Li-Sr-Nd isotope signatures of the plume and cratonic lithospheric mantle beneath the margin of the rifted Tanzanian craton (Labait)

Lithium concentrations and isotopic compositions of olivine and ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd of coexisting clinopyroxene from peridotite xenoliths from the Quaternary Labait volcano, Tanzania, document the influence of rift-related metasomatism on the ancient cratonic mantle. Olivines show negative correlations between Fo content and both δ⁷Li and Li concentrations. Olivines in iron-rich peridotites (Fo_85–87) have high Li concentrations (3.2–4.8 ppm) and heavy δ⁷Li (+5.2 to +6.6). In contrast, olivines in ancient, refractory peridotites have lower Li concentrations (∼2 ppm) and relatively light δ⁷Li (+2.6 to +3.5). This reflects mixing between ancient, refractory cratonic lithosphere and asthenosphere-derived rift magmas. A uniquely fertile, deformed, high-temperature garnet lherzolite, interpreted to be from the base of the lithosphere, has a ⁸⁷Sr/⁸⁶Sr of 0.7029 and ¹⁴³Nd/¹⁴⁴Nd of 0.51286, similar to HIMU oceanic basalts. It provides the best estimate of the Sr–Nd isotope composition of the upwelling mantle (i.e., plume, sensu lato) underlying this portion of the East African Rift, and is slightly less radiogenic compared to previous estimates of the plume that were based on rift basalts. Although elevated δ⁷Li are not exclusive to HIMU source regions, the data collectively indicate that the plume beneath Labait has HIMU characteristics in Sr, Nd and Li isotope composition. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Factors affecting spatial and temporal variability in material exchange between the Southern Everglades wetlands and Florida Bay (USA)

Physical and biological processes controlling spatial and temporal variations in material concentration and exchange between the Southern Everglades wetlands and Florida Bay were studied for 2.5 years in three of the five major creek systems draining the watershed. Daily total nitrogen (TN), and total phosphorus (TP) fluxes were measured for 2 years in Taylor River, and ten 10-day intensive studies were conducted in this creek to estimate the seasonal flux of dissolved inorganic nitrogen (N), phosphorus (P), total organic carbon (TOC), and suspended matter. Four 10-day studies were conducted simultaneously in Taylor, McCormick, and Trout Creeks to study the spatial variation in concentration and flux. The annual fluxes of TOC, TN, and TP from the Southern Everglades were estimated from regression equations. The Southern Everglades watershed, a 460-km² area that includes Taylor Slough and the area south of the C-111 canal, exported 7.1 g C m⁻², 0.46 g N m⁻², and 0.007 g P m⁻², annually. Everglades P flux is three to four orders of magnitude lower than published flux estimates from wetlands influenced by terrigenous sedimentary inputs. These low P flux values reflect both the inherently low P content of Everglades surface water and the efficiency of Everglades carbonate sediments and biota in conserving and recycling this limiting nutrient. The seasonal variation of freshwater input to the watershed was responsible for major temporal variations in N, P, and C export to Florida Bay; approximately 99% of the export occurred during the rainy season. Wind-driven forcing was most important during the later stages of the dry season when low freshwater head coincided with southerly winds, resulting in a net import of water and materials into the wetlands. We also observed an east to west decrease in TN:TP ratio from 212:1 to 127:1. Major spatial gradients in N:P ratios and nutrient concentration and flux among the creek were consistent with the westward decrease in surface water runoff from the P-limited Everglades and increased advection of relatively P-rich Gulf of Mexico (GOM) waters into Florida Bay. Comparison of measured nutrient flux from Everglades surface water inputs from this study with published estimates of other sources of nutrients to Florida Bay (i.e. atmospheric deposition, anthropogenic inputs from the Florida Keys, advection from the GOM) show that Everglades runoff represents only 2% of N inputs and 0.5% of P input to Florida Bay.     

Evidence for high‐temperature fractionation of lithium isotopes during differentiation of the Moon

Lithium isotope and abundance data are reported for Apollo 15 and 17 mare basalts and the LaPaz low‐Ti mare basalt meteorites, along with lithium isotope data for carbonaceous, ordinary, and enstatite chondrites, and chondrules from the Allende CV3 meteorite. Apollo 15 low‐Ti mare basalts have lower Li contents and lower δ⁷Li (3.8 ± 1.2‰; all uncertainties are 2 standard deviations) than Apollo 17 high‐Ti mare basalts (δ⁷Li = 5.2 ± 1.2‰), with evolved LaPaz mare basalts having high Li contents, but similar low δ⁷Li (3.7 ± 0.5‰) to Apollo 15 mare basalts. In low‐Ti mare basalt 15555, the highest concentrations of Li occur in late‐stage tridymite (>20 ppm) and plagioclase (11 ± 3 ppm), with olivine (6.1 ± 3.8 ppm), pyroxene (4.2 ± 1.6 ppm), and ilmenite (0.8 ± 0.7 ppm) having lower Li concentrations. Values of δ⁷Li in low‐ and high‐Ti mare basalt sources broadly correlate negatively with ¹⁸O/¹⁶O and positively with ⁵⁶Fe/⁵⁴Fe (low‐Ti: δ⁷Li ≤4‰; δ⁵⁶Fe ≤0.04‰; δ¹⁸O ≥5.7‰; high‐Ti: δ⁷Li >6‰; δ⁵⁶Fe >0.18‰; δ¹⁸O <5.4‰). Lithium does not appear to have acted as a volatile element during planetary formation, with subequal Li contents in mare basalts compared with terrestrial, martian, or vestan basaltic rocks. Observed Li isotopic fractionations in mare basalts can potentially be explained through large‐degree, high‐temperature igneous differentiation of their source regions. Progressive magma ocean crystallization led to enrichment in Li and δ⁷Li in late‐stage liquids, probably as a consequence of preferential retention of ⁷Li and Li in the melt relative to crystallizing solids. Lithium isotopic fractionation has not been observed during extensive differentiation in terrestrial magmatic systems and may only be recognizable during extensive planetary magmatic differentiation under volatile‐poor conditions, as expected for the lunar magma ocean. Our new analyses of chondrites show that they have δ⁷Li ranging between ?2.5‰ and 4‰. The higher δ⁷Li in planetary basalts than in the compilation of chondrites (2.1 ± 1.3‰) demonstrates that differentiated planetary basalts are, on average, isotopically heavier than most chondrites.     

Determination of Ga,Ge, Mo,Ag, Cd,In, Sn,Sb, W,Tl and Bi in USGS Whole‐Rock Reference Materials by Standard Addition ICP‐MS

A procedure for determining a wide range of chalcophile and siderophile elements in typical crustal rocks using standard addition and ICP‐SFMS (inductively coupled plasma sector field mass spectrometry) is presented. New results for Ga, Ge, Mo, Ag, Cd, In, Sn, Sb, W, Tl and Bi abundances in USGS whole‐rock reference materials AGV‐2, BHVO‐1, BIR‐1, G‐2, GSP‐1 and W‐2 are reported using this analytical procedure. Intermediate precision of means based on multiple dissolved aliquots of each USGS reference material was 10% RSD or better for Ga, Ge, In and Sn in all, and similarly good for Ag, Cd, Sb, Tl and Bi in most reference materials. Poorer intermediate precision of Mo and W measurements in several reference materials is probably due to higher analytical blanks on these elements and powder heterogeneity due to a sulfide‐related nugget effect in the specific case of Mo in GSP‐1. Results for all elements fell within the range of available published data with the exception of Ag, which yielded systematically higher concentrations than found in the literature for five of the six reference materials, likely reflecting interference from unresolved polyatomic species.     

The use of proxy chemical records in Coral skeletons to ascertain past environmental conditions in Florida Bay

This paper will discuss the use of chemical proxies in coral skeletons to reconstruct the history of salinity (from the δ¹⁸O of the skeleton) and nutrients in the water (from the δ¹³C) in Florida Bay between 1824 and 1994. Monthly salinity and water temperature data collected since 1989 were used to establish a correlation between salinity, temperature, and the δ¹⁸O of the skeleton of the coralSolenastrea bournoni from Lignumvitae Basin in Florida Bay. This relationship explains over 50% of the variance in the δ¹⁸O of the skeleton. Assuming that interannual variations in the temperature of the water are small, we have applied this relationship to the δ¹⁸O measured in the coral skeleton collected from Lignumvitae Basin which has a record between 1824 and 1993. These data provide a revised estimate of salinity variation in Lignumvitae Basin for the period when historical records for salinity were not available, and show that the highest salinity events occurred in the past 30 yr. Using the relationships between the salinity in Lignumvitate Basin and other basins, obtained using a modern dataset, we are able to estimate ranges in salinity for other portions of Florida Bay. Skeletons of specimens of the coral speciesSiderastrea radians collected from other areas of Florida Bay show similar patterns in the δ¹⁸O over the past 10 yr, indicating that corals in most portions of Florida Bay are recording salinity variations in their skeletons and therefore support the idea that salinity variations in different portions of Florida Bay can be related. Fluorescence analysis of the coral from Lignumvitae Basin shows a large change in the magnitude of the 10-yr signal coincident with the construction of the railway, confirming that this event had a significant impact upon Florida Bay. The δ¹³C of the coral skeletons reveals a long-term history of the oxidation of organic material, fixation of carbon by photosynthesis (algal blooms), and the intrusion of marine water into the bay. Since the construction of the railway from Miami to Key West there has been a long-term decrease in the δ¹³C of the coral skeleton from Lignumvitae Basin, suggesting the increased oxidation of organic material in this area. This decrease in δ¹³C appears to have reached a minimum value around 1984 and has increased since this time in the western portions of Florida Bay. The increase may be related to the algal blooms prevalent in the area or alternatively could result from intrusion of more marine water. In the eastern areas, a small increase in the δ¹⁸C between 1984 and 1988 was followed by further decline suggesting more oxidation of organic material. We have also attempted to use the concentration of barium in the coral skeleton as a proxy indicator of the nutrient status in Florida Bay.     

Phosphorus and nitrogen inputs to Florida Bay: The importance of the everglades watershed

A large environmental restoration project designed to improve the hydrological conditions of the Florida Everglades and increase freshwater flow to Florida Bay is underway. Here we explore how changing freshwater inflow to the southern Everglades is likely to change the input of nutrients to Florida Bay. We calculated annual inputs of water, total phosphorus (TP), total nitrogen (TN), and dissolved inorganic nitrogen (DIN) to Everglades National Park (ENP) since the early 1980s. We also examined changes in these nutrient concentrations along transects through the wetland to Florida Bay and the Gulf of Mexico. We found that the interannual variability of the water discharge into ENP greatly exceeded the interannual variability of flow-weighted mean nutrient concentrations in this water. Nutrient inputs to ENP were largely determined by discharge volume. These inputs were high in TN and low in TP; for two ENP watersheds TN averaged 1.5 mg l^?1 (0.11 mM) and 0.9 mg l^?1 (0.06 mM) and TP averaged 15 μg l^?1 (0.47 μM) and 9 μg l^?1 (0.28 μM). Both TP and DIN that flowed into ENP wetlands were rapidly removed from the water. Over a 3-km section of Taylor Slough, TP decreased from a flow-weighted mean of 11.6 μg l^?1 (0.37 μM) (0.20 μM) and DIN decreased from 240 μg l^?1 (17μM) to 36 μ l^?1 (2.6 μM). In contrast, TN, which was generally 95% organic N, changed little as it passed through the wetland. This resulted in molar TN:TP ratios exceeding 400 in the wetland. Decreases in TN concentrations only occurred in areas with relatively high P availability, such as the wetlands to the north of ENP and in the mangrove streams of western ENP. Increasing freshwater flow to Florida Bay in an effort to restore the Everglades and Florida Bay ecosystems is thus not likely to increase P inputs from the freshwater Everglades but is likely to increase TN inputs. Based on a nutrient budget of Florida Bay, both N and P inputs from the Gulf of Mexico greatly exceed inputs from the Everglades, as well as inputs from the atmosphere and the Florida Keys. We estimate that the freshwater Everglades contribute <3% of all P inputs and <12% of all N inputs to the bay. Evaluating the effect of ecosystem restoration efforts on Florida Bay requires greater understanding of the interactions of the bay with the Gulf of Mexico and adjacent mangrove ecosystems.     

Investigating Groundwater‐Lake Interactions by Hydraulic Heads and a Water Balance

Discharge of groundwater into lakes (lacustrine groundwater discharge, LGD) can play a major role in water balances of lakes. Unfortunately, studies often neglect this input path because of methodological difficulties in its determination. Direct measurements of LGD are labor‐consuming and prone to error. The present study uses both spatially variable hydraulic‐head data and meteorological data to estimate groundwater input by LGD and lake water output through infiltration. The study sites are two shallow, groundwater‐fed lakes without any surface inflows or outflows. Horizontally interpolated groundwater heads were combined with lake water levels to obtain vertical hydraulic gradients between the aquifer and the lake, which are separated by a thick layer of lake bed sediment which has a much lower hydraulic conductivity than the underlying aquifer. By fitting the hydraulic gradient to the results of a simple mass balance and considering the process of clogging, we were able to estimate the hydraulic conductivity of the lake bed sediments. We calculated groundwater inputs by LGD and lake water outputs by infiltration on an annual basis. Although our method requires several assumptions, the results are reasonable and provide useful information about the exchange between the aquifer and the lake, which can, for example, be used for the calculation of nutrient mass balances.     

Thermal history and origin of the Tanzanian Craton from Pb isotope thermochronology of feldspars from lower crustal xenoliths

Common and radiogenic Pb isotopic compositions of plagioclase and anti-perthitic feldspars from granulite-facies lower crustal xenoliths from the Labait Volcano on the eastern margin of the Tanzanian Craton have been measured via laser ablation MC-ICP-MS. Common Pb in plagioclase and a single stage Pb evolution model indicate that the lower crust of the Tanzanian Craton was extracted from mantle having a ²³⁸U/²⁰⁴Pb of 8.1 ± 0.3 and a ²³²Th/²³⁸U of 4.3 ± 0.1 at 2.71 ± 0.09 Ga (all uncertainties are 2σ). Since 2.4 Ga, some orthoclase domains within anti-perthites have evolved with a maximum ²³⁸U/²⁰⁴Pb of 6 and ²³²Th/²³⁸U of 4.3. The spread in Pb isotopic composition in the anti-perthitic feldspars yields single crystal Pb–Pb isochrons of ～ 2.4 Ga, within uncertainty of U–Pb zircon ages from the same sample suite. The Pb isotopic heterogeneities imply that these granulites resided at temperatures < 600 °C in the lower crust of the Tanzanian Craton from ca. 2.4 Ga to the present. In concert with the chemistry of surface samples, mantle xenoliths, and lower crustal xenoliths, our data imply that the cratonic lithosphere in Tanzania formed ca. ～ 2.7 Ga, in a convergent margin setting, and has remained undisturbed since 2.7 Ga.     

Wetland-water column exchanges of carbon, nitrogen, and phosphorus in a southern Everglades dwarf mangrove

We used enclosures to quantify wetland-water column nutrient exchanges in a dwarf red mangrove, (Rhizophora mangle L.) system near Taylor River, an important hydraulic linkage between the southern Everglades and eastern Florida Bay, Florida, USA. Circular enclosures were constructed around small (2.5–4 m diam) mangrove islands (n=3) and sampled quarterly from August 1996 to May 1998 to quantify net exchanges of carbon, nitrogen, and phosphorus. The dwarf mangrove wetland was a net nitrifying environment with consistent uptake of ammonium (6.6–31.4 μmol m⁻² h⁻¹) and release of nitrite +nitrate (7.1–139.5 μmol m⁻² h⁻¹) to the water column. Significant flux of soluble reactive phosphorus was rarely detected in this nutrient-poor, P-limited environment. We did observe recurrent uptake of total phosphorus and nitrogen (2.1–8.3 and 98–502 μmol m⁻² h⁻¹, respectively), as well as dissolved organic carbon (1.8–6.9 μmol m⁻² h⁻¹) from the water column. Total organic carbon flux shifted unexplainably from uptake, during Year 1, to export, during Year 2. The use of unvegetated (control) enclosures during the second year allowed us to distinguish the influence of mangrove vegetation from soil-water column processes on these fluxes. Nutrient fluxes in control chambers typically paralleled the direction (uptake or release) of mangrove enclosure fluxes, but not the magnitude. In several instances, nutrient fluxes were more than twofold greater in the absence of mangroves, suggesting an influence of the vegetation on wetland-water column processes. Our findings characterize wetland nutrient exchanges, in a mangrove forest type that has received such little attention in the past, and serve as baseline data for a system undergoing hydrologic restoration.     

The effects of tributyltin within aThalassia seagrass ecosystem

Flow-through seagrass core microcosms were used to examine responses of species and processes to a logarithmic gradient of dosing with¹⁴C-labeled tributyltin-chloride (TBT-CI). Experiments involved delivery of TBT-CI to the water column of replicate cores of a treatment (n=16) once per week; one-half of the cores were sacrificed after 3 wk of dosing, the others were dosed for 6 wk. Initial water column concentrations for the three treatments averaged 0.205, 2.23, and 22.21 μg I^?1, expressed as the TBT⁺ cation, but these concentrations dropped rapidly. Retained¹⁴C tracer, an estimate of total organotin species, was distributed to sediments, plants, and other biological tissues, all of whose tracer concentrations increased with time. Measures to indicate responses of both autotrophic and heterotrophic organisms were made; in general, treatment effects were demonstrable statistically only at the highest dose level. Accumulation of chlorophyll and biomass on glass slides was highest when suspended for the entire experiment in the water of the highest treatment; this unexpected result was perhaps an indirect effect related to reduced grazing activity in the microcosms. The highest dose of TBT-CI resulted in virtual population mortality of a few macrobenthic species and decreased loss of plant material in litter bags, both demonstrated within the first 3 wk of dosing. Reduced litter loss was coincident with mortality of an amphipod (Cymadusa compta) capable of shredding plant material, and a causal relation between the two effects is plausible. Thus, if concentrated to similar levels in aThalassia bed, TBT⁺ may have direct species-level effects and process-level effects, potentially causing ecosystem change via disruption of a species-process linkage influential in seagrass detrital food web dynamics.