Effects of increased urban and agricultural land use on the anthropogenic loading to southwest Florida estuaries

South Florida has been subject to considerable changes during the last 100 years. This study provides a detailed survey of the presence, concentration levels, and spatial distribution of organic and inorganic contaminants in sediment samples collected within the coastal environments of southwest Florida. It evaluates the potential contributions and effects of the urban and agricultural development to the pollution loading of the estuarine sediments. And it also provides information regarding chronology of contamination at impacted sites. Copper was found to be the most critical contaminant among the trace metals. 12% of the samples exceeded the Threshold Effects Level (TEL). None of organic contaminants measured exceeded the Probable Effects Level (PEL) criteria. Total PAHs concentrations exceeded the TEL criteria in 6% of the samples. The evaluation for the chronology of contamination showed a significant increase with time of every contaminant analyzed. Fluorescence spectroscopy proves to be a good method for fast screening PAHs.

Evidence of climate variability and tropical cyclone activity from diatom assemblage dynamics in coastal southwest Florida

Estuaries are dynamic on many spatial and temporal scales. Distinguishing effects of unpredictable events from cyclical patterns can be challenging but important to predict the influence of press and pulse drivers in the face of climate change. Diatom assemblages respond rapidly to changing environmental conditions and characterize change on multiple time scales. The goals of this research were to 1) characterize diatom assemblages in the Charlotte Harbor watershed, their relationships with water quality parameters, and how they change in response to climate; and 2) use assemblages in sediment cores to interpret past climate changes and tropical cyclone activity. ^ Diatom assemblages had strong relationships with salinity and nutrient concentrations, and a quantitative tool was developed to reconstruct past values of these parameters. Assemblages were stable between the wet and dry seasons, and were more similar to each other than to assemblages found following a tropical cyclone. Diatom assemblages following the storm showed a decrease in dispersion among sites, a pattern that was consistent on different spatial scales but may depend on hydrological management regimes. ^ Analysis of sediment cores from two southwest Florida estuaries showed that locally-developed diatom inference models can be applied with caution on regional scales. Large-scale climate changes were suggested by environmental reconstructions in both estuaries, but with slightly different temporal pacing. Estimates of salinity and nutrient concentrations suggested that major hydrological patterns changed at approximately 5.5 and 3 kyrs BP. A highly temporally-resolved sediment core from Charlotte Harbor provided evidence for past changes that correspond with known climate records. Diatom assemblages had significant relationships with the three-year average index values of the Atlantic Multidecadal Oscillation and the El Niño Southern Oscillation. Assemblages that predicted low salinity and high total phosphorus also had the lowest dispersion and corresponded with some major storms in the known record, which together may provide a proxy for evidence of severe storms in the paleoecological record. ^

Planktic foraminiferal and sea surface temperature record during the last 1 Myr across the Subtropical Front, Southwest Pacific

Planktic foraminiferal faunas and modern analogue technique estimates of sea surface temperature (SST) for the last 1 million years (Myr) are compared between core sites to the north (ODP 1125, 178 faunas) and south (DSDP 594, 374 faunas) of the present location of the Subtropical Front (STF), east of New Zealand. Faunas beneath cool subtropical water (STW) north of the STF are dominated by dextral Neogloboquadrina pachyderma, Globorotalia inflata, and Globigerina bulloides, whereas faunas to the south are strongly dominated by sinistral N. pachyderma (80-95% in glacials), with increased G. bulloides (20-50%) and dextral N. pachyderma (15-50%) in interglacials (beneath Subantarctic Water, or SAW). Canonical correspondence analysis indicates that at both sites, SST and related factors were the most important environmental influences on faunal composition. Greater climate-related faunal fluctuations occur in the south. Significant faunal changes occur through time at both sites, particularly towards the end of the mid-Pleistocene climate transition, MIS18-15 (e.g., decline of Globorotalia crassula in STW, disappearance of Globorotalia puncticulata in SAW), and during MIS8-5. Interglacial SST estimates in the north are similar to the present day throughout the last 1 Myr. To the south, interglacial SSTs are more variable with peaks 4-7 °C cooler than present through much of the early and middle Pleistocene, but in MIS11, MIS5.5, and early MIS1, peaks are estimated to have been 2-4 °C warmer than present. These high temperatures are attributed to southward spread of the STF across the submarine Chatham Rise, along which the STF appears to have been dynamically positioned throughout most of the last 1 Myr. For much of the last 1 Myr, glacial SST estimates in the north were only 1-2 °C cooler than the present interglacial, except in MIS16, MIS8, MIS6, and MIS4-2 when estimates are 4-7 °C cooler. These cooler temperatures are attributed to jetting of SAW through the Mernoo Saddle (across the Chatham Rise) and/or waning of the STW current. To the south, glacial SST estimates were consistently 10-11 °C cooler than present, similar to temperatures and faunas currently found in the vicinity of the Polar Front. One interpretation is that these cold temperatures reflect thermocline changes and increased Circumpolar Surface Water spinning off the Subantarctic Front as an enhanced Bounty Gyre along the south side of the Chatham Rise. For most of the last 1 Myr, the temperature gradient across the STF has been considerably greater than the present 4 °C. During glacial episodes, the STF in this region did not migrate northwards, but instead there was an intensification of the temperature gradient across it (interglacials 4-11 °C; glacials 8-14 °C).

Benthic foraminifera in Southwest Indian Ocean surface sediments

The distribution of deep-sea benthonic foraminifera in core top samples from the southwest Indian Ocean is examined. Principal component analysis reveals two major assemblages. One assemblages between 3600 and 4800-m water depth is dominated by Episominella umbonifera and is associated with cold (Theta = -0.3 to 0.8°C), low salinity (34.66 to 34.72 * 10**-3) Antarctic Bottom Water in the Crozet Basin, in fracture zones, and on the flanks of the Southwest Indian Ridge. A second assemblage, dominated by Planulina wuellerstorfi, Globocassidulina subglobasa, Astrononion echolsi and Pullenia bulloides, is between 1600 and 3800 m on the Crozet Plateau, Madagascar Ridge, Central Indian Ridge, and Southwest Indian Ridge and is associated with relatively warm (Theta = 0.8 to 2.6°C), high salinity (34.72 to 34.76 * 10**-3) North Atlantic Deep Water. The third principal component divides the P. wuellerstorfi assemblage into two subgroups. One is dominated by Epistominella exigua, P. bulloides, P. wuellerstorfi, and A. echolsi and a second is dominated by G. subglobosa. The distribution of the E. umbonifera assemblage and previous hydrographic studies suggest that AABW flows as a western boundary contour current in the Crozet Basin and penetrates fracture zones in the Southwest Indian Ridge between 55 and 57°E and near 66°E as it travels northward into the Madagascar and Mascarene basins. The faunal-water mass associations from the southeast Indian Ocean are compared; the most notable faunal difference is the absence of Uvigerina as a dominant taxon in the southwest Indian Ocean. A comparison of dissolved oxygen and Uvigerina data shows that oxygen is not a major influence upon the distribution of Uvigerina. A correlation analysis of the faunal data and water depth, potential temperature, in situ temperature, salinity, dissolved oxygen, and 1 - Omega, an index of calcium carbonate undersaturation, was carried out to determine the relationships between fauna and hydrography. The second principal component has a significant positive correlation at the 99.9% level with temperature and negative correlations with water depth and 1 - Omega. A general faunal-water mass correlation exists, but it is not possible to determine which variable controls the faunal distributions.

Radiocarbon ages measured in core PSh63-5159R from the southwest Barents Sea

Environmental changes in the surface and bottom water layers of the Ingøydjupet Basin and history of Atlantic water inflow to the southwestern Barents Sea during the last 16 ka are reconstructed on the base of planktic and benthic foraminiferal assemblages. A multiproxy study of sediment cores PSh-5159R and PSh-5159N, including AMS 14C dating, provides time resolution of about 200 years for the deglaciation period, 100 years for Holocene, and 25-50 years for the last 400 years. Stable polar conditions with sea ice on the surface were typical for the early deglaciation period. Unstable bottom settings and onset of ice rafting marked Oldest Dryas. Cold Atlantic water inflow increased notably during the Boiling-Allerod interstadial nearby the site location and then decreased during the Younger Dryas. Early Holocene was characterized by abrupt warming in the bottom and surface water layers, especially ~9.7-7.6 ka BP. Stable conditions prevailed during Middle Holocene. Remarkable changes in the sea-surface temperature and bottom environments occurred during last 2.5 cal. ka BP.

Age, 232Th, 230Th, 238U, CaCO3, organic carbon, lithogenic fraction and opal concentrations of 4 sediment cores from the southwest Pacific, with calculated 230Th-normalized mass flux

No clear scenario has yet been able to explain the full carbon drawdown that occurred during the Last Glacial Maximum (LGM); however, increased export production (EP) in the Subantarctic Zone (SAZ) of the Southern Ocean due to iron (Fe) fertilisation has been proposed to have provided a key mechanism affecting the air-sea partitioning of carbon. We chronicle changes in marine EP based on four sediment cores in Subtropical Waters (STW) and SAZ around New Zealand since the LGM. For the first time in this region, we present 230-Thorium normalised fluxes of biogenic opal, carbonate (CaCO3), excess Barium (xsBa), and organic Carbon (Corg). In STW and SAZ, these flux variations show that EP did not change markedly since the LGM. The only exception was a site in the SAZ close to the STF, where we suggest the STF shifted over the core site, driving increased EP. To understand why EP was mostly low and constant we investigated dust deposition changes by measuring lithogenic fluxes at the four sites. These data are coherent with an increased dust deposition in the southwest Pacific during the LGM. Additionally, we infer an increased lithogenic material discharge from erosion and glacier melts during the deglaciation, limited to the Campbell Plateau. Therefore, we propose that even though increased glacial dust deposition may have relieved Fe limitation within the SAZ, the availability of silicic acid (Si(OH)4) limited any resultant increase in carbon export during the LGM. Consequently, we infer low Si(OH)4 concentrations in the SAZ that have not significantly changed since the LGM. This result suggests that both Si(OH)4 and Fe co-limit EP in the SAZ around New Zealand, which would be consistent with modern process studies.

Basalt analyses from different DSDP Holes in the Mozambique Basin and Ridge and from the Southwest Indian Ridge

Basalts from DSDP Sites 248, 249, 250 and 251 in the southwestern Indian Ocean formed in a complex tectonic region affected by the separation of Africa and South America. The different ages and variable geochemical features of these DSDP basalts probably reflect this tectonic complexity. For example, Site 251 on the flanks of the Southwest Indian Ridge is represented by normal MORB which probably originated at the Southwest Indian Ridge. Site 250 in the Mozambique Basin includes an older incompatible- element enriched unit which may represent basalt associated with the Prince Edward Fracture Zone; the upper unit is normal MORB. Basalts at Site 248 also in the Mozambique Basin are geochemically very unlike MORB and have strong continental affinities; they are also comparable in age to some of the continental Karroo basalts. They appear to be related to a subcontinental mantle source or to contamination by continental basement associated with the tectonic elevation of the Mozambique Ridge. Basalts from Site 249 on the Mozambique Ridge are relatively weathered but appear to be normal MORB. Their age, location, and composition are consistent with their origin at an early Cretaceous rift which has been postulated to have separated the Falkland Plateau from the Mozambique Ridge.

Bulk 15N, and 13Corg ratios, and calculation of unutilized nitrate of surface samples off the southwest coast of Africa (Table 1)

Bulk delta15N values in surface sediment samples off the southwestern coast of Africa were measured to investigate the biogeochemical processes occurring in the water column. Nitrate concentrations and the degree of utilization of the nitrate pool are the predominant controls on sedimentary delta15N in the Benguela Current region. Denitrification does not appear to have had an important effect on the delta15N signal of these sediments and, based on delta15N and delta13C, there is little terrestrial input.

Hydrogen isotope compositions of terrestrial plant-wax n-alkanes analysed on a transect of marine surface sediment samples from 1°N to 28°S off southwest Africa

A transect of marine surface sediment samples from 1° N to 28° S off southwest Africa was analysed to verify the application of hydrogen isotope compositions of terrestrial plant-wax n-alkanes preserved in ocean sediments as a proxy for continental hydrological conditions. Conditions on the adjacent continent range from humid evergreen forests to deciduous forests, wood- and shrub land and further to arid grasslands and deserts. The hydrogen isotope values for the dominant n-alkane homologues (C29, C31 and C33) vary from -123 per mil to -141 per mil VSMOW and correlate with the modelled hydrogen isotope composition of mean annual and growing season precipitation of postulated continental source areas (r up to 0.8, p < 0.01). The apparent hydrogen isotope fractionation between alkanes and mean annual precipitation is remarkably uniform (-109 per mil on average, Sigma <= 5 per mil, n = 27). Potentially, effects of aridity on the apparent hydrogen isotope fractionation are concealed by the contribution of different plants (C3 dicotyledons vs C4 grasses). Thus, isotope ratios of leaf wax n-alkanes preserved in ocean margin sediments in these and similar tropical regions may be directly converted to dD ratios of ancient precipitation by employing a constant hydrogen isotope fractionation.

(Supplement Table1) Abundances of major elements from KH93-3_DR10 at the Southwest Indian Ridge near the Rodriguez Triple Junction

Petrographic and geochemical analyses of basaltic rocks dredged from the first segment of the Southwest Indian Ridge near the Rodriguez Triple Junction have been completed in order to investigate water-rock interaction processes during mid-ocean ridge (MOR) hydrothermal alteration in the Indian Ocean. In the study area, we have successfully recovered a serial section of upper oceanic crust exposed along a steep rift valley wall which was uplifted and emplaced along a low angle normal fault. On the basis of microscopic observation, dredged samples are classified into three types: fresh lavas, low-temperature altered rocks, and high-temperature altered rocks. The fresh lavas have essentially the same chemical composition as typical N-MORB, although LILE and Nb are slightly enriched and depleted, respectively. Low temperature alteration brought about the enrichment of K2O, Rb, and U due to the presence of K-rich celadonite and U-adsorption onto Fe-oxyhydroxide and clay minerals. On the other hand, chloritization, albitization, and addition of base metals by high temperature hydrothermal alteration result in enrichments of MnO, MgO, Na2O, Cu, and Zn and depletions of CaO, K2O, Cr, Co, Ni, Rb, Sr, and Ba. In addition, U-enrichment is also observable in the high temperature altered rocks probably due to the decrease of uranite solubility in the reducing high-temperature hydrothermal solution. These petrological and geochemical features are comparable to those of the volcanic zone to transition zone rocks in the DSDP/ODP Hole 504B, indicating that our samples were recovered from the upper ~1000 m section of the oceanic crust. Only the alteration minerals related to off-axis alteration are absent in our samples dredged from near the spreading axis. The similarity of alteration between our samples from the Indian Ocean and the Hole 504B rocks from the Pacific Ocean suggests that MOR hydrothermal systems are probably similar across all world oceans.