can be attributed to non-lattice-bound trace elements associated with the organic fraction. The differences in [M]/Ca ratios were also consistent with the calcification rate-dependent ion transport model developed by Carré et al. [Carré M., Bentaleb I., Bruguier O., Ordinola E., Barrett N. T. and Fontugne M. (2006) Calcification rate influence on trace element concentrations in aragonitic bivalve shells: evidences and mechanisms. Geochim. Cosmochim. Acta70, 4906-4920] which predicts that [M]/Ca ratios increase as calcification rates increase and Ca²⁺ channel specificity decreases. This result, in combination with the possibility that there were ontogenetic variations in growth rates among individuals younger than 2 years, underscores the need to develop an independent age model for C. amurensis shells. If growth-rate effects on lattice-bound [M]/Ca ratios can be constrained, it may yet be possible to develop high-resolution geochemical proxies for external solution chemistry in low-salinity regions of SFB.     

锆石微量元素及其揭示的深部过程

近十年来对锆石研究已从早期的U-Pb放射性同位素定年和锆石同位素分析,发展到大量研究锆石的微量元素。锆石微量元素不仅可以作为锆石Ti温度计估算岩浆温度,也可以用来识别锆石及其母岩的岩石类型和成因,区分岩浆熔体或者流体控制的岩浆作用、变质作用、成矿作用等深部作用过程。文中在归纳总结岩浆锆石、变质锆石、热液锆石、碎屑锆石等不同类型锆石的微量元素成分基础上,以青藏高原碰撞后超钾质岩石中产出的锆石为例,系统介绍了超钾质岩石中各类锆石的结构、年龄和微量元素特征,并应用于解释超钾质岩石成因、岩浆源区成分、岩浆演化和上部地壳物质的混染、下地壳加厚和高原隆升之间的关系。     

The concept of a equilibrium surface applied to particle sources and contaminant distributions in estuarine sediments

Studies have shown that many chemically-reactive contaminants become associated with fine particles in coastal waters and that the rate, patterns, and extent of contaminant accumulation within estuarine systems are extremely variable. In this paper, we briefly review our findings concerning the accumulation patterns of contaminants in several estuarine systems along the eastern coastline of the United States, and have applied a well-established concept in geology, that is “an equilibrium profile,” to explain the observed large variations in these patterns. We show that fine-particle deposition is the most important factor affecting contaminant accumulation in estuarine areas, and that accumulation patterns are governed by physical processes acting to establish or maintain a sediment surface in dynamic equilibrium with respect to sea level, river discharge, tidal currents, and wave activity. Net long-term particle and particle-associated contaminant accumulations are negliglible in areas where the sediment surface has attained “dynamic equilibrium” with the hydraulic regime. Contaminant, accumulation in these areas primarily occurs by the exchange of contaminant-poor sedimentary particles with contaminant-rich suspended particles during physical or biological mixing of the surface sediment. Virtually the entire estuarine particulate and contaminant load bypasses these “equilibrium” areas to accumulate at extremely rapid in relatively small areas that are temporally out of equilibriums as a result of natural processes or human activities. These relatively small areas serve as major sinks for particles from riverine and marine sources, and for biogenic carbon formed in situ within estuaries or on the inner shelf.     

Stratigraphy of late Quaternary estuarine deposits and amino acid stereochemistry of oyster shells beneath San Francisco Bay,California

The sequence of Quaternary deposits beneath the floor of San Francisco Bay includes four to seven noncontemporaneous estuarine units intercalated with alluvium and dune sand. Units L (0–10,000 B.P.), M (>40,000 B.P., probably ca. 80,000–140,000 B.P.), and N (older than unit M) are distinctly superposed. The dominant molluscan fossil in each of these three units is Ostrea lurida Carpenter, the native oyster along much of the pacific Coast of North America. Despite a lamellar structure that suggests vulnerability to contamination, O. lurida shells generally yield amino acid enantiomeric ratios that are analytically reproducible and stratigraphically consistent. The kinetics of racemization in O. lurida conceivably resembles that of Protothaca and Saxidomus, other bivalves whose kinetics of racemization are relatively well understood. Assuming such a resemblance, enantiomeric ratios in O. lurida imply that (1) unit M is the same approximate age as estuarine terrace deposits bordering San Pablo Bay and Carquinez Strait, providing that the terrace deposits have been at diagenetic temperatures 1°-2°C warmer than unit M; and (2) the age of unit N is about four times greater than that of unit M, providing that both units have been at the same approximate diagenetic temperature.     

Authigenic associations between selected rare earth elements and trace metals in lacustrine sediments

Surficial sediment samples were collected at 47 stations in Little Traverse Bay, Lake Michigan, to determine the geochemical associations between certain rare earth elements (REE's) and trace metals. Each sample was analyzed for carbonate carbon, organic carbon, grain size, and the elements Al, Ca, Ce, Co, Cr, Eu, Fe, Hf, La, and Mn. Two distinct Ce subpopulatins were identified by graphical analysis, and an R-mode factor analysis was applied to data from the “enriched” Ce subpopulation (18 samples). Results show that the REE's and trace metals are primarily enriched in the authigenic phase of these sediments. Partial correlation analyses indicate that the REE's are primarily associated with hydrous Fe oxides relative to organic matter in this phase. The ratio of Ce/La concentrations increased markedly from the bay margins to the central trough of the bay, indicating that Ce, similar to Fe, exhibits a variable oxidation state in the authigenic phase of nearshore fine-grained sediments. The results of the present study suggest that the REE's and trace metals behave coherently in the authigenic phase of recent lacustrine sediments, and the REE's may be useful as geochemical tracers to differentiate between trace metal enrichments in surface sediments as a result of diagenesis and pollution loadings.     

Seasonal variability in response of estuarine phytoplankton communities to stress: Linkages between toxic trace elements and nutrient enrichment

We examined individual and interactive effects of two stressors—nutrients (nitrogen [N] and phosphorus [P]) and trace elements (a mix of arsenic [As], copper [Cu], and cadmium [Cd], and in a second experiment also zinc [Zn] and nickel [Ni])—on phytoplankton of the mesohaline Patuxent River, a tributary of Chesapeake Bay. Experiments were conducted in twenty 1-m³ mesocosms. Four mesocosm runs used two levels of nutrient loadings (0.7–1.0 × ambient N loading and enriched to 1.3–1.6 × ambient N loading) crossed with two levels of trace elements (ambient and enriched approximately 2–5 × higher than ambient concentrations) crossed with five progressive levels of ecosystem complexity. To examine seasonal patterns of responses to stressors, data from these experiments were combined with results of a similar experiment conducted during 1996 (Breitburg et al. 1999a). A second mesocosm experiment examined effects of individual and mixed trace elements, both alone and in combination with nutrients, to further examine which nutrient-trace element interactions were important. Nutrients consistently increased phytoplankton productivity and biomass. Most of the increased biomass was created by large centric diatoms, which increased the mean cell size of the phytoplankton community. Trace element additions decreased phytoplankton productivity and biomass, as well as the contribution of large centric diatoms to phytoplankton biomass. When both trace elements and nutrients were added, trace elements reduced nutrient stimulation. Although the magnitude of the response to nutrient additions tended to be somewhat greater in spring, the seasonal patterns of trace element effects, and nutrient-trace element interactions were far more striking with significant responses restricted to spring mesocosm runs. The second experiment indicated that both As and Cu were more inhibitory to phytoplankton in spring than in summer, but As was more inhibitory in the low nutrient treatments and Cu was more inhibitory in the nutrient enrichment treatments. The potential for strong seasonal patterns and high temporal variability in stressor effects and multiple stressor interactiosn will require close attention in the design and interpretation of management-relevant research and monitoring and may indicate the need for seasonally varying management strategies.